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The structures of dichloro{2-[(5-methyl-1H-pyrazol-3-yl-κN2)methyl]-1H-1,3-benzimidazole-κN3}copper(II), [CuCl2(C12H12N4)], and di-μ-chloro-bis(chloro{2-[(5-methyl-1H-pyrazol-3-yl-κN2)methyl]-1H-1,3-benzimidazole-κN3}cadmium(II)), [Cd2Cl4(C12H12N4)2], show that these compounds have the structural formula [ML(Cl)2]n, where L is 2-[(5-methylpyrazolyl)methyl]benzimidazole. When M is copper, the complex is a monomer (n = 1), with a tetrahedral coordination for the Cu atom. When M is cadmium (n = 2), the complex lies about an inversion centre giving rise to a centrosymmetric dimer in which the Cd atoms are bridged by two chloride ions and are pentacoordinated.
Supporting information
CCDC references: 219556; 219557
Complexe de cuivre: A une solution de 1,25.10−4 mole (26 mg) du 2-[(5-méthylpyrazolyl) méthyle)]benzimidazole solubilisé dans 5 ml d'acétone on ajoute une solution de 1,25.10−4 mole (21 mg) de chlorure de cuivre dissout dans 5 ml d'acétone, après agitation pendant quelques minutes on laisse reposer le mélange réactionnel à température ambiante. Après 24 h de s monocristaux transparents de couleur verte sont formés.
Complexe de cadmium: A une solution de 2,5.10−4 mole (53 mg) du 2- [(5-méthylpyrazolyl)méthyle)] benzimidazole solubilisé dans 10 ml de méthanol on ajoute une solution de 1,25.10−4 mole (23 mg) de chlorure de cadmium dissout dans 5 ml de méthanol, après agitation de quelques minutes on laisse reposer le mélange réactionnel à température ambiante sous forme de poudre jaune apparaît. Une recristallization dans l'éthanol donne après 48 h de s monocristaux transparents de couleur jaune.
For both compounds, data collection: KappaCCD (Nonius, 1998); data reduction: DENZO and Scalepak (Otwinowski & Minor, 1997). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); SHELXS97 (Sheldrick, 1990) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Crystal data top
[CuCl2(C12H12N4)] | F(000) = 700 |
Mr = 346.70 | Dx = 1.684 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9873 reflections |
a = 13.4356 (6) Å | θ = 2–26.4° |
b = 7.2183 (2) Å | µ = 1.98 mm−1 |
c = 16.0421 (6) Å | T = 293 K |
β = 118.510 (2)° | Needle, blue |
V = 1367.11 (9) Å3 | 0.25 × 0.08 × 0.05 mm |
Z = 4 | |
Data collection top
KappaCCD diffractometer | 2492 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 26.4°, θmin = 2.6° |
ϕ scan | h = 0→16 |
9873 measured reflections | k = −8→0 |
2744 independent reflections | l = −19→16 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0248P)2 + 1.7253P] where P = (Fo2 + 2Fc2)/3 |
2744 reflections | (Δ/σ)max = 0.001 |
173 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
[CuCl2(C12H12N4)] | V = 1367.11 (9) Å3 |
Mr = 346.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.4356 (6) Å | µ = 1.98 mm−1 |
b = 7.2183 (2) Å | T = 293 K |
c = 16.0421 (6) Å | 0.25 × 0.08 × 0.05 mm |
β = 118.510 (2)° | |
Data collection top
KappaCCD diffractometer | 2492 reflections with I > 2σ(I) |
9873 measured reflections | Rint = 0.037 |
2744 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.61 e Å−3 |
2744 reflections | Δρmin = −0.34 e Å−3 |
173 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 | 0.37965 (2) | 0.20934 (4) | 0.321607 (19) | 0.02965 (11) | |
Cl2 | 0.27315 (6) | 0.41367 (11) | 0.20989 (5) | 0.04647 (19) | |
Cl3 | 0.41050 (7) | 0.00258 (10) | 0.23329 (4) | 0.04723 (19) | |
N1 | 0.31181 (17) | 0.2444 (3) | 0.40433 (14) | 0.0295 (4) | |
N8 | 0.29066 (19) | 0.3038 (3) | 0.52960 (15) | 0.0359 (5) | |
H8 | 0.3078 | 0.3292 | 0.5873 | 0.043* | |
N12 | 0.53108 (17) | 0.1884 (3) | 0.43342 (14) | 0.0303 (4) | |
N13 | 0.62656 (17) | 0.1623 (3) | 0.42593 (14) | 0.0329 (5) | |
H13 | 0.6270 | 0.1238 | 0.3754 | 0.040* | |
C2 | 0.1961 (2) | 0.2409 (4) | 0.37664 (18) | 0.0351 (6) | |
C3 | 0.1033 (2) | 0.1962 (5) | 0.2904 (2) | 0.0512 (8) | |
H3 | 0.1112 | 0.1686 | 0.2372 | 0.061* | |
C4 | −0.0009 (3) | 0.1947 (6) | 0.2873 (2) | 0.0637 (10) | |
H4 | −0.0645 | 0.1630 | 0.2308 | 0.076* | |
C5 | −0.0140 (3) | 0.2392 (6) | 0.3657 (3) | 0.0641 (10) | |
H5 | −0.0863 | 0.2396 | 0.3599 | 0.077* | |
C6 | 0.0774 (3) | 0.2825 (5) | 0.4519 (2) | 0.0534 (8) | |
H6 | 0.0689 | 0.3121 | 0.5046 | 0.064* | |
C7 | 0.1829 (2) | 0.2798 (4) | 0.45596 (18) | 0.0364 (6) | |
C9 | 0.3648 (2) | 0.2809 (3) | 0.49660 (16) | 0.0271 (5) | |
C10 | 0.4887 (2) | 0.2950 (3) | 0.56127 (16) | 0.0291 (5) | |
H10A | 0.5072 | 0.2148 | 0.6152 | 0.035* | |
H10B | 0.5050 | 0.4210 | 0.5851 | 0.035* | |
C11 | 0.5664 (2) | 0.2481 (3) | 0.52220 (16) | 0.0271 (5) | |
C14 | 0.7199 (2) | 0.2036 (4) | 0.50669 (19) | 0.0357 (6) | |
C15 | 0.6837 (2) | 0.2587 (4) | 0.57039 (18) | 0.0358 (6) | |
H15 | 0.7289 | 0.2954 | 0.6330 | 0.043* | |
C16 | 0.8353 (2) | 0.1945 (5) | 0.5150 (2) | 0.0519 (8) | |
H16A | 0.8332 | 0.1174 | 0.4654 | 0.078* | |
H16B | 0.8875 | 0.1433 | 0.5756 | 0.078* | |
H16C | 0.8594 | 0.3169 | 0.5094 | 0.078* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.03491 (17) | 0.03676 (19) | 0.01630 (15) | 0.00303 (13) | 0.01142 (12) | 0.00022 (11) |
Cl2 | 0.0541 (4) | 0.0574 (4) | 0.0315 (3) | 0.0205 (3) | 0.0234 (3) | 0.0169 (3) |
Cl3 | 0.0739 (5) | 0.0424 (4) | 0.0234 (3) | 0.0169 (3) | 0.0216 (3) | 0.0010 (3) |
N1 | 0.0304 (10) | 0.0379 (11) | 0.0194 (9) | −0.0011 (9) | 0.0113 (8) | 0.0010 (8) |
N8 | 0.0398 (12) | 0.0494 (14) | 0.0227 (10) | −0.0007 (10) | 0.0184 (9) | −0.0026 (9) |
N12 | 0.0326 (11) | 0.0353 (11) | 0.0228 (10) | 0.0023 (9) | 0.0131 (8) | −0.0006 (8) |
N13 | 0.0361 (11) | 0.0388 (12) | 0.0271 (10) | −0.0007 (9) | 0.0176 (9) | −0.0024 (9) |
C2 | 0.0338 (13) | 0.0441 (15) | 0.0282 (12) | −0.0019 (11) | 0.0154 (11) | 0.0023 (11) |
C3 | 0.0381 (15) | 0.082 (2) | 0.0286 (14) | −0.0088 (15) | 0.0119 (12) | −0.0010 (14) |
C4 | 0.0337 (15) | 0.105 (3) | 0.0420 (17) | −0.0099 (17) | 0.0096 (13) | 0.0064 (18) |
C5 | 0.0342 (16) | 0.101 (3) | 0.059 (2) | −0.0012 (17) | 0.0236 (15) | 0.014 (2) |
C6 | 0.0463 (17) | 0.078 (2) | 0.0468 (17) | 0.0038 (16) | 0.0306 (15) | 0.0055 (16) |
C7 | 0.0363 (13) | 0.0453 (15) | 0.0279 (12) | −0.0007 (11) | 0.0155 (11) | 0.0024 (11) |
C9 | 0.0360 (12) | 0.0253 (11) | 0.0215 (11) | −0.0002 (9) | 0.0148 (10) | 0.0012 (9) |
C10 | 0.0353 (12) | 0.0313 (12) | 0.0190 (11) | 0.0012 (10) | 0.0115 (10) | −0.0001 (9) |
C11 | 0.0346 (12) | 0.0234 (11) | 0.0210 (11) | 0.0005 (9) | 0.0113 (9) | 0.0022 (8) |
C14 | 0.0348 (13) | 0.0367 (14) | 0.0366 (14) | −0.0017 (11) | 0.0179 (11) | 0.0005 (11) |
C15 | 0.0339 (13) | 0.0414 (14) | 0.0273 (12) | −0.0020 (11) | 0.0106 (10) | −0.0042 (11) |
C16 | 0.0377 (15) | 0.067 (2) | 0.0537 (18) | −0.0088 (14) | 0.0240 (14) | −0.0132 (16) |
Geometric parameters (Å, º) top
Cu1—N1 | 1.952 (2) | C4—C5 | 1.390 (5) |
Cu1—N12 | 1.974 (2) | C4—H4 | 0.9300 |
Cu1—Cl3 | 2.2286 (7) | C5—C6 | 1.377 (5) |
Cu1—Cl2 | 2.2331 (8) | C5—H5 | 0.9300 |
N1—C9 | 1.327 (3) | C6—C7 | 1.388 (4) |
N1—C2 | 1.398 (3) | C6—H6 | 0.9300 |
N8—C9 | 1.343 (3) | C9—C10 | 1.486 (3) |
N8—C7 | 1.374 (3) | C10—C11 | 1.490 (3) |
N8—H8 | 0.8600 | C10—H10A | 0.9700 |
N12—C11 | 1.340 (3) | C10—H10B | 0.9700 |
N12—N13 | 1.357 (3) | C11—C15 | 1.387 (3) |
N13—C14 | 1.337 (3) | C14—C15 | 1.383 (4) |
N13—H13 | 0.8600 | C14—C16 | 1.493 (4) |
C2—C3 | 1.388 (4) | C15—H15 | 0.9300 |
C2—C7 | 1.395 (4) | C16—H16A | 0.9600 |
C3—C4 | 1.377 (4) | C16—H16B | 0.9600 |
C3—H3 | 0.9300 | C16—H16C | 0.9600 |
| | | |
N1—Cu1—N12 | 90.31 (8) | C5—C6—C7 | 116.5 (3) |
N1—Cu1—Cl3 | 143.89 (7) | C5—C6—H6 | 121.8 |
N12—Cu1—Cl3 | 95.90 (6) | C7—C6—H6 | 121.8 |
N1—Cu1—Cl2 | 97.57 (6) | N8—C7—C6 | 132.2 (3) |
N12—Cu1—Cl2 | 140.13 (7) | N8—C7—C2 | 105.6 (2) |
Cl3—Cu1—Cl2 | 100.05 (3) | C6—C7—C2 | 122.1 (3) |
C9—N1—C2 | 106.3 (2) | N1—C9—N8 | 111.1 (2) |
C9—N1—Cu1 | 127.43 (17) | N1—C9—C10 | 128.2 (2) |
C2—N1—Cu1 | 126.21 (16) | N8—C9—C10 | 120.7 (2) |
C9—N8—C7 | 108.7 (2) | C9—C10—C11 | 117.8 (2) |
C9—N8—H8 | 125.6 | C9—C10—H10A | 107.9 |
C7—N8—H8 | 125.6 | C11—C10—H10A | 107.9 |
C11—N12—N13 | 105.60 (19) | C9—C10—H10B | 107.9 |
C11—N12—Cu1 | 129.04 (17) | C11—C10—H10B | 107.9 |
N13—N12—Cu1 | 122.54 (15) | H10A—C10—H10B | 107.2 |
C14—N13—N12 | 111.8 (2) | N12—C11—C15 | 110.0 (2) |
C14—N13—H13 | 124.1 | N12—C11—C10 | 123.8 (2) |
N12—N13—H13 | 124.1 | C15—C11—C10 | 126.2 (2) |
C3—C2—C7 | 120.8 (2) | N13—C14—C15 | 106.4 (2) |
C3—C2—N1 | 130.8 (2) | N13—C14—C16 | 122.0 (2) |
C7—C2—N1 | 108.2 (2) | C15—C14—C16 | 131.5 (3) |
C4—C3—C2 | 116.8 (3) | C14—C15—C11 | 106.2 (2) |
C4—C3—H3 | 121.6 | C14—C15—H15 | 126.9 |
C2—C3—H3 | 121.6 | C11—C15—H15 | 126.9 |
C3—C4—C5 | 122.1 (3) | C14—C16—H16A | 109.5 |
C3—C4—H4 | 118.9 | C14—C16—H16B | 109.5 |
C5—C4—H4 | 118.9 | H16A—C16—H16B | 109.5 |
C6—C5—C4 | 121.6 (3) | C14—C16—H16C | 109.5 |
C6—C5—H5 | 119.2 | H16A—C16—H16C | 109.5 |
C4—C5—H5 | 119.2 | H16B—C16—H16C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl3i | 0.86 | 2.40 | 3.194 (2) | 153 |
N8—H8···Cl2i | 0.86 | 2.83 | 3.396 (2) | 125 |
N13—H13···Cl2ii | 0.86 | 2.78 | 3.548 (2) | 150 |
N13—H13···Cl3 | 0.86 | 2.84 | 3.278 (2) | 113 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Crystal data top
[Cd2Cl4(C12H12N4)2] | Z = 1 |
Mr = 791.13 | F(000) = 388 |
Triclinic, P1 | Dx = 1.906 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8306 (2) Å | Cell parameters from 10163 reflections |
b = 9.7979 (3) Å | θ = 2–26° |
c = 10.1976 (4) Å | µ = 1.96 mm−1 |
α = 92.861 (1)° | T = 293 K |
β = 112.014 (1)° | Needle, colourless |
γ = 105.493 (1)° | 0.20 × 0.08 × 0.05 mm |
V = 689.07 (4) Å3 | |
Data collection top
KappaCCD diffractometer | 2474 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 26°, θmin = 2.8° |
ϕ scan | h = 0→9 |
10163 measured reflections | k = −12→11 |
2614 independent reflections | l = −12→11 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0041P)2 + 0.8027P] where P = (Fo2 + 2Fc2)/3 |
2614 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
Crystal data top
[Cd2Cl4(C12H12N4)2] | γ = 105.493 (1)° |
Mr = 791.13 | V = 689.07 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8306 (2) Å | Mo Kα radiation |
b = 9.7979 (3) Å | µ = 1.96 mm−1 |
c = 10.1976 (4) Å | T = 293 K |
α = 92.861 (1)° | 0.20 × 0.08 × 0.05 mm |
β = 112.014 (1)° | |
Data collection top
KappaCCD diffractometer | 2474 reflections with I > 2σ(I) |
10163 measured reflections | Rint = 0.027 |
2614 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.35 e Å−3 |
2614 reflections | Δρmin = −0.47 e Å−3 |
173 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 | |
Cd1 | 0.27325 (3) | 0.336088 (19) | 0.47595 (2) | 0.02774 (7) | |
Cl3 | −0.03141 (10) | 0.33503 (8) | 0.28348 (8) | 0.04374 (17) | |
Cl2 | 0.56172 (10) | 0.38913 (7) | 0.40148 (8) | 0.03556 (15) | |
N1 | 0.2474 (3) | 0.0970 (2) | 0.4594 (2) | 0.0284 (4) | |
N8 | 0.2560 (3) | −0.1181 (2) | 0.5112 (2) | 0.0337 (5) | |
H8 | 0.2621 | −0.1874 | 0.5596 | 0.040* | |
N12 | 0.2414 (3) | 0.2942 (2) | 0.6848 (2) | 0.0330 (5) | |
N13 | 0.2332 (4) | 0.3980 (2) | 0.7738 (3) | 0.0366 (5) | |
H13 | 0.2133 | 0.4770 | 0.7494 | 0.044* | |
C2 | 0.2329 (3) | 0.0118 (3) | 0.3394 (3) | 0.0287 (5) | |
C3 | 0.2122 (4) | 0.0431 (3) | 0.2043 (3) | 0.0369 (6) | |
H3 | 0.2076 | 0.1332 | 0.1815 | 0.044* | |
C4 | 0.1985 (4) | −0.0644 (3) | 0.1050 (3) | 0.0413 (6) | |
H4 | 0.1832 | −0.0467 | 0.0131 | 0.050* | |
C5 | 0.2072 (4) | −0.1989 (3) | 0.1391 (3) | 0.0432 (7) | |
H5 | 0.1989 | −0.2684 | 0.0695 | 0.052* | |
C6 | 0.2275 (4) | −0.2320 (3) | 0.2722 (3) | 0.0413 (7) | |
H6 | 0.2332 | −0.3220 | 0.2947 | 0.050* | |
C7 | 0.2392 (4) | −0.1239 (3) | 0.3715 (3) | 0.0310 (5) | |
C9 | 0.2613 (3) | 0.0142 (3) | 0.5594 (3) | 0.0278 (5) | |
C10 | 0.2836 (4) | 0.0500 (3) | 0.7095 (3) | 0.0332 (6) | |
H10A | 0.4079 | 0.0420 | 0.7720 | 0.040* | |
H10B | 0.1851 | −0.0243 | 0.7238 | 0.040* | |
C11 | 0.2728 (3) | 0.1912 (3) | 0.7619 (3) | 0.0284 (5) | |
C14 | 0.2595 (4) | 0.3633 (3) | 0.9036 (3) | 0.0363 (6) | |
C15 | 0.2882 (4) | 0.2321 (3) | 0.8999 (3) | 0.0366 (6) | |
H15 | 0.3132 | 0.1799 | 0.9749 | 0.044* | |
C16 | 0.2523 (5) | 0.4585 (4) | 1.0182 (3) | 0.0481 (7) | |
H16A | 0.3503 | 0.5496 | 1.0398 | 0.072* | |
H16B | 0.2748 | 0.4149 | 1.1029 | 0.072* | |
H16C | 0.1272 | 0.4726 | 0.9861 | 0.072* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cd1 | 0.03186 (11) | 0.02158 (11) | 0.03359 (11) | 0.00968 (7) | 0.01548 (8) | 0.01136 (8) |
Cl3 | 0.0408 (4) | 0.0419 (4) | 0.0461 (4) | 0.0201 (3) | 0.0090 (3) | 0.0142 (3) |
Cl2 | 0.0427 (3) | 0.0232 (3) | 0.0500 (4) | 0.0088 (3) | 0.0294 (3) | 0.0076 (3) |
N1 | 0.0311 (10) | 0.0206 (11) | 0.0367 (11) | 0.0096 (8) | 0.0155 (9) | 0.0093 (9) |
N8 | 0.0397 (12) | 0.0211 (12) | 0.0405 (12) | 0.0122 (9) | 0.0135 (10) | 0.0114 (10) |
N12 | 0.0468 (13) | 0.0263 (12) | 0.0339 (11) | 0.0157 (10) | 0.0211 (10) | 0.0120 (10) |
N13 | 0.0513 (14) | 0.0282 (13) | 0.0413 (13) | 0.0192 (11) | 0.0247 (11) | 0.0131 (10) |
C2 | 0.0262 (12) | 0.0217 (13) | 0.0382 (13) | 0.0073 (10) | 0.0131 (10) | 0.0053 (11) |
C3 | 0.0437 (15) | 0.0284 (15) | 0.0420 (15) | 0.0104 (12) | 0.0208 (13) | 0.0099 (12) |
C4 | 0.0474 (16) | 0.0350 (17) | 0.0404 (15) | 0.0082 (13) | 0.0200 (13) | 0.0034 (13) |
C5 | 0.0453 (16) | 0.0326 (17) | 0.0482 (17) | 0.0103 (13) | 0.0176 (14) | −0.0040 (14) |
C6 | 0.0463 (16) | 0.0254 (15) | 0.0527 (17) | 0.0157 (12) | 0.0173 (14) | 0.0069 (13) |
C7 | 0.0276 (12) | 0.0249 (14) | 0.0387 (14) | 0.0083 (10) | 0.0108 (11) | 0.0075 (11) |
C9 | 0.0231 (11) | 0.0205 (13) | 0.0393 (13) | 0.0067 (9) | 0.0115 (10) | 0.0092 (11) |
C10 | 0.0403 (14) | 0.0235 (14) | 0.0375 (14) | 0.0105 (11) | 0.0161 (12) | 0.0139 (11) |
C11 | 0.0271 (12) | 0.0258 (14) | 0.0348 (13) | 0.0080 (10) | 0.0144 (10) | 0.0126 (11) |
C14 | 0.0377 (14) | 0.0347 (16) | 0.0407 (15) | 0.0105 (12) | 0.0202 (12) | 0.0095 (13) |
C15 | 0.0447 (15) | 0.0350 (16) | 0.0386 (14) | 0.0154 (12) | 0.0225 (12) | 0.0175 (13) |
C16 | 0.062 (2) | 0.045 (2) | 0.0484 (17) | 0.0190 (16) | 0.0327 (16) | 0.0077 (15) |
Geometric parameters (Å, º) top
Cd1—N12 | 2.280 (2) | C4—C5 | 1.392 (4) |
Cd1—N1 | 2.289 (2) | C4—H4 | 0.9300 |
Cd1—Cl3 | 2.4533 (7) | C5—C6 | 1.372 (4) |
Cd1—Cl2 | 2.5783 (6) | C5—H5 | 0.9300 |
Cd1—Cl2i | 2.6600 (7) | C6—C7 | 1.389 (4) |
N1—C9 | 1.325 (3) | C6—H6 | 0.9300 |
N1—C2 | 1.397 (3) | C9—C10 | 1.486 (4) |
N8—C9 | 1.348 (3) | C10—C11 | 1.492 (4) |
N8—C7 | 1.378 (4) | C10—H10A | 0.9700 |
N8—H8 | 0.8600 | C10—H10B | 0.9700 |
N12—C11 | 1.328 (3) | C11—C15 | 1.395 (4) |
N12—N13 | 1.360 (3) | C14—C15 | 1.364 (4) |
N13—C14 | 1.337 (4) | C14—C16 | 1.486 (4) |
N13—H13 | 0.8600 | C15—H15 | 0.9300 |
C2—C3 | 1.386 (4) | C16—H16A | 0.9600 |
C2—C7 | 1.394 (3) | C16—H16B | 0.9600 |
C3—C4 | 1.378 (4) | C16—H16C | 0.9600 |
C3—H3 | 0.9300 | | |
| | | |
N12—Cd1—N1 | 80.44 (8) | C6—C5—H5 | 119.0 |
N12—Cd1—Cl3 | 112.74 (6) | C4—C5—H5 | 119.0 |
N1—Cd1—Cl3 | 102.18 (6) | C5—C6—C7 | 116.4 (3) |
N12—Cd1—Cl2 | 133.64 (6) | C5—C6—H6 | 121.8 |
N1—Cd1—Cl2 | 91.02 (5) | C7—C6—H6 | 121.8 |
Cl3—Cd1—Cl2 | 113.61 (3) | N8—C7—C6 | 132.8 (2) |
N12—Cd1—Cl2i | 86.40 (6) | N8—C7—C2 | 104.9 (2) |
N1—Cd1—Cl2i | 154.17 (6) | C6—C7—C2 | 122.3 (3) |
Cl3—Cd1—Cl2i | 103.40 (2) | N1—C9—N8 | 111.6 (2) |
Cl2—Cd1—Cl2i | 82.09 (2) | N1—C9—C10 | 128.9 (2) |
Cd1—Cl2—Cd1i | 97.91 (2) | N8—C9—C10 | 119.5 (2) |
C9—N1—C2 | 105.6 (2) | C9—C10—C11 | 120.6 (2) |
C9—N1—Cd1 | 129.45 (18) | C9—C10—H10A | 107.2 |
C2—N1—Cd1 | 124.67 (16) | C11—C10—H10A | 107.2 |
C9—N8—C7 | 108.6 (2) | C9—C10—H10B | 107.2 |
C9—N8—H8 | 125.7 | C11—C10—H10B | 107.2 |
C7—N8—H8 | 125.7 | H10A—C10—H10B | 106.8 |
C11—N12—N13 | 105.2 (2) | N12—C11—C15 | 109.8 (2) |
C11—N12—Cd1 | 131.02 (18) | N12—C11—C10 | 125.9 (2) |
N13—N12—Cd1 | 121.92 (15) | C15—C11—C10 | 124.3 (2) |
C14—N13—N12 | 112.3 (2) | N13—C14—C15 | 105.9 (2) |
C14—N13—H13 | 123.8 | N13—C14—C16 | 122.1 (3) |
N12—N13—H13 | 123.8 | C15—C14—C16 | 131.9 (3) |
C3—C2—C7 | 120.5 (2) | C14—C15—C11 | 106.8 (2) |
C3—C2—N1 | 130.2 (2) | C14—C15—H15 | 126.6 |
C7—C2—N1 | 109.3 (2) | C11—C15—H15 | 126.6 |
C4—C3—C2 | 117.4 (3) | C14—C16—H16A | 109.5 |
C4—C3—H3 | 121.3 | C14—C16—H16B | 109.5 |
C2—C3—H3 | 121.3 | H16A—C16—H16B | 109.5 |
C3—C4—C5 | 121.5 (3) | C14—C16—H16C | 109.5 |
C3—C4—H4 | 119.3 | H16A—C16—H16C | 109.5 |
C5—C4—H4 | 119.3 | H16B—C16—H16C | 109.5 |
C6—C5—C4 | 122.0 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl2ii | 0.86 | 2.66 | 3.345 (2) | 137 |
N8—H8···Cl3iii | 0.86 | 2.99 | 3.633 (2) | 134 |
N13—H13···Cl3iv | 0.86 | 2.58 | 3.369 (2) | 154 |
N13—H13···Cl2i | 0.86 | 2.86 | 3.295 (2) | 113 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [CuCl2(C12H12N4)] | [Cd2Cl4(C12H12N4)2] |
Mr | 346.70 | 791.13 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 13.4356 (6), 7.2183 (2), 16.0421 (6) | 7.8306 (2), 9.7979 (3), 10.1976 (4) |
α, β, γ (°) | 90, 118.510 (2), 90 | 92.861 (1), 112.014 (1), 105.493 (1) |
V (Å3) | 1367.11 (9) | 689.07 (4) |
Z | 4 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.98 | 1.96 |
Crystal size (mm) | 0.25 × 0.08 × 0.05 | 0.20 × 0.08 × 0.05 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9873, 2744, 2492 | 10163, 2614, 2474 |
Rint | 0.037 | 0.027 |
(sin θ/λ)max (Å−1) | 0.625 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.078, 1.07 | 0.022, 0.051, 1.09 |
No. of reflections | 2744 | 2614 |
No. of parameters | 173 | 173 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.34 | 0.35, −0.47 |
Selected geometric parameters (Å, º) for (I) topCu1—N1 | 1.952 (2) | Cu1—Cl3 | 2.2286 (7) |
Cu1—N12 | 1.974 (2) | Cu1—Cl2 | 2.2331 (8) |
| | | |
N1—Cu1—N12 | 90.31 (8) | N1—Cu1—Cl2 | 97.57 (6) |
N1—Cu1—Cl3 | 143.89 (7) | N12—Cu1—Cl2 | 140.13 (7) |
N12—Cu1—Cl3 | 95.90 (6) | Cl3—Cu1—Cl2 | 100.05 (3) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl3i | 0.86 | 2.40 | 3.194 (2) | 152.9 |
N8—H8···Cl2i | 0.86 | 2.83 | 3.396 (2) | 124.5 |
N13—H13···Cl2ii | 0.86 | 2.78 | 3.548 (2) | 149.6 |
N13—H13···Cl3 | 0.86 | 2.84 | 3.278 (2) | 113.0 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topCd1—N12 | 2.280 (2) | Cd1—Cl2 | 2.5783 (6) |
Cd1—N1 | 2.289 (2) | Cd1—Cl2i | 2.6600 (7) |
Cd1—Cl3 | 2.4533 (7) | | |
| | | |
N12—Cd1—N1 | 80.44 (8) | N12—Cd1—Cl2i | 86.40 (6) |
N12—Cd1—Cl3 | 112.74 (6) | N1—Cd1—Cl2i | 154.17 (6) |
N1—Cd1—Cl3 | 102.18 (6) | Cl3—Cd1—Cl2i | 103.40 (2) |
N12—Cd1—Cl2 | 133.64 (6) | Cl2—Cd1—Cl2i | 82.09 (2) |
N1—Cd1—Cl2 | 91.02 (5) | Cd1—Cl2—Cd1i | 97.91 (2) |
Cl3—Cd1—Cl2 | 113.61 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N8—H8···Cl2ii | 0.86 | 2.66 | 3.345 (2) | 137.1 |
N8—H8···Cl3iii | 0.86 | 2.99 | 3.633 (2) | 133.6 |
N13—H13···Cl3iv | 0.86 | 2.58 | 3.369 (2) | 153.6 |
N13—H13···Cl2i | 0.86 | 2.86 | 3.295 (2) | 113.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1. |
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Les systèmes macrocycliques dérivés du benzimidazole et du pyrazole présentent des propriétés complexantes vis-à-vis des métaux de transition (Sbai et al., 2002) et des cations d'alcalins. Ce type de complexes possède des propriétés électrochimiques, photochimiques (Baitalik & Floerke, 1994) et catalytiques (Malachowski et al., 1996), en plus de leurs activités fongicides (Mishra et al., 1996) et antibactériens (Mishra & Sinha, 1999). Dans notre laboratoire de nombreux travaux de réactivité et de complexation ont été réalisés sur le ligand L, 2-[(5-méthylpyrazolyl)méthyle] benzimidazole (Essassi et al., 1987). Avec le nickel, un complexe cationique de type [ML2+2, 2X−],nH2O est obtenu (Sbai et al., 2002), alors que, avec Cd ou Cu, on obtient des complexes neutres de type [ML(Cl)2]n. Avec le cuivre, le complexe (I) obtenu est un monomère CuL(Cl)2 dans lequel le métal est coordonné à deux atomes de Cl et à deux atomes d'azote, Fig. 1. Les distances et angles caractéristiques sont reportés dans le Tableau 1. Les angles du tétraèdre de coordination du cuivre, qui varient entre 90.31 (8) e t 143.89 (7)°, et l'angle dièdre entre les plans N1CuN12 et Cl2CuCl3 [128,02 (7)°] indiquent une géométrie intermédiaire entre une pyramide plan-carré et un tétraèdre, comme cela se rencontre souvent (Bhalla et al., 1997; Thorhauge, 2002). L'atome de cuivre est à 0,329 (3) Å au dessus du cycle formé par les atomes N1C9C10C11N12 Le ligand L est plan, on note un angle de 6.3 (1)° entre le cycle pyrazole C11N12N13C14C15 et le bicycle benzamidazole N1C2–C7N8C9. Dans le cristal, les molécules s'empilent parall`element entre elles, dans un plan proche du plan (010). Entre ces plans, les atomes de Cl établissent des liaisons de type hydrogène avec les groupements N/H voisins (Fig. 2 e t Tableau 2).
Le pontage de deux atomes métalliques par un ou plusieurs atomes de Cl est une situation assez fréquente qui conduit à la dimérization de composés de coordination. On peut citer l'exemple du µ-chloro-bis bis[2,2'-pyridylethylamino]cuivre(II) trishexafluorophosphate dans lequel un atome de Cl est lié à deux atomes de Cu (Alilou et al., 1992). Pour le complexe [FeCl2(tmmn)]2 [tmmn est N, N, N', N'- tétraméthylméthanediamine; Handley et al., 2001], le dimère résulte de l'établissement de deux ponts Fe—Cl—Fe. Pour le composé [Cd(L)Cl2]2 [L est 1-(5,6-diméthylbenzimidazoyl)-benzimidazoyl-2- thiapropane], deux ponts Cd—Cl—Cd sont également à l'origine de la formation d'un dimère (Matthews et al., 1998). Le complexe (II) obtenu dans le cas du cadmium (Fig. 3) e s t un dimère [CdL(Cl)2]2 dans lequel l'atome de Cl2 ponte deux atomes de Cd distants de 3.9511 (3) Å (Fig. 3). Le Tableau 3 contient les distances et angles importants. Les deux ponts Cd—Cl—Cd présentent une légère dissymétrie, les distances Cd—Cl, égales à 2.5783 (6) e t 2.6600 (7) Å, sont proches de celles données pour des composés voisins (Matthews et al., 1998; Long et al., 1993). L'atome de Cd est pentacoordonné selon une pyramide à base carrée formée par deux atomes de Cl et deux atomes d'azote du ligand, l'atome de Cl3 occupant la position apicale. Les distances et angles de coordination du cadmium sont proches de celles trouvées dans des composés voisins (Matthews et al., 1998; Long et al., 1993) dans lesquels le cadmium présente aussi une pentacoordination. Les plans CdCl2Cl2' et CdN1N12 forment un angle de 66.19 (6)° et l'atome de Cd est à 0.423 (4) Å du cycle N1C8C9C10N12. Le ligand L est plan, l'angle entre le cycle pyrazole C11N12N13C14C15 et le bicycle benzamidazole N1C2–C7N8C9 est égal à 7.5 (1) Å. Comme cela est le cas pour le composé de cuivre (I), les dimères (II), s'empilent dans le cristal parallèlement au plan (100) en établissant des liaisons hydrogène entre les atomes de Cl et les groupement N/H (Fig. 4 e t Tableau 4). De telles liaisons hydrogène ont été mizes en évidence dans d'autres complexes du cadmium, avec des distances Cl—N voisines (Matthews et al., 1998).