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In the polymeric title compound, [Cu(im)Cl(phen)]n, where im is the imidazolate anion (C3H3N2) and phen is 1,10-phenanthroline (C12H8N2), each CuII 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 [pi]-[pi] 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010402311X/ta1475sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010402311X/ta1475Isup2.hkl
Contains datablock I

CCDC reference: 256992

Comment top

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 ππ 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 ππ 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.

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The coordination environment of the CuII ion in (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) x − 1/2, y, 1/2 − z.]
[Figure 2] Fig. 2. A view of the one-dimensional zigzag chain of (I), along the a axis. H atoms have been omitted for clarity. [Symmetry code: (i) x − 1/2, y, 1/2 − z.]
[Figure 3] Fig. 3. A perspective view of the two-dimensional network in (I), along the b axis. H atoms have been omitted for clarity.
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 = 346.27Dx = 1.689 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4117 reflections
a = 9.5540 (5) Åθ = 2.6–25.0°
b = 15.4561 (11) ŵ = 1.80 mm1
c = 18.4412 (9) ÅT = 298 K
V = 2723.2 (3) Å3Block, green
Z = 80.17 × 0.15 × 0.14 mm
Data collection top
Bruker APEX CCD area-detector
diffractometer
2443 independent reflections
Radiation source: fine-focus sealed tube2096 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 25.2°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = 1011
Tmin = 0.750, Tmax = 0.787k = 1816
13486 measured reflectionsl = 2214
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H-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 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
[Cu(C3H3N2)Cl(C12H8N2)]V = 2723.2 (3) Å3
Mr = 346.27Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 9.5540 (5) ŵ = 1.80 mm1
b = 15.4561 (11) ÅT = 298 K
c = 18.4412 (9) Å0.17 × 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 = 0.787Rint = 0.031
13486 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 1.05Δρmax = 0.38 e Å3
2443 reflectionsΔρmin = 0.22 e Å3
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
xyzUiso*/Ueq
Cu10.21624 (3)0.875133 (18)0.342460 (15)0.02647 (11)
Cl10.20368 (7)0.71854 (4)0.31943 (4)0.03611 (17)
N10.0401 (2)0.89634 (13)0.41078 (11)0.0293 (5)
N20.3035 (2)0.85807 (13)0.44281 (11)0.0288 (5)
N30.3999 (2)0.91447 (13)0.30275 (10)0.0291 (5)
N40.6030 (2)0.90960 (13)0.24255 (11)0.0304 (5)
C10.0904 (3)0.91788 (16)0.39392 (15)0.0364 (6)
H10.11230.92870.34560.044*
C20.1961 (3)0.92497 (18)0.44612 (17)0.0433 (7)
H20.28640.94050.43230.052*
C30.1665 (3)0.90903 (19)0.51732 (16)0.0455 (7)
H30.23650.91330.55220.055*
C40.0294 (3)0.88618 (16)0.53755 (14)0.0373 (6)
C50.0129 (3)0.86706 (19)0.61057 (15)0.0478 (8)
H50.05310.86900.64760.057*
C60.1458 (3)0.8464 (2)0.62631 (15)0.0470 (7)
H60.17030.83470.67410.056*
C70.2504 (3)0.84217 (17)0.57104 (14)0.0373 (6)
C80.3919 (3)0.82269 (17)0.58382 (15)0.0429 (7)
H80.42270.81080.63060.052*
C90.4833 (3)0.82133 (17)0.52747 (16)0.0416 (7)
H90.57720.80860.53560.050*
C100.4362 (3)0.83911 (17)0.45716 (15)0.0362 (6)
H100.50010.83760.41910.043*
C110.2119 (3)0.85946 (15)0.49912 (14)0.0295 (5)
C120.0698 (3)0.88142 (14)0.48163 (13)0.0286 (5)
C130.4912 (2)0.86555 (16)0.26610 (13)0.0305 (5)
H130.47830.80670.25780.037*
C140.4584 (3)0.99542 (17)0.30289 (15)0.0363 (6)
H140.41991.04430.32440.044*
C150.5817 (3)0.99249 (16)0.26647 (14)0.0355 (6)
H150.64171.03900.25900.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02188 (17)0.0370 (2)0.02048 (18)0.00109 (12)0.00074 (11)0.00062 (12)
Cl10.0376 (4)0.0350 (3)0.0357 (4)0.0015 (3)0.0033 (3)0.0009 (3)
N10.0266 (11)0.0346 (11)0.0266 (11)0.0004 (8)0.0013 (9)0.0024 (9)
N20.0276 (11)0.0346 (11)0.0241 (11)0.0007 (8)0.0009 (9)0.0016 (9)
N30.0263 (10)0.0354 (11)0.0256 (11)0.0014 (9)0.0020 (9)0.0012 (9)
N40.0269 (11)0.0410 (12)0.0232 (11)0.0023 (9)0.0021 (9)0.0007 (9)
C10.0324 (14)0.0400 (15)0.0369 (15)0.0011 (11)0.0006 (12)0.0036 (12)
C20.0258 (14)0.0483 (17)0.0556 (19)0.0009 (12)0.0031 (13)0.0070 (14)
C30.0392 (15)0.0508 (17)0.0465 (18)0.0084 (13)0.0170 (14)0.0138 (14)
C40.0383 (15)0.0416 (15)0.0321 (15)0.0107 (11)0.0096 (12)0.0061 (12)
C50.061 (2)0.0566 (19)0.0258 (15)0.0180 (15)0.0162 (14)0.0059 (13)
C60.063 (2)0.0568 (18)0.0216 (14)0.0157 (15)0.0013 (14)0.0037 (13)
C70.0505 (17)0.0352 (14)0.0263 (14)0.0064 (12)0.0057 (12)0.0002 (11)
C80.0570 (19)0.0388 (16)0.0330 (15)0.0052 (13)0.0199 (14)0.0052 (12)
C90.0369 (15)0.0417 (16)0.0462 (17)0.0007 (12)0.0156 (14)0.0018 (13)
C100.0300 (13)0.0413 (15)0.0373 (15)0.0005 (11)0.0026 (12)0.0015 (12)
C110.0339 (13)0.0291 (13)0.0256 (13)0.0037 (10)0.0015 (11)0.0017 (10)
C120.0330 (13)0.0296 (13)0.0232 (13)0.0060 (10)0.0024 (11)0.0039 (10)
C130.0300 (13)0.0352 (14)0.0262 (13)0.0003 (10)0.0030 (11)0.0005 (10)
C140.0357 (14)0.0334 (14)0.0397 (16)0.0005 (11)0.0044 (12)0.0079 (11)
C150.0330 (13)0.0386 (15)0.0349 (14)0.0075 (11)0.0010 (12)0.0038 (11)
Geometric parameters (Å, º) top
Cu1—N4i1.978 (2)C3—H30.9300
Cu1—N31.996 (2)C4—C121.403 (3)
Cu1—N22.047 (2)C4—C51.436 (4)
Cu1—N12.128 (2)C5—C61.341 (4)
Cu1—Cl12.4603 (7)C5—H50.9300
Cu1—Cu1i5.8693 (4)C6—C71.429 (4)
N1—C11.327 (3)C6—H60.9300
N1—C121.357 (3)C7—C111.402 (4)
N2—C101.328 (3)C7—C81.405 (4)
N2—C111.358 (3)C8—C91.358 (4)
N3—C131.338 (3)C8—H80.9300
N3—C141.370 (3)C9—C101.400 (4)
N4—C131.339 (3)C9—H90.9300
N4—C151.370 (3)C10—H100.9300
N4—Cu1ii1.978 (2)C11—C121.436 (3)
C1—C21.400 (4)C13—H130.9300
C1—H10.9300C14—C151.357 (4)
C2—C31.366 (4)C14—H140.9300
C2—H20.9300C15—H150.9300
C3—C41.407 (4)
N4i—Cu1—N396.20 (8)C12—C4—C3116.6 (3)
N4i—Cu1—N2166.95 (8)C12—C4—C5119.2 (3)
N3—Cu1—N290.74 (8)C3—C4—C5124.2 (3)
N4i—Cu1—N189.72 (8)C6—C5—C4121.2 (3)
N3—Cu1—N1149.95 (8)C6—C5—H5119.4
N2—Cu1—N178.85 (8)C4—C5—H5119.4
N4i—Cu1—Cl195.82 (6)C5—C6—C7121.3 (3)
N3—Cu1—Cl1106.21 (6)C5—C6—H6119.4
N2—Cu1—Cl192.82 (6)C7—C6—H6119.4
N1—Cu1—Cl1102.43 (6)C11—C7—C8116.9 (3)
N4i—Cu1—Cu1i25.07 (6)C11—C7—C6118.9 (3)
N3—Cu1—Cu1i120.15 (6)C8—C7—C6124.3 (3)
N2—Cu1—Cu1i148.97 (6)C9—C8—C7119.6 (2)
N1—Cu1—Cu1i72.56 (5)C9—C8—H8120.2
Cl1—Cu1—Cu1i81.953 (16)C7—C8—H8120.2
C1—N1—C12117.7 (2)C8—C9—C10119.9 (3)
C1—N1—Cu1130.00 (18)C8—C9—H9120.0
C12—N1—Cu1112.25 (16)C10—C9—H9120.0
C10—N2—C11117.8 (2)N2—C10—C9122.3 (3)
C10—N2—Cu1126.70 (18)N2—C10—H10118.8
C11—N2—Cu1115.26 (16)C9—C10—H10118.8
C13—N3—C14104.5 (2)N2—C11—C7123.5 (2)
C13—N3—Cu1125.90 (17)N2—C11—C12116.2 (2)
C14—N3—Cu1129.50 (17)C7—C11—C12120.4 (2)
C13—N4—C15104.6 (2)N1—C12—C4123.9 (2)
C13—N4—Cu1ii123.81 (17)N1—C12—C11117.0 (2)
C15—N4—Cu1ii126.03 (17)C4—C12—C11119.1 (2)
N1—C1—C2122.4 (3)N3—C13—N4113.4 (2)
N1—C1—H1118.8N3—C13—H13123.3
C2—C1—H1118.8N4—C13—H13123.3
C3—C2—C1119.8 (3)C15—C14—N3108.8 (2)
C3—C2—H2120.1C15—C14—H14125.6
C1—C2—H2120.1N3—C14—H14125.6
C2—C3—C4119.6 (3)C14—C15—N4108.6 (2)
C2—C3—H3120.2C14—C15—H15125.7
C4—C3—H3120.2N4—C15—H15125.7
Symmetry codes: (i) x1/2, y, z+1/2; (ii) x+1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···Cl1iii0.932.823.741 (3)170
C5—H5···Cl1iv0.932.763.485 (3)136
Symmetry codes: (iii) x, y+3/2, z+1/2; (iv) x1/2, y+3/2, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C3H3N2)Cl(C12H8N2)]
Mr346.27
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)298
a, b, c (Å)9.5540 (5), 15.4561 (11), 18.4412 (9)
V3)2723.2 (3)
Z8
Radiation typeMo Kα
µ (mm1)1.80
Crystal size (mm)0.17 × 0.15 × 0.14
Data collection
DiffractometerBruker APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.750, 0.787
No. of measured, independent and
observed [I > 2σ(I)] reflections
13486, 2443, 2096
Rint0.031
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.074, 1.05
No. of reflections2443
No. of parameters190
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.22

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 2002), SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—N4i1.978 (2)Cu1—N12.128 (2)
Cu1—N31.996 (2)Cu1—Cl12.4603 (7)
Cu1—N22.047 (2)Cu1—Cu1i5.8693 (4)
N4i—Cu1—N396.20 (8)N2—Cu1—N178.85 (8)
N4i—Cu1—N2166.95 (8)N4i—Cu1—Cl195.82 (6)
N3—Cu1—N290.74 (8)N3—Cu1—Cl1106.21 (6)
N4i—Cu1—N189.72 (8)N2—Cu1—Cl192.82 (6)
N3—Cu1—N1149.95 (8)N1—Cu1—Cl1102.43 (6)
Symmetry code: (i) x1/2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···Cl1ii0.932.823.741 (3)170
C5—H5···Cl1iii0.932.763.485 (3)136
Symmetry codes: (ii) x, y+3/2, z+1/2; (iii) x1/2, y+3/2, z+1.
 

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