catena-Poly[2-methyl-1H-imidazol-3-ium [(aqua­chloridocadmate)-di-μ-chlorido]]

Zhu, R.-Q.

doi:10.1107/S1600536811042905

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1584

doi:10.1107/S1600536811042905

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catena-Poly[2-methyl-1H-imidazol-3-ium [(aquachloridocadmate)-di-μ-chlorido]]

Run-Qiang Zhu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: zhurunqiang@163.com

(Received 6 October 2011; accepted 17 October 2011; online 22 October 2011)

The asymmetric unit of the title compound, {(C₄H₇N₂)[CdCl₃(H₂O)]}_n, contains one 1-methyl-1H-imidazol-3-ium cation, one Cd^II atom, three Cl atoms and one water molecule. Adjacent Cd ions are interconnected alternately by paired Cl⁻ bridges to generate an infinite one-dimensional coordination chain along the b axis. In the chain, the crystallographically unique Cd^II atom, with a distorted octahedral geometry, is coordinated by five Cl⁻ ions and one water molecule. Intra-chain O—H⋯Cl hydrogen bonding and N—H⋯Cl hydrogen bonding between the cations and the anionic chains consolidate the crystal packing.

Related literature

For general background to ferroelectric metal-organic compounds with framework structures, see: Fu et al. (2009 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ).

Experimental

Crystal data

(C₄H₇N₂)[CdCl₃(H₂O)]
M_r = 319.88
Monoclinic, P 2₁ /c
a = 9.0479 (18) Å
b = 14.922 (3) Å
c = 7.4711 (15) Å
β = 94.17 (3)°
V = 1006.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.92 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.421, T_max = 0.558
10317 measured reflections
2308 independent reflections
2038 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.083
S = 1.12
2308 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.13	2.884 (3)	146
N1—H1D⋯Cl1ⁱ	0.86	2.33	3.163 (3)	164
O1—H1G⋯Cl1ⁱⁱ	0.85	2.40	3.250 (2)	174
O1—H1F⋯Cl1ⁱⁱⁱ	0.85	2.44	3.174 (2)	146
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042905/vm2126sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042905/vm2126Isup2.hkl

checkCIF report

Comment top

The basic method to find potential ferroelectric phase change materials is the measurement of the dielectric constant as function of temperature (Fu et al., 2009; Ye et al., 2006; Zhang et al., 2008, 2010). Unfortunately, the title compound's dielectric constant does not change from 80 K to 298 K (m.p. 319–329).

X-ray analysis (Fig. 1) revealed that the title compound possesses 1-D chain structures. In the chain, the Cd atoms are connected by two Cl atoms acting as bridges between Cd1 and Cd1[x, 0.5 - y, 1/2 + z] centers. The Cd—Cl(µ₂) distances from 2.5973 (11) to 2.6293 (12) Å are slightly longer than that of Cd—Cl(terminal) 2.5916 (10) Å. It is interesting to note that the free 2-methyl imidazole molecules extend the 1-D host chains into a 3-D supramolecular network via the hydrogen-bonded interactions (Table 1, Fig. 2).

Related literature top

For general background on ferroelectric metal–organic frameworks, see: Fu et al. (2009); Ye et al. (2006); Zhang et al. (2008, 2010).

Experimental top

A mixture of 2-methyl imidazole (2.4 g, 30 mmol), cadmium chloride (3.15 g, 10 mmol) in water was stirred for several days at ambient temperature. Colourless block crystals were obtained.

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: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A partial packing diagram of the title compound, with the displacement ellipsoids drawn at the 30% probability level, the intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. Packing diagram of the title compound, hydrogen bonds are shown as dashed lines.

catena-Poly[2-methyl-1H-imidazol-3-ium [(aquachloridocadmate)-di-µ-chlorido]] top

Crystal data top

(C₄H₇N₂)[CdCl₃(H₂O)]	F(000) = 616
M_r = 319.88	D_x = 2.112 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2308 reflections
a = 9.0479 (18) Å	θ = 2.2–27.5°
b = 14.922 (3) Å	µ = 2.92 mm⁻¹
c = 7.4711 (15) Å	T = 293 K
β = 94.17 (3)°	Block, colourless
V = 1006.0 (3) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2038 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.082
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −19→19
T_min = 0.421, T_max = 0.558	l = −9→9
10317 measured reflections	2 standard reflections every 150 reflections
2308 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0174P)² + 0.0243P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max = 0.001
2308 reflections	Δρ_max = 0.72 e Å⁻³
102 parameters	Δρ_min = −0.71 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0729 (19)

Crystal data top

(C₄H₇N₂)[CdCl₃(H₂O)]	V = 1006.0 (3) Å³
M_r = 319.88	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0479 (18) Å	µ = 2.92 mm⁻¹
b = 14.922 (3) Å	T = 293 K
c = 7.4711 (15) Å	0.30 × 0.25 × 0.20 mm
β = 94.17 (3)°

Data collection top

Rigaku SCXmini diffractometer	2038 reflections with I > 2σ(I)
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	R_int = 0.082
T_min = 0.421, T_max = 0.558	2 standard reflections every 150 reflections
10317 measured reflections	intensity decay: none
2308 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.12	Δρ_max = 0.72 e Å⁻³
2308 reflections	Δρ_min = −0.71 e Å⁻³
102 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
Cd1	0.57821 (2)	0.235443 (17)	0.32343 (3)	0.02778 (14)
Cl3	0.38194 (10)	0.26229 (6)	0.06038 (12)	0.0358 (2)
Cl2	0.78469 (10)	0.25735 (5)	0.08951 (12)	0.0318 (2)
Cl1	0.59444 (8)	0.06319 (6)	0.28507 (11)	0.0381 (2)
N2	0.8602 (3)	0.4748 (2)	0.2374 (4)	0.0461 (8)
H2A	0.8000	0.4318	0.2563	0.055*
C2	1.0070 (4)	0.4697 (2)	0.2644 (4)	0.0395 (8)
C3	0.8185 (4)	0.5580 (3)	0.1755 (5)	0.0487 (10)
H3	0.7224	0.5780	0.1460	0.058*
C1	1.0943 (4)	0.3909 (3)	0.3283 (5)	0.0588 (12)
H1A	1.1219	0.3567	0.2272	0.088*
H1B	1.0357	0.3544	0.4018	0.088*
H1C	1.1819	0.4105	0.3975	0.088*
N1	1.0572 (3)	0.5493 (2)	0.2218 (4)	0.0458 (8)
H1D	1.1492	0.5643	0.2283	0.055*
C4	0.9424 (4)	0.6046 (3)	0.1659 (5)	0.0509 (10)
H4	0.9500	0.6637	0.1282	0.061*
O1	0.5944 (2)	0.39528 (16)	0.3580 (3)	0.0371 (6)
H1G	0.5922	0.4101	0.4677	0.045*
H1F	0.5230	0.4207	0.2978	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0307 (2)	0.0277 (2)	0.02493 (19)	−0.00076 (9)	0.00188 (13)	0.00017 (8)
Cl3	0.0272 (5)	0.0527 (6)	0.0275 (5)	0.0054 (3)	0.0023 (4)	0.0021 (3)
Cl2	0.0266 (4)	0.0399 (5)	0.0287 (4)	−0.0026 (3)	0.0010 (4)	0.0007 (3)
Cl1	0.0325 (4)	0.0251 (4)	0.0565 (5)	−0.0026 (3)	0.0024 (4)	−0.0006 (4)
N2	0.0311 (15)	0.044 (2)	0.063 (2)	−0.0122 (14)	0.0037 (15)	0.0024 (15)
C2	0.0347 (19)	0.040 (2)	0.044 (2)	−0.0029 (16)	0.0047 (17)	−0.0045 (16)
C3	0.0349 (19)	0.049 (2)	0.063 (2)	0.0025 (18)	0.0062 (18)	0.002 (2)
C1	0.057 (3)	0.057 (3)	0.062 (3)	0.012 (2)	0.000 (2)	0.0006 (19)
N1	0.0290 (15)	0.049 (2)	0.060 (2)	−0.0095 (14)	0.0037 (14)	−0.0025 (16)
C4	0.052 (2)	0.037 (2)	0.064 (3)	−0.0008 (18)	0.004 (2)	0.0003 (18)
O1	0.0370 (12)	0.0341 (15)	0.0402 (12)	0.0050 (10)	0.0029 (10)	0.0065 (10)

Geometric parameters (Å, º) top

Cd1—O1	2.402 (2)	C2—C1	1.476 (5)
Cd1—Cl3	2.5824 (12)	C3—C4	1.325 (5)
Cd1—Cl1	2.5916 (10)	C3—H3	0.9300
Cd1—Cl3ⁱ	2.5973 (11)	C1—H1A	0.9600
Cd1—Cl2ⁱ	2.6293 (12)	C1—H1B	0.9600
Cd1—Cl2	2.6694 (11)	C1—H1C	0.9600
Cl3—Cd1ⁱⁱ	2.5973 (11)	N1—C4	1.368 (4)
Cl2—Cd1ⁱⁱ	2.6293 (12)	N1—H1D	0.8600
N2—C2	1.331 (4)	C4—H4	0.9300
N2—C3	1.369 (5)	O1—H1G	0.8501
N2—H2A	0.8600	O1—H1F	0.8500
C2—N1	1.318 (4)

O1—Cd1—Cl3	87.77 (5)	N1—C2—C1	127.5 (3)
O1—Cd1—Cl1	173.24 (5)	N2—C2—C1	126.8 (4)
Cl3—Cd1—Cl1	96.38 (3)	C4—C3—N2	106.3 (3)
O1—Cd1—Cl3ⁱ	87.31 (5)	C4—C3—H3	126.9
Cl3—Cd1—Cl3ⁱ	92.88 (3)	N2—C3—H3	126.9
Cl1—Cd1—Cl3ⁱ	97.78 (3)	C2—C1—H1A	109.5
O1—Cd1—Cl2ⁱ	81.00 (5)	C2—C1—H1B	109.5
Cl3—Cd1—Cl2ⁱ	168.67 (3)	H1A—C1—H1B	109.5
Cl1—Cd1—Cl2ⁱ	94.66 (2)	C2—C1—H1C	109.5
Cl3ⁱ—Cd1—Cl2ⁱ	88.14 (3)	H1A—C1—H1C	109.5
O1—Cd1—Cl2	84.77 (5)	H1B—C1—H1C	109.5
Cl3—Cd1—Cl2	87.60 (3)	C2—N1—C4	110.4 (3)
Cl1—Cd1—Cl2	90.06 (3)	C2—N1—H1D	124.8
Cl3ⁱ—Cd1—Cl2	172.04 (3)	C4—N1—H1D	124.8
Cl2ⁱ—Cd1—Cl2	89.85 (3)	C3—C4—N1	107.1 (4)
Cd1—Cl3—Cd1ⁱⁱ	93.11 (3)	C3—C4—H4	126.4
Cd1ⁱⁱ—Cl2—Cd1	90.42 (3)	N1—C4—H4	126.4
C2—N2—C3	110.5 (3)	Cd1—O1—H1G	110.9
C2—N2—H2A	124.8	Cd1—O1—H1F	110.4
C3—N2—H2A	124.8	H1G—O1—H1F	108.9
N1—C2—N2	105.7 (3)

O1—Cd1—Cl3—Cd1ⁱⁱ	91.33 (5)	Cl2ⁱ—Cd1—Cl2—Cd1ⁱⁱ	−175.35 (4)
Cl1—Cd1—Cl3—Cd1ⁱⁱ	−83.31 (3)	C3—N2—C2—N1	0.7 (4)
Cl3ⁱ—Cd1—Cl3—Cd1ⁱⁱ	178.53 (4)	C3—N2—C2—C1	−179.2 (3)
Cl2ⁱ—Cd1—Cl3—Cd1ⁱⁱ	83.60 (12)	C2—N2—C3—C4	−0.4 (4)
Cl2—Cd1—Cl3—Cd1ⁱⁱ	6.48 (3)	N2—C2—N1—C4	−0.7 (4)
O1—Cd1—Cl2—Cd1ⁱⁱ	−94.37 (5)	C1—C2—N1—C4	179.1 (3)
Cl3—Cd1—Cl2—Cd1ⁱⁱ	−6.39 (2)	N2—C3—C4—N1	0.0 (4)
Cl1—Cd1—Cl2—Cd1ⁱⁱ	89.99 (3)	C2—N1—C4—C3	0.4 (4)
Cl3ⁱ—Cd1—Cl2—Cd1ⁱⁱ	−100.00 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.13	2.884 (3)	146
N1—H1D···Cl1ⁱⁱⁱ	0.86	2.33	3.163 (3)	164
O1—H1G···Cl1ⁱ	0.85	2.40	3.250 (2)	174
O1—H1F···Cl1^iv	0.85	2.44	3.174 (2)	146

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

Experimental details

Crystal data
Chemical formula	(C₄H₇N₂)[CdCl₃(H₂O)]
M_r	319.88
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.0479 (18), 14.922 (3), 7.4711 (15)
β (°)	94.17 (3)
V (Å³)	1006.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.92
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.421, 0.558
No. of measured, independent and observed [I > 2σ(I)] reflections	10317, 2308, 2038
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.083, 1.12
No. of reflections	2308
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.72, −0.71

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.13	2.884 (3)	146.0
N1—H1D···Cl1ⁱ	0.86	2.33	3.163 (3)	163.5
O1—H1G···Cl1ⁱⁱ	0.85	2.40	3.250 (2)	174.2
O1—H1F···Cl1ⁱⁱⁱ	0.85	2.44	3.174 (2)	145.6

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

Acknowledgements

This work was supported by Southeast University.

References

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