Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048581/hk2335sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048581/hk2335Isup2.hkl |
CCDC reference: 667126
For the preparation of the title compound, (I), N,N'-bis(salicylidene)-1,3 -propanediamine (1.410 g, 5 mmol) was dissolved in hot EtOH (50 ml), and then added to a solution of NiCl2.6H2O (1.185 g, 5 mmol) in hot water (30 ml) and ammonia (10 ml, 20%). The mixture was kept on the bench for 1–2 h. The pink precipitate was filtered and dried in an oven at 423 K. This complex (0.338 g, 1 mmol) was dissolved in hot dioxane (50 ml) and 4-methylpyridine (0.5 ml), and then added to a solution of ZnBr2 (0.226 g, 1 mmol) in hot MeOH (20 ml). The resulting mixture was set aside for 2 d and the precipitated crystals were filtered and dried on air.
The highest peak in the final difference electron-density map is located 1.81 Å from the Br1 atom. H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.
Zinc and nickel elements are important essential rare elements for living beings (Bertini et al., 1994), in this respect the zinc and nickel compounds are very important in medicine. Some dinuclear zinc-nickel metal compounds of Schiff-base ligands have been studied in our laboratory (Tatar Yıldırım et al., 2007; Tatar, 2002; Tatar et al., 2002; Arıcı et al., 2001). We report herein the structure of the title compound, (I), a new hetero-dinuclear [ZnBr2Ni(salpd2-)(C6H7N)2] complex [where salpd2- is N,N'-bis- (salicylidene)-1,3-propanediamine].
In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles (Table 1) are generally in good agreement with the corresponding values in similar oxygen-bridged dinuclear complexes reported, previously (Tatar et al., 2007; Tatar, 2002; Tatar, Atakol et al., 2002; Svoboda et al., 2001; Arıcı et al., 2001). The two bridging O atoms of salpd2- ligand and two Br atoms constitute a distorted tetrahedral coordination environment around the ZnII ion, while the NiII ion has a distorted octahedral coordination environment formed by two O and two N atoms of salpd2- ligand in the equatorial plane and two N atoms of two methylpyridine ligands in the axial positions (Table 1). The Ni atom is -0.017 (2) Å away from the equatorial plane. The Zn···Ni distance is 3.062 (3) Å. The dihedral angle between (O1/Zn/O2) and (Br1/Zn/Br2) planes is 88.1 (3)°.
Rings B (Ni/O1/N1/C1/C6/C7), C (Ni/N1/N2/C8—C10) and D (Ni/O2/N2/C11/C12/C17) are not planar, having total puckering amplitudes, QT, of 0.190 (2), 1.143 (3) and 0.248 (2) Å, respectively [φ = 128.66 (5)°, θ = 92.56 (4)°; φ = 102.38 (6)°, θ = 85.87 (5)° and φ = 15.97 (6)°, θ = 43.44 (5)°, respectively] (Cremer & Pople, 1975). Rings B and D have flattened boat conformations, while ring A adopts a twisted conformation. Rings A (C1—C6), E (C12—C17), F (N3/C18—C22) and G (N4/C24—C28) are, of course, planar and the dihedral angles between them are A/E = 6.02 (3)° and F/G = 22.77 (2)°.
In the crystal structure, weak intermolecular C—H···Br hydrogen bonds (Table 2) link the molecules into chains along the c axis (Fig. 2); weak intramolecular C—H···O and C—H···N hydrogen bonds are also present.
For general background, see: Bertini et al. (1994); For related structures, see: Tatar et al. (2002); Tatar (2002); Tatar Yıldırım et al. (2007); Svoboda et al. (2001); Arıcı et al. (2001). For ring conformation puckering parameters, see: Cremer & Pople (1975).
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[NiZnBr2(C17H16N2O2)(C6H7N)2] | F(000) = 1504 |
Mr = 750.45 | Dx = 1.674 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 15 reflections |
a = 19.357 (3) Å | θ = 10.2–11.6° |
b = 9.2130 (7) Å | µ = 4.16 mm−1 |
c = 18.3269 (15) Å | T = 294 K |
β = 114.382 (10)° | Prism, pink |
V = 2976.9 (6) Å3 | 0.20 × 0.15 × 0.15 mm |
Z = 4 |
Enraf–Nonius TurboCAD-4 diffractometer | Rint = 0.050 |
non–profiled ω scans | θmax = 27.1°, θmin = 2.3° |
Absorption correction: ψ scan (North et al., 1968) | h = −24→0 |
Tmin = 0.478, Tmax = 0.536 | k = −11→0 |
3381 measured reflections | l = −21→23 |
3379 independent reflections | 3 standard reflections every 120 min |
2118 reflections with I > 2σ(I) | intensity decay: 2% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.066 | w = 1/[σ2(Fo2) + (0.1221P)2 + 7.1119P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.206 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 1.30 e Å−3 |
3379 reflections | Δρmin = −1.42 e Å−3 |
353 parameters | Absolute structure: Flack (1983), with 95 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.25 (7) |
Secondary atom site location: difference Fourier map |
[NiZnBr2(C17H16N2O2)(C6H7N)2] | V = 2976.9 (6) Å3 |
Mr = 750.45 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 19.357 (3) Å | µ = 4.16 mm−1 |
b = 9.2130 (7) Å | T = 294 K |
c = 18.3269 (15) Å | 0.20 × 0.15 × 0.15 mm |
β = 114.382 (10)° |
Enraf–Nonius TurboCAD-4 diffractometer | 2118 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
Tmin = 0.478, Tmax = 0.536 | 3 standard reflections every 120 min |
3381 measured reflections | intensity decay: 2% |
3379 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters not refined |
wR(F2) = 0.206 | Δρmax = 1.30 e Å−3 |
S = 1.04 | Δρmin = −1.42 e Å−3 |
3379 reflections | Absolute structure: Flack (1983), with 95 Friedel pairs |
353 parameters | Absolute structure parameter: 0.25 (7) |
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 | ||
Br1 | 0.9306 (8) | 0.0500 (10) | 0.8991 (6) | 0.0763 (6) | |
Br2 | 0.82738 (13) | 0.2500 (2) | 0.99821 (11) | 0.0761 (6) | |
Zn | 0.94119 (8) | 0.26209 (17) | 0.97905 (8) | 0.0440 (4) | |
Ni | 1.05439 (11) | 0.51344 (17) | 1.01890 (11) | 0.0402 (4) | |
O1 | 1.0376 (5) | 0.3234 (10) | 1.0686 (5) | 0.041 (2) | |
O2 | 0.9577 (6) | 0.4444 (11) | 0.9314 (5) | 0.045 (2) | |
N1 | 1.1532 (7) | 0.5472 (14) | 1.1188 (8) | 0.052 (3) | |
N2 | 1.0548 (8) | 0.6930 (12) | 0.9518 (8) | 0.051 (3) | |
N3 | 0.9881 (7) | 0.6331 (12) | 1.0703 (7) | 0.044 (3) | |
N4 | 1.1205 (7) | 0.3862 (13) | 0.9650 (8) | 0.050 (3) | |
C1 | 1.0756 (9) | 0.2743 (14) | 1.1395 (9) | 0.045 (4) | |
C2 | 1.0492 (11) | 0.1485 (18) | 1.1622 (9) | 0.059 (4) | |
H2 | 1.0062 | 0.1023 | 1.1255 | 0.07* | |
C3 | 1.0881 (12) | 0.089 (2) | 1.2422 (11) | 0.076 (5) | |
H3 | 1.0708 | 0.0052 | 1.2575 | 0.091* | |
C4 | 1.1524 (12) | 0.162 (2) | 1.2954 (9) | 0.068 (5) | |
H4 | 1.1773 | 0.1271 | 1.3475 | 0.081* | |
C5 | 1.1783 (10) | 0.278 (2) | 1.2733 (10) | 0.064 (5) | |
H5 | 1.223 | 0.3193 | 1.3099 | 0.077* | |
C6 | 1.1416 (8) | 0.3440 (16) | 1.1959 (8) | 0.046 (3) | |
C7 | 1.1783 (9) | 0.4710 (17) | 1.1806 (9) | 0.049 (4) | |
H7 | 1.2248 | 0.4979 | 1.2206 | 0.059* | |
C8 | 1.1958 (9) | 0.678 (2) | 1.1167 (11) | 0.071 (5) | |
H8A | 1.2263 | 0.6562 | 1.0875 | 0.085* | |
H8B | 1.2302 | 0.7026 | 1.1712 | 0.085* | |
C9 | 1.1480 (11) | 0.8090 (19) | 1.0793 (13) | 0.075 (6) | |
H9A | 1.1794 | 0.8951 | 1.0971 | 0.09* | |
H9B | 1.1083 | 0.8161 | 1.0984 | 0.09* | |
C10 | 1.1114 (12) | 0.807 (2) | 0.9876 (13) | 0.076 (5) | |
H10A | 1.0875 | 0.9005 | 0.9687 | 0.091* | |
H10B | 1.1511 | 0.7957 | 0.9687 | 0.091* | |
C11 | 1.0092 (11) | 0.7073 (16) | 0.8786 (10) | 0.054 (4) | |
H11 | 1.0164 | 0.7906 | 0.8539 | 0.065* | |
C12 | 0.9484 (8) | 0.6153 (16) | 0.8280 (8) | 0.043 (3) | |
C13 | 0.9113 (11) | 0.6499 (18) | 0.7485 (11) | 0.061 (4) | |
H13 | 0.928 | 0.7312 | 0.7304 | 0.073* | |
C14 | 0.8516 (10) | 0.574 (2) | 0.6936 (11) | 0.065 (4) | |
H14 | 0.8291 | 0.6001 | 0.6397 | 0.078* | |
C15 | 0.8280 (9) | 0.461 (2) | 0.7228 (9) | 0.064 (5) | |
H15 | 0.7861 | 0.4092 | 0.688 | 0.077* | |
C16 | 0.8633 (9) | 0.4150 (17) | 0.8041 (9) | 0.053 (4) | |
H16 | 0.8454 | 0.3349 | 0.822 | 0.063* | |
C17 | 0.9239 (9) | 0.4915 (16) | 0.8546 (8) | 0.043 (4) | |
C18 | 0.9394 (9) | 0.7358 (16) | 1.0269 (10) | 0.053 (4) | |
H18 | 0.9305 | 0.7469 | 0.9733 | 0.064* | |
C19 | 0.9030 (10) | 0.8235 (18) | 1.0583 (11) | 0.060 (4) | |
H19 | 0.8689 | 0.8915 | 1.0254 | 0.073* | |
C20 | 0.9143 (11) | 0.8160 (17) | 1.1361 (12) | 0.065 (5) | |
C21 | 0.9650 (11) | 0.7132 (18) | 1.1828 (10) | 0.058 (4) | |
H21 | 0.9758 | 0.7046 | 1.237 | 0.07* | |
C22 | 1.0002 (9) | 0.6211 (19) | 1.1465 (9) | 0.056 (4) | |
H22 | 1.033 | 0.5494 | 1.1774 | 0.067* | |
C23 | 0.8732 (15) | 0.914 (3) | 1.1757 (14) | 0.101 (8) | |
H23A | 0.8893 | 0.8872 | 1.2309 | 0.151* | |
H23B | 0.8193 | 0.9012 | 1.148 | 0.151* | |
H23C | 0.8857 | 1.014 | 1.1723 | 0.151* | |
C24 | 1.1542 (18) | 0.266 (2) | 0.9967 (17) | 0.096 (8) | |
H24 | 1.1477 | 0.2289 | 1.0406 | 0.116* | |
C25 | 1.2003 (19) | 0.189 (2) | 0.9673 (16) | 0.117 (11) | |
H25A | 1.2247 | 0.105 | 0.9933 | 0.14* | |
C26 | 1.2093 (11) | 0.2337 (17) | 0.9045 (12) | 0.064 (5) | |
C27 | 1.174 (2) | 0.355 (4) | 0.8725 (18) | 0.165 (18) | |
H27 | 1.1786 | 0.3922 | 0.8272 | 0.096 (8)* | |
C28 | 1.133 (2) | 0.427 (4) | 0.904 (2) | 0.064 (5) | |
H28 | 1.1107 | 0.5146 | 0.8802 | 0.225* | |
C29 | 1.2598 (13) | 0.156 (2) | 0.8728 (15) | 0.091 (7) | |
H29A | 1.2554 | 0.201 | 0.8238 | 0.137* | |
H29B | 1.2446 | 0.0561 | 0.8628 | 0.137* | |
H29C | 1.3115 | 0.1613 | 0.9116 | 0.137* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0643 (12) | 0.1029 (15) | 0.0706 (12) | −0.0122 (10) | 0.0342 (9) | 0.0016 (10) |
Br2 | 0.0633 (12) | 0.1009 (15) | 0.0707 (12) | −0.0110 (10) | 0.0341 (9) | 0.0014 (10) |
Zn | 0.0447 (9) | 0.0470 (10) | 0.0406 (8) | −0.0113 (8) | 0.0177 (7) | −0.0003 (7) |
Ni | 0.0399 (8) | 0.0403 (10) | 0.0443 (8) | −0.0041 (8) | 0.0215 (6) | −0.0002 (8) |
O1 | 0.035 (5) | 0.043 (5) | 0.037 (5) | 0.000 (4) | 0.008 (4) | 0.003 (4) |
O2 | 0.048 (6) | 0.054 (6) | 0.034 (5) | −0.008 (5) | 0.017 (4) | 0.008 (4) |
N1 | 0.040 (7) | 0.057 (7) | 0.071 (9) | −0.018 (6) | 0.034 (7) | −0.019 (7) |
N2 | 0.064 (8) | 0.032 (6) | 0.075 (9) | −0.005 (6) | 0.046 (8) | 0.007 (6) |
N3 | 0.037 (6) | 0.048 (7) | 0.058 (7) | −0.004 (5) | 0.029 (5) | 0.000 (6) |
N4 | 0.043 (6) | 0.045 (7) | 0.068 (8) | −0.008 (6) | 0.030 (6) | −0.005 (6) |
C1 | 0.059 (9) | 0.035 (8) | 0.052 (9) | 0.011 (7) | 0.035 (8) | 0.001 (6) |
C2 | 0.073 (11) | 0.055 (9) | 0.045 (8) | 0.005 (8) | 0.022 (8) | 0.005 (7) |
C3 | 0.091 (13) | 0.067 (11) | 0.071 (11) | 0.017 (11) | 0.034 (11) | 0.033 (10) |
C4 | 0.075 (12) | 0.074 (12) | 0.033 (8) | 0.024 (10) | 0.002 (8) | 0.010 (8) |
C5 | 0.057 (11) | 0.076 (12) | 0.057 (10) | 0.016 (9) | 0.021 (8) | −0.013 (9) |
C6 | 0.034 (7) | 0.049 (8) | 0.049 (8) | 0.012 (6) | 0.010 (6) | −0.008 (7) |
C7 | 0.039 (8) | 0.062 (9) | 0.040 (8) | 0.003 (7) | 0.009 (6) | −0.014 (7) |
C8 | 0.042 (9) | 0.088 (13) | 0.075 (11) | −0.024 (9) | 0.017 (8) | 0.001 (10) |
C9 | 0.062 (11) | 0.050 (10) | 0.123 (17) | −0.031 (9) | 0.049 (11) | −0.028 (10) |
C10 | 0.068 (12) | 0.071 (12) | 0.091 (14) | −0.019 (10) | 0.034 (11) | 0.000 (11) |
C11 | 0.079 (11) | 0.033 (7) | 0.068 (10) | 0.006 (7) | 0.049 (9) | 0.011 (7) |
C12 | 0.043 (8) | 0.048 (8) | 0.040 (7) | 0.011 (7) | 0.018 (6) | 0.007 (6) |
C13 | 0.074 (11) | 0.052 (9) | 0.069 (10) | 0.033 (9) | 0.042 (9) | 0.033 (9) |
C14 | 0.063 (11) | 0.071 (11) | 0.067 (11) | 0.021 (9) | 0.032 (9) | 0.011 (9) |
C15 | 0.045 (8) | 0.089 (13) | 0.045 (8) | 0.011 (9) | 0.005 (7) | 0.004 (8) |
C16 | 0.057 (9) | 0.048 (9) | 0.053 (8) | 0.020 (7) | 0.024 (8) | 0.012 (7) |
C17 | 0.044 (8) | 0.055 (9) | 0.029 (7) | 0.026 (7) | 0.016 (6) | 0.011 (6) |
C18 | 0.042 (8) | 0.060 (9) | 0.056 (9) | 0.007 (7) | 0.018 (7) | 0.011 (7) |
C19 | 0.060 (10) | 0.051 (9) | 0.085 (12) | 0.020 (8) | 0.044 (9) | 0.008 (8) |
C20 | 0.082 (13) | 0.042 (9) | 0.096 (13) | 0.001 (9) | 0.061 (11) | −0.003 (9) |
C21 | 0.081 (12) | 0.060 (10) | 0.055 (9) | 0.002 (9) | 0.049 (9) | 0.002 (8) |
C22 | 0.050 (9) | 0.069 (11) | 0.053 (9) | 0.007 (8) | 0.026 (7) | 0.012 (8) |
C23 | 0.13 (2) | 0.084 (15) | 0.116 (18) | 0.015 (14) | 0.083 (17) | −0.027 (13) |
C24 | 0.15 (2) | 0.059 (12) | 0.13 (2) | 0.031 (12) | 0.112 (19) | 0.030 (11) |
C25 | 0.21 (3) | 0.063 (13) | 0.14 (2) | 0.067 (17) | 0.13 (2) | 0.033 (13) |
C26 | 0.063 (11) | 0.050 (9) | 0.096 (13) | 0.007 (8) | 0.049 (10) | −0.007 (9) |
C27 | 0.152 (2) | 0.059 (12) | 0.131 (2) | 0.030 (12) | 0.112 (19) | 0.031 (11) |
C28 | 0.065 (11) | 0.051 (9) | 0.096 (13) | 0.007 (8) | 0.049 (10) | −0.007 (9) |
C29 | 0.084 (14) | 0.079 (13) | 0.127 (19) | 0.001 (11) | 0.060 (14) | −0.030 (13) |
Zn—Br1 | 2.400 (10) | C10—H10A | 0.97 |
Zn—Br2 | 2.372 (3) | C10—H10B | 0.97 |
Zn—O1 | 1.992 (9) | C11—H11 | 0.93 |
Zn—O2 | 1.979 (10) | C12—C13 | 1.37 (2) |
Ni—O1 | 2.060 (10) | C12—C11 | 1.44 (2) |
Ni—O2 | 2.000 (10) | C13—C14 | 1.37 (3) |
Ni—N1 | 2.054 (14) | C13—H13 | 0.93 |
Ni—N2 | 2.063 (12) | C14—H14 | 0.93 |
Ni—N3 | 2.180 (12) | C15—C14 | 1.34 (3) |
Ni—N4 | 2.243 (13) | C15—H15 | 0.93 |
O1—C1 | 1.283 (18) | C16—C15 | 1.42 (2) |
O2—C17 | 1.355 (16) | C16—H16 | 0.93 |
N1—C8 | 1.47 (2) | C17—C16 | 1.35 (2) |
N2—C10 | 1.46 (2) | C17—C12 | 1.40 (2) |
N2—C11 | 1.27 (2) | C18—C19 | 1.35 (2) |
N3—C18 | 1.341 (19) | C18—H18 | 0.93 |
N3—C22 | 1.321 (19) | C19—H19 | 0.93 |
N4—C24 | 1.29 (2) | C20—C19 | 1.35 (2) |
N4—C28 | 1.29 (3) | C20—C23 | 1.57 (2) |
C1—C2 | 1.40 (2) | C21—C20 | 1.38 (3) |
C1—C6 | 1.42 (2) | C21—H21 | 0.93 |
C2—H2 | 0.93 | C22—C21 | 1.41 (2) |
C3—C2 | 1.45 (2) | C22—H22 | 0.93 |
C3—H3 | 0.93 | C23—H23A | 0.96 |
C4—C3 | 1.39 (3) | C23—H23B | 0.96 |
C4—H4 | 0.93 | C23—H23C | 0.96 |
C5—C4 | 1.32 (3) | C24—C25 | 1.41 (3) |
C5—H5 | 0.93 | C24—H24 | 0.93 |
C6—C5 | 1.44 (2) | C25—H25A | 0.93 |
C7—N1 | 1.25 (2) | C26—C25 | 1.30 (3) |
C7—C6 | 1.45 (2) | C26—C27 | 1.31 (3) |
C7—H7 | 0.93 | C26—C29 | 1.51 (2) |
C8—H8A | 0.97 | C27—C28 | 1.35 (3) |
C8—H8B | 0.97 | C27—H27 | 0.93 |
C9—C8 | 1.50 (3) | C28—H28 | 0.93 |
C9—H9A | 0.97 | C29—H29A | 0.96 |
C9—H9B | 0.97 | C29—H29B | 0.96 |
C9—C10 | 1.53 (3) | C29—H29C | 0.96 |
O2—Zn—O1 | 81.7 (4) | H9A—C9—H9B | 107.6 |
O2—Zn—Br2 | 115.7 (3) | N2—C10—C9 | 114.9 (15) |
O1—Zn—Br2 | 120.2 (3) | N2—C10—H10A | 108.5 |
O2—Zn—Br1 | 114.2 (4) | C9—C10—H10A | 108.5 |
O1—Zn—Br1 | 123.3 (4) | N2—C10—H10B | 108.5 |
Br2—Zn—Br1 | 101.6 (3) | C9—C10—H10B | 108.5 |
O2—Ni—N1 | 169.1 (5) | H10A—C10—H10B | 107.5 |
O2—Ni—O1 | 79.5 (4) | N2—C11—C12 | 130.3 (14) |
N1—Ni—O1 | 89.6 (4) | N2—C11—H11 | 114.9 |
O2—Ni—N2 | 90.6 (5) | C12—C11—H11 | 114.9 |
N1—Ni—N2 | 100.3 (6) | C13—C12—C17 | 117.2 (15) |
O1—Ni—N2 | 170.1 (5) | C13—C12—C11 | 118.7 (15) |
O2—Ni—N3 | 89.1 (5) | C17—C12—C11 | 124.2 (13) |
N1—Ni—N3 | 92.1 (5) | C14—C13—C12 | 125.3 (16) |
O1—Ni—N3 | 90.6 (4) | C14—C13—H13 | 117.4 |
N2—Ni—N3 | 90.0 (5) | C12—C13—H13 | 117.4 |
O2—Ni—N4 | 89.8 (5) | C15—C14—C13 | 115.3 (16) |
N1—Ni—N4 | 88.9 (5) | C15—C14—H14 | 122.4 |
O1—Ni—N4 | 88.5 (4) | C13—C14—H14 | 122.4 |
N2—Ni—N4 | 90.8 (5) | C14—C15—C16 | 123.7 (17) |
N3—Ni—N4 | 178.7 (5) | C14—C15—H15 | 118.1 |
C1—O1—Zn | 133.3 (10) | C16—C15—H15 | 118.1 |
C1—O1—Ni | 128.2 (9) | C17—C16—C15 | 117.8 (16) |
Zn—O1—Ni | 98.2 (4) | C17—C16—H16 | 121.1 |
C17—O2—Zn | 129.3 (10) | C15—C16—H16 | 121.1 |
C17—O2—Ni | 128.4 (10) | C16—C17—O2 | 117.0 (14) |
Zn—O2—Ni | 100.6 (4) | C16—C17—C12 | 120.6 (13) |
C7—N1—C8 | 118.2 (14) | O2—C17—C12 | 122.4 (14) |
C7—N1—Ni | 126.4 (11) | N3—C18—C19 | 122.1 (16) |
C8—N1—Ni | 115.3 (11) | N3—C18—H18 | 118.9 |
C11—N2—C10 | 117.6 (14) | C19—C18—H18 | 118.9 |
C11—N2—Ni | 122.7 (11) | C18—C19—C20 | 122.3 (16) |
C10—N2—Ni | 119.7 (12) | C18—C19—H19 | 118.8 |
C22—N3—C18 | 117.5 (14) | C20—C19—H19 | 118.8 |
C22—N3—Ni | 122.4 (10) | C19—C20—C21 | 117.0 (15) |
C18—N3—Ni | 119.7 (10) | C19—C20—C23 | 124.5 (17) |
C28—N4—C24 | 113.8 (17) | C21—C20—C23 | 118.5 (17) |
C28—N4—Ni | 124.6 (13) | C20—C21—C22 | 118.5 (15) |
C24—N4—Ni | 121.5 (13) | C20—C21—H21 | 120.7 |
O1—C1—C2 | 117.8 (14) | C22—C21—H21 | 120.7 |
O1—C1—C6 | 123.0 (14) | N3—C22—C21 | 122.5 (15) |
C2—C1—C6 | 119.2 (14) | N3—C22—H22 | 118.8 |
C1—C2—C3 | 120.8 (17) | C21—C22—H22 | 118.8 |
C1—C2—H2 | 119.6 | C20—C23—H23A | 109.5 |
C3—C2—H2 | 119.6 | C20—C23—H23B | 109.5 |
C4—C3—C2 | 117.8 (17) | H23A—C23—H23B | 109.5 |
C4—C3—H3 | 121.1 | C20—C23—H23C | 109.5 |
C2—C3—H3 | 121.1 | H23A—C23—H23C | 109.5 |
C5—C4—C3 | 121.3 (16) | H23B—C23—H23C | 109.5 |
C5—C4—H4 | 119.4 | N4—C24—C25 | 123 (2) |
C3—C4—H4 | 119.4 | N4—C24—H24 | 118.7 |
C4—C5—C6 | 123.7 (16) | C25—C24—H24 | 118.7 |
C4—C5—H5 | 118.2 | C26—C25—C24 | 121.2 (19) |
C6—C5—H5 | 118.2 | C26—C25—H25A | 119.4 |
C1—C6—C5 | 117.1 (15) | C24—C25—H25A | 119.4 |
C1—C6—C7 | 125.9 (14) | C25—C26—C27 | 115.5 (17) |
C5—C6—C7 | 116.8 (14) | C25—C26—C29 | 122.5 (18) |
N1—C7—C6 | 126.1 (14) | C27—C26—C29 | 122 (2) |
N1—C7—H7 | 116.9 | C26—C27—C28 | 121 (2) |
C6—C7—H7 | 116.9 | C26—C27—H27 | 119.5 |
N1—C8—C9 | 115.1 (14) | C28—C27—H27 | 119.5 |
N1—C8—H8A | 108.5 | N4—C28—C27 | 126 (2) |
C9—C8—H8A | 108.5 | N4—C28—H28 | 116.0 |
N1—C8—H8B | 108.5 | C27—C28—H28 | 117.2 |
C9—C8—H8B | 108.5 | C26—C29—H29A | 109.5 |
H8A—C8—H8B | 107.5 | C26—C29—H29B | 109.5 |
C8—C9—C10 | 114.3 (16) | H29A—C29—H29B | 109.5 |
C8—C9—H9A | 108.7 | C26—C29—H29C | 109.5 |
C10—C9—H9A | 108.7 | H29A—C29—H29C | 109.5 |
C8—C9—H9B | 108.7 | H29B—C29—H29C | 109.5 |
C10—C9—H9B | 108.7 | ||
O2—Zn—O1—C1 | 173.2 (13) | Zn—O1—C1—C2 | 3 (2) |
Br2—Zn—O1—C1 | 58.2 (13) | Ni—O1—C1—C2 | 174.3 (10) |
Br1—Zn—O1—C1 | −73.2 (13) | Zn—O1—C1—C6 | −175.4 (10) |
O2—Zn—O1—Ni | 0.1 (5) | Ni—O1—C1—C6 | −4 (2) |
Br2—Zn—O1—Ni | −114.8 (3) | Zn—O2—C17—C16 | 9.8 (19) |
Br1—Zn—O1—Ni | 113.7 (4) | Ni—O2—C17—C16 | 172.0 (10) |
O1—Zn—O2—C17 | 165.8 (12) | Zn—O2—C17—C12 | −171.8 (10) |
Br2—Zn—O2—C17 | −74.7 (12) | Ni—O2—C17—C12 | −10 (2) |
Br1—Zn—O2—C17 | 42.9 (13) | C7—N1—C8—C9 | −138.9 (17) |
O1—Zn—O2—Ni | −0.1 (5) | Ni—N1—C8—C9 | 39 (2) |
Br2—Zn—O2—Ni | 119.5 (3) | C11—N2—C10—C9 | 162.5 (17) |
Br1—Zn—O2—Ni | −123.0 (5) | Ni—N2—C10—C9 | −20 (2) |
O2—Ni—O1—C1 | −173.7 (12) | C10—N2—C11—C12 | −179.6 (17) |
N1—Ni—O1—C1 | 7.3 (12) | Ni—N2—C11—C12 | 3 (2) |
N3—Ni—O1—C1 | −84.8 (12) | C22—N3—C18—C19 | −1 (2) |
N4—Ni—O1—C1 | 96.2 (12) | Ni—N3—C18—C19 | −172.9 (13) |
O2—Ni—O1—Zn | −0.1 (5) | C18—N3—C22—C21 | −1 (2) |
N1—Ni—O1—Zn | −179.1 (5) | Ni—N3—C22—C21 | 170.8 (12) |
N3—Ni—O1—Zn | 88.8 (5) | C28—N4—C24—C25 | 1 (4) |
N4—Ni—O1—Zn | −90.2 (5) | Ni—N4—C24—C25 | −176 (2) |
N1—Ni—O2—C17 | −161 (2) | C24—N4—C28—C27 | 2 (6) |
O1—Ni—O2—C17 | −165.9 (12) | Ni—N4—C28—C27 | 178 (4) |
N2—Ni—O2—C17 | 13.3 (12) | O1—C1—C2—C3 | −178.2 (15) |
N3—Ni—O2—C17 | 103.3 (11) | C6—C1—C2—C3 | 0 (2) |
N4—Ni—O2—C17 | −77.5 (12) | O1—C1—C6—C5 | 179.5 (13) |
N1—Ni—O2—Zn | 5 (3) | C2—C1—C6—C5 | 1 (2) |
O1—Ni—O2—Zn | 0.1 (5) | O1—C1—C6—C7 | −5 (2) |
N2—Ni—O2—Zn | 179.4 (5) | C2—C1—C6—C7 | 176.8 (14) |
N3—Ni—O2—Zn | −90.6 (5) | C4—C3—C2—C1 | 0 (3) |
N4—Ni—O2—Zn | 88.6 (5) | C5—C4—C3—C2 | −2 (3) |
O2—Ni—N1—C7 | −10 (4) | C6—C5—C4—C3 | 4 (3) |
O1—Ni—N1—C7 | −4.2 (13) | C1—C6—C5—C4 | −3 (2) |
N2—Ni—N1—C7 | 176.7 (13) | C7—C6—C5—C4 | −179.2 (16) |
N3—Ni—N1—C7 | 86.3 (13) | N1—C7—C6—C1 | 8 (3) |
N4—Ni—N1—C7 | −92.7 (13) | N1—C7—C6—C5 | −176.2 (15) |
O2—Ni—N1—C8 | 173 (2) | C6—C7—N1—C8 | 175.4 (15) |
O1—Ni—N1—C8 | 178.4 (12) | C6—C7—N1—Ni | −2 (2) |
N2—Ni—N1—C8 | −0.6 (12) | C10—C9—C8—N1 | −78 (2) |
N3—Ni—N1—C8 | −91.0 (12) | C8—C9—C10—N2 | 66 (2) |
N4—Ni—N1—C8 | 89.9 (12) | C13—C12—C11—N2 | −174.7 (16) |
O2—Ni—N2—C11 | −9.6 (13) | C17—C12—C11—N2 | 5 (3) |
N1—Ni—N2—C11 | 169.2 (13) | C17—C12—C13—C14 | 1 (2) |
N3—Ni—N2—C11 | −98.7 (13) | C11—C12—C13—C14 | −178.7 (16) |
N4—Ni—N2—C11 | 80.2 (13) | C12—C13—C14—C15 | 2 (3) |
O2—Ni—N2—C10 | 173.0 (14) | C16—C15—C14—C13 | −3 (3) |
N1—Ni—N2—C10 | −8.2 (14) | C17—C16—C15—C14 | 1 (2) |
N3—Ni—N2—C10 | 83.9 (14) | C16—C17—C12—C13 | −4 (2) |
N4—Ni—N2—C10 | −97.2 (14) | O2—C17—C12—C13 | 178.2 (13) |
O2—Ni—N3—C22 | 128.7 (12) | C16—C17—C12—C11 | 176.2 (14) |
N1—Ni—N3—C22 | −40.5 (12) | O2—C17—C12—C11 | −2 (2) |
O1—Ni—N3—C22 | 49.1 (12) | O2—C17—C16—C15 | −178.8 (14) |
N2—Ni—N3—C22 | −140.8 (12) | C12—C17—C16—C15 | 3 (2) |
O2—Ni—N3—C18 | −59.6 (11) | N3—C18—C19—C20 | 1 (3) |
N1—Ni—N3—C18 | 131.3 (11) | C21—C20—C19—C18 | 0 (3) |
O1—Ni—N3—C18 | −139.1 (11) | C23—C20—C19—C18 | −179.5 (19) |
N2—Ni—N3—C18 | 31.0 (12) | C22—C21—C20—C19 | −1 (3) |
O2—Ni—N4—C28 | 79 (3) | C22—C21—C20—C23 | 177.8 (18) |
N1—Ni—N4—C28 | −112 (3) | N3—C22—C21—C20 | 2 (3) |
O1—Ni—N4—C28 | 159 (3) | N4—C24—C25—C26 | −2 (5) |
N2—Ni—N4—C28 | −11 (3) | C27—C26—C25—C24 | 2 (5) |
O2—Ni—N4—C24 | −105.0 (19) | C29—C26—C25—C24 | 178 (3) |
N1—Ni—N4—C24 | 64 (2) | C25—C26—C27—C28 | 0 (6) |
O1—Ni—N4—C24 | −25.5 (19) | C29—C26—C27—C28 | −176 (4) |
N2—Ni—N4—C24 | 164.4 (19) | C26—C27—C28—N4 | −2 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Br2i | 0.93 | 2.93 | 3.78 (2) | 153 |
C23—H23A···Br1ii | 0.96 | 2.91 | 3.79 (3) | 153 |
C24—H24···O1 | 0.93 | 2.54 | 3.09 (4) | 118 |
C28—H28···N2 | 0.93 | 2.60 | 3.18 (4) | 121 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [NiZnBr2(C17H16N2O2)(C6H7N)2] |
Mr | 750.45 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 294 |
a, b, c (Å) | 19.357 (3), 9.2130 (7), 18.3269 (15) |
β (°) | 114.382 (10) |
V (Å3) | 2976.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.16 |
Crystal size (mm) | 0.20 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Enraf–Nonius TurboCAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.478, 0.536 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3381, 3379, 2118 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.640 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.206, 1.04 |
No. of reflections | 3379 |
No. of parameters | 353 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 1.30, −1.42 |
Absolute structure | Flack (1983), with 95 Friedel pairs |
Absolute structure parameter | 0.25 (7) |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Zn—Br1 | 2.400 (10) | Ni—O2 | 2.000 (10) |
Zn—Br2 | 2.372 (3) | Ni—N1 | 2.054 (14) |
Zn—O1 | 1.992 (9) | Ni—N2 | 2.063 (12) |
Zn—O2 | 1.979 (10) | Ni—N3 | 2.180 (12) |
Ni—O1 | 2.060 (10) | Ni—N4 | 2.243 (13) |
O2—Zn—O1 | 81.7 (4) | O1—Ni—N2 | 170.1 (5) |
O2—Zn—Br2 | 115.7 (3) | O2—Ni—N3 | 89.1 (5) |
O1—Zn—Br2 | 120.2 (3) | N1—Ni—N3 | 92.1 (5) |
O2—Zn—Br1 | 114.2 (4) | O1—Ni—N3 | 90.6 (4) |
O1—Zn—Br1 | 123.3 (4) | N2—Ni—N3 | 90.0 (5) |
Br2—Zn—Br1 | 101.6 (3) | O2—Ni—N4 | 89.8 (5) |
O2—Ni—N1 | 169.1 (5) | N1—Ni—N4 | 88.9 (5) |
O2—Ni—O1 | 79.5 (4) | O1—Ni—N4 | 88.5 (4) |
N1—Ni—O1 | 89.6 (4) | N2—Ni—N4 | 90.8 (5) |
O2—Ni—N2 | 90.6 (5) | N3—Ni—N4 | 178.7 (5) |
N1—Ni—N2 | 100.3 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···Br2i | 0.93 | 2.93 | 3.78 (2) | 153 |
C23—H23A···Br1ii | 0.96 | 2.91 | 3.79 (3) | 153 |
C24—H24···O1 | 0.93 | 2.54 | 3.09 (4) | 118 |
C28—H28···N2 | 0.93 | 2.60 | 3.18 (4) | 121 |
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2. |
Zinc and nickel elements are important essential rare elements for living beings (Bertini et al., 1994), in this respect the zinc and nickel compounds are very important in medicine. Some dinuclear zinc-nickel metal compounds of Schiff-base ligands have been studied in our laboratory (Tatar Yıldırım et al., 2007; Tatar, 2002; Tatar et al., 2002; Arıcı et al., 2001). We report herein the structure of the title compound, (I), a new hetero-dinuclear [ZnBr2Ni(salpd2-)(C6H7N)2] complex [where salpd2- is N,N'-bis- (salicylidene)-1,3-propanediamine].
In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles (Table 1) are generally in good agreement with the corresponding values in similar oxygen-bridged dinuclear complexes reported, previously (Tatar et al., 2007; Tatar, 2002; Tatar, Atakol et al., 2002; Svoboda et al., 2001; Arıcı et al., 2001). The two bridging O atoms of salpd2- ligand and two Br atoms constitute a distorted tetrahedral coordination environment around the ZnII ion, while the NiII ion has a distorted octahedral coordination environment formed by two O and two N atoms of salpd2- ligand in the equatorial plane and two N atoms of two methylpyridine ligands in the axial positions (Table 1). The Ni atom is -0.017 (2) Å away from the equatorial plane. The Zn···Ni distance is 3.062 (3) Å. The dihedral angle between (O1/Zn/O2) and (Br1/Zn/Br2) planes is 88.1 (3)°.
Rings B (Ni/O1/N1/C1/C6/C7), C (Ni/N1/N2/C8—C10) and D (Ni/O2/N2/C11/C12/C17) are not planar, having total puckering amplitudes, QT, of 0.190 (2), 1.143 (3) and 0.248 (2) Å, respectively [φ = 128.66 (5)°, θ = 92.56 (4)°; φ = 102.38 (6)°, θ = 85.87 (5)° and φ = 15.97 (6)°, θ = 43.44 (5)°, respectively] (Cremer & Pople, 1975). Rings B and D have flattened boat conformations, while ring A adopts a twisted conformation. Rings A (C1—C6), E (C12—C17), F (N3/C18—C22) and G (N4/C24—C28) are, of course, planar and the dihedral angles between them are A/E = 6.02 (3)° and F/G = 22.77 (2)°.
In the crystal structure, weak intermolecular C—H···Br hydrogen bonds (Table 2) link the molecules into chains along the c axis (Fig. 2); weak intramolecular C—H···O and C—H···N hydrogen bonds are also present.