catena-Poly[[bis­(1H-imidazole-κN3)copper(II)]-μ-benzene-1,4-dicarboxyl­ato-κ2O1:O4]

Xu, Q.

doi:10.1107/S1600536811024822

metal-organic compounds

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Volume 67| Part 8| August 2011| Page m1014

doi:10.1107/S1600536811024822

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catena-Poly[[bis(1H-imidazole-κN³)copper(II)]-μ-benzene-1,4-dicarboxylato-κ²O¹:O⁴]

Qian Xu ^a ^*

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

(Received 23 June 2011; accepted 24 June 2011; online 2 July 2011)

In the title compound, [Cu(C₈H₄O₄)(C₃H₄N₂)₂]_n, the Cu^II atom is four-coordinated by two carboxylate O atoms from two different terephthalate ligands and two N atoms from two imidazole ligands in a slightly distorted square-planar coordination environment. Each terephthalate ligand acts as a bis-monodentate ligand that binds two Cu^II atoms, thus forming two unique chains extending parallel to [110]. The imidazole ligands are attached on both sides of the chains.

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

[Cu(C₈H₄O₄)(C₃H₄N₂)₂]
M_r = 363.82
Monoclinic, C 2/c
a = 21.435 (4) Å
b = 5.2740 (11) Å
c = 14.164 (3) Å
β = 116.65 (3)°
V = 1431.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.55 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 = 0.634, T_max = 0.733
6976 measured reflections
1641 independent reflections
1440 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.08
1641 reflections
110 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.78 (4)	2.11 (4)	2.851 (3)	157 (4)
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024822/jh2303sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024822/jh2303Isup2.hkl

checkCIF report

Comment top

Dielectric constant measurements of compounds as a function of temperature is the basic method to find potential ferroelectric phase change materials (Fu et al., 2009; Ye et al., 2006; Zhang et al., 2008; Zhang et al., 2010). Unfortunately, the study carried out on the title compound indicated that the permittivity is temperature-independent, suggesting that there may be no dielectric disuniformity between 80 K to 350 K (m.p. 393–381 K). In this report the crystal structure of the title compound is reported.

An ORTEP diagram showing the structure of the title compound with the symmetry related fragments and atom-numbering scheme is shown in Fig. 1. The Cu(II) atom,with an inversion center, adopts a distorted octahedral geometry comprising two nitrogen atoms of two pyrazole ligands [Cu1–N1 = 1.9859 (19) Å] and two oxygen atoms of two different tp ligands [Cu1–O1 = 1.9408 (14) Å]. The N2O2 moiety defines the equatorial plane of the octahedron. In the equatorial plane, the angles between the cis-positioned atoms are close to 90° and those of the transpositioned atoms are identical to 180° since the Cu atom resides at the inversion center.

Related literature top

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

Experimental top

An aqueous solution of imidazole (1.64 g, 20 mmol) and terephthalic acid (10 mmol) was treated with CuCl₂(1.35 g, 10 mmol). After the mixture was churned for a few minutes, slow evaporation of the resulting solution yielded blue crystals after a few days.

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 the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes for A: 1 - x, 2 - y, 2 - z. Symmetry codes for B: 1.5 - x, 1.5 - y, 2 - z. Symmetry codes for C: 0.5 - x, 2.5 - y, 2 - z.
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

catena-Poly[[bis(1H-imidazole-κN³)copper(II)]-µ- benzene-1,4-dicarboxylato-κ²O¹:O⁴] top

Crystal data top

[Cu(C₈H₄O₄)(C₃H₄N₂)₂]	Z = 4
M_r = 363.82	F(000) = 740
Monoclinic, C2/c	D_x = 1.689 Mg m⁻³
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.435 (4) Å	θ = 2.8–27.5°
b = 5.2740 (11) Å	µ = 1.55 mm⁻¹
c = 14.164 (3) Å	T = 293 K
β = 116.65 (3)°	Block, blue
V = 1431.1 (5) Å³	0.30 × 0.25 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1641 independent reflections
Radiation source: fine-focus sealed tube	1440 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 4.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −27→27
T_min = 0.634, T_max = 0.733	k = −6→6
6976 measured reflections	l = −18→18

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 atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.040P)² + 0.9748P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1641 reflections	Δρ_max = 0.26 e Å⁻³
110 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

Crystal data top

[Cu(C₈H₄O₄)(C₃H₄N₂)₂]	V = 1431.1 (5) Å³
M_r = 363.82	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 21.435 (4) Å	µ = 1.55 mm⁻¹
b = 5.2740 (11) Å	T = 293 K
c = 14.164 (3) Å	0.30 × 0.25 × 0.20 mm
β = 116.65 (3)°

Data collection top

Rigaku SCXmini diffractometer	1641 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1440 reflections with I > 2σ(I)
T_min = 0.634, T_max = 0.733	R_int = 0.048
6976 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.26 e Å⁻³
1641 reflections	Δρ_min = −0.32 e Å⁻³
110 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	0.37485 (12)	0.7554 (5)	0.82142 (19)	0.0385 (5)
H1	0.3432	0.8726	0.8240	0.046*
C2	0.35883 (15)	0.5594 (5)	0.7531 (2)	0.0460 (6)
H2	0.3148	0.5180	0.7002	0.055*
C3	0.47038 (14)	0.5553 (5)	0.8563 (2)	0.0387 (6)
H3	0.5170	0.5067	0.8866	0.046*
C4	0.38692 (10)	1.0497 (4)	1.04391 (18)	0.0269 (5)
C5	0.31559 (10)	1.1531 (4)	1.02048 (16)	0.0249 (4)
C6	0.29077 (11)	1.3731 (4)	0.96075 (18)	0.0303 (5)
H6	0.3179	1.4565	0.9344	0.036*
C7	0.27444 (12)	1.0321 (4)	1.05946 (19)	0.0301 (5)
H7	0.2908	0.8856	1.0997	0.036*
N1	0.44579 (9)	0.7532 (3)	0.88681 (14)	0.0303 (4)
N2	0.41890 (14)	0.4355 (5)	0.77617 (19)	0.0447 (6)
O1	0.41430 (8)	0.8830 (3)	1.11055 (14)	0.0426 (4)
O2	0.41356 (7)	1.1465 (3)	0.98747 (12)	0.0306 (3)
Cu1	0.5000	1.0000	1.0000	0.02373 (14)
H2A	0.4238 (19)	0.322 (7)	0.744 (3)	0.074 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0315 (12)	0.0408 (13)	0.0383 (13)	0.0008 (10)	0.0112 (10)	−0.0025 (11)
C2	0.0446 (16)	0.0497 (15)	0.0364 (14)	−0.0083 (12)	0.0118 (12)	−0.0049 (11)
C3	0.0433 (14)	0.0348 (12)	0.0468 (15)	0.0008 (10)	0.0281 (12)	−0.0052 (10)
C4	0.0204 (10)	0.0273 (10)	0.0356 (12)	0.0022 (8)	0.0149 (9)	−0.0036 (8)
C5	0.0185 (9)	0.0276 (10)	0.0313 (11)	0.0029 (7)	0.0136 (8)	−0.0019 (8)
C6	0.0234 (10)	0.0324 (11)	0.0412 (12)	0.0028 (9)	0.0200 (9)	0.0061 (10)
C7	0.0252 (11)	0.0280 (11)	0.0411 (13)	0.0065 (8)	0.0184 (10)	0.0076 (9)
N1	0.0278 (9)	0.0327 (9)	0.0348 (10)	0.0012 (7)	0.0179 (8)	−0.0024 (8)
N2	0.0651 (16)	0.0371 (11)	0.0443 (13)	−0.0095 (11)	0.0354 (12)	−0.0117 (10)
O1	0.0308 (8)	0.0477 (10)	0.0555 (11)	0.0185 (8)	0.0248 (8)	0.0186 (9)
O2	0.0226 (7)	0.0345 (8)	0.0408 (9)	0.0066 (6)	0.0197 (7)	0.0009 (7)
Cu1	0.0187 (2)	0.0272 (2)	0.0299 (2)	0.00423 (13)	0.01502 (16)	0.00013 (14)

Geometric parameters (Å, º) top

C1—C2	1.351 (4)	C5—C7	1.388 (3)
C1—N1	1.381 (3)	C5—C6	1.393 (3)
C1—H1	0.9300	C6—C7ⁱ	1.388 (3)
C2—N2	1.347 (4)	C6—H6	0.9300
C2—H2	0.9300	C7—C6ⁱ	1.388 (3)
C3—N1	1.326 (3)	C7—H7	0.9300
C3—N2	1.335 (4)	N1—Cu1	1.9857 (19)
C3—H3	0.9300	N2—H2A	0.78 (4)
C4—O1	1.229 (3)	O2—Cu1	1.9408 (14)
C4—O2	1.279 (3)	Cu1—O2ⁱⁱ	1.9408 (14)
C4—C5	1.513 (3)	Cu1—N1ⁱⁱ	1.9857 (19)

C2—C1—N1	108.9 (2)	C5—C6—H6	120.0
C2—C1—H1	125.5	C6ⁱ—C7—C5	120.9 (2)
N1—C1—H1	125.5	C6ⁱ—C7—H7	119.6
N2—C2—C1	106.8 (2)	C5—C7—H7	119.6
N2—C2—H2	126.6	C3—N1—C1	105.5 (2)
C1—C2—H2	126.6	C3—N1—Cu1	127.21 (17)
N1—C3—N2	110.6 (2)	C1—N1—Cu1	127.28 (15)
N1—C3—H3	124.7	C3—N2—C2	108.2 (2)
N2—C3—H3	124.7	C3—N2—H2A	125 (3)
O1—C4—O2	124.91 (19)	C2—N2—H2A	126 (3)
O1—C4—C5	120.90 (19)	C4—O2—Cu1	117.36 (13)
O2—C4—C5	114.17 (18)	O2ⁱⁱ—Cu1—O2	180.000 (1)
C7—C5—C6	119.12 (18)	O2ⁱⁱ—Cu1—N1	90.10 (7)
C7—C5—C4	120.45 (19)	O2—Cu1—N1	89.90 (7)
C6—C5—C4	120.42 (18)	O2ⁱⁱ—Cu1—N1ⁱⁱ	89.90 (7)
C7ⁱ—C6—C5	120.00 (19)	O2—Cu1—N1ⁱⁱ	90.10 (7)
C7ⁱ—C6—H6	120.0	N1—Cu1—N1ⁱⁱ	180.0

Symmetry codes: (i) −x+1/2, −y+5/2, −z+2; (ii) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱⁱ	0.78 (4)	2.11 (4)	2.851 (3)	157 (4)

Symmetry code: (iii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₄O₄)(C₃H₄N₂)₂]
M_r	363.82
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	21.435 (4), 5.2740 (11), 14.164 (3)
β (°)	116.65 (3)
V (Å³)	1431.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.55
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	0.634, 0.733
No. of measured, independent and observed [I > 2σ(I)] reflections	6976, 1641, 1440
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.08
No. of reflections	1641
No. of parameters	110
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.32

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.78 (4)	2.11 (4)	2.851 (3)	157 (4)

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

This work was supported by a start-up grant from Southeast University.

References

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