Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042109/cv2291sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042109/cv2291Isup2.hkl |
CCDC reference: 660732
The reaction of CuCl2.2H2O(0.85 g, 5 mmol) with o-phthalic acid (0.83 g, 5 mmol) in an aqueous-alcohol(3:1) solution(40 ml) at 363 K for 30 min produced a blue solution, to which 1-vinylimidazole (0.94 g, 10 mmol) was added. The reaction solution was kept at room temperature after stirring for an hour at 333 K. Blue crystals were obtained after a few days.
All H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 Ueq(C).
In the title compound, (I) (Fig. 1), the copper(II) centers are bridged by the carboxylate groups of o-phthalate ligiands and saturated by two 1-vinylimidazole ligands. Each CuII ion is located on a crystallographic center of symmetry being coordinated by two N [Cu—N 1.993 (3) Å] and two O [Cu—O 1.952 (2) Å] atoms in a distorted square-planar geometry. All these values agree well with those observed in [Cu(phthalato)(1-methylimidazole)2] (Baca et al., 2004), where CuII ions have a distorted tetrahedral environment. Each o-phthalate dianion acts as a bidentate ligand to bridge two CuII ions through two monodentate carboxylate groups, building a zigzag infinate chain structure along the c axis. The metal-metal distances across each polymer backbone are 7.231 (6) Å.
In the crystal, weak C—H···O (Table 1) interactions contribute to the crystal packing stability.
In the corresponding compound [Cu(phthalato)(1-methylimidazole)2] (Baca et al., 2004), CuII ions have a distorted tetrahedral environment.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.
[Cu(C8H4O4)(C5H6N2)2] | F(000) = 852 |
Mr = 415.90 | Dx = 1.537 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3318 reflections |
a = 16.527 (3) Å | θ = 2.5–25.1° |
b = 8.1800 (16) Å | µ = 1.25 mm−1 |
c = 14.463 (3) Å | T = 293 K |
β = 113.19 (3)° | Block, blue |
V = 1797.3 (7) Å3 | 0.30 × 0.20 × 0.10 mm |
Z = 4 |
Bruker SMART 1K CCD area-detector diffractometer | 1768 independent reflections |
Radiation source: fine-focus sealed tube | 1344 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
thin–slice ω scans | θmax = 26.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −20→20 |
Tmin = 0.706, Tmax = 0.885 | k = 0→10 |
3525 measured reflections | l = −17→17 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0844P)2 + 0.9237P] where P = (Fo2 + 2Fc2)/3 |
1768 reflections | (Δ/σ)max < 0.001 |
124 parameters | Δρmax = 0.75 e Å−3 |
40 restraints | Δρmin = −0.63 e Å−3 |
[Cu(C8H4O4)(C5H6N2)2] | V = 1797.3 (7) Å3 |
Mr = 415.90 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.527 (3) Å | µ = 1.25 mm−1 |
b = 8.1800 (16) Å | T = 293 K |
c = 14.463 (3) Å | 0.30 × 0.20 × 0.10 mm |
β = 113.19 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 1768 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1344 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.885 | Rint = 0.023 |
3525 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 40 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.75 e Å−3 |
1768 reflections | Δρmin = −0.63 e Å−3 |
124 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu | 0.0000 | 0.0000 | 0.0000 | 0.0333 (2) | |
O1 | −0.06590 (16) | −0.0922 (3) | 0.14946 (17) | 0.0480 (6) | |
O2 | 0.01489 (15) | −0.2039 (3) | 0.07497 (16) | 0.0423 (5) | |
N1 | 0.11711 (18) | 0.0724 (4) | 0.0994 (2) | 0.0431 (6) | |
C6 | 0.1839 (3) | 0.1421 (6) | 0.0812 (3) | 0.0679 (12) | |
H6A | 0.1818 | 0.1666 | 0.0175 | 0.081* | |
C1 | −0.0087 (3) | −0.6538 (5) | 0.1984 (3) | 0.0627 (11) | |
H1A | −0.0156 | −0.7519 | 0.1637 | 0.075* | |
C2 | −0.0155 (3) | −0.5079 (4) | 0.1493 (3) | 0.0486 (9) | |
H2B | −0.0253 | −0.5085 | 0.0814 | 0.058* | |
C3 | −0.00809 (19) | −0.3593 (4) | 0.1982 (2) | 0.0341 (7) | |
C4 | −0.0211 (2) | −0.2048 (4) | 0.1387 (2) | 0.0375 (7) | |
C5 | 0.1469 (2) | 0.0592 (5) | 0.1980 (3) | 0.0478 (8) | |
H5A | 0.1153 | 0.0148 | 0.2328 | 0.057* | |
N2 | 0.22960 (19) | 0.1189 (4) | 0.2419 (2) | 0.0533 (8) | |
C7 | 0.2538 (3) | 0.1709 (7) | 0.1679 (3) | 0.0728 (13) | |
H7A | 0.3074 | 0.2169 | 0.1752 | 0.087* | |
C8 | 0.2838 (3) | 0.1327 (6) | 0.3459 (3) | 0.0695 (12) | |
H8A | 0.3422 | 0.1638 | 0.3639 | 0.083* | |
C9 | 0.2577 (4) | 0.1057 (9) | 0.4147 (4) | 0.107 (2) | |
H9C | 0.1997 | 0.0745 | 0.3990 | 0.128* | |
H9A | 0.2963 | 0.1168 | 0.4816 | 0.128* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0317 (3) | 0.0411 (4) | 0.0270 (3) | 0.0012 (2) | 0.0114 (2) | 0.0024 (2) |
O1 | 0.0608 (15) | 0.0420 (14) | 0.0393 (13) | 0.0160 (11) | 0.0178 (11) | 0.0031 (10) |
O2 | 0.0444 (12) | 0.0481 (14) | 0.0360 (11) | 0.0018 (10) | 0.0176 (10) | 0.0065 (10) |
N1 | 0.0390 (14) | 0.0504 (16) | 0.0354 (14) | −0.0037 (13) | 0.0098 (11) | 0.0025 (13) |
C6 | 0.050 (2) | 0.103 (3) | 0.047 (2) | −0.020 (2) | 0.0159 (17) | 0.002 (2) |
C1 | 0.090 (3) | 0.038 (2) | 0.070 (3) | −0.0032 (19) | 0.042 (3) | −0.0090 (18) |
C2 | 0.059 (2) | 0.045 (2) | 0.046 (2) | −0.0037 (16) | 0.0252 (18) | −0.0069 (15) |
C3 | 0.0355 (15) | 0.0318 (16) | 0.0368 (16) | −0.0003 (12) | 0.0161 (13) | 0.0005 (13) |
C4 | 0.0365 (15) | 0.0401 (17) | 0.0311 (15) | −0.0041 (13) | 0.0082 (13) | −0.0012 (13) |
C5 | 0.0463 (19) | 0.0520 (19) | 0.0411 (17) | −0.0077 (16) | 0.0129 (15) | 0.0031 (16) |
N2 | 0.0452 (16) | 0.063 (2) | 0.0390 (15) | −0.0081 (14) | 0.0029 (13) | −0.0029 (14) |
C7 | 0.048 (2) | 0.105 (4) | 0.063 (2) | −0.026 (2) | 0.0194 (19) | 0.000 (2) |
C8 | 0.052 (2) | 0.090 (3) | 0.052 (2) | −0.018 (2) | 0.0054 (19) | −0.002 (2) |
C9 | 0.084 (4) | 0.165 (6) | 0.061 (3) | −0.039 (4) | 0.017 (3) | −0.019 (4) |
Cu—O2 | 1.952 (2) | C2—C3 | 1.387 (4) |
Cu—O2i | 1.952 (2) | C2—H2B | 0.9300 |
Cu—N1i | 1.993 (3) | C3—C3ii | 1.415 (6) |
Cu—N1 | 1.993 (3) | C3—C4 | 1.496 (4) |
O1—C4 | 1.228 (4) | C5—N2 | 1.351 (4) |
O2—C4 | 1.280 (4) | C5—H5A | 0.9300 |
N1—C5 | 1.317 (4) | N2—C7 | 1.351 (5) |
N1—C6 | 1.358 (5) | N2—C8 | 1.420 (5) |
C6—C7 | 1.350 (6) | C7—H7A | 0.9300 |
C6—H6A | 0.9300 | C8—C9 | 1.250 (7) |
C1—C2 | 1.371 (5) | C8—H8A | 0.9300 |
C1—C1ii | 1.405 (8) | C9—H9C | 0.9300 |
C1—H1A | 0.9300 | C9—H9A | 0.9300 |
O2—Cu—O2i | 180.00 (13) | C2—C3—C4 | 118.9 (3) |
O2—Cu—N1i | 91.21 (11) | C3ii—C3—C4 | 122.22 (16) |
O2i—Cu—N1i | 88.79 (11) | O1—C4—O2 | 124.1 (3) |
O2—Cu—N1 | 88.79 (11) | O1—C4—C3 | 121.2 (3) |
O2i—Cu—N1 | 91.21 (11) | O2—C4—C3 | 114.6 (3) |
N1i—Cu—N1 | 180.0 (2) | N1—C5—N2 | 110.9 (3) |
C4—O2—Cu | 114.3 (2) | N1—C5—H5A | 124.5 |
C5—N1—C6 | 105.0 (3) | N2—C5—H5A | 124.5 |
C5—N1—Cu | 126.9 (2) | C7—N2—C5 | 107.6 (3) |
C6—N1—Cu | 128.1 (2) | C7—N2—C8 | 123.6 (3) |
C7—C6—N1 | 110.9 (4) | C5—N2—C8 | 128.8 (3) |
C7—C6—H6A | 124.6 | C6—C7—N2 | 105.6 (3) |
N1—C6—H6A | 124.6 | C6—C7—H7A | 127.2 |
C2—C1—C1ii | 119.4 (2) | N2—C7—H7A | 127.2 |
C2—C1—H1A | 120.3 | C9—C8—N2 | 123.8 (4) |
C1ii—C1—H1A | 120.3 | C9—C8—H8A | 118.1 |
C1—C2—C3 | 121.7 (4) | N2—C8—H8A | 118.1 |
C1—C2—H2B | 119.2 | C8—C9—H9C | 120.0 |
C3—C2—H2B | 119.2 | C8—C9—H9A | 120.0 |
C2—C3—C3ii | 118.8 (2) | H9C—C9—H9A | 120.0 |
N1i—Cu—O2—C4 | −84.6 (2) | C2—C3—C4—O1 | 135.5 (3) |
N1—Cu—O2—C4 | 95.4 (2) | C3ii—C3—C4—O1 | −42.0 (5) |
O2—Cu—N1—C5 | −44.5 (3) | C2—C3—C4—O2 | −42.0 (4) |
O2i—Cu—N1—C5 | 135.5 (3) | C3ii—C3—C4—O2 | 140.5 (4) |
O2—Cu—N1—C6 | 133.9 (4) | C6—N1—C5—N2 | 0.3 (5) |
O2i—Cu—N1—C6 | −46.1 (4) | Cu—N1—C5—N2 | 179.1 (3) |
C5—N1—C6—C7 | 0.1 (5) | N1—C5—N2—C7 | −0.6 (5) |
Cu—N1—C6—C7 | −178.7 (3) | N1—C5—N2—C8 | 177.6 (4) |
C1ii—C1—C2—C3 | −1.9 (8) | N1—C6—C7—N2 | −0.4 (6) |
C1—C2—C3—C3ii | 0.9 (6) | C5—N2—C7—C6 | 0.6 (5) |
C1—C2—C3—C4 | −176.6 (4) | C8—N2—C7—C6 | −177.7 (4) |
Cu—O2—C4—O1 | 4.0 (4) | C7—N2—C8—C9 | 169.9 (6) |
Cu—O2—C4—C3 | −178.59 (18) | C5—N2—C8—C9 | −8.1 (9) |
Symmetry codes: (i) −x, −y, −z; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1ii | 0.93 | 2.33 | 3.243 (5) | 167 |
C6—H6A···O1i | 0.93 | 2.50 | 3.158 (5) | 128 |
C8—H8A···O2iii | 0.93 | 2.43 | 3.342 (6) | 168 |
C9—H9C···O1ii | 0.93 | 2.45 | 3.349 (8) | 162 |
Symmetry codes: (i) −x, −y, −z; (ii) −x, y, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H4O4)(C5H6N2)2] |
Mr | 415.90 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.527 (3), 8.1800 (16), 14.463 (3) |
β (°) | 113.19 (3) |
V (Å3) | 1797.3 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.706, 0.885 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3525, 1768, 1344 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.136, 1.00 |
No. of reflections | 1768 |
No. of parameters | 124 |
No. of restraints | 40 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −0.63 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2001) and local programs.
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1i | 0.93 | 2.33 | 3.243 (5) | 167 |
C6—H6A···O1ii | 0.93 | 2.50 | 3.158 (5) | 128 |
C8—H8A···O2iii | 0.93 | 2.43 | 3.342 (6) | 168 |
C9—H9C···O1i | 0.93 | 2.45 | 3.349 (8) | 162 |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y, −z; (iii) −x+1/2, y+1/2, −z+1/2. |
In the title compound, (I) (Fig. 1), the copper(II) centers are bridged by the carboxylate groups of o-phthalate ligiands and saturated by two 1-vinylimidazole ligands. Each CuII ion is located on a crystallographic center of symmetry being coordinated by two N [Cu—N 1.993 (3) Å] and two O [Cu—O 1.952 (2) Å] atoms in a distorted square-planar geometry. All these values agree well with those observed in [Cu(phthalato)(1-methylimidazole)2] (Baca et al., 2004), where CuII ions have a distorted tetrahedral environment. Each o-phthalate dianion acts as a bidentate ligand to bridge two CuII ions through two monodentate carboxylate groups, building a zigzag infinate chain structure along the c axis. The metal-metal distances across each polymer backbone are 7.231 (6) Å.
In the crystal, weak C—H···O (Table 1) interactions contribute to the crystal packing stability.