Related literature   {#sec1}
====================

For background to the biological activity of synthetic pyrano\[2,3-*c*\] pyrazole compounds, see: Nasr *et al.* (2002[@bb11]); Ismail *et al.* (2003[@bb8]); Foloppe *et al.* (2006[@bb7]); Mohamed *et al.* (2010[@bb10]); Zonouz *et al.* (2012[@bb17]); Kuo *et al.* (1984[@bb9]); Zaki *et al.* (2006[@bb16]); Ahluwalia *et al.* (1997[@bb1]); Bhavanarushi *et al.* (2013[@bb3]). For the synthesis of the title compound, see: Brahmachari & Banerjee (2014[@bb4]). For a related structure, see: Topno *et al.* (2011[@bb15]). For standard bond-length data, see: Allen *et al.* (1987[@bb2]). For ring conformations, see: Duax & Norton (1975[@bb5]).

Experimental   {#sec2}
==============

 {#sec2.1}

### Crystal data   {#sec2.1.1}

C~16~H~14~N~4~O~3~·C~2~H~6~OS*M* *~r~* = 388.44Monoclinic,*a* = 28.018 (5) Å*b* = 9.196 (5) Å*c* = 15.396 (5) Åβ = 93.376 (5)°*V* = 3960 (3) Å^3^*Z* = 8Mo *K*α radiationμ = 0.19 mm^−1^*T* = 293 K0.30 × 0.20 × 0.20 mm

### Data collection   {#sec2.1.2}

Oxford Diffraction Xcalibur Sapphire3 diffractometerAbsorption correction: multi-scan (*CrysAlis RED*; Oxford Diffraction, 2010[@bb12]) *T* ~min~ = 0.805, *T* ~max~ = 1.00013653 measured reflections6946 independent reflections3460 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.052

### Refinement   {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.068*wR*(*F* ^2^) = 0.210*S* = 1.006946 reflections510 parametersH-atom parameters constrainedΔρ~max~ = 0.32 e Å^−3^Δρ~min~ = −0.24 e Å^−3^

 {#d5e663}

Data collection: *CrysAlis PRO* (Oxford Diffraction, 2010[@bb12]); cell refinement: *CrysAlis PRO*; data reduction: *CrysAlis PRO*; program(s) used to solve structure: *SHELXS97* (Sheldrick, 2008[@bb13]); program(s) used to refine structure: *SHELXL97* (Sheldrick, 2008[@bb13]); molecular graphics: *ORTEP-3 for Windows* (Farrugia, 2012[@bb6]); software used to prepare material for publication: *PLATON* (Spek, 2009[@bb14]).

Supplementary Material
======================

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: [10.1107/S1600536814013270/lh5712sup1.cif](http://dx.doi.org/10.1107/S1600536814013270/lh5712sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S1600536814013270/lh5712Isup2.hkl](http://dx.doi.org/10.1107/S1600536814013270/lh5712Isup2.hkl)

###### 

Click here for additional data file.

Supporting information file. DOI: [10.1107/S1600536814013270/lh5712Isup3.cml](http://dx.doi.org/10.1107/S1600536814013270/lh5712Isup3.cml)

CCDC reference: [1006444](http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=1006444)

Additional supporting information: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?lh5712&file=lh5712sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?lh5712sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?lh5712&checkcif=yes)

Supporting information for this paper is available from the IUCr electronic archives (Reference: [LH5712](http://scripts.iucr.org/cgi-bin/sendsup?lh5712)).

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. GB is thankful to the CSIR, New Delhi, for financial support \[grant No. 02 (110)/12/EMR-II\]. BB is grateful to the UGC, New Delhi for the award of a Senior Research Fellowship.

S1. Comment {#comment}
===========

Pyrano\[2,3-*c*\]pyrazole scaffolds represent a \"privileged\" structural motif well distributed in naturally occurring compounds with a broad spectrum of significant biological activities. Recently, a series of synthetic pyrano\[2,3-*c*\] pyrazole compounds have been evaluated and possess potent bactericidal (Nasr *et al.*, 2002), insecticidal (Ismail *et al.*, 2003), molluscicidal (Zonouz *et al.*, 2012), analgestic (Kuo *et al.*, 1984), anti-inflammatory activities (Zaki *et al.*, 2006), hypotensive (Ahluwalia *et al.*, 1997), hypoglycemic, and anticancer agents (Mohamed *et al.*, 2010; Bhavanarushi *et al.*, 2013). They are also potential inhibitors of human Chk1 kinase (Foloppe *et al.*, 2006). Hence, investigation of the structural features of biologically relevant pyrano\[2,3-*c*\]pyrazole derivatives is of both scientific and practical interest. In continuation of our efforts to develop useful synthetic protocols for biologically significant molecules, we report herein an efficient and environmentally benign synthesis and the crystal structure of the title compound (I)

The asymmetric unit of the title compound is shown in Fig. 1. There are two crystallographically independent molecules (A and B). The geometry of both molecules is similar and in terms of their bond lengths and bond angles and are in good agreement with the standard values (Allen *et al.*, 1987) and corresponds to those observed in a related structure (Topno *et al.*, 2011). The double bond length C13A═O13A \[1.212 (5) Å\] and C13B═O13B \[1.210 (5) Å\] indicates the C═O double bond slightly longer than that observed for carbonyl bonds, probably because atoms O13A and O13B are involved in intermolecular N---H···O hydrogen bonds. The pyran ring (ring II) adopts a flattned sofa conformation in molecule A and a flattened boat conformation in molecule B with asymmetry parameters \[ΔCs(C4) = 2.73\] (molecule A) and \[ΔCs(C4)) = 1.03, ΔC2(C4---C5) = 1.14\] (molecule B) (Duax & Norton, 1975). The mean planes the pyrazole (ring I) and phenyl (ring III) rings from dihedral angles of 84.4 (2)° and 84.9 (2)°, respectively for molecules A and B. In the crystal, N---H···O and N---H···N hydrogen bonds link the components of the structure into chains along \[010\] (Fig. 2). In both solvent molecules, the S atoms are disordered over two sites with occupancy ratios of 0.679 (4):0.321 (4) and 0.546 (6):0.454 (6).

S2. Experimental {#experimental}
================

The synthesis of the title compound, ethyl 6-amino-5-cyano-4-phenyl-2, 4-dihydropyrano\[2,3-*c*\]pyrazole-3-carboxylate (I), was carried out *via* one-pot multi-component reaction in aqueous ethanol using low-cost and environmentally benign urea as catalyst at room temperature. An oven-dried screw cap test tube was charged with a magnetic stir bar, diethyl acetylenedicarboxylate (0.170 g, 1.0 mmol) and hydrazine hydrate (0.050 g, 1 mmol); the reaction mixture was then stirred at room temperature for about 10 min. After that, benzaldehyde (0.106 g, 1 mmol), malononitrile (0.066 g, 1.1 mmol), urea (0.007 g, 10 mol % as organo-catalyst) and EtOH:H~2~O (1:1 *v*/*v*; 4 ml) was added in a sequential manner (Brahmachari and Banerjee, 2014). The reaction mixture was then stirred vigorously at room temperature and the stirring was continued for 10 h. The progress of the reaction was monitored by TLC. On completion of the reaction, a solid mass was precipitated out, filtered off and repeatedly washed with aqueous ethanol to obtain a crude product which was purified just by recrystallization from ethanol without carrying out column chromatography. The structure of (I) was confirmed by analytical as well as spectral studies including ^1^H NMR, ^13^C NMR, and TOF-MS. The single crystal was obtained from DMSO as a solvent. For crystallization 50 mg of (I) dissolved in 5 ml DMSO was left for several days at ambient temperature which yielded white block shaped crystals. Ethyl 6-amino-5-cyano-4-phenyl-2,4-dihydropyrano\[2,3-*c*\] pyrazole-3-carboxylate (1). White solid. Yield 91%. Mp: 521--523 K. ^1^H NMR (400 MHz, DMSO-d~6~) δ /p.p.m.: 13.76 (1*H*, s, NH), 7.28 (2*H*, t, *J* = 7.2 Hz, aromatic H), 7.19 (1*H*, t, *J* = 7.2 Hz, aromatic H), 7.10 (2*H*, d, *J* = 7.2 Hz, aromatic H), 7.03 (2*H*, s, NH~2~), 4.76 (1*H*, s, CH), 4.07 (2*H*, q, *J* = 7.2 \\ 6.8 Hz, CH~3~), 1.03 (3*H*, t, *J* = 7.2 & 6.8 Hz, CH~3~). ^13^C NMR (100 MHz, DMSO-d~6~) δ /p.p.m.: 160.43, 158.56, 156.01, 145.31, 129.48, 128.66 (2 C), 127.73 (2 C), 127.04, 120.71, 104.03, 61.24, 58.32, 37.38, 14.14. TOF-MS: 333.0961 \[*M*+Na\]^+^. Elemental analysis: Calcd. (%) for C~16~H~14~N~4~O~3~: C, 61.93; H, 4.55; N, 18.06; found: C, C, 61.96; H, 4.53; N, 18.04.

S3. Refinement {#refinement}
==============

All H atoms were geometrically fixed and allowed to ride on their parent C atoms, with C---H distances of 0.93--0.98 Å, N---H = 0.86Å and with *U*~iso~(H) = 1.2*U*~eq~(C,N).

Figures
=======

![The asymmetric unit of (I). with ellipsoids drawn at the 40% probability level. H atoms are shown as small spheres of arbitrary radii.](e-70-0o795-fig1){#Fap1}

![Part of the crystal structure with hydrogen bonds shown as dahed lines.](e-70-0o795-fig2){#Fap2}

Crystal data {#tablewrapcrystaldatalong}
============

  ------------------------------- ---------------------------------------
  C~16~H~14~N~4~O~3~·C~2~H~6~OS   *F*(000) = 1632
  *M~r~* = 388.44                 *D*~x~ = 1.303 Mg m^−3^
  Monoclinic, *P*2~1~/*c*         Mo *K*α radiation, λ = 0.71073 Å
  Hall symbol: -P 2ybc            Cell parameters from 1789 reflections
  *a* = 28.018 (5) Å              θ = 4.1--26.7°
  *b* = 9.196 (5) Å               µ = 0.19 mm^−1^
  *c* = 15.396 (5) Å              *T* = 293 K
  β = 93.376 (5)°                 Block, white
  *V* = 3960 (3) Å^3^             0.30 × 0.20 × 0.20 mm
  *Z* = 8                         
  ------------------------------- ---------------------------------------

Data collection {#tablewrapdatacollectionlong}
===============

  ------------------------------------------------------------------------------ --------------------------------------
  Oxford Diffraction Xcalibur Sapphire3 diffractometer                           6946 independent reflections
  Radiation source: fine-focus sealed tube                                       3460 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                                         *R*~int~ = 0.052
  Detector resolution: 16.1049 pixels mm^-1^                                     θ~max~ = 25.0°, θ~min~ = 3.4°
  ω scans                                                                        *h* = −31→33
  Absorption correction: multi-scan (*CrysAlis RED*; Oxford Diffraction, 2010)   *k* = −6→10
  *T*~min~ = 0.805, *T*~max~ = 1.000                                             *l* = −18→9
  13653 measured reflections                                                     
  ------------------------------------------------------------------------------ --------------------------------------

Refinement {#tablewraprefinementdatalong}
==========

  ------------------------------------- -------------------------------------------------------------------------------------
  Refinement on *F*^2^                  Primary atom site location: structure-invariant direct methods
  Least-squares matrix: full            Secondary atom site location: difference Fourier map
  *R*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.068   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.210                  H-atom parameters constrained
  *S* = 1.00                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0876*P*)^2^\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  6946 reflections                      (Δ/σ)~max~ \< 0.001
  510 parameters                        Δρ~max~ = 0.32 e Å^−3^
  0 restraints                          Δρ~min~ = −0.24 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------

Special details {#specialdetails}
===============

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  Experimental. *CrysAlis PRO*, Agilent Technologies, Version 1.171.36.28 (release 01--02-2013 CrysAlis171. NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
  Geometry. All e.s.d.\'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.\'s are taken into account individually in the estimation of e.s.d.\'s in distances, angles and torsion angles; correlations between e.s.d.\'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.\'s is used for estimating e.s.d.\'s involving l.s. planes.
  Refinement. Refinement of *F*^2^ against ALL reflections. The weighted *R*-factor *wR* and goodness of fit *S* are based on *F*^2^, conventional *R*-factors *R* are based on *F*, with *F* set to zero for negative *F*^2^. The threshold expression of *F*^2^ \> σ(*F*^2^) is used only for calculating *R*-factors(gt) *etc*. and is not relevant to the choice of reflections for refinement. *R*-factors based on *F*^2^ are statistically about twice as large as those based on *F*, and *R*- factors based on ALL data will be even larger.
  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å^2^) {#tablewrapcoords}
==================================================================================================

  ------ -------------- ------------- -------------- -------------------- ------------
         *x*            *y*           *z*            *U*~iso~\*/*U*~eq~   Occ. (\<1)
  N1A    0.53193 (10)   0.7819 (3)    0.8897 (2)     0.0695 (9)           
  N2A    0.52515 (10)   0.6372 (3)    0.8921 (2)     0.0677 (9)           
  H2A    0.4974         0.5974        0.8917         0.081\*              
  C3A    0.56660 (11)   0.5602 (3)    0.8952 (2)     0.0561 (9)           
  C4A    0.65667 (11)   0.6520 (3)    0.8983 (2)     0.0512 (8)           
  H4A    0.6677         0.5907        0.9476         0.061\*              
  C5A    0.67549 (11)   0.8066 (3)    0.9139 (2)     0.0502 (8)           
  C6A    0.64854 (12)   0.9290 (3)    0.9073 (2)     0.0571 (9)           
  O7A    0.60010 (8)    0.9282 (2)    0.89259 (17)   0.0674 (7)           
  C8A    0.57909 (12)   0.7925 (3)    0.8921 (3)     0.0616 (9)           
  C9A    0.60339 (11)   0.6616 (3)    0.8957 (2)     0.0530 (9)           
  C10A   0.72495 (13)   0.8238 (3)    0.9324 (2)     0.0585 (9)           
  N11A   0.76529 (12)   0.8350 (3)    0.9473 (2)     0.0823 (11)          
  N12A   0.66396 (11)   1.0672 (3)    0.9145 (2)     0.0810 (11)          
  H50A   0.6939         1.0850        0.9243         0.097\*              
  H40A   0.6439         1.1377        0.9092         0.097\*              
  C13A   0.56757 (12)   0.4028 (4)    0.9000 (3)     0.0638 (10)          
  O13A   0.60412 (9)    0.3324 (2)    0.90798 (19)   0.0771 (8)           
  O14A   0.52397 (8)    0.3481 (2)    0.89287 (19)   0.0786 (8)           
  C15A   0.51823 (14)   0.1906 (4)    0.8995 (3)     0.0886 (14)          
  H15C   0.5253         0.1586        0.9589         0.106\*              
  H15D   0.5396         0.1410        0.8619         0.106\*              
  C16A   0.46789 (17)   0.1595 (5)    0.8721 (4)     0.1174 (18)          
  H16D   0.4473         0.2176        0.9056         0.176\*              
  H16E   0.4613         0.0583        0.8813         0.176\*              
  H16F   0.4623         0.1822        0.8115         0.176\*              
  C17A   0.67533 (11)   0.5887 (3)    0.8153 (2)     0.0547 (9)           
  C18A   0.66234 (14)   0.6484 (4)    0.7353 (3)     0.0740 (11)          
  H18A   0.6414         0.7270        0.7316         0.089\*              
  C19A   0.6800 (2)     0.5929 (6)    0.6608 (3)     0.1099 (18)          
  H19A   0.6710         0.6338        0.6071         0.132\*              
  C20A   0.7113 (2)     0.4757 (8)    0.6657 (5)     0.128 (3)            
  H20A   0.7238         0.4384        0.6156         0.154\*              
  C21A   0.72347 (18)   0.4168 (6)    0.7438 (5)     0.118 (2)            
  H21A   0.7442         0.3378        0.7471         0.141\*              
  C22A   0.70605 (13)   0.4704 (4)    0.8190 (3)     0.0791 (12)          
  H22A   0.7148         0.4273        0.8722         0.095\*              
  N1B    0.98769 (10)   0.2450 (3)    0.1030 (2)     0.0690 (9)           
  N2B    0.99344 (10)   0.3898 (3)    0.1081 (2)     0.0637 (8)           
  H2B    1.0203         0.4307        0.1231         0.076\*              
  C3B    0.95301 (11)   0.4650 (3)    0.0872 (2)     0.0517 (8)           
  C4B    0.86559 (10)   0.3732 (3)    0.0388 (2)     0.0462 (8)           
  H4B    0.8622         0.4317        −0.0144        0.055\*              
  C5B    0.84917 (11)   0.2186 (3)    0.0175 (2)     0.0490 (8)           
  C6B    0.87600 (12)   0.0964 (3)    0.0311 (2)     0.0575 (9)           
  O7B    0.92214 (8)    0.0970 (2)    0.06421 (18)   0.0714 (8)           
  C8B    0.94166 (12)   0.2333 (3)    0.0776 (2)     0.0595 (9)           
  C9B    0.91763 (11)   0.3640 (3)    0.0674 (2)     0.0478 (8)           
  C10B   0.80137 (13)   0.2011 (3)    −0.0144 (2)    0.0554 (9)           
  N11B   0.76248 (11)   0.1905 (3)    −0.0413 (2)    0.0784 (10)          
  N12B   0.86195 (11)   −0.0413 (3)   0.0170 (2)     0.0860 (11)          
  H50B   0.8332         −0.0594       −0.0027        0.103\*              
  H40B   0.8817         −0.1116       0.0276         0.103\*              
  C13B   0.95170 (12)   0.6237 (3)    0.0869 (2)     0.0547 (9)           
  O13B   0.91680 (8)    0.6936 (2)    0.06285 (18)   0.0737 (8)           
  O14B   0.99271 (8)    0.6791 (2)    0.11744 (18)   0.0717 (8)           
  C15B   0.99710 (13)   0.8366 (3)    0.1205 (3)     0.0745 (11)          
  H15A   0.9726         0.8784        0.1547         0.089\*              
  H15B   0.9940         0.8773        0.0623         0.089\*              
  C16B   1.04599 (15)   0.8670 (4)    0.1622 (3)     0.0955 (14)          
  H16A   1.0480         0.8295        0.2205         0.143\*              
  H16B   1.0515         0.9700        0.1636         0.143\*              
  H16C   1.0697         0.8208        0.1292         0.143\*              
  C17B   0.83482 (11)   0.4393 (3)    0.1059 (2)     0.0532 (9)           
  C18B   0.80440 (13)   0.5537 (4)    0.0831 (3)     0.0793 (12)          
  H18B   0.8049         0.5913        0.0270         0.095\*              
  C19B   0.77395 (18)   0.6138 (6)    0.1384 (5)     0.1173 (19)          
  H19B   0.7543         0.6912        0.1210         0.141\*              
  C20B   0.7730 (2)     0.5589 (8)    0.2185 (5)     0.119 (2)            
  H20B   0.7518         0.5985        0.2563         0.143\*              
  C21B   0.8023 (2)     0.4450 (7)    0.2477 (3)     0.1114 (19)          
  H21B   0.8013         0.4093        0.3041         0.134\*              
  C22B   0.83403 (15)   0.3849 (4)    0.1877 (3)     0.0790 (12)          
  H22B   0.8542         0.3085        0.2049         0.095\*              
  S1     0.39614 (7)    0.6010 (2)    0.82388 (15)   0.0969 (9)           0.679 (4)
  S1A    0.39306 (13)   0.6880 (5)    0.8912 (3)     0.0895 (19)          0.321 (4)
  S2     0.87312 (9)    0.6108 (4)    0.8352 (3)     0.1088 (15)          0.546 (6)
  S2B    0.88926 (12)   0.5896 (3)    0.7732 (3)     0.0929 (15)          0.454 (6)
  O1S    0.43139 (10)   0.5574 (4)    0.9002 (3)     0.1292 (14)          
  O2S    0.91562 (11)   0.5181 (3)    0.8424 (3)     0.1368 (16)          
  C1S    0.40250 (19)   0.7830 (6)    0.8178 (5)     0.160 (3)            
  H1S    0.4319         0.8055        0.7917         0.192\*              0.679 (4)
  H2S    0.4030         0.8239        0.8752         0.192\*              0.679 (4)
  H3S    0.3762         0.8232        0.7830         0.192\*              0.679 (4)
  H4S    0.4315         0.8365        0.8307         0.192\*              0.321 (4)
  H5S    0.3764         0.8496        0.8077         0.192\*              0.321 (4)
  H6S    0.4058         0.7249        0.7667         0.192\*              0.321 (4)
  C2S    0.34120 (18)   0.5886 (6)    0.8717 (5)     0.158 (3)            
  H7S    0.3331         0.4882        0.8791         0.190\*              0.679 (4)
  H8S    0.3169         0.6350        0.8348         0.190\*              0.679 (4)
  H9S    0.3434         0.6360        0.9273         0.190\*              0.679 (4)
  H10S   0.3362         0.5275        0.9209         0.190\*              0.321 (4)
  H11S   0.3440         0.5295        0.8209         0.190\*              0.321 (4)
  H12S   0.3146         0.6537        0.8625         0.190\*              0.321 (4)
  C3S    0.8903 (2)     0.7740 (5)    0.7998 (5)     0.186 (3)            
  H13S   0.9146         0.8131        0.8398         0.223\*              0.546 (6)
  H14S   0.8633         0.8385        0.7960         0.223\*              0.546 (6)
  H15S   0.9028         0.7638        0.7434         0.223\*              0.546 (6)
  H16S   0.9228         0.8059        0.8086         0.223\*              0.454 (6)
  H17S   0.8740         0.7890        0.8522         0.223\*              0.454 (6)
  H18S   0.8746         0.8286        0.7532         0.223\*              0.454 (6)
  C4S    0.8336 (3)     0.5660 (7)    0.7631 (8)     0.290 (7)            
  H19S   0.8211         0.4720        0.7765         0.348\*              0.546 (6)
  H20S   0.8474         0.5624        0.7075         0.348\*              0.546 (6)
  H21S   0.8082         0.6362        0.7612         0.348\*              0.546 (6)
  H22S   0.8269         0.4662        0.7485         0.348\*              0.454 (6)
  H23S   0.8202         0.6278        0.7177         0.348\*              0.454 (6)
  H24S   0.8198         0.5894        0.8169         0.348\*              0.454 (6)
  ------ -------------- ------------- -------------- -------------------- ------------

Atomic displacement parameters (Å^2^) {#tablewrapadps}
=====================================

  ------ ------------- ------------- ------------- -------------- -------------- --------------
         *U*^11^       *U*^22^       *U*^33^       *U*^12^        *U*^13^        *U*^23^
  N1A    0.0434 (18)   0.0496 (17)   0.116 (3)     0.0062 (13)    0.0079 (18)    0.0038 (17)
  N2A    0.0419 (17)   0.0522 (18)   0.110 (3)     0.0025 (13)    0.0132 (17)    0.0062 (17)
  C3A    0.0414 (19)   0.0483 (19)   0.079 (2)     0.0043 (16)    0.0087 (18)    0.0002 (17)
  C4A    0.0442 (19)   0.0511 (18)   0.058 (2)     0.0037 (15)    0.0051 (16)    0.0021 (16)
  C5A    0.0453 (19)   0.0419 (17)   0.063 (2)     0.0083 (15)    −0.0021 (16)   −0.0056 (15)
  C6A    0.0456 (19)   0.049 (2)     0.076 (2)     −0.0005 (16)   −0.0011 (18)   −0.0025 (17)
  O7A    0.0427 (13)   0.0423 (13)   0.116 (2)     0.0063 (10)    −0.0014 (14)   0.0028 (13)
  C8A    0.046 (2)     0.048 (2)     0.091 (3)     0.0053 (16)    0.0059 (19)    0.0017 (19)
  C9A    0.0428 (19)   0.0455 (18)   0.071 (2)     0.0135 (16)    0.0085 (17)    0.0045 (16)
  C10A   0.052 (2)     0.0449 (19)   0.078 (3)     0.0035 (16)    −0.007 (2)     −0.0057 (17)
  N11A   0.054 (2)     0.065 (2)     0.126 (3)     0.0044 (16)    −0.017 (2)     −0.0027 (19)
  N12A   0.0544 (19)   0.0475 (17)   0.139 (3)     0.0040 (15)    −0.013 (2)     −0.0031 (18)
  C13A   0.039 (2)     0.055 (2)     0.098 (3)     0.0024 (17)    0.013 (2)      0.001 (2)
  O13A   0.0498 (15)   0.0545 (14)   0.128 (2)     0.0064 (12)    0.0092 (15)    −0.0029 (14)
  O14A   0.0476 (15)   0.0529 (14)   0.135 (2)     −0.0020 (12)   0.0061 (16)    0.0037 (15)
  C15A   0.068 (3)     0.050 (2)     0.148 (4)     −0.0094 (19)   0.008 (3)      0.007 (2)
  C16A   0.081 (3)     0.088 (3)     0.182 (5)     −0.024 (3)     −0.006 (4)     −0.005 (3)
  C17A   0.0368 (18)   0.0492 (19)   0.079 (3)     −0.0042 (15)   0.0072 (18)    −0.0056 (18)
  C18A   0.074 (3)     0.070 (2)     0.079 (3)     −0.013 (2)     0.011 (2)      −0.006 (2)
  C19A   0.127 (5)     0.124 (4)     0.082 (3)     −0.051 (4)     0.040 (3)      −0.025 (3)
  C20A   0.095 (5)     0.142 (6)     0.153 (6)     −0.046 (4)     0.064 (5)      −0.085 (5)
  C21A   0.065 (3)     0.119 (4)     0.173 (6)     0.009 (3)      0.036 (4)      −0.066 (5)
  C22A   0.048 (2)     0.073 (3)     0.116 (4)     0.0119 (19)    0.010 (2)      −0.017 (2)
  N1B    0.0415 (17)   0.0492 (16)   0.115 (3)     −0.0001 (13)   −0.0089 (17)   0.0045 (17)
  N2B    0.0425 (17)   0.0493 (17)   0.098 (2)     −0.0002 (13)   −0.0072 (16)   0.0051 (16)
  C3B    0.0394 (18)   0.0441 (18)   0.071 (2)     0.0053 (15)    0.0009 (17)    0.0052 (16)
  C4B    0.0385 (17)   0.0445 (17)   0.0552 (19)   0.0047 (14)    0.0004 (15)    0.0006 (15)
  C5B    0.0398 (18)   0.0418 (17)   0.064 (2)     0.0058 (14)    −0.0055 (16)   −0.0009 (15)
  C6B    0.0425 (19)   0.0478 (19)   0.081 (3)     0.0004 (16)    −0.0052 (18)   0.0016 (18)
  O7B    0.0514 (15)   0.0407 (13)   0.120 (2)     0.0091 (11)    −0.0164 (15)   0.0007 (13)
  C8B    0.049 (2)     0.0416 (19)   0.087 (3)     0.0041 (16)    −0.0036 (19)   −0.0002 (18)
  C9B    0.0418 (18)   0.0410 (17)   0.060 (2)     0.0055 (14)    −0.0018 (16)   0.0017 (15)
  C10B   0.050 (2)     0.0428 (18)   0.072 (2)     −0.0001 (15)   −0.0093 (19)   −0.0079 (16)
  N11B   0.056 (2)     0.0639 (19)   0.111 (3)     0.0036 (16)    −0.023 (2)     −0.0106 (18)
  N12B   0.0582 (19)   0.0449 (16)   0.151 (3)     0.0027 (14)    −0.027 (2)     −0.0107 (19)
  C13B   0.0408 (19)   0.052 (2)     0.071 (2)     0.0008 (16)    −0.0001 (18)   0.0024 (18)
  O13B   0.0480 (15)   0.0526 (14)   0.119 (2)     0.0049 (11)    −0.0078 (15)   0.0049 (14)
  O14B   0.0503 (15)   0.0462 (13)   0.117 (2)     −0.0033 (11)   −0.0111 (15)   0.0011 (13)
  C15B   0.064 (3)     0.047 (2)     0.112 (3)     −0.0085 (18)   0.006 (2)      −0.006 (2)
  C16B   0.083 (3)     0.076 (3)     0.126 (4)     −0.027 (2)     −0.005 (3)     −0.009 (3)
  C17B   0.0435 (19)   0.0493 (19)   0.067 (2)     −0.0116 (16)   0.0032 (17)    −0.0086 (16)
  C18B   0.054 (2)     0.076 (3)     0.109 (3)     0.017 (2)      0.010 (2)      −0.018 (2)
  C19B   0.075 (4)     0.134 (5)     0.146 (5)     0.020 (3)      0.029 (4)      −0.053 (4)
  C20B   0.082 (4)     0.135 (5)     0.145 (6)     −0.024 (4)     0.047 (4)      −0.062 (5)
  C21B   0.126 (5)     0.136 (5)     0.075 (3)     −0.068 (4)     0.035 (3)      −0.029 (3)
  C22B   0.087 (3)     0.077 (3)     0.074 (3)     −0.016 (2)     0.013 (2)      −0.007 (2)
  S1     0.0793 (13)   0.0955 (14)   0.1160 (19)   −0.0053 (10)   0.0069 (12)    −0.0162 (12)
  S1A    0.065 (2)     0.121 (4)     0.083 (3)     0.018 (2)      0.0102 (19)    0.013 (2)
  S2     0.0635 (16)   0.153 (3)     0.111 (3)     0.0201 (15)    0.0120 (16)    0.056 (2)
  S2B    0.0635 (19)   0.114 (2)     0.101 (3)     −0.0011 (15)   0.0044 (19)    −0.0174 (17)
  O1S    0.0506 (17)   0.134 (3)     0.203 (4)     0.0091 (17)    0.006 (2)      0.077 (3)
  O2S    0.067 (2)     0.092 (2)     0.245 (5)     0.0036 (17)    −0.047 (3)     0.029 (2)
  C1S    0.086 (4)     0.125 (4)     0.270 (8)     0.003 (3)      0.004 (5)      0.099 (5)
  C2S    0.067 (3)     0.160 (5)     0.245 (8)     −0.025 (3)     −0.012 (4)     0.086 (5)
  C3S    0.127 (5)     0.088 (4)     0.333 (10)    −0.006 (3)     −0.069 (6)     0.031 (5)
  C4S    0.142 (6)     0.142 (6)     0.56 (2)      0.003 (5)      −0.198 (10)    −0.020 (8)
  ------ ------------- ------------- ------------- -------------- -------------- --------------

Geometric parameters (Å, º) {#tablewrapgeomlong}
===========================

  --------------------------- ------------ --------------------------- ------------
  N1A---C8A                   1.323 (4)    C13B---O14B                 1.318 (4)
  N1A---N2A                   1.345 (4)    O14B---C15B                 1.454 (4)
  N2A---C3A                   1.359 (4)    C15B---C16B                 1.505 (5)
  N2A---H2A                   0.8600       C15B---H15A                 0.9700
  C3A---C9A                   1.390 (4)    C15B---H15B                 0.9700
  C3A---C13A                  1.450 (5)    C16B---H16A                 0.9600
  C4A---C9A                   1.494 (4)    C16B---H16B                 0.9600
  C4A---C17A                  1.524 (4)    C16B---H16C                 0.9600
  C4A---C5A                   1.530 (4)    C17B---C22B                 1.357 (5)
  C4A---H4A                   0.9800       C17B---C18B                 1.387 (5)
  C5A---C6A                   1.356 (4)    C18B---C19B                 1.358 (6)
  C5A---C10A                  1.407 (4)    C18B---H18B                 0.9300
  C6A---N12A                  1.345 (4)    C19B---C20B                 1.333 (8)
  C6A---O7A                   1.363 (4)    C19B---H19B                 0.9300
  O7A---C8A                   1.379 (4)    C20B---C21B                 1.390 (7)
  C8A---C9A                   1.383 (4)    C20B---H20B                 0.9300
  C10A---N11A                 1.145 (4)    C21B---C22B                 1.430 (6)
  N12A---H50A                 0.8600       C21B---H21B                 0.9300
  N12A---H40A                 0.8600       C22B---H22B                 0.9300
  C13A---O13A                 1.212 (4)    S1---O1S                    1.543 (4)
  C13A---O14A                 1.319 (4)    S1---C1S                    1.686 (5)
  O14A---C15A                 1.462 (4)    S1---C2S                    1.749 (6)
  C15A---C16A                 1.476 (5)    S1---H6S                    1.4746
  C15A---H15C                 0.9700       S1---H11S                   1.6005
  C15A---H15D                 0.9700       S1A---C1S                   1.464 (6)
  C16A---H16D                 0.9600       S1A---O1S                   1.612 (5)
  C16A---H16E                 0.9600       S1A---C2S                   1.728 (6)
  C16A---H16F                 0.9600       S2---O2S                    1.463 (4)
  C17A---C18A                 1.378 (5)    S2---C4S                    1.576 (8)
  C17A---C22A                 1.387 (5)    S2---C3S                    1.677 (6)
  C18A---C19A                 1.374 (6)    S2---H17S                   1.6594
  C18A---H18A                 0.9300       S2---H24S                   1.5180
  C19A---C20A                 1.390 (8)    S2B---O2S                   1.421 (5)
  C19A---H19A                 0.9300       S2B---C4S                   1.573 (8)
  C20A---C21A                 1.344 (8)    S2B---C3S                   1.744 (6)
  C20A---H20A                 0.9300       C1S---H1S                   0.9600
  C21A---C22A                 1.374 (7)    C1S---H2S                   0.9600
  C21A---H21A                 0.9300       C1S---H3S                   0.9600
  C22A---H22A                 0.9300       C1S---H4S                   0.9600
  N1B---C8B                   1.330 (4)    C1S---H5S                   0.9600
  N1B---N2B                   1.344 (4)    C1S---H6S                   0.9601
  N2B---C3B                   1.350 (4)    C2S---H7S                   0.9600
  N2B---H2B                   0.8600       C2S---H8S                   0.9600
  C3B---C9B                   1.379 (4)    C2S---H9S                   0.9600
  C3B---C13B                  1.459 (4)    C2S---H10S                  0.9600
  C4B---C9B                   1.501 (4)    C2S---H11S                  0.9600
  C4B---C17B                  1.511 (4)    C2S---H12S                  0.9600
  C4B---C5B                   1.524 (4)    C3S---H13S                  0.9600
  C4B---H4B                   0.9800       C3S---H14S                  0.9600
  C5B---C6B                   1.361 (4)    C3S---H15S                  0.9600
  C5B---C10B                  1.408 (4)    C3S---H16S                  0.9600
  C6B---N12B                  1.340 (4)    C3S---H17S                  0.9600
  C6B---O7B                   1.362 (4)    C3S---H18S                  0.9600
  O7B---C8B                   1.378 (4)    C4S---H19S                  0.9600
  C8B---C9B                   1.382 (4)    C4S---H20S                  0.9600
  C10B---N11B                 1.147 (4)    C4S---H21S                  0.9600
  N12B---H50B                 0.8600       C4S---H22S                  0.9600
  N12B---H40B                 0.8600       C4S---H23S                  0.9600
  C13B---O13B                 1.210 (4)    C4S---H24S                  0.9600
                                                                       
  C8A---N1A---N2A             102.4 (3)    O1S---S1---C1S              103.6 (3)
  N1A---N2A---C3A             113.3 (3)    O1S---S1---C2S              101.7 (3)
  N1A---N2A---H2A             123.4        C1S---S1---C2S              100.8 (3)
  C3A---N2A---H2A             123.4        O1S---S1---H6S              121.5
  N2A---C3A---C9A             106.4 (3)    C2S---S1---H6S              120.0
  N2A---C3A---C13A            122.4 (3)    O1S---S1---H11S             117.2
  C9A---C3A---C13A            131.2 (3)    C1S---S1---H11S             120.4
  C9A---C4A---C17A            113.1 (3)    H6S---S1---H11S             120.0
  C9A---C4A---C5A             106.5 (2)    C1S---S1A---O1S             111.2 (4)
  C17A---C4A---C5A            110.7 (3)    C1S---S1A---C2S             111.7 (4)
  C9A---C4A---H4A             108.8        O1S---S1A---C2S             99.8 (3)
  C17A---C4A---H4A            108.8        O2S---S2---C4S              115.8 (5)
  C5A---C4A---H4A             108.8        O2S---S2---C3S              107.4 (3)
  C6A---C5A---C10A            117.3 (3)    C4S---S2---C3S              102.0 (4)
  C6A---C5A---C4A             125.1 (3)    O2S---S2---H17S             124.0
  C10A---C5A---C4A            117.6 (3)    C4S---S2---H17S             111.9
  N12A---C6A---C5A            127.1 (3)    O2S---S2---H24S             136.6
  N12A---C6A---O7A            109.3 (3)    C3S---S2---H24S             110.7
  C5A---C6A---O7A             123.6 (3)    H17S---S2---H24S            99.3
  C6A---O7A---C8A             115.2 (2)    O2S---S2B---C4S             118.6 (5)
  N1A---C8A---O7A             119.5 (3)    O2S---S2B---C3S             105.9 (3)
  N1A---C8A---C9A             115.2 (3)    C4S---S2B---C3S             99.2 (4)
  O7A---C8A---C9A             125.3 (3)    S1---O1S---S1A              49.26 (17)
  C8A---C9A---C3A             102.8 (3)    S1A---C1S---S1              48.8 (2)
  C8A---C9A---C4A             122.8 (3)    S1A---C1S---H1S             130.5
  C3A---C9A---C4A             134.4 (3)    S1---C1S---H1S              109.5
  N11A---C10A---C5A           178.7 (4)    S1A---C1S---H2S             61.1
  C6A---N12A---H50A           120.0        S1---C1S---H2S              109.5
  C6A---N12A---H40A           120.0        H1S---C1S---H2S             109.5
  H50A---N12A---H40A          120.0        S1A---C1S---H3S             119.5
  O13A---C13A---O14A          125.3 (3)    S1---C1S---H3S              109.5
  O13A---C13A---C3A           123.5 (3)    H1S---C1S---H3S             109.5
  O14A---C13A---C3A           111.2 (3)    H2S---C1S---H3S             109.5
  C13A---O14A---C15A          118.5 (3)    S1A---C1S---H4S             109.6
  O14A---C15A---C16A          106.2 (3)    S1---C1S---H4S              126.0
  O14A---C15A---H15C          110.5        H2S---C1S---H4S             69.0
  C16A---C15A---H15C          110.5        H3S---C1S---H4S             122.0
  O14A---C15A---H15D          110.5        S1A---C1S---H5S             109.5
  C16A---C15A---H15D          110.5        S1---C1S---H5S              124.1
  H15C---C15A---H15D          108.7        H1S---C1S---H5S             117.4
  C15A---C16A---H16D          109.5        H2S---C1S---H5S             82.5
  C15A---C16A---H16E          109.5        H4S---C1S---H5S             109.5
  H16D---C16A---H16E          109.5        S1A---C1S---H6S             109.3
  C15A---C16A---H16F          109.5        S1---C1S---H6S              60.6
  H16D---C16A---H16F          109.5        H1S---C1S---H6S             69.5
  H16E---C16A---H16F          109.5        H2S---C1S---H6S             167.3
  C18A---C17A---C22A          118.7 (4)    H3S---C1S---H6S             82.3
  C18A---C17A---C4A           120.8 (3)    H4S---C1S---H6S             109.5
  C22A---C17A---C4A           120.5 (3)    H5S---C1S---H6S             109.5
  C19A---C18A---C17A          120.6 (4)    S1A---C2S---H7S             133.7
  C19A---C18A---H18A          119.7        S1---C2S---H7S              109.5
  C17A---C18A---H18A          119.7        S1A---C2S---H8S             115.3
  C18A---C19A---C20A          120.0 (5)    S1---C2S---H8S              109.5
  C18A---C19A---H19A          120.0        H7S---C2S---H8S             109.5
  C20A---C19A---H19A          120.0        S1A---C2S---H9S             66.1
  C21A---C20A---C19A          119.1 (5)    S1---C2S---H9S              109.5
  C21A---C20A---H20A          120.4        H7S---C2S---H9S             109.5
  C19A---C20A---H20A          120.4        H8S---C2S---H9S             109.5
  C20A---C21A---C22A          121.7 (5)    S1A---C2S---H10S            109.4
  C20A---C21A---H21A          119.1        S1---C2S---H10S             122.8
  C22A---C21A---H21A          119.1        H7S---C2S---H10S            45.2
  C21A---C22A---C17A          119.8 (5)    H8S---C2S---H10S            126.6
  C21A---C22A---H22A          120.1        H9S---C2S---H10S            64.3
  C17A---C22A---H22A          120.1        S1A---C2S---H11S            109.5
  C8B---N1B---N2B             102.0 (3)    S1---C2S---H11S             65.0
  N1B---N2B---C3B             113.4 (3)    H7S---C2S---H11S            65.4
  N1B---N2B---H2B             123.3        H8S---C2S---H11S            81.9
  C3B---N2B---H2B             123.3        H9S---C2S---H11S            168.7
  N2B---C3B---C9B             106.8 (3)    H10S---C2S---H11S           109.5
  N2B---C3B---C13B            122.2 (3)    S1A---C2S---H12S            109.5
  C9B---C3B---C13B            130.9 (3)    S1---C2S---H12S             126.4
  C9B---C4B---C17B            113.9 (3)    H7S---C2S---H12S            115.5
  C9B---C4B---C5B             106.6 (2)    H9S---C2S---H12S            81.8
  C17B---C4B---C5B            110.2 (2)    H10S---C2S---H12S           109.5
  C9B---C4B---H4B             108.7        H11S---C2S---H12S           109.5
  C17B---C4B---H4B            108.7        S2---C3S---H13S             109.5
  C5B---C4B---H4B             108.7        S2B---C3S---H13S            121.1
  C6B---C5B---C10B            117.7 (3)    S2---C3S---H14S             109.5
  C6B---C5B---C4B             125.5 (3)    S2B---C3S---H14S            125.8
  C10B---C5B---C4B            116.8 (2)    H13S---C3S---H14S           109.5
  N12B---C6B---C5B            126.9 (3)    S2---C3S---H15S             109.5
  N12B---C6B---O7B            109.1 (3)    S2B---C3S---H15S            72.2
  C5B---C6B---O7B             123.9 (3)    H13S---C3S---H15S           109.5
  C6B---O7B---C8B             114.8 (2)    H14S---C3S---H15S           109.5
  N1B---C8B---O7B             119.1 (3)    S2---C3S---H16S             121.1
  N1B---C8B---C9B             114.9 (3)    S2B---C3S---H16S            109.4
  O7B---C8B---C9B             126.0 (3)    H14S---C3S---H16S           123.9
  C3B---C9B---C8B             102.8 (3)    H15S---C3S---H16S           76.3
  C3B---C9B---C4B             134.4 (3)    S2---C3S---H17S             72.3
  C8B---C9B---C4B             122.7 (3)    S2B---C3S---H17S            109.6
  N11B---C10B---C5B           178.2 (4)    H13S---C3S---H17S           76.3
  C6B---N12B---H50B           120.0        H14S---C3S---H17S           63.3
  C6B---N12B---H40B           120.0        H15S---C3S---H17S           172.4
  H50B---N12B---H40B          120.0        H16S---C3S---H17S           109.5
  O13B---C13B---O14B          125.1 (3)    S2---C3S---H18S             125.7
  O13B---C13B---C3B           123.5 (3)    S2B---C3S---H18S            109.4
  O14B---C13B---C3B           111.4 (3)    H13S---C3S---H18S           123.9
  C13B---O14B---C15B          117.9 (3)    H14S---C3S---H18S           46.2
  O14B---C15B---C16B          105.8 (3)    H15S---C3S---H18S           63.3
  O14B---C15B---H15A          110.6        H16S---C3S---H18S           109.5
  C16B---C15B---H15A          110.6        H17S---C3S---H18S           109.5
  O14B---C15B---H15B          110.6        S2B---C4S---H19S            118.3
  C16B---C15B---H15B          110.6        S2---C4S---H19S             109.5
  H15A---C15B---H15B          108.7        S2B---C4S---H20S            69.1
  C15B---C16B---H16A          109.5        S2---C4S---H20S             109.5
  C15B---C16B---H16B          109.5        H19S---C4S---H20S           109.5
  H16A---C16B---H16B          109.5        S2B---C4S---H21S            129.7
  C15B---C16B---H16C          109.5        S2---C4S---H21S             109.5
  H16A---C16B---H16C          109.5        H19S---C4S---H21S           109.5
  H16B---C16B---H16C          109.5        H20S---C4S---H21S           109.5
  C22B---C17B---C18B          118.1 (4)    S2B---C4S---H22S            109.5
  C22B---C17B---C4B           121.8 (3)    S2---C4S---H22S             122.2
  C18B---C17B---C4B           119.9 (3)    H20S---C4S---H22S           80.9
  C19B---C18B---C17B          123.3 (5)    H21S---C4S---H22S           120.2
  C19B---C18B---H18B          118.3        S2B---C4S---H23S            109.6
  C17B---C18B---H18B          118.3        S2---C4S---H23S             125.9
  C20B---C19B---C18B          118.3 (6)    H19S---C4S---H23S           123.9
  C20B---C19B---H19B          120.9        H20S---C4S---H23S           62.2
  C18B---C19B---H19B          120.9        H21S---C4S---H23S           47.3
  C19B---C20B---C21B          122.7 (5)    H22S---C4S---H23S           109.5
  C19B---C20B---H20B          118.6        S2B---C4S---H24S            109.4
  C21B---C20B---H20B          118.6        S2---C4S---H24S             68.7
  C20B---C21B---C22B          117.4 (5)    H19S---C4S---H24S           81.1
  C20B---C21B---H21B          121.3        H20S---C4S---H24S           168.9
  C22B---C21B---H21B          121.3        H21S---C4S---H24S           62.5
  C17B---C22B---C21B          120.1 (5)    H22S---C4S---H24S           109.5
  C17B---C22B---H22B          119.9        H23S---C4S---H24S           109.5
  C21B---C22B---H22B          119.9                                    
                                                                       
  C8A---N1A---N2A---C3A       −0.4 (4)     C5B---C6B---O7B---C8B       −4.7 (5)
  N1A---N2A---C3A---C9A       0.6 (4)      N2B---N1B---C8B---O7B       179.4 (3)
  N1A---N2A---C3A---C13A      178.7 (3)    N2B---N1B---C8B---C9B       −0.8 (4)
  C9A---C4A---C5A---C6A       −12.8 (4)    C6B---O7B---C8B---N1B       −174.5 (3)
  C17A---C4A---C5A---C6A      110.5 (4)    C6B---O7B---C8B---C9B       5.8 (5)
  C9A---C4A---C5A---C10A      170.4 (3)    N2B---C3B---C9B---C8B       −0.9 (4)
  C17A---C4A---C5A---C10A     −66.3 (4)    C13B---C3B---C9B---C8B      178.2 (3)
  C10A---C5A---C6A---N12A     1.7 (5)      N2B---C3B---C9B---C4B       −179.2 (3)
  C4A---C5A---C6A---N12A      −175.1 (3)   C13B---C3B---C9B---C4B      −0.1 (6)
  C10A---C5A---C6A---O7A      −177.7 (3)   N1B---C8B---C9B---C3B       1.1 (4)
  C4A---C5A---C6A---O7A       5.5 (5)      O7B---C8B---C9B---C3B       −179.1 (3)
  N12A---C6A---O7A---C8A      −174.1 (3)   N1B---C8B---C9B---C4B       179.7 (3)
  C5A---C6A---O7A---C8A       5.4 (5)      O7B---C8B---C9B---C4B       −0.6 (5)
  N2A---N1A---C8A---O7A       −178.6 (3)   C17B---C4B---C9B---C3B      −65.1 (5)
  N2A---N1A---C8A---C9A       0.1 (5)      C5B---C4B---C9B---C3B       173.1 (4)
  C6A---O7A---C8A---N1A       171.2 (3)    C17B---C4B---C9B---C8B      116.8 (3)
  C6A---O7A---C8A---C9A       −7.3 (5)     C5B---C4B---C9B---C8B       −5.0 (4)
  N1A---C8A---C9A---C3A       0.2 (5)      N2B---C3B---C13B---O13B     174.8 (3)
  O7A---C8A---C9A---C3A       178.8 (4)    C9B---C3B---C13B---O13B     −4.2 (6)
  N1A---C8A---C9A---C4A       179.7 (3)    N2B---C3B---C13B---O14B     −6.4 (4)
  O7A---C8A---C9A---C4A       −1.7 (6)     C9B---C3B---C13B---O14B     174.6 (4)
  N2A---C3A---C9A---C8A       −0.5 (4)     O13B---C13B---O14B---C15B   −1.8 (5)
  C13A---C3A---C9A---C8A      −178.3 (4)   C3B---C13B---O14B---C15B    179.5 (3)
  N2A---C3A---C9A---C4A       −179.8 (4)   C13B---O14B---C15B---C16B   177.0 (3)
  C13A---C3A---C9A---C4A      2.4 (7)      C9B---C4B---C17B---C22B     −55.6 (4)
  C17A---C4A---C9A---C8A      −111.1 (4)   C5B---C4B---C17B---C22B     64.2 (4)
  C5A---C4A---C9A---C8A       10.7 (4)     C9B---C4B---C17B---C18B     127.9 (3)
  C17A---C4A---C9A---C3A      68.1 (5)     C5B---C4B---C17B---C18B     −112.3 (3)
  C5A---C4A---C9A---C3A       −170.0 (4)   C22B---C17B---C18B---C19B   0.0 (6)
  N2A---C3A---C13A---O13A     −175.5 (4)   C4B---C17B---C18B---C19B    176.5 (4)
  C9A---C3A---C13A---O13A     2.1 (7)      C17B---C18B---C19B---C20B   −0.7 (7)
  N2A---C3A---C13A---O14A     5.7 (5)      C18B---C19B---C20B---C21B   1.1 (9)
  C9A---C3A---C13A---O14A     −176.7 (4)   C19B---C20B---C21B---C22B   −0.9 (8)
  O13A---C13A---O14A---C15A   3.4 (6)      C18B---C17B---C22B---C21B   0.3 (5)
  C3A---C13A---O14A---C15A    −177.8 (3)   C4B---C17B---C22B---C21B    −176.2 (3)
  C13A---O14A---C15A---C16A   −169.0 (4)   C20B---C21B---C22B---C17B   0.1 (6)
  C9A---C4A---C17A---C18A     54.5 (4)     C1S---S1---O1S---S1A        45.2 (3)
  C5A---C4A---C17A---C18A     −64.9 (4)    C2S---S1---O1S---S1A        −59.0 (3)
  C9A---C4A---C17A---C22A     −126.0 (3)   C1S---S1A---O1S---S1        −58.4 (4)
  C5A---C4A---C17A---C22A     114.6 (3)    C2S---S1A---O1S---S1        59.6 (3)
  C22A---C17A---C18A---C19A   −0.8 (5)     C4S---S2B---O2S---S2        −51.6 (5)
  C4A---C17A---C18A---C19A    178.7 (3)    C3S---S2B---O2S---S2        58.6 (3)
  C17A---C18A---C19A---C20A   −0.1 (7)     C4S---S2---O2S---S2B        49.6 (6)
  C18A---C19A---C20A---C21A   0.9 (8)      C3S---S2---O2S---S2B        −63.5 (4)
  C19A---C20A---C21A---C22A   −0.6 (9)     O1S---S1A---C1S---S1        51.7 (3)
  C20A---C21A---C22A---C17A   −0.4 (8)     C2S---S1A---C1S---S1        −58.8 (4)
  C18A---C17A---C22A---C21A   1.1 (6)      O1S---S1---C1S---S1A        −51.9 (3)
  C4A---C17A---C22A---C21A    −178.4 (4)   C2S---S1---C1S---S1A        53.0 (3)
  C8B---N1B---N2B---C3B       0.2 (4)      C1S---S1A---C2S---S1        62.2 (4)
  N1B---N2B---C3B---C9B       0.5 (4)      O1S---S1A---C2S---S1        −55.3 (3)
  N1B---N2B---C3B---C13B      −178.7 (3)   O1S---S1---C2S---S1A        59.9 (3)
  C9B---C4B---C5B---C6B       6.1 (4)      C1S---S1---C2S---S1A        −46.6 (3)
  C17B---C4B---C5B---C6B      −118.0 (4)   O2S---S2---C3S---S2B        57.7 (3)
  C9B---C4B---C5B---C10B      −177.6 (3)   C4S---S2---C3S---S2B        −64.5 (5)
  C17B---C4B---C5B---C10B     58.3 (4)     O2S---S2B---C3S---S2        −59.7 (3)
  C10B---C5B---C6B---N12B     0.3 (6)      C4S---S2B---C3S---S2        63.7 (5)
  C4B---C5B---C6B---N12B      176.6 (3)    O2S---S2B---C4S---S2        51.5 (4)
  C10B---C5B---C6B---O7B      −177.9 (3)   C3S---S2B---C4S---S2        −62.3 (4)
  C4B---C5B---C6B---O7B       −1.5 (5)     O2S---S2---C4S---S2B        −47.8 (5)
  N12B---C6B---O7B---C8B      176.9 (3)    C3S---S2---C4S---S2B        68.4 (4)
  --------------------------- ------------ --------------------------- ------------

Hydrogen-bond geometry (Å, º) {#tablewraphbondslong}
=============================

Cg is the centroid of the N1B--C9B/C8B ring.

  ------------------------------- --------- --------- ----------- ---------------
  *D*---H···*A*                   *D*---H   H···*A*   *D*···*A*   *D*---H···*A*
  N2*A*---H2*A*···O1*S*           0.86      1.90      2.737 (4)   165
  N2*B*---H2*B*···O2*S*^i^        0.86      1.90      2.750 (5)   168
  N12*A*---H50*A*···N11*B*^ii^    0.86      2.19      3.024 (5)   164
  N12*A*---H40*A*···O13*A*^iii^   0.86      2.11      2.958 (4)   170
  N12*B*---H50*B*···N11*A*^iv^    0.86      2.23      3.072 (5)   165
  N12*B*---H40*B*···O13*B*^v^     0.86      2.10      2.945 (4)   168
  ------------------------------- --------- --------- ----------- ---------------

Symmetry codes: (i) −*x*+2, −*y*+1, −*z*+1; (ii) *x*, *y*+1, *z*+1; (iii) *x*, *y*+1, *z*; (iv) *x*, *y*−1, *z*−1; (v) *x*, *y*−1, *z*.

###### Hydrogen-bond geometry (Å, °)

*Cg* is the centroid of the N1*B*--C9*B*/C8*B* ring.

  *D*---H⋯*A*                    *D*---H   H⋯*A*   *D*⋯*A*     *D*---H⋯*A*
  ------------------------------ --------- ------- ----------- -------------
  N2*A*---H2*A*⋯O1*S*            0.86      1.90    2.737 (4)   165
  N2*B*---H2*B*⋯O2*S* ^i^        0.86      1.90    2.750 (5)   168
  N12*A*---H50*A*⋯N11*B* ^ii^    0.86      2.19    3.024 (5)   164
  N12*A*---H40*A*⋯O13*A* ^iii^   0.86      2.11    2.958 (4)   170
  N12*B*---H50*B*⋯N11*A* ^iv^    0.86      2.23    3.072 (5)   165
  N12*B*---H40*B*⋯O13*B* ^v^     0.86      2.10    2.945 (4)   168

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .
