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

Abstract

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,

• a = 16.057 (3) Å

• b = 6.3709 (10) Å

• c = 15.630 (3) Å

• β = 95.393 (4)°

• V = 1591.8 (5) ų

• 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[F ² > 2σ(F ²)] = 0.028

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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%.

Refinement

H atoms could be located from difference Fourier maps, but were subsequently placed in calculated positions and treated as riding, with C–H = 0.93 (aromatic), 0.97 (methylene) and O–H = 0.82 Å. All H atoms were allocated displacement parameters related to those of their parent atoms [U_iso(H) = 1.2 U_eq(C, O)].

Figures

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.

Crystal data

[Zn(C7H6NO2S)2(H2O)]	F(000) = 856
Mr = 419.76	Dx = 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

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

Refinement

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(Fo2) + (0.0333P)2 + 2.8608P] where P = (Fo2 + 2Fc2)/3
1403 reflections	(Δ/σ)max < 0.001
110 parameters	Δρmax = 0.57 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

Zn1—O3	2.119 (3)	O2—Zn1iv	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—Zn1iv	2.398 (3)	C6—H6B	0.9700
O2—C7	1.231 (4)
O3—Zn1—N1	91.34 (5)	C7—O2—Zn1iv	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—Zn1iv	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)	Zn1iv—O2—C7—O1	−0.1 (3)
O1ii—Zn1—N1—C3	−131.3 (2)	Zn1iv—O2—C7—C6	−177.97 (17)
O1iii—Zn1—N1—C3	154.3 (2)	Zn1iv—O1—C7—O2	0.1 (3)
C6—S1—C1—C2	−1.8 (3)	Zn1iv—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, °)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3'···O1v	0.82	2.18	2.754 (3)	128

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