Bis(2-amino-1,3-benzothia-zol-3-ium) bis-(7-oxabicyclo-[2.2.1]heptane-2,3-dicarboxyl-ato)cadmate hexa-hydrate.

In the structure of the title complex, (C(7)H(7)N(2)S)(2)[Cd(C(8)H(8)O(5))(2)]·6H(2)O, the Cd(II) atom is located on an inversion center and is O,O',O''-chelated by two symmetry-related 7-oxabicyclo-[2.2.1]heptane-2,3-dicarboxyl-ate ligands in a distorted octa-hedral geometry. The 2-amino-benzothia-zolium cation links with the Cd complex anion via N-H⋯O hydrogen bonding. Extensive O-H⋯O and N-H⋯O hydrogen bonds involving lattice water mol-ecules occur in the crystal structure.

Related literature

For background to the applications of 7-oxabicyclo­[2,2,1]heptane-2,3-dicarb­oxy­lic anhydride (norcantharidin), see: Yin et al. (2005 ▶). For a manganese(II) analogue, see: Wang et al. (2010a ▶), for a cobalt(II) analogue, see: Wang et al. (2010b ▶), for a nickel(II) analogue, see: Wang et al. (2012 ▶) and for a zinc(II) analogue, see: Zhang et al. (2012 ▶).

Experimental

Crystal data

(C7H7N2S)2[Cd(C8H8O5)2]·6H2O

M = 891.23

Triclinic,

a = 6.6990 (8) Å

b = 10.3103 (10) Å

c = 13.0979 (13) Å

α = 89.039 (7)°

β = 89.004 (7)°

γ = 82.062 (7)°

V = 895.76 (16) Å3

Z = 1

Mo Kα radiation

μ = 0.81 mm−1

T = 296 K

0.12 × 0.08 × 0.06 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.927, T max = 0.957

12401 measured reflections

3138 independent reflections

2782 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.070

S = 1.07

3138 reflections

250 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.33 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 datablock(s) I, global. DOI: 10.1107/S1600536812022593/vn2038sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812022593/vn2038Isup2.hkl

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

(C7H7N2S)2[Cd(C8H8O5)2]·6H2O	Z = 1
Mr = 891.23	F(000) = 458
Triclinic, P1	Dx = 1.652 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6990 (8) Å	Cell parameters from 3684 reflections
b = 10.3103 (10) Å	θ = 1.6–25.0°
c = 13.0979 (13) Å	µ = 0.81 mm−1
α = 89.039 (7)°	T = 296 K
β = 89.004 (7)°	Block, colourless
γ = 82.062 (7)°	0.12 × 0.08 × 0.06 mm
V = 895.76 (16) Å3

Bruker APEXII area-detector diffractometer	3138 independent reflections
Radiation source: fine-focus sealed tube	2782 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.927, Tmax = 0.957	k = −12→12
12401 measured reflections	l = −15→15

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.070	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0329P)2 + 0.3371P] where P = (Fo2 + 2Fc2)/3
3138 reflections	(Δ/σ)max = 0.001
250 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cd1	0.5000	0.0000	0.0000	0.02740 (11)
S1	0.67420 (11)	0.26053 (7)	0.52095 (5)	0.03489 (19)
N1	0.7260 (3)	0.0299 (2)	0.59906 (16)	0.0269 (5)
H1A	0.7363	−0.0334	0.6431	0.032*
N2	0.6614 (4)	0.1938 (2)	0.71990 (17)	0.0357 (6)
H2A	0.6700	0.1374	0.7693	0.043*
H2B	0.6361	0.2761	0.7325	0.043*
O1	0.6235 (3)	0.16660 (17)	0.06762 (15)	0.0342 (5)
O1W	0.4780 (4)	0.5348 (2)	0.28331 (18)	0.0480 (6)
H1WA	0.5186	0.4890	0.2317	0.072*
H1WB	0.3871	0.4986	0.3141	0.072*
O2	0.6139 (3)	0.35871 (19)	0.14105 (15)	0.0394 (5)
O2W	0.1911 (4)	0.4499 (3)	0.59727 (19)	0.0624 (7)
H2WA	0.3036	0.4588	0.6234	0.094*
H2WB	0.2054	0.4335	0.5340	0.094*
O3	0.2779 (3)	0.01702 (17)	0.13613 (13)	0.0333 (5)
O3W	0.1839 (4)	0.3984 (2)	0.37312 (18)	0.0552 (6)
H3WA	0.0724	0.4490	0.3713	0.083*
H3WB	0.1880	0.3405	0.3274	0.083*
O4	0.2247 (3)	0.16445 (18)	0.25914 (14)	0.0342 (5)
O5	0.2679 (3)	0.16742 (17)	−0.07122 (13)	0.0297 (4)
C6	0.1262 (4)	0.3800 (3)	−0.1106 (2)	0.0329 (6)
H6A	0.1338	0.3824	−0.1846	0.039*
H6B	0.1048	0.4688	−0.0854	0.039*
C5	−0.0403 (4)	0.3011 (3)	−0.0718 (2)	0.0348 (7)
H5A	−0.1379	0.3537	−0.0286	0.042*
H5B	−0.1095	0.2677	−0.1280	0.042*
C1	0.3151 (4)	0.3013 (2)	−0.06518 (19)	0.0268 (6)
H1B	0.4400	0.3149	−0.1013	0.032*
C4	0.0804 (4)	0.1902 (3)	−0.0110 (2)	0.0290 (6)
H4A	0.0123	0.1123	−0.0029	0.035*
C2	0.3217 (4)	0.3217 (2)	0.05110 (19)	0.0236 (6)
H2C	0.2807	0.4145	0.0659	0.028*
C3	0.1510 (4)	0.2401 (2)	0.08993 (19)	0.0240 (6)
H3A	0.0406	0.2998	0.1206	0.029*
C7	0.5339 (4)	0.2791 (3)	0.0913 (2)	0.0264 (6)
C8	0.2237 (4)	0.1329 (3)	0.1673 (2)	0.0266 (6)
C9	0.7242 (4)	0.1270 (3)	0.4387 (2)	0.0300 (6)
C10	0.7405 (4)	0.1277 (3)	0.3330 (2)	0.0395 (7)
H10A	0.7240	0.2058	0.2956	0.047*
C11	0.7818 (5)	0.0087 (3)	0.2852 (2)	0.0451 (8)
H11A	0.7938	0.0065	0.2144	0.054*
C12	0.8059 (4)	−0.1076 (3)	0.3408 (2)	0.0408 (7)
H12A	0.8337	−0.1865	0.3065	0.049*
C13	0.7897 (4)	−0.1093 (3)	0.4460 (2)	0.0327 (6)
H13A	0.8053	−0.1876	0.4831	0.039*
C14	0.7494 (4)	0.0096 (3)	0.49408 (19)	0.0257 (6)
C15	0.6867 (4)	0.1544 (3)	0.6253 (2)	0.0269 (6)

	U11	U22	U33	U12	U13	U23
Cd1	0.03353 (18)	0.01935 (16)	0.02779 (17)	0.00173 (11)	0.00364 (12)	−0.00422 (11)
S1	0.0462 (5)	0.0268 (4)	0.0307 (4)	−0.0022 (3)	−0.0007 (3)	0.0056 (3)
N1	0.0304 (13)	0.0259 (12)	0.0248 (12)	−0.0054 (9)	−0.0008 (9)	0.0044 (9)
N2	0.0538 (16)	0.0271 (13)	0.0257 (12)	−0.0046 (11)	0.0014 (11)	−0.0006 (10)
O1	0.0308 (11)	0.0251 (10)	0.0456 (12)	0.0010 (8)	−0.0048 (9)	−0.0076 (9)
O1W	0.0570 (16)	0.0340 (12)	0.0522 (14)	−0.0043 (10)	0.0143 (11)	−0.0108 (10)
O2	0.0370 (12)	0.0364 (12)	0.0467 (12)	−0.0089 (9)	−0.0047 (9)	−0.0161 (10)
O2W	0.0599 (16)	0.0736 (18)	0.0512 (15)	0.0011 (14)	−0.0085 (12)	−0.0075 (14)
O3	0.0461 (12)	0.0223 (10)	0.0289 (10)	0.0031 (8)	0.0099 (9)	0.0026 (8)
O3W	0.0620 (16)	0.0484 (15)	0.0533 (15)	−0.0003 (12)	0.0115 (12)	−0.0161 (12)
O4	0.0501 (13)	0.0284 (10)	0.0235 (10)	−0.0034 (9)	0.0028 (9)	0.0002 (8)
O5	0.0389 (11)	0.0233 (10)	0.0255 (10)	0.0012 (8)	−0.0019 (8)	−0.0045 (8)
C6	0.0436 (18)	0.0274 (15)	0.0262 (14)	0.0003 (12)	−0.0045 (12)	0.0035 (12)
C5	0.0343 (17)	0.0332 (16)	0.0357 (16)	0.0002 (12)	−0.0086 (13)	−0.0007 (13)
C1	0.0333 (15)	0.0227 (14)	0.0240 (14)	−0.0036 (11)	0.0058 (11)	0.0021 (11)
C4	0.0282 (15)	0.0226 (14)	0.0364 (16)	−0.0041 (11)	−0.0021 (12)	−0.0001 (12)
C2	0.0302 (15)	0.0151 (13)	0.0250 (13)	−0.0004 (10)	0.0003 (11)	−0.0035 (10)
C3	0.0250 (14)	0.0203 (13)	0.0254 (13)	0.0009 (10)	0.0052 (11)	−0.0013 (11)
C7	0.0310 (15)	0.0238 (15)	0.0251 (14)	−0.0066 (12)	0.0041 (11)	−0.0012 (11)
C8	0.0243 (14)	0.0258 (15)	0.0295 (15)	−0.0040 (11)	0.0086 (11)	0.0030 (12)
C9	0.0268 (15)	0.0329 (16)	0.0302 (15)	−0.0037 (12)	−0.0033 (11)	0.0037 (12)
C10	0.0404 (18)	0.052 (2)	0.0262 (15)	−0.0056 (14)	−0.0030 (13)	0.0081 (14)
C11	0.0399 (19)	0.072 (2)	0.0240 (15)	−0.0108 (16)	0.0002 (13)	−0.0062 (16)
C12	0.0357 (17)	0.0481 (19)	0.0387 (18)	−0.0045 (14)	0.0006 (13)	−0.0152 (15)
C13	0.0289 (16)	0.0330 (16)	0.0367 (16)	−0.0048 (12)	−0.0021 (12)	−0.0043 (13)
C14	0.0188 (14)	0.0331 (15)	0.0253 (14)	−0.0034 (11)	−0.0022 (10)	−0.0004 (12)
C15	0.0273 (15)	0.0267 (15)	0.0270 (14)	−0.0046 (11)	−0.0025 (11)	0.0020 (12)

Cd1—O1i	2.2108 (18)	C6—C1	1.530 (4)
Cd1—O1	2.2108 (18)	C6—C5	1.543 (4)
Cd1—O3	2.2954 (18)	C6—H6A	0.9700
Cd1—O3i	2.2954 (18)	C6—H6B	0.9700
Cd1—O5i	2.3499 (17)	C5—C4	1.527 (4)
Cd1—O5	2.3499 (17)	C5—H5A	0.9700
S1—C15	1.733 (3)	C5—H5B	0.9700
S1—C9	1.754 (3)	C1—C2	1.543 (3)
N1—C15	1.324 (3)	C1—H1B	0.9800
N1—C14	1.397 (3)	C4—C3	1.532 (4)
N1—H1A	0.8600	C4—H4A	0.9800
N2—C15	1.311 (3)	C2—C7	1.528 (4)
N2—H2A	0.8600	C2—C3	1.583 (3)
N2—H2B	0.8600	C2—H2C	0.9800
O1—C7	1.271 (3)	C3—C8	1.522 (3)
O1W—H1WA	0.8501	C3—H3A	0.9800
O1W—H1WB	0.8500	C9—C10	1.388 (4)
O2—C7	1.240 (3)	C9—C14	1.391 (4)
O2W—H2WA	0.8499	C10—C11	1.378 (4)
O2W—H2WB	0.8500	C10—H10A	0.9300
O3—C8	1.271 (3)	C11—C12	1.384 (4)
O3W—H3WA	0.8500	C11—H11A	0.9300
O3W—H3WB	0.8500	C12—C13	1.381 (4)
O4—C8	1.252 (3)	C12—H12A	0.9300
O5—C1	1.461 (3)	C13—C14	1.378 (4)
O5—C4	1.464 (3)	C13—H13A	0.9300
O1i—Cd1—O1	180.00 (10)	C2—C1—H1B	113.6
O1i—Cd1—O3	94.23 (7)	O5—C4—C5	101.6 (2)
O1—Cd1—O3	85.77 (7)	O5—C4—C3	102.5 (2)
O1i—Cd1—O3i	85.77 (7)	C5—C4—C3	110.9 (2)
O1—Cd1—O3i	94.23 (7)	O5—C4—H4A	113.6
O3—Cd1—O3i	180.00 (6)	C5—C4—H4A	113.6
O1i—Cd1—O5i	82.90 (6)	C3—C4—H4A	113.6
O1—Cd1—O5i	97.10 (6)	C7—C2—C1	110.9 (2)
O3—Cd1—O5i	96.23 (6)	C7—C2—C3	116.9 (2)
O3i—Cd1—O5i	83.77 (6)	C1—C2—C3	100.8 (2)
O1i—Cd1—O5	97.10 (6)	C7—C2—H2C	109.3
O1—Cd1—O5	82.90 (6)	C1—C2—H2C	109.3
O3—Cd1—O5	83.77 (6)	C3—C2—H2C	109.3
O3i—Cd1—O5	96.23 (6)	C8—C3—C4	114.5 (2)
O5i—Cd1—O5	180.00 (8)	C8—C3—C2	113.7 (2)
C15—S1—C9	90.15 (13)	C4—C3—C2	101.3 (2)
C15—N1—C14	114.6 (2)	C8—C3—H3A	109.0
C15—N1—H1A	122.7	C4—C3—H3A	109.0
C14—N1—H1A	122.7	C2—C3—H3A	109.0
C15—N2—H2A	120.0	O2—C7—O1	123.2 (3)
C15—N2—H2B	120.0	O2—C7—C2	118.2 (2)
H2A—N2—H2B	120.0	O1—C7—C2	118.5 (2)
C7—O1—Cd1	129.36 (17)	O4—C8—O3	123.6 (2)
H1WA—O1W—H1WB	108.2	O4—C8—C3	117.4 (2)
H2WA—O2W—H2WB	110.7	O3—C8—C3	119.0 (2)
C8—O3—Cd1	115.11 (15)	C10—C9—C14	120.7 (3)
H3WA—O3W—H3WB	110.4	C10—C9—S1	128.6 (2)
C1—O5—C4	95.87 (18)	C14—C9—S1	110.64 (19)
C1—O5—Cd1	117.20 (15)	C11—C10—C9	117.7 (3)
C4—O5—Cd1	112.02 (14)	C11—C10—H10A	121.1
C1—C6—C5	101.8 (2)	C9—C10—H10A	121.1
C1—C6—H6A	111.4	C10—C11—C12	121.2 (3)
C5—C6—H6A	111.4	C10—C11—H11A	119.4
C1—C6—H6B	111.4	C12—C11—H11A	119.4
C5—C6—H6B	111.4	C13—C12—C11	121.5 (3)
H6A—C6—H6B	109.3	C13—C12—H12A	119.3
C4—C5—C6	102.0 (2)	C11—C12—H12A	119.3
C4—C5—H5A	111.4	C14—C13—C12	117.5 (3)
C6—C5—H5A	111.4	C14—C13—H13A	121.2
C4—C5—H5B	111.4	C12—C13—H13A	121.2
C6—C5—H5B	111.4	C13—C14—C9	121.4 (2)
H5A—C5—H5B	109.2	C13—C14—N1	126.8 (2)
O5—C1—C6	101.6 (2)	C9—C14—N1	111.9 (2)
O5—C1—C2	102.46 (18)	N2—C15—N1	124.0 (2)
C6—C1—C2	110.8 (2)	N2—C15—S1	123.3 (2)
O5—C1—H1B	113.6	N1—C15—S1	112.69 (19)
C6—C1—H1B	113.6
O3—Cd1—O1—C7	−55.7 (2)	C5—C4—C3—C2	−72.4 (2)
O3i—Cd1—O1—C7	124.3 (2)	C7—C2—C3—C8	2.8 (3)
O5i—Cd1—O1—C7	−151.4 (2)	C1—C2—C3—C8	123.0 (2)
O5—Cd1—O1—C7	28.6 (2)	C7—C2—C3—C4	−120.5 (2)
O1i—Cd1—O3—C8	−146.03 (18)	C1—C2—C3—C4	−0.3 (2)
O1—Cd1—O3—C8	33.97 (18)	Cd1—O1—C7—O2	170.25 (19)
O5i—Cd1—O3—C8	130.68 (18)	Cd1—O1—C7—C2	−13.6 (3)
O5—Cd1—O3—C8	−49.32 (18)	C1—C2—C7—O2	126.0 (2)
O1i—Cd1—O5—C1	−167.19 (16)	C3—C2—C7—O2	−119.3 (3)
O1—Cd1—O5—C1	12.81 (16)	C1—C2—C7—O1	−50.4 (3)
O3—Cd1—O5—C1	99.31 (16)	C3—C2—C7—O1	64.3 (3)
O3i—Cd1—O5—C1	−80.69 (16)	Cd1—O3—C8—O4	−131.4 (2)
O1i—Cd1—O5—C4	83.43 (16)	Cd1—O3—C8—C3	49.3 (3)
O1—Cd1—O5—C4	−96.57 (16)	C4—C3—C8—O4	−158.7 (2)
O3—Cd1—O5—C4	−10.07 (15)	C2—C3—C8—O4	85.5 (3)
O3i—Cd1—O5—C4	169.93 (15)	C4—C3—C8—O3	20.6 (3)
C1—C6—C5—C4	−0.2 (3)	C2—C3—C8—O3	−95.1 (3)
C4—O5—C1—C6	−57.3 (2)	C15—S1—C9—C10	179.8 (3)
Cd1—O5—C1—C6	−175.78 (14)	C15—S1—C9—C14	−0.5 (2)
C4—O5—C1—C2	57.3 (2)	C14—C9—C10—C11	0.1 (4)
Cd1—O5—C1—C2	−61.1 (2)	S1—C9—C10—C11	179.8 (2)
C5—C6—C1—O5	35.4 (2)	C9—C10—C11—C12	0.2 (5)
C5—C6—C1—C2	−72.9 (3)	C10—C11—C12—C13	0.0 (5)
C1—O5—C4—C5	57.2 (2)	C11—C12—C13—C14	−0.3 (4)
Cd1—O5—C4—C5	179.65 (15)	C12—C13—C14—C9	0.6 (4)
C1—O5—C4—C3	−57.6 (2)	C12—C13—C14—N1	179.6 (2)
Cd1—O5—C4—C3	64.89 (19)	C10—C9—C14—C13	−0.5 (4)
C6—C5—C4—O5	−34.9 (3)	S1—C9—C14—C13	179.8 (2)
C6—C5—C4—C3	73.4 (3)	C10—C9—C14—N1	−179.6 (2)
O5—C1—C2—C7	89.5 (2)	S1—C9—C14—N1	0.7 (3)
C6—C1—C2—C7	−162.8 (2)	C15—N1—C14—C13	−179.6 (3)
O5—C1—C2—C3	−34.9 (2)	C15—N1—C14—C9	−0.5 (3)
C6—C1—C2—C3	72.8 (2)	C14—N1—C15—N2	−179.4 (2)
O5—C4—C3—C8	−87.4 (2)	C14—N1—C15—S1	0.1 (3)
C5—C4—C3—C8	164.8 (2)	C9—S1—C15—N2	179.7 (2)
O5—C4—C3—C2	35.3 (2)	C9—S1—C15—N1	0.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O2	0.85	1.85	2.682 (3)	167
O2W—H2WB···O3W	0.85	2.15	2.995 (3)	170
O1W—H1WB···O3W	0.85	1.96	2.806 (3)	173
O3W—H3WB···O4	0.85	2.02	2.837 (3)	161
N1—H1A···O4ii	0.86	1.84	2.700 (3)	176
N2—H2A···O3ii	0.86	2.00	2.845 (3)	169
N2—H2B···O1Wiii	0.86	2.00	2.824 (3)	160
O2W—H2WA···O1Wiii	0.85	1.93	2.758 (4)	164
O3W—H3WA···O2Wiv	0.85	1.96	2.794 (3)	166

Table 1

Selected bond lengths (Å)

Cd1—O1	2.2108 (18)
Cd1—O3	2.2954 (18)
Cd1—O5	2.3499 (17)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O2	0.85	1.85	2.682 (3)	167
O2W—H2WB⋯O3W	0.85	2.15	2.995 (3)	170
O1W—H1WB⋯O3W	0.85	1.96	2.806 (3)	173
O3W—H3WB⋯O4	0.85	2.02	2.837 (3)	161
N1—H1A⋯O4i	0.86	1.84	2.700 (3)	176
N2—H2A⋯O3i	0.86	2.00	2.845 (3)	169
N2—H2B⋯O1Wii	0.86	2.00	2.824 (3)	160
O2W—H2WA⋯O1Wii	0.85	1.93	2.758 (4)	164
O3W—H3WA⋯O2Wiii	0.85	1.96	2.794 (3)	166

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