Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015808/fr1306sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015808/fr1306Isup2.hkl |
CCDC reference: 159978
Caution: perchlorate salts of metal complexes with organic ligands are potentially explosive. Only a small quantity of materials should be handled with caution. The Schiff base ligand was prepared by the reaction of 1,3-diaminopropane-2-ol (0.1 mmol) with 5-chlorosalicylaldehyde (0.2 mmol) in methanol (100 ml). The yellow Schiff base precipitated from solution on cooling. The dinuclear complex, (I), was obtained when a sample of ligand (0.1 mmol) in methanol (50 ml) was added dropwise to a stirred mixture containing 3,5-dimethylpyrazole (0.1 mmol) and nickel(II)perchlorate hexahydrate (0.2 mmol) in methanol (25 ml). Triethylamine (0.3 mmol) was added to the solution. The mixture was stirred and thin brown crystals of (I) were collected and washed with methanol. Recrystallization from acetone afforded suitable single crystals.
The positions of the H atoms bonded to C were calculated (C—H distances 0.96 Å) and refined using a riding model, with H-atom displacement parameters constrained to be 1.2Ueq of the parent atom.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); cell refinement: CAD-4 EXPRESS; data reduction: RC93 (Watkin et al., 1994); program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Ni2(C17H13Cl2N2O3)(C5H7N2)] | F(000) = 1176 |
Mr = 576.70 | Dx = 1.71 Mg m−3 |
Orthorhombic, Pnma | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 24 reflections |
a = 7.492 (3) Å | θ = 12–20° |
b = 28.929 (7) Å | µ = 4.57 mm−1 |
c = 10.334 (5) Å | T = 293 K |
V = 2239.8 (15) Å3 | Plate, brown |
Z = 4 | 0.19 × 0.15 × 0.09 mm |
Enraf-Nonius CAD-4 diffractometer | 1070 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 74.2°, θmin = 4.5° |
ω/2θ scans | h = 0→9 |
Absorption correction: ψ-scans (North et al., 1968) | k = −36→0 |
Tmin = 0.482, Tmax = 0.663 | l = 0→12 |
2284 measured reflections | 3 standard reflections every 120 min |
2284 independent reflections | intensity decay: 1.2% |
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) = 0.155 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0672P)2 + 2.4402P] where P = (Fo2 + 2Fc2)/3 |
2284 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Ni2(C17H13Cl2N2O3)(C5H7N2)] | V = 2239.8 (15) Å3 |
Mr = 576.70 | Z = 4 |
Orthorhombic, Pnma | Cu Kα radiation |
a = 7.492 (3) Å | µ = 4.57 mm−1 |
b = 28.929 (7) Å | T = 293 K |
c = 10.334 (5) Å | 0.19 × 0.15 × 0.09 mm |
Enraf-Nonius CAD-4 diffractometer | 1070 reflections with I > 2σ(I) |
Absorption correction: ψ-scans (North et al., 1968) | Rint = 0.000 |
Tmin = 0.482, Tmax = 0.663 | 3 standard reflections every 120 min |
2284 measured reflections | intensity decay: 1.2% |
2284 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2284 reflections | Δρmin = −0.31 e Å−3 |
154 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. The structure was solved by direct phase determination. The parameters of the complete structure could be refined by full-matrix anisotropic least-squares including anisotropic displacement parameters for non-H atoms. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.11467 (10) | 0.69543 (3) | 0.31511 (7) | 0.0561 (3) | |
Cl1 | −0.1578 (2) | 0.46218 (5) | 0.18574 (15) | 0.0855 (5) | |
O2 | 0.1756 (6) | 0.7500 | 0.2335 (4) | 0.0610 (11) | |
O1 | 0.0416 (5) | 0.64295 (12) | 0.3938 (3) | 0.0665 (9) | |
N1 | 0.0982 (5) | 0.67114 (14) | 0.1479 (4) | 0.0600 (10) | |
N2 | 0.1425 (4) | 0.72652 (14) | 0.4771 (3) | 0.0534 (9) | |
C1 | −0.0007 (5) | 0.60325 (18) | 0.3415 (5) | 0.0544 (12) | |
C2 | −0.0579 (7) | 0.56695 (19) | 0.4222 (6) | 0.0721 (14) | |
H2 | −0.0607 | 0.5714 | 0.5113 | 0.108* | |
C3 | −0.1087 (8) | 0.5257 (2) | 0.3727 (5) | 0.0727 (15) | |
H3 | −0.1480 | 0.5027 | 0.4288 | 0.109* | |
C4 | −0.1041 (7) | 0.51684 (17) | 0.2436 (6) | 0.0651 (12) | |
C5 | −0.0524 (7) | 0.5505 (2) | 0.1591 (5) | 0.0692 (14) | |
H5 | −0.0511 | 0.5445 | 0.0707 | 0.104* | |
C6 | 0.0000 (6) | 0.59511 (18) | 0.2062 (5) | 0.0598 (13) | |
C7 | 0.0496 (6) | 0.62977 (18) | 0.1156 (5) | 0.0588 (12) | |
H7 | 0.0471 | 0.6223 | 0.0280 | 0.088* | |
C8 | 0.1504 (7) | 0.70477 (19) | 0.0466 (5) | 0.0663 (14) | |
H8A | 0.0853 | 0.6994 | −0.0332 | 0.099* | |
H8B | 0.2775 | 0.7033 | 0.0290 | 0.099* | |
C9 | 0.1002 (10) | 0.7500 | 0.1061 (6) | 0.0661 (19) | |
H9 | −0.0299 | 0.7500 | 0.1162 | 0.099* | |
C10 | 0.1876 (6) | 0.71168 (19) | 0.5976 (5) | 0.0631 (13) | |
C11 | 0.2110 (11) | 0.7500 | 0.6742 (6) | 0.074 (2) | |
H11 | 0.2379 | 0.7500 | 0.7620 | 0.110* | |
C12 | 0.1989 (9) | 0.6619 (2) | 0.6404 (6) | 0.0912 (19) | |
H12A | 0.1779 | 0.6420 | 0.5676 | 0.137* | |
H12B | 0.1105 | 0.6561 | 0.7057 | 0.137* | |
H12C | 0.3154 | 0.6559 | 0.6751 | 0.137* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0556 (4) | 0.0573 (5) | 0.0555 (5) | 0.0029 (4) | 0.0002 (4) | −0.0005 (4) |
Cl1 | 0.0943 (10) | 0.0701 (8) | 0.0922 (10) | −0.0158 (7) | −0.0047 (8) | −0.0078 (9) |
O2 | 0.077 (3) | 0.058 (3) | 0.049 (2) | 0.000 | −0.002 (2) | 0.000 |
O1 | 0.085 (2) | 0.055 (2) | 0.060 (2) | −0.0003 (18) | 0.0077 (18) | −0.0028 (18) |
N1 | 0.066 (2) | 0.054 (2) | 0.061 (2) | −0.002 (2) | 0.017 (2) | −0.0034 (19) |
N2 | 0.0424 (16) | 0.069 (3) | 0.0489 (19) | −0.0014 (17) | −0.0011 (15) | −0.0060 (18) |
C1 | 0.043 (2) | 0.061 (3) | 0.059 (3) | 0.019 (2) | 0.012 (2) | 0.005 (2) |
C2 | 0.076 (3) | 0.065 (3) | 0.075 (3) | 0.004 (3) | −0.003 (3) | 0.001 (3) |
C3 | 0.087 (4) | 0.071 (3) | 0.061 (3) | −0.016 (3) | −0.004 (3) | −0.001 (3) |
C4 | 0.074 (3) | 0.048 (2) | 0.073 (3) | −0.006 (3) | 0.007 (3) | 0.005 (3) |
C5 | 0.072 (3) | 0.077 (4) | 0.058 (3) | 0.004 (3) | 0.001 (2) | −0.007 (3) |
C6 | 0.048 (2) | 0.069 (3) | 0.063 (3) | 0.010 (2) | −0.008 (2) | 0.000 (3) |
C7 | 0.047 (2) | 0.068 (3) | 0.061 (3) | −0.003 (2) | 0.003 (2) | 0.000 (3) |
C8 | 0.065 (3) | 0.079 (4) | 0.056 (3) | 0.002 (3) | −0.002 (2) | −0.010 (3) |
C9 | 0.069 (4) | 0.088 (5) | 0.041 (3) | 0.000 | −0.009 (3) | 0.000 |
C10 | 0.043 (2) | 0.081 (3) | 0.065 (3) | −0.002 (2) | −0.001 (2) | −0.009 (3) |
C11 | 0.092 (5) | 0.090 (6) | 0.038 (4) | 0.000 | −0.001 (4) | 0.000 |
C12 | 0.109 (5) | 0.095 (5) | 0.070 (4) | 0.007 (4) | −0.009 (3) | 0.024 (3) |
Ni1—O1 | 1.807 (4) | C4—C5 | 1.365 (7) |
Ni1—O2 | 1.847 (2) | C5—C6 | 1.434 (7) |
Ni1—N1 | 1.869 (4) | C5—H5 | 0.9300 |
Ni1—N2 | 1.912 (4) | C6—C7 | 1.421 (7) |
Cl1—C4 | 1.738 (5) | C7—H7 | 0.9300 |
O2—C9 | 1.432 (8) | C8—C9 | 1.494 (6) |
O2—Ni1i | 1.847 (2) | C8—H8A | 0.9700 |
O1—C1 | 1.308 (6) | C8—H8B | 0.9700 |
N1—C7 | 1.295 (6) | C9—C8i | 1.494 (6) |
N1—C8 | 1.482 (7) | C9—H9 | 0.9800 |
N2—N2i | 1.358 (8) | C10—C11 | 1.373 (6) |
N2—C10 | 1.360 (6) | C10—C12 | 1.509 (8) |
C1—C2 | 1.407 (7) | C11—C10i | 1.373 (6) |
C1—C6 | 1.418 (7) | C11—H11 | 0.9300 |
C2—C3 | 1.353 (7) | C12—H12A | 0.9600 |
C2—H2 | 0.9300 | C12—H12B | 0.9600 |
C3—C4 | 1.359 (7) | C12—H12C | 0.9600 |
C3—H3 | 0.9300 | ||
O1—Ni1—O2 | 176.66 (19) | C1—C6—C7 | 122.2 (5) |
O1—Ni1—N1 | 94.60 (18) | C1—C6—C5 | 118.9 (5) |
O2—Ni1—N1 | 85.14 (18) | C7—C6—C5 | 118.9 (5) |
O1—Ni1—N2 | 91.96 (17) | N1—C7—C6 | 123.7 (5) |
O2—Ni1—N2 | 88.34 (17) | N1—C7—H7 | 118.1 |
N1—Ni1—N2 | 173.43 (17) | C6—C7—H7 | 118.1 |
C9—O2—Ni1i | 108.8 (2) | N1—C8—C9 | 102.5 (4) |
C9—O2—Ni1 | 108.8 (2) | N1—C8—H8A | 111.3 |
Ni1i—O2—Ni1 | 117.4 (2) | C9—C8—H8A | 111.3 |
C1—O1—Ni1 | 128.7 (3) | N1—C8—H8B | 111.3 |
C7—N1—C8 | 119.9 (4) | C9—C8—H8B | 111.3 |
C7—N1—Ni1 | 127.2 (4) | H8A—C8—H8B | 109.2 |
C8—N1—Ni1 | 112.9 (3) | O2—C9—C8 | 106.2 (4) |
N2i—N2—C10 | 108.4 (3) | O2—C9—C8i | 106.2 (4) |
N2i—N2—Ni1 | 118.06 (12) | C8—C9—C8i | 122.2 (6) |
C10—N2—Ni1 | 132.9 (4) | O2—C9—H9 | 107.1 |
O1—C1—C2 | 118.9 (4) | C8—C9—H9 | 107.1 |
O1—C1—C6 | 123.5 (5) | C8i—C9—H9 | 107.1 |
C2—C1—C6 | 117.5 (5) | N2—C10—C11 | 107.7 (5) |
C3—C2—C1 | 121.3 (5) | N2—C10—C12 | 125.7 (5) |
C3—C2—H2 | 119.3 | C11—C10—C12 | 126.5 (5) |
C1—C2—H2 | 119.3 | C10—C11—C10i | 107.7 (7) |
C2—C3—C4 | 122.1 (5) | C10—C11—H11 | 126.2 |
C2—C3—H3 | 119.0 | C10i—C11—H11 | 126.2 |
C4—C3—H3 | 119.0 | C10—C12—H12A | 109.5 |
C3—C4—C5 | 120.0 (5) | C10—C12—H12B | 109.5 |
C3—C4—Cl1 | 120.3 (4) | H12A—C12—H12B | 109.5 |
C5—C4—Cl1 | 119.7 (4) | C10—C12—H12C | 109.5 |
C4—C5—C6 | 120.2 (5) | H12A—C12—H12C | 109.5 |
C4—C5—H5 | 119.9 | H12B—C12—H12C | 109.5 |
C6—C5—H5 | 119.9 | ||
N1—Ni1—O2—C9 | 26.0 (4) | C2—C1—C6—C7 | 177.9 (4) |
N2—Ni1—O2—C9 | −154.9 (4) | O1—C1—C6—C5 | −178.7 (4) |
N1—Ni1—O2—Ni1i | 150.0 (3) | C2—C1—C6—C5 | −1.6 (6) |
N2—Ni1—O2—Ni1i | −30.8 (3) | C4—C5—C6—C1 | 0.8 (7) |
N1—Ni1—O1—C1 | 1.4 (4) | C4—C5—C6—C7 | −178.7 (5) |
N2—Ni1—O1—C1 | −178.1 (4) | C8—N1—C7—C6 | 179.0 (4) |
O1—Ni1—N1—C7 | −0.4 (5) | Ni1—N1—C7—C6 | −0.2 (7) |
O2—Ni1—N1—C7 | −177.0 (4) | C1—C6—C7—N1 | 0.2 (7) |
O1—Ni1—N1—C8 | −179.7 (3) | C5—C6—C7—N1 | 179.7 (5) |
O2—Ni1—N1—C8 | 3.6 (3) | C7—N1—C8—C9 | 150.5 (5) |
O1—Ni1—N2—N2i | −159.1 (3) | Ni1—N1—C8—C9 | −30.1 (5) |
O2—Ni1—N2—N2i | 17.56 (15) | Ni1i—O2—C9—C8 | −178.8 (4) |
O1—Ni1—N2—C10 | 31.4 (4) | Ni1—O2—C9—C8 | −49.7 (6) |
O2—Ni1—N2—C10 | −151.9 (4) | Ni1i—O2—C9—C8i | 49.7 (6) |
Ni1—O1—C1—C2 | −178.8 (3) | Ni1—O2—C9—C8i | 178.8 (4) |
Ni1—O1—C1—C6 | −1.7 (6) | N1—C8—C9—O2 | 49.7 (6) |
O1—C1—C2—C3 | 177.8 (5) | N1—C8—C9—C8i | 171.5 (5) |
C6—C1—C2—C3 | 0.6 (7) | N2i—N2—C10—C11 | 1.7 (5) |
C1—C2—C3—C4 | 1.3 (9) | Ni1—N2—C10—C11 | 171.9 (4) |
C2—C3—C4—C5 | −2.1 (9) | N2i—N2—C10—C12 | 178.4 (4) |
C2—C3—C4—Cl1 | 176.1 (4) | Ni1—N2—C10—C12 | −11.4 (7) |
C3—C4—C5—C6 | 1.0 (8) | N2—C10—C11—C10i | −2.7 (8) |
Cl1—C4—C5—C6 | −177.2 (4) | C12—C10—C11—C10i | −179.4 (4) |
O1—C1—C6—C7 | 0.8 (7) |
Symmetry code: (i) x, −y+3/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C17H13Cl2N2O3)(C5H7N2)] |
Mr | 576.70 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 7.492 (3), 28.929 (7), 10.334 (5) |
V (Å3) | 2239.8 (15) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.57 |
Crystal size (mm) | 0.19 × 0.15 × 0.09 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ-scans (North et al., 1968) |
Tmin, Tmax | 0.482, 0.663 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2284, 2284, 1070 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.155, 1.04 |
No. of reflections | 2284 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.31 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1993), CAD-4 EXPRESS, RC93 (Watkin et al., 1994), SHELXS86 (Sheldrick, 1986), SHELXL97 (Sheldrick, 1997), ORTEPIII (Farrugia, 1997), SHELXL97.
Ni1—O1 | 1.807 (4) | Ni1—N2 | 1.912 (4) |
Ni1—O2 | 1.847 (2) | N2—N2i | 1.358 (8) |
Ni1—N1 | 1.869 (4) | ||
O1—Ni1—O2 | 176.66 (19) | O2—Ni1—N2 | 88.34 (17) |
O1—Ni1—N1 | 94.60 (18) | N1—Ni1—N2 | 173.43 (17) |
O2—Ni1—N1 | 85.14 (18) | Ni1i—O2—Ni1 | 117.4 (2) |
O1—Ni1—N2 | 91.96 (17) | N2i—N2—Ni1 | 118.06 (12) |
Symmetry code: (i) x, −y+3/2, z. |
The field of binucleating ligands and their metal complexes has developed considerably in recent years (Fenton & Okawa 1993; Guerriero et al., 1992; Bond et al., 1989). Although a large number of unsymmetric doubly bridged dinuclear copper(II) complexes have been extensively studied (Mazurek et al., 1982, 1985; Nishida & Kida, 1988; Doman et al., 1990; Tandon et al., 1993; Chen et al., 1996; Li et al., 1997), relatively few structures of unsymmetric doubly bridged dinuclear nickel(II) complexes have been reported (Mikuriya et al., 1992; Kruger et al., 1994; Kondrad et al., 1999). We have therefore made a detailed structural study of the title dinuclear µ-pyrazolato-N,N'-bridged nickel(II) complex of 1,3-bis(5-chlorosalicylideneamino)propan-2-ol, (I). \sch
The crystal structure of (I) is illustrated in Fig. 1 and selected bond distances and angles are listed in Table 1. The Ni atoms in the dinuclear structure are linked symmetrically by the N atoms of the 3,5-dimethylpyrazole group and by the alkoxo O atom. Each NiII ion is coordinated by two N atoms and two O atoms, forming a square plane with trans-N2O2 geometry. The molecular structure of (I) has crystallographic mirror symmetry, so the asymmetric unit contains only half of the molecule.
The Ni—O and Ni—N bond distances in (I) are in the range of those of conventional Schiff base and alkoxide-bridged nickel(II) complexes of square-planar coordination (Mikuriya et al., 1992; Kruger et al., 1994). The Ni···Ni separation [3.157 (3) Å] and the Ni—O—Ni angle [117.4 (2)°] are smaller than those reported for unsymmetrical doubly bridged dinuclear nickel(II) complexes (Mikuriya et al., 1992; Kruger et al., 1994). The dihedral angle between the coordinated planes is 33.52 (8)°, showing a considerable bending of the two coordination planes. Thus, the molecule of (I) has a bent structure. This bending of the molecule is caused by the twisting of the Schiff base backbone and leads to a smaller Ni···Ni separation and a smaller Ni—O—Ni angle.
The NiII ion is square-planar, with the mean deviation from the least-squares plane defined by Ni1/O1/N1/O2/N2 being 0.03 Å and the mean deviation from the Ni1/O2/Ni1i/N2i/N2 plane being 0.17 Å [symmetry code: (i) x, 3/2 - y, z]. The remaining five-membered rings are not planar, as seen from the N1—C8—C9—O2 torsion angle of 49.7 (6)°. The six-membered rings are each planar to within 0.007 Å. Another important feature is the geometry of the bridging atom, O2: the bond angles around O2 of 108.8 (2), 117.4 (2) and 108.8 (2)° indicate the pyramidal stereochemistry at this atom.
Complex (I) is diamagnetic, which is consistent with a planar geometry around the NiII ions.