Bis(2-amino-3H-benzothia-zolium) bis-(7-oxabicyclo-[2.2.1]heptane-2,3-dicarboxyl-ato)cobaltate(II) hexa-hydrate.

In the crystal structure of the title salt, (C(7)H(7)N(2)S)(2)[Co(C(8)H(8)O(5))(2)]·6H(2)O, the heterocyclic N atom of the 2-amino-benzothia-zole mol-ecule is protonated. The Co(II) atom is situated on an inversion centre and exhibits a slightly distorted octa-hedral CoO(6) coordination defined by the bridging O atoms of the bicyclo-heptane unit and four carboxyl-ate 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 mol-ecules.

Related literature

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

Crystal data

(C7H7N2S)2[Co(C8H8O5)2]·6H2O

M = 837.73

Triclinic,

a = 6.6924 (4) Å

b = 10.1294 (5) Å

c = 13.1860 (7) Å

α = 90.094 (4)°

β = 91.112 (4)°

γ = 99.314 (4)°

V = 881.92 (8) Å3

Z = 1

Mo Kα radiation

μ = 0.69 mm−1

T = 296 K

0.19 × 0.16 × 0.07 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan SADABS (Sheldrick, 1996 ▶) T min = 0.876, T max = 0.953

13051 measured reflections

3999 independent reflections

2460 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.130

S = 1.03

3999 reflections

262 parameters

10 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810020921/wm2351sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020921/wm2351Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C7H7N2S)2[Co(C8H8O5)2]·6H2O	Z = 1
Mr = 837.73	F(000) = 437
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0599P)2] where P = (Fo2 + 2Fc2)/3
3999 reflections	(Δ/σ)max < 0.001
262 parameters	Δρmax = 0.47 e Å−3
10 restraints	Δρmin = −0.44 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···O3Wiv	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)

Table 1

Selected bond lengths (Å)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.84 (2)	1.85 (2)	2.675 (3)	169 (3)
N2—H2C⋯O2i	0.86	2.00	2.851 (3)	173
N2—H2D⋯O2Wii	0.86	2.01	2.828 (4)	160
O1W—H1WA⋯O3Wii	0.82 (2)	2.21 (2)	3.030 (4)	176 (4)
O1W—H1WB⋯O3Wiii	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: (i) ; (ii) ; (iii) .