In the polymeric title compound, [Cu(im)Cl(phen)]
n, where im is the imidazolate anion (C
3H
3N
2) and phen is 1,10-phenanthroline (C
12H
8N
2), each Cu
II ion is five-coordinated by four basal N atoms (two from two different im anions and two from one phen ligand) and one axial Cl atom, in a distorted square-pyramidal coordination geometry. Moreover, each im anion bridges two identical {CuCl(phen)}
+ cations through its two N atoms, resulting in a one-dimensional zigzag chain along the crystallographic
a axis. In addition, pairs of adjacent chains are staggered by
-
interactions, generating a two-dimensional layer, and neighbouring layers are further linked by two different kinds of C-H
Cl interactions, producing a three-dimensional network.
Supporting information
CCDC reference: 256992
The title compound was synthesized by a hydrothermal method from a mixture of imidzole (2 mmol, 0.14 g), CuCl2·2H2O (1 mmol, 0.17 g) and 1,10-phenanthroline (3 mmol, 0.54 g) in water (20 ml) in a 30 ml Teflon-lined stainless steel reactor. The solution was heated to 425 K for 5 d, after which the reaction system was slowly cooled to room temperature. Green block crystals of (I) were collected and washed with distilled water.
The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances of 0.93 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.
catena-Poly[[chloro(1,10-phenanthroline-
κ2N,
N')copper(II)]-µ-1,3- imidazolato-
κ2N:
N']
top
Crystal data top
[Cu(C3H3N2)Cl(C12H8N2)] | F(000) = 1400 |
Mr = 346.27 | Dx = 1.689 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4117 reflections |
a = 9.5540 (5) Å | θ = 2.6–25.0° |
b = 15.4561 (11) Å | µ = 1.80 mm−1 |
c = 18.4412 (9) Å | T = 298 K |
V = 2723.2 (3) Å3 | Block, green |
Z = 8 | 0.17 × 0.15 × 0.14 mm |
Data collection top
Bruker APEX CCD area-detector diffractometer | 2443 independent reflections |
Radiation source: fine-focus sealed tube | 2096 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ϕ and ω scans | θmax = 25.2°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −10→11 |
Tmin = 0.750, Tmax = 0.787 | k = −18→16 |
13486 measured reflections | l = −22→14 |
Refinement top
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0344P)2 + 1.7259P] where P = (Fo2 + 2Fc2)/3 |
2443 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
[Cu(C3H3N2)Cl(C12H8N2)] | V = 2723.2 (3) Å3 |
Mr = 346.27 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.5540 (5) Å | µ = 1.80 mm−1 |
b = 15.4561 (11) Å | T = 298 K |
c = 18.4412 (9) Å | 0.17 × 0.15 × 0.14 mm |
Data collection top
Bruker APEX CCD area-detector diffractometer | 2443 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 2096 reflections with I > 2σ(I) |
Tmin = 0.750, Tmax = 0.787 | Rint = 0.031 |
13486 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.38 e Å−3 |
2443 reflections | Δρmin = −0.22 e Å−3 |
190 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 | Uiso*/Ueq | |
Cu1 | 0.21624 (3) | 0.875133 (18) | 0.342460 (15) | 0.02647 (11) | |
Cl1 | 0.20368 (7) | 0.71854 (4) | 0.31943 (4) | 0.03611 (17) | |
N1 | 0.0401 (2) | 0.89634 (13) | 0.41078 (11) | 0.0293 (5) | |
N2 | 0.3035 (2) | 0.85807 (13) | 0.44281 (11) | 0.0288 (5) | |
N3 | 0.3999 (2) | 0.91447 (13) | 0.30275 (10) | 0.0291 (5) | |
N4 | 0.6030 (2) | 0.90960 (13) | 0.24255 (11) | 0.0304 (5) | |
C1 | −0.0904 (3) | 0.91788 (16) | 0.39392 (15) | 0.0364 (6) | |
H1 | −0.1123 | 0.9287 | 0.3456 | 0.044* | |
C2 | −0.1961 (3) | 0.92497 (18) | 0.44612 (17) | 0.0433 (7) | |
H2 | −0.2864 | 0.9405 | 0.4323 | 0.052* | |
C3 | −0.1665 (3) | 0.90903 (19) | 0.51732 (16) | 0.0455 (7) | |
H3 | −0.2365 | 0.9133 | 0.5522 | 0.055* | |
C4 | −0.0294 (3) | 0.88618 (16) | 0.53755 (14) | 0.0373 (6) | |
C5 | 0.0129 (3) | 0.86706 (19) | 0.61057 (15) | 0.0478 (8) | |
H5 | −0.0531 | 0.8690 | 0.6476 | 0.057* | |
C6 | 0.1458 (3) | 0.8464 (2) | 0.62631 (15) | 0.0470 (7) | |
H6 | 0.1703 | 0.8347 | 0.6741 | 0.056* | |
C7 | 0.2504 (3) | 0.84217 (17) | 0.57104 (14) | 0.0373 (6) | |
C8 | 0.3919 (3) | 0.82269 (17) | 0.58382 (15) | 0.0429 (7) | |
H8 | 0.4227 | 0.8108 | 0.6306 | 0.052* | |
C9 | 0.4833 (3) | 0.82133 (17) | 0.52747 (16) | 0.0416 (7) | |
H9 | 0.5772 | 0.8086 | 0.5356 | 0.050* | |
C10 | 0.4362 (3) | 0.83911 (17) | 0.45716 (15) | 0.0362 (6) | |
H10 | 0.5001 | 0.8376 | 0.4191 | 0.043* | |
C11 | 0.2119 (3) | 0.85946 (15) | 0.49912 (14) | 0.0295 (5) | |
C12 | 0.0698 (3) | 0.88142 (14) | 0.48163 (13) | 0.0286 (5) | |
C13 | 0.4912 (2) | 0.86555 (16) | 0.26610 (13) | 0.0305 (5) | |
H13 | 0.4783 | 0.8067 | 0.2578 | 0.037* | |
C14 | 0.4584 (3) | 0.99542 (17) | 0.30289 (15) | 0.0363 (6) | |
H14 | 0.4199 | 1.0443 | 0.3244 | 0.044* | |
C15 | 0.5817 (3) | 0.99249 (16) | 0.26647 (14) | 0.0355 (6) | |
H15 | 0.6417 | 1.0390 | 0.2590 | 0.043* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.02188 (17) | 0.0370 (2) | 0.02048 (18) | −0.00109 (12) | −0.00074 (11) | 0.00062 (12) |
Cl1 | 0.0376 (4) | 0.0350 (3) | 0.0357 (4) | −0.0015 (3) | −0.0033 (3) | −0.0009 (3) |
N1 | 0.0266 (11) | 0.0346 (11) | 0.0266 (11) | −0.0004 (8) | 0.0013 (9) | −0.0024 (9) |
N2 | 0.0276 (11) | 0.0346 (11) | 0.0241 (11) | −0.0007 (8) | −0.0009 (9) | −0.0016 (9) |
N3 | 0.0263 (10) | 0.0354 (11) | 0.0256 (11) | −0.0014 (9) | 0.0020 (9) | −0.0012 (9) |
N4 | 0.0269 (11) | 0.0410 (12) | 0.0232 (11) | −0.0023 (9) | 0.0021 (9) | −0.0007 (9) |
C1 | 0.0324 (14) | 0.0400 (15) | 0.0369 (15) | 0.0011 (11) | −0.0006 (12) | −0.0036 (12) |
C2 | 0.0258 (14) | 0.0483 (17) | 0.0556 (19) | −0.0009 (12) | 0.0031 (13) | −0.0070 (14) |
C3 | 0.0392 (15) | 0.0508 (17) | 0.0465 (18) | −0.0084 (13) | 0.0170 (14) | −0.0138 (14) |
C4 | 0.0383 (15) | 0.0416 (15) | 0.0321 (15) | −0.0107 (11) | 0.0096 (12) | −0.0061 (12) |
C5 | 0.061 (2) | 0.0566 (19) | 0.0258 (15) | −0.0180 (15) | 0.0162 (14) | −0.0059 (13) |
C6 | 0.063 (2) | 0.0568 (18) | 0.0216 (14) | −0.0157 (15) | −0.0013 (14) | 0.0037 (13) |
C7 | 0.0505 (17) | 0.0352 (14) | 0.0263 (14) | −0.0064 (12) | −0.0057 (12) | 0.0002 (11) |
C8 | 0.0570 (19) | 0.0388 (16) | 0.0330 (15) | −0.0052 (13) | −0.0199 (14) | 0.0052 (12) |
C9 | 0.0369 (15) | 0.0417 (16) | 0.0462 (17) | 0.0007 (12) | −0.0156 (14) | 0.0018 (13) |
C10 | 0.0300 (13) | 0.0413 (15) | 0.0373 (15) | 0.0005 (11) | −0.0026 (12) | −0.0015 (12) |
C11 | 0.0339 (13) | 0.0291 (13) | 0.0256 (13) | −0.0037 (10) | −0.0015 (11) | −0.0017 (10) |
C12 | 0.0330 (13) | 0.0296 (13) | 0.0232 (13) | −0.0060 (10) | 0.0024 (11) | −0.0039 (10) |
C13 | 0.0300 (13) | 0.0352 (14) | 0.0262 (13) | 0.0003 (10) | 0.0030 (11) | −0.0005 (10) |
C14 | 0.0357 (14) | 0.0334 (14) | 0.0397 (16) | −0.0005 (11) | 0.0044 (12) | −0.0079 (11) |
C15 | 0.0330 (13) | 0.0386 (15) | 0.0349 (14) | −0.0075 (11) | 0.0010 (12) | −0.0038 (11) |
Geometric parameters (Å, º) top
Cu1—N4i | 1.978 (2) | C3—H3 | 0.9300 |
Cu1—N3 | 1.996 (2) | C4—C12 | 1.403 (3) |
Cu1—N2 | 2.047 (2) | C4—C5 | 1.436 (4) |
Cu1—N1 | 2.128 (2) | C5—C6 | 1.341 (4) |
Cu1—Cl1 | 2.4603 (7) | C5—H5 | 0.9300 |
Cu1—Cu1i | 5.8693 (4) | C6—C7 | 1.429 (4) |
N1—C1 | 1.327 (3) | C6—H6 | 0.9300 |
N1—C12 | 1.357 (3) | C7—C11 | 1.402 (4) |
N2—C10 | 1.328 (3) | C7—C8 | 1.405 (4) |
N2—C11 | 1.358 (3) | C8—C9 | 1.358 (4) |
N3—C13 | 1.338 (3) | C8—H8 | 0.9300 |
N3—C14 | 1.370 (3) | C9—C10 | 1.400 (4) |
N4—C13 | 1.339 (3) | C9—H9 | 0.9300 |
N4—C15 | 1.370 (3) | C10—H10 | 0.9300 |
N4—Cu1ii | 1.978 (2) | C11—C12 | 1.436 (3) |
C1—C2 | 1.400 (4) | C13—H13 | 0.9300 |
C1—H1 | 0.9300 | C14—C15 | 1.357 (4) |
C2—C3 | 1.366 (4) | C14—H14 | 0.9300 |
C2—H2 | 0.9300 | C15—H15 | 0.9300 |
C3—C4 | 1.407 (4) | | |
| | | |
N4i—Cu1—N3 | 96.20 (8) | C12—C4—C3 | 116.6 (3) |
N4i—Cu1—N2 | 166.95 (8) | C12—C4—C5 | 119.2 (3) |
N3—Cu1—N2 | 90.74 (8) | C3—C4—C5 | 124.2 (3) |
N4i—Cu1—N1 | 89.72 (8) | C6—C5—C4 | 121.2 (3) |
N3—Cu1—N1 | 149.95 (8) | C6—C5—H5 | 119.4 |
N2—Cu1—N1 | 78.85 (8) | C4—C5—H5 | 119.4 |
N4i—Cu1—Cl1 | 95.82 (6) | C5—C6—C7 | 121.3 (3) |
N3—Cu1—Cl1 | 106.21 (6) | C5—C6—H6 | 119.4 |
N2—Cu1—Cl1 | 92.82 (6) | C7—C6—H6 | 119.4 |
N1—Cu1—Cl1 | 102.43 (6) | C11—C7—C8 | 116.9 (3) |
N4i—Cu1—Cu1i | 25.07 (6) | C11—C7—C6 | 118.9 (3) |
N3—Cu1—Cu1i | 120.15 (6) | C8—C7—C6 | 124.3 (3) |
N2—Cu1—Cu1i | 148.97 (6) | C9—C8—C7 | 119.6 (2) |
N1—Cu1—Cu1i | 72.56 (5) | C9—C8—H8 | 120.2 |
Cl1—Cu1—Cu1i | 81.953 (16) | C7—C8—H8 | 120.2 |
C1—N1—C12 | 117.7 (2) | C8—C9—C10 | 119.9 (3) |
C1—N1—Cu1 | 130.00 (18) | C8—C9—H9 | 120.0 |
C12—N1—Cu1 | 112.25 (16) | C10—C9—H9 | 120.0 |
C10—N2—C11 | 117.8 (2) | N2—C10—C9 | 122.3 (3) |
C10—N2—Cu1 | 126.70 (18) | N2—C10—H10 | 118.8 |
C11—N2—Cu1 | 115.26 (16) | C9—C10—H10 | 118.8 |
C13—N3—C14 | 104.5 (2) | N2—C11—C7 | 123.5 (2) |
C13—N3—Cu1 | 125.90 (17) | N2—C11—C12 | 116.2 (2) |
C14—N3—Cu1 | 129.50 (17) | C7—C11—C12 | 120.4 (2) |
C13—N4—C15 | 104.6 (2) | N1—C12—C4 | 123.9 (2) |
C13—N4—Cu1ii | 123.81 (17) | N1—C12—C11 | 117.0 (2) |
C15—N4—Cu1ii | 126.03 (17) | C4—C12—C11 | 119.1 (2) |
N1—C1—C2 | 122.4 (3) | N3—C13—N4 | 113.4 (2) |
N1—C1—H1 | 118.8 | N3—C13—H13 | 123.3 |
C2—C1—H1 | 118.8 | N4—C13—H13 | 123.3 |
C3—C2—C1 | 119.8 (3) | C15—C14—N3 | 108.8 (2) |
C3—C2—H2 | 120.1 | C15—C14—H14 | 125.6 |
C1—C2—H2 | 120.1 | N3—C14—H14 | 125.6 |
C2—C3—C4 | 119.6 (3) | C14—C15—N4 | 108.6 (2) |
C2—C3—H3 | 120.2 | C14—C15—H15 | 125.7 |
C4—C3—H3 | 120.2 | N4—C15—H15 | 125.7 |
Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cl1iii | 0.93 | 2.82 | 3.741 (3) | 170 |
C5—H5···Cl1iv | 0.93 | 2.76 | 3.485 (3) | 136 |
Symmetry codes: (iii) x, −y+3/2, z+1/2; (iv) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Cu(C3H3N2)Cl(C12H8N2)] |
Mr | 346.27 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 9.5540 (5), 15.4561 (11), 18.4412 (9) |
V (Å3) | 2723.2 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.17 × 0.15 × 0.14 |
|
Data collection |
Diffractometer | Bruker APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.750, 0.787 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13486, 2443, 2096 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.074, 1.05 |
No. of reflections | 2443 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.22 |
Selected geometric parameters (Å, º) topCu1—N4i | 1.978 (2) | Cu1—N1 | 2.128 (2) |
Cu1—N3 | 1.996 (2) | Cu1—Cl1 | 2.4603 (7) |
Cu1—N2 | 2.047 (2) | Cu1—Cu1i | 5.8693 (4) |
| | | |
N4i—Cu1—N3 | 96.20 (8) | N2—Cu1—N1 | 78.85 (8) |
N4i—Cu1—N2 | 166.95 (8) | N4i—Cu1—Cl1 | 95.82 (6) |
N3—Cu1—N2 | 90.74 (8) | N3—Cu1—Cl1 | 106.21 (6) |
N4i—Cu1—N1 | 89.72 (8) | N2—Cu1—Cl1 | 92.82 (6) |
N3—Cu1—N1 | 149.95 (8) | N1—Cu1—Cl1 | 102.43 (6) |
Symmetry code: (i) x−1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···Cl1ii | 0.93 | 2.82 | 3.741 (3) | 170 |
C5—H5···Cl1iii | 0.93 | 2.76 | 3.485 (3) | 136 |
Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, −z+1. |
Imidazole plays an important role in biological systems, since the imidazole moiety of the histidyl residues in a large number of metalloproteins constitutes all or part of the binding sites of various transition metal ions (Messerschmidt, 1993). For example, studies of bovine erythrocyte superoxide dismutase reveal the presence of an imidazolate-bridged CuII—ZnII centre at the active site, and it can catalyze some biological reactions (Bertini et al., 1990; Kolks & Lippard, 1977). Furthermore, it is of interest that polydentate ligands incorporating an imidazole moiety can be used to synthesize metal complexes that are capable of undergoing reversible interconversions between a monomer and a self-assembled oligomer by the alteration of external conditions, specifically a change of pH (Matsumoto et al., 1999). By controlling the pH, it is then possible to interconvert a protonated monomer to an imidazolate-bridged deprotonated oligomer and vice versa, thus affording new functional materials with potential switching ability. In view of all this, studies aimed at characterizing the bonding between imidazole and transition metal ions are of considerable interest. There are numerous examples of synthesis, crystal structure determinations and characterizations of imidazolate-bridged complexes (Mao et al., 1995; Koch et al., 1989; Colacio et al., 1998, and references therein). We have selected the Cu-im-phen system to extend this research and we present here the crystal structure of the title compound, [Cu(im)(phen)Cl]n, (I). \sch
In the molecule of (I), each CuII ion is five-coordinated, with a distorted square-pyramidal geometry (Fig. 1 and Table 1). The basal plane is formed by atoms N1 and N2 from one phen ligand, along with atoms N3 and N4i from two im anions, with a mean deviation of 0.1785 Å, with a Cl− ion, Cl1, occupying the apical position [symmetry code: (i) x − 1/2, y, 1/2 − z]. The Cu—Nimidazolate bond lengths are similar to those observed in imidazolate-bridged dicopper(II) complexes (Drew et al., 1980; Salata et al., 1991) and are shorter than the average basal Cu—N bond length (2.037 Å) around Cu1 in (I). Atom Cu1 is not on the basal plane, but is located 0.335 (1) Å out of the mean basal plane towards atom Cl1.
According to the valence-bond theory, if a Cu(d9) ion is five-coordinated, there will be two probable coordination geometries around the metal ion, trigonal-bipyramidal and square pyramidal. In the former, the Cu ion adopts dsp3 or sp3d hybridization, and in the latter d2sp2 or sp2d2. These two configurations of a d9 ion possess approximately equal energy and they can interconvert. If the coordination polyhedron is a regular square pyramid, the distortion value is 0, and if it is a regular trigonal bipyramid, the distortion value is 1. The distortion value of the coordination polyhedron for CuIIion in (I) has been calculated according to the method reported by van Albada and Addison (van Albada et al., 1999; Addison et al., 1984). The distortion value of 0.283 obtained for Cu1 indicates that the coordination geometry around each CuII ion in (I) is a distorted square pyramid and that the Cu(d9) ions probably adopt sp2d2 hybrid orbitals to accept the electrons of the ligands, which may be favourable to the paramagnetism and stability of (I).
Each im anion in (I) acts as a bidentate ligand, connecting two CuII ions through its two N atoms, resulting in a one-dimensional zigzag chain along the crystallographic a axis with a Cu1···Cu1i separation of 5.8693 (4) Å (Fig. 2). In order to minimize steric effects, the dihedral angle between the im ring and the heterocyclic ring of phen in each subunit is 89.44 (8)° and within the chain all heterocyclic rings are approximately parallel to each other. Interestingly, the im plane is approximately perpendicular to the basal plane [88.80 (9)°], while the dihedral angle between the heterocyclic rings and the basal plane is only 10.65 (4)°.
In the crystal of (I), there are π–π interactions between inversion-related rings of the phen moieties [at (x, y, z) and (-x, 2 − y, 1 − z)], with the ring centroids separated by 3.489 Å. These π–π interactions link chains into extended layers approximately parallel to (010) (Fig. 3). The layers are linked into a three-dimensional network by the insertion of the apical Cl− ions of one layer into an adjacent layer and their stabilization there via C—H···Cl interactions (Table 2).
Table 2. Geometry of C—H···Cl interactions.