metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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 CuII 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 CuII 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[Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994-997.]); Ye et al. (2006[Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554-6555.]); Zhang et al. (2008[Zhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468-10469.], 2010[Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300-7302.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C8H4O4)(C3H4N2)2]

  • Mr = 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.634, Tmax = 0.733

  • 6976 measured reflections

  • 1641 independent reflections

  • 1440 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms except H2A with C—H = 0.93 Å, with Uiso(H) = 1.2 Uiso(C).

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
[Figure 1] 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.
[Figure 2] 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
Mr = 363.82F(000) = 740
Monoclinic, C2/cDx = 1.689 Mg m3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 21.435 (4) Åθ = 2.8–27.5°
b = 5.2740 (11) ŵ = 1.55 mm1
c = 14.164 (3) ÅT = 293 K
β = 116.65 (3)°Block, blue
V = 1431.1 (5) Å30.30 × 0.25 × 0.20 mm
Data collection top
Rigaku SCXmini
diffractometer
1641 independent reflections
Radiation source: fine-focus sealed tube1440 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.048
CCD_Profile_fitting scansθmax = 27.5°, θmin = 4.0°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
h = 2727
Tmin = 0.634, Tmax = 0.733k = 66
6976 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085 w = 1/[σ2(Fo2) + (0.040P)2 + 0.9748P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1641 reflectionsΔρmax = 0.26 e Å3
110 parametersΔρmin = 0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0
Crystal data top
[Cu(C8H4O4)(C3H4N2)2]V = 1431.1 (5) Å3
Mr = 363.82Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.435 (4) ŵ = 1.55 mm1
b = 5.2740 (11) ÅT = 293 K
c = 14.164 (3) Å0.30 × 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)
Tmin = 0.634, Tmax = 0.733Rint = 0.048
6976 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.26 e Å3
1641 reflectionsΔρmin = 0.32 e Å3
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
xyzUiso*/Ueq
C10.37485 (12)0.7554 (5)0.82142 (19)0.0385 (5)
H10.34320.87260.82400.046*
C20.35883 (15)0.5594 (5)0.7531 (2)0.0460 (6)
H20.31480.51800.70020.055*
C30.47038 (14)0.5553 (5)0.8563 (2)0.0387 (6)
H30.51700.50670.88660.046*
C40.38692 (10)1.0497 (4)1.04391 (18)0.0269 (5)
C50.31559 (10)1.1531 (4)1.02048 (16)0.0249 (4)
C60.29077 (11)1.3731 (4)0.96075 (18)0.0303 (5)
H60.31791.45650.93440.036*
C70.27444 (12)1.0321 (4)1.05946 (19)0.0301 (5)
H70.29080.88561.09970.036*
N10.44579 (9)0.7532 (3)0.88681 (14)0.0303 (4)
N20.41890 (14)0.4355 (5)0.77617 (19)0.0447 (6)
O10.41430 (8)0.8830 (3)1.11055 (14)0.0426 (4)
O20.41356 (7)1.1465 (3)0.98747 (12)0.0306 (3)
Cu10.50001.00001.00000.02373 (14)
H2A0.4238 (19)0.322 (7)0.744 (3)0.074 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0315 (12)0.0408 (13)0.0383 (13)0.0008 (10)0.0112 (10)0.0025 (11)
C20.0446 (16)0.0497 (15)0.0364 (14)0.0083 (12)0.0118 (12)0.0049 (11)
C30.0433 (14)0.0348 (12)0.0468 (15)0.0008 (10)0.0281 (12)0.0052 (10)
C40.0204 (10)0.0273 (10)0.0356 (12)0.0022 (8)0.0149 (9)0.0036 (8)
C50.0185 (9)0.0276 (10)0.0313 (11)0.0029 (7)0.0136 (8)0.0019 (8)
C60.0234 (10)0.0324 (11)0.0412 (12)0.0028 (9)0.0200 (9)0.0061 (10)
C70.0252 (11)0.0280 (11)0.0411 (13)0.0065 (8)0.0184 (10)0.0076 (9)
N10.0278 (9)0.0327 (9)0.0348 (10)0.0012 (7)0.0179 (8)0.0024 (8)
N20.0651 (16)0.0371 (11)0.0443 (13)0.0095 (11)0.0354 (12)0.0117 (10)
O10.0308 (8)0.0477 (10)0.0555 (11)0.0185 (8)0.0248 (8)0.0186 (9)
O20.0226 (7)0.0345 (8)0.0408 (9)0.0066 (6)0.0197 (7)0.0009 (7)
Cu10.0187 (2)0.0272 (2)0.0299 (2)0.00423 (13)0.01502 (16)0.00013 (14)
Geometric parameters (Å, º) top
C1—C21.351 (4)C5—C71.388 (3)
C1—N11.381 (3)C5—C61.393 (3)
C1—H10.9300C6—C7i1.388 (3)
C2—N21.347 (4)C6—H60.9300
C2—H20.9300C7—C6i1.388 (3)
C3—N11.326 (3)C7—H70.9300
C3—N21.335 (4)N1—Cu11.9857 (19)
C3—H30.9300N2—H2A0.78 (4)
C4—O11.229 (3)O2—Cu11.9408 (14)
C4—O21.279 (3)Cu1—O2ii1.9408 (14)
C4—C51.513 (3)Cu1—N1ii1.9857 (19)
C2—C1—N1108.9 (2)C5—C6—H6120.0
C2—C1—H1125.5C6i—C7—C5120.9 (2)
N1—C1—H1125.5C6i—C7—H7119.6
N2—C2—C1106.8 (2)C5—C7—H7119.6
N2—C2—H2126.6C3—N1—C1105.5 (2)
C1—C2—H2126.6C3—N1—Cu1127.21 (17)
N1—C3—N2110.6 (2)C1—N1—Cu1127.28 (15)
N1—C3—H3124.7C3—N2—C2108.2 (2)
N2—C3—H3124.7C3—N2—H2A125 (3)
O1—C4—O2124.91 (19)C2—N2—H2A126 (3)
O1—C4—C5120.90 (19)C4—O2—Cu1117.36 (13)
O2—C4—C5114.17 (18)O2ii—Cu1—O2180.000 (1)
C7—C5—C6119.12 (18)O2ii—Cu1—N190.10 (7)
C7—C5—C4120.45 (19)O2—Cu1—N189.90 (7)
C6—C5—C4120.42 (18)O2ii—Cu1—N1ii89.90 (7)
C7i—C6—C5120.00 (19)O2—Cu1—N1ii90.10 (7)
C7i—C6—H6120.0N1—Cu1—N1ii180.0
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···AD—HH···AD···AD—H···A
N2—H2A···O1iii0.78 (4)2.11 (4)2.851 (3)157 (4)
Symmetry code: (iii) x, y+1, z1/2.

Experimental details

Crystal data
Chemical formula[Cu(C8H4O4)(C3H4N2)2]
Mr363.82
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)21.435 (4), 5.2740 (11), 14.164 (3)
β (°) 116.65 (3)
V3)1431.1 (5)
Z4
Radiation typeMo Kα
µ (mm1)1.55
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.634, 0.733
No. of measured, independent and
observed [I > 2σ(I)] reflections
6976, 1641, 1440
Rint0.048
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.085, 1.08
No. of reflections1641
No. of parameters110
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···O1i0.78 (4)2.11 (4)2.851 (3)157 (4)
Symmetry code: (i) x, y+1, z1/2.
 

Acknowledgements

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

References

First citationFu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997.  Web of Science CSD CrossRef CAS Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYe, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554–6555.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationZhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationZhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300–7302.  Web of Science CSD CrossRef CAS PubMed Google Scholar

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ISSN: 2056-9890
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