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

For background to phenothia­zine as a pharmacophore, see: Albery *et al.* (1979[@bb1]); Tsakovska & Pajeva (2006[@bb10]). For compounds with organic framework structures and with electro-optic or electronic properties, see: Chakraborty *et al.* (2005[@bb4]); Cho *et al.* (2006[@bb5]); Park *et al.* (2008[@bb7]); Krämer *et al.* (2001[@bb6]); Zhang *et al.* (2007[@bb11]). For structure elucidation, see: Spek (2009[@bb9]).

Experimental   {#sec2}
==============

 {#sec2.1}

### Crystal data   {#sec2.1.1}

\[Co(C~15~H~9~NO~4~S)(H~2~O)~3~\]·H~2~O*M* *~r~* = 430.30Orthorhombic,*a* = 15.3105 (8) Å*b* = 7.2983 (4) Å*c* = 29.5679 (15) Å*V* = 3303.9 (3) Å^3^*Z* = 8Mo *K*α radiationμ = 1.21 mm^−1^*T* = 291 K0.30 × 0.26 × 0.24 mm

### Data collection   {#sec2.1.2}

Bruker SMART CCD diffractometerAbsorption correction: multi-scan (*SADABS*; Bruker, 2000[@bb3]) *T* ~min~ = 0.703, *T* ~max~ = 0.75916812 measured reflections3236 independent reflections2650 reflections with *I* \> 2σ(*I*)*R* ~int~ = 0.049

### Refinement   {#sec2.1.3}

*R*\[*F* ^2^ \> 2σ(*F* ^2^)\] = 0.043*wR*(*F* ^2^) = 0.104*S* = 1.083236 reflections236 parametersH-atom parameters constrainedΔρ~max~ = 0.62 e Å^−3^Δρ~min~ = −0.52 e Å^−3^

 {#d5e658}

Data collection: *SMART* (Bruker, 2000[@bb3]); cell refinement: *SAINT* (Bruker, 2000[@bb3]); data reduction: *SAINT*; program(s) used to solve structure: *SHELXTL* (Sheldrick, 2008[@bb8]); program(s) used to refine structure: *SHELXTL*; molecular graphics: *SHELXTL* and *DIAMOND* (Brandenburg, 2006[@bb2]); software used to prepare material for publication: *SHELXTL*.

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

Crystal structure: contains datablock(s) I, global. DOI: [10.1107/S1600536812009580/wm2597sup1.cif](http://dx.doi.org/10.1107/S1600536812009580/wm2597sup1.cif)

Structure factors: contains datablock(s) I. DOI: [10.1107/S1600536812009580/wm2597Isup2.hkl](http://dx.doi.org/10.1107/S1600536812009580/wm2597Isup2.hkl)

Additional supplementary materials: [crystallographic information](http://scripts.iucr.org/cgi-bin/sendsupfiles?wm2597&file=wm2597sup0.html&mime=text/html); [3D view](http://scripts.iucr.org/cgi-bin/sendcif?wm2597sup1&Qmime=cif); [checkCIF report](http://scripts.iucr.org/cgi-bin/paper?wm2597&checkcif=yes)

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: [WM2597](http://scripts.iucr.org/cgi-bin/sendsup?wm2597)).

The authors gratefully acknowledge financial support from the Natural Science Foundation of China, the Opening Project of Xinjiang Laboratory of Phase Transitions and Microstructures of Condensed Matter (XJDX0912--2011-01) and the Foundation of Yili Normal University (2011YNYB034).

Comment
=======

Phenothiazine, an intriguing type of biologically and pharmaceutically active heterocyclic compound well known as a pharmacophore in tranquilizers, antituberculosis agents, anti-tumor agents, bactericides, *etc*. (Albery *et al.*, 1979; Tsakovska & Pajeva, 2006), is now widely studied as an electron donor component and electrically conducting charge-transfer composite on account of its unique electro-optic properties in materials science (Chakraborty *et al.*, 2005; Cho *et al.*, 2006; Park *et al.*, 2008). Previous studies involving this compound had more emphasis on the large π-electron conjugated system (Krämer *et al.*, 2001; Zhang *et al.*, 2007); however, less work is reported on the construction of metal-organic frameworks using it as a building block. Here we employed the 10-methyl-10*H*-phenothiazine-3,7-dicarboxylate (MPTD) anion as a ligand to crystallize the title complex.

The title compound, {\[Co(C~15~H~9~NO~4~S)(H~2~O)~3~\]^.^H~2~O}, consists of a three-dimensional supramolecular network built up from coordination bonds, hydrogen bonds, and π---π interactions. As shown in Fig. 1, the Co^2+^ ion has a slightly distorted octahedral coordination environment formed by three O atoms from two different carboxylate ligands and three O atoms from three coordinated water molecules. Each MPTD ligand bridges two Co atoms *via* two carboxylate groups in a monodentate and a bidentate coordination mode into a one-dimensional zigzag chain parallel to \[001\]. These chains are assembled in an antiparallel manner into two-dimensional sheets parallel (100) based on strong interchain π---π interactions between the ligands \[centroid-centroid distance = 3.656, 3.669 Å\]. The sheets are further connected to form a three-dimensional supramolecular network (Fig. 2) *via* interlayer O---H···O hydrogen bond interactions. A *PLATON* calculation (Spek, 2009) shows that the structure has 13.6% solvent accessible voids when the coordinated and lattice water molecules are neglected. The resulting framework structure contains channels with approximate dimensions of 2.9×4.9 Å^2^ and 1.9×1.9 Å^2^ along \[010\] and \[001\], respectively. All the lattice water molecules and the coordinating water molecules are situated in these channels and are involved in the above extensive interlayer and intralayer H-bonding.

Experimental {#experimental}
============

The educt 10-methyl-10*H*-phenothiazine-3,7-dicarboxylic acid used to construct the title compound {\[Co(C~15~H~9~NO~4~S)(H~2~O)~3~\]^.^H~2~O} was prepared by oxidation of 10-methyl-10*H*-phenothiazine-3,7-dicarbaldehyde using silver nitrate as oxidant in an alkaline medium. 10-Methyl-10*H*-phenothiazine-3,7-dicarbaldehyde (0.6417 g, 2.38 mmol) (Cho *et al.*, 2006) was dissolved in 35 ml solution of KOH (10.0 g, 0.178 mol), then a 5 ml solution of AgNO~3~ (1.3 g, 7.65 mmol) was added slowly. The mixture was filtered after heating at 103 K overnight, then HCl (2 *M*) was added to the filtrate until the pH value reached 1\~2, during which a large amount of precipitate formed. The precipitate was filtered off, washed with distilled water, re-dissolved in KOH solution, and again acidified to pH 1\~2. The final acidification product was obtained by filtration and dried *in vacuo* (yield 0.4323 g, 60.3%). ^1^H NMR (300 MHz; DMSO-d^6^): *δ*~H~ 3.31 (3 H, s, CH~3~), 7.03 (2 H, s, ArH), 7.22 (2 H, d, ArH), 7.70 (2 H, d, ArH), 12.70 (2*H*, br, COOH). ^13^C NMR (300 MHz; DMSO-d^6^): *δ*~C~ 40.13 (CH~3~), 115.41 (Ar), 122.24 (Ar), 126.10 (Ar), 128.86 (Ar), 130.52 (Ar), 148.80 (Ar), 167.23 (COOH). MS: *m*/*z* 300.01 \[*M*-1\]^--^ (Calcd 300.03).

Single crystals of {\[Co(C~15~H~9~NO~4~S)(H~2~O)~3~\]^.^H~2~O} were obtained by solvothermal reaction of Co(NO~3~)~2~^.^6H~2~O (58.2 mg, 0.2 mmol) and 10-methyl-10*H*-phenothiazine-3,7-dicarboxylic acid (15.6 mg, 0.05 mmol) in a mixed solvent of ethanol and H~2~O (8 ml, volume ratio 1:4) at 393 K for 86 h and finally cooled to room temperature. The resulting products were filtered off, washed thoroughly with distilled water and dried in air at room temperature. The yield was 38.7 mg (45%).

Refinement {#refinement}
==========

All the H atoms were fixed geometrically and treated as riding with C---H = 0.96 Å, O--H = 0.85 Å and with *U*~iso~ (H) = 1.2*U*~eq~(C) or 1.5*U*~eq~(C, O) for methyl and water H atoms.

Figures
=======

![ORTEP plot of the title compound showing the local coordination environment of Co2+ with displacement ellipsoids at the 50% probability levels and H atoms shown as small spheres of arbitrary radius. \[Symmetry code: i = x, 0.5 - y, 0.5 + z.\]](e-68-0m402-fig1){#Fap1}

![The crystal packing diagram showing the 3-dimensional network. Inter-chain (blue dotted lines), intra-chain (bright green dotted lines), hydrogen bonds and inter-chain π---π interactions (yellow and rose dashed lines) are displayed.](e-68-0m402-fig2){#Fap2}

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

  ----------------------------------------- ---------------------------------------
  \[Co(C~15~H~9~NO~4~S)(H~2~O)~3~\]·H~2~O   *F*(000) = 1768
  *M~r~* = 430.30                           *D*~x~ = 1.730 Mg m^−3^
  Orthorhombic, *Pbca*                      Mo *K*α radiation, λ = 0.71073 Å
  Hall symbol: -P 2ac 2ab                   Cell parameters from 8389 reflections
  *a* = 15.3105 (8) Å                       θ = 2.7--28.1°
  *b* = 7.2983 (4) Å                        µ = 1.21 mm^−1^
  *c* = 29.5679 (15) Å                      *T* = 291 K
  *V* = 3303.9 (3) Å^3^                     Block, dark blue
  *Z* = 8                                   0.30 × 0.26 × 0.24 mm
  ----------------------------------------- ---------------------------------------

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

  ------------------------------------------------------------ --------------------------------------
  Bruker SMART CCD diffractometer                              3236 independent reflections
  Radiation source: sealed tube                                2650 reflections with *I* \> 2σ(*I*)
  Graphite monochromator                                       *R*~int~ = 0.049
  φ and ω scans                                                θ~max~ = 26.0°, θ~min~ = 1.9°
  Absorption correction: multi-scan (*SADABS*; Bruker, 2000)   *h* = −18→18
  *T*~min~ = 0.703, *T*~max~ = 0.759                           *k* = −8→9
  16812 measured reflections                                   *l* = −36→25
  ------------------------------------------------------------ --------------------------------------

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*\[*F*^2^ \> 2σ(*F*^2^)\] = 0.043   Hydrogen site location: inferred from neighbouring sites
  *wR*(*F*^2^) = 0.104                  H-atom parameters constrained
  *S* = 1.08                            *w* = 1/\[σ^2^(*F*~o~^2^) + (0.0596*P*)^2^\] where *P* = (*F*~o~^2^ + 2*F*~c~^2^)/3
  3236 reflections                      (Δ/σ)~max~ \< 0.001
  236 parameters                        Δρ~max~ = 0.62 e Å^−3^
  0 restraints                          Δρ~min~ = −0.52 e Å^−3^
  ------------------------------------- -------------------------------------------------------------------------------------

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

  -----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
  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~   
  C1     0.64689 (18)   0.1531 (4)      0.11609 (9)     0.0251 (6)           
  C2     0.69797 (18)   0.0972 (4)      0.15690 (8)     0.0226 (6)           
  C3     0.65262 (17)   0.0449 (4)      0.19532 (9)     0.0231 (6)           
  H3A    0.5899         0.0458          0.1951          0.028\*              
  C4     0.69635 (17)   −0.0086 (4)     0.23421 (8)     0.0208 (5)           
  C5     0.78763 (17)   −0.0105 (4)     0.23556 (8)     0.0186 (5)           
  C6     0.83264 (19)   0.0454 (4)      0.19657 (9)     0.0250 (6)           
  H6A    0.8953         0.0471          0.1969          0.030\*              
  C7     0.78842 (19)   0.0987 (4)      0.15843 (9)     0.0256 (6)           
  H7A    0.8207         0.1367          0.1323          0.031\*              
  C8     0.79744 (17)   −0.0200 (4)     0.31735 (8)     0.0193 (5)           
  C9     0.70693 (17)   −0.0173 (4)     0.32467 (8)     0.0197 (5)           
  C10    0.67305 (17)   0.0274 (4)      0.36651 (9)     0.0211 (5)           
  H10A   0.6109         0.0300          0.3708          0.025\*              
  C11    0.72820 (17)   0.0696 (3)      0.40252 (8)     0.0210 (5)           
  C12    0.69238 (17)   0.1164 (4)      0.44740 (8)     0.0208 (5)           
  C13    0.81794 (18)   0.0699 (4)      0.39510 (9)     0.0234 (6)           
  H13A   0.8563         0.1008          0.4196          0.028\*              
  C14    0.85212 (17)   0.0271 (4)      0.35350 (9)     0.0230 (6)           
  H14A   0.9142         0.0295          0.3491          0.028\*              
  C15    0.92396 (18)   −0.1018 (4)     0.27125 (10)    0.0302 (6)           
  H15A   0.9461         −0.1404         0.3001          0.045\*              
  H15B   0.9348         −0.1955         0.2492          0.045\*              
  H15C   0.9527         0.0093          0.2622          0.045\*              
  Co1    0.63098 (2)    0.19466 (5)     0.523713 (12)   0.02238 (13)         
  N1     0.83090 (14)   −0.0684 (3)     0.27475 (7)     0.0212 (5)           
  O1     0.74252 (13)   0.1653 (3)      0.47923 (6)     0.0267 (4)           
  O2     0.61043 (12)   0.1094 (3)      0.45464 (6)     0.0266 (4)           
  O3     0.56576 (13)   0.1431 (3)      0.11768 (7)     0.0363 (5)           
  O4     0.68927 (13)   0.2090 (3)      0.08152 (6)     0.0285 (5)           
  O5     0.64958 (14)   −0.0747 (3)     0.54390 (8)     0.0359 (5)           
  H5X    0.6117         −0.1448         0.5558          0.043\*              
  H5Y    0.7035         −0.1014         0.5420          0.043\*              
  O6     0.61132 (15)   0.4686 (3)      0.50278 (7)     0.0356 (5)           
  H6X    0.6603         0.5165          0.4962          0.043\*              
  H6Y    0.5731         0.5414          0.5134          0.043\*              
  O7     0.50146 (14)   0.1985 (3)      0.54566 (7)     0.0333 (5)           
  H7X    0.4691         0.1071          0.5516          0.040\*              
  H7Y    0.4990         0.2478          0.5717          0.040\*              
  O8     0.53016 (16)   0.7045 (4)      0.58142 (10)    0.0592 (8)           
  H8X    0.5528         0.6002          0.5865          0.071\*              
  H8Y    0.4840         0.7002          0.5655          0.071\*              
  S1     0.63643 (4)    −0.08955 (10)   0.28101 (2)     0.02552 (18)         
  ------ -------------- --------------- --------------- -------------------- --

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

  ----- ------------- ------------- ------------- --------------- -------------- ---------------
        *U*^11^       *U*^22^       *U*^33^       *U*^12^         *U*^13^        *U*^23^
  C1    0.0279 (14)   0.0268 (15)   0.0205 (13)   −0.0044 (11)    −0.0003 (11)   0.0048 (11)
  C2    0.0303 (14)   0.0213 (13)   0.0163 (13)   0.0022 (11)     0.0007 (10)    0.0014 (10)
  C3    0.0219 (13)   0.0276 (14)   0.0199 (14)   −0.0005 (10)    −0.0005 (10)   0.0009 (10)
  C4    0.0221 (13)   0.0243 (14)   0.0158 (12)   −0.0015 (10)    0.0014 (9)     0.0006 (10)
  C5    0.0233 (13)   0.0200 (13)   0.0126 (12)   0.0005 (10)     −0.0016 (9)    −0.0027 (10)
  C6    0.0250 (13)   0.0341 (15)   0.0160 (14)   −0.0021 (11)    0.0010 (10)    −0.0019 (11)
  C7    0.0288 (14)   0.0294 (15)   0.0186 (13)   −0.0013 (12)    0.0050 (10)    0.0015 (11)
  C8    0.0237 (13)   0.0192 (13)   0.0151 (12)   0.0016 (10)     0.0011 (10)    0.0031 (9)
  C9    0.0229 (13)   0.0180 (13)   0.0182 (12)   −0.0023 (10)    −0.0015 (10)   0.0019 (9)
  C10   0.0206 (12)   0.0253 (14)   0.0176 (13)   0.0011 (11)     0.0017 (10)    −0.0001 (10)
  C11   0.0261 (14)   0.0212 (14)   0.0156 (12)   −0.0004 (10)    0.0016 (10)    0.0009 (10)
  C12   0.0271 (13)   0.0194 (13)   0.0160 (12)   0.0010 (10)     0.0018 (10)    −0.0015 (10)
  C13   0.0239 (13)   0.0296 (14)   0.0168 (13)   −0.0050 (11)    −0.0028 (10)   −0.0035 (10)
  C14   0.0181 (12)   0.0320 (15)   0.0188 (13)   0.0001 (10)     −0.0017 (10)   −0.0007 (11)
  C15   0.0241 (14)   0.0416 (18)   0.0250 (14)   0.0104 (12)     −0.0048 (11)   −0.0042 (12)
  Co1   0.0213 (2)    0.0297 (2)    0.0162 (2)    −0.00106 (14)   0.00060 (14)   −0.00571 (14)
  N1    0.0172 (10)   0.0312 (13)   0.0151 (11)   0.0037 (9)      −0.0023 (8)    −0.0009 (9)
  O1    0.0220 (10)   0.0381 (12)   0.0201 (9)    −0.0026 (8)     0.0000 (8)     −0.0081 (8)
  O2    0.0229 (9)    0.0386 (12)   0.0183 (10)   0.0004 (8)      0.0013 (7)     −0.0063 (8)
  O3    0.0260 (11)   0.0556 (14)   0.0273 (11)   −0.0009 (10)    −0.0025 (9)    0.0148 (10)
  O4    0.0304 (11)   0.0395 (13)   0.0156 (9)    −0.0006 (9)     0.0002 (8)     0.0092 (8)
  O5    0.0358 (12)   0.0328 (12)   0.0392 (13)   0.0047 (9)      −0.0013 (9)    0.0018 (9)
  O6    0.0328 (11)   0.0358 (12)   0.0382 (13)   0.0003 (10)     0.0049 (9)     0.0062 (10)
  O7    0.0272 (11)   0.0420 (12)   0.0308 (12)   −0.0065 (9)     0.0057 (9)     −0.0104 (9)
  O8    0.0315 (13)   0.0651 (19)   0.081 (2)     −0.0039 (12)    −0.0143 (13)   0.0253 (14)
  S1    0.0230 (3)    0.0396 (4)    0.0139 (3)    −0.0101 (3)     −0.0013 (2)    0.0024 (3)
  ----- ------------- ------------- ------------- --------------- -------------- ---------------

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

  ------------------------ -------------- ------------------------ --------------
  C1---O3                  1.245 (3)      C12---O2                 1.274 (3)
  C1---O4                  1.278 (3)      C12---Co1                2.510 (2)
  C1---C2                  1.495 (4)      C13---C14                1.373 (4)
  C2---C3                  1.385 (4)      C13---H13A               0.9601
  C2---C7                  1.386 (4)      C14---H14A               0.9600
  C3---C4                  1.387 (4)      C15---N1                 1.449 (3)
  C3---H3A                 0.9600         C15---H15A               0.9601
  C4---C5                  1.398 (4)      C15---H15B               0.9599
  C4---S1                  1.762 (3)      C15---H15C               0.9600
  C5---N1                  1.400 (3)      Co1---O4^i^              2.0523 (19)
  C5---C6                  1.404 (4)      Co1---O5                 2.074 (2)
  C6---C7                  1.371 (4)      Co1---O7                 2.087 (2)
  C6---H6A                 0.9601         Co1---O6                 2.114 (2)
  C7---H7A                 0.9594         Co1---O2                 2.1581 (19)
  C8---C14                 1.400 (4)      Co1---O1                 2.1661 (19)
  C8---C9                  1.403 (4)      O4---Co1^ii^             2.0523 (19)
  C8---N1                  1.405 (3)      O5---H5X                 0.8497
  C9---C10                 1.381 (4)      O5---H5Y                 0.8500
  C9---S1                  1.763 (3)      O6---H6X                 0.8499
  C10---C11                1.393 (4)      O6---H6Y                 0.8500
  C10---H10A               0.9601         O7---H7X                 0.8500
  C11---C13                1.391 (4)      O7---H7Y                 0.8500
  C11---C12                1.476 (3)      O8---H8X                 0.8500
  C12---O1                 1.266 (3)      O8---H8Y                 0.8499
                                                                   
  O3---C1---O4             123.7 (3)      N1---C15---H15A          109.5
  O3---C1---C2             118.4 (2)      N1---C15---H15B          109.8
  O4---C1---C2             117.9 (2)      H15A---C15---H15B        109.5
  C3---C2---C7             118.5 (2)      N1---C15---H15C          109.2
  C3---C2---C1             118.4 (2)      H15A---C15---H15C        109.5
  C7---C2---C1             123.2 (2)      H15B---C15---H15C        109.5
  C2---C3---C4             121.0 (2)      O4^i^---Co1---O5         91.44 (9)
  C2---C3---H3A            119.7          O4^i^---Co1---O7         98.60 (8)
  C4---C3---H3A            119.3          O5---Co1---O7            93.09 (9)
  C3---C4---C5             120.6 (2)      O4^i^---Co1---O6         88.96 (9)
  C3---C4---S1             119.6 (2)      O5---Co1---O6            179.58 (10)
  C5---C4---S1             119.6 (2)      O7---Co1---O6            86.73 (9)
  C4---C5---N1             120.0 (2)      O4^i^---Co1---O2         161.86 (8)
  C4---C5---C6             117.7 (2)      O5---Co1---O2            91.09 (9)
  N1---C5---C6             122.4 (2)      O7---Co1---O2            99.19 (8)
  C7---C6---C5             121.0 (3)      O6---Co1---O2            88.56 (8)
  C7---C6---H6A            119.9          O4^i^---Co1---O1         101.35 (8)
  C5---C6---H6A            119.1          O5---Co1---O1            88.44 (8)
  C6---C7---C2             121.2 (3)      O7---Co1---O1            159.95 (8)
  C6---C7---H7A            119.4          O6---Co1---O1            91.61 (8)
  C2---C7---H7A            119.4          O2---Co1---O1            60.78 (7)
  C14---C8---C9            118.0 (2)      O4^i^---Co1---C12        131.59 (8)
  C14---C8---N1            121.9 (2)      O5---Co1---C12           89.52 (9)
  C9---C8---N1             120.1 (2)      O7---Co1---C12           129.68 (9)
  C10---C9---C8            120.8 (2)      O6---Co1---C12           90.31 (9)
  C10---C9---S1            119.8 (2)      O2---Co1---C12           30.49 (8)
  C8---C9---S1             119.19 (19)    O1---Co1---C12           30.29 (8)
  C9---C10---C11           120.6 (2)      C5---N1---C8             119.6 (2)
  C9---C10---H10A          119.7          C5---N1---C15            117.2 (2)
  C11---C10---H10A         119.6          C8---N1---C15            117.7 (2)
  C13---C11---C10          118.6 (2)      C12---O1---Co1           90.08 (16)
  C13---C11---C12          120.6 (2)      C12---O2---Co1           90.23 (15)
  C10---C11---C12          120.9 (2)      C1---O4---Co1^ii^        123.71 (18)
  O1---C12---O2            118.9 (2)      Co1---O5---H5X           126.6
  O1---C12---C11           120.6 (2)      Co1---O5---H5Y           109.4
  O2---C12---C11           120.5 (2)      H5X---O5---H5Y           123.5
  O1---C12---Co1           59.64 (13)     Co1---O6---H6X           109.3
  O2---C12---Co1           59.28 (13)     Co1---O6---H6Y           125.5
  C11---C12---Co1          179.7 (2)      H6X---O6---H6Y           115.7
  C14---C13---C11          121.2 (2)      Co1---O7---H7X           127.4
  C14---C13---H13A         119.8          Co1---O7---H7Y           109.3
  C11---C13---H13A         119.1          H7X---O7---H7Y           96.8
  C13---C14---C8           120.8 (2)      H8X---O8---H8Y           113.8
  C13---C14---H14A         119.7          C4---S1---C9             98.98 (12)
  C8---C14---H14A          119.5                                   
                                                                   
  O3---C1---C2---C3        −2.9 (4)       O1---C12---Co1---O5      −87.73 (16)
  O4---C1---C2---C3        176.9 (3)      O2---C12---Co1---O5      92.97 (16)
  O3---C1---C2---C7        178.4 (3)      O1---C12---Co1---O7      178.66 (15)
  O4---C1---C2---C7        −1.8 (4)       O2---C12---Co1---O7      −0.6 (2)
  C7---C2---C3---C4        −1.4 (4)       O1---C12---Co1---O6      92.65 (16)
  C1---C2---C3---C4        179.9 (3)      O2---C12---Co1---O6      −86.64 (16)
  C2---C3---C4---C5        0.2 (4)        O1---C12---Co1---O2      179.3 (3)
  C2---C3---C4---S1        −175.5 (2)     O2---C12---Co1---O1      −179.3 (3)
  C3---C4---C5---N1        −178.7 (2)     C4---C5---N1---C8        −38.7 (4)
  S1---C4---C5---N1        −3.0 (3)       C6---C5---N1---C8        141.9 (3)
  C3---C4---C5---C6        0.7 (4)        C4---C5---N1---C15       168.1 (2)
  S1---C4---C5---C6        176.5 (2)      C6---C5---N1---C15       −11.3 (4)
  C4---C5---C6---C7        −0.5 (4)       C14---C8---N1---C5       −141.7 (3)
  N1---C5---C6---C7        178.9 (3)      C9---C8---N1---C5        38.1 (4)
  C5---C6---C7---C2        −0.7 (4)       C14---C8---N1---C15      11.3 (4)
  C3---C2---C7---C6        1.6 (4)        C9---C8---N1---C15       −168.9 (2)
  C1---C2---C7---C6        −179.7 (3)     O2---C12---O1---Co1      0.7 (3)
  C14---C8---C9---C10      −1.1 (4)       C11---C12---O1---Co1     −179.8 (2)
  N1---C8---C9---C10       179.1 (2)      O4^i^---Co1---O1---C12   −177.13 (16)
  C14---C8---C9---S1       −176.1 (2)     O5---Co1---O1---C12      91.71 (17)
  N1---C8---C9---S1        4.1 (3)        O7---Co1---O1---C12      −3.0 (3)
  C8---C9---C10---C11      −0.5 (4)       O6---Co1---O1---C12      −87.87 (17)
  S1---C9---C10---C11      174.5 (2)      O2---Co1---O1---C12      −0.41 (15)
  C9---C10---C11---C13     1.5 (4)        O1---C12---O2---Co1      −0.7 (3)
  C9---C10---C11---C12     −179.6 (2)     C11---C12---O2---Co1     179.8 (2)
  C13---C11---C12---O1     3.2 (4)        O4^i^---Co1---O2---C12   10.8 (4)
  C10---C11---C12---O1     −175.7 (3)     O5---Co1---O2---C12      −87.19 (16)
  C13---C11---C12---O2     −177.3 (3)     O7---Co1---O2---C12      179.51 (16)
  C10---C11---C12---O2     3.8 (4)        O6---Co1---O2---C12      93.05 (16)
  C10---C11---C13---C14    −0.9 (4)       O1---Co1---O2---C12      0.41 (15)
  C12---C11---C13---C14    −179.9 (3)     O3---C1---O4---Co1^ii^   3.4 (4)
  C11---C13---C14---C8     −0.6 (4)       C2---C1---O4---Co1^ii^   −176.40 (18)
  C9---C8---C14---C13      1.7 (4)        C3---C4---S1---C9        −149.7 (2)
  N1---C8---C14---C13      −178.5 (3)     C5---C4---S1---C9        34.6 (2)
  O1---C12---Co1---O4^i^   3.8 (2)        C10---C9---S1---C4       150.0 (2)
  O2---C12---Co1---O4^i^   −175.52 (15)   C8---C9---S1---C4        −35.0 (2)
  ------------------------ -------------- ------------------------ --------------

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

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

  ---------------------- --------- --------- ----------- ---------------
  *D*---H···*A*          *D*---H   H···*A*   *D*···*A*   *D*---H···*A*
  O5---H5*X*···O8^iii^   0.85      1.83      2.678 (4)   180
  O5---H5*Y*···O4^iv^    0.85      2.16      2.879 (3)   142
  O6---H6*X*···O1^v^     0.85      1.91      2.748 (3)   169
  O6---H6*Y*···O8        0.85      2.43      3.149 (4)   143
  O7---H7*X*···O2^vi^    0.85      2.00      2.826 (3)   163
  O7---H7*Y*···O3^i^     0.85      1.88      2.615 (3)   144
  O8---H8*X*···O3^i^     0.85      2.01      2.808 (4)   156
  O8---H8*Y*···O2^vii^   0.85      2.09      2.760 (3)   135
  ---------------------- --------- --------- ----------- ---------------

Symmetry codes: (i) *x*, −*y*+1/2, *z*+1/2; (iii) *x*, *y*−1, *z*; (iv) −*x*+3/2, −*y*, *z*+1/2; (v) −*x*+3/2, *y*+1/2, *z*; (vi) −*x*+1, −*y*, −*z*+1; (vii) −*x*+1, −*y*+1, −*z*+1.

###### Selected bond lengths (Å)

  ------------- -------------
  Co1---O4^i^   2.0523 (19)
  Co1---O5      2.074 (2)
  Co1---O7      2.087 (2)
  Co1---O6      2.114 (2)
  Co1---O2      2.1581 (19)
  Co1---O1      2.1661 (19)
  ------------- -------------

Symmetry code: (i) .

###### Hydrogen-bond geometry (Å, °)

  *D*---H⋯*A*          *D*---H   H⋯*A*   *D*⋯*A*     *D*---H⋯*A*
  -------------------- --------- ------- ----------- -------------
  O5---H5*X*⋯O8^ii^    0.85      1.83    2.678 (4)   180
  O5---H5*Y*⋯O4^iii^   0.85      2.16    2.879 (3)   142
  O6---H6*X*⋯O1^iv^    0.85      1.91    2.748 (3)   169
  O6---H6*Y*⋯O8        0.85      2.43    3.149 (4)   143
  O7---H7*X*⋯O2^v^     0.85      2.00    2.826 (3)   163
  O7---H7*Y*⋯O3^i^     0.85      1.88    2.615 (3)   144
  O8---H8*X*⋯O3^i^     0.85      2.01    2.808 (4)   156
  O8---H8*Y*⋯O2^vi^    0.85      2.09    2.760 (3)   135

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