Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007838/ci6029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007838/ci6029Isup2.hkl |
CCDC reference: 170732
A solution of NiCl2·6H2O (2 g) in methanol (25 ml) was added to a solution of 2,2-bipyridine (2.75 g) in methanol. This mixture was agitated for 1 h and concentrated under vacuum to a volume of 10 ml. Slow evaporation of the solvent in air allowed the formation of green crystals.
H atoms were constrained to the parent site using a riding model (C—H 0.93–0.96 and O—H 0.82 Å). The isotropic displacement parameters, Uiso, were adjusted to a value 50% higher than that of the parent site (methyl and OH) and 20% higher (others).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRC-2 and NRC-2A (Ahmed et al., 1973); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL96 (Sheldrick, 1996); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL96.
Fig. 1. The structure of the title complex showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
[NiCl2(C10H8N2)2]·CH4O | Dx = 1.526 Mg m−3 |
Mr = 474.02 | Cu Kα radiation, λ = 1.54056 Å |
Orthorhombic, Pbca | Cell parameters from 25 reflections |
a = 10.455 (3) Å | θ = 20.0–23.0° |
b = 13.830 (4) Å | µ = 3.90 mm−1 |
c = 28.548 (10) Å | T = 293 K |
V = 4128 (2) Å3 | Block, dark green |
Z = 8 | 0.23 × 0.23 × 0.16 mm |
F(000) = 1952.0 |
Nonius CAD-4 diffractometer | 2054 reflections with I > 2σ(I) |
Radiation source: normal-focus xray tube | Rint = 0.073 |
Graphite monochromator | θmax = 69.9°, θmin = 3.1° |
ω/2θ scans | h = 0→12 |
Absorption correction: integration (ABSORP in NRCVAX; Gabe et al., 1989) | k = 0→16 |
Tmin = 0.432, Tmax = 0.593 | l = 0→34 |
22288 measured reflections | 5 standard reflections every 60 min |
3908 independent reflections | intensity decay: no decay, variation 0.0% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.79 | (Δ/σ)max = 0.001 |
3908 reflections | Δρmax = 0.31 e Å−3 |
265 parameters | Δρmin = −0.65 e Å−3 |
0 restraints | Extinction correction: SHELXL96 (Sheldrick, 1996), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00066 (5) |
[NiCl2(C10H8N2)2]·CH4O | V = 4128 (2) Å3 |
Mr = 474.02 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 10.455 (3) Å | µ = 3.90 mm−1 |
b = 13.830 (4) Å | T = 293 K |
c = 28.548 (10) Å | 0.23 × 0.23 × 0.16 mm |
Nonius CAD-4 diffractometer | 2054 reflections with I > 2σ(I) |
Absorption correction: integration (ABSORP in NRCVAX; Gabe et al., 1989) | Rint = 0.073 |
Tmin = 0.432, Tmax = 0.593 | 5 standard reflections every 60 min |
22288 measured reflections | intensity decay: no decay, variation 0.0% |
3908 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 0.79 | Δρmax = 0.31 e Å−3 |
3908 reflections | Δρmin = −0.65 e Å−3 |
265 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. |
Refinement. Refinement of F2 against ALL reflections. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor_obs 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. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.14225 (6) | 0.39332 (5) | 0.38102 (2) | 0.0470 (2) | |
Cl1 | 0.28217 (11) | 0.26123 (7) | 0.36335 (4) | 0.0605 (3) | |
Cl2 | 0.29823 (10) | 0.47056 (8) | 0.43132 (4) | 0.0577 (3) | |
N1 | 0.2053 (3) | 0.4614 (2) | 0.32013 (12) | 0.0471 (9) | |
N2 | 0.0161 (3) | 0.3383 (2) | 0.33035 (13) | 0.0501 (9) | |
C1 | 0.3009 (4) | 0.5259 (3) | 0.31710 (18) | 0.0573 (12) | |
H1 | 0.3350 | 0.5512 | 0.3446 | 0.069* | |
C2 | 0.3506 (4) | 0.5561 (3) | 0.27465 (19) | 0.0651 (14) | |
H2 | 0.4182 | 0.5998 | 0.2737 | 0.078* | |
C3 | 0.2991 (5) | 0.5209 (3) | 0.23441 (19) | 0.0650 (14) | |
H3 | 0.3321 | 0.5399 | 0.2056 | 0.078* | |
C4 | 0.1980 (4) | 0.4573 (3) | 0.23634 (17) | 0.0584 (12) | |
H4 | 0.1599 | 0.4343 | 0.2091 | 0.070* | |
C5 | 0.1548 (4) | 0.4286 (3) | 0.27983 (17) | 0.0485 (11) | |
C6 | 0.0469 (4) | 0.3582 (3) | 0.28575 (17) | 0.0490 (11) | |
C7 | −0.0171 (4) | 0.3162 (3) | 0.24814 (18) | 0.0579 (12) | |
H7 | 0.0078 | 0.3294 | 0.2175 | 0.069* | |
C8 | −0.1182 (4) | 0.2547 (3) | 0.2571 (2) | 0.0669 (14) | |
H8 | −0.1625 | 0.2257 | 0.2325 | 0.080* | |
C9 | −0.1520 (4) | 0.2370 (3) | 0.30239 (18) | 0.0655 (14) | |
H9 | −0.2209 | 0.1968 | 0.3091 | 0.079* | |
C10 | −0.0836 (4) | 0.2789 (3) | 0.33783 (18) | 0.0599 (13) | |
H10 | −0.1073 | 0.2656 | 0.3686 | 0.072* | |
N3 | 0.0100 (3) | 0.4972 (2) | 0.40138 (12) | 0.0476 (9) | |
N4 | 0.0490 (3) | 0.3248 (2) | 0.43582 (12) | 0.0473 (9) | |
C11 | −0.0042 (4) | 0.5849 (3) | 0.38084 (16) | 0.0526 (11) | |
H11 | 0.0460 | 0.6004 | 0.3550 | 0.063* | |
C12 | −0.0910 (4) | 0.6517 (3) | 0.39726 (18) | 0.0613 (14) | |
H12 | −0.0989 | 0.7116 | 0.3827 | 0.074* | |
C13 | −0.1652 (4) | 0.6296 (3) | 0.43496 (18) | 0.0641 (14) | |
H13 | −0.2248 | 0.6740 | 0.4460 | 0.077* | |
C14 | −0.1515 (4) | 0.5405 (3) | 0.45685 (17) | 0.0566 (12) | |
H14 | −0.2004 | 0.5246 | 0.4830 | 0.068* | |
C15 | −0.0625 (4) | 0.4757 (3) | 0.43855 (15) | 0.0459 (10) | |
C16 | −0.0420 (4) | 0.3774 (3) | 0.45807 (15) | 0.0472 (11) | |
C17 | −0.1105 (4) | 0.3419 (3) | 0.49582 (16) | 0.0570 (12) | |
H17 | −0.1710 | 0.3802 | 0.5108 | 0.068* | |
C18 | −0.0872 (4) | 0.2482 (4) | 0.51086 (17) | 0.0638 (14) | |
H18 | −0.1318 | 0.2226 | 0.5362 | 0.077* | |
C19 | 0.0029 (5) | 0.1934 (3) | 0.48768 (17) | 0.0632 (14) | |
H19 | 0.0186 | 0.1299 | 0.4968 | 0.076* | |
C20 | 0.0697 (4) | 0.2334 (3) | 0.45087 (16) | 0.0557 (12) | |
H20 | 0.1313 | 0.1962 | 0.4358 | 0.067* | |
O1 | 0.5478 (3) | 0.3869 (3) | 0.36236 (13) | 0.0820 (11) | |
H1A | 0.4736 | 0.3835 | 0.3716 | 0.123* | |
C21 | 0.6168 (5) | 0.4483 (5) | 0.3914 (2) | 0.110 (2) | |
H21A | 0.5642 | 0.5023 | 0.4001 | 0.165* | |
H21B | 0.6912 | 0.4711 | 0.3751 | 0.165* | |
H21C | 0.6425 | 0.4139 | 0.4190 | 0.165* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0391 (4) | 0.0358 (3) | 0.0661 (5) | −0.0005 (3) | 0.0029 (4) | 0.0016 (4) |
Cl1 | 0.0551 (7) | 0.0446 (6) | 0.0817 (8) | 0.0097 (5) | 0.0058 (6) | 0.0002 (6) |
Cl2 | 0.0476 (6) | 0.0519 (6) | 0.0737 (8) | −0.0042 (6) | −0.0020 (6) | −0.0024 (6) |
N1 | 0.0394 (19) | 0.0383 (18) | 0.063 (2) | 0.0000 (17) | 0.0034 (18) | 0.0029 (18) |
N2 | 0.041 (2) | 0.043 (2) | 0.066 (3) | −0.0018 (17) | 0.0044 (19) | 0.0034 (19) |
C1 | 0.043 (2) | 0.042 (2) | 0.087 (4) | −0.005 (2) | 0.005 (3) | 0.006 (3) |
C2 | 0.049 (3) | 0.042 (2) | 0.105 (4) | −0.002 (2) | 0.014 (3) | 0.018 (3) |
C3 | 0.062 (3) | 0.054 (3) | 0.079 (4) | 0.006 (3) | 0.010 (3) | 0.014 (3) |
C4 | 0.054 (3) | 0.052 (3) | 0.070 (3) | 0.002 (2) | 0.004 (3) | 0.008 (3) |
C5 | 0.040 (2) | 0.039 (2) | 0.066 (3) | 0.008 (2) | 0.003 (2) | 0.008 (2) |
C6 | 0.038 (2) | 0.039 (2) | 0.070 (3) | 0.0038 (19) | −0.002 (2) | 0.001 (2) |
C7 | 0.057 (3) | 0.052 (3) | 0.065 (3) | 0.007 (2) | −0.007 (3) | 0.003 (3) |
C8 | 0.063 (3) | 0.049 (3) | 0.089 (4) | −0.008 (3) | −0.009 (3) | −0.010 (3) |
C9 | 0.054 (3) | 0.057 (3) | 0.085 (4) | −0.016 (3) | −0.007 (3) | −0.004 (3) |
C10 | 0.047 (3) | 0.059 (3) | 0.074 (3) | −0.015 (2) | 0.003 (3) | 0.000 (3) |
N3 | 0.0374 (19) | 0.0407 (19) | 0.065 (2) | −0.0018 (15) | −0.0017 (18) | −0.0010 (18) |
N4 | 0.040 (2) | 0.0401 (19) | 0.062 (2) | −0.0041 (16) | −0.0027 (18) | 0.0038 (18) |
C11 | 0.044 (2) | 0.045 (2) | 0.069 (3) | 0.004 (2) | 0.000 (2) | 0.004 (2) |
C12 | 0.054 (3) | 0.040 (2) | 0.090 (4) | 0.006 (2) | −0.006 (3) | −0.005 (3) |
C13 | 0.049 (3) | 0.051 (3) | 0.092 (4) | 0.007 (2) | 0.004 (3) | −0.013 (3) |
C14 | 0.038 (2) | 0.058 (3) | 0.074 (3) | 0.001 (2) | 0.001 (2) | −0.007 (3) |
C15 | 0.034 (2) | 0.044 (2) | 0.060 (3) | −0.005 (2) | 0.000 (2) | −0.002 (2) |
C16 | 0.037 (2) | 0.050 (3) | 0.055 (3) | −0.005 (2) | 0.000 (2) | 0.001 (2) |
C17 | 0.044 (3) | 0.058 (3) | 0.069 (3) | −0.006 (2) | 0.006 (2) | 0.002 (3) |
C18 | 0.055 (3) | 0.068 (3) | 0.068 (4) | −0.016 (3) | 0.004 (3) | 0.009 (3) |
C19 | 0.062 (3) | 0.050 (3) | 0.077 (4) | −0.011 (3) | −0.005 (3) | 0.015 (3) |
C20 | 0.052 (3) | 0.044 (2) | 0.071 (3) | 0.001 (2) | −0.004 (3) | 0.008 (2) |
O1 | 0.057 (2) | 0.090 (3) | 0.098 (3) | −0.018 (2) | 0.002 (2) | 0.001 (2) |
C21 | 0.075 (4) | 0.148 (6) | 0.107 (5) | −0.039 (4) | 0.001 (4) | −0.028 (5) |
Ni—N4 | 2.073 (3) | N3—C15 | 1.338 (5) |
Ni—N3 | 2.077 (3) | N3—C11 | 1.356 (5) |
Ni—N1 | 2.084 (3) | N4—C20 | 1.351 (5) |
Ni—N2 | 2.100 (4) | N4—C16 | 1.357 (5) |
Ni—Cl1 | 2.3940 (13) | C11—C12 | 1.377 (5) |
Ni—Cl2 | 2.4213 (13) | C11—H11 | 0.9300 |
N1—C1 | 1.342 (5) | C12—C13 | 1.361 (6) |
N1—C5 | 1.344 (5) | C12—H12 | 0.9300 |
N2—C6 | 1.342 (5) | C13—C14 | 1.389 (6) |
N2—C10 | 1.344 (5) | C13—H13 | 0.9300 |
C1—C2 | 1.384 (6) | C14—C15 | 1.394 (5) |
C1—H1 | 0.9300 | C14—H14 | 0.9300 |
C2—C3 | 1.359 (6) | C15—C16 | 1.484 (5) |
C2—H2 | 0.9300 | C16—C17 | 1.384 (5) |
C3—C4 | 1.376 (6) | C17—C18 | 1.387 (6) |
C3—H3 | 0.9300 | C17—H17 | 0.9300 |
C4—C5 | 1.380 (6) | C18—C19 | 1.378 (6) |
C4—H4 | 0.9300 | C18—H18 | 0.9300 |
C5—C6 | 1.500 (5) | C19—C20 | 1.378 (6) |
C6—C7 | 1.392 (6) | C19—H19 | 0.9300 |
C7—C8 | 1.380 (6) | C20—H20 | 0.9300 |
C7—H7 | 0.9300 | O1—C21 | 1.388 (5) |
C8—C9 | 1.364 (6) | O1—H1A | 0.8200 |
C8—H8 | 0.9300 | C21—H21A | 0.9600 |
C9—C10 | 1.368 (6) | C21—H21B | 0.9600 |
C9—H9 | 0.9300 | C21—H21C | 0.9600 |
C10—H10 | 0.9300 | ||
N4—Ni—N3 | 78.00 (14) | C10—C9—H9 | 120.3 |
N4—Ni—N1 | 170.07 (14) | N2—C10—C9 | 123.1 (5) |
N3—Ni—N1 | 97.58 (13) | N2—C10—H10 | 118.4 |
N4—Ni—N2 | 93.37 (14) | C9—C10—H10 | 118.4 |
N3—Ni—N2 | 91.44 (13) | C15—N3—C11 | 118.7 (4) |
N1—Ni—N2 | 77.75 (14) | C15—N3—Ni | 116.5 (3) |
N4—Ni—Cl1 | 95.58 (10) | C11—N3—Ni | 124.8 (3) |
N3—Ni—Cl1 | 173.48 (10) | C20—N4—C16 | 117.7 (4) |
N1—Ni—Cl1 | 88.60 (10) | C20—N4—Ni | 126.3 (3) |
N2—Ni—Cl1 | 87.84 (10) | C16—N4—Ni | 115.9 (3) |
N4—Ni—Cl2 | 94.06 (10) | N3—C11—C12 | 121.7 (4) |
N3—Ni—Cl2 | 88.70 (10) | N3—C11—H11 | 119.2 |
N1—Ni—Cl2 | 94.73 (11) | C12—C11—H11 | 119.2 |
N2—Ni—Cl2 | 172.43 (11) | C13—C12—C11 | 119.6 (4) |
Cl1—Ni—Cl2 | 92.87 (5) | C13—C12—H12 | 120.2 |
C1—N1—C5 | 117.5 (4) | C11—C12—H12 | 120.2 |
C1—N1—Ni | 126.1 (3) | C12—C13—C14 | 119.7 (4) |
C5—N1—Ni | 115.9 (3) | C12—C13—H13 | 120.1 |
C6—N2—C10 | 117.6 (4) | C14—C13—H13 | 120.1 |
C6—N2—Ni | 115.3 (3) | C13—C14—C15 | 118.1 (4) |
C10—N2—Ni | 126.8 (3) | C13—C14—H14 | 121.0 |
N1—C1—C2 | 122.5 (5) | C15—C14—H14 | 121.0 |
N1—C1—H1 | 118.7 | N3—C15—C14 | 122.2 (4) |
C2—C1—H1 | 118.7 | N3—C15—C16 | 114.8 (4) |
C3—C2—C1 | 118.9 (4) | C14—C15—C16 | 123.0 (4) |
C3—C2—H2 | 120.6 | N4—C16—C17 | 122.5 (4) |
C1—C2—H2 | 120.6 | N4—C16—C15 | 114.7 (4) |
C2—C3—C4 | 120.0 (5) | C17—C16—C15 | 122.9 (4) |
C2—C3—H3 | 120.0 | C16—C17—C18 | 118.8 (5) |
C4—C3—H3 | 120.0 | C16—C17—H17 | 120.6 |
C3—C4—C5 | 118.1 (5) | C18—C17—H17 | 120.6 |
C3—C4—H4 | 120.9 | C19—C18—C17 | 119.0 (5) |
C5—C4—H4 | 120.9 | C19—C18—H18 | 120.5 |
N1—C5—C4 | 123.0 (4) | C17—C18—H18 | 120.5 |
N1—C5—C6 | 114.7 (4) | C20—C19—C18 | 119.5 (5) |
C4—C5—C6 | 122.3 (4) | C20—C19—H19 | 120.3 |
N2—C6—C7 | 122.0 (4) | C18—C19—H19 | 120.3 |
N2—C6—C5 | 114.9 (4) | N4—C20—C19 | 122.5 (4) |
C7—C6—C5 | 123.1 (4) | N4—C20—H20 | 118.8 |
C8—C7—C6 | 118.9 (5) | C19—C20—H20 | 118.8 |
C8—C7—H7 | 120.5 | C21—O1—H1A | 109.5 |
C6—C7—H7 | 120.5 | O1—C21—H21A | 109.5 |
C9—C8—C7 | 118.9 (5) | O1—C21—H21B | 109.5 |
C9—C8—H8 | 120.5 | H21A—C21—H21B | 109.5 |
C7—C8—H8 | 120.5 | O1—C21—H21C | 109.5 |
C8—C9—C10 | 119.4 (5) | H21A—C21—H21C | 109.5 |
C8—C9—H9 | 120.3 | H21B—C21—H21C | 109.5 |
N3—Ni—N1—C1 | 88.3 (3) | N4—Ni—N3—C15 | 3.2 (3) |
N2—Ni—N1—C1 | 178.2 (3) | N1—Ni—N3—C15 | 174.2 (3) |
Cl1—Ni—N1—C1 | −93.8 (3) | N2—Ni—N3—C15 | 96.3 (3) |
Cl2—Ni—N1—C1 | −1.0 (3) | Cl2—Ni—N3—C15 | −91.2 (3) |
N3—Ni—N1—C5 | −99.9 (3) | N4—Ni—N3—C11 | −179.2 (4) |
N2—Ni—N1—C5 | −10.1 (3) | N1—Ni—N3—C11 | −8.2 (4) |
Cl1—Ni—N1—C5 | 78.0 (3) | N2—Ni—N3—C11 | −86.1 (3) |
Cl2—Ni—N1—C5 | 170.7 (3) | Cl2—Ni—N3—C11 | 86.4 (3) |
N4—Ni—N2—C6 | −174.3 (3) | N3—Ni—N4—C20 | 176.9 (4) |
N3—Ni—N2—C6 | 107.6 (3) | N2—Ni—N4—C20 | 86.1 (4) |
N1—Ni—N2—C6 | 10.2 (3) | Cl2—Ni—N4—C20 | −95.3 (3) |
Cl1—Ni—N2—C6 | −78.9 (3) | N3—Ni—N4—C16 | −2.5 (3) |
N4—Ni—N2—C10 | −0.9 (4) | N2—Ni—N4—C16 | −93.2 (3) |
N3—Ni—N2—C10 | −79.0 (4) | Cl1—Ni—N4—C16 | 178.6 (3) |
N1—Ni—N2—C10 | −176.4 (4) | Cl2—Ni—N4—C16 | 85.3 (3) |
Cl1—Ni—N2—C10 | 94.5 (3) | C15—N3—C11—C12 | −0.1 (6) |
C5—N1—C1—C2 | −2.3 (6) | Ni—N3—C11—C12 | −177.7 (3) |
Ni—N1—C1—C2 | 169.3 (3) | N3—C11—C12—C13 | −0.2 (7) |
N1—C1—C2—C3 | 1.5 (7) | C11—C12—C13—C14 | 0.8 (7) |
C1—C2—C3—C4 | 0.8 (7) | C12—C13—C14—C15 | −1.1 (7) |
C2—C3—C4—C5 | −2.2 (7) | C11—N3—C15—C14 | −0.2 (6) |
C1—N1—C5—C4 | 0.8 (6) | Ni—N3—C15—C14 | 177.6 (3) |
Ni—N1—C5—C4 | −171.6 (3) | C11—N3—C15—C16 | 178.9 (3) |
C1—N1—C5—C6 | −178.9 (3) | Ni—N3—C15—C16 | −3.3 (5) |
Ni—N1—C5—C6 | 8.6 (4) | C13—C14—C15—N3 | 0.8 (6) |
C3—C4—C5—N1 | 1.4 (6) | C13—C14—C15—C16 | −178.2 (4) |
C3—C4—C5—C6 | −178.9 (4) | C20—N4—C16—C17 | 1.8 (6) |
C10—N2—C6—C7 | −2.8 (6) | Ni—N4—C16—C17 | −178.8 (3) |
Ni—N2—C6—C7 | 171.3 (3) | C20—N4—C16—C15 | −177.9 (4) |
C10—N2—C6—C5 | 177.2 (3) | Ni—N4—C16—C15 | 1.5 (4) |
Ni—N2—C6—C5 | −8.8 (4) | N3—C15—C16—N4 | 1.2 (5) |
N1—C5—C6—N2 | 0.2 (5) | C14—C15—C16—N4 | −179.7 (4) |
C4—C5—C6—N2 | −179.6 (4) | N3—C15—C16—C17 | −178.5 (4) |
N1—C5—C6—C7 | −179.8 (4) | C14—C15—C16—C17 | 0.6 (7) |
C4—C5—C6—C7 | 0.4 (6) | N4—C16—C17—C18 | −1.5 (7) |
N2—C6—C7—C8 | 2.1 (6) | C15—C16—C17—C18 | 178.2 (4) |
C5—C6—C7—C8 | −177.8 (4) | C16—C17—C18—C19 | −0.2 (7) |
C6—C7—C8—C9 | 0.0 (7) | C17—C18—C19—C20 | 1.4 (7) |
C7—C8—C9—C10 | −1.3 (7) | C16—N4—C20—C19 | −0.5 (6) |
C6—N2—C10—C9 | 1.4 (6) | Ni—N4—C20—C19 | −179.9 (3) |
Ni—N2—C10—C9 | −171.9 (3) | C18—C19—C20—N4 | −1.1 (7) |
C8—C9—C10—N2 | 0.6 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Cl1 | 0.82 | 2.63 | 3.276 (3) | 137 |
O1—H1A···Cl2 | 0.82 | 2.78 | 3.467 (3) | 143 |
Experimental details
Crystal data | |
Chemical formula | [NiCl2(C10H8N2)2]·CH4O |
Mr | 474.02 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 10.455 (3), 13.830 (4), 28.548 (10) |
V (Å3) | 4128 (2) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 3.90 |
Crystal size (mm) | 0.23 × 0.23 × 0.16 |
Data collection | |
Diffractometer | Nonius CAD-4 diffractometer |
Absorption correction | Integration (ABSORP in NRCVAX; Gabe et al., 1989) |
Tmin, Tmax | 0.432, 0.593 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22288, 3908, 2054 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.101, 0.79 |
No. of reflections | 3908 |
No. of parameters | 265 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.65 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, NRC-2 and NRC-2A (Ahmed et al., 1973), SHELXS97 (Sheldrick, 1997), SHELXL96 (Sheldrick, 1996), SHELXTL (Bruker, 1997), SHELXL96.
Ni—N4 | 2.073 (3) | Ni—N2 | 2.100 (4) |
Ni—N3 | 2.077 (3) | Ni—Cl1 | 2.3940 (13) |
Ni—N1 | 2.084 (3) | Ni—Cl2 | 2.4213 (13) |
N4—Ni—N3 | 78.00 (14) | N1—Ni—Cl1 | 88.60 (10) |
N4—Ni—N1 | 170.07 (14) | N2—Ni—Cl1 | 87.84 (10) |
N3—Ni—N1 | 97.58 (13) | N4—Ni—Cl2 | 94.06 (10) |
N4—Ni—N2 | 93.37 (14) | N3—Ni—Cl2 | 88.70 (10) |
N3—Ni—N2 | 91.44 (13) | N1—Ni—Cl2 | 94.73 (11) |
N1—Ni—N2 | 77.75 (14) | N2—Ni—Cl2 | 172.43 (11) |
N4—Ni—Cl1 | 95.58 (10) | Cl1—Ni—Cl2 | 92.87 (5) |
N3—Ni—Cl1 | 173.48 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Cl1 | 0.82 | 2.63 | 3.276 (3) | 136.6 |
O1—H1A···Cl2 | 0.82 | 2.78 | 3.467 (3) | 142.8 |
In the course of our studies, the synthesis of [Ni(bipy)2Cl2]·CH3OH, (I), was carried out using a method previously reported for the synthesis of Ni(pyridine)4Cl2 (Long et al., 1978). The molecule adopts a pseudo-octahedral geometry with N—Ni—N bite angles of 77.75 (14) and 78.00 (14) Å, and cis angles between 87.84 (10) and 97.58 (13) Å; trans angles are also close to linearity. The structure of this complex (Fig. 1) is similar to the two structures of Ni(bipy)2Cl2 previously reported.
If CH3CN is used for recrystallization (Ferbinteanu et al., 1998), two water molecules make strong hydrogen bonds with the chlorides. The structure of the dimethylformamide (DMF) solvate was also published the same year (Hipler et al., 1998). In both published structures, a C2 axis is observed on the nickel making both chlorides and bipy ligands equivalent by symmetry. Our studies revealed that the Ni—Cl bond lengths are quite different (more than 20σ) from one another. We believe that this is due to a methanol being hydrogen bonded only to Cl1 [3.276 (3) versus 3.467 (3) Å]. Also unexpected is that one of the bipy shows both of its Ni—N lengths [2.073 (3) and 2.077 (3) Å] shorter than the other bipy [2.084 (3) and 2.100 (4) Å].