Bis(2-amino­benzothia­zol-3-ium) bis­(7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxyl­ato-κ3O2,O3,O7)nickelate(II) hexa­hydrate

Wang, G.-X.; Zhang, Q.-W.; Zhang, F.

doi:10.1107/S1600536812017722

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m683

doi:10.1107/S1600536812017722

Open

access

Bis(2-aminobenzothiazol-3-ium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato-κ³O²,O³,O⁷)nickelate(II) hexahydrate

Gui-Xian Wang,^a ^* Qi-Wei Zhang ^a and Fan Zhang ^b

^aDepartment of Chemistry, Lishui University, Lishui 323000, Zhejiang, People's Republic of China, and ^bCollege of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: wangguixian@126.com

(Received 18 April 2012; accepted 20 April 2012; online 28 April 2012)

In the title compound, (C₇H₇N₂S)₂[Ni(C₈H₈O₅)₂]·6H₂O, 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-dicarboxylate anions in a distorted octahedral geometry. The 2-aminobenzothiazol-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 molecules 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 Mn^II, Co^II and Ni^II 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_r = 837.51
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.06
3083 reflections
241 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.44 e Å⁻³

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⋯O1W^iv	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) -x+1, -y+1, -z+1; (ii) x, y-1, z; (iii) -x+1, -y, -z+1; (iv) -x, -y, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017722/xu5517sup1.cif

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

checkCIF report

Comment top

7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride (norcantharidin), which has been considered as potent inhibitor of the serine/threonine protein, has great anti-cancer activity (Hill et al., 2007). A isostructural manganese complex (Wang et al., 2010a) and a cobalt complex (Wang et al., 2010b) has been reported. The molecular structure of the title complex is shown in Fig.1. The nickel atom is six-coordinated in a distorted octahedral coordination mode, binding to two bridging O atoms of the bicycloheptane unit and four carboxylate O atoms of two symmetry-related and fully deprotonated ligands. 2-aminobenzothiazole don't involved the coordination, and N atom of thiazole ring is protonated. The crystal structure is stabilized by N—H···O hydrogen-bonding interactions between the cations and anions and O—H···O hydrogen bonds including the crystal water molecules.

Related literature top

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 Mn^II, Co^II and Ni^II analogues were reported by Wang et al. (2010a,b and Zhang et al. (2012), respectively.

Experimental top

A mixture of 0.5 mmol norcantharidin, 0.5 mmol nickel acetate, 0.5 mmol 2-aminobenzothiazole and 15 mL distilled water was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. The solution was filtered and block green crystals 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 molecule of (I) showing the atom-labelling scheme with displacement ellipsoids drawn at the 30% probability.

Bis(2-aminobenzothiazol-3-ium) bis(7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato- κ³O²,O³,O⁷)nickelate(II) hexahydrate top

Crystal data top

(C₇H₇N₂S)₂[Ni(C₈H₈O₅)₂]·6H₂O	Z = 1
M_r = 837.51	F(000) = 438
Triclinic, P1	D_x = 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

Data collection top

Bruker APEXII area-detector diffractometer	3083 independent reflections
Radiation source: fine-focus sealed tube	2654 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.828, T_max = 0.951	k = −11→11
11942 measured reflections	l = −15→15

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0485P)² + 0.2846P] where P = (F_o² + 2F_c²)/3
3083 reflections	(Δ/σ)_max < 0.001
241 parameters	Δρ_max = 0.38 e Å⁻³
3 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

(C₇H₇N₂S)₂[Ni(C₈H₈O₅)₂]·6H₂O	γ = 99.709 (1)°
M_r = 837.51	V = 880.57 (3) Å³
Triclinic, P1	Z = 1
a = 6.6907 (1) Å	Mo Kα radiation
b = 10.0963 (2) Å	µ = 0.75 mm⁻¹
c = 13.2283 (3) Å	T = 296 K
α = 90.284 (1)°	0.27 × 0.21 × 0.07 mm
β = 91.192 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	3083 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2654 reflections with I > 2σ(I)
T_min = 0.828, T_max = 0.951	R_int = 0.032
11942 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	Δρ_max = 0.38 e Å⁻³
3083 reflections	Δρ_min = −0.44 e Å⁻³
241 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
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

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···O1W^iv	0.85	1.95	2.798 (3)	178
O3W—H3WA···O1W^v	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

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

Experimental details

Crystal data
Chemical formula	(C₇H₇N₂S)₂[Ni(C₈H₈O₅)₂]·6H₂O
M_r	837.51
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.6907 (1), 10.0963 (2), 13.2283 (3)
α, β, γ (°)	90.284 (1), 91.192 (1), 99.709 (1)
V (Å³)	880.57 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.27 × 0.21 × 0.07

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.828, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	11942, 3083, 2654
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.06
No. of reflections	3083
No. of parameters	241
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.44

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱ	0.85	1.97	2.815 (2)	178.5
O1W—H1WB···O3W	0.85	2.28	3.029 (3)	147.2
O2W—H2WA···O2ⁱⁱ	0.85	1.83	2.682 (2)	178.7
O2W—H2WB···O1Wⁱⁱⁱ	0.85	1.95	2.798 (3)	177.8
O3W—H3WA···O1W^iv	0.85	1.92	2.769 (3)	178.9
O3W—H3WB···O2W	0.85	1.95	2.772 (3)	161.2
N1—H1A···O4ⁱ	0.86	1.82	2.673 (2)	172.6
N2—H2A···O3ⁱ	0.86	2.01	2.863 (2)	172.5
N2—H2B···O2Wⁱ	0.86	2.00	2.818 (3)	158.4

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

Acknowledgements

The authors thank the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301) for financial support.

References

Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hill, T.-A., Stewart, S.-G., Sauer, B., Gilbert, J., Ackland, S.-P., Sakoff, J.-A. & McCluskey, A. (2007). Bioorg. Med. Chem. Lett. 17, 3392–3397. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, N., Lin, Q.-Y., Feng, J., Li, S.-K. & Zhao, J.-J. (2010b). Acta Cryst. E66, m763–m764. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, N., Wen, Y.-H., Lin, Q.-Y. & Feng, J. (2010a). Acta Cryst. E66, m762. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, F., Lv, T.-X., Feng, J. & Lin, Q. Y. (2012). Acta Cryst. E68, m684. CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.