Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106003118/hj3001sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003118/hj3001Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106003118/hj3001IIsup3.hkl |
CCDC references: 603182; 603183
For the preparation of complex (I), 5-chloro-2-hydroxybenzaldehyde (0.1 mmol, 15.6 mg) and N,N-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in methanol (10 ml). The mixture was stirred at room temperature for about 10 min to give a clear yellow solution, to which was added an aqueous solution (2 ml) of NH4NCS (0.1 mmol, 7.6 mg) and a methanol solution (5 ml) of Ni(CH3COO)2·4H2O (0.1 mmol, 24.9 mg) with stirring. The mixture was stirred for another 10 min at room temperature. After the filtrate had been kept in air for 3 d, green needle-shaped crystals were formed. Complex (II) was prepared by a procedure similar to that described for (I), with NH4NCS replaced by NaN3 (0.1 mmol, 6.5 mg). Green block-shaped crystals of (II) were obtained after evaporating the solvents from the filtrate in air for 8 d.
All H atoms in (I) and (II) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å and with Uiso(H) values of 1.2 or 1.5 times Ueq(C). The C9H2, C10H3 and C11H3 groups in (I) were disordered over two distinct sites, with occupancies of 0.492 (3) and 0.508 (3). The C—C and C—N distances of the disordered groups were restrained to 1.53 (1) and 1.46 (1) Å, respectively.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Ni(C11H14ClN2O)(NCS)] | F(000) = 704 |
Mr = 342.48 | Dx = 1.576 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.980 (1) Å | Cell parameters from 2348 reflections |
b = 10.936 (2) Å | θ = 2.3–25.4° |
c = 18.955 (3) Å | µ = 1.67 mm−1 |
β = 93.901 (2)° | T = 298 K |
V = 1443.6 (4) Å3 | Needle, green |
Z = 4 | 0.22 × 0.12 × 0.08 mm |
Bruker SMART APEX area-detector diffractometer | 3293 independent reflections |
Radiation source: fine-focus sealed tube | 2526 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.711, Tmax = 0.878 | k = −14→14 |
12176 measured reflections | l = −23→24 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.4314P] where P = (Fo2 + 2Fc2)/3 |
3293 reflections | (Δ/σ)max < 0.001 |
204 parameters | Δρmax = 0.35 e Å−3 |
14 restraints | Δρmin = −0.38 e Å−3 |
[Ni(C11H14ClN2O)(NCS)] | V = 1443.6 (4) Å3 |
Mr = 342.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.980 (1) Å | µ = 1.67 mm−1 |
b = 10.936 (2) Å | T = 298 K |
c = 18.955 (3) Å | 0.22 × 0.12 × 0.08 mm |
β = 93.901 (2)° |
Bruker SMART APEX area-detector diffractometer | 3293 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2526 reflections with I > 2σ(I) |
Tmin = 0.711, Tmax = 0.878 | Rint = 0.043 |
12176 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 14 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.35 e Å−3 |
3293 reflections | Δρmin = −0.38 e Å−3 |
204 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. 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.26818 (6) | 0.84248 (4) | 0.31685 (2) | 0.03870 (15) | |
Cl1 | 0.21309 (15) | 1.17273 (9) | 0.64156 (5) | 0.0589 (3) | |
S1 | 0.17535 (18) | 0.95182 (10) | 0.08135 (5) | 0.0670 (3) | |
O1 | 0.2580 (3) | 0.9998 (2) | 0.35102 (11) | 0.0459 (5) | |
N1 | 0.2937 (4) | 0.7710 (2) | 0.40486 (13) | 0.0413 (6) | |
N2 | 0.2772 (5) | 0.6768 (2) | 0.27882 (15) | 0.0518 (7) | |
N3 | 0.2388 (5) | 0.9070 (3) | 0.22490 (15) | 0.0554 (8) | |
C1 | 0.2615 (4) | 0.9523 (3) | 0.47462 (15) | 0.0337 (6) | |
C2 | 0.2506 (4) | 1.0343 (3) | 0.41686 (16) | 0.0372 (7) | |
C3 | 0.2300 (5) | 1.1586 (3) | 0.43193 (19) | 0.0472 (8) | |
H3 | 0.2240 | 1.2143 | 0.3948 | 0.057* | |
C4 | 0.2185 (5) | 1.2012 (3) | 0.49960 (19) | 0.0491 (8) | |
H4 | 0.2037 | 1.2843 | 0.5079 | 0.059* | |
C5 | 0.2291 (4) | 1.1189 (3) | 0.55558 (16) | 0.0409 (7) | |
C6 | 0.2504 (4) | 0.9972 (3) | 0.54399 (16) | 0.0384 (7) | |
H6 | 0.2578 | 0.9432 | 0.5820 | 0.046* | |
C7 | 0.2849 (5) | 0.8250 (3) | 0.46474 (16) | 0.0408 (7) | |
H7 | 0.2948 | 0.7764 | 0.5051 | 0.049* | |
C12 | 0.2125 (5) | 0.9260 (3) | 0.16522 (18) | 0.0472 (8) | |
C8 | 0.3243 (8) | 0.6397 (3) | 0.4040 (2) | 0.0770 (13) | |
H8A | 0.4231 | 0.6177 | 0.4403 | 0.092* | |
H8B | 0.2068 | 0.5980 | 0.4143 | 0.092* | |
C9 | 0.3815 (17) | 0.6020 (7) | 0.3364 (3) | 0.056 (3) | 0.492 (15) |
H9A | 0.3522 | 0.5160 | 0.3292 | 0.067* | 0.492 (15) |
H9B | 0.5190 | 0.6127 | 0.3344 | 0.067* | 0.492 (15) |
C10 | 0.425 (4) | 0.657 (3) | 0.2286 (18) | 0.089 (11) | 0.492 (15) |
H10A | 0.4500 | 0.5706 | 0.2248 | 0.133* | 0.492 (15) |
H10B | 0.5412 | 0.6979 | 0.2452 | 0.133* | 0.492 (15) |
H10C | 0.3816 | 0.6883 | 0.1831 | 0.133* | 0.492 (15) |
C11 | 0.091 (3) | 0.646 (2) | 0.243 (2) | 0.087 (10) | 0.492 (15) |
H11A | 0.1063 | 0.5782 | 0.2112 | 0.131* | 0.492 (15) |
H11B | 0.0417 | 0.7150 | 0.2162 | 0.131* | 0.492 (15) |
H11C | 0.0021 | 0.6234 | 0.2771 | 0.131* | 0.492 (15) |
C9' | 0.241 (2) | 0.5917 (6) | 0.3375 (3) | 0.063 (3) | 0.508 (15) |
H9'A | 0.1038 | 0.5809 | 0.3402 | 0.075* | 0.508 (15) |
H9'B | 0.2968 | 0.5125 | 0.3284 | 0.075* | 0.508 (15) |
C10' | 0.440 (4) | 0.660 (3) | 0.2342 (16) | 0.074 (9) | 0.508 (15) |
H10D | 0.4281 | 0.5832 | 0.2101 | 0.111* | 0.508 (15) |
H10E | 0.5582 | 0.6618 | 0.2634 | 0.111* | 0.508 (15) |
H10F | 0.4407 | 0.7252 | 0.2001 | 0.111* | 0.508 (15) |
C11' | 0.106 (4) | 0.640 (3) | 0.234 (2) | 0.098 (10) | 0.508 (15) |
H11D | 0.0978 | 0.5523 | 0.2328 | 0.147* | 0.508 (15) |
H11E | 0.1151 | 0.6708 | 0.1871 | 0.147* | 0.508 (15) |
H11F | −0.0070 | 0.6725 | 0.2536 | 0.147* | 0.508 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0440 (3) | 0.0414 (3) | 0.0306 (2) | −0.00188 (18) | 0.00186 (16) | −0.00263 (17) |
Cl1 | 0.0691 (6) | 0.0627 (6) | 0.0459 (5) | −0.0018 (5) | 0.0119 (4) | −0.0157 (4) |
S1 | 0.1067 (9) | 0.0628 (6) | 0.0311 (5) | 0.0050 (6) | 0.0020 (5) | −0.0014 (4) |
O1 | 0.0670 (15) | 0.0421 (13) | 0.0285 (11) | −0.0037 (11) | 0.0020 (10) | −0.0002 (9) |
N1 | 0.0533 (16) | 0.0345 (14) | 0.0360 (15) | −0.0026 (12) | 0.0022 (12) | −0.0021 (11) |
N2 | 0.072 (2) | 0.0434 (17) | 0.0405 (17) | 0.0040 (15) | 0.0050 (15) | −0.0076 (13) |
N3 | 0.075 (2) | 0.0547 (19) | 0.0358 (16) | −0.0007 (16) | 0.0007 (14) | −0.0031 (14) |
C1 | 0.0305 (15) | 0.0379 (16) | 0.0325 (15) | −0.0030 (12) | 0.0010 (12) | 0.0009 (13) |
C2 | 0.0353 (16) | 0.0401 (17) | 0.0353 (16) | −0.0022 (13) | −0.0044 (13) | 0.0000 (14) |
C3 | 0.058 (2) | 0.0386 (18) | 0.0441 (19) | −0.0002 (15) | −0.0009 (15) | 0.0052 (15) |
C4 | 0.054 (2) | 0.0392 (18) | 0.053 (2) | −0.0009 (16) | 0.0023 (17) | −0.0072 (16) |
C5 | 0.0366 (17) | 0.0502 (19) | 0.0362 (17) | −0.0034 (14) | 0.0044 (13) | −0.0088 (15) |
C6 | 0.0368 (16) | 0.0462 (19) | 0.0322 (15) | −0.0026 (14) | 0.0026 (12) | 0.0008 (13) |
C7 | 0.0521 (19) | 0.0385 (18) | 0.0315 (16) | −0.0032 (14) | 0.0001 (14) | 0.0047 (13) |
C12 | 0.063 (2) | 0.0392 (18) | 0.0396 (19) | 0.0002 (16) | 0.0065 (16) | −0.0065 (15) |
C8 | 0.133 (4) | 0.039 (2) | 0.058 (3) | 0.009 (2) | −0.002 (3) | −0.0028 (18) |
C9 | 0.072 (7) | 0.041 (4) | 0.056 (5) | 0.001 (4) | 0.015 (4) | −0.007 (4) |
C10 | 0.064 (14) | 0.09 (2) | 0.11 (2) | −0.006 (11) | −0.003 (12) | −0.028 (17) |
C11 | 0.052 (10) | 0.053 (10) | 0.16 (2) | −0.020 (7) | 0.021 (12) | −0.069 (13) |
C9' | 0.095 (9) | 0.041 (4) | 0.055 (5) | −0.015 (5) | 0.027 (5) | −0.007 (4) |
C10' | 0.048 (10) | 0.089 (19) | 0.086 (14) | 0.017 (10) | 0.014 (9) | −0.056 (14) |
C11' | 0.055 (11) | 0.12 (2) | 0.119 (16) | −0.019 (10) | 0.025 (11) | −0.063 (16) |
Ni1—N1 | 1.840 (3) | C5—C6 | 1.359 (4) |
Ni1—O1 | 1.842 (2) | C6—H6 | 0.9300 |
Ni1—N3 | 1.879 (3) | C7—H7 | 0.9300 |
Ni1—N2 | 1.953 (3) | C8—C9 | 1.429 (7) |
Cl1—C5 | 1.744 (3) | C8—C9' | 1.451 (7) |
S1—C12 | 1.618 (4) | C8—H8A | 0.9700 |
O1—C2 | 1.308 (4) | C8—H8B | 0.9700 |
N1—C7 | 1.285 (4) | C9—H9A | 0.9700 |
N1—C8 | 1.452 (4) | C9—H9B | 0.9700 |
N2—C10 | 1.468 (9) | C10—H10A | 0.9600 |
N2—C11 | 1.469 (9) | C10—H10B | 0.9600 |
N2—C11' | 1.473 (9) | C10—H10C | 0.9600 |
N2—C10' | 1.475 (8) | C11—H11A | 0.9600 |
N2—C9' | 1.484 (7) | C11—H11B | 0.9600 |
N2—C9 | 1.511 (7) | C11—H11C | 0.9600 |
N3—C12 | 1.153 (4) | C9'—H9'A | 0.9700 |
C1—C6 | 1.410 (4) | C9'—H9'B | 0.9700 |
C1—C2 | 1.413 (4) | C10'—H10D | 0.9600 |
C1—C7 | 1.415 (4) | C10'—H10E | 0.9600 |
C2—C3 | 1.399 (4) | C10'—H10F | 0.9600 |
C3—C4 | 1.372 (5) | C11'—H11D | 0.9600 |
C3—H3 | 0.9300 | C11'—H11E | 0.9600 |
C4—C5 | 1.389 (5) | C11'—H11F | 0.9600 |
C4—H4 | 0.9300 | ||
N1—Ni1—O1 | 94.70 (10) | C5—C6—H6 | 119.8 |
N1—Ni1—N3 | 176.86 (12) | C1—C6—H6 | 119.8 |
O1—Ni1—N3 | 88.34 (12) | N1—C7—C1 | 125.6 (3) |
N1—Ni1—N2 | 86.38 (12) | N1—C7—H7 | 117.2 |
O1—Ni1—N2 | 178.89 (11) | C1—C7—H7 | 117.2 |
N3—Ni1—N2 | 90.58 (12) | N3—C12—S1 | 179.7 (3) |
C2—O1—Ni1 | 127.6 (2) | C9—C8—N1 | 110.2 (4) |
C7—N1—C8 | 118.7 (3) | C9'—C8—N1 | 108.4 (4) |
C7—N1—Ni1 | 126.7 (2) | C9—C8—H8A | 109.6 |
C8—N1—Ni1 | 114.6 (2) | C9'—C8—H8A | 138.6 |
C10—N2—C11 | 108 (2) | N1—C8—H8A | 109.6 |
C10—N2—C11' | 100 (2) | C9—C8—H8B | 109.6 |
C11—N2—C10' | 114 (2) | C9'—C8—H8B | 73.1 |
C11'—N2—C10' | 105 (2) | N1—C8—H8B | 109.6 |
C10—N2—C9' | 123.6 (16) | H8A—C8—H8B | 108.1 |
C11—N2—C9' | 90.7 (16) | C8—C9—N2 | 110.0 (5) |
C11'—N2—C9' | 94.9 (18) | C8—C9—H9A | 109.7 |
C10'—N2—C9' | 122.0 (15) | N2—C9—H9A | 109.7 |
C10—N2—C9 | 93.5 (17) | C8—C9—H9B | 109.7 |
C11—N2—C9 | 125.4 (14) | N2—C9—H9B | 109.7 |
C11'—N2—C9 | 126.8 (15) | H9A—C9—H9B | 108.2 |
C10'—N2—C9 | 89.7 (15) | N2—C10—H10A | 109.5 |
C10—N2—Ni1 | 114.8 (14) | N2—C10—H10B | 109.5 |
C11—N2—Ni1 | 109.7 (11) | N2—C10—H10C | 109.5 |
C11'—N2—Ni1 | 114.9 (12) | N2—C11—H11A | 109.5 |
C10'—N2—Ni1 | 111.7 (12) | N2—C11—H11B | 109.5 |
C9'—N2—Ni1 | 107.1 (3) | N2—C11—H11C | 109.5 |
C9—N2—Ni1 | 105.2 (3) | C8—C9'—N2 | 110.2 (5) |
C12—N3—Ni1 | 168.1 (3) | C8—C9'—H9'A | 109.6 |
C6—C1—C2 | 119.9 (3) | N2—C9'—H9'A | 109.6 |
C6—C1—C7 | 118.7 (3) | C8—C9'—H9'B | 109.6 |
C2—C1—C7 | 121.5 (3) | N2—C9'—H9'B | 109.6 |
O1—C2—C3 | 119.1 (3) | H9'A—C9'—H9'B | 108.1 |
O1—C2—C1 | 123.6 (3) | N2—C10'—H10D | 109.5 |
C3—C2—C1 | 117.3 (3) | N2—C10'—H10E | 109.5 |
C4—C3—C2 | 122.3 (3) | H10D—C10'—H10E | 109.5 |
C4—C3—H3 | 118.9 | N2—C10'—H10F | 109.5 |
C2—C3—H3 | 118.9 | H10D—C10'—H10F | 109.5 |
C3—C4—C5 | 119.4 (3) | H10E—C10'—H10F | 109.5 |
C3—C4—H4 | 120.3 | N2—C11'—H11D | 109.5 |
C5—C4—H4 | 120.3 | N2—C11'—H11E | 109.5 |
C6—C5—C4 | 120.8 (3) | H11D—C11'—H11E | 109.5 |
C6—C5—Cl1 | 119.8 (3) | N2—C11'—H11F | 109.5 |
C4—C5—Cl1 | 119.5 (3) | H11D—C11'—H11F | 109.5 |
C5—C6—C1 | 120.3 (3) | H11E—C11'—H11F | 109.5 |
[Ni(C11H14ClN2O)(N3)] | Dx = 1.569 Mg m−3 |
Mr = 326.43 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 6155 reflections |
a = 6.750 (1) Å | θ = 2.5–26.9° |
b = 19.893 (2) Å | µ = 1.60 mm−1 |
c = 20.585 (2) Å | T = 298 K |
V = 2764.1 (6) Å3 | Block, green |
Z = 8 | 0.20 × 0.19 × 0.10 mm |
F(000) = 1344 |
Bruker SMART APEX area-detector diffractometer | 3166 independent reflections |
Radiation source: fine-focus sealed tube | 2647 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −8→8 |
Tmin = 0.741, Tmax = 0.857 | k = −25→25 |
22079 measured reflections | l = −26→26 |
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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0353P)2 + 0.6214P] where P = (Fo2 + 2Fc2)/3 |
3166 reflections | (Δ/σ)max < 0.001 |
174 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
[Ni(C11H14ClN2O)(N3)] | V = 2764.1 (6) Å3 |
Mr = 326.43 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 6.750 (1) Å | µ = 1.60 mm−1 |
b = 19.893 (2) Å | T = 298 K |
c = 20.585 (2) Å | 0.20 × 0.19 × 0.10 mm |
Bruker SMART APEX area-detector diffractometer | 3166 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2647 reflections with I > 2σ(I) |
Tmin = 0.741, Tmax = 0.857 | Rint = 0.033 |
22079 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.38 e Å−3 |
3166 reflections | Δρmin = −0.21 e Å−3 |
174 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. 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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.94020 (3) | 0.190305 (11) | 0.485400 (11) | 0.03505 (9) | |
Cl1 | 0.57260 (8) | −0.05102 (3) | 0.71792 (3) | 0.05522 (15) | |
O1 | 0.94054 (19) | 0.17193 (7) | 0.57661 (6) | 0.0443 (3) | |
N1 | 0.8552 (2) | 0.09955 (7) | 0.46320 (7) | 0.0361 (3) | |
N2 | 0.9382 (2) | 0.20582 (8) | 0.38551 (8) | 0.0392 (4) | |
N3 | 1.0629 (2) | 0.27877 (8) | 0.50320 (8) | 0.0441 (4) | |
N4 | 0.9563 (2) | 0.32630 (9) | 0.50753 (8) | 0.0450 (4) | |
N5 | 0.8584 (3) | 0.37395 (11) | 0.51166 (11) | 0.0712 (6) | |
C1 | 0.7835 (2) | 0.06319 (8) | 0.57265 (9) | 0.0358 (4) | |
C2 | 0.8607 (3) | 0.12037 (9) | 0.60545 (9) | 0.0376 (4) | |
C3 | 0.8468 (3) | 0.12059 (10) | 0.67399 (9) | 0.0467 (5) | |
H3 | 0.8987 | 0.1569 | 0.6968 | 0.056* | |
C4 | 0.7601 (3) | 0.06952 (10) | 0.70788 (10) | 0.0466 (5) | |
H4 | 0.7527 | 0.0714 | 0.7530 | 0.056* | |
C5 | 0.6828 (3) | 0.01456 (9) | 0.67456 (9) | 0.0418 (4) | |
C6 | 0.6948 (3) | 0.01107 (9) | 0.60863 (9) | 0.0408 (4) | |
H6 | 0.6439 | −0.0262 | 0.5871 | 0.049* | |
C7 | 0.7893 (3) | 0.05572 (8) | 0.50330 (9) | 0.0378 (4) | |
H7 | 0.7413 | 0.0157 | 0.4861 | 0.045* | |
C8 | 0.8476 (3) | 0.08672 (9) | 0.39328 (9) | 0.0443 (4) | |
H8A | 0.7449 | 0.0542 | 0.3834 | 0.053* | |
H8B | 0.9735 | 0.0692 | 0.3781 | 0.053* | |
C9 | 0.8028 (3) | 0.15327 (10) | 0.36089 (9) | 0.0435 (4) | |
H9A | 0.8184 | 0.1489 | 0.3142 | 0.052* | |
H9B | 0.6668 | 0.1660 | 0.3697 | 0.052* | |
C10 | 1.1404 (3) | 0.19725 (11) | 0.35898 (11) | 0.0564 (6) | |
H10A | 1.1893 | 0.1535 | 0.3702 | 0.085* | |
H10B | 1.2261 | 0.2309 | 0.3770 | 0.085* | |
H10C | 1.1368 | 0.2018 | 0.3126 | 0.085* | |
C11 | 0.8645 (3) | 0.27248 (10) | 0.36505 (10) | 0.0521 (5) | |
H11A | 0.8515 | 0.2735 | 0.3186 | 0.078* | |
H11B | 0.9564 | 0.3066 | 0.3786 | 0.078* | |
H11C | 0.7378 | 0.2807 | 0.3847 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.04247 (15) | 0.03269 (14) | 0.03001 (14) | −0.00599 (9) | −0.00206 (9) | −0.00441 (9) |
Cl1 | 0.0563 (3) | 0.0577 (3) | 0.0516 (3) | −0.0084 (2) | 0.0013 (2) | 0.0124 (2) |
O1 | 0.0534 (8) | 0.0429 (7) | 0.0366 (7) | −0.0101 (6) | −0.0069 (6) | −0.0027 (6) |
N1 | 0.0358 (8) | 0.0367 (8) | 0.0358 (8) | 0.0019 (6) | −0.0031 (6) | −0.0072 (6) |
N2 | 0.0382 (8) | 0.0426 (8) | 0.0369 (8) | 0.0017 (6) | 0.0041 (6) | −0.0038 (7) |
N3 | 0.0459 (10) | 0.0387 (9) | 0.0478 (9) | −0.0065 (7) | −0.0002 (7) | −0.0055 (7) |
N4 | 0.0432 (10) | 0.0459 (10) | 0.0459 (10) | −0.0120 (8) | 0.0052 (7) | −0.0108 (7) |
N5 | 0.0580 (12) | 0.0577 (12) | 0.0980 (17) | 0.0058 (11) | 0.0054 (11) | −0.0271 (11) |
C1 | 0.0345 (9) | 0.0354 (9) | 0.0375 (9) | 0.0030 (7) | −0.0041 (7) | −0.0032 (7) |
C2 | 0.0366 (9) | 0.0375 (9) | 0.0387 (10) | 0.0023 (8) | −0.0063 (8) | −0.0002 (8) |
C3 | 0.0558 (12) | 0.0450 (11) | 0.0392 (10) | −0.0030 (9) | −0.0094 (9) | −0.0050 (8) |
C4 | 0.0505 (11) | 0.0521 (11) | 0.0370 (10) | 0.0024 (9) | −0.0026 (8) | 0.0008 (9) |
C5 | 0.0377 (10) | 0.0416 (10) | 0.0459 (11) | 0.0034 (8) | −0.0010 (8) | 0.0073 (8) |
C6 | 0.0399 (10) | 0.0374 (9) | 0.0450 (10) | 0.0009 (8) | −0.0040 (8) | −0.0023 (8) |
C7 | 0.0371 (10) | 0.0321 (9) | 0.0441 (10) | 0.0010 (8) | −0.0051 (8) | −0.0070 (7) |
C8 | 0.0496 (11) | 0.0453 (11) | 0.0381 (10) | −0.0003 (9) | −0.0024 (9) | −0.0101 (8) |
C9 | 0.0457 (11) | 0.0511 (11) | 0.0336 (9) | 0.0008 (9) | −0.0031 (8) | −0.0061 (8) |
C10 | 0.0450 (12) | 0.0685 (15) | 0.0558 (13) | −0.0005 (10) | 0.0086 (10) | −0.0065 (11) |
C11 | 0.0624 (13) | 0.0485 (12) | 0.0453 (11) | 0.0060 (10) | 0.0060 (10) | 0.0032 (9) |
Ni1—O1 | 1.913 (2) | C3—H3 | 0.9300 |
Ni1—N1 | 1.949 (2) | C4—C5 | 1.392 (3) |
Ni1—N3 | 1.979 (2) | C4—H4 | 0.9300 |
Ni1—N2 | 2.079 (2) | C5—C6 | 1.361 (3) |
Cl1—C5 | 1.747 (2) | C6—H6 | 0.9300 |
O1—C2 | 1.302 (2) | C7—H7 | 0.9300 |
N1—C7 | 1.280 (2) | C8—C9 | 1.513 (3) |
N1—C8 | 1.463 (2) | C8—H8A | 0.9700 |
N2—C11 | 1.478 (2) | C8—H8B | 0.9700 |
N2—C9 | 1.478 (2) | C9—H9A | 0.9700 |
N2—C10 | 1.480 (3) | C9—H9B | 0.9700 |
N3—N4 | 1.192 (2) | C10—H10A | 0.9600 |
N4—N5 | 1.159 (3) | C10—H10B | 0.9600 |
C1—C6 | 1.408 (3) | C10—H10C | 0.9600 |
C1—C2 | 1.422 (2) | C11—H11A | 0.9600 |
C1—C7 | 1.436 (3) | C11—H11B | 0.9600 |
C2—C3 | 1.414 (3) | C11—H11C | 0.9600 |
C3—C4 | 1.364 (3) | ||
O1—Ni1—N1 | 93.07 (6) | C4—C5—Cl1 | 119.63 (15) |
O1—Ni1—N3 | 89.30 (6) | C5—C6—C1 | 120.82 (17) |
N1—Ni1—N3 | 172.04 (7) | C5—C6—H6 | 119.6 |
O1—Ni1—N2 | 177.50 (6) | C1—C6—H6 | 119.6 |
N1—Ni1—N2 | 84.48 (6) | N1—C7—C1 | 125.46 (16) |
N3—Ni1—N2 | 93.08 (7) | N1—C7—H7 | 117.3 |
C2—O1—Ni1 | 126.70 (12) | C1—C7—H7 | 117.3 |
C7—N1—C8 | 120.23 (15) | N1—C8—C9 | 106.73 (14) |
C7—N1—Ni1 | 125.59 (12) | N1—C8—H8A | 110.4 |
C8—N1—Ni1 | 113.75 (12) | C9—C8—H8A | 110.4 |
C11—N2—C9 | 109.20 (15) | N1—C8—H8B | 110.4 |
C11—N2—C10 | 107.98 (16) | C9—C8—H8B | 110.4 |
C9—N2—C10 | 111.23 (15) | H8A—C8—H8B | 108.6 |
C11—N2—Ni1 | 114.66 (12) | N2—C9—C8 | 110.14 (15) |
C9—N2—Ni1 | 103.77 (11) | N2—C9—H9A | 109.6 |
C10—N2—Ni1 | 110.00 (13) | C8—C9—H9A | 109.6 |
N4—N3—Ni1 | 117.80 (13) | N2—C9—H9B | 109.6 |
N5—N4—N3 | 177.6 (2) | C8—C9—H9B | 109.6 |
C6—C1—C2 | 119.69 (17) | H9A—C9—H9B | 108.1 |
C6—C1—C7 | 117.29 (16) | N2—C10—H10A | 109.5 |
C2—C1—C7 | 123.01 (16) | N2—C10—H10B | 109.5 |
O1—C2—C3 | 118.69 (17) | H10A—C10—H10B | 109.5 |
O1—C2—C1 | 124.44 (17) | N2—C10—H10C | 109.5 |
C3—C2—C1 | 116.86 (17) | H10A—C10—H10C | 109.5 |
C4—C3—C2 | 122.44 (18) | H10B—C10—H10C | 109.5 |
C4—C3—H3 | 118.8 | N2—C11—H11A | 109.5 |
C2—C3—H3 | 118.8 | N2—C11—H11B | 109.5 |
C3—C4—C5 | 119.58 (19) | H11A—C11—H11B | 109.5 |
C3—C4—H4 | 120.2 | N2—C11—H11C | 109.5 |
C5—C4—H4 | 120.2 | H11A—C11—H11C | 109.5 |
C6—C5—C4 | 120.59 (18) | H11B—C11—H11C | 109.5 |
C6—C5—Cl1 | 119.78 (15) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Ni(C11H14ClN2O)(NCS)] | [Ni(C11H14ClN2O)(N3)] |
Mr | 342.48 | 326.43 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pbca |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 6.980 (1), 10.936 (2), 18.955 (3) | 6.750 (1), 19.893 (2), 20.585 (2) |
α, β, γ (°) | 90, 93.901 (2), 90 | 90, 90, 90 |
V (Å3) | 1443.6 (4) | 2764.1 (6) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.67 | 1.60 |
Crystal size (mm) | 0.22 × 0.12 × 0.08 | 0.20 × 0.19 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART APEX area-detector diffractometer | Bruker SMART APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.711, 0.878 | 0.741, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12176, 3293, 2526 | 22079, 3166, 2647 |
Rint | 0.043 | 0.033 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.113, 1.03 | 0.030, 0.074, 1.07 |
No. of reflections | 3293 | 3166 |
No. of parameters | 204 | 174 |
No. of restraints | 14 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.38 | 0.38, −0.21 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXTL (Bruker, 2000), SHELXTL.
Ni1—N1 | 1.840 (3) | Ni1—N3 | 1.879 (3) |
Ni1—O1 | 1.842 (2) | Ni1—N2 | 1.953 (3) |
N1—Ni1—O1 | 94.70 (10) | N1—Ni1—N2 | 86.38 (12) |
N1—Ni1—N3 | 176.86 (12) | O1—Ni1—N2 | 178.89 (11) |
O1—Ni1—N3 | 88.34 (12) | N3—Ni1—N2 | 90.58 (12) |
Ni1—O1 | 1.913 (2) | Ni1—N3 | 1.979 (2) |
Ni1—N1 | 1.949 (2) | Ni1—N2 | 2.079 (2) |
O1—Ni1—N1 | 93.07 (6) | O1—Ni1—N2 | 177.50 (6) |
O1—Ni1—N3 | 89.30 (6) | N1—Ni1—N2 | 84.48 (6) |
N1—Ni1—N3 | 172.04 (7) | N3—Ni1—N2 | 93.08 (7) |
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Transition metal complexes containing bridging ligands are currentlt attracting attention because of their interesting molecular topologies and crystal-packing motifs, as well as the fact that they may be designed with specific functionalities (Mukherjee et al., 2001; Meyer & Pritzkow, 2001; Goher et al., 2002). The prime strategy for designing these polynuclear materials is to use suitable bridging ligands (Koner et al., 2003). Owing to the coordination modes of the thiocyanate and azide anions, these ligands make good bridging groups. However, to the present state of our knowledge, it is hardly possible to determine which coordination mode will be adopted by the thiocyanate or azide anion and whether the sought-after alternating structure will be formed (Bhaduri et al., 2003; Romero et al., 2002; Tercero et al., 2002; Ribas et al., 1999).
In the present paper, the tridentate Schiff base ligand 4-chloro-2-[(2-dimethylaminoethylimino)methyl]phenol was used as the first ligand. The reason we use this ligand is that it can adopt an almost fixed coordination mode through the three N– and O-donor atoms (You & Zhu, 2005; You, 2005). The secondary ligand, viz. thiocyanate or azide, is a well known bridging group. It readily bridges different metal ions through the donor atoms, forming polynuclear complexes. The author reports here two complexes, [Ni(C11H14ClN2O)(NCS)], (I), and [Ni(C11H14ClN2O)(N3)]n, (II). The azide anion acts as a bridging ligand in (II) and ligates two different metal atoms through the same teminal N atom (Fig. 1). This contrasts with the monomeric structure, (I), where the thiocyanate coordinates to a single Ni atom (Fig. 2).
In (I), the Ni atom is four-coordinated in a square-planar geometry by the NNO-donor set of the Schiff base and by the N atom of the thiocyanate ligand. In (II), each repeated unit contains one [Ni(C11H14ClN2O)]+ cation and one bridging azide anion. The Ni atom in (II) is five-coordinated in a square-pyramidal geometry by the NNO-donor set of the Schiff base and by two N atoms from two bridging azide groups.
In (II), all the bond lengths subtended at atom Ni1 are longer than those observed in (I) (Table 1). The coordination of the bridging N atom at the apical position of the Ni atom in (II) leads to the deviation of the metal from the basal donor atoms by 0.070 (2) Å, while in (I), the Ni atom lies nearly in the square plane, with a deviation of 0.009 (2) Å. In each of the complexes, the bond lengths subtended at the metal atoms are within normal ranges and, as expected, the bonds involving the pyridine N atoms are longer than those involving the imine N atoms.
The terminal thiocyanate group always adopts a nearly linear coordination mode to metal ions through the terminal N atom (Moore & Squattrito, 1999; Mondal et al., 2001), while the bridging azide group easily adopts a bent coordination mode to metal ions through one of the terminal N atoms (Zhang et al., 2000). In this paper, the terminal thiocyanate ligand in (I) is nearly linear and shows also a nearly linear coordination mode with the metal atom [the N3—C12—S1 and Ni1—N3—C12 angles are 179.7 (3) and 168.1 (3)°, respectively], while the bridging azide ligand in (II) is also nearly linear but shows a bent coordination mode with the metal atoms [the N3—N4—N5, Ni1—N3—N4 and Ni1i—N3—N4 angles are 177.6 (2), 117.80 (13) and 113.12 (13)°, respectively; symmetry code: (i) x − 1/2, −y + 1/2, −z + 1].
In conclusion, the similar small ligands used as the secondary ligand in the preparation of the title complexes severely influence the final structures.