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))nickelate(II) hexa-hydrate.

In the title compound, (C(7)H(7)N(2)S)(2)[Ni(C(8)H(8)O(5))(2)]·6H(2)O, the Ni(II) cation 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 anions in a distorted octa-hedral geometry. The 2-amino-benzothia-zol-3-ium cation links with the Ni complex anion via N-H⋯O hydrogen bonding. Extensive O-H⋯O and N-H⋯O hydrogen bonds involving the lattice water mol-ecules also occur in the crystal structure.

Related literature

For background to the applications of norcantharidin (systematic name: 7-oxabicyclo­[2,2,1]heptane-2,3-dicarb­oxy­lic anhydride), see: Hill et al. (2007 ▶). The isotypic MnII, CoII and NiII analogues were reported by Wang et al. (2010a ▶,b ▶) and Zhang et al. (2012 ▶), respectively.

Experimental

Crystal data

(C7H7N2S)2[Ni(C8H8O5)2]·6H2O

M = 837.51

Triclinic,

a = 6.6907 (1) Å

b = 10.0963 (2) Å

c = 13.2283 (3) Å

α = 90.284 (1)°

β = 91.192 (1)°

γ = 99.709 (1)°

V = 880.57 (3) Å3

Z = 1

Mo Kα radiation

μ = 0.75 mm−1

T = 296 K

0.27 × 0.21 × 0.07 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.828, T max = 0.951

11942 measured reflections

3083 independent reflections

2654 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.089

S = 1.06

3083 reflections

241 parameters

3 restraints

H-atom parameters constrained

Δρmax = 0.38 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 datablock(s) I, global. DOI: 10.1107/S1600536812017722/xu5517sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017722/xu5517Isup2.hkl

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

(C7H7N2S)2[Ni(C8H8O5)2]·6H2O	Z = 1
Mr = 837.51	F(000) = 438
Triclinic, P1	Dx = 1.579 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6907 (1) Å	Cell parameters from 3486 reflections
b = 10.0963 (2) Å	θ = 1.5–25.0°
c = 13.2283 (3) Å	µ = 0.75 mm−1
α = 90.284 (1)°	T = 296 K
β = 91.192 (1)°	Block, green
γ = 99.709 (1)°	0.27 × 0.21 × 0.07 mm
V = 880.57 (3) Å3

Bruker APEXII area-detector diffractometer	3083 independent reflections
Radiation source: fine-focus sealed tube	2654 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.828, Tmax = 0.951	k = −11→11
11942 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0485P)2 + 0.2846P] where P = (Fo2 + 2Fc2)/3
3083 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 0.38 e Å−3
3 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
Ni1	0.5000	0.5000	0.0000	0.02482 (13)
S1	0.32763 (10)	0.76888 (6)	0.52853 (4)	0.03601 (17)
O1	0.3599 (2)	0.64286 (15)	0.06025 (12)	0.0324 (4)
O1W	0.1930 (3)	0.1034 (2)	0.62809 (15)	0.0559 (5)
H1WA	0.2029	0.1747	0.6636	0.084*
H1WB	0.2102	0.1218	0.5659	0.084*
H2WA	0.4613	−0.0379	0.2341	0.084*
H2WB	0.6001	−0.0155	0.3078	0.084*
H3WA	0.0734	−0.0017	0.3946	0.084*
H3WB	0.2721	0.0206	0.3603	0.084*
O2	0.3555 (2)	0.83685 (16)	0.13816 (12)	0.0374 (4)
O2W	0.5108 (3)	0.02150 (17)	0.27766 (14)	0.0495 (5)
O3	0.6790 (2)	0.51244 (15)	0.13147 (11)	0.0330 (4)
O3W	0.1917 (3)	0.0438 (2)	0.40342 (16)	0.0651 (6)
O4	0.7719 (3)	0.65778 (16)	0.25730 (11)	0.0358 (4)
O5	0.7091 (2)	0.65098 (14)	−0.06734 (11)	0.0284 (3)
N1	0.2773 (3)	0.53206 (18)	0.60097 (13)	0.0275 (4)
H1A	0.2670	0.4669	0.6432	0.033*
N2	0.3472 (3)	0.6994 (2)	0.72380 (14)	0.0369 (5)
H2A	0.3401	0.6413	0.7715	0.044*
H2B	0.3734	0.7838	0.7380	0.044*
C6	0.8514 (4)	0.8692 (2)	−0.10948 (17)	0.0347 (5)
H6A	0.8737	0.9613	−0.0848	0.042*
H6B	0.8424	0.8689	−0.1828	0.042*
C5	1.0189 (4)	0.7933 (2)	−0.07100 (18)	0.0356 (5)
H5A	1.0851	0.7565	−0.1266	0.043*
H5B	1.1199	0.8510	−0.0299	0.043*
C1	0.6635 (3)	0.7873 (2)	−0.06430 (16)	0.0277 (5)
H1B	0.5377	0.7965	−0.1009	0.033*
C4	0.8995 (3)	0.6828 (2)	−0.00850 (16)	0.0286 (5)
H4A	0.9683	0.6053	0.0013	0.034*
C2	0.6554 (3)	0.8135 (2)	0.04989 (15)	0.0253 (5)
H2C	0.6916	0.9099	0.0643	0.030*
C3	0.8288 (3)	0.7379 (2)	0.08999 (16)	0.0259 (5)
H3A	0.9391	0.8026	0.1208	0.031*
C7	0.4422 (3)	0.7606 (2)	0.08724 (16)	0.0271 (5)
C8	0.7543 (3)	0.6281 (2)	0.16535 (16)	0.0261 (5)
C9	0.2752 (3)	0.6322 (2)	0.44420 (17)	0.0305 (5)
C10	0.2573 (4)	0.6336 (3)	0.34006 (18)	0.0417 (6)
H10A	0.2723	0.7142	0.3050	0.050*
C11	0.2165 (4)	0.5119 (3)	0.28954 (19)	0.0466 (7)
H11A	0.2056	0.5102	0.2193	0.056*
C12	0.1917 (4)	0.3922 (3)	0.34191 (19)	0.0433 (6)
H12A	0.1622	0.3114	0.3062	0.052*
C13	0.2098 (3)	0.3900 (3)	0.44640 (18)	0.0356 (5)
H13A	0.1941	0.3093	0.4813	0.043*
C14	0.2521 (3)	0.5118 (2)	0.49681 (16)	0.0278 (5)
C15	0.3181 (3)	0.6592 (2)	0.62951 (16)	0.0284 (5)

	U11	U22	U33	U12	U13	U23
Ni1	0.0312 (2)	0.0187 (2)	0.0230 (2)	0.00043 (16)	−0.00167 (16)	−0.00208 (15)
S1	0.0480 (4)	0.0277 (3)	0.0308 (3)	0.0020 (3)	−0.0013 (3)	0.0062 (2)
O1	0.0328 (8)	0.0246 (8)	0.0385 (9)	0.0009 (7)	0.0025 (7)	−0.0048 (7)
O1W	0.0682 (13)	0.0494 (12)	0.0491 (11)	0.0083 (10)	−0.0104 (10)	−0.0136 (9)
O2	0.0374 (9)	0.0340 (9)	0.0420 (9)	0.0097 (7)	0.0030 (8)	−0.0128 (7)
O2W	0.0574 (12)	0.0350 (10)	0.0550 (11)	0.0068 (9)	−0.0154 (9)	−0.0122 (8)
O3	0.0443 (9)	0.0234 (8)	0.0281 (8)	−0.0023 (7)	−0.0070 (7)	0.0032 (6)
O3W	0.0550 (12)	0.0735 (15)	0.0625 (13)	−0.0023 (11)	0.0085 (10)	−0.0073 (11)
O4	0.0520 (10)	0.0285 (9)	0.0250 (8)	0.0017 (7)	−0.0048 (7)	0.0019 (6)
O5	0.0357 (8)	0.0213 (8)	0.0266 (8)	0.0006 (6)	−0.0005 (7)	−0.0037 (6)
N1	0.0330 (10)	0.0266 (10)	0.0230 (9)	0.0049 (8)	−0.0001 (8)	0.0033 (7)
N2	0.0556 (13)	0.0273 (10)	0.0265 (10)	0.0036 (9)	−0.0016 (9)	0.0004 (8)
C6	0.0505 (15)	0.0250 (12)	0.0266 (11)	0.0000 (10)	0.0037 (11)	0.0014 (9)
C5	0.0372 (13)	0.0330 (13)	0.0352 (13)	0.0012 (10)	0.0068 (11)	−0.0012 (10)
C1	0.0339 (12)	0.0226 (11)	0.0264 (11)	0.0051 (9)	−0.0043 (9)	0.0014 (9)
C4	0.0284 (11)	0.0247 (11)	0.0328 (12)	0.0051 (9)	−0.0005 (10)	−0.0011 (9)
C2	0.0317 (12)	0.0176 (10)	0.0256 (11)	0.0021 (9)	−0.0015 (9)	−0.0012 (8)
C3	0.0284 (11)	0.0209 (11)	0.0263 (11)	−0.0014 (9)	−0.0034 (9)	−0.0013 (9)
C7	0.0331 (12)	0.0251 (12)	0.0235 (10)	0.0062 (9)	−0.0029 (9)	−0.0015 (9)
C8	0.0260 (11)	0.0251 (11)	0.0261 (11)	0.0019 (9)	−0.0059 (9)	0.0025 (9)
C9	0.0291 (12)	0.0351 (13)	0.0267 (11)	0.0039 (10)	0.0005 (9)	0.0016 (9)
C10	0.0430 (14)	0.0522 (16)	0.0298 (12)	0.0069 (12)	0.0026 (11)	0.0089 (12)
C11	0.0444 (15)	0.071 (2)	0.0244 (12)	0.0112 (14)	0.0016 (11)	−0.0049 (13)
C12	0.0362 (14)	0.0556 (17)	0.0378 (14)	0.0075 (12)	−0.0013 (11)	−0.0194 (12)
C13	0.0319 (12)	0.0374 (14)	0.0379 (13)	0.0067 (10)	0.0014 (10)	−0.0053 (11)
C14	0.0230 (11)	0.0353 (13)	0.0253 (11)	0.0051 (9)	0.0023 (9)	0.0016 (9)
C15	0.0298 (12)	0.0292 (12)	0.0262 (11)	0.0049 (9)	0.0006 (9)	0.0024 (9)

Ni1—O1i	2.0174 (15)	C6—C1	1.520 (3)
Ni1—O1	2.0174 (15)	C6—C5	1.541 (3)
Ni1—O3i	2.0823 (15)	C6—H6A	0.9700
Ni1—O3	2.0823 (15)	C6—H6B	0.9700
Ni1—O5	2.1024 (14)	C5—C4	1.517 (3)
Ni1—O5i	2.1024 (14)	C5—H5A	0.9700
S1—C15	1.735 (2)	C5—H5B	0.9700
S1—C9	1.754 (2)	C1—C2	1.536 (3)
O1—C7	1.269 (3)	C1—H1B	0.9800
O1W—H1WA	0.8500	C4—C3	1.529 (3)
O1W—H1WB	0.8500	C4—H4A	0.9800
O2—C7	1.243 (3)	C2—C7	1.529 (3)
O2W—H2WA	0.8502	C2—C3	1.577 (3)
O2W—H2WB	0.8503	C2—H2C	0.9800
O3—C8	1.267 (3)	C3—C8	1.522 (3)
O3W—H3WA	0.8503	C3—H3A	0.9800
O3W—H3WB	0.8503	C9—C10	1.381 (3)
O4—C8	1.250 (3)	C9—C14	1.391 (3)
O5—C1	1.459 (3)	C10—C11	1.379 (4)
O5—C4	1.467 (3)	C10—H10A	0.9300
N1—C15	1.318 (3)	C11—C12	1.383 (4)
N1—C14	1.394 (3)	C11—H11A	0.9300
N1—H1A	0.8600	C12—C13	1.386 (3)
N2—C15	1.310 (3)	C12—H12A	0.9300
N2—H2A	0.8600	C13—C14	1.380 (3)
N2—H2B	0.8600	C13—H13A	0.9300
O1i—Ni1—O1	180.0	C2—C1—H1B	113.3
O1i—Ni1—O3i	87.63 (6)	O5—C4—C5	101.81 (17)
O1—Ni1—O3i	92.37 (6)	O5—C4—C3	101.95 (16)
O1i—Ni1—O3	92.37 (6)	C5—C4—C3	111.62 (18)
O1—Ni1—O3	87.63 (6)	O5—C4—H4A	113.4
O3i—Ni1—O3	180.00 (9)	C5—C4—H4A	113.4
O1i—Ni1—O5	90.51 (6)	C3—C4—H4A	113.4
O1—Ni1—O5	89.49 (6)	C7—C2—C1	109.66 (17)
O3i—Ni1—O5	89.20 (6)	C7—C2—C3	116.01 (17)
O3—Ni1—O5	90.80 (6)	C1—C2—C3	100.63 (16)
O1i—Ni1—O5i	89.49 (6)	C7—C2—H2C	110.0
O1—Ni1—O5i	90.51 (6)	C1—C2—H2C	110.0
O3i—Ni1—O5i	90.80 (6)	C3—C2—H2C	110.0
O3—Ni1—O5i	89.20 (6)	C8—C3—C4	112.85 (17)
O5—Ni1—O5i	180.0	C8—C3—C2	112.99 (17)
C15—S1—C9	90.16 (11)	C4—C3—C2	101.37 (16)
C7—O1—Ni1	126.63 (14)	C8—C3—H3A	109.8
H1WA—O1W—H1WB	111.0	C4—C3—H3A	109.8
H2WA—O2W—H2WB	102.3	C2—C3—H3A	109.8
C8—O3—Ni1	118.10 (13)	O2—C7—O1	123.6 (2)
H3WA—O3W—H3WB	110.3	O2—C7—C2	118.55 (19)
C1—O5—C4	95.27 (15)	O1—C7—C2	117.79 (18)
C1—O5—Ni1	116.89 (12)	O4—C8—O3	123.94 (19)
C4—O5—Ni1	112.33 (12)	O4—C8—C3	117.72 (19)
C15—N1—C14	114.58 (18)	O3—C8—C3	118.34 (18)
C15—N1—H1A	122.7	C10—C9—C14	121.1 (2)
C14—N1—H1A	122.7	C10—C9—S1	128.6 (2)
C15—N2—H2A	120.0	C14—C9—S1	110.31 (16)
C15—N2—H2B	120.0	C11—C10—C9	118.0 (2)
H2A—N2—H2B	120.0	C11—C10—H10A	121.0
C1—C6—C5	101.64 (17)	C9—C10—H10A	121.0
C1—C6—H6A	111.4	C10—C11—C12	120.9 (2)
C5—C6—H6A	111.4	C10—C11—H11A	119.6
C1—C6—H6B	111.4	C12—C11—H11A	119.6
C5—C6—H6B	111.4	C11—C12—C13	121.4 (2)
H6A—C6—H6B	109.3	C11—C12—H12A	119.3
C4—C5—C6	101.95 (19)	C13—C12—H12A	119.3
C4—C5—H5A	111.4	C14—C13—C12	117.6 (2)
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	120.9 (2)
H5A—C5—H5B	109.2	C13—C14—N1	126.8 (2)
O5—C1—C6	102.53 (17)	C9—C14—N1	112.23 (19)
O5—C1—C2	102.03 (16)	N2—C15—N1	124.1 (2)
C6—C1—C2	111.26 (18)	N2—C15—S1	123.20 (17)
O5—C1—H1B	113.3	N1—C15—S1	112.73 (16)
C6—C1—H1B	113.3
O3i—Ni1—O1—C7	−120.43 (17)	C5—C4—C3—C2	72.7 (2)
O3—Ni1—O1—C7	59.57 (17)	C7—C2—C3—C8	−3.4 (2)
O5—Ni1—O1—C7	−31.25 (17)	C1—C2—C3—C8	−121.57 (18)
O5i—Ni1—O1—C7	148.75 (17)	C7—C2—C3—C4	117.67 (19)
O1i—Ni1—O3—C8	134.35 (16)	C1—C2—C3—C4	−0.53 (19)
O1—Ni1—O3—C8	−45.65 (16)	Ni1—O1—C7—O2	−168.26 (16)
O5—Ni1—O3—C8	43.80 (16)	Ni1—O1—C7—C2	15.2 (3)
O5i—Ni1—O3—C8	−136.20 (16)	C1—C2—C7—O2	−128.9 (2)
O1i—Ni1—O5—C1	169.62 (13)	C3—C2—C7—O2	118.0 (2)
O1—Ni1—O5—C1	−10.38 (13)	C1—C2—C7—O1	47.8 (2)
O3i—Ni1—O5—C1	82.01 (13)	C3—C2—C7—O1	−65.2 (2)
O3—Ni1—O5—C1	−97.99 (13)	Ni1—O3—C8—O4	142.42 (18)
O1i—Ni1—O5—C4	−81.74 (13)	Ni1—O3—C8—C3	−37.8 (2)
O1—Ni1—O5—C4	98.26 (13)	C4—C3—C8—O4	151.24 (19)
O3i—Ni1—O5—C4	−169.35 (13)	C2—C3—C8—O4	−94.5 (2)
O3—Ni1—O5—C4	10.65 (13)	C4—C3—C8—O3	−28.5 (3)
C1—C6—C5—C4	−1.2 (2)	C2—C3—C8—O3	85.8 (2)
C4—O5—C1—C6	56.54 (18)	C15—S1—C9—C10	−179.3 (2)
Ni1—O5—C1—C6	174.86 (12)	C15—S1—C9—C14	0.40 (17)
C4—O5—C1—C2	−58.75 (18)	C14—C9—C10—C11	−0.2 (4)
Ni1—O5—C1—C2	59.58 (17)	S1—C9—C10—C11	179.49 (19)
C5—C6—C1—O5	−34.3 (2)	C9—C10—C11—C12	0.8 (4)
C5—C6—C1—C2	74.1 (2)	C10—C11—C12—C13	−1.0 (4)
C1—O5—C4—C5	−57.14 (18)	C11—C12—C13—C14	0.5 (4)
Ni1—O5—C4—C5	−179.07 (13)	C12—C13—C14—C9	0.1 (3)
C1—O5—C4—C3	58.27 (18)	C12—C13—C14—N1	−179.7 (2)
Ni1—O5—C4—C3	−63.67 (16)	C10—C9—C14—C13	−0.2 (3)
C6—C5—C4—O5	36.1 (2)	S1—C9—C14—C13	180.00 (18)
C6—C5—C4—C3	−72.0 (2)	C10—C9—C14—N1	179.5 (2)
O5—C1—C2—C7	−86.34 (19)	S1—C9—C14—N1	−0.2 (2)
C6—C1—C2—C7	164.94 (18)	C15—N1—C14—C13	179.6 (2)
O5—C1—C2—C3	36.40 (19)	C15—N1—C14—C9	−0.2 (3)
C6—C1—C2—C3	−72.3 (2)	C14—N1—C15—N2	−179.9 (2)
O5—C4—C3—C8	85.9 (2)	C14—N1—C15—S1	0.5 (2)
C5—C4—C3—C8	−166.13 (18)	C9—S1—C15—N2	179.9 (2)
O5—C4—C3—C2	−35.25 (19)	C9—S1—C15—N1	−0.52 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ii	0.85	1.97	2.815 (2)	179
O1W—H1WB···O3W	0.85	2.28	3.029 (3)	147
O2W—H2WA···O2iii	0.85	1.83	2.682 (2)	179
O2W—H2WB···O1Wiv	0.85	1.95	2.798 (3)	178
O3W—H3WA···O1Wv	0.85	1.92	2.769 (3)	179
O3W—H3WB···O2W	0.85	1.95	2.772 (3)	161
N1—H1A···O4ii	0.86	1.82	2.673 (2)	173
N2—H2A···O3ii	0.86	2.01	2.863 (2)	173
N2—H2B···O2Wii	0.86	2.00	2.818 (3)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4i	0.85	1.97	2.815 (2)	179
O1W—H1WB⋯O3W	0.85	2.28	3.029 (3)	147
O2W—H2WA⋯O2ii	0.85	1.83	2.682 (2)	179
O2W—H2WB⋯O1Wiii	0.85	1.95	2.798 (3)	178
O3W—H3WA⋯O1Wiv	0.85	1.92	2.769 (3)	179
O3W—H3WB⋯O2W	0.85	1.95	2.772 (3)	161
N1—H1A⋯O4i	0.86	1.82	2.673 (2)	173
N2—H2A⋯O3i	0.86	2.01	2.863 (2)	173
N2—H2B⋯O2Wi	0.86	2.00	2.818 (3)	158

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