Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104009102/sq1155sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104009102/sq1155Isup2.hkl |
CCDC reference: 243577
A solution (5 ml) of CuCl2·4H2O (20.6 mg, 0.1 mmol) in water was added to an aqueous solution (5 ml) of Hambi·2HCl (22.1 mg, 0.1 mmol). Blue microcrystals were obtained by adding KSCN (19.6 mg, 0.2 mmol) dissolved in a minimum volume of water. Acetonitrile (~5 ml) was added until all of the precipitate dissolved. The mixture was filtered and the filtrate was evaporated slowly, generating blue–green needle-shaped single crystals suitable for X-ray diffraction analysis (yield 60%).
H atoms bound to C and N atoms were visible in difference maps and were placed using the HFIX commands in SHELXL97. All H atoms were allowed for as riding atoms (C—H = 0.97 Å and N—H = 0.86 Å).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97.
[Cu(NCS)2(C8H9N3)] | F(000) = 660 |
Mr = 326.88 | Dx = 1.691 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1428 reflections |
a = 9.522 (3) Å | θ = 2.5–25° |
b = 12.707 (4) Å | µ = 2.01 mm−1 |
c = 10.757 (3) Å | T = 293 K |
β = 99.418 (6)° | Prism, blue |
V = 1284.0 (7) Å3 | 0.14 × 0.10 × 0.06 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2257 independent reflections |
Radiation source: fine-focus sealed tube | 1428 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 15×15 microns pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −15→12 |
Tmin = 0.708, Tmax = 0.886 | l = −12→8 |
6534 measured reflections |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.029P)2] where P = (Fo2 + 2Fc2)/3 |
2257 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Cu(NCS)2(C8H9N3)] | V = 1284.0 (7) Å3 |
Mr = 326.88 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.522 (3) Å | µ = 2.01 mm−1 |
b = 12.707 (4) Å | T = 293 K |
c = 10.757 (3) Å | 0.14 × 0.10 × 0.06 mm |
β = 99.418 (6)° |
Bruker SMART CCD area-detector diffractometer | 2257 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1428 reflections with I > 2σ(I) |
Tmin = 0.708, Tmax = 0.886 | Rint = 0.073 |
6534 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.35 e Å−3 |
2257 reflections | Δρmin = −0.42 e Å−3 |
163 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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.34356 (6) | 0.29937 (5) | 0.24114 (5) | 0.03576 (19) | |
S2 | 0.60937 (13) | 0.20985 (11) | 0.63538 (11) | 0.0424 (3) | |
S1 | 0.25003 (16) | −0.03217 (11) | 0.05239 (13) | 0.0549 (4) | |
N5 | 0.2285 (4) | 0.3738 (3) | 0.0991 (3) | 0.0312 (9) | |
N1 | 0.2954 (4) | 0.1596 (3) | 0.1765 (4) | 0.0418 (11) | |
N2 | 0.4389 (5) | 0.2509 (3) | 0.4042 (4) | 0.0480 (12) | |
C5 | 0.1150 (5) | 0.4422 (4) | −0.0856 (4) | 0.0321 (12) | |
N4 | 0.2109 (4) | 0.5146 (3) | −0.0226 (4) | 0.0385 (10) | |
H4A | 0.2269 | 0.5769 | −0.0482 | 0.046* | |
N3 | 0.4007 (4) | 0.4486 (3) | 0.2917 (3) | 0.0440 (11) | |
H3A | 0.3455 | 0.4726 | 0.3460 | 0.053* | |
H3D | 0.4917 | 0.4493 | 0.3311 | 0.053* | |
C2 | 0.5113 (5) | 0.2341 (4) | 0.4995 (5) | 0.0367 (12) | |
C1 | 0.2756 (5) | 0.0804 (4) | 0.1242 (4) | 0.0361 (12) | |
C8 | −0.0487 (5) | 0.2705 (4) | −0.1558 (5) | 0.0475 (14) | |
H8A | −0.1055 | 0.2125 | −0.1817 | 0.057* | |
C3 | 0.3859 (5) | 0.5180 (4) | 0.1814 (4) | 0.0426 (13) | |
H3B | 0.4753 | 0.5228 | 0.1496 | 0.051* | |
H3C | 0.3577 | 0.5881 | 0.2032 | 0.051* | |
C6 | 0.0216 (5) | 0.4463 (4) | −0.1994 (4) | 0.0390 (13) | |
H6A | 0.0147 | 0.5057 | −0.2505 | 0.047* | |
C9 | 0.0428 (5) | 0.2656 (4) | −0.0431 (5) | 0.0443 (13) | |
H9A | 0.0481 | 0.2062 | 0.0080 | 0.053* | |
C4 | 0.2740 (5) | 0.4698 (4) | 0.0853 (4) | 0.0332 (12) | |
C10 | 0.1272 (5) | 0.3536 (4) | −0.0089 (4) | 0.0341 (12) | |
C7 | −0.0593 (5) | 0.3591 (4) | −0.2323 (5) | 0.0465 (14) | |
H7A | −0.1230 | 0.3589 | −0.3077 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0415 (4) | 0.0367 (4) | 0.0269 (3) | −0.0016 (3) | −0.0008 (2) | −0.0001 (3) |
S2 | 0.0421 (8) | 0.0520 (9) | 0.0304 (7) | 0.0069 (7) | −0.0026 (6) | −0.0037 (6) |
S1 | 0.0664 (10) | 0.0425 (9) | 0.0545 (10) | −0.0116 (8) | 0.0063 (7) | −0.0079 (7) |
N5 | 0.032 (2) | 0.028 (2) | 0.032 (2) | −0.0020 (18) | 0.0000 (18) | 0.0003 (17) |
N1 | 0.043 (3) | 0.038 (3) | 0.040 (3) | −0.006 (2) | −0.004 (2) | 0.005 (2) |
N2 | 0.058 (3) | 0.059 (3) | 0.025 (3) | −0.004 (2) | 0.002 (2) | 0.003 (2) |
C5 | 0.028 (3) | 0.037 (3) | 0.033 (3) | −0.002 (2) | 0.008 (2) | 0.004 (2) |
N4 | 0.040 (3) | 0.029 (2) | 0.046 (3) | −0.002 (2) | 0.007 (2) | 0.0075 (19) |
N3 | 0.041 (3) | 0.052 (3) | 0.037 (3) | −0.004 (2) | −0.0016 (19) | −0.012 (2) |
C2 | 0.043 (3) | 0.034 (3) | 0.036 (3) | −0.005 (2) | 0.014 (2) | −0.005 (2) |
C1 | 0.022 (3) | 0.051 (4) | 0.033 (3) | −0.008 (3) | −0.004 (2) | 0.014 (3) |
C8 | 0.043 (3) | 0.045 (4) | 0.047 (3) | −0.007 (3) | −0.018 (3) | −0.005 (3) |
C3 | 0.040 (3) | 0.038 (3) | 0.048 (3) | −0.006 (3) | 0.003 (2) | −0.008 (3) |
C6 | 0.037 (3) | 0.050 (4) | 0.028 (3) | 0.010 (3) | 0.003 (2) | 0.014 (2) |
C9 | 0.047 (3) | 0.035 (3) | 0.045 (3) | −0.005 (3) | −0.007 (3) | 0.006 (2) |
C4 | 0.029 (3) | 0.033 (3) | 0.037 (3) | 0.004 (2) | 0.005 (2) | −0.004 (2) |
C10 | 0.032 (3) | 0.038 (3) | 0.032 (3) | 0.000 (2) | 0.005 (2) | 0.001 (2) |
C7 | 0.041 (3) | 0.056 (4) | 0.039 (3) | 0.003 (3) | −0.005 (3) | 0.002 (3) |
Cu1—N1 | 1.935 (4) | N4—H4A | 0.8600 |
Cu1—N2 | 1.938 (4) | N3—C3 | 1.466 (6) |
Cu1—N5 | 1.970 (4) | N3—H3A | 0.9000 |
Cu1—N3 | 2.022 (4) | N3—H3D | 0.9000 |
Cu1—S2i | 2.942 (1) | C8—C9 | 1.374 (6) |
S2—C2 | 1.630 (5) | C8—C7 | 1.388 (7) |
S1—C1 | 1.625 (6) | C8—H8A | 0.9300 |
N5—C4 | 1.311 (6) | C3—C4 | 1.489 (6) |
N5—C10 | 1.407 (5) | C3—H3B | 0.9700 |
N1—C1 | 1.154 (6) | C3—H3C | 0.9700 |
N2—C2 | 1.158 (5) | C6—C7 | 1.363 (6) |
C5—C10 | 1.390 (6) | C6—H6A | 0.9300 |
C5—C6 | 1.390 (6) | C9—C10 | 1.390 (6) |
C5—N4 | 1.392 (5) | C9—H9A | 0.9300 |
N4—C4 | 1.342 (5) | C7—H7A | 0.9300 |
N1—Cu1—N2 | 94.68 (17) | C9—C8—C7 | 122.3 (5) |
N1—Cu1—N5 | 95.35 (16) | C9—C8—H8A | 118.9 |
N2—Cu1—N5 | 166.60 (17) | C7—C8—H8A | 118.9 |
N1—Cu1—N3 | 174.14 (17) | N3—C3—C4 | 106.1 (4) |
N2—Cu1—N3 | 89.38 (16) | N3—C3—H3B | 110.5 |
N5—Cu1—N3 | 81.33 (16) | C4—C3—H3B | 110.5 |
C4—N5—C10 | 105.7 (4) | N3—C3—H3C | 110.5 |
C4—N5—Cu1 | 112.5 (3) | C4—C3—H3C | 110.5 |
C10—N5—Cu1 | 140.5 (3) | H3B—C3—H3C | 108.7 |
C1—N1—Cu1 | 170.5 (4) | C7—C6—C5 | 116.8 (4) |
C2—N2—Cu1 | 169.3 (4) | C7—C6—H6A | 121.6 |
C10—C5—C6 | 122.2 (5) | C5—C6—H6A | 121.6 |
C10—C5—N4 | 105.2 (4) | C8—C9—C10 | 116.9 (5) |
C6—C5—N4 | 132.7 (4) | C8—C9—H9A | 121.6 |
C4—N4—C5 | 107.8 (4) | C10—C9—H9A | 121.6 |
C4—N4—H4A | 126.1 | N5—C4—N4 | 112.5 (4) |
C5—N4—H4A | 126.1 | N5—C4—C3 | 121.0 (4) |
C3—N3—Cu1 | 111.1 (3) | N4—C4—C3 | 126.5 (4) |
C3—N3—H3A | 109.4 | C5—C10—C9 | 120.4 (4) |
Cu1—N3—H3A | 109.4 | C5—C10—N5 | 108.7 (4) |
C3—N3—H3D | 109.4 | C9—C10—N5 | 130.9 (4) |
Cu1—N3—H3D | 109.4 | C6—C7—C8 | 121.5 (5) |
H3A—N3—H3D | 108.0 | C6—C7—H7A | 119.3 |
N2—C2—S2 | 178.4 (5) | C8—C7—H7A | 119.3 |
N1—C1—S1 | 178.9 (5) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(NCS)2(C8H9N3)] |
Mr | 326.88 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.522 (3), 12.707 (4), 10.757 (3) |
β (°) | 99.418 (6) |
V (Å3) | 1284.0 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.01 |
Crystal size (mm) | 0.14 × 0.10 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.708, 0.886 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6534, 2257, 1428 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.085, 0.92 |
No. of reflections | 2257 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.42 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97.
Cu1—N1 | 1.935 (4) | S2—C2 | 1.630 (5) |
Cu1—N2 | 1.938 (4) | S1—C1 | 1.625 (6) |
Cu1—N5 | 1.970 (4) | N1—C1 | 1.154 (6) |
Cu1—N3 | 2.022 (4) | N2—C2 | 1.158 (5) |
Cu1—S2i | 2.942 (1) | ||
N1—Cu1—N2 | 94.68 (17) | N2—Cu1—N3 | 89.38 (16) |
N1—Cu1—N5 | 95.35 (16) | N5—Cu1—N3 | 81.33 (16) |
N2—Cu1—N5 | 166.60 (17) | N2—C2—S2 | 178.4 (5) |
N1—Cu1—N3 | 174.14 (17) | N1—C1—S1 | 178.9 (5) |
Symmetry code: (i) x, −y+1/2, z−1/2. |
2-Aminomethylbenzimidazole (Hambi) is a bidentate ligand that can coordinate to metal ions via two N atoms. The complex of cobalt(III) and ambi has been synthesized but has not been structurally characterized by X-ray diffraction analysis (Gable et al., 1996). However, the crystal structure of the mixed-ligand cobalt(III) complex with Hambi and acac− has been reported (Cardwell et al., 1997), and the mixed-ligand copper(II) complex with Hambi and iminodiacetate (de la Cueva et al., 1998), and the nickel–Hambi/ambi− (He et al., 2002) and copper–Hambi–dicyanamide (He, Kou, Wang & Li., 2003) complexes, have also been prepared and their structures determined.
Thiocyanate, NCS−, is a common versatile pseudohalogen ligand for bridging metal ions. A considerable number of double thiocyanate-bridged copper(II) complexes have been reported (Julve et al., 1993; Liu et al., 2003); however, single thiocyanate-bridged complexes are comparatively rare (Moustarder et al., 2000; Cano et al., 2000; Karan et al., 2002).
A displacement ellipsoid drawing of the title complex is shown in Fig. 1, and selected bond lengths and angles are listed in Table 1. According to Brophy et al. (1999), the coordination geometry about the Cu atom is that of a slightly distorted square pyramid (τ = 0.126), with one N atom each from the pendant aminomethyl group and the imidazole ring, one N atom from the terminal thiocyanate ligand, and one N atom from the bridging thiocyanate ion defining the basal plane, and with one S atom from another bridging thiocyanate ligand occupying the apical position [Cu1—S2A = 2.942 (1) Å; (A) x, 0.5 − y, z − 0.5]. The Cu atom lies 0.0393 (4) Å above the basal plane, towards the apical S2A atom, suggesting of the presence of a weak Cu—S coordination interaction. As a result, an SCN−-bridged chain-like structure is obtained. The chains are connected by interchain S···H—N hydrogen bonds, giving rise to a waved layer. As shown in Fig. 1, atom S1 of the terminal thiocyanate ligand interacts with the H atom of the pendant aminomethyl group of the neighboring chain, with an S···H distance of 2.644 (3) Å and an S···H—N angle of 136.6 (5)°. At the same time, atom S1 exhibits a hydrogen-bonding interaction with the intrachain primary amine H atom [S···H = 2.582 (3) Å and S···H—N = 175.3 (5)°]. Atom S2 atom of the bridging NCS− ion is also involved in hydrogen bonding with the H atom attached to the benzimidazole N atom of the adjacent chain [S···H = 2.577 (3) Å and S···H—N = 150.4 (5)°].
The title complex is unlike the dicyanamide-bridged CuII analogue Cu(Hambi)(dca)2 (dca− is the dicyanamide anion; Kou et al., 2003) in that no π–π contacts between conjugated benzimidazole cycles of the Hambi ligands are observed in (I). This difference which may be due to the existence of different interchain hydrogen bonding in two complexes.