catena-Poly[[diaqua­bis­(2-ethyl-1H-imidazole-κN ³)cadmium]-μ-sulfato-κ² O:O′]

Abstract

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,

• a = 14.465 (10) Å

• b = 15.83 (1) Å

• c = 6.990 (5) Å

• V = 1600.6 (19) ų

• 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[F ² > 2σ(F ²)] = 0.035

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms but for H1A and H1B with C—H = 0.93 Å, with U_iso(H) = 1.2 U_iso(C).

Figures

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.

Crystal data

[Cd(SO4)(C5H8N2)2(H2O)2]	F(000) = 880
Mr = 436.78	Dx = 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

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

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)] = 0.035	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(Fo2) + (0.0278P)2 + 5.5521P] where P = (Fo2 + 2Fc2)/3
1838 reflections	(Δ/σ)max < 0.001
107 parameters	Δρmax = 0.91 e Å−3
3 restraints	Δρmin = −1.51 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	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 (Ų)

	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)

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)

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···O3iv	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.