catena-Poly[[diaqua­bis­(2-ethyl-1H-imidazole-κN3)cadmium]-μ-sulfato-κ2O:O′]

Yu, C.-H.

doi:10.1107/S1600536812017059

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m655

doi:10.1107/S1600536812017059

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catena-Poly[[diaquabis(2-ethyl-1H-imidazole-κN³)cadmium]-μ-sulfato-κ²O:O′]

Chua-Hua Yu ^a ^*

^aOrderd Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jxyuchunhua@163.com

(Received 17 March 2012; accepted 18 April 2012; online 21 April 2012)

In the title one-dimensional coordination polymer, [Cd(SO₄)(C₅H₈N₂)₂(H₂O)₂]_n, the Cd^II atom (site symmetry 2) is coordinated by two sulfate O atoms, two water molecules and two 2-ethylimidazole ligands in a distorted cis-CdN₂O₄ octahedral geometry. The water molecules have a cis disposition. The bridging sulfate ions (site symmetry 2) link the Cd^II ions into a polymeric chain extending along [001]. The chains are linked by N—H⋯O and O—H⋯O hydrogen bonds. The terminal –CH₃ group of the ligand is disordered over two orientations in a 0.61 (5):0.39 (5) ratio.

Related literature

For background to ferroelectric materials, see: Zhang et al. (2010 ). For a related structure, see: Zhu & Yu (2011 ).

Experimental

Crystal data

[Cd(SO₄)(C₅H₈N₂)₂(H₂O)₂]
M_r = 436.78
Orthorhombic, P b c n
a = 14.465 (10) Å
b = 15.83 (1) Å
c = 6.990 (5) Å
V = 1600.6 (19) Å³
Z = 4
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 293 K
0.34 × 0.28 × 0.24 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.604, T_max = 0.693
15289 measured reflections
1838 independent reflections
1617 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.082
S = 1.06
1838 reflections
107 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.91 e Å⁻³
Δρ_min = −1.51 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N2	2.255 (3)
Cd1—O2	2.437 (3)
Cd1—O1W	2.339 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯O3ⁱ	0.86	2.11	2.936 (4)	160
O1W—H1WA⋯O3ⁱⁱ	0.81 (2)	1.93 (2)	2.732 (4)	172 (5)
O1W—H1WB⋯O3ⁱⁱⁱ	0.80 (2)	1.97 (2)	2.762 (4)	169 (5)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+1, y, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+2, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017059/hb6691sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017059/hb6691Isup2.hkl

checkCIF report

Comment top

According to finding potential ferroelectric phase change materials via dielectric constant measurements of compounds on the basis of temperature (Zhang et al., 2010). Unluckily, no dielectric anomaly was observed ranging from 120 K to near 290 K. In this report the crystal structure of the title compound is herein reported. A structure chart showing the structure of the title compound (Scheme 1). A viewgraph of with the symmetry related fragments and atom-numbering scheme is shown in Fig. 1. The Cd(II) atom adopts two nitrogen atoms of two 2-ethylimidazole ligands [Cd1—N2 = 2.255 (3) Å], two O atoms from two water [Cd1—O1W = 2.339 (3) Å] and two oxygen atoms of two different sulfate radical ligands [Cd1—O2 = 2.437 (3) Å]. Besides, atom C1 swings between the two positions 1:1 ration. In addition, the unite exists O—H···O and N—H···O hydrogen bonds are also present (Table 1).

Related literature top

For background to ferroelectric materials, see: Zhang et al. (2010). For a related structure, see: Zhu & Yu (2011).

Experimental top

2.4 g (25 mmol) of 2-ethylimidazole was dissolved in 20 ml water, dropping 1.23 g (12.5 mmol) of H₂SO₄ into it, and 6.4 g (8.3 mmol) 3CdSO₄.8H₂O was added to the solution. After stirring the mixture for several minutes, 6.18 g (25 mmol) of Ba(NO₂)₂ was joined into it forming precipitation. The turbid liquid was filtered to give a light yellow solution. Yellow blocks were obtained, but not the expecting things, by the slow evaporation of the above solution after sever days at the ambient temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Symmetry codes: (i) 1-x, y, 1/2-z; (ii) 1-x, y, 3/2-z.
	Fig. 2. A view of the packing of the title compound, stacking along the c axis. Dashed lines indicate hydrogen bonds.

catena-Poly[[diaquabis(2-ethyl-1H-imidazole- κN³)cadmium]-µ-sulfato-κ²O:O'] top

Crystal data top

[Cd(SO₄)(C₅H₈N₂)₂(H₂O)₂]	F(000) = 880
M_r = 436.78	D_x = 1.813 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1838 reflections
a = 14.465 (10) Å	θ = 3.9–27.5°
b = 15.83 (1) Å	µ = 1.53 mm⁻¹
c = 6.990 (5) Å	T = 293 K
V = 1600.6 (19) Å³	Block, yellow
Z = 4	0.34 × 0.28 × 0.24 mm

Data collection top

Rigaku SCXmini diffractometer	1617 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.035
Graphite monochromator	θ_max = 27.5°, θ_min = 3.9°
ω scans	h = −18→18
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −20→20
T_min = 0.604, T_max = 0.693	l = −9→9
15289 measured reflections	3 standard reflections every 180 reflections
1838 independent reflections	intensity decay: none

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0278P)² + 5.5521P] where P = (F_o² + 2F_c²)/3
1838 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.91 e Å⁻³
3 restraints	Δρ_min = −1.51 e Å⁻³

Crystal data top

[Cd(SO₄)(C₅H₈N₂)₂(H₂O)₂]	V = 1600.6 (19) Å³
M_r = 436.78	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 14.465 (10) Å	µ = 1.53 mm⁻¹
b = 15.83 (1) Å	T = 293 K
c = 6.990 (5) Å	0.34 × 0.28 × 0.24 mm

Data collection top

Rigaku SCXmini diffractometer	1617 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.035
T_min = 0.604, T_max = 0.693	3 standard reflections every 180 reflections
15289 measured reflections	intensity decay: none
1838 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.91 e Å⁻³
1838 reflections	Δρ_min = −1.51 e Å⁻³
107 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	Occ. (<1)
C1	0.5943 (16)	0.5775 (16)	0.464 (3)	0.0460 (9)	0.39 (5)
H1A	0.5329	0.6000	0.4539	0.069*	0.39 (5)
H1B	0.5961	0.5354	0.5625	0.069*	0.39 (5)
H1C	0.6117	0.5524	0.3440	0.069*	0.39 (5)
C1'	0.6100 (10)	0.5679 (10)	0.4805 (19)	0.0460 (9)	0.61 (5)
H1'A	0.6529	0.5216	0.4781	0.069*	0.61 (5)
H1'B	0.5778	0.5707	0.3607	0.069*	0.61 (5)
H1'C	0.5664	0.5596	0.5823	0.069*	0.61 (5)
C2	0.6611 (3)	0.6480 (3)	0.5124 (6)	0.0460 (9)
H2A	0.7211	0.6343	0.4589	0.055*
H2B	0.6399	0.6995	0.4513	0.055*
C3	0.6724 (2)	0.6645 (2)	0.7199 (4)	0.0249 (7)
C4	0.7286 (3)	0.6571 (2)	1.0116 (5)	0.0341 (8)
H4	0.7662	0.6443	1.1155	0.041*
C5	0.6496 (3)	0.7023 (2)	1.0139 (5)	0.0317 (8)
H5	0.6230	0.7263	1.1220	0.038*
N1	0.7422 (2)	0.63387 (19)	0.8256 (4)	0.0312 (6)
H1D	0.7878	0.6045	0.7833	0.037*
N2	0.61447 (19)	0.70720 (17)	0.8301 (4)	0.0250 (6)
O1W	0.60396 (17)	0.90785 (16)	0.8035 (4)	0.0272 (5)
O2	0.53001 (17)	0.82007 (15)	0.4109 (3)	0.0282 (5)
O3	0.42204 (16)	0.92697 (15)	0.3118 (3)	0.0263 (5)
S1	0.5000	0.87254 (6)	0.2500	0.0176 (2)
Cd1	0.5000	0.797187 (19)	0.7500	0.02068 (12)
H1WA	0.599 (3)	0.917 (3)	0.917 (3)	0.049 (14)*
H1WB	0.594 (4)	0.9529 (17)	0.756 (6)	0.044 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (2)	0.061 (2)	0.0379 (18)	−0.0057 (17)	−0.0050 (15)	−0.0052 (16)
C1'	0.039 (2)	0.061 (2)	0.0379 (18)	−0.0057 (17)	−0.0050 (15)	−0.0052 (16)
C2	0.039 (2)	0.061 (2)	0.0379 (18)	−0.0057 (17)	−0.0050 (15)	−0.0052 (16)
C3	0.0262 (16)	0.0247 (15)	0.0240 (16)	0.0032 (12)	0.0015 (12)	0.0034 (12)
C4	0.0300 (19)	0.044 (2)	0.0285 (18)	0.0064 (15)	−0.0084 (14)	0.0021 (16)
C5	0.0338 (18)	0.0401 (19)	0.0214 (16)	0.0082 (15)	−0.0046 (14)	−0.0020 (14)
N1	0.0232 (14)	0.0384 (16)	0.0321 (15)	0.0094 (12)	0.0006 (12)	0.0029 (13)
N2	0.0249 (13)	0.0298 (14)	0.0202 (13)	0.0046 (11)	−0.0018 (11)	0.0004 (11)
O1W	0.0305 (12)	0.0280 (12)	0.0230 (12)	−0.0035 (8)	0.0025 (10)	0.0009 (10)
O2	0.0322 (12)	0.0342 (12)	0.0181 (11)	0.0069 (10)	0.0012 (9)	0.0066 (9)
O3	0.0244 (11)	0.0297 (12)	0.0248 (11)	0.0057 (9)	0.0018 (9)	0.0005 (9)
S1	0.0186 (5)	0.0204 (5)	0.0139 (4)	0.000	0.0004 (4)	0.000
Cd1	0.01904 (17)	0.02334 (18)	0.01966 (18)	0.000	−0.00215 (12)	0.000

Geometric parameters (Å, º) top

C1—C2	1.52 (2)	C5—N2	1.384 (4)
C1—H1A	0.9600	C5—H5	0.9300
C1—H1B	0.9600	N1—H1D	0.8600
C1—H1C	0.9600	O1W—H1WA	0.807 (19)
C1'—C2	1.485 (14)	O1W—H1WB	0.799 (19)
C1'—H1'A	0.9600	O2—S1	1.464 (2)
C1'—H1'B	0.9600	O3—S1	1.484 (2)
C1'—H1'C	0.9600	S1—O2ⁱ	1.464 (2)
C2—C3	1.483 (5)	S1—O3ⁱ	1.484 (2)
C2—H2A	0.9700	Cd1—N2	2.255 (3)
C2—H2B	0.9700	Cd1—O2	2.437 (3)
C3—N2	1.324 (4)	Cd1—O1W	2.339 (3)
C3—N1	1.341 (4)	Cd1—N2ⁱⁱ	2.255 (3)
C4—C5	1.348 (5)	Cd1—O1Wⁱⁱ	2.339 (3)
C4—N1	1.365 (5)	Cd1—O2ⁱⁱ	2.437 (3)
C4—H4	0.9300

C2—C1—H1A	109.5	C3—N1—C4	108.6 (3)
C2—C1—H1B	109.5	C3—N1—H1D	125.7
H1A—C1—H1B	109.5	C4—N1—H1D	125.7
C2—C1—H1C	109.5	C3—N2—C5	106.2 (3)
H1A—C1—H1C	109.5	C3—N2—Cd1	130.0 (2)
H1B—C1—H1C	109.5	C5—N2—Cd1	122.4 (2)
C2—C1'—H1'A	109.5	Cd1—O1W—H1WA	104 (3)
C2—C1'—H1'B	109.5	Cd1—O1W—H1WB	119 (4)
H1'A—C1'—H1'B	109.5	H1WA—O1W—H1WB	103 (4)
C2—C1'—H1'C	109.5	S1—O2—Cd1	141.16 (14)
H1'A—C1'—H1'C	109.5	O2ⁱ—S1—O2	110.9 (2)
H1'B—C1'—H1'C	109.5	O2ⁱ—S1—O3	109.14 (14)
C3—C2—C1'	110.6 (6)	O2—S1—O3	109.34 (13)
C3—C2—C1	114.8 (9)	O2ⁱ—S1—O3ⁱ	109.34 (13)
C1'—C2—C1	11.3 (9)	O2—S1—O3ⁱ	109.14 (14)
C3—C2—H2A	108.6	O3—S1—O3ⁱ	109.0 (2)
C1'—C2—H2A	101.3	N2ⁱⁱ—Cd1—N2	101.65 (15)
C1—C2—H2A	108.6	N2ⁱⁱ—Cd1—O1W	170.07 (10)
C3—C2—H2B	108.6	N2—Cd1—O1W	87.78 (11)
C1'—C2—H2B	119.6	N2ⁱⁱ—Cd1—O1Wⁱⁱ	87.78 (11)
C1—C2—H2B	108.6	N2—Cd1—O1Wⁱⁱ	170.07 (10)
H2A—C2—H2B	107.5	O1W—Cd1—O1Wⁱⁱ	82.99 (14)
N2—C3—N1	109.9 (3)	N2ⁱⁱ—Cd1—O2ⁱⁱ	101.81 (9)
N2—C3—C2	126.1 (3)	N2—Cd1—O2ⁱⁱ	89.03 (10)
N1—C3—C2	123.9 (3)	O1W—Cd1—O2ⁱⁱ	81.24 (8)
C5—C4—N1	106.1 (3)	O1Wⁱⁱ—Cd1—O2ⁱⁱ	85.96 (9)
C5—C4—H4	127.0	N2ⁱⁱ—Cd1—O2	89.03 (10)
N1—C4—H4	127.0	N2—Cd1—O2	101.81 (9)
C4—C5—N2	109.3 (3)	O1W—Cd1—O2	85.96 (9)
C4—C5—H5	125.4	O1Wⁱⁱ—Cd1—O2	81.24 (8)
N2—C5—H5	125.4	O2ⁱⁱ—Cd1—O2	162.90 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O3ⁱⁱⁱ	0.86	2.11	2.936 (4)	160
O1W—H1WA···O3ⁱⁱ	0.81 (2)	1.93 (2)	2.732 (4)	172 (5)
O1W—H1WB···O3^iv	0.80 (2)	1.97 (2)	2.762 (4)	169 (5)

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

Experimental details

Crystal data
Chemical formula	[Cd(SO₄)(C₅H₈N₂)₂(H₂O)₂]
M_r	436.78
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	14.465 (10), 15.83 (1), 6.990 (5)
V (Å³)	1600.6 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.53
Crystal size (mm)	0.34 × 0.28 × 0.24

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.604, 0.693
No. of measured, independent and observed [I > 2σ(I)] reflections	15289, 1838, 1617
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.082, 1.06
No. of reflections	1838
No. of parameters	107
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.91, −1.51

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cd1—N2	2.255 (3)	Cd1—O1W	2.339 (3)
Cd1—O2	2.437 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O3ⁱ	0.86	2.11	2.936 (4)	160
O1W—H1WA···O3ⁱⁱ	0.807 (19)	1.93 (2)	2.732 (4)	172 (5)
O1W—H1WB···O3ⁱⁱⁱ	0.799 (19)	1.97 (2)	2.762 (4)	169 (5)

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

Acknowledgements

The author thanks an anonymous advisor from the Ordered Matter Science Research Centre, Southeast University, for great help in the revision of this paper.

References

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z., Xiong, R.-G. & Huang, S.-P. D. (2010). J. Am. Chem. Soc. 132, 7300–7302. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zhu, R.-Q. & Yu, C.-H. (2011). Acta Cryst. E67, o2746. Web of Science CSD CrossRef IUCr Journals Google Scholar