Poly[[diaqua(μ2-4,4′-dipyridyl sulfide-κ2N:N′)(4,4′-dipyridyl sulfide-κN)(2-hydroxy-5-sulfonatobenzoato-κO1)nickel(II)] dihydrate]

Du, Z.-X.; Li, J.-X.

doi:10.1107/S1600536808029206

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Pages m1278-m1279

doi:10.1107/S1600536808029206

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Poly[[diaqua(μ₂-4,4′-dipyridyl sulfide-κ²N:N′)(4,4′-dipyridyl sulfide-κN)(2-hydroxy-5-sulfonatobenzoato-κO¹)nickel(II)] dihydrate]

Zhong-Xiang Du ^a ^* and Jun-Xia Li ^a

^aDepartment of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471022, People's Republic of China
^*Correspondence e-mail: dzx6281@126.com

(Received 8 September 2008; accepted 11 September 2008; online 20 September 2008)

The asymmetric unit of the title helical coordination polymer, {[Ni(C₇H₄O₆S)(C₁₀H₈N₂S)₂(H₂O)₂]·2H₂O}_n, is comprised of an Ni^II ion, one 5-sulfosalicylic acid dianion (HSSA), two 4,4′-dipyridylsulfide (4,4′-dps) ligands, and two coordinated and two uncoordinated water molecules. The Ni^II ion is coordinated by two water molecules, one carboxylate O atom of the HSSA dianion and three N atoms from three 4,4′-dps ligands in a distorted octahedral environment. Half of the 4,4′-dps ligands are μ₂-bridging ligands which link adjacent Ni^II centers, forming a one-dimensional helical structure along the b axis. This helical structure is further stabilized by O—H⋯O intra- and intermolecular hydrogen bonds.

Related literature

For related structures, see: Fujita et al. (1994 ); Hao & Zhang (2007 ); Hou et al. (2001 ); Jung et al. (1999 , 2000 ); Niu et al. (2006 ); Vaganova et al. (2004 ); Wen et al. (2004 ); Zeng et al. (2006 ); Zheng & Vittal (2001 ); Zheng et al. (1999 ).

Experimental

Crystal data

[Ni(C₇H₄O₆S)(C₁₀H₈N₂S)₂(H₂O)₂]·2H₂O
M_r = 723.42
Monoclinic, P 2₁ /n
a = 11.4649 (10) Å
b = 13.9441 (12) Å
c = 20.7051 (18) Å
β = 96.5520 (10)°
V = 3288.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 291 (2) K
0.44 × 0.26 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.709, T_max = 0.866
23823 measured reflections
6054 independent reflections
4328 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.178
S = 1.02
6054 reflections
426 parameters
219 restraints
H-atom parameters constrained
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Ni1—O9	1.981 (3)
Ni1—N4ⁱ	2.040 (3)
Ni1—N1	2.041 (4)
Ni1—N3	2.055 (4)
Ni1—O2	2.430 (3)
Ni1—O5	2.437 (3)

O9—Ni1—N4ⁱ	173.60 (14)
O9—Ni1—N1	88.00 (13)
O9—Ni1—N3	87.87 (13)
N1—Ni1—N3	175.23 (14)
O9—Ni1—O2	92.99 (12)
N1—Ni1—O2	87.06 (14)
O9—Ni1—O5	80.75 (12)
N1—Ni1—O5	93.08 (14)
O2—Ni1—O5	173.73 (12)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O10	0.82	1.84	2.535 (5)	142
O5—H10W⋯O3ⁱⁱ	0.83	1.98	2.797 (5)	170
O5—H9W⋯O4ⁱⁱⁱ	0.85	2.04	2.721 (8)	136
O4—H7W⋯O8^iv	0.83	2.30	2.713 (9)	112
O3—H6W⋯O6^v	0.83	2.10	2.811 (7)	143
O3—H5W⋯O6^vi	0.83	2.24	2.765 (8)	122
O2—H4W⋯O10	0.83	1.95	2.690 (5)	149
O2—H3W⋯O7^v	0.84	1.87	2.652 (7)	155
O1—H1W⋯O11^vii	0.85	2.03	2.876 (7)	180
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x, y-1, z; (iv) x-1, y+1, z; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) x-1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); 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 global, I. DOI: 10.1107/S1600536808029206/at2628sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029206/at2628Isup2.hkl

checkCIF report

Comment top

Recently, the use of bipyridyl based bridging ligands and transition metal centers in the preparation of various coordination compounds have attracted considerable interests not only because of their structural novelty but also for their potential properties in magnetism (Zheng et al., 1999), nonlinear optics (Hou et al., 2001), catalysts (Fujita et al., 1994) and so on. 4,4'-dps possesses a magic angle (the angle of C—S—C almost equals to 100°) and conformational nonrigidity so it has some flexibility in contrast to linear rigid ligands such as simple 4,4'-bipyridine analogues. A number of metal complexes derived from 4,4'-dps have been reported previously. Among them, the 4,4'-dps has three kind of coordination modes and they are non-coordinate (Zeng et al., 2006; Wen et al., 2004; Vaganova et al., 2004),µ₂-bridging (Zheng & Vittal, 2001; Jung et al., 2000; Hao & Zhang, 2007; Niu et al., 2006), µ₂ and µ₃ together (Jung et al., 1999). In this paper, we describe another new compound in which the 4,4'-dps is monodentate and µ₂-bridging together, (I), (Fig. 1).

Complex (I) is composed of [Ni(C₁₀H₈N₂S)₂)(C₇H₄O₆S)(H₂O)₂].2H₂O units, in which the Ni^II ion is six-coordinated in a distorted octahedral geometry (Table 1) formed by two coordinate water molecules, one carboxylate O atom of HSSA dianion, one N atoms from monodentate 4,4'-dps ligand and another two N atoms from another two µ₂-bridging 4,4'-dps ligands. Half of the 4,4'-dps are monodentate and the other half are µ₂-bridging. It is just through the µ₂-bridging function that the adjacent Ni^II centers are joined to form a one-dimensional helix structure (Fig. 2, 3 & 4) along b axis in the monoclinic unit cell, with the Ni···Ni(1/2 - x, 1/2 + y, 3/2 - z) distance of 10.6096 (10) Å. The phenolic hydroxyl and carboxyl of HSSA dianion are involved in intramolecular hydrogen bonding (Table 2). Together with the other O—H···O intermolecular hydrogen bonds with participation of water molecules, the helix structure are further stabilized.

Related literature top

For related literature, see: Fujita et al. (1994); Hao & Zhang (2007); Hou et al. (2001); Jung et al. (1999, 2000); Niu et al. (2006); Vaganova et al. (2004); Wen et al. (2004); Zeng et al. (2006); Zheng & Vittal (2001); Zheng et al. (1999). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···.? etc. Please revise this section as indicated.

Experimental top

The ligand 4,4'-dps (0.5 mmol, 0.14 g), 5-sulfosalicylic acid (0.5 mmol, 0.13 g) and NaOH (1.0 mmol, 0.04 g) were dissolved in water and methanol mixed solvent (30 ml, v/v 1:1). To this solution, Ni(CH₃COO)₂.4H₂O (0.5 mmol, 0.13 g) was added and the resulting mixture was stirred and refluxed at 353 K for 2.5 h, then cooled to room temperature. After filtration and evaporation in air for 3 days, green block-shaped crystals were obtained in a yield of 32%. Analysis, found (%): C, 44.83; H 3.84, N 7.79, S13.22. C₂₇H₂₈N₄NiO₁₀S₃ requires (%): C 44.78, H 3.87, N 7.74, S 13.27. [CCDC number 656224].

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 coordination environment of Ni^II ion in (I), with displacement ellipsoids shown at the 30% probability level. Uncoordinate water molecules and H atoms have been omitted [Symmetry codes: (A) 1/2 - x, 1/2 + y, 3/2 - z; (B) 1/2 - x, -1/2 + y, 3/2 - z].
	Fig. 2. The helix structure for (I) along b axis. Uncoordinate water molecules and H atoms on C atoms have been omitted.
	Fig. 3. The helix structure for (I) along b axis with a helix axis. Uncoordinate water molecules and H atoms have been omitted.
	Fig. 4. The space filled diagram of the helix structure for (I) along b axis. Uncoordinate water molecules and H atoms have been omitted.

Poly[[diaqua(µ₂-4,4'-dipyridyl sulfide-κ²N:N')(4,4'-dipyridyl sulfide-κN)(2-hydroxy-5-sulfonatobenzoato-κO¹)nickel(II)] dihydrate] top

Crystal data top

[Ni(C₇H₄O₆S)(C₁₀H₈N₂S)₂(H₂O)₂]·2H₂O	F(000) = 1496
M_r = 723.42	D_x = 1.461 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4865 reflections
a = 11.4649 (10) Å	θ = 2.3–21.6°
b = 13.9441 (12) Å	µ = 0.84 mm⁻¹
c = 20.7051 (18) Å	T = 291 K
β = 96.552 (1)°	Block, green
V = 3288.5 (5) Å³	0.44 × 0.26 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	6054 independent reflections
Radiation source: fine-focus sealed tube	4328 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.709, T_max = 0.866	k = −16→16
23823 measured reflections	l = −25→25

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0999P)² + 2.6202P] where P = (F_o² + 2F_c²)/3
6054 reflections	(Δ/σ)_max = 0.001
426 parameters	Δρ_max = 0.96 e Å⁻³
219 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Ni(C₇H₄O₆S)(C₁₀H₈N₂S)₂(H₂O)₂]·2H₂O	V = 3288.5 (5) Å³
M_r = 723.42	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.4649 (10) Å	µ = 0.84 mm⁻¹
b = 13.9441 (12) Å	T = 291 K
c = 20.7051 (18) Å	0.44 × 0.26 × 0.18 mm
β = 96.552 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	6054 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4328 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.866	R_int = 0.037
23823 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	219 restraints
wR(F²) = 0.178	H-atom parameters constrained
S = 1.03	Δρ_max = 0.96 e Å⁻³
6054 reflections	Δρ_min = −0.58 e Å⁻³
426 parameters

Special details top

Experimental. The sulfonic group of HSSA dianion is in disorder and has been refined but not satisfactory.

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	Occ. (<1)
S3	1.11886 (11)	−0.14488 (10)	0.89754 (7)	0.0681 (4)	0.622 (5)
O6	1.0657 (6)	−0.0994 (5)	0.9516 (3)	0.0971 (16)	0.622 (5)
O7	1.0712 (6)	−0.2372 (4)	0.8826 (3)	0.0973 (17)	0.622 (5)
O8	1.2456 (4)	−0.1450 (6)	0.9124 (4)	0.1026 (19)	0.622 (5)
S3'	1.11886 (11)	−0.14488 (10)	0.89754 (7)	0.0681 (4)	0.378 (5)
O6'	1.0085 (7)	−0.1624 (8)	0.9241 (5)	0.0971 (16)	0.378 (5)
O7'	1.1545 (9)	−0.2352 (6)	0.8675 (5)	0.0973 (17)	0.378 (5)
O8'	1.2068 (8)	−0.1005 (8)	0.9383 (6)	0.1026 (19)	0.378 (5)
Ni1	0.59573 (4)	0.10463 (4)	0.80537 (3)	0.04492 (19)
S1	0.86708 (13)	0.45268 (11)	0.97477 (9)	0.0867 (5)
S2	0.42135 (12)	−0.26440 (11)	0.61663 (7)	0.0762 (4)
O1	0.2056 (7)	0.1245 (5)	0.6004 (4)	0.081 (2)	0.50
H1W	0.1451	0.1176	0.6202	0.122*	0.50
H2W	0.2395	0.1543	0.6298	0.122*	0.50
O2	0.5916 (3)	0.2119 (3)	0.71261 (17)	0.0762 (10)
H3W	0.5535	0.2426	0.6827	0.114*
H4W	0.6615	0.2079	0.7065	0.114*
O3	0.6648 (4)	0.4534 (3)	0.5299 (2)	0.0938 (12)
H5W	0.6367	0.4593	0.4912	0.141*
H6W	0.6116	0.4399	0.5528	0.141*
O4	0.4748 (7)	0.8801 (5)	0.9582 (4)	0.084 (2)	0.50
H7W	0.4223	0.8558	0.9771	0.127*	0.50
H8W	0.4646	0.8593	0.9178	0.127*	0.50
O5	0.6211 (3)	−0.0084 (3)	0.89567 (18)	0.0763 (10)
H9W	0.5833	−0.0606	0.8975	0.114*
H10W	0.6840	−0.0261	0.9156	0.114*
O9	0.7577 (2)	0.0611 (2)	0.79683 (15)	0.0566 (7)
O10	0.8024 (3)	0.1301 (3)	0.70624 (19)	0.0765 (10)
O11	1.0017 (3)	0.1011 (3)	0.6679 (2)	0.0915 (13)
H11	0.9311	0.1125	0.6621	0.137*
N1	0.6667 (3)	0.2157 (3)	0.86085 (17)	0.0531 (9)
N2	0.6301 (7)	0.7173 (4)	0.9694 (4)	0.119 (2)
N3	0.5365 (3)	−0.0069 (3)	0.74554 (18)	0.0545 (9)
N4	0.0690 (3)	−0.3576 (3)	0.67586 (18)	0.0512 (8)
C1	0.7555 (4)	0.1994 (3)	0.9076 (2)	0.0577 (11)
H1	0.7793	0.1363	0.9159	0.069*
C2	0.8125 (4)	0.2702 (4)	0.9436 (2)	0.0609 (12)
H2	0.8734	0.2553	0.9756	0.073*
C3	0.7792 (4)	0.3647 (3)	0.9322 (2)	0.0591 (11)
C4	0.6873 (5)	0.3829 (4)	0.8847 (3)	0.0680 (13)
H4	0.6615	0.4454	0.8760	0.082*
C5	0.6349 (4)	0.3076 (3)	0.8506 (2)	0.0628 (12)
H5	0.5736	0.3208	0.8184	0.075*
C6	0.7725 (5)	0.5558 (4)	0.9719 (3)	0.0777 (15)
C7	0.8082 (7)	0.6385 (5)	0.9465 (3)	0.097 (2)
H7	0.8803	0.6426	0.9302	0.116*
C8	0.7340 (9)	0.7170 (5)	0.9456 (4)	0.113 (2)
H8	0.7579	0.7735	0.9272	0.135*
C9	0.5986 (7)	0.6361 (6)	0.9958 (4)	0.115 (2)
H9	0.5272	0.6343	1.0130	0.138*
C10	0.6680 (6)	0.5523 (5)	0.9989 (4)	0.0945 (19)
H10	0.6442	0.4967	1.0185	0.113*
C11	0.4525 (4)	0.0005 (4)	0.6954 (2)	0.0617 (12)
H11A	0.4178	0.0600	0.6866	0.074*
C12	0.4151 (4)	−0.0753 (4)	0.6564 (2)	0.0647 (12)
H12	0.3560	−0.0664	0.6222	0.078*
C13	0.4639 (4)	−0.1637 (3)	0.6674 (2)	0.0592 (11)
C14	0.5518 (5)	−0.1722 (4)	0.7173 (3)	0.0743 (14)
H14	0.5884	−0.2311	0.7258	0.089*
C15	0.5863 (5)	−0.0938 (4)	0.7548 (3)	0.0733 (14)
H15	0.6471	−0.1012	0.7882	0.088*
C16	0.2851 (4)	−0.2967 (3)	0.6419 (2)	0.0548 (10)
C17	0.2466 (4)	−0.2696 (4)	0.7005 (2)	0.0635 (12)
H17	0.2928	−0.2305	0.7295	0.076*
C18	0.1396 (4)	−0.3014 (4)	0.7149 (2)	0.0614 (12)
H18	0.1148	−0.2827	0.7542	0.074*
C19	0.1080 (4)	−0.3847 (4)	0.6199 (2)	0.0628 (12)
H19	0.0610	−0.4249	0.5921	0.075*
C20	0.2136 (4)	−0.3559 (4)	0.6018 (2)	0.0645 (12)
H20	0.2369	−0.3763	0.5625	0.077*
C21	0.8262 (4)	0.0772 (3)	0.7551 (2)	0.0487 (10)
C22	0.9428 (4)	0.0302 (3)	0.7648 (2)	0.0500 (10)
C23	0.9732 (4)	−0.0280 (3)	0.8182 (2)	0.0520 (10)
H23	0.9185	−0.0395	0.8471	0.062*
C24	1.0833 (4)	−0.0692 (3)	0.8294 (2)	0.0558 (11)
C25	1.1637 (4)	−0.0526 (4)	0.7859 (3)	0.0692 (13)
H25	1.2382	−0.0795	0.7934	0.083*
C26	1.1358 (4)	0.0022 (4)	0.7325 (3)	0.0786 (16)
H26	1.1907	0.0115	0.7033	0.094*
C27	1.0251 (4)	0.0452 (4)	0.7209 (2)	0.0638 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S3	0.0600 (7)	0.0674 (8)	0.0720 (8)	0.0162 (6)	−0.0135 (6)	−0.0046 (6)
O6	0.097 (3)	0.101 (4)	0.091 (3)	0.027 (3)	0.001 (3)	0.014 (3)
O7	0.114 (4)	0.080 (3)	0.090 (3)	−0.011 (3)	−0.024 (3)	0.010 (2)
O8	0.074 (3)	0.118 (4)	0.108 (4)	0.007 (3)	−0.026 (3)	0.012 (3)
S3'	0.0600 (7)	0.0674 (8)	0.0720 (8)	0.0162 (6)	−0.0135 (6)	−0.0046 (6)
O6'	0.097 (3)	0.101 (4)	0.091 (3)	0.027 (3)	0.001 (3)	0.014 (3)
O7'	0.114 (4)	0.080 (3)	0.090 (3)	−0.011 (3)	−0.024 (3)	0.010 (2)
O8'	0.074 (3)	0.118 (4)	0.108 (4)	0.007 (3)	−0.026 (3)	0.012 (3)
Ni1	0.0342 (3)	0.0437 (3)	0.0563 (3)	0.0050 (2)	0.0026 (2)	−0.0027 (2)
S1	0.0655 (8)	0.0828 (10)	0.1068 (12)	−0.0091 (7)	−0.0121 (8)	−0.0239 (8)
S2	0.0628 (8)	0.0861 (9)	0.0849 (9)	−0.0234 (7)	0.0313 (7)	−0.0296 (7)
O1	0.090 (5)	0.062 (4)	0.103 (5)	−0.020 (3)	0.061 (4)	−0.011 (3)
O2	0.068 (2)	0.088 (2)	0.073 (2)	0.0191 (18)	0.0125 (17)	0.0177 (19)
O3	0.081 (3)	0.122 (3)	0.076 (2)	0.007 (2)	−0.003 (2)	−0.007 (2)
O4	0.069 (4)	0.059 (4)	0.127 (6)	0.001 (3)	0.020 (4)	0.031 (4)
O5	0.067 (2)	0.072 (2)	0.088 (2)	0.0028 (17)	0.0020 (18)	0.0209 (19)
O9	0.0428 (16)	0.0611 (18)	0.0661 (19)	0.0083 (14)	0.0075 (14)	0.0037 (15)
O10	0.059 (2)	0.089 (2)	0.082 (2)	0.0182 (18)	0.0104 (17)	0.026 (2)
O11	0.068 (2)	0.119 (3)	0.092 (3)	0.016 (2)	0.027 (2)	0.039 (2)
N1	0.0474 (19)	0.053 (2)	0.058 (2)	0.0062 (16)	0.0000 (16)	0.0026 (16)
N2	0.142 (6)	0.066 (4)	0.140 (6)	0.004 (4)	−0.027 (5)	−0.021 (4)
N3	0.0425 (18)	0.057 (2)	0.063 (2)	0.0050 (16)	0.0035 (16)	0.0009 (18)
N4	0.0455 (19)	0.051 (2)	0.057 (2)	−0.0061 (16)	0.0047 (16)	−0.0015 (17)
C1	0.054 (3)	0.053 (3)	0.064 (3)	0.006 (2)	−0.003 (2)	0.008 (2)
C2	0.054 (3)	0.069 (3)	0.057 (3)	0.004 (2)	−0.005 (2)	0.007 (2)
C3	0.056 (3)	0.061 (3)	0.059 (3)	−0.004 (2)	0.004 (2)	−0.009 (2)
C4	0.071 (3)	0.055 (3)	0.073 (3)	0.006 (2)	−0.014 (3)	−0.001 (2)
C5	0.058 (3)	0.057 (3)	0.069 (3)	0.012 (2)	−0.014 (2)	−0.001 (2)
C6	0.081 (4)	0.072 (4)	0.075 (3)	−0.015 (3)	−0.014 (3)	−0.017 (3)
C7	0.125 (6)	0.084 (4)	0.079 (4)	−0.019 (4)	−0.001 (4)	−0.005 (3)
C8	0.148 (8)	0.073 (5)	0.111 (6)	−0.006 (5)	−0.012 (5)	0.001 (4)
C9	0.109 (6)	0.098 (6)	0.135 (7)	0.002 (5)	−0.002 (5)	−0.027 (5)
C10	0.085 (4)	0.072 (4)	0.124 (5)	−0.005 (3)	0.001 (4)	−0.014 (4)
C11	0.050 (2)	0.064 (3)	0.071 (3)	0.008 (2)	0.002 (2)	0.001 (2)
C12	0.055 (3)	0.073 (3)	0.064 (3)	−0.006 (2)	0.000 (2)	−0.005 (2)
C13	0.047 (2)	0.062 (3)	0.071 (3)	−0.010 (2)	0.015 (2)	−0.009 (2)
C14	0.081 (4)	0.051 (3)	0.088 (4)	0.002 (2)	−0.003 (3)	−0.006 (3)
C15	0.074 (3)	0.061 (3)	0.079 (3)	0.013 (3)	−0.018 (3)	−0.002 (3)
C16	0.049 (2)	0.059 (3)	0.057 (3)	−0.003 (2)	0.0089 (19)	−0.002 (2)
C17	0.052 (3)	0.074 (3)	0.066 (3)	−0.020 (2)	0.012 (2)	−0.024 (2)
C18	0.056 (3)	0.071 (3)	0.059 (3)	−0.013 (2)	0.013 (2)	−0.012 (2)
C19	0.060 (3)	0.067 (3)	0.061 (3)	−0.015 (2)	0.006 (2)	−0.011 (2)
C20	0.067 (3)	0.072 (3)	0.057 (3)	−0.017 (2)	0.016 (2)	−0.015 (2)
C21	0.044 (2)	0.045 (2)	0.056 (2)	−0.0004 (17)	−0.0016 (19)	0.0009 (19)
C22	0.041 (2)	0.047 (2)	0.062 (3)	0.0018 (17)	0.0029 (19)	−0.008 (2)
C23	0.047 (2)	0.050 (2)	0.057 (2)	0.0039 (18)	−0.0016 (19)	−0.004 (2)
C24	0.044 (2)	0.051 (2)	0.070 (3)	0.0082 (19)	−0.003 (2)	−0.010 (2)
C25	0.048 (3)	0.069 (3)	0.090 (4)	0.013 (2)	0.005 (3)	−0.007 (3)
C26	0.051 (3)	0.097 (4)	0.091 (4)	0.017 (3)	0.023 (3)	0.006 (3)
C27	0.051 (3)	0.075 (3)	0.066 (3)	0.000 (2)	0.007 (2)	0.008 (2)

Geometric parameters (Å, º) top

S3—O7	1.418 (5)	C2—H2	0.9300
S3—O8	1.450 (5)	C3—C4	1.381 (7)
S3—O6	1.477 (5)	C4—C5	1.365 (7)
S3—C24	1.771 (5)	C4—H4	0.9300
Ni1—O9	1.981 (3)	C5—H5	0.9300
Ni1—N4ⁱ	2.040 (3)	C6—C7	1.349 (8)
Ni1—N1	2.041 (4)	C6—C10	1.379 (9)
Ni1—N3	2.055 (4)	C7—C8	1.385 (11)
Ni1—O2	2.430 (3)	C7—H7	0.9300
Ni1—O5	2.437 (3)	C8—H8	0.9300
S1—C3	1.759 (5)	C9—C10	1.411 (9)
S1—C6	1.798 (6)	C9—H9	0.9300
S2—C16	1.762 (4)	C10—H10	0.9300
S2—C13	1.789 (5)	C11—C12	1.369 (7)
O1—H1W	0.8504	C11—H11A	0.9300
O1—H2W	0.8000	C12—C13	1.362 (7)
O2—H3W	0.8350	C12—H12	0.9300
O2—H4W	0.8278	C13—C14	1.363 (7)
O3—H5W	0.8338	C14—C15	1.373 (7)
O3—H6W	0.8347	C14—H14	0.9300
O4—H7W	0.8256	C15—H15	0.9300
O4—H8W	0.8821	C16—C20	1.375 (6)
O5—H9W	0.8501	C16—C17	1.390 (6)
O5—H10W	0.8267	C17—C18	1.369 (6)
O9—C21	1.252 (5)	C17—H17	0.9300
O10—C21	1.256 (5)	C18—H18	0.9300
O11—C27	1.348 (6)	C19—C20	1.367 (7)
O11—H11	0.8200	C19—H19	0.9300
N1—C1	1.342 (5)	C20—H20	0.9300
N1—C5	1.343 (6)	C21—C22	1.482 (6)
N2—C9	1.324 (10)	C22—C23	1.384 (6)
N2—C8	1.340 (11)	C22—C27	1.397 (6)
N3—C11	1.337 (6)	C23—C24	1.382 (6)
N3—C15	1.344 (6)	C23—H23	0.9300
N4—C18	1.332 (6)	C24—C25	1.380 (7)
N4—C19	1.344 (6)	C25—C26	1.352 (8)
N4—Ni1ⁱⁱ	2.040 (3)	C25—H25	0.9300
C1—C2	1.358 (6)	C26—C27	1.399 (7)
C1—H1	0.9300	C26—H26	0.9300
C2—C3	1.385 (7)

O7—S3—O8	113.4 (4)	C6—C7—H7	121.1
O7—S3—O6	111.9 (4)	C8—C7—H7	121.1
O8—S3—O6	109.2 (4)	N2—C8—C7	124.5 (8)
O7—S3—C24	108.6 (3)	N2—C8—H8	117.7
O8—S3—C24	107.7 (4)	C7—C8—H8	117.7
O6—S3—C24	105.7 (3)	N2—C9—C10	123.2 (8)
O9—Ni1—N4ⁱ	173.60 (14)	N2—C9—H9	118.4
O9—Ni1—N1	88.00 (13)	C10—C9—H9	118.4
N4ⁱ—Ni1—N1	90.87 (14)	C6—C10—C9	117.6 (7)
O9—Ni1—N3	87.87 (13)	C6—C10—H10	121.2
N4ⁱ—Ni1—N3	93.50 (14)	C9—C10—H10	121.2
N1—Ni1—N3	175.23 (14)	N3—C11—C12	123.3 (5)
O9—Ni1—O2	92.99 (12)	N3—C11—H11A	118.4
N4ⁱ—Ni1—O2	93.24 (13)	C12—C11—H11A	118.4
N1—Ni1—O2	87.06 (14)	C13—C12—C11	120.3 (5)
N3—Ni1—O2	90.79 (14)	C13—C12—H12	119.9
O9—Ni1—O5	80.75 (12)	C11—C12—H12	119.9
N4ⁱ—Ni1—O5	93.03 (13)	C12—C13—C14	117.4 (4)
N1—Ni1—O5	93.08 (14)	C12—C13—S2	122.2 (4)
N3—Ni1—O5	88.60 (14)	C14—C13—S2	120.3 (4)
O2—Ni1—O5	173.73 (12)	C13—C14—C15	120.0 (5)
C3—S1—C6	103.4 (2)	C13—C14—H14	120.0
C16—S2—C13	102.6 (2)	C15—C14—H14	120.0
H1W—O1—H2W	92.5	N3—C15—C14	123.1 (5)
Ni1—O2—H3W	149.8	N3—C15—H15	118.4
Ni1—O2—H4W	98.5	C14—C15—H15	118.4
H3W—O2—H4W	110.7	C20—C16—C17	117.7 (4)
H5W—O3—H6W	109.9	C20—C16—S2	117.5 (3)
H7W—O4—H8W	106.8	C17—C16—S2	124.8 (3)
Ni1—O5—H9W	124.9	C18—C17—C16	118.9 (4)
Ni1—O5—H10W	126.7	C18—C17—H17	120.6
H9W—O5—H10W	98.2	C16—C17—H17	120.6
C21—O9—Ni1	132.4 (3)	N4—C18—C17	123.8 (4)
C27—O11—H11	109.5	N4—C18—H18	118.1
C1—N1—C5	116.5 (4)	C17—C18—H18	118.1
C1—N1—Ni1	119.9 (3)	N4—C19—C20	123.1 (4)
C5—N1—Ni1	123.5 (3)	N4—C19—H19	118.5
C9—N2—C8	116.5 (7)	C20—C19—H19	118.5
C11—N3—C15	115.9 (4)	C19—C20—C16	119.7 (4)
C11—N3—Ni1	124.7 (3)	C19—C20—H20	120.1
C15—N3—Ni1	119.4 (3)	C16—C20—H20	120.1
C18—N4—C19	116.7 (4)	O9—C21—O10	124.4 (4)
C18—N4—Ni1ⁱⁱ	123.2 (3)	O9—C21—C22	117.0 (4)
C19—N4—Ni1ⁱⁱ	119.9 (3)	O10—C21—C22	118.6 (4)
N1—C1—C2	123.3 (4)	C23—C22—C27	118.7 (4)
N1—C1—H1	118.3	C23—C22—C21	120.5 (4)
C2—C1—H1	118.3	C27—C22—C21	120.8 (4)
C1—C2—C3	119.6 (4)	C24—C23—C22	121.3 (4)
C1—C2—H2	120.2	C24—C23—H23	119.3
C3—C2—H2	120.2	C22—C23—H23	119.3
C4—C3—C2	118.0 (4)	C25—C24—C23	119.0 (5)
C4—C3—S1	125.2 (4)	C25—C24—S3	120.6 (3)
C2—C3—S1	116.6 (4)	C23—C24—S3	120.3 (4)
C5—C4—C3	118.8 (4)	C26—C25—C24	121.0 (4)
C5—C4—H4	120.6	C26—C25—H25	119.5
C3—C4—H4	120.6	C24—C25—H25	119.5
N1—C5—C4	123.9 (4)	C25—C26—C27	120.5 (5)
N1—C5—H5	118.1	C25—C26—H26	119.8
C4—C5—H5	118.1	C27—C26—H26	119.8
C7—C6—C10	120.3 (7)	O11—C27—C22	121.9 (4)
C7—C6—S1	119.2 (6)	O11—C27—C26	118.7 (5)
C10—C6—S1	120.4 (5)	C22—C27—C26	119.4 (5)
C6—C7—C8	117.9 (8)

N4ⁱ—Ni1—O9—C21	−172.7 (11)	Ni1—N3—C11—C12	180.0 (4)
N1—Ni1—O9—C21	−92.8 (4)	N3—C11—C12—C13	−0.3 (8)
N3—Ni1—O9—C21	84.9 (4)	C11—C12—C13—C14	−1.4 (7)
O2—Ni1—O9—C21	−5.8 (4)	C11—C12—C13—S2	−178.2 (4)
O5—Ni1—O9—C21	173.8 (4)	C16—S2—C13—C12	−76.2 (4)
O9—Ni1—N1—C1	−45.1 (3)	C16—S2—C13—C14	107.0 (4)
N4ⁱ—Ni1—N1—C1	128.6 (4)	C12—C13—C14—C15	1.2 (8)
N3—Ni1—N1—C1	−74.9 (18)	S2—C13—C14—C15	178.0 (4)
O2—Ni1—N1—C1	−138.2 (3)	C11—N3—C15—C14	−2.3 (8)
O5—Ni1—N1—C1	35.6 (4)	Ni1—N3—C15—C14	179.7 (5)
O9—Ni1—N1—C5	130.2 (4)	C13—C14—C15—N3	0.7 (9)
N4ⁱ—Ni1—N1—C5	−56.1 (4)	C13—S2—C16—C20	163.6 (4)
N3—Ni1—N1—C5	100.3 (17)	C13—S2—C16—C17	−18.9 (5)
O2—Ni1—N1—C5	37.1 (4)	C20—C16—C17—C18	−1.1 (8)
O5—Ni1—N1—C5	−149.2 (4)	S2—C16—C17—C18	−178.6 (4)
O9—Ni1—N3—C11	−134.4 (4)	C19—N4—C18—C17	1.0 (7)
N4ⁱ—Ni1—N3—C11	51.8 (4)	Ni1ⁱⁱ—N4—C18—C17	−174.8 (4)
N1—Ni1—N3—C11	−104.5 (17)	C16—C17—C18—N4	0.1 (8)
O2—Ni1—N3—C11	−41.5 (4)	C18—N4—C19—C20	−1.1 (7)
O5—Ni1—N3—C11	144.8 (4)	Ni1ⁱⁱ—N4—C19—C20	174.8 (4)
O9—Ni1—N3—C15	43.4 (4)	N4—C19—C20—C16	0.2 (8)
N4ⁱ—Ni1—N3—C15	−130.3 (4)	C17—C16—C20—C19	0.9 (8)
N1—Ni1—N3—C15	73.3 (18)	S2—C16—C20—C19	178.6 (4)
O2—Ni1—N3—C15	136.4 (4)	Ni1—O9—C21—O10	0.8 (7)
O5—Ni1—N3—C15	−37.4 (4)	Ni1—O9—C21—C22	−179.4 (3)
C5—N1—C1—C2	−0.1 (7)	O9—C21—C22—C23	−0.4 (6)
Ni1—N1—C1—C2	175.4 (4)	O10—C21—C22—C23	179.4 (4)
N1—C1—C2—C3	−0.3 (8)	O9—C21—C22—C27	−179.2 (4)
C1—C2—C3—C4	0.8 (7)	O10—C21—C22—C27	0.6 (6)
C1—C2—C3—S1	−173.6 (4)	C27—C22—C23—C24	1.5 (6)
C6—S1—C3—C4	26.3 (5)	C21—C22—C23—C24	−177.4 (4)
C6—S1—C3—C2	−159.8 (4)	C22—C23—C24—C25	−0.7 (7)
C2—C3—C4—C5	−1.0 (8)	C22—C23—C24—S3	−179.0 (3)
S1—C3—C4—C5	172.8 (4)	O7—S3—C24—C25	−98.3 (5)
C1—N1—C5—C4	−0.1 (8)	O8—S3—C24—C25	24.9 (5)
Ni1—N1—C5—C4	−175.5 (4)	O6—S3—C24—C25	141.5 (5)
C3—C4—C5—N1	0.7 (8)	O7—S3—C24—C23	80.1 (5)
C3—S1—C6—C7	−123.6 (5)	O8—S3—C24—C23	−156.8 (5)
C3—S1—C6—C10	60.5 (5)	O6—S3—C24—C23	−40.1 (5)
C10—C6—C7—C8	−3.4 (9)	C23—C24—C25—C26	−0.8 (7)
S1—C6—C7—C8	−179.3 (5)	S3—C24—C25—C26	177.6 (4)
C9—N2—C8—C7	0.4 (12)	C24—C25—C26—C27	1.4 (9)
C6—C7—C8—N2	1.5 (11)	C23—C22—C27—O11	−179.9 (5)
C8—N2—C9—C10	−0.5 (12)	C21—C22—C27—O11	−1.0 (7)
C7—C6—C10—C9	3.3 (9)	C23—C22—C27—C26	−0.8 (7)
S1—C6—C10—C9	179.2 (5)	C21—C22—C27—C26	178.0 (5)
N2—C9—C10—C6	−1.3 (11)	C25—C26—C27—O11	178.5 (5)
C15—N3—C11—C12	2.1 (7)	C25—C26—C27—C22	−0.6 (8)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O10	0.82	1.84	2.535 (5)	142
O5—H10W···O3ⁱⁱⁱ	0.83	1.98	2.797 (5)	170
O5—H9W···O4^iv	0.85	2.04	2.721 (8)	136
O4—H7W···O8^v	0.83	2.30	2.713 (9)	112
O3—H6W···O6^vi	0.83	2.10	2.811 (7)	143
O3—H5W···O6^vii	0.83	2.24	2.765 (8)	122
O2—H4W···O10	0.83	1.95	2.690 (5)	149
O2—H3W···O7^vi	0.84	1.87	2.652 (7)	155
O1—H1W···O11^viii	0.85	2.03	2.876 (7)	180

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₄O₆S)(C₁₀H₈N₂S)₂(H₂O)₂]·2H₂O
M_r	723.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	11.4649 (10), 13.9441 (12), 20.7051 (18)
β (°)	96.552 (1)
V (Å³)	3288.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.44 × 0.26 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.709, 0.866
No. of measured, independent and observed [I > 2σ(I)] reflections	23823, 6054, 4328
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.178, 1.03
No. of reflections	6054
No. of parameters	426
No. of restraints	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.96, −0.58

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Ni1—O9	1.981 (3)	Ni1—N3	2.055 (4)
Ni1—N4ⁱ	2.040 (3)	Ni1—O2	2.430 (3)
Ni1—N1	2.041 (4)	Ni1—O5	2.437 (3)

O9—Ni1—N4ⁱ	173.60 (14)	N1—Ni1—O2	87.06 (14)
O9—Ni1—N1	88.00 (13)	O9—Ni1—O5	80.75 (12)
O9—Ni1—N3	87.87 (13)	N1—Ni1—O5	93.08 (14)
N1—Ni1—N3	175.23 (14)	O2—Ni1—O5	173.73 (12)
O9—Ni1—O2	92.99 (12)

Symmetry code: (i) −x+1/2, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O10	0.82	1.84	2.535 (5)	141.9
O5—H10W···O3ⁱⁱ	0.83	1.98	2.797 (5)	170.3
O5—H9W···O4ⁱⁱⁱ	0.85	2.04	2.721 (8)	136.4
O4—H7W···O8^iv	0.83	2.30	2.713 (9)	111.6
O3—H6W···O6^v	0.83	2.10	2.811 (7)	143.3
O3—H5W···O6^vi	0.83	2.24	2.765 (8)	121.5
O2—H4W···O10	0.83	1.95	2.690 (5)	148.9
O2—H3W···O7^v	0.84	1.87	2.652 (7)	154.7
O1—H1W···O11^vii	0.85	2.03	2.876 (7)	179.7

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20471026) and the Natural Science Foundation of Henan Province (No. 0311021200).

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