Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100005710/fr1273sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100005710/fr1273Isup2.hkl |
CCDC reference: 150304
The title compound was synthesized by adding 1.0 mmol of CoCl2·6H20 to 2.0 mmol of clemizole hydrochloride in 20 ml of ethanol. NH4OH was added until the pH was 8–9. The solution was evaporated slowly at room temperature and blue prismatic crystals separated after a few days.
The C atoms of the pyrrolidinyl ring were disordered with inequivalent site-occupancy factors 0.76 and 0.24 which were established in the early refinement cycles. In the final rounds of calculations, the site-occupancy factors of these C atoms were fixed and the atoms of the minor conformer were refined with isotropic displacement parameters; the N—C and C—C distances in the pyrrolidinyl ring were fixed at 1.48 (1) and 1.50 (1) Å, respectively, using the command DFIX in SHELXL97 (Sheldrick, 1997). H atoms were included in the refinement at idealized positions with aromatic C—H and methylene C—H distances of 0.95 and 0.99 Å, respectively. The isotropicdisplacement parameters of the H atoms were set equal to 1.2Ueq of the C atoms to which they were bonded.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Fig. 1. ORTEPII (Johnson, 1976) drawing of (I) with displacement ellipsoids plotted at 50% probability level. The minor fraction of the disordered pyrrolidinyl ring atoms are not shown. |
[CoCl2(C19H20ClN3)] | F(000) = 932 |
Mr = 455.66 | Dx = 1.516 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 9.647 (6) Å | Cell parameters from 25 reflections |
b = 12.675 (6) Å | θ = 10.0–25.0° |
c = 16.359 (5) Å | µ = 1.27 mm−1 |
β = 93.77 (4)° | T = 170 K |
V = 1996 (2) Å3 | Prismatic, blue |
Z = 4 | 0.40 × 0.22 × 0.16 mm |
Rigaku AFC-6S diffractometer | 1425 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.097 |
Graphite monochromator | θmax = 25.0°, θmin = 2.5° |
ω/2θ scans | h = 0→11 |
Absorption correction: empirical (using intensity measurements) ψ scan (3 reflections; North et al., 1968) | k = 0→15 |
Tmin = 0.63, Tmax = 0.82 | l = −19→19 |
3754 measured reflections | 3 standard reflections every 200 reflections |
3533 independent reflections | intensity decay: none |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0384P)2] where P = (Fo2 + 2Fc2)/3 |
3533 reflections | (Δ/σ)max < 0.001 |
251 parameters | Δρmax = 0.40 e Å−3 |
34 restraints | Δρmin = −0.44 e Å−3 |
[CoCl2(C19H20ClN3)] | V = 1996 (2) Å3 |
Mr = 455.66 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.647 (6) Å | µ = 1.27 mm−1 |
b = 12.675 (6) Å | T = 170 K |
c = 16.359 (5) Å | 0.40 × 0.22 × 0.16 mm |
β = 93.77 (4)° |
Rigaku AFC-6S diffractometer | 1425 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) ψ scan (3 reflections; North et al., 1968) | Rint = 0.097 |
Tmin = 0.63, Tmax = 0.82 | 3 standard reflections every 200 reflections |
3754 measured reflections | intensity decay: none |
3533 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 34 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.40 e Å−3 |
3533 reflections | Δρmin = −0.44 e Å−3 |
251 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.84005 (8) | 0.49515 (8) | 0.68276 (5) | 0.0383 (3) | |
Cl1 | 0.1710 (2) | 1.07964 (15) | 0.60736 (13) | 0.0659 (6) | |
Cl2 | 0.91205 (18) | 0.33425 (15) | 0.64955 (11) | 0.0542 (5) | |
Cl3 | 1.00581 (18) | 0.61391 (15) | 0.70886 (12) | 0.0571 (5) | |
N1 | 0.4642 (5) | 0.6056 (4) | 0.5979 (3) | 0.0398 (14) | |
N2 | 0.6872 (5) | 0.5596 (4) | 0.6135 (3) | 0.0341 (13) | |
N3 | 0.6877 (5) | 0.4875 (4) | 0.7708 (3) | 0.0371 (13) | |
C1 | 0.5240 (6) | 0.6347 (5) | 0.5259 (4) | 0.0371 (17) | |
C2 | 0.4696 (7) | 0.6844 (5) | 0.4549 (4) | 0.0408 (17) | |
H2 | 0.3744 | 0.7036 | 0.4477 | 0.049* | |
C3 | 0.5608 (7) | 0.7042 (6) | 0.3959 (4) | 0.0513 (19) | |
H3 | 0.5281 | 0.7393 | 0.3471 | 0.062* | |
C4 | 0.7011 (7) | 0.6743 (5) | 0.4054 (4) | 0.0446 (18) | |
H4 | 0.7602 | 0.6875 | 0.3623 | 0.054* | |
C5 | 0.7544 (7) | 0.6259 (5) | 0.4763 (4) | 0.0405 (17) | |
H5 | 0.8498 | 0.6073 | 0.4834 | 0.049* | |
C6 | 0.6637 (6) | 0.6055 (5) | 0.5369 (4) | 0.0366 (16) | |
C7 | 0.5645 (6) | 0.5611 (5) | 0.6470 (4) | 0.0353 (16) | |
C8 | 0.3168 (6) | 0.6190 (5) | 0.6155 (4) | 0.0415 (17) | |
H8A | 0.3015 | 0.5876 | 0.6695 | 0.050* | |
H8B | 0.2574 | 0.5806 | 0.5736 | 0.050* | |
C9 | 0.2739 (6) | 0.7344 (5) | 0.6157 (4) | 0.0346 (15) | |
C10 | 0.3348 (6) | 0.8014 (6) | 0.6741 (4) | 0.0413 (17) | |
H10 | 0.4006 | 0.7748 | 0.7147 | 0.050* | |
C11 | 0.3004 (7) | 0.9063 (6) | 0.6735 (4) | 0.0437 (18) | |
H11 | 0.3405 | 0.9523 | 0.7144 | 0.052* | |
C12 | 0.2073 (7) | 0.9447 (5) | 0.6132 (4) | 0.0400 (18) | |
C13 | 0.1423 (7) | 0.8783 (6) | 0.5565 (4) | 0.0485 (19) | |
H13 | 0.0748 | 0.9047 | 0.5168 | 0.058* | |
C14 | 0.1766 (6) | 0.7724 (6) | 0.5579 (4) | 0.0414 (17) | |
H14 | 0.1327 | 0.7257 | 0.5188 | 0.050* | |
C15 | 0.5513 (7) | 0.5190 (6) | 0.7311 (4) | 0.057 (2) | |
H15A | 0.5091 | 0.5736 | 0.7649 | 0.069* | |
H15B | 0.4885 | 0.4572 | 0.7282 | 0.069* | |
C16 | 0.7306 (12) | 0.5653 (7) | 0.8370 (5) | 0.050 (3) | 0.76 |
H16A | 0.6515 | 0.5831 | 0.8700 | 0.059* | 0.76 |
H16B | 0.7668 | 0.6309 | 0.8134 | 0.059* | 0.76 |
C17 | 0.8437 (10) | 0.5083 (8) | 0.8886 (6) | 0.056 (3) | 0.76 |
H17A | 0.9363 | 0.5244 | 0.8690 | 0.067* | 0.76 |
H17B | 0.8427 | 0.5295 | 0.9468 | 0.067* | 0.76 |
C18 | 0.8108 (11) | 0.3928 (9) | 0.8785 (7) | 0.068 (3) | 0.76 |
H18A | 0.7892 | 0.3614 | 0.9316 | 0.081* | 0.76 |
H18B | 0.8905 | 0.3546 | 0.8574 | 0.081* | 0.76 |
C19 | 0.6855 (10) | 0.3869 (7) | 0.8177 (6) | 0.052 (3) | 0.76 |
H19A | 0.6927 | 0.3255 | 0.7807 | 0.062* | 0.76 |
H19B | 0.5987 | 0.3806 | 0.8464 | 0.062* | 0.76 |
C16' | 0.727 (5) | 0.534 (3) | 0.8521 (13) | 0.051 (6)* | 0.24 |
H16C | 0.6464 | 0.5403 | 0.8863 | 0.061* | 0.24 |
H16D | 0.7707 | 0.6046 | 0.8472 | 0.061* | 0.24 |
C17' | 0.830 (4) | 0.453 (2) | 0.885 (3) | 0.048 (6)* | 0.24 |
H17C | 0.9241 | 0.4688 | 0.8680 | 0.057* | 0.24 |
H17D | 0.8330 | 0.4507 | 0.9458 | 0.057* | 0.24 |
C18' | 0.778 (4) | 0.350 (2) | 0.849 (2) | 0.063 (6)* | 0.24 |
H18C | 0.7447 | 0.3043 | 0.8929 | 0.076* | 0.24 |
H18D | 0.8538 | 0.3132 | 0.8231 | 0.076* | 0.24 |
C19' | 0.661 (4) | 0.3744 (12) | 0.787 (2) | 0.046 (6)* | 0.24 |
H19C | 0.6670 | 0.3312 | 0.7367 | 0.055* | 0.24 |
H19D | 0.5694 | 0.3636 | 0.8093 | 0.055* | 0.24 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0285 (4) | 0.0470 (5) | 0.0400 (5) | 0.0027 (5) | 0.0065 (3) | 0.0030 (5) |
Cl1 | 0.0694 (14) | 0.0401 (11) | 0.0922 (16) | 0.0049 (10) | 0.0347 (12) | 0.0068 (11) |
Cl2 | 0.0467 (11) | 0.0645 (13) | 0.0505 (11) | 0.0199 (9) | −0.0042 (9) | −0.0150 (10) |
Cl3 | 0.0399 (10) | 0.0549 (12) | 0.0766 (14) | −0.0089 (9) | 0.0040 (9) | 0.0162 (11) |
N1 | 0.031 (3) | 0.038 (3) | 0.051 (4) | 0.002 (3) | 0.008 (3) | −0.001 (3) |
N2 | 0.030 (3) | 0.039 (3) | 0.034 (3) | 0.004 (3) | 0.005 (2) | 0.001 (3) |
N3 | 0.039 (3) | 0.039 (3) | 0.034 (3) | 0.008 (3) | 0.009 (2) | 0.003 (3) |
C1 | 0.038 (4) | 0.031 (4) | 0.042 (4) | −0.010 (3) | 0.006 (3) | −0.003 (3) |
C2 | 0.037 (4) | 0.030 (4) | 0.055 (5) | 0.007 (3) | −0.002 (3) | 0.006 (4) |
C3 | 0.051 (5) | 0.054 (5) | 0.048 (5) | 0.005 (4) | −0.001 (4) | 0.014 (4) |
C4 | 0.053 (5) | 0.032 (4) | 0.049 (5) | −0.004 (4) | 0.011 (4) | 0.004 (4) |
C5 | 0.038 (4) | 0.030 (4) | 0.053 (5) | −0.002 (3) | 0.004 (3) | 0.000 (3) |
C6 | 0.032 (4) | 0.034 (4) | 0.044 (4) | −0.005 (3) | 0.012 (3) | −0.004 (3) |
C7 | 0.033 (4) | 0.036 (4) | 0.038 (4) | −0.006 (3) | 0.011 (3) | −0.004 (3) |
C8 | 0.028 (4) | 0.040 (4) | 0.056 (5) | −0.004 (3) | 0.008 (3) | 0.000 (4) |
C9 | 0.024 (3) | 0.036 (4) | 0.045 (4) | −0.001 (3) | 0.006 (3) | −0.001 (3) |
C10 | 0.028 (3) | 0.049 (5) | 0.047 (4) | 0.000 (4) | 0.000 (3) | −0.005 (4) |
C11 | 0.034 (4) | 0.050 (5) | 0.048 (5) | −0.004 (3) | 0.010 (3) | −0.010 (4) |
C12 | 0.043 (4) | 0.035 (4) | 0.045 (4) | 0.004 (4) | 0.024 (4) | −0.001 (4) |
C13 | 0.039 (4) | 0.062 (5) | 0.044 (5) | 0.013 (4) | 0.003 (3) | 0.001 (4) |
C14 | 0.034 (4) | 0.053 (5) | 0.037 (4) | −0.001 (4) | 0.000 (3) | −0.012 (4) |
C15 | 0.036 (4) | 0.085 (6) | 0.053 (4) | 0.009 (4) | 0.014 (3) | 0.007 (5) |
C16 | 0.043 (5) | 0.055 (7) | 0.052 (6) | 0.003 (5) | 0.018 (5) | −0.008 (5) |
C17 | 0.051 (5) | 0.082 (7) | 0.036 (5) | 0.002 (6) | 0.008 (4) | −0.008 (6) |
C18 | 0.075 (7) | 0.079 (7) | 0.050 (6) | 0.025 (7) | 0.017 (5) | 0.017 (6) |
C19 | 0.050 (6) | 0.054 (6) | 0.055 (7) | 0.000 (5) | 0.025 (5) | 0.009 (5) |
Co1—N2 | 1.976 (5) | C10—H10 | 0.9500 |
Co1—N3 | 2.126 (5) | C11—C12 | 1.379 (9) |
Co1—Cl3 | 2.217 (2) | C11—H11 | 0.9500 |
Co1—Cl2 | 2.233 (2) | C12—C13 | 1.373 (9) |
Cl1—C12 | 1.747 (7) | C13—C14 | 1.382 (9) |
N1—C7 | 1.340 (7) | C13—H13 | 0.9500 |
N1—C1 | 1.394 (7) | C14—H14 | 0.9500 |
N1—C8 | 1.479 (7) | C15—H15A | 0.9900 |
N2—C7 | 1.337 (7) | C15—H15B | 0.9900 |
N2—C6 | 1.386 (7) | C16—C17 | 1.517 (8) |
N3—C19' | 1.482 (10) | C16—H16A | 0.9900 |
N3—C16' | 1.485 (10) | C16—H16B | 0.9900 |
N3—C15 | 1.484 (8) | C17—C18 | 1.505 (9) |
N3—C19 | 1.489 (7) | C17—H17A | 0.9900 |
N3—C16 | 1.503 (7) | C17—H17B | 0.9900 |
C1—C2 | 1.394 (8) | C18—C19 | 1.516 (8) |
C1—C6 | 1.399 (8) | C18—H18A | 0.9900 |
C2—C3 | 1.370 (9) | C18—H18B | 0.9900 |
C2—H2 | 0.9500 | C19—H19A | 0.9900 |
C3—C4 | 1.404 (9) | C19—H19B | 0.9900 |
C3—H3 | 0.9500 | C16'—C17' | 1.508 (10) |
C4—C5 | 1.382 (8) | C16'—H16C | 0.9900 |
C4—H4 | 0.9500 | C16'—H16D | 0.9900 |
C5—C6 | 1.389 (8) | C17'—C18' | 1.501 (10) |
C5—H5 | 0.9500 | C17'—H17C | 0.9900 |
C7—C15 | 1.489 (8) | C17'—H17D | 0.9900 |
C8—C9 | 1.521 (8) | C18'—C19' | 1.503 (10) |
C8—H8A | 0.9900 | C18'—H18C | 0.9900 |
C8—H8B | 0.9900 | C18'—H18D | 0.9900 |
C9—C14 | 1.374 (8) | C19'—H19C | 0.9900 |
C9—C10 | 1.381 (8) | C19'—H19D | 0.9900 |
C10—C11 | 1.370 (9) | ||
N2—Co1—N3 | 83.34 (18) | C13—C12—C11 | 120.9 (6) |
N2—Co1—Cl3 | 109.35 (16) | C13—C12—Cl1 | 118.8 (6) |
N3—Co1—Cl3 | 115.01 (15) | C11—C12—Cl1 | 120.2 (6) |
N2—Co1—Cl2 | 118.05 (16) | C12—C13—C14 | 119.1 (7) |
N3—Co1—Cl2 | 111.27 (15) | C12—C13—H13 | 120.5 |
Cl3—Co1—Cl2 | 115.79 (8) | C14—C13—H13 | 120.5 |
C7—N1—C1 | 107.2 (5) | C9—C14—C13 | 120.2 (6) |
C7—N1—C8 | 126.7 (5) | C9—C14—H14 | 119.9 |
C1—N1—C8 | 126.2 (5) | C13—C14—H14 | 119.9 |
C7—N2—C6 | 105.6 (5) | N3—C15—C7 | 111.9 (5) |
C7—N2—Co1 | 114.7 (4) | N3—C15—H15A | 109.2 |
C6—N2—Co1 | 139.7 (4) | C7—C15—H15A | 109.2 |
C19'—N3—C16' | 105 (2) | N3—C15—H15B | 109.2 |
C19'—N3—C15 | 100.4 (13) | C7—C15—H15B | 109.2 |
C16'—N3—C15 | 116.9 (16) | H15A—C15—H15B | 107.9 |
C19'—N3—C19 | 21.9 (14) | N3—C16—C17 | 104.1 (7) |
C16'—N3—C19 | 83.9 (15) | N3—C16—H16A | 110.9 |
C15—N3—C19 | 114.5 (6) | C17—C16—H16A | 110.9 |
C19'—N3—C16 | 123.3 (15) | N3—C16—H16B | 110.9 |
C16'—N3—C16 | 17.9 (17) | C17—C16—H16B | 110.9 |
C15—N3—C16 | 109.5 (6) | H16A—C16—H16B | 109.0 |
C19—N3—C16 | 101.7 (6) | C18—C17—C16 | 105.2 (7) |
C19'—N3—Co1 | 107.4 (17) | C18—C17—H17A | 110.7 |
C16'—N3—Co1 | 116.2 (19) | C16—C17—H17A | 110.7 |
C15—N3—Co1 | 108.9 (3) | C18—C17—H17B | 110.7 |
C19—N3—Co1 | 115.0 (5) | C16—C17—H17B | 110.7 |
C16—N3—Co1 | 106.7 (5) | H17A—C17—H17B | 108.8 |
N1—C1—C2 | 132.1 (6) | C17—C18—C19 | 105.9 (7) |
N1—C1—C6 | 105.7 (6) | C17—C18—H18A | 110.6 |
C2—C1—C6 | 122.2 (6) | C19—C18—H18A | 110.6 |
C3—C2—C1 | 116.5 (6) | C17—C18—H18B | 110.6 |
C3—C2—H2 | 121.8 | C19—C18—H18B | 110.6 |
C1—C2—H2 | 121.8 | H18A—C18—H18B | 108.7 |
C2—C3—C4 | 122.1 (6) | N3—C19—C18 | 104.9 (7) |
C2—C3—H3 | 118.9 | N3—C19—H19A | 110.8 |
C4—C3—H3 | 118.9 | C18—C19—H19A | 110.8 |
C5—C4—C3 | 121.0 (6) | N3—C19—H19B | 110.8 |
C5—C4—H4 | 119.5 | C18—C19—H19B | 110.8 |
C3—C4—H4 | 119.5 | H19A—C19—H19B | 108.8 |
C4—C5—C6 | 117.7 (6) | N3—C16'—C17' | 100 (2) |
C4—C5—H5 | 121.1 | N3—C16'—H16C | 111.8 |
C6—C5—H5 | 121.1 | C17'—C16'—H16C | 111.8 |
N2—C6—C5 | 130.6 (6) | N3—C16'—H16D | 111.8 |
N2—C6—C1 | 109.0 (5) | C17'—C16'—H16D | 111.8 |
C5—C6—C1 | 120.4 (6) | H16C—C16'—H16D | 109.5 |
N2—C7—N1 | 112.6 (5) | C18'—C17'—C16' | 105 (3) |
N2—C7—C15 | 120.4 (6) | C18'—C17'—H17C | 110.7 |
N1—C7—C15 | 127.0 (6) | C16'—C17'—H17C | 110.7 |
N1—C8—C9 | 112.1 (5) | C18'—C17'—H17D | 110.7 |
N1—C8—H8A | 109.2 | C16'—C17'—H17D | 110.7 |
C9—C8—H8A | 109.2 | H17C—C17'—H17D | 108.8 |
N1—C8—H8B | 109.2 | C17'—C18'—C19' | 108 (3) |
C9—C8—H8B | 109.2 | C17'—C18'—H18C | 110.2 |
H8A—C8—H8B | 107.9 | C19'—C18'—H18C | 110.2 |
C14—C9—C10 | 120.1 (6) | C17'—C18'—H18D | 110.2 |
C14—C9—C8 | 120.6 (6) | C19'—C18'—H18D | 110.2 |
C10—C9—C8 | 119.3 (6) | H18C—C18'—H18D | 108.5 |
C11—C10—C9 | 120.0 (6) | N3—C19'—C18' | 100.8 (19) |
C11—C10—H10 | 120.0 | N3—C19'—H19C | 111.6 |
C9—C10—H10 | 120.0 | C18'—C19'—H19C | 111.6 |
C10—C11—C12 | 119.6 (7) | N3—C19'—H19D | 111.6 |
C10—C11—H11 | 120.2 | C18'—C19'—H19D | 111.6 |
C12—C11—H11 | 120.2 | H19C—C19'—H19D | 109.4 |
N3—Co1—N2—C7 | −5.1 (4) | C7—N1—C8—C9 | 119.4 (7) |
Cl3—Co1—N2—C7 | −119.3 (4) | C1—N1—C8—C9 | −62.3 (8) |
Cl2—Co1—N2—C7 | 105.5 (4) | N1—C8—C9—C14 | 115.0 (6) |
N3—Co1—N2—C6 | 175.7 (7) | N1—C8—C9—C10 | −64.3 (8) |
Cl3—Co1—N2—C6 | 61.5 (7) | C14—C9—C10—C11 | −1.3 (9) |
Cl2—Co1—N2—C6 | −73.7 (7) | C8—C9—C10—C11 | 178.0 (5) |
N2—Co1—N3—C19' | 115.3 (12) | C9—C10—C11—C12 | −1.5 (9) |
Cl3—Co1—N3—C19' | −136.4 (12) | C10—C11—C12—C13 | 3.8 (9) |
Cl2—Co1—N3—C19' | −2.3 (12) | C10—C11—C12—Cl1 | −175.6 (5) |
N2—Co1—N3—C16' | −127.0 (15) | C11—C12—C13—C14 | −3.2 (10) |
Cl3—Co1—N3—C16' | −18.7 (15) | Cl1—C12—C13—C14 | 176.3 (5) |
Cl2—Co1—N3—C16' | 115.4 (15) | C10—C9—C14—C13 | 1.9 (9) |
N2—Co1—N3—C15 | 7.4 (5) | C8—C9—C14—C13 | −177.4 (6) |
Cl3—Co1—N3—C15 | 115.7 (4) | C12—C13—C14—C9 | 0.3 (10) |
Cl2—Co1—N3—C15 | −110.1 (4) | C19'—N3—C15—C7 | −120.9 (18) |
N2—Co1—N3—C19 | 137.4 (5) | C16'—N3—C15—C7 | 126 (2) |
Cl3—Co1—N3—C19 | −114.3 (5) | C19—N3—C15—C7 | −138.6 (7) |
Cl2—Co1—N3—C19 | 19.8 (5) | C16—N3—C15—C7 | 108.0 (7) |
N2—Co1—N3—C16 | −110.7 (5) | Co1—N3—C15—C7 | −8.3 (7) |
Cl3—Co1—N3—C16 | −2.4 (5) | N2—C7—C15—N3 | 5.0 (9) |
Cl2—Co1—N3—C16 | 131.8 (4) | N1—C7—C15—N3 | −173.0 (6) |
C7—N1—C1—C2 | −179.3 (6) | C19'—N3—C16—C17 | 46 (2) |
C8—N1—C1—C2 | 2.1 (10) | C16'—N3—C16—C17 | 46 (6) |
C7—N1—C1—C6 | −0.6 (7) | C15—N3—C16—C17 | 163.2 (7) |
C8—N1—C1—C6 | −179.1 (5) | C19—N3—C16—C17 | 41.7 (9) |
N1—C1—C2—C3 | 178.1 (7) | Co1—N3—C16—C17 | −79.1 (7) |
C6—C1—C2—C3 | −0.5 (9) | N3—C16—C17—C18 | −27.9 (10) |
C1—C2—C3—C4 | 1.3 (10) | C16—C17—C18—C19 | 3.3 (11) |
C2—C3—C4—C5 | −2.0 (11) | C19'—N3—C19—C18 | 149 (5) |
C3—C4—C5—C6 | 1.7 (10) | C16'—N3—C19—C18 | −40.8 (19) |
C7—N2—C6—C5 | 178.9 (6) | C15—N3—C19—C18 | −157.6 (7) |
Co1—N2—C6—C5 | −2.0 (11) | C16—N3—C19—C18 | −39.7 (9) |
C7—N2—C6—C1 | 0.3 (7) | Co1—N3—C19—C18 | 75.2 (8) |
Co1—N2—C6—C1 | 179.5 (5) | C17—C18—C19—N3 | 22.7 (10) |
C4—C5—C6—N2 | −179.3 (6) | C19'—N3—C16'—C17' | 46 (4) |
C4—C5—C6—C1 | −0.9 (9) | C15—N3—C16'—C17' | 157 (2) |
N1—C1—C6—N2 | 0.2 (7) | C19—N3—C16'—C17' | 43 (3) |
C2—C1—C6—N2 | 179.1 (5) | C16—N3—C16'—C17' | −134 (9) |
N1—C1—C6—C5 | −178.6 (5) | Co1—N3—C16'—C17' | −72 (3) |
C2—C1—C6—C5 | 0.3 (9) | N3—C16'—C17'—C18' | −33 (4) |
C6—N2—C7—N1 | −0.7 (7) | C16'—C17'—C18'—C19' | 9 (5) |
Co1—N2—C7—N1 | 179.9 (4) | C16'—N3—C19'—C18' | −41 (3) |
C6—N2—C7—C15 | −179.0 (6) | C15—N3—C19'—C18' | −163 (2) |
Co1—N2—C7—C15 | 1.6 (8) | C19—N3—C19'—C18' | −30 (3) |
C1—N1—C7—N2 | 0.8 (7) | C16—N3—C19'—C18' | −41 (3) |
C8—N1—C7—N2 | 179.4 (5) | Co1—N3—C19'—C18' | 83 (3) |
C1—N1—C7—C15 | 178.9 (6) | C17'—C18'—C19'—N3 | 19 (4) |
C8—N1—C7—C15 | −2.5 (10) |
Experimental details
Crystal data | |
Chemical formula | [CoCl2(C19H20ClN3)] |
Mr | 455.66 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 170 |
a, b, c (Å) | 9.647 (6), 12.675 (6), 16.359 (5) |
β (°) | 93.77 (4) |
V (Å3) | 1996 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.40 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Rigaku AFC-6S diffractometer |
Absorption correction | Empirical (using intensity measurements) ψ scan (3 reflections; North et al., 1968) |
Tmin, Tmax | 0.63, 0.82 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3754, 3533, 1425 |
Rint | 0.097 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.136, 0.98 |
No. of reflections | 3533 |
No. of parameters | 251 |
No. of restraints | 34 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.44 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN.
Co1—N2 | 1.976 (5) | N2—C7 | 1.337 (7) |
Co1—N3 | 2.126 (5) | N2—C6 | 1.386 (7) |
Co1—Cl3 | 2.217 (2) | N3—C19' | 1.482 (10) |
Co1—Cl2 | 2.233 (2) | N3—C16' | 1.485 (10) |
Cl1—C12 | 1.747 (7) | N3—C15 | 1.484 (8) |
N1—C7 | 1.340 (7) | N3—C19 | 1.489 (7) |
N1—C1 | 1.394 (7) | N3—C16 | 1.503 (7) |
N1—C8 | 1.479 (7) | ||
N2—Co1—N3 | 83.34 (18) | C7—N2—C6 | 105.6 (5) |
N2—Co1—Cl3 | 109.35 (16) | C7—N2—Co1 | 114.7 (4) |
N3—Co1—Cl3 | 115.01 (15) | C6—N2—Co1 | 139.7 (4) |
N2—Co1—Cl2 | 118.05 (16) | C15—N3—C19 | 114.5 (6) |
N3—Co1—Cl2 | 111.27 (15) | C15—N3—C16 | 109.5 (6) |
Cl3—Co1—Cl2 | 115.79 (8) | C19—N3—C16 | 101.7 (6) |
C7—N1—C1 | 107.2 (5) | C15—N3—Co1 | 108.9 (3) |
C7—N1—C8 | 126.7 (5) | C19—N3—Co1 | 115.0 (5) |
C1—N1—C8 | 126.2 (5) | C16—N3—Co1 | 106.7 (5) |
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The crystal structures of clemizole hydrochloride (Parvez, 1996), clemizoledichlorozinc(II) (Parvez & Sabir, 1996a), clemizole as a free base (Parvez & Sabir, 1996b), clemizole tetrachlorocuprate(II) and clemizole tetrachlorocobaltate(II) (Parvez & Sabir, 1997) have been reported from our laboratory. This H1 antihistamine has now been incorporated into a cobalt complex to investigate further the effects such complex formation may have on the conformation of the clemizole moiety. In this paper, we report the structure of clemizoledichlorocobalt(II), (I).
In (I) (Fig. 1), the clemizole is coordinated in a bidentate manner to cobalt via pyrrolidinyl and imidazole N atoms with significantly different Co—N distances of 1.976 (5) and 2.125 (5) Å, respectively. The Co atom is also bound to two Cl atoms with Co—Cl distances of 2.233 (2) and 2.217 (2) Å. The geometry around cobalt is distorted tetrahedral. Similar distances and geometry have been reported for a number of closely related cobalt complexes, e.g. dichlorobis(2-methoxypyridine)cobalt(II) (Allan et al., 1981), bis(1,3-benzothiazole)dichlorocobalt(II) (Oughtred et al., 1982), dichlorobis[2-(4-thiazolyl)-1H-benzimidazole-N,N']cobalt(II) monohydrate (Umadevi et al., 1995), dichloro[phenylbis(2-pyridyl)phosphine-N,N']cobalt(II) ethanol solvate (Ehrlich et al., 1984) and bis(N-2-propylsalicylideneamino-N,O)cobalt(II) (Elerman et al., 1996).
The molecular dimensions in the benzimidazole part of the ligand are normal while the pyrrolidinyl ring is disordered. The important bond distances are: Csp2—Cl 1.747 (7) Å and mean Csp3—Csp2 1.51 (2), C—Caromatic 1.383 (11), N—Csp2 1.390 (4) and N—Csp3 1.482 (3) Å, not including the disordered pyrrolidinyl ring. It is interesting to note that the N1—C7 bond [1.340 (7) Å] is much shorter than expected for a single bond and that the N2—C7 bond [1.337 (7) Å] is much longer than a double bond; these bonds must represent a delocalized system with a mean N ≐C distance of 1.339 (2) Å; the corresponding distances in the structure of clemizoledichlorozinc(II) (Parvez & Sabir, 1996a) were 1.357 (5) and 1.321 (5) Å, respectively. The pyrrolidinyl ring in (I) is disordered over two sites with inequivalent site-occupancy factors, therefore, its N—C and C—C distances were constrained at 1.48 (1) and 1.50 (1) Å during refinement. The separation between pairs of C atoms of the pyrrolidinyl ring is in the range 0.47–0.77 Å.
The benzimidazole and phenyl rings are essentially planar, with maximum deviations of atoms from the least-squares planes being 0.013 (6) and 0.021 (4) Å, respectively. The dihedral angle between these planes is 86.2 (2)°; the corresponding angle in the structures of clemizole dichlorozinc, clemizole hydrochloride, clemizole as a free base, clemizole tetrachlorocuperate(II) and clemizole tetrachlorocobaltate(II) are 81.1 (4) (Parvez & Sabir, 1996a), 82.8 (9) (Parvez, 1996), 68.8 (6) (Parvez & Sabir, 1996b), 70.5 (6) and 82.7 (9)° (Parvez & Sabir, 1997), respectively. An examination of the N1—C8—C9—C14 torsion angle in these complex molecules shows that the orientation of the phenyl ring with respect to the imidazole ring in (I) [torsion angle 115.0 (6)°] is somewhat similar to the orientation of these rings in the free base (torsion angle 125°) and clemizole tetrachlorocobaltate(II) (torsion angle 116°); the rest of the structures have torsion angles in the range of 133–153°. The major and minor conformers of the disordered pyrrolidinyl ring have an N3-envelope conformation with N3 0.62 (5) and 0.64 (5) Å out of the planes composed of the C16–C19 and C16'–C19' atoms, respectively; a similar conformation of the five-membered ring has been observed in the crystal structures mentioned above.
The structure of (I) is composed of independent complex molecules separated by normal van der Waals distances and is devoid of any intermolecular interactions. The imidazole moieties of the molecules, which lie about inversion centers, are stacked parallel to each other.