Tetra­aqua­bis­[2-(4-pyridyl­sulfan­yl)acetato-κN]nickel(II)

Wang, J.-Y.; Wang, X.-G.; Zhao, X.-J.

doi:10.1107/S1600536811019131

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page m795

doi:10.1107/S1600536811019131

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Tetraaquabis[2-(4-pyridylsulfanyl)acetato-κN]nickel(II)

Jing-Yi Wang,^a Xiu-Guang Wang ^a and Xiao-Jun Zhao ^a ^*

^aCollege of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: xiaojun_zhao15@yahoo.com.cn

(Received 15 May 2011; accepted 19 May 2011; online 25 May 2011)

In the centrosymmetric title complex, [Ni(C₇H₆NO₂S)₂(H₂O)₄], the Ni^II atom, located on a centre of inversion, is coordinated by two N atoms from two 2-(4-pyridylsulfanyl)acetate ligands and four water O atoms in an octahedral geometry. In the crystal, intermolecular O—H⋯O hydrogen bonds between the coordinated water molecules and the carboxylate group of the anionic 2-(4-pyridylsulfanyl)acetate ligands link these discrete mononuclear units into a three-dimensional network.

Related literature

For structures and applications of metal complexes with polycarboxylate-based pyridine ligands, see: Zhao et al. (2010 ); Wang et al. (2007 ). For metal complexes with 2-(4-pyridylsulfanyl)acetate ligands, see: Kondo et al. (2002 ); Zhang et al. (2004 ); Qin et al. (2004 ).

Experimental

Crystal data

[Ni(C₇H₆NO₂S)₂(H₂O)₄]
M_r = 467.15
Triclinic, $[P \overline 1]$
a = 6.3577 (4) Å
b = 7.0330 (5) Å
c = 11.7624 (8) Å
α = 92.713 (1)°
β = 103.440 (1)°
γ = 115.120 (1)°
V = 456.75 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.34 mm⁻¹
T = 296 K
0.22 × 0.20 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.758, T_max = 0.835
2358 measured reflections
1610 independent reflections
1525 reflections with I > 2σ(I)
R_int = 0.008

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.061
S = 1.05
1610 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.85	2.13	2.951 (2)	161
O3—H3B⋯O1ⁱⁱ	0.85	1.92	2.7265 (18)	158
O4—H4A⋯O1ⁱⁱⁱ	0.85	1.83	2.6697 (18)	168
O4—H4B⋯O2^iv	0.85	2.01	2.855 (2)	172
Symmetry codes: (i) x-1, y, z-1; (ii) x, y, z-1; (iii) -x+1, -y, -z+1; (iv) x-1, y-1, z-1.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001); 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) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811019131/bt5549sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811019131/bt5549Isup2.hkl

checkCIF report

Comment top

Recently, functional metal complexes with polycarboxylate-based pyridine ligands have gained more and more interest due to their intriguing structures and potential applications in magnetism (Zhao et al. 2010), and luminescence (Wang et al. 2007). Acting as one of flexible multifunctional building blocks, 2-(4-pyridylsulfanyl)acetic acid with three potential metal binding sites and various flexible connection modes (Kondo et al., 2002; Zhang et al., 2004; Qin et al., 2004) has been extensively used to construct novel metal complexes with discrete mononuclear structure or polymeric coordination framework with variable dimensionality. Herein, as the continuing investigations on the coordination chemistry of the ligand, we report the crystal structure of a tetraaquonickel(II) complex with deprotonated 2-(4-pyridylsulfanyl)acetate ligand, (I).

The molecular structure of the title mononuclear complex is show Fig.1 and selected bond lengths and angles are listed in Table 1. The Ni^II atom in the mononuclear structure of I lies on an inversion centre and is in a octahedral coordination environment involving two pyridyl N atoms from two different 2-(4-pyridylsulfanyl)acetate ligand and four O donors from four water molecules. In the crystal structure, four intermolecular O—H···O hydrogen bonds between the coordinated water molecules and the carboxylate group of 2-(4-pyridylsulfanyl)acetate ligand link adjacent mononuclear structures into a three-dimensional supramolecular network (Fig.2 and Table 2).

Related literature top

For structures and applications of metal complexes with polycarboxylate-based pyridine ligands, see Zhao et al. (2010); Wang et al. (2007). For metal complexes with 2-(4-pyridylsulfanyl)acetate ligands, see: Kondo et al. (2002); Zhang et al. (2004); Qin et al. (2004).

Experimental top

A methanol solution of 2-(4-pyridylsulfanyl)acetic acid (25.3 mg, 0.1 mmol) was carefully layered onto a buffer layer of ethyl acetate (2.0 ml) in a straight glass tube, meanwhile the pH value of the top layer was carefully adjusted to 7.0 by slow addition of triethylamine. Below which an aqueous solution containing NiCl₂.6H₂O (23.7 mg, 0.1 mmol) was placed. The test tube was left in air under room temperature. Blue block-shaped crystals were harvested within three weeks. Yield: 50% based on 2-(4-pyridylsulfanyl)acetic acid. Anal. Calcd. for C₁₄H₂₀N₂NiO₈S₂: C, 36.00; H, 4.32; N, 6.00%. Found: C, 35.98; H, 4.34; N, 6.03%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probablity level. [Symmetry code: (A) –x, –y, –z.]
	Fig. 2. Crystal packing of the title compound, showing O—H···O hydrogen bonds as dashed lines. Only H atoms involved in hydrogen bonds have been included.

Tetraaquabis[2-(4-pyridylsulfanyl)acetato-κN]nickel(II) top

Crystal data top

[Ni(C₇H₆NO₂S)₂(H₂O)₄]	Z = 1
M_r = 467.15	F(000) = 242
Triclinic, P1	D_x = 1.698 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3577 (4) Å	Cell parameters from 2208 reflections
b = 7.0330 (5) Å	θ = 3.2–27.8°
c = 11.7624 (8) Å	µ = 1.34 mm⁻¹
α = 92.713 (1)°	T = 296 K
β = 103.440 (1)°	Block, blue
γ = 115.120 (1)°	0.22 × 0.20 × 0.14 mm
V = 456.75 (5) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	1610 independent reflections
Radiation source: fine-focus sealed tube	1525 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.008
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
T_min = 0.758, T_max = 0.835	k = −5→8
2358 measured reflections	l = −13→13

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0331P)² + 0.2312P] where P = (F_o² + 2F_c²)/3
1610 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Ni(C₇H₆NO₂S)₂(H₂O)₄]	γ = 115.120 (1)°
M_r = 467.15	V = 456.75 (5) Å³
Triclinic, P1	Z = 1
a = 6.3577 (4) Å	Mo Kα radiation
b = 7.0330 (5) Å	µ = 1.34 mm⁻¹
c = 11.7624 (8) Å	T = 296 K
α = 92.713 (1)°	0.22 × 0.20 × 0.14 mm
β = 103.440 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1610 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1525 reflections with I > 2σ(I)
T_min = 0.758, T_max = 0.835	R_int = 0.008
2358 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.05	Δρ_max = 0.22 e Å⁻³
1610 reflections	Δρ_min = −0.28 e Å⁻³
124 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	0.0000	0.0000	0.0000	0.02365 (11)
S1	0.72786 (9)	0.33945 (8)	0.54727 (4)	0.03489 (14)
O1	0.5787 (3)	0.2690 (3)	0.84929 (12)	0.0430 (4)
O2	0.9194 (3)	0.4387 (2)	0.79704 (12)	0.0423 (4)
O3	0.2259 (2)	0.2716 (2)	−0.05684 (11)	0.0347 (3)
H3A	0.1377	0.3317	−0.0833	0.052*
H3B	0.3544	0.3065	−0.0783	0.052*
O4	0.1770 (2)	−0.1742 (2)	−0.03636 (11)	0.0302 (3)
H4A	0.2585	−0.1876	0.0284	0.045*
H4B	0.0891	−0.2861	−0.0878	0.045*
N1	0.2203 (3)	0.1150 (2)	0.17292 (13)	0.0275 (3)
C1	0.5198 (3)	0.2521 (3)	0.40628 (15)	0.0268 (4)
C2	0.2691 (3)	0.1584 (3)	0.38241 (16)	0.0307 (4)
H2	0.1970	0.1401	0.4440	0.037*
C3	0.1292 (3)	0.0933 (3)	0.26627 (16)	0.0315 (4)
H3	−0.0381	0.0307	0.2517	0.038*
C4	0.4625 (3)	0.2085 (3)	0.19676 (16)	0.0313 (4)
H4	0.5298	0.2269	0.1334	0.038*
C5	0.6160 (3)	0.2784 (3)	0.30962 (16)	0.0312 (4)
H5	0.7827	0.3427	0.3216	0.037*
C6	0.5391 (3)	0.2753 (3)	0.64667 (15)	0.0301 (4)
H6A	0.4421	0.3520	0.6348	0.036*
H6B	0.4304	0.1240	0.6296	0.036*
C7	0.6951 (3)	0.3354 (3)	0.77521 (16)	0.0306 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02087 (17)	0.03278 (19)	0.01705 (17)	0.01169 (14)	0.00582 (12)	0.00240 (12)
S1	0.0305 (3)	0.0442 (3)	0.0201 (2)	0.0099 (2)	0.00367 (18)	0.0011 (2)
O1	0.0413 (8)	0.0722 (10)	0.0279 (7)	0.0330 (8)	0.0153 (6)	0.0169 (7)
O2	0.0346 (8)	0.0547 (9)	0.0266 (7)	0.0118 (7)	0.0058 (6)	0.0018 (6)
O3	0.0292 (7)	0.0405 (7)	0.0353 (7)	0.0138 (6)	0.0139 (6)	0.0101 (6)
O4	0.0297 (6)	0.0415 (7)	0.0210 (6)	0.0189 (6)	0.0049 (5)	0.0013 (5)
N1	0.0264 (8)	0.0353 (8)	0.0218 (7)	0.0146 (7)	0.0075 (6)	0.0035 (6)
C1	0.0321 (9)	0.0247 (8)	0.0219 (9)	0.0131 (7)	0.0044 (7)	0.0015 (7)
C2	0.0327 (10)	0.0376 (10)	0.0221 (9)	0.0146 (8)	0.0104 (7)	0.0042 (8)
C3	0.0272 (9)	0.0424 (11)	0.0244 (9)	0.0147 (8)	0.0081 (8)	0.0039 (8)
C4	0.0304 (10)	0.0406 (10)	0.0228 (9)	0.0146 (8)	0.0103 (7)	0.0028 (8)
C5	0.0254 (9)	0.0374 (10)	0.0270 (9)	0.0115 (8)	0.0066 (7)	0.0011 (8)
C6	0.0337 (10)	0.0320 (9)	0.0237 (9)	0.0143 (8)	0.0070 (8)	0.0055 (7)
C7	0.0361 (10)	0.0358 (10)	0.0233 (9)	0.0198 (9)	0.0073 (8)	0.0041 (7)

Geometric parameters (Å, º) top

Ni1—O4	2.0727 (12)	N1—C3	1.342 (2)
Ni1—O4ⁱ	2.0727 (12)	N1—C4	1.344 (2)
Ni1—N1	2.0762 (15)	C1—C2	1.392 (3)
Ni1—N1ⁱ	2.0762 (15)	C1—C5	1.396 (3)
Ni1—O3ⁱ	2.0967 (13)	C2—C3	1.377 (3)
Ni1—O3	2.0967 (13)	C2—H2	0.9300
S1—C1	1.7524 (18)	C3—H3	0.9300
S1—C6	1.8035 (19)	C4—C5	1.373 (3)
O1—C7	1.253 (2)	C4—H4	0.9300
O2—C7	1.249 (2)	C5—H5	0.9300
O3—H3A	0.8501	C6—C7	1.528 (3)
O3—H3B	0.8503	C6—H6A	0.9700
O4—H4A	0.8501	C6—H6B	0.9700
O4—H4B	0.8501

O4—Ni1—O4ⁱ	179.999 (1)	C2—C1—C5	117.45 (16)
O4—Ni1—N1	92.68 (5)	C2—C1—S1	125.97 (14)
O4ⁱ—Ni1—N1	87.32 (5)	C5—C1—S1	116.57 (14)
O4—Ni1—N1ⁱ	87.32 (5)	C3—C2—C1	119.08 (17)
O4ⁱ—Ni1—N1ⁱ	92.68 (5)	C3—C2—H2	120.5
N1—Ni1—N1ⁱ	180.0	C1—C2—H2	120.5
O4—Ni1—O3ⁱ	86.23 (5)	N1—C3—C2	123.81 (17)
O4ⁱ—Ni1—O3ⁱ	93.77 (5)	N1—C3—H3	118.1
N1—Ni1—O3ⁱ	89.32 (5)	C2—C3—H3	118.1
N1ⁱ—Ni1—O3ⁱ	90.69 (5)	N1—C4—C5	123.50 (17)
O4—Ni1—O3	93.77 (5)	N1—C4—H4	118.3
O4ⁱ—Ni1—O3	86.23 (5)	C5—C4—H4	118.3
N1—Ni1—O3	90.69 (5)	C4—C5—C1	119.45 (17)
N1ⁱ—Ni1—O3	89.31 (5)	C4—C5—H5	120.3
O3ⁱ—Ni1—O3	180.0	C1—C5—H5	120.3
C1—S1—C6	103.65 (9)	C7—C6—S1	110.25 (13)
Ni1—O3—H3A	105.2	C7—C6—H6A	109.6
Ni1—O3—H3B	134.1	S1—C6—H6A	109.6
H3A—O3—H3B	117.1	C7—C6—H6B	109.6
Ni1—O4—H4A	109.3	S1—C6—H6B	109.6
Ni1—O4—H4B	114.5	H6A—C6—H6B	108.1
H4A—O4—H4B	117.0	O2—C7—O1	126.41 (18)
C3—N1—C4	116.70 (16)	O2—C7—C6	119.17 (17)
C3—N1—Ni1	122.04 (12)	O1—C7—C6	114.39 (17)
C4—N1—Ni1	121.22 (12)

O4—Ni1—N1—C3	−125.81 (15)	C4—N1—C3—C2	−0.8 (3)
O4ⁱ—Ni1—N1—C3	54.19 (15)	Ni1—N1—C3—C2	176.86 (15)
O3ⁱ—Ni1—N1—C3	−39.62 (15)	C1—C2—C3—N1	−0.1 (3)
O3—Ni1—N1—C3	140.38 (15)	C3—N1—C4—C5	0.8 (3)
O4—Ni1—N1—C4	51.79 (15)	Ni1—N1—C4—C5	−176.94 (14)
O4ⁱ—Ni1—N1—C4	−128.21 (15)	N1—C4—C5—C1	0.2 (3)
O3ⁱ—Ni1—N1—C4	137.98 (15)	C2—C1—C5—C4	−1.2 (3)
O3—Ni1—N1—C4	−42.02 (15)	S1—C1—C5—C4	178.42 (14)
C6—S1—C1—C2	0.69 (19)	C1—S1—C6—C7	178.07 (12)
C6—S1—C1—C5	−178.92 (14)	S1—C6—C7—O2	8.2 (2)
C5—C1—C2—C3	1.2 (3)	S1—C6—C7—O1	−170.33 (14)
S1—C1—C2—C3	−178.44 (14)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱⁱ	0.85	2.13	2.951 (2)	161
O3—H3B···O1ⁱⁱⁱ	0.85	1.92	2.7265 (18)	158
O4—H4A···O1^iv	0.85	1.83	2.6697 (18)	168
O4—H4B···O2^v	0.85	2.01	2.855 (2)	172

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₆NO₂S)₂(H₂O)₄]
M_r	467.15
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.3577 (4), 7.0330 (5), 11.7624 (8)
α, β, γ (°)	92.713 (1), 103.440 (1), 115.120 (1)
V (Å³)	456.75 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.34
Crystal size (mm)	0.22 × 0.20 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.758, 0.835
No. of measured, independent and observed [I > 2σ(I)] reflections	2358, 1610, 1525
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.061, 1.05
No. of reflections	1610
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.85	2.13	2.951 (2)	161
O3—H3B···O1ⁱⁱ	0.85	1.92	2.7265 (18)	158
O4—H4A···O1ⁱⁱⁱ	0.85	1.83	2.6697 (18)	168
O4—H4B···O2^iv	0.85	2.01	2.855 (2)	172

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

Acknowledgements

The authors gratefully acknowledge financial support from Tianjin Normal University.

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