Diaqua­bis­{4-[(pyridin-2-yl)methyl­idene­amino]­benzene­sulfonato-κ2N,N′}nickel(II) tetra­hydrate

Li, C.-Z.; Huang, X.-R.

doi:10.1107/S1600536812022179

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages m809-m810

doi:10.1107/S1600536812022179

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Diaquabis{4-[(pyridin-2-yl)methylideneamino]benzenesulfonato-κ²N,N′}nickel(II) tetrahydrate

Chao-Zhu Li ^a and Xue-Ren Huang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Qinzhou University, Qinzhou, Guangxi 535000, People's Republic of China
^*Correspondence e-mail: 499122835@qq.com

(Received 4 May 2012; accepted 16 May 2012; online 26 May 2012)

In the title complex, [Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂]·4H₂O, the Ni^II ion is coordinated by four N atoms from two bidentate chelating 4-[(pyridin-2-yl)methylideneamino]benzenesulfonate ligands and two O atoms from cis-related water molecules in a slightly distorted octahedral environment [Ni—N = 2.071 (3)–2.121 (3) Å and Ni—O = 2.071 (2) and 2.073 (3) Å]. In the crystal, the coordinated water molecules and the four water molecules of solvation are involved in intermolecular O—H⋯O hydrogen-bonding interactions with water and sulfonate O-atom acceptors, giving a three-dimensional framework structure.

Related literature

For the synthesis of the ligand, see: Casella & Gullotti (1981 ). For the synthesis, structures and applications of similar complexes, see: Zhang et al. (2007 , 2008 ). For the structures of the mainly tridentate complexes with the title ligand and similar ligands, see: Correia et al. (2003 ); Jiang et al. (2006 ); Ou-Yang et al. (2008 ); Li et al. (2006 ); Huang et al. (2009 ).

Experimental

Crystal data

[Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂]·4H₂O
M_r = 689.35
Orthorhombic, P n a 2₁
a = 13.865 (2) Å
b = 11.5310 (18) Å
c = 18.860 (3) Å
V = 3015.3 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.36 × 0.19 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.821, T_max = 0.889
16541 measured reflections
5315 independent reflections
4983 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.100
S = 0.96
5315 reflections
388 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 2540 Friedel pairs
Flack parameter: 0.00 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.85	1.92	2.748 (4)	166
O1—H1A⋯O7ⁱⁱ	0.85	2.08	2.876 (4)	156
O2—H2A⋯O1W	0.85	1.94	2.752 (4)	159
O2—H2B⋯O3Wⁱⁱⁱ	0.85	1.82	2.659 (4)	171
O1W—H1WA⋯O4W	0.85	2.00	2.804 (5)	156
O1W—H1WB⋯O2W^iv	0.85	1.90	2.733 (5)	167
O2W—H2WA⋯O3^v	0.87	2.13	2.833 (5)	137
O2W—H2WB⋯O7^vi	0.86	2.29	2.874 (5)	125
O3W—H3WB⋯O6^v	0.85	2.00	2.813 (6)	160
O3W—H3WA⋯O5^vii	0.85	2.15	2.930 (5)	152
O4W—H4WB⋯O8^vi	0.85	2.17	2.846 (5)	136
O4W—H4WA⋯O5^viii	0.85	2.06	2.903 (5)	169
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{5\over 2}}, z]$ ; (ii) $[-x, -y+2, z-{\script{1\over 2}}]$ ; (iii) x-1, y+1, z; (iv) x, y+1, z; (v) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (vi) $[-x, -y+1, z-{\script{1\over 2}}]$ ; (vii) x, y-1, z; (viii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022179/zs2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022179/zs2208Isup2.hkl

checkCIF report

Comment top

The design and control of supramolecular coordination complex networks in which both coordinate bonds and hydrogen bonds take part in the molecular self-assenbly, have recently attracted increasing interest. Schiff base complexes that contain both sulfur and amino acid functionalities have also received much attention due to their potential application in pharmacy (Jiang et al., 2006; Zhang et al., 2007, 2008). We report here the synthesis and the stucture of the mononuclear Ni^II complex with the potentially tridentate monoanionic ligand from the acid (4-pyridylmethylimine)benzenesulfonic acid (BfbaH), the title complex [Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂] . 4H₂O. Other complexes with this ligand or similar ligands in the N,N',O-tridentate mode are known (Correia et al., 2003; Li et al., 2006; Huang et al., 2009; Ou-Yang et al., 2008).

The asymmetric unit of the title complex (Fig. 1) comprises a Ni²⁺ cation, coordinated by four N atoms from two bidentate Bfba ligands and two O atoms from cis-related water molecules in a slightly distorted octahedral environment [Ni—N, 2.071 (3)–2.121 (3) Å; Ni—O, 2.071 (3), 2.079 (3) Å], together with four water molecules of solvation. The two ligands are conformationally different [dihedral angles between the pyridine and benzene rings in each: 55.85 (18) and 43.2 (2)°]. In the crystal structure, the coordinated water molecules and the water molecules of solvation are involved in intermolecular O—H···O hydrogen-bonding interactions with water and sulfonate O-atom acceptors (Table 1) giving a three-dimensional framework structure (Fig. 2).

Related literature top

For the synthesis of the ligand, see: Casella & Gullotti (1981). For the synthesis, structures and applications of similar complexes, see: Zhang et al. (2007, 2008). For the structures of the mainly tridentate complexes with the title ligand and similar ligands, see: Correia et al. (2003); Jiang et al. (2006); Ou-Yang et al. (2008); Li et al. (2006); Huang et al. (2009).

Experimental top

The potassium salt of (4-pyridylmethylimine)benzenesulfonic acid (BfbaK) was synthesized according to the literature method (Casella & Gullotti, 1981). To prepare the title complex, the ligand BfbaK (1 mmol) was dissolved in methanol (10 ml) at 333 K and an aqueous solution (10 ml) containing Ni(AcO)₂ . 4H₂O (0.5 mmol) was added. The resulting solution was stirred at 333 K for 4 h, then cooled to room temperature and filtered. Blue crystals of the title complex suitable for X-ray diffraction were obtained by slow evaporation of this solution over a period of several days (yield 50%).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, showing the atom-numbering scheme. All H atoms have been omitted for clarity.
	Fig. 2. The packing of the title complex, showing the two-dimensional sheet structure in the ac plane.

Diaquabis{4-[(pyridin-2-yl)methylideneamino]benzenesulfonato- κ²N,N'}nickel(II) tetrahydrate top

Crystal data top

[Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂]·4H₂O	F(000) = 1432
M_r = 689.35	D_x = 1.518 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 5315 reflections
a = 13.865 (2) Å	θ = 2.1–25.1°
b = 11.5310 (18) Å	µ = 0.85 mm⁻¹
c = 18.860 (3) Å	T = 296 K
V = 3015.3 (8) Å³	Prism, blue
Z = 4	0.36 × 0.19 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5315 independent reflections
Radiation source: fine-focus sealed tube	4983 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −16→15
T_min = 0.821, T_max = 0.889	k = −12→13
16541 measured reflections	l = −21→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0792P)² + 0.0306P] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
5315 reflections	Δρ_max = 0.44 e Å⁻³
388 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2540 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (1)

Crystal data top

[Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂]·4H₂O	V = 3015.3 (8) Å³
M_r = 689.35	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 13.865 (2) Å	µ = 0.85 mm⁻¹
b = 11.5310 (18) Å	T = 296 K
c = 18.860 (3) Å	0.36 × 0.19 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5315 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	4983 reflections with I > 2σ(I)
T_min = 0.821, T_max = 0.889	R_int = 0.028
16541 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.100	Δρ_max = 0.44 e Å⁻³
S = 0.96	Δρ_min = −0.20 e Å⁻³
5315 reflections	Absolute structure: Flack (1983), 2540 Friedel pairs
388 parameters	Absolute structure parameter: 0.00 (1)
1 restraint

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	0.20498 (2)	1.02094 (3)	0.40723 (2)	0.02752 (11)
S1	0.73596 (6)	1.04204 (7)	0.44399 (5)	0.03481 (19)
S2	−0.05169 (7)	0.72312 (8)	0.70323 (5)	0.0424 (2)
C1	0.1419 (2)	0.8284 (3)	0.51959 (18)	0.0344 (7)
C2	0.0425 (3)	0.8359 (3)	0.51285 (19)	0.0416 (8)
H2	0.0154	0.8610	0.4704	0.050*
C3	−0.0162 (3)	0.8060 (3)	0.5690 (2)	0.0433 (8)
H3	−0.0829	0.8099	0.5643	0.052*
C4	0.0244 (3)	0.7701 (3)	0.63258 (18)	0.0367 (7)
C5	0.1233 (3)	0.7666 (4)	0.64016 (19)	0.0446 (9)
H5	0.1505	0.7449	0.6832	0.053*
C6	0.1825 (3)	0.7957 (4)	0.5830 (2)	0.0439 (9)
H6	0.2492	0.7930	0.5879	0.053*
C7	0.2621 (3)	0.7887 (3)	0.4372 (2)	0.0383 (7)
H7	0.2700	0.7168	0.4588	0.046*
C8	0.3219 (2)	0.8221 (3)	0.37556 (19)	0.0345 (7)
C9	0.3888 (3)	0.7478 (4)	0.3452 (2)	0.0517 (9)
H9	0.3983	0.6740	0.3637	0.062*
C10	0.4408 (3)	0.7847 (4)	0.2875 (2)	0.0613 (12)
H10	0.4874	0.7369	0.2673	0.074*
C11	0.4233 (3)	0.8925 (4)	0.2600 (2)	0.0554 (11)
H11	0.4573	0.9190	0.2207	0.067*
C12	0.3539 (3)	0.9611 (3)	0.2919 (2)	0.0407 (8)
H12	0.3417	1.0342	0.2730	0.049*
C13	0.4683 (2)	1.0089 (3)	0.52834 (19)	0.0393 (8)
H13	0.4397	0.9777	0.5687	0.047*
C14	0.5673 (3)	1.0014 (3)	0.5188 (2)	0.0399 (8)
H14	0.6053	0.9657	0.5530	0.048*
C15	0.6096 (2)	1.0470 (3)	0.45836 (18)	0.0335 (7)
C16	0.5529 (2)	1.0996 (3)	0.4065 (2)	0.0369 (7)
H16	0.5814	1.1292	0.3657	0.044*
C17	0.4550 (2)	1.1077 (3)	0.41573 (19)	0.0356 (7)
H17	0.4171	1.1426	0.3811	0.043*
C18	0.4121 (2)	1.0635 (3)	0.47707 (18)	0.0316 (6)
C19	0.2719 (2)	1.1073 (3)	0.54054 (19)	0.0383 (8)
H19	0.3101	1.1220	0.5801	0.046*
C20	0.1660 (2)	1.1226 (3)	0.5437 (2)	0.0390 (8)
C21	0.1207 (3)	1.1581 (6)	0.6040 (3)	0.0727 (16)
H21	0.1552	1.1711	0.6455	0.087*
C22	0.0210 (3)	1.1745 (6)	0.6016 (3)	0.0765 (16)
H22	−0.0121	1.1990	0.6418	0.092*
C23	−0.0268 (3)	1.1544 (4)	0.5405 (2)	0.0517 (10)
H23	−0.0932	1.1646	0.5382	0.062*
C24	0.0239 (2)	1.1186 (3)	0.4818 (2)	0.0399 (8)
H24	−0.0093	1.1060	0.4397	0.048*
N1	0.20060 (18)	0.8593 (2)	0.45990 (15)	0.0318 (6)
N2	0.30403 (16)	0.9275 (2)	0.34813 (15)	0.0292 (6)
N3	0.30951 (17)	1.0737 (2)	0.48275 (15)	0.0297 (6)
N4	0.11907 (18)	1.1011 (2)	0.48314 (14)	0.0318 (6)
O1	0.22444 (18)	1.1677 (2)	0.34556 (13)	0.0394 (5)
H1A	0.2096	1.1876	0.3036	0.059*
H1	0.2364	1.2285	0.3694	0.059*
O2	0.09435 (18)	0.9625 (2)	0.34255 (14)	0.0463 (6)
H2B	0.0449	1.0005	0.3295	0.069*
H2A	0.1204	0.9324	0.3061	0.069*
O3	0.77809 (19)	0.9764 (2)	0.50163 (16)	0.0438 (6)
O4	0.76778 (18)	1.1617 (2)	0.44222 (19)	0.0562 (7)
O5	0.7506 (2)	0.9857 (3)	0.37643 (17)	0.0624 (8)
O6	0.0109 (2)	0.7141 (3)	0.76410 (16)	0.0728 (9)
O7	−0.1269 (2)	0.8077 (3)	0.71181 (17)	0.0644 (8)
O8	−0.0890 (3)	0.6119 (3)	0.68130 (19)	0.0814 (12)
O1W	0.1482 (2)	0.8187 (3)	0.23302 (17)	0.0613 (8)
H1WA	0.1788	0.7548	0.2339	0.092*
H1WB	0.1766	0.8647	0.2047	0.092*
O2W	0.2203 (3)	−0.0066 (3)	0.1507 (2)	0.0764 (10)
H2WA	0.2499	0.0164	0.1126	0.115*
H2WB	0.1642	0.0260	0.1517	0.115*
O4W	0.1939 (3)	0.5819 (3)	0.2341 (2)	0.0784 (10)
H4WB	0.1951	0.5164	0.2134	0.118*
H4WA	0.2094	0.5718	0.2775	0.118*
O3W	0.9288 (2)	0.0644 (4)	0.3082 (2)	0.0940 (13)
H3WB	0.9386	0.1276	0.2860	0.141*
H3WA	0.8695	0.0599	0.3187	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02597 (19)	0.0301 (2)	0.0265 (2)	0.00072 (14)	0.00129 (17)	0.00007 (19)
S1	0.0260 (4)	0.0403 (4)	0.0381 (4)	0.0023 (3)	−0.0034 (4)	0.0044 (4)
S2	0.0496 (5)	0.0457 (5)	0.0319 (4)	−0.0013 (4)	0.0112 (4)	0.0058 (4)
C1	0.0388 (17)	0.0286 (16)	0.0359 (18)	−0.0041 (13)	0.0049 (14)	0.0026 (13)
C2	0.0422 (18)	0.053 (2)	0.0296 (18)	−0.0063 (16)	−0.0020 (14)	0.0095 (15)
C3	0.0361 (17)	0.057 (2)	0.0371 (19)	−0.0087 (16)	0.0010 (15)	0.0071 (16)
C4	0.0438 (18)	0.0354 (17)	0.0308 (17)	−0.0037 (15)	0.0077 (14)	0.0043 (13)
C5	0.044 (2)	0.056 (2)	0.0336 (19)	0.0032 (17)	−0.0003 (15)	0.0141 (16)
C6	0.0357 (17)	0.055 (2)	0.041 (2)	0.0057 (16)	0.0024 (15)	0.0056 (17)
C7	0.0445 (17)	0.0305 (16)	0.0398 (18)	0.0017 (14)	0.0043 (15)	0.0059 (15)
C8	0.0350 (16)	0.0336 (18)	0.0348 (16)	0.0045 (14)	0.0023 (14)	−0.0009 (14)
C9	0.051 (2)	0.050 (2)	0.054 (2)	0.0147 (18)	0.0089 (18)	0.0039 (19)
C10	0.057 (2)	0.070 (3)	0.057 (3)	0.026 (2)	0.021 (2)	0.000 (2)
C11	0.047 (2)	0.076 (3)	0.043 (2)	0.002 (2)	0.0176 (17)	0.003 (2)
C12	0.0419 (19)	0.042 (2)	0.038 (2)	−0.0046 (15)	0.0028 (15)	0.0034 (15)
C13	0.0344 (19)	0.048 (2)	0.0360 (19)	0.0017 (14)	0.0031 (15)	0.0152 (15)
C14	0.0326 (18)	0.051 (2)	0.036 (2)	0.0058 (15)	−0.0025 (15)	0.0153 (15)
C15	0.0310 (16)	0.0329 (16)	0.0366 (19)	−0.0008 (13)	−0.0035 (13)	0.0025 (14)
C16	0.0287 (14)	0.0475 (18)	0.0345 (16)	−0.0057 (12)	−0.0021 (15)	0.0108 (17)
C17	0.0296 (14)	0.0442 (18)	0.0330 (17)	−0.0031 (12)	−0.0049 (14)	0.0097 (15)
C18	0.0263 (14)	0.0344 (16)	0.0340 (17)	−0.0036 (13)	−0.0017 (13)	0.0031 (13)
C19	0.0304 (16)	0.056 (2)	0.0288 (18)	−0.0049 (15)	−0.0009 (13)	−0.0048 (15)
C20	0.0333 (17)	0.048 (2)	0.0353 (18)	−0.0010 (15)	−0.0001 (14)	−0.0068 (15)
C21	0.038 (2)	0.137 (5)	0.043 (2)	0.002 (2)	0.0019 (18)	−0.031 (3)
C22	0.041 (2)	0.130 (5)	0.059 (3)	0.001 (3)	0.014 (2)	−0.039 (3)
C23	0.0325 (18)	0.068 (3)	0.055 (2)	0.0020 (16)	0.0051 (17)	−0.014 (2)
C24	0.0313 (16)	0.0436 (18)	0.045 (2)	0.0031 (14)	−0.0040 (15)	−0.0055 (15)
N1	0.0340 (14)	0.0281 (13)	0.0332 (15)	−0.0024 (10)	0.0056 (10)	0.0037 (11)
N2	0.0262 (12)	0.0304 (15)	0.0309 (15)	−0.0020 (10)	0.0041 (10)	−0.0031 (11)
N3	0.0272 (12)	0.0332 (14)	0.0287 (14)	−0.0021 (10)	−0.0006 (11)	0.0004 (11)
N4	0.0301 (13)	0.0322 (14)	0.0331 (15)	0.0001 (10)	0.0037 (11)	−0.0023 (11)
O1	0.0539 (13)	0.0300 (12)	0.0342 (13)	0.0023 (10)	−0.0040 (11)	0.0049 (10)
O2	0.0380 (13)	0.0588 (16)	0.0421 (15)	0.0019 (11)	−0.0068 (11)	−0.0094 (12)
O3	0.0369 (13)	0.0453 (15)	0.0491 (17)	0.0051 (10)	−0.0089 (11)	0.0065 (12)
O4	0.0345 (12)	0.0447 (15)	0.089 (2)	−0.0049 (11)	−0.0096 (14)	0.0229 (16)
O5	0.0443 (17)	0.097 (2)	0.0458 (17)	0.0119 (15)	0.0030 (14)	−0.0110 (17)
O6	0.075 (2)	0.107 (3)	0.0359 (16)	−0.002 (2)	0.0060 (14)	0.0233 (17)
O7	0.0660 (18)	0.077 (2)	0.0499 (18)	0.0180 (15)	0.0253 (15)	0.0135 (16)
O8	0.110 (3)	0.061 (2)	0.073 (2)	−0.0346 (18)	0.047 (2)	−0.0115 (16)
O1W	0.0578 (17)	0.0614 (18)	0.065 (2)	−0.0034 (14)	0.0028 (14)	−0.0054 (15)
O2W	0.096 (3)	0.081 (2)	0.052 (2)	0.0126 (19)	0.0092 (17)	0.0085 (18)
O4W	0.100 (3)	0.062 (2)	0.073 (2)	−0.0125 (18)	−0.0150 (19)	0.0097 (18)
O3W	0.0498 (19)	0.129 (3)	0.103 (3)	0.015 (2)	0.0142 (19)	0.046 (3)

Geometric parameters (Å, º) top

Ni1—N2	2.071 (3)	C12—H12	0.9300
Ni1—O1	2.071 (2)	C13—C14	1.387 (5)
Ni1—O2	2.073 (3)	C13—C18	1.392 (5)
Ni1—N4	2.079 (3)	C13—H13	0.9300
Ni1—N1	2.113 (3)	C14—C15	1.385 (5)
Ni1—N3	2.121 (3)	C14—H14	0.9300
S1—O5	1.444 (3)	C15—C16	1.393 (5)
S1—O3	1.448 (3)	C16—C17	1.371 (4)
S1—O4	1.449 (3)	C16—H16	0.9300
S1—C15	1.774 (3)	C17—C18	1.397 (5)
S2—O7	1.437 (3)	C17—H17	0.9300
S2—O8	1.443 (3)	C18—N3	1.431 (4)
S2—O6	1.443 (3)	C19—N3	1.269 (5)
S2—C4	1.784 (3)	C19—C20	1.480 (5)
C1—C6	1.375 (5)	C19—H19	0.9300
C1—C2	1.387 (5)	C20—N4	1.338 (5)
C1—N1	1.434 (4)	C20—C21	1.362 (6)
C2—C3	1.380 (5)	C21—C22	1.396 (6)
C2—H2	0.9300	C21—H21	0.9300
C3—C4	1.387 (5)	C22—C23	1.349 (6)
C3—H3	0.9300	C22—H22	0.9300
C4—C5	1.379 (5)	C23—C24	1.375 (5)
C5—C6	1.395 (5)	C23—H23	0.9300
C5—H5	0.9300	C24—N4	1.335 (4)
C6—H6	0.9300	C24—H24	0.9300
C7—N1	1.254 (4)	O1—H1A	0.8499
C7—C8	1.479 (5)	O1—H1	0.8500
C7—H7	0.9300	O2—H2B	0.8500
C8—N2	1.344 (4)	O2—H2A	0.8500
C8—C9	1.386 (5)	O1W—H1WA	0.8506
C9—C10	1.374 (6)	O1W—H1WB	0.8501
C9—H9	0.9300	O2W—H2WA	0.8684
C10—C11	1.369 (6)	O2W—H2WB	0.8637
C10—H10	0.9300	O4W—H4WB	0.8501
C11—C12	1.384 (6)	O4W—H4WA	0.8538
C11—H11	0.9300	O3W—H3WB	0.8511
C12—N2	1.324 (4)	O3W—H3WA	0.8476

N2—Ni1—O1	92.09 (10)	N2—C12—H12	118.5
N2—Ni1—O2	90.27 (10)	C11—C12—H12	118.5
O1—Ni1—O2	91.81 (10)	C14—C13—C18	119.4 (3)
N2—Ni1—N4	169.04 (11)	C14—C13—H13	120.3
O1—Ni1—N4	95.63 (10)	C18—C13—H13	120.3
O2—Ni1—N4	97.23 (11)	C15—C14—C13	120.1 (3)
N2—Ni1—N1	79.24 (11)	C15—C14—H14	119.9
O1—Ni1—N1	171.32 (10)	C13—C14—H14	119.9
O2—Ni1—N1	88.20 (10)	C14—C15—C16	120.2 (3)
N4—Ni1—N1	92.98 (11)	C14—C15—S1	122.1 (3)
N2—Ni1—N3	93.30 (10)	C16—C15—S1	117.6 (3)
O1—Ni1—N3	93.09 (10)	C17—C16—C15	119.9 (3)
O2—Ni1—N3	173.83 (11)	C17—C16—H16	120.0
N4—Ni1—N3	78.55 (10)	C15—C16—H16	120.0
N1—Ni1—N3	87.53 (11)	C16—C17—C18	120.1 (3)
O5—S1—O3	111.75 (17)	C16—C17—H17	120.0
O5—S1—O4	111.4 (2)	C18—C17—H17	120.0
O3—S1—O4	113.12 (18)	C13—C18—C17	120.1 (3)
O5—S1—C15	106.73 (18)	C13—C18—N3	122.8 (3)
O3—S1—C15	107.49 (16)	C17—C18—N3	117.1 (3)
O4—S1—C15	105.88 (15)	N3—C19—C20	118.6 (3)
O7—S2—O8	112.0 (2)	N3—C19—H19	120.7
O7—S2—O6	113.3 (2)	C20—C19—H19	120.7
O8—S2—O6	112.3 (2)	N4—C20—C21	123.0 (3)
O7—S2—C4	107.90 (17)	N4—C20—C19	115.2 (3)
O8—S2—C4	105.55 (18)	C21—C20—C19	121.8 (3)
O6—S2—C4	105.09 (17)	C20—C21—C22	118.1 (4)
C6—C1—C2	120.2 (3)	C20—C21—H21	120.9
C6—C1—N1	121.3 (3)	C22—C21—H21	120.9
C2—C1—N1	118.5 (3)	C23—C22—C21	119.3 (4)
C3—C2—C1	120.0 (3)	C23—C22—H22	120.3
C3—C2—H2	120.0	C21—C22—H22	120.3
C1—C2—H2	120.0	C22—C23—C24	119.2 (3)
C2—C3—C4	119.9 (3)	C22—C23—H23	120.4
C2—C3—H3	120.1	C24—C23—H23	120.4
C4—C3—H3	120.1	N4—C24—C23	122.3 (3)
C5—C4—C3	120.2 (3)	N4—C24—H24	118.8
C5—C4—S2	120.1 (3)	C23—C24—H24	118.8
C3—C4—S2	119.7 (3)	C7—N1—C1	119.5 (3)
C4—C5—C6	119.8 (3)	C7—N1—Ni1	113.1 (2)
C4—C5—H5	120.1	C1—N1—Ni1	127.2 (2)
C6—C5—H5	120.1	C12—N2—C8	118.5 (3)
C1—C6—C5	119.8 (3)	C12—N2—Ni1	128.7 (2)
C1—C6—H6	120.1	C8—N2—Ni1	112.7 (2)
C5—C6—H6	120.1	C19—N3—C18	119.9 (3)
N1—C7—C8	118.7 (3)	C19—N3—Ni1	112.6 (2)
N1—C7—H7	120.7	C18—N3—Ni1	127.2 (2)
C8—C7—H7	120.7	C20—N4—C24	118.0 (3)
N2—C8—C9	121.5 (3)	C20—N4—Ni1	113.0 (2)
N2—C8—C7	115.8 (3)	C24—N4—Ni1	128.3 (2)
C9—C8—C7	122.6 (3)	Ni1—O1—H1A	135.5
C10—C9—C8	119.2 (4)	Ni1—O1—H1	113.7
C10—C9—H9	120.4	H1A—O1—H1	108.5
C8—C9—H9	120.4	Ni1—O2—H2B	126.8
C9—C10—C11	119.2 (4)	Ni1—O2—H2A	107.1
C9—C10—H10	120.4	H2B—O2—H2A	108.6
C11—C10—H10	120.4	H1WA—O1W—H1WB	108.8
C10—C11—C12	118.6 (4)	H2WA—O2W—H2WB	108.2
C10—C11—H11	120.7	H4WB—O4W—H4WA	108.3
C12—C11—H11	120.7	H3WB—O3W—H3WA	108.7
N2—C12—C11	123.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.85	1.92	2.748 (4)	166
O1—H1A···O7ⁱⁱ	0.85	2.08	2.876 (4)	156
O2—H2A···O1W	0.85	1.94	2.752 (4)	159
O2—H2B···O3Wⁱⁱⁱ	0.85	1.82	2.659 (4)	171
O1W—H1WA···O4W	0.85	2.00	2.804 (5)	156
O1W—H1WB···O2W^iv	0.85	1.90	2.733 (5)	167
O2W—H2WA···O3^v	0.87	2.13	2.833 (5)	137
O2W—H2WB···O7^vi	0.86	2.29	2.874 (5)	125
O3W—H3WB···O6^v	0.85	2.00	2.813 (6)	160
O3W—H3WA···O5^vii	0.85	2.15	2.930 (5)	152
O4W—H4WB···O8^vi	0.85	2.17	2.846 (5)	136
O4W—H4WA···O5^viii	0.85	2.06	2.903 (5)	169

Symmetry codes: (i) x−1/2, −y+5/2, z; (ii) −x, −y+2, z−1/2; (iii) x−1, y+1, z; (iv) x, y+1, z; (v) −x+1, −y+1, z−1/2; (vi) −x, −y+1, z−1/2; (vii) x, y−1, z; (viii) x−1/2, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₂H₉N₂O₃S)₂(H₂O)₂]·4H₂O
M_r	689.35
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	296
a, b, c (Å)	13.865 (2), 11.5310 (18), 18.860 (3)
V (Å³)	3015.3 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.36 × 0.19 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.821, 0.889
No. of measured, independent and observed [I > 2σ(I)] reflections	16541, 5315, 4983
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.100, 0.96
No. of reflections	5315
No. of parameters	388
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.20
Absolute structure	Flack (1983), 2540 Friedel pairs
Absolute structure parameter	0.00 (1)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
O1—H1···O4ⁱ	0.85	1.92	2.748 (4)	166
O1—H1A···O7ⁱⁱ	0.85	2.08	2.876 (4)	156
O2—H2A···O1W	0.85	1.94	2.752 (4)	159
O2—H2B···O3Wⁱⁱⁱ	0.85	1.82	2.659 (4)	171
O1W—H1WA···O4W	0.85	2.00	2.804 (5)	156
O1W—H1WB···O2W^iv	0.85	1.90	2.733 (5)	167
O2W—H2WA···O3^v	0.87	2.13	2.833 (5)	137
O2W—H2WB···O7^vi	0.86	2.29	2.874 (5)	125
O3W—H3WB···O6^v	0.85	2.00	2.813 (6)	160
O3W—H3WA···O5^vii	0.85	2.15	2.930 (5)	152
O4W—H4WB···O8^vi	0.85	2.17	2.846 (5)	136
O4W—H4WA···O5^viii	0.85	2.06	2.903 (5)	169

Acknowledgements

This work was funded by the Guangxi Science Foundation and Qinzhou University Science Foundation and the Guangxi Zhuang Autonomous Region of the People's Republic of China (grant Nos. 2010GXNSFA013017, 2010GXNSFA013062 and 2011XJKY-14B).

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