Bis(2-amino-3H-benzothia­zolium) bis­(7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxyl­ato)cobaltate(II) hexa­hydrate

Wang, N.; Lin, Q.-Y.; Feng, J.; Li, S.-K.; Zhao, J.-J.

doi:10.1107/S1600536810020921

Bis(2-amino-3H-benzothiazolium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)cobaltate(II) hexahydrate

N. Wang, Q.-Y. Lin, J. Feng, S.-K. Li and J.-J. Zhao

In the crystal structure of the title salt, (C₇H₇N₂S)₂[Co(C₈H₈O₅)₂]·6H₂O, the heterocyclic N atom of the 2-aminobenzothiazole molecule is protonated. The Co^II atom is situated on an inversion centre and exhibits a slightly distorted octahedral CoO₆ coordination defined by the bridging O atoms of the bicycloheptane unit and four carboxylate O atoms of two symmetry-related and fully deprotonated ligands. The crystal packing is stabilized by N—H

O hydrogen bonds between the cations and anions and by O—H

O hydrogen bonds including the crystal water molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810020921/wm2351sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810020921/wm2351Isup2.hkl Contains datablock I

CCDC reference: 773901

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
R factor = 0.052
wR factor = 0.130
Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found





Alert level A
PLAT900_ALERT_1_A No Matching Reflection File Found ..............          !
PLAT900_ALERT_1_A No Matching Reflection File Found ..............          !
PLAT902_ALERT_1_A No (Interpretable) Reflections found in FCF ....          !

Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT731_ALERT_1_C Bond    Calc     0.84(4), Rep   0.839(19) ......       2.11 su-Ra
              O1W  -H1WB    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.83(4), Rep   0.831(18) ......       2.22 su-Ra
              O3W  -H3WB    1.555   1.555

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        400 Deg.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          6
PLAT793_ALERT_4_G The Model has Chirality at C1      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C4      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C5      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C6      (Verify) ....          R

   3 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

7-oxabicyclo[2,2,1] heptane-2,3-dicarboxylic anhydride (norcantharidin) derived from cantharidin is a lower toxicity anticancer drug (Shimi et al., 1982). Cobalt was recognized as an essential metal element widely distributed in biological systems such as cells and body (Jiao et al., 2005). Several related cobalt complexes with the same ligand (Wang et al., 1988) and with the ligand and with imidazole (Wang et al., 2009) have been reported.

In the title complex, (C₇H₇N₂S)⁺₂[Co(C₈H₈O₅)₂]^2-(H₂O)₆, the Co^II ion is located on a crystallographic centre of inversion. Two bridging oxygen atoms of the bicycloheptane units and four carboxylate oxygen atoms give rise to a slightly distorted octahedral coordination environment around the Co^II atom. The bond angles O2—Co1—O2ⁱ, O4—Co1—O4ⁱ and O5—Co1—O5ⁱ (i: -x+1, -y, -z.) are 180°, while the bond angles O4—Co1—O2 and O2—Co1—O4ⁱ open up slightly from 87.71 (9)° to 92.29 (9)°, resulting in a slight distortion from the ideal octahedral geometry. The crystal packing is stabilized by N—H···O hydrogen bonds between the cations and anions and by O—H···O hydrogen bonds including the crystal water molecules.

The crystal structure of (C₇H₇N₂S)⁺₂[Co(C₈H₈O₅)₂]^2-(H₂O)₆ is isotypic with that of the Mn analogue (Wang et al., 2010) where slightly longer metal—oxygen bonds are observed.

Related literature top

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982). For the importance of cobalt in biological systems, see: Jiao et al. (2005). For the isotypic structure of the Mn analogue, see: Wang et al. (2010). For related cobalt complexes, see: Wang et al. (1988, 2009).

Experimental top

Norcantharidin, cobalt acetate and 2-aminobenzothiazole were dissolved in 15 mL distilled water. The mixture was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. Pink crystals suitable for X-ray diffraction were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecular units of the title salt showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability. Symmetry code: A (-x+2, -y, -z).

Bis(2-amino-3H-benzothiazolium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)cobaltate(II) hexahydrate top

Crystal data top

(C₇H₇N₂S)₂[Co(C₈H₈O₅)₂]·6H₂O	Z = 1
M_r = 837.73	F(000) = 437
Triclinic, P1	D_x = 1.577 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6924 (4) Å	Cell parameters from 2197 reflections
b = 10.1294 (5) Å	θ = 1.5–27.6°
c = 13.1860 (7) Å	µ = 0.69 mm⁻¹
α = 90.094 (4)°	T = 296 K
β = 91.112 (4)°	Block, pink
γ = 99.314 (4)°	0.19 × 0.16 × 0.07 mm
V = 881.92 (8) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3999 independent reflections
Radiation source: fine-focus sealed tube	2460 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 27.6°, θ_min = 1.5°
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	h = −8→8
T_min = 0.876, T_max = 0.953	k = −11→13
13051 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0599P)²] where P = (F_o² + 2F_c²)/3
3999 reflections	(Δ/σ)_max < 0.001
262 parameters	Δρ_max = 0.47 e Å⁻³
10 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

(C₇H₇N₂S)₂[Co(C₈H₈O₅)₂]·6H₂O	γ = 99.314 (4)°
M_r = 837.73	V = 881.92 (8) Å³
Triclinic, P1	Z = 1
a = 6.6924 (4) Å	Mo Kα radiation
b = 10.1294 (5) Å	µ = 0.69 mm⁻¹
c = 13.1860 (7) Å	T = 296 K
α = 90.094 (4)°	0.19 × 0.16 × 0.07 mm
β = 91.112 (4)°

Data collection top

Bruker APEXII area-detector diffractometer	3999 independent reflections
Absorption correction: multi-scan SADABS (Sheldrick, 1996)	2460 reflections with I > 2σ(I)
T_min = 0.876, T_max = 0.953	R_int = 0.051
13051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	10 restraints
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.47 e Å⁻³
3999 reflections	Δρ_min = −0.44 e Å⁻³
262 parameters

Special details top

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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.5000	0.0000	0.0000	0.0303 (2)
S1	0.32716 (14)	0.26697 (8)	0.52780 (6)	0.0399 (2)
N1	0.2766 (4)	0.0309 (2)	0.60086 (19)	0.0302 (6)
H1N	0.277 (5)	−0.031 (3)	0.644 (2)	0.045*
N2	0.3473 (4)	0.1974 (3)	0.7234 (2)	0.0406 (7)
H2C	0.3394	0.1394	0.7713	0.049*
H2D	0.3742	0.2814	0.7375	0.049*
O1	0.7726 (3)	0.1597 (2)	0.25745 (15)	0.0384 (6)
O1W	0.1942 (5)	0.5445 (3)	0.4012 (2)	0.0706 (8)
H1WA	0.199 (7)	0.563 (5)	0.4621 (17)	0.106*
H1WB	0.085 (5)	0.492 (4)	0.393 (3)	0.106*
O2	0.6869 (3)	0.0130 (2)	0.13153 (15)	0.0376 (6)
O2W	0.5190 (4)	0.5231 (2)	0.2784 (2)	0.0546 (7)
H2WA	0.478 (6)	0.473 (4)	0.228 (2)	0.082*
H2WB	0.416 (4)	0.522 (4)	0.313 (3)	0.082*
O3	0.3619 (3)	0.3400 (2)	0.13885 (17)	0.0429 (6)
O3W	0.8114 (5)	0.3962 (3)	0.3736 (2)	0.0608 (7)
H3WA	0.828 (6)	0.334 (3)	0.334 (3)	0.091*
H3WB	0.723 (6)	0.432 (4)	0.345 (3)	0.091*
O4	0.3648 (3)	0.14697 (19)	0.06047 (16)	0.0369 (5)
O5	0.7143 (3)	0.15513 (19)	−0.06851 (15)	0.0327 (5)
C1	0.9035 (5)	0.1842 (3)	−0.0093 (2)	0.0334 (8)
H1A	0.9718	0.1064	−0.0002	0.040*
C2	1.0232 (5)	0.2949 (3)	−0.0715 (2)	0.0396 (8)
H2A	1.0898	0.2587	−0.1274	0.047*
H2B	1.1237	0.3514	−0.0299	0.047*
C3	0.8570 (5)	0.3722 (3)	−0.1100 (2)	0.0397 (8)
H3A	0.8797	0.4637	−0.0851	0.048*
H3B	0.8483	0.3724	−0.1835	0.048*
C4	0.6689 (5)	0.2912 (3)	−0.0646 (2)	0.0321 (7)
H4A	0.5435	0.3016	−0.1011	0.039*
C5	0.6600 (5)	0.3150 (3)	0.0495 (2)	0.0298 (7)
H5A	0.6967	0.4107	0.0645	0.036*
C6	0.8339 (5)	0.2379 (3)	0.0895 (2)	0.0301 (7)
H6A	0.9443	0.3018	0.1201	0.036*
C7	0.7589 (5)	0.1300 (3)	0.1659 (2)	0.0307 (7)
C8	0.4489 (5)	0.2639 (3)	0.0876 (2)	0.0314 (7)
C9	0.2570 (5)	0.1328 (4)	0.3395 (2)	0.0444 (9)
H9A	0.2729	0.2130	0.3041	0.053*
C10	0.2146 (5)	0.0118 (4)	0.2888 (3)	0.0497 (10)
H10A	0.2011	0.0102	0.2185	0.060*
C11	0.1922 (5)	−0.1068 (4)	0.3421 (3)	0.0466 (9)
H11A	0.1645	−0.1874	0.3067	0.056*
C12	0.2099 (5)	−0.1089 (3)	0.4467 (2)	0.0373 (8)
H12A	0.1936	−0.1892	0.4820	0.045*
C13	0.2522 (4)	0.0113 (3)	0.4966 (2)	0.0291 (7)
C14	0.2750 (5)	0.1318 (3)	0.4437 (2)	0.0325 (7)
C15	0.3185 (5)	0.1578 (3)	0.6290 (2)	0.0297 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0393 (4)	0.0196 (3)	0.0308 (4)	0.0010 (3)	−0.0019 (3)	−0.0021 (2)
S1	0.0525 (6)	0.0285 (5)	0.0373 (5)	0.0028 (4)	−0.0009 (4)	0.0063 (4)
N1	0.0372 (16)	0.0244 (15)	0.0291 (16)	0.0053 (12)	0.0018 (12)	0.0021 (11)
N2	0.058 (2)	0.0267 (15)	0.0354 (16)	0.0027 (13)	−0.0010 (13)	0.0014 (12)
O1	0.0575 (16)	0.0301 (12)	0.0265 (13)	0.0042 (11)	−0.0040 (10)	0.0005 (10)
O1W	0.068 (2)	0.074 (2)	0.0641 (19)	−0.0052 (16)	0.0018 (16)	−0.0069 (17)
O2	0.0504 (15)	0.0225 (12)	0.0367 (13)	−0.0029 (10)	−0.0079 (10)	0.0022 (9)
O2W	0.0644 (19)	0.0363 (15)	0.0614 (18)	0.0040 (13)	−0.0083 (14)	−0.0138 (13)
O3	0.0439 (15)	0.0339 (13)	0.0519 (15)	0.0093 (11)	0.0025 (11)	−0.0134 (11)
O3W	0.067 (2)	0.0509 (18)	0.0643 (19)	0.0122 (14)	−0.0146 (15)	−0.0112 (14)
O4	0.0377 (14)	0.0221 (12)	0.0493 (14)	−0.0002 (10)	0.0026 (10)	−0.0065 (10)
O5	0.0406 (13)	0.0233 (11)	0.0322 (12)	−0.0005 (10)	0.0010 (10)	−0.0025 (9)
C1	0.0352 (19)	0.0254 (17)	0.041 (2)	0.0085 (14)	0.0014 (15)	0.0004 (14)
C2	0.042 (2)	0.0328 (18)	0.042 (2)	0.0004 (16)	0.0076 (16)	0.0011 (15)
C3	0.059 (2)	0.0243 (17)	0.0333 (19)	−0.0023 (16)	0.0036 (16)	−0.0004 (14)
C4	0.042 (2)	0.0235 (16)	0.0312 (18)	0.0070 (14)	−0.0053 (14)	0.0016 (13)
C5	0.040 (2)	0.0162 (15)	0.0319 (18)	0.0022 (13)	−0.0031 (14)	−0.0021 (13)
C6	0.0338 (19)	0.0221 (16)	0.0325 (18)	−0.0005 (14)	−0.0042 (14)	−0.0009 (13)
C7	0.0327 (19)	0.0261 (17)	0.0334 (19)	0.0062 (14)	−0.0048 (14)	0.0034 (14)
C8	0.042 (2)	0.0246 (17)	0.0281 (17)	0.0072 (15)	−0.0037 (14)	0.0006 (14)
C9	0.048 (2)	0.053 (2)	0.032 (2)	0.0084 (18)	0.0041 (16)	0.0076 (17)
C10	0.047 (2)	0.075 (3)	0.0282 (19)	0.014 (2)	0.0015 (16)	−0.006 (2)
C11	0.039 (2)	0.053 (2)	0.047 (2)	0.0080 (18)	−0.0002 (17)	−0.0193 (19)
C12	0.037 (2)	0.0364 (19)	0.040 (2)	0.0114 (15)	0.0021 (15)	−0.0044 (16)
C13	0.0247 (18)	0.0316 (18)	0.0316 (18)	0.0061 (14)	0.0033 (13)	−0.0007 (14)
C14	0.0300 (18)	0.0328 (18)	0.0342 (19)	0.0038 (14)	0.0025 (14)	0.0029 (14)
C15	0.0334 (19)	0.0268 (17)	0.0283 (18)	0.0032 (14)	0.0024 (14)	−0.0019 (13)

Geometric parameters (Å, º) top

Co1—O4	2.033 (2)	C1—C2	1.520 (4)
Co1—O4ⁱ	2.033 (2)	C1—C6	1.521 (4)
Co1—O2	2.110 (2)	C1—H1A	0.9800
Co1—O2ⁱ	2.110 (2)	C2—C3	1.539 (5)
Co1—O5ⁱ	2.160 (2)	C2—H2A	0.9700
Co1—O5	2.160 (2)	C2—H2B	0.9700
S1—C15	1.730 (3)	C3—C4	1.521 (4)
S1—C14	1.747 (3)	C3—H3A	0.9700
N1—C15	1.322 (4)	C3—H3B	0.9700
N1—C13	1.392 (4)	C4—C5	1.527 (4)
N1—H1N	0.840 (17)	C4—H4A	0.9800
N2—C15	1.308 (4)	C5—C8	1.519 (4)
N2—H2C	0.8600	C5—C6	1.585 (4)
N2—H2D	0.8600	C5—H5A	0.9800
O1—C7	1.242 (3)	C6—C7	1.519 (4)
O1W—H1WA	0.823 (18)	C6—H6A	0.9800
O1W—H1WB	0.839 (19)	C9—C14	1.377 (4)
O2—C7	1.283 (3)	C9—C10	1.380 (5)
O2W—H2WA	0.852 (18)	C9—H9A	0.9300
O2W—H2WB	0.828 (18)	C10—C11	1.381 (5)
O3—C8	1.245 (4)	C10—H10A	0.9300
O3W—H3WA	0.842 (18)	C11—C12	1.383 (4)
O3W—H3WB	0.831 (18)	C11—H11A	0.9300
O4—C8	1.274 (3)	C12—C13	1.369 (4)
O5—C4	1.460 (3)	C12—H12A	0.9300
O5—C1	1.463 (4)	C13—C14	1.395 (4)

O4—Co1—O4ⁱ	180.00 (14)	H3A—C3—H3B	109.3
O4—Co1—O2	87.71 (9)	O5—C4—C3	102.3 (2)
O4ⁱ—Co1—O2	92.29 (9)	O5—C4—C5	101.9 (2)
O4—Co1—O2ⁱ	92.29 (9)	C3—C4—C5	111.7 (3)
O4ⁱ—Co1—O2ⁱ	87.71 (9)	O5—C4—H4A	113.3
O2—Co1—O2ⁱ	180.00 (6)	C3—C4—H4A	113.3
O4—Co1—O5ⁱ	92.19 (8)	C5—C4—H4A	113.3
O4ⁱ—Co1—O5ⁱ	87.81 (8)	C8—C5—C4	110.4 (2)
O2—Co1—O5ⁱ	90.69 (8)	C8—C5—C6	115.9 (2)
O2ⁱ—Co1—O5ⁱ	89.31 (8)	C4—C5—C6	100.7 (2)
O4—Co1—O5	87.81 (8)	C8—C5—H5A	109.8
O4ⁱ—Co1—O5	92.19 (8)	C4—C5—H5A	109.8
O2—Co1—O5	89.31 (8)	C6—C5—H5A	109.8
O2ⁱ—Co1—O5	90.69 (8)	C7—C6—C1	113.9 (2)
O5ⁱ—Co1—O5	180.00 (12)	C7—C6—C5	112.7 (2)
C15—S1—C14	90.24 (14)	C1—C6—C5	101.1 (2)
C15—N1—C13	114.3 (2)	C7—C6—H6A	109.6
C15—N1—H1N	121 (2)	C1—C6—H6A	109.6
C13—N1—H1N	125 (2)	C5—C6—H6A	109.6
C15—N2—H2C	120.0	O1—C7—O2	124.1 (3)
C15—N2—H2D	120.0	O1—C7—C6	118.3 (3)
H2C—N2—H2D	120.0	O2—C7—C6	117.7 (3)
H1WA—O1W—H1WB	104 (3)	O3—C8—O4	123.0 (3)
C7—O2—Co1	117.83 (18)	O3—C8—C5	118.9 (3)
H2WA—O2W—H2WB	104 (3)	O4—C8—C5	118.0 (3)
H3WA—O3W—H3WB	104 (3)	C14—C9—C10	118.4 (3)
C8—O4—Co1	127.4 (2)	C14—C9—H9A	120.8
C4—O5—C1	95.5 (2)	C10—C9—H9A	120.8
C4—O5—Co1	117.10 (17)	C9—C10—C11	120.3 (3)
C1—O5—Co1	111.96 (16)	C9—C10—H10A	119.8
O5—C1—C2	101.5 (2)	C11—C10—H10A	119.8
O5—C1—C6	102.2 (2)	C10—C11—C12	121.7 (3)
C2—C1—C6	111.5 (3)	C10—C11—H11A	119.1
O5—C1—H1A	113.5	C12—C11—H11A	119.1
C2—C1—H1A	113.5	C13—C12—C11	117.7 (3)
C6—C1—H1A	113.5	C13—C12—H12A	121.1
C1—C2—C3	102.2 (3)	C11—C12—H12A	121.1
C1—C2—H2A	111.3	C12—C13—N1	126.7 (3)
C3—C2—H2A	111.3	C12—C13—C14	121.1 (3)
C1—C2—H2B	111.3	N1—C13—C14	112.2 (3)
C3—C2—H2B	111.3	C9—C14—C13	120.7 (3)
H2A—C2—H2B	109.2	C9—C14—S1	128.9 (3)
C4—C3—C2	101.5 (2)	C13—C14—S1	110.4 (2)
C4—C3—H3A	111.5	N2—C15—N1	123.8 (3)
C2—C3—H3A	111.5	N2—C15—S1	123.3 (2)
C4—C3—H3B	111.5	N1—C15—S1	112.9 (2)
C2—C3—H3B	111.5

O4—Co1—O2—C7	−42.6 (2)	C2—C1—C6—C5	72.9 (3)
O4ⁱ—Co1—O2—C7	137.4 (2)	C8—C5—C6—C7	−3.8 (3)
O5ⁱ—Co1—O2—C7	−134.8 (2)	C4—C5—C6—C7	−122.9 (3)
O5—Co1—O2—C7	45.2 (2)	C8—C5—C6—C1	118.2 (3)
O2—Co1—O4—C8	58.0 (2)	C4—C5—C6—C1	−0.9 (3)
O2ⁱ—Co1—O4—C8	−122.0 (2)	Co1—O2—C7—O1	139.8 (2)
O5ⁱ—Co1—O4—C8	148.6 (2)	Co1—O2—C7—C6	−40.9 (3)
O5—Co1—O4—C8	−31.4 (2)	C1—C6—C7—O1	152.8 (3)
O4—Co1—O5—C4	−10.50 (18)	C5—C6—C7—O1	−92.7 (3)
O4ⁱ—Co1—O5—C4	169.50 (18)	C1—C6—C7—O2	−26.5 (4)
O2—Co1—O5—C4	−98.23 (18)	C5—C6—C7—O2	87.9 (3)
O2ⁱ—Co1—O5—C4	81.77 (18)	Co1—O4—C8—O3	−167.9 (2)
O4—Co1—O5—C1	98.29 (18)	Co1—O4—C8—C5	16.1 (4)
O4ⁱ—Co1—O5—C1	−81.71 (18)	C4—C5—C8—O3	−128.2 (3)
O2—Co1—O5—C1	10.55 (18)	C6—C5—C8—O3	118.2 (3)
O2ⁱ—Co1—O5—C1	−169.45 (18)	C4—C5—C8—O4	48.0 (3)
C4—O5—C1—C2	−57.1 (3)	C6—C5—C8—O4	−65.7 (3)
Co1—O5—C1—C2	−179.28 (17)	C14—C9—C10—C11	−0.3 (5)
C4—O5—C1—C6	58.2 (2)	C9—C10—C11—C12	0.4 (5)
Co1—O5—C1—C6	−64.0 (2)	C10—C11—C12—C13	−0.5 (5)
O5—C1—C2—C3	35.8 (3)	C11—C12—C13—N1	−179.8 (3)
C6—C1—C2—C3	−72.4 (3)	C11—C12—C13—C14	0.5 (5)
C1—C2—C3—C4	−0.9 (3)	C15—N1—C13—C12	179.5 (3)
C1—O5—C4—C3	56.9 (3)	C15—N1—C13—C14	−0.8 (4)
Co1—O5—C4—C3	175.04 (17)	C10—C9—C14—C13	0.4 (5)
C1—O5—C4—C5	−58.7 (3)	C10—C9—C14—S1	180.0 (3)
Co1—O5—C4—C5	59.4 (2)	C12—C13—C14—C9	−0.5 (5)
C2—C3—C4—O5	−34.6 (3)	N1—C13—C14—C9	179.7 (3)
C2—C3—C4—C5	73.7 (3)	C12—C13—C14—S1	179.8 (2)
O5—C4—C5—C8	−86.5 (3)	N1—C13—C14—S1	0.1 (3)
C3—C4—C5—C8	165.0 (3)	C15—S1—C14—C9	−179.2 (3)
O5—C4—C5—C6	36.5 (3)	C15—S1—C14—C13	0.5 (2)
C3—C4—C5—C6	−72.0 (3)	C13—N1—C15—N2	−179.9 (3)
O5—C1—C6—C7	86.2 (3)	C13—N1—C15—S1	1.2 (3)
C2—C1—C6—C7	−166.0 (3)	C14—S1—C15—N2	−179.9 (3)
O5—C1—C6—C5	−34.9 (3)	C14—S1—C15—N1	−0.9 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱⁱ	0.84 (2)	1.85 (2)	2.675 (3)	169 (3)
N2—H2C···O2ⁱⁱ	0.86	2.00	2.851 (3)	173
N2—H2D···O2Wⁱⁱⁱ	0.86	2.01	2.828 (4)	160
O1W—H1WA···O3Wⁱⁱⁱ	0.82 (2)	2.21 (2)	3.030 (4)	176 (4)
O1W—H1WB···O3W^iv	0.84 (4)	1.94 (2)	2.769 (4)	171 (5)
O2W—H2WA···O3	0.85 (2)	1.85 (2)	2.686 (3)	167 (4)
O2W—H2WB···O1W	0.83 (2)	1.95 (2)	2.772 (4)	171 (4)
O3W—H3WA···O1	0.84 (2)	2.01 (2)	2.815 (3)	160 (4)
O3W—H3WB···O2W	0.83 (4)	1.96 (4)	2.790 (4)	178 (4)

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

Experimental details

Crystal data
Chemical formula	(C₇H₇N₂S)₂[Co(C₈H₈O₅)₂]·6H₂O
M_r	837.73
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.6924 (4), 10.1294 (5), 13.1860 (7)
α, β, γ (°)	90.094 (4), 91.112 (4), 99.314 (4)
V (Å³)	881.92 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.19 × 0.16 × 0.07

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan SADABS (Sheldrick, 1996)
T_min, T_max	0.876, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	13051, 3999, 2460
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.130, 1.03
No. of reflections	3999
No. of parameters	262
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.44

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O4	2.033 (2)	Co1—O5	2.160 (2)
Co1—O2	2.110 (2)