Diaqua­bis[3-(2-sulfanylphen­yl)prop-2-enoato]zinc(II) dihydrate

Wang, Q.; Hou, J.; Wang, L.-J.; Zeng, Q.-F.

doi:10.1107/S1600536809034473

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1183

doi:10.1107/S1600536809034473

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Diaquabis[3-(2-sulfanylphenyl)prop-2-enoato]zinc(II) dihydrate

Qiang Wang,^a Jian Hou,^a Li-Jun Wang ^a and Qing-Fu Zeng ^a ^*

^aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: qfzeng@wuse.edu.cn

(Received 27 August 2009; accepted 28 August 2009; online 9 September 2009)

In the title compound, [Zn(C₉H₇O₂S)₂(H₂O)₂]·2H₂O, the Zn^II atom (site symmetry $[\overline{1}]$ ) is four-coordinated by two O atoms from 3-(2-sulfanylphenyl)prop-2-enoate anions and two aqua O atoms in a slightly distorted ZnO₄ square-planar arrangement. In the crystal, O—H⋯O hydrogen bonds help to establish the packing.

Related literature

For background to coordination networks, see: Cheng et al., (2006 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Zn(C₉H₇O₂S)₂(H₂O)₂]·2H₂O
M_r = 495.85
Monoclinic, P 2₁ /c
a = 18.4398 (5) Å
b = 7.7188 (3) Å
c = 7.3258 (2) Å
β = 98.578 (2)°
V = 1031.04 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.14 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.673, T_max = 0.824
6272 measured reflections
1811 independent reflections
1441 reflections with I > 2σ(I)
R_int = 0.092
200 standard reflections every 3 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.185
S = 1.06
1811 reflections
146 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	1.969 (4)
Zn1—O3	1.953 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O4ⁱ	0.82 (4)	2.56 (5)	3.033 (7)	118 (5)
O3—H3B⋯O1ⁱⁱ	0.82 (4)	2.44 (5)	3.221 (6)	159 (4)
O4—H4A⋯O2	0.83 (3)	1.95 (4)	2.716 (7)	155 (5)
O4—H4B⋯O2ⁱⁱⁱ	0.83 (4)	2.30 (6)	2.951 (7)	136 (4)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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/S1600536809034473/hb5073sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034473/hb5073Isup2.hkl

checkCIF report

Comment top

There has been much research interest in acid metal complexes due to their molecular architectures and biological activities (e.g. Cheng et al., 2006). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The Zn^II atom is four-coordinated by two O atoms from the 3-(2-sulfanylphenyl)propanoate and two O atoms from the water molecules, forming a slightly distorted square-planar coordination.

Related literature top

For background to coordination networks, see: Cheng et al., (2006). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of 3-(2-sulfanylphenyl)propanoic acid (364 mg, 2 mmol) and ZnCl₂ (1 mmol, 134 mg) in methanol (10 ml) was stirred for 3 h. After keeping the filtrate in air for 7 d, colourless blocks of (I) were formed.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 (I) showing 30% probability displacement ellipsoids. Atoms with the suffix A are generated by the symmetry operation (2–x, 1–y, 1–z).

Diaquabis[3-(2-sulfanylphenyl)prop-2-enoato]zinc(II) dihydrate top

Crystal data top

[Zn(C₉H₇O₂S)₂(H₂O)₂]·2H₂O	F(000) = 512
M_r = 495.85	D_x = 1.597 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 18.4398 (5) Å	θ = 9–12°
b = 7.7188 (3) Å	µ = 1.44 mm⁻¹
c = 7.3258 (2) Å	T = 298 K
β = 98.578 (2)°	Block, colourless
V = 1031.04 (6) Å³	0.30 × 0.20 × 0.14 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1441 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.092
Graphite monochromator	θ_max = 25.0°, θ_min = 2.2°
ω/2θ scans	h = −21→18
Absorption correction: ψ scan (North et al., 1968)	k = −9→8
T_min = 0.673, T_max = 0.824	l = −8→8
6272 measured reflections	200 standard reflections every 3 reflections
1811 independent reflections	intensity decay: 1%

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.185	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.1071P)² + 0.9875P] where P = (F_o² + 2F_c²)/3
1811 reflections	(Δ/σ)_max = 0.001
146 parameters	Δρ_max = 0.93 e Å⁻³
6 restraints	Δρ_min = −0.88 e Å⁻³

Crystal data top

[Zn(C₉H₇O₂S)₂(H₂O)₂]·2H₂O	V = 1031.04 (6) Å³
M_r = 495.85	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.4398 (5) Å	µ = 1.44 mm⁻¹
b = 7.7188 (3) Å	T = 298 K
c = 7.3258 (2) Å	0.30 × 0.20 × 0.14 mm
β = 98.578 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1441 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.092
T_min = 0.673, T_max = 0.824	200 standard reflections every 3 reflections
6272 measured reflections	intensity decay: 1%
1811 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	6 restraints
wR(F²) = 0.185	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.93 e Å⁻³
1811 reflections	Δρ_min = −0.88 e Å⁻³
146 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
C1	0.6975 (3)	0.9228 (8)	0.6126 (7)	0.0401 (13)
C2	0.6254 (3)	0.8922 (8)	0.6435 (8)	0.0442 (14)
C3	0.5803 (4)	1.0275 (10)	0.6681 (10)	0.0590 (19)
H3	0.5327	1.0042	0.6892	0.071*
C4	0.6020 (4)	1.1926 (10)	0.6630 (11)	0.070 (2)
H4	0.5700	1.2818	0.6811	0.084*
C5	0.6739 (4)	1.2307 (10)	0.6300 (10)	0.066 (2)
H5	0.6898	1.3446	0.6253	0.079*
C6	0.7196 (3)	1.0945 (8)	0.6051 (9)	0.0500 (16)
H6	0.7669	1.1183	0.5825	0.060*
C7	0.7479 (3)	0.7796 (7)	0.5892 (7)	0.0374 (12)
H7	0.7326	0.6685	0.6150	0.045*
C8	0.8132 (3)	0.7942 (7)	0.5345 (7)	0.0361 (12)
H8	0.8281	0.9030	0.5003	0.043*
C9	0.8630 (3)	0.6463 (7)	0.5254 (7)	0.0354 (12)
H3A	1.0261 (19)	0.464 (7)	0.180 (6)	0.043*
H4A	0.866 (2)	0.294 (4)	0.419 (8)	0.043*
H3B	0.964 (2)	0.558 (6)	0.165 (6)	0.043*
H4B	0.861 (2)	0.133 (5)	0.346 (8)	0.043*
O1	0.92576 (19)	0.6850 (5)	0.4821 (5)	0.0401 (9)
O2	0.8441 (3)	0.4964 (5)	0.5594 (7)	0.0530 (12)
O3	0.9908 (3)	0.4908 (6)	0.2311 (6)	0.0499 (11)
O4	0.8892 (3)	0.2064 (6)	0.3989 (8)	0.0666 (13)
S1	0.59232 (9)	0.6819 (2)	0.6468 (3)	0.0601 (6)
H1	0.5970	0.6126	0.5024	0.090*
Zn1	1.0000	0.5000	0.5000	0.0327 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.038 (3)	0.044 (3)	0.039 (3)	0.008 (3)	0.008 (2)	−0.006 (3)
C2	0.040 (3)	0.050 (4)	0.045 (3)	0.005 (3)	0.013 (3)	0.001 (3)
C3	0.040 (4)	0.071 (5)	0.069 (5)	0.018 (3)	0.018 (3)	0.003 (4)
C4	0.063 (5)	0.062 (5)	0.088 (5)	0.033 (4)	0.020 (4)	−0.004 (4)
C5	0.078 (5)	0.042 (4)	0.079 (5)	0.013 (4)	0.021 (4)	−0.012 (3)
C6	0.040 (3)	0.041 (4)	0.072 (4)	0.005 (3)	0.017 (3)	−0.004 (3)
C7	0.034 (3)	0.034 (3)	0.045 (3)	0.005 (2)	0.008 (2)	0.002 (2)
C8	0.037 (3)	0.032 (3)	0.040 (3)	0.005 (2)	0.011 (2)	0.003 (2)
C9	0.037 (3)	0.038 (3)	0.032 (3)	0.007 (2)	0.009 (2)	−0.002 (2)
O1	0.032 (2)	0.045 (2)	0.045 (2)	0.0091 (16)	0.0099 (17)	0.0037 (17)
O2	0.052 (3)	0.035 (3)	0.075 (3)	0.0035 (19)	0.019 (2)	0.000 (2)
O3	0.062 (3)	0.052 (3)	0.040 (2)	0.017 (2)	0.021 (2)	0.0060 (18)
O4	0.074 (3)	0.049 (3)	0.082 (4)	0.014 (2)	0.030 (3)	−0.004 (3)
S1	0.0465 (9)	0.0555 (11)	0.0842 (13)	−0.0072 (8)	0.0287 (9)	0.0035 (9)
Zn1	0.0348 (6)	0.0360 (6)	0.0300 (5)	0.0075 (4)	0.0139 (4)	0.0046 (3)

Geometric parameters (Å, º) top

C1—C6	1.390 (10)	C8—C9	1.473 (7)
C1—C2	1.402 (8)	C8—H8	0.9300
C1—C7	1.470 (8)	C9—O2	1.245 (6)
C2—C3	1.364 (9)	C9—O1	1.280 (6)
C2—S1	1.735 (7)	Zn1—O1	1.969 (4)
C3—C4	1.338 (10)	Zn1—O3	1.953 (4)
C3—H3	0.9300	O3—H3A	0.824 (10)
C4—C5	1.413 (11)	O3—H3B	0.823 (10)
C4—H4	0.9300	O4—H4A	0.821 (10)
C5—C6	1.376 (9)	O4—H4B	0.819 (10)
C5—H5	0.9300	S1—H1	1.2000
C6—H6	0.9300	Zn1—O3ⁱ	1.953 (4)
C7—C8	1.330 (7)	Zn1—O1ⁱ	1.969 (4)
C7—H7	0.9300

C6—C1—C2	117.2 (5)	C1—C7—H7	117.0
C6—C1—C7	121.3 (5)	C7—C8—C9	123.2 (5)
C2—C1—C7	121.5 (6)	C7—C8—H8	118.4
C3—C2—C1	120.3 (6)	C9—C8—H8	118.4
C3—C2—S1	119.4 (5)	O2—C9—O1	123.9 (5)
C1—C2—S1	120.3 (5)	O2—C9—C8	121.0 (5)
C4—C3—C2	122.3 (7)	O1—C9—C8	115.0 (5)
C4—C3—H3	118.9	C9—O1—Zn1	117.3 (4)
C2—C3—H3	118.9	Zn1—O3—H3A	121 (4)
C3—C4—C5	119.7 (6)	Zn1—O3—H3B	121 (4)
C3—C4—H4	120.1	H3A—O3—H3B	110.2 (18)
C5—C4—H4	120.1	H4A—O4—H4B	110.3 (18)
C6—C5—C4	118.2 (7)	C2—S1—H1	109.5
C6—C5—H5	120.9	O3ⁱ—Zn1—O3	180.0
C4—C5—H5	120.9	O3ⁱ—Zn1—O1ⁱ	90.25 (17)
C5—C6—C1	122.3 (6)	O3—Zn1—O1ⁱ	89.75 (17)
C5—C6—H6	118.8	O3ⁱ—Zn1—O1	89.75 (17)
C1—C6—H6	118.8	O3—Zn1—O1	90.25 (17)
C8—C7—C1	126.0 (5)	O1ⁱ—Zn1—O1	180.0
C8—C7—H7	117.0

C6—C1—C2—C3	−1.1 (9)	C7—C1—C6—C5	−178.8 (6)
C7—C1—C2—C3	178.8 (6)	C6—C1—C7—C8	−10.0 (9)
C6—C1—C2—S1	177.7 (4)	C2—C1—C7—C8	170.1 (6)
C7—C1—C2—S1	−2.4 (8)	C1—C7—C8—C9	175.9 (5)
C1—C2—C3—C4	0.4 (11)	C7—C8—C9—O2	4.1 (8)
S1—C2—C3—C4	−178.5 (6)	C7—C8—C9—O1	−175.4 (5)
C2—C3—C4—C5	0.4 (12)	O2—C9—O1—Zn1	−7.6 (7)
C3—C4—C5—C6	−0.4 (11)	C8—C9—O1—Zn1	171.9 (3)
C4—C5—C6—C1	−0.4 (10)	C9—O1—Zn1—O3ⁱ	−70.7 (4)
C2—C1—C6—C5	1.2 (9)	C9—O1—Zn1—O3	109.3 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4ⁱⁱ	0.82 (4)	2.56 (5)	3.033 (7)	118 (5)
O3—H3B···O1ⁱⁱⁱ	0.82 (4)	2.44 (5)	3.221 (6)	159 (4)
O4—H4A···O2	0.83 (3)	1.95 (4)	2.716 (7)	155 (5)
O4—H4B···O2^iv	0.83 (4)	2.30 (6)	2.951 (7)	136 (4)

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

Experimental details

Crystal data
Chemical formula	[Zn(C₉H₇O₂S)₂(H₂O)₂]·2H₂O
M_r	495.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	18.4398 (5), 7.7188 (3), 7.3258 (2)
β (°)	98.578 (2)
V (Å³)	1031.04 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.30 × 0.20 × 0.14

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.673, 0.824
No. of measured, independent and observed [I > 2σ(I)] reflections	6272, 1811, 1441
R_int	0.092
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.185, 1.06
No. of reflections	1811
No. of parameters	146
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.93, −0.88

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O1

1.969 (4)

Zn1—O3

1.953 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4ⁱ	0.82 (4)	2.56 (5)	3.033 (7)	118 (5)
O3—H3B···O1ⁱⁱ	0.82 (4)	2.44 (5)	3.221 (6)	159 (4)
O4—H4A···O2	0.83 (3)	1.95 (4)	2.716 (7)	155 (5)
O4—H4B···O2ⁱⁱⁱ	0.83 (4)	2.30 (6)	2.951 (7)	136 (4)

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

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

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