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

In the title hydrated mol-ecular salt, (C(7)H(7)N(2)S)(2)[Zn(C(8)H(8)O(5))(2)]·6H(2)O, which is isotypic with its Mn(II), Co(II) and Ni(II) analogues, the Zn(2+) ion lies on a crystallographic inversion centre and a distorted ZnO(6) octa-hedral coordination geometry arises from the two doubly deprotonated O,O',O''-tridentate ligands. In the crystal, the components are linked by N-H⋯O(a), N-H⋯O(w), O(w)-H⋯O(a) and O(w)-H⋯O(w) hydrogen bonds (w = water and a = anion).

Related literature

For background to the applications of norcantharidin (systematic name: 7-oxabicyclo­[2,2,1]heptane-2,3-dicarb­oxy­lic anhydride), see: Zeng & Lu (2006 ▶). For the isotypic MnII, CoII and NiII structures, see: Wang et al. (2010a ▶,b ▶, 2012 ▶).

Experimental

Crystal data

(C7H7N2S)2[Zn(C8H8O5)2]·6H2O

M = 844.21

Triclinic,

a = 6.6983 (7) Å

b = 10.1497 (11) Å

c = 13.2082 (14) Å

α = 90.172 (7)°

β = 91.097 (7)°

γ = 99.251 (7)°

V = 886.11 (16) Å3

Z = 1

Mo Kα radiation

μ = 0.89 mm−1

T = 296 K

0.12 × 0.08 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.914, T max = 0.951

11657 measured reflections

3108 independent reflections

1839 reflections with I > 2σ(I)

R int = 0.228

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.087

S = 0.91

3108 reflections

241 parameters

9 restraints

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.74 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/S1600536812017886/hb6746sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017886/hb6746Isup2.hkl

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

(C7H7N2S)2[Zn(C8H8O5)2]·6H2O	Z = 1
Mr = 844.21	F(000) = 440
Triclinic, P1	Dx = 1.582 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6983 (7) Å	Cell parameters from 2505 reflections
b = 10.1497 (11) Å	θ = 1.5–25.0°
c = 13.2082 (14) Å	µ = 0.89 mm−1
α = 90.172 (7)°	T = 296 K
β = 91.097 (7)°	Block, colorless
γ = 99.251 (7)°	0.12 × 0.08 × 0.06 mm
V = 886.11 (16) Å3

Bruker APEXII CCD diffractometer	3108 independent reflections
Radiation source: fine-focus sealed tube	1839 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.228
ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.914, Tmax = 0.951	k = −12→12
11657 measured reflections	l = −15→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 0.91	w = 1/[σ2(Fo2) + (0.0123P)2] where P = (Fo2 + 2Fc2)/3
3108 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 0.48 e Å−3
9 restraints	Δρmin = −0.74 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
Zn1	0.5000	0.0000	0.0000	0.0324 (2)
S1	0.32760 (16)	0.26730 (12)	0.52749 (7)	0.0407 (3)
O1	0.3674 (4)	0.1456 (3)	0.06056 (17)	0.0375 (8)
O1W	0.8090 (4)	0.3956 (3)	0.37387 (17)	0.0545 (9)
H1WA	0.8277	0.3325	0.3345	0.082*
H1WB	0.7307	0.4430	0.3454	0.082*
H2WA	0.4603	0.4745	0.2298	0.082*
H2WB	0.4268	0.5366	0.3202	0.082*
H3WA	0.1928	0.5407	0.4659	0.082*
H3WB	0.0922	0.4941	0.3767	0.082*
O2	0.3636 (4)	0.3401 (3)	0.13832 (18)	0.0398 (8)
O2W	0.5164 (4)	0.5222 (3)	0.27869 (18)	0.0509 (9)
O3	0.6904 (4)	0.0121 (3)	0.13199 (17)	0.0372 (8)
O3W	0.1943 (4)	0.5453 (3)	0.40167 (19)	0.0681 (11)
O4	0.7729 (4)	0.1592 (3)	0.25795 (16)	0.0391 (8)
O5	0.7162 (3)	0.1550 (3)	−0.06915 (16)	0.0318 (8)
N1	0.2772 (4)	0.0314 (3)	0.6011 (2)	0.0314 (9)
H1A	0.2680	−0.0334	0.6434	0.038*
N2	0.3461 (4)	0.1984 (3)	0.7235 (2)	0.0407 (10)
H2A	0.3394	0.1405	0.7712	0.049*
H2B	0.3717	0.2822	0.7379	0.049*
C6	0.8584 (6)	0.3726 (4)	−0.1096 (2)	0.0353 (11)
H6A	0.8806	0.4636	−0.0841	0.042*
H6B	0.8494	0.3736	−0.1829	0.042*
C5	1.0257 (5)	0.2946 (4)	−0.0715 (3)	0.0360 (11)
H5A	1.0917	0.2585	−0.1276	0.043*
H5B	1.1265	0.3507	−0.0300	0.043*
C1	0.6712 (5)	0.2907 (4)	−0.0644 (2)	0.0318 (11)
H1B	0.5458	0.3011	−0.1008	0.038*
C4	0.9066 (5)	0.1842 (4)	−0.0096 (3)	0.0313 (11)
H4A	0.9750	0.1065	−0.0007	0.038*
C2	0.6616 (5)	0.3148 (4)	0.0498 (2)	0.0284 (10)
H2C	0.6979	0.4103	0.0652	0.034*
C3	0.8342 (5)	0.2369 (4)	0.0902 (2)	0.0281 (11)
H3A	0.9440	0.3005	0.1213	0.034*
C7	0.4500 (6)	0.2624 (4)	0.0880 (3)	0.0326 (11)
C8	0.7611 (5)	0.1281 (4)	0.1656 (3)	0.0299 (10)
C9	0.2753 (5)	0.1307 (4)	0.4436 (3)	0.0335 (11)
C10	0.2575 (5)	0.1337 (4)	0.3394 (3)	0.0407 (12)
H10A	0.2714	0.2138	0.3043	0.049*
C11	0.2178 (6)	0.0109 (5)	0.2894 (3)	0.0468 (14)
H11A	0.2094	0.0088	0.2190	0.056*
C12	0.1909 (6)	−0.1066 (5)	0.3418 (3)	0.0467 (14)
H12A	0.1586	−0.1865	0.3061	0.056*
C13	0.2104 (5)	−0.1101 (4)	0.4473 (3)	0.0386 (12)
H13A	0.1969	−0.1901	0.4826	0.046*
C14	0.2511 (5)	0.0122 (4)	0.4961 (3)	0.0293 (11)
C15	0.3173 (5)	0.1590 (4)	0.6289 (3)	0.0304 (11)

	U11	U22	U33	U12	U13	U23
Zn1	0.0350 (4)	0.0305 (5)	0.0304 (4)	0.0014 (4)	−0.0001 (3)	−0.0092 (3)
S1	0.0497 (7)	0.0374 (9)	0.0338 (6)	0.0033 (6)	0.0004 (5)	−0.0002 (6)
O1	0.0345 (16)	0.038 (2)	0.0393 (16)	0.0037 (15)	0.0032 (12)	−0.0124 (15)
O1W	0.066 (2)	0.045 (2)	0.0543 (19)	0.0145 (18)	−0.0097 (15)	−0.0099 (17)
O2	0.0357 (16)	0.038 (2)	0.0468 (17)	0.0079 (15)	0.0043 (13)	−0.0186 (15)
O2W	0.056 (2)	0.041 (2)	0.0537 (18)	0.0038 (17)	−0.0062 (14)	−0.0156 (17)
O3	0.0510 (19)	0.027 (2)	0.0307 (15)	−0.0005 (16)	−0.0063 (13)	−0.0028 (14)
O3W	0.063 (2)	0.083 (3)	0.053 (2)	−0.002 (2)	0.0003 (16)	−0.014 (2)
O4	0.0530 (19)	0.037 (2)	0.0254 (15)	0.0015 (16)	−0.0020 (13)	−0.0036 (14)
O5	0.0363 (16)	0.032 (2)	0.0266 (14)	0.0046 (15)	0.0020 (12)	−0.0110 (14)
N1	0.0330 (19)	0.033 (3)	0.0284 (18)	0.0064 (18)	0.0029 (14)	0.0008 (17)
N2	0.055 (2)	0.036 (3)	0.0313 (19)	0.007 (2)	0.0034 (16)	−0.0062 (18)
C6	0.051 (3)	0.026 (3)	0.028 (2)	0.004 (2)	0.0034 (19)	−0.003 (2)
C5	0.039 (3)	0.035 (3)	0.032 (2)	0.000 (2)	0.0097 (18)	−0.002 (2)
C1	0.034 (2)	0.031 (3)	0.031 (2)	0.005 (2)	−0.0005 (18)	−0.003 (2)
C4	0.027 (2)	0.030 (3)	0.037 (2)	0.008 (2)	−0.0026 (18)	−0.005 (2)
C2	0.036 (2)	0.021 (3)	0.028 (2)	0.005 (2)	0.0018 (17)	−0.0092 (19)
C3	0.025 (2)	0.028 (3)	0.029 (2)	0.001 (2)	−0.0013 (17)	−0.011 (2)
C7	0.031 (2)	0.043 (3)	0.024 (2)	0.010 (2)	−0.0052 (17)	−0.007 (2)
C8	0.025 (2)	0.031 (3)	0.034 (2)	0.007 (2)	−0.0009 (18)	0.008 (2)
C9	0.024 (2)	0.043 (3)	0.032 (2)	0.001 (2)	0.0043 (18)	−0.004 (2)
C10	0.039 (3)	0.049 (4)	0.034 (2)	0.007 (2)	0.0040 (19)	0.007 (2)
C11	0.042 (3)	0.070 (4)	0.026 (2)	0.002 (3)	0.004 (2)	−0.008 (3)
C12	0.033 (3)	0.061 (4)	0.046 (3)	0.006 (3)	0.000 (2)	−0.024 (3)
C13	0.029 (2)	0.048 (3)	0.039 (2)	0.008 (2)	0.0051 (18)	−0.012 (2)
C14	0.023 (2)	0.042 (3)	0.023 (2)	0.005 (2)	0.0062 (16)	−0.002 (2)
C15	0.028 (2)	0.030 (3)	0.033 (2)	0.003 (2)	0.0066 (18)	−0.006 (2)

Zn1—O1	2.014 (2)	C6—C1	1.521 (5)
Zn1—O1i	2.014 (2)	C6—C5	1.550 (5)
Zn1—O3i	2.132 (2)	C6—H6A	0.9700
Zn1—O3	2.132 (2)	C6—H6B	0.9700
Zn1—O5i	2.176 (3)	C5—C4	1.518 (5)
Zn1—O5	2.176 (3)	C5—H5A	0.9700
S1—C15	1.731 (4)	C5—H5B	0.9700
S1—C9	1.759 (4)	C1—C2	1.532 (4)
O1—C7	1.274 (4)	C1—H1B	0.9800
O1W—H1WA	0.8499	C4—C3	1.536 (4)
O1W—H1WB	0.8500	C4—H4A	0.9800
O2—C7	1.248 (3)	C2—C7	1.527 (5)
O2W—H2WA	0.8499	C2—C3	1.587 (5)
O2W—H2WB	0.8501	C2—H2C	0.9800
O3—C8	1.272 (4)	C3—C8	1.517 (5)
O3W—H3WA	0.8504	C3—H3A	0.9800
O3W—H3WB	0.8502	C9—C14	1.379 (5)
O4—C8	1.257 (3)	C9—C10	1.379 (4)
O5—C1	1.458 (4)	C10—C11	1.393 (5)
O5—C4	1.473 (4)	C10—H10A	0.9300
N1—C15	1.329 (4)	C11—C12	1.370 (5)
N1—C14	1.403 (4)	C11—H11A	0.9300
N1—H1A	0.8600	C12—C13	1.398 (5)
N2—C15	1.312 (4)	C12—H12A	0.9300
N2—H2A	0.8600	C13—C14	1.382 (5)
N2—H2B	0.8600	C13—H13A	0.9300
O1—Zn1—O1i	180.0	C2—C1—H1B	113.1
O1—Zn1—O3i	92.14 (9)	O5—C4—C5	101.4 (3)
O1i—Zn1—O3i	87.86 (9)	O5—C4—C3	101.8 (3)
O1—Zn1—O3	87.86 (9)	C5—C4—C3	112.1 (3)
O1i—Zn1—O3	92.14 (9)	O5—C4—H4A	113.4
O3i—Zn1—O3	180.0	C5—C4—H4A	113.4
O1—Zn1—O5i	91.98 (9)	C3—C4—H4A	113.4
O1i—Zn1—O5i	88.02 (9)	C7—C2—C1	110.4 (3)
O3i—Zn1—O5i	89.22 (10)	C7—C2—C3	115.0 (3)
O3—Zn1—O5i	90.78 (10)	C1—C2—C3	100.7 (2)
O1—Zn1—O5	88.02 (9)	C7—C2—H2C	110.1
O1i—Zn1—O5	91.98 (9)	C1—C2—H2C	110.1
O3i—Zn1—O5	90.78 (10)	C3—C2—H2C	110.1
O3—Zn1—O5	89.22 (10)	C8—C3—C4	113.7 (3)
O5i—Zn1—O5	180.0	C8—C3—C2	113.7 (3)
C15—S1—C9	90.10 (19)	C4—C3—C2	101.0 (3)
C7—O1—Zn1	128.1 (2)	C8—C3—H3A	109.4
H1WA—O1W—H1WB	110.0	C4—C3—H3A	109.4
H2WA—O2W—H2WB	109.4	C2—C3—H3A	109.4
C8—O3—Zn1	117.2 (3)	O2—C7—O1	124.0 (4)
H3WA—O3W—H3WB	109.6	O2—C7—C2	117.8 (4)
C1—O5—C4	95.2 (3)	O1—C7—C2	118.0 (3)
C1—O5—Zn1	116.69 (19)	O4—C8—O3	124.0 (4)
C4—O5—Zn1	112.0 (2)	O4—C8—C3	117.5 (3)
C15—N1—C14	113.7 (3)	O3—C8—C3	118.5 (3)
C15—N1—H1A	123.1	C14—C9—C10	121.7 (4)
C14—N1—H1A	123.1	C14—C9—S1	110.6 (3)
C15—N2—H2A	120.0	C10—C9—S1	127.7 (4)
C15—N2—H2B	120.0	C9—C10—C11	116.9 (4)
H2A—N2—H2B	120.0	C9—C10—H10A	121.6
C1—C6—C5	101.2 (3)	C11—C10—H10A	121.6
C1—C6—H6A	111.5	C12—C11—C10	121.3 (4)
C5—C6—H6A	111.5	C12—C11—H11A	119.4
C1—C6—H6B	111.5	C10—C11—H11A	119.4
C5—C6—H6B	111.5	C11—C12—C13	122.0 (4)
H6A—C6—H6B	109.4	C11—C12—H12A	119.0
C4—C5—C6	102.2 (3)	C13—C12—H12A	119.0
C4—C5—H5A	111.3	C14—C13—C12	116.1 (4)
C6—C5—H5A	111.3	C14—C13—H13A	121.9
C4—C5—H5B	111.3	C12—C13—H13A	121.9
C6—C5—H5B	111.3	C9—C14—C13	121.9 (4)
H5A—C5—H5B	109.2	C9—C14—N1	112.6 (3)
O5—C1—C6	102.7 (3)	C13—C14—N1	125.4 (4)
O5—C1—C2	102.4 (3)	N2—C15—N1	123.4 (4)
C6—C1—C2	111.6 (3)	N2—C15—S1	123.7 (3)
O5—C1—H1B	113.1	N1—C15—S1	113.0 (3)
C6—C1—H1B	113.1
O3i—Zn1—O1—C7	−122.1 (3)	C5—C4—C3—C2	72.1 (4)
O3—Zn1—O1—C7	57.9 (3)	C7—C2—C3—C8	−3.6 (4)
O5i—Zn1—O1—C7	148.6 (3)	C1—C2—C3—C8	−122.3 (3)
O5—Zn1—O1—C7	−31.4 (3)	C7—C2—C3—C4	118.6 (3)
O1—Zn1—O3—C8	−42.4 (3)	C1—C2—C3—C4	−0.1 (3)
O1i—Zn1—O3—C8	137.6 (3)	Zn1—O1—C7—O2	−169.1 (3)
O5i—Zn1—O3—C8	−134.3 (2)	Zn1—O1—C7—C2	16.1 (5)
O5—Zn1—O3—C8	45.7 (2)	C1—C2—C7—O2	−127.5 (4)
O1—Zn1—O5—C1	−10.4 (2)	C3—C2—C7—O2	119.3 (4)
O1i—Zn1—O5—C1	169.6 (2)	C1—C2—C7—O1	47.6 (5)
O3i—Zn1—O5—C1	81.7 (2)	C3—C2—C7—O1	−65.6 (4)
O3—Zn1—O5—C1	−98.3 (2)	Zn1—O3—C8—O4	138.6 (3)
O1—Zn1—O5—C4	97.84 (19)	Zn1—O3—C8—C3	−40.8 (4)
O1i—Zn1—O5—C4	−82.16 (19)	C4—C3—C8—O4	153.4 (3)
O3i—Zn1—O5—C4	−170.05 (19)	C2—C3—C8—O4	−91.7 (4)
O3—Zn1—O5—C4	9.95 (19)	C4—C3—C8—O3	−27.2 (5)
C1—C6—C5—C4	−1.3 (3)	C2—C3—C8—O3	87.7 (4)
C4—O5—C1—C6	57.0 (3)	C15—S1—C9—C14	0.6 (3)
Zn1—O5—C1—C6	174.86 (19)	C15—S1—C9—C10	−179.7 (3)
C4—O5—C1—C2	−58.8 (3)	C14—C9—C10—C11	−1.2 (5)
Zn1—O5—C1—C2	59.0 (3)	S1—C9—C10—C11	179.2 (3)
C5—C6—C1—O5	−34.6 (3)	C9—C10—C11—C12	2.2 (6)
C5—C6—C1—C2	74.5 (3)	C10—C11—C12—C13	−2.9 (6)
C1—O5—C4—C5	−57.3 (3)	C11—C12—C13—C14	2.3 (5)
Zn1—O5—C4—C5	−178.88 (18)	C10—C9—C14—C13	0.9 (6)
C1—O5—C4—C3	58.4 (3)	S1—C9—C14—C13	−179.4 (3)
Zn1—O5—C4—C3	−63.2 (3)	C10—C9—C14—N1	179.5 (3)
C6—C5—C4—O5	36.1 (3)	S1—C9—C14—N1	−0.9 (4)
C6—C5—C4—C3	−71.8 (3)	C12—C13—C14—C9	−1.4 (5)
O5—C1—C2—C7	−85.8 (3)	C12—C13—C14—N1	−179.7 (3)
C6—C1—C2—C7	165.0 (3)	C15—N1—C14—C9	0.8 (4)
O5—C1—C2—C3	36.2 (3)	C15—N1—C14—C13	179.3 (3)
C6—C1—C2—C3	−73.0 (4)	C14—N1—C15—N2	179.8 (3)
O5—C4—C3—C8	86.7 (4)	C14—N1—C15—S1	−0.3 (4)
C5—C4—C3—C8	−165.7 (3)	C9—S1—C15—N2	179.8 (3)
O5—C4—C3—C2	−35.5 (4)	C9—S1—C15—N1	−0.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ii	0.86	1.82	2.675 (4)	173
N2—H2A···O3ii	0.86	2.00	2.853 (4)	172
N2—H2B···O2Wiii	0.86	2.02	2.838 (4)	158
O1W—H1WA···O4	0.85	2.01	2.818 (3)	160
O1W—H1WB···O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA···O2	0.85	1.85	2.683 (3)	167
O2W—H2WB···O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA···O1Wiii	0.85	2.21	3.024 (3)	160
O3W—H3WB···O1Wiv	0.85	2.00	2.793 (4)	156

Table 1

Selected bond lengths (Å)

Zn1—O1	2.014 (2)
Zn1—O3	2.132 (2)
Zn1—O5	2.176 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.86	1.82	2.675 (4)	173
N2—H2A⋯O3i	0.86	2.00	2.853 (4)	172
N2—H2B⋯O2Wii	0.86	2.02	2.838 (4)	158
O1W—H1WA⋯O4	0.85	2.01	2.818 (3)	160
O1W—H1WB⋯O2W	0.85	1.95	2.793 (4)	170
O2W—H2WA⋯O2	0.85	1.85	2.683 (3)	167
O2W—H2WB⋯O3W	0.85	1.92	2.765 (3)	170
O3W—H3WA⋯O1Wii	0.85	2.21	3.024 (3)	160
O3W—H3WB⋯O1Wiii	0.85	2.00	2.793 (4)	156

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