Poly[aqua­bis­[μ2-2-(pyridin-4-ylsulfan­yl)acetato]­zinc]

Wang, Z.-C.; Ding, B.; Wang, X.-G.; Zhao, X.-J.

doi:10.1107/S1600536811024512

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m995

doi:10.1107/S1600536811024512

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Poly[aquabis[μ₂-2-(pyridin-4-ylsulfanyl)acetato]zinc]

Zhi-Chao Wang,^a Bo Ding,^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 25 May 2011; accepted 22 June 2011; online 30 June 2011)

The crystal structure of the title complex, [Zn(C₇H₆NO₂S)₂(H₂O)]_n, consists of extended layers parallel to (001) with 2-(pyridin-4-ylsulfanyl)acetate ligands bridging the Zn^II atoms. The Zn^II atom shows a distorted pentagonal–bipyramidal coordination environment. The Zn^II and one O atom are situated on a crystallographic twofold rotation axis. In the crystal, intralayer O—H⋯O hydrogen-bond interactions help to consolidate the coordination layer.

Related literature

For metal complexes with polycarboxylate aromatic ligands and their applications, see: Yang et al. (2007 , 2010 ); Yu et al. (2010 ). For solid-state structures of metal complexes with pyridine-4-sulfanyl-acetate ligands, see Wang et al. (2011 ); Kondo et al. (2002 ).

Experimental

Crystal data

[Zn(C₇H₆NO₂S)₂(H₂O)]
M_r = 419.76
Monoclinic, C 2/c
a = 16.057 (3) Å
b = 6.3709 (10) Å
c = 15.630 (3) Å
β = 95.393 (4)°
V = 1591.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.83 mm⁻¹
T = 296 K
0.20 × 0.17 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.711, T_max = 0.758
3842 measured reflections
1403 independent reflections
1308 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.04
1403 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3′⋯O1ⁱ	0.82	2.18	2.754 (3)	128
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536811024512/im2292sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024512/im2292Isup2.hkl

checkCIF report

Comment top

Recently, metal complexes constructed from aromatic polycarboxylate ligands and transition metal ions have received more and more interest due to their interesting architectures, amazing topologies and potentially technological applications in magnetism (Yang et al. 2010), luminesence (Yang et al. 2007) and gas storage (Yu et al. 2010). The anionic pyridine-4-sulfanyl-acetate ligand has three different potential binding sites upon coordination with metal ions and has exhibited various binding modes through the pyridyl N atom or carboxylate O donors. As a result, diverse complexes with discrete mononuclear (Wang et al. 2011), polymeric one-dimensional chains or two-dimensional layers (Kondo et al. 2002) have been obtained up to date. As a continuation of this research the crystal structure of a Zn^II complex with pyridine-4-sulfanyl-acetate ligands, (I), is reported herein.

A cut-out of the polymeric structure of the title compound showing one Zn^II atom in it's complete coordination environment is shown in Fig. 1. The Zn^II atom exhibits a distorted pentagonal bipyramidal coordination environment involving two pyridyl N atoms from two separate pyridine-4-sulfanyl-acetate ligands in trans-position, four O atoms from a pair of chelating carboxylate groups of pyridine-4-sulfanyl-acetate ligands and one O atom of a terminal water molecule. Each anionic pyridine-4-sulfanyl-acetate ligand acts as a ditopic connector to bridge adjacent Zn^II ions by a pyridyl N donor and a bidentate chelating carboxylate to generate a two-dimensional (4, 4) coordination layer with a Zn··· Zn distance of 6.3709 (10) Å. Additionally, O—H ···O hydrogen bonds between the coordinated water molecule and the deprotonated carboxylate (Table 1) help to consolidate the two-dimensional covalent layer (Fig. 2).

Related literature top

For metal complexes with polycarboxylate aromatic ligands and their applications, see: Yang et al. (2007, 2010); Yu et al. (2010). For solid-state structures of metal complexes with pyridine-4-sulfanyl-acetate ligands, see Wang et al. (2011); Kondo et al. (2002).

Experimental top

A methanolic solution of pyridine-4-sulfanyl-acetic acid (50.6 mg, 0.2 mmol) was carefully layered onto a buffer layer of ethyl acetate (2.0 ml) in a straight glass tube below which an aqueous solution containing Zn(NO₃)₂.6 H₂O (44.6 mg, 0.15 mmol) was placed. The test tube was left in air at room temperature. Colorless block-shaped crystals were harvested within three weeks. Yield: 40% based on Zn^II salt. Anal. Calcd. for C₁₄H₁₄ZnN₂O₅S₂: C, 40.06; H, 3.36; N, 6.67%. Found: C, 40.12; H, 3.26; N, 6.73%.

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. A portion of the two-dimensional structure of the title comlex. Displacement ellipsoids are drawn at the 30% probablity level. [Symmetry code: (A) 1 – x, y, 0.5 – z; (B) 1/2 + x, y, 0.5 – z; (C) 1/2 - x, 1/2 + y, 0.5 – z]
	Fig. 2. Part of the two-dimensional chain of (I), with hydrogen bonds shown as dashed lines.

Poly[aquabis[µ₂-2-(pyridin-4-ylsulfanyl)acetato]zinc] top

Crystal data top

[Zn(C₇H₆NO₂S)₂(H₂O)]	F(000) = 856
M_r = 419.76	D_x = 1.752 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3018 reflections
a = 16.057 (3) Å	θ = 2.6–27.8°
b = 6.3709 (10) Å	µ = 1.83 mm⁻¹
c = 15.630 (3) Å	T = 296 K
β = 95.393 (4)°	Block, colourless
V = 1591.8 (5) Å³	0.20 × 0.17 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1403 independent reflections
Radiation source: fine-focus sealed tube	1308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→8
T_min = 0.711, T_max = 0.758	k = −7→7
3842 measured reflections	l = −17→18

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0333P)² + 2.8608P] where P = (F_o² + 2F_c²)/3
1403 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Zn(C₇H₆NO₂S)₂(H₂O)]	V = 1591.8 (5) Å³
M_r = 419.76	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.057 (3) Å	µ = 1.83 mm⁻¹
b = 6.3709 (10) Å	T = 296 K
c = 15.630 (3) Å	0.20 × 0.17 × 0.16 mm
β = 95.393 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1403 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1308 reflections with I > 2σ(I)
T_min = 0.711, T_max = 0.758	R_int = 0.016
3842 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.04	Δρ_max = 0.57 e Å⁻³
1403 reflections	Δρ_min = −0.34 e Å⁻³
110 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
Zn1	0.5000	0.96825 (6)	0.2500	0.03315 (15)
S1	0.12091 (5)	0.98792 (11)	0.03086 (5)	0.0547 (2)
N1	0.37305 (12)	0.9762 (3)	0.19086 (13)	0.0350 (4)
O1	0.03140 (13)	0.7681 (4)	0.16602 (14)	0.0766 (7)
O2	0.05159 (15)	0.4525 (4)	0.12413 (14)	0.0710 (7)
O3	0.5000	0.6356 (4)	0.2500	0.0511 (7)
H3'	0.4845	0.5927	0.2954	0.077*
C1	0.21478 (15)	0.9755 (4)	0.09745 (16)	0.0366 (5)
C2	0.24687 (15)	0.7966 (4)	0.13868 (17)	0.0429 (6)
H2	0.2162	0.6726	0.1360	0.051*
C3	0.32493 (15)	0.8043 (4)	0.18384 (17)	0.0445 (6)
H3	0.3454	0.6825	0.2111	0.053*
C4	0.34017 (16)	1.1504 (4)	0.15408 (17)	0.0432 (6)
H4	0.3713	1.2735	0.1597	0.052*
C5	0.26277 (16)	1.1574 (4)	0.10832 (18)	0.0458 (6)
H5	0.2425	1.2835	0.0846	0.055*
C6	0.08449 (15)	0.7230 (4)	0.02936 (15)	0.0384 (5)
H6A	0.0389	0.7099	−0.0156	0.046*
H6B	0.1294	0.6325	0.0142	0.046*
C7	0.05446 (15)	0.6435 (5)	0.11276 (16)	0.0481 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0299 (2)	0.0337 (2)	0.0348 (2)	0.000	−0.00208 (15)	0.000
S1	0.0409 (4)	0.0454 (4)	0.0725 (5)	−0.0058 (3)	−0.0227 (3)	0.0140 (3)
N1	0.0325 (10)	0.0370 (11)	0.0346 (10)	−0.0009 (8)	−0.0018 (8)	0.0017 (8)
O1	0.0574 (13)	0.121 (2)	0.0539 (12)	−0.0035 (13)	0.0178 (10)	−0.0277 (13)
O2	0.0762 (16)	0.0738 (16)	0.0580 (13)	−0.0330 (13)	−0.0205 (11)	0.0193 (11)
O3	0.0532 (16)	0.0350 (13)	0.0644 (17)	0.000	0.0022 (13)	0.000
C1	0.0305 (12)	0.0402 (13)	0.0383 (12)	−0.0005 (10)	−0.0013 (10)	0.0013 (10)
C2	0.0331 (13)	0.0370 (14)	0.0574 (15)	−0.0068 (10)	−0.0020 (11)	0.0082 (12)
C3	0.0362 (13)	0.0403 (14)	0.0554 (15)	−0.0010 (11)	−0.0040 (11)	0.0138 (12)
C4	0.0401 (13)	0.0344 (13)	0.0529 (15)	−0.0055 (11)	−0.0067 (11)	0.0005 (11)
C5	0.0428 (14)	0.0321 (13)	0.0598 (16)	0.0004 (11)	−0.0101 (12)	0.0059 (12)
C6	0.0336 (12)	0.0466 (14)	0.0341 (12)	−0.0047 (11)	−0.0023 (9)	−0.0056 (10)
C7	0.0284 (12)	0.077 (2)	0.0368 (13)	−0.0153 (13)	−0.0071 (10)	−0.0071 (14)

Geometric parameters (Å, º) top

Zn1—O3	2.119 (3)	O2—Zn1^iv	2.208 (3)
Zn1—N1	2.158 (2)	O3—H3'	0.8200
Zn1—N1ⁱ	2.158 (2)	C1—C2	1.384 (3)
Zn1—O2ⁱⁱ	2.208 (3)	C1—C5	1.393 (3)
Zn1—O2ⁱⁱⁱ	2.208 (3)	C2—C3	1.380 (3)
Zn1—O1ⁱⁱ	2.398 (3)	C2—H2	0.9300
Zn1—O1ⁱⁱⁱ	2.398 (3)	C3—H3	0.9300
S1—C1	1.751 (2)	C4—C5	1.375 (4)
S1—C6	1.786 (3)	C4—H4	0.9300
N1—C4	1.336 (3)	C5—H5	0.9300
N1—C3	1.338 (3)	C6—C7	1.519 (4)
O1—C7	1.232 (4)	C6—H6A	0.9700
O1—Zn1^iv	2.398 (3)	C6—H6B	0.9700
O2—C7	1.231 (4)

O3—Zn1—N1	91.34 (5)	C7—O2—Zn1^iv	96.1 (2)
O3—Zn1—N1ⁱ	91.34 (5)	Zn1—O3—H3'	109.5
N1—Zn1—N1ⁱ	177.32 (10)	C2—C1—C5	116.8 (2)
O3—Zn1—O2ⁱⁱ	87.40 (6)	C2—C1—S1	125.16 (19)
N1—Zn1—O2ⁱⁱ	87.95 (8)	C5—C1—S1	118.04 (19)
N1ⁱ—Zn1—O2ⁱⁱ	92.17 (8)	C3—C2—C1	119.3 (2)
O3—Zn1—O2ⁱⁱⁱ	87.40 (6)	C3—C2—H2	120.4
N1—Zn1—O2ⁱⁱⁱ	92.17 (8)	C1—C2—H2	120.4
N1ⁱ—Zn1—O2ⁱⁱⁱ	87.96 (8)	N1—C3—C2	124.1 (2)
O2ⁱⁱ—Zn1—O2ⁱⁱⁱ	174.79 (13)	N1—C3—H3	118.0
O3—Zn1—O1ⁱⁱ	142.81 (5)	C2—C3—H3	118.0
N1—Zn1—O1ⁱⁱ	88.69 (8)	N1—C4—C5	123.5 (2)
N1ⁱ—Zn1—O1ⁱⁱ	89.18 (7)	N1—C4—H4	118.2
O2ⁱⁱ—Zn1—O1ⁱⁱ	55.43 (8)	C5—C4—H4	118.2
O2ⁱⁱⁱ—Zn1—O1ⁱⁱ	129.77 (8)	C4—C5—C1	119.9 (2)
O3—Zn1—O1ⁱⁱⁱ	142.81 (5)	C4—C5—H5	120.0
N1—Zn1—O1ⁱⁱⁱ	89.18 (7)	C1—C5—H5	120.0
N1ⁱ—Zn1—O1ⁱⁱⁱ	88.69 (8)	C7—C6—S1	115.73 (18)
O2ⁱⁱ—Zn1—O1ⁱⁱⁱ	129.78 (8)	C7—C6—H6A	108.3
O2ⁱⁱⁱ—Zn1—O1ⁱⁱⁱ	55.43 (8)	S1—C6—H6A	108.3
O1ⁱⁱ—Zn1—O1ⁱⁱⁱ	74.38 (11)	C7—C6—H6B	108.3
C1—S1—C6	103.16 (11)	S1—C6—H6B	108.3
C4—N1—C3	116.3 (2)	H6A—C6—H6B	107.4
C4—N1—Zn1	121.53 (16)	O2—C7—O1	121.4 (3)
C3—N1—Zn1	122.05 (16)	O2—C7—C6	118.2 (3)
C7—O1—Zn1^iv	87.0 (2)	O1—C7—C6	120.3 (3)

O3—Zn1—N1—C4	−163.91 (19)	C4—N1—C3—C2	2.8 (4)
N1ⁱ—Zn1—N1—C4	16.09 (19)	Zn1—N1—C3—C2	−172.8 (2)
O2ⁱⁱ—Zn1—N1—C4	108.7 (2)	C1—C2—C3—N1	0.0 (4)
O2ⁱⁱⁱ—Zn1—N1—C4	−76.5 (2)	C3—N1—C4—C5	−2.4 (4)
O1ⁱⁱ—Zn1—N1—C4	53.3 (2)	Zn1—N1—C4—C5	173.3 (2)
O1ⁱⁱⁱ—Zn1—N1—C4	−21.1 (2)	N1—C4—C5—C1	−0.9 (4)
O3—Zn1—N1—C3	11.5 (2)	C2—C1—C5—C4	3.7 (4)
N1ⁱ—Zn1—N1—C3	−168.5 (2)	S1—C1—C5—C4	−174.5 (2)
O2ⁱⁱ—Zn1—N1—C3	−75.8 (2)	C1—S1—C6—C7	70.1 (2)
O2ⁱⁱⁱ—Zn1—N1—C3	99.0 (2)	Zn1^iv—O2—C7—O1	−0.1 (3)
O1ⁱⁱ—Zn1—N1—C3	−131.3 (2)	Zn1^iv—O2—C7—C6	−177.97 (17)
O1ⁱⁱⁱ—Zn1—N1—C3	154.3 (2)	Zn1^iv—O1—C7—O2	0.1 (3)
C6—S1—C1—C2	−1.8 (3)	Zn1^iv—O1—C7—C6	177.9 (2)
C6—S1—C1—C5	176.2 (2)	S1—C6—C7—O2	−159.5 (2)
C5—C1—C2—C3	−3.2 (4)	S1—C6—C7—O1	22.6 (3)
S1—C1—C2—C3	174.8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3′···O1^v	0.82	2.18	2.754 (3)	128

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₆NO₂S)₂(H₂O)]
M_r	419.76
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	16.057 (3), 6.3709 (10), 15.630 (3)
β (°)	95.393 (4)
V (Å³)	1591.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.83
Crystal size (mm)	0.20 × 0.17 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.711, 0.758
No. of measured, independent and observed [I > 2σ(I)] reflections	3842, 1403, 1308
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.04
No. of reflections	1403
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.34

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—H3'···O1ⁱ	0.82	2.18	2.754 (3)	128

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

Acknowledgements

The authors gratefully acknowledge financial support from Tianjin Normal University.

References

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