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
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.029 Å
- R factor = 0.066
- wR factor = 0.206
- Data-to-parameter ratio = 9.6
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Br1 - Zn .. 30.06 su PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C25 PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C27 PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C26 PLAT341_ALERT_3_B Low Bond Precision on C-C Bonds (x 1000) Ang ... 29 PLAT413_ALERT_2_B Short Inter XH3 .. XHn H4 .. H29B .. 2.08 Ang.
Alert level C PLAT034_ALERT_1_C No Flack Parameter Given. Z .GT. Si, NonCentro . ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.83 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.81 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Br2 - Zn .. 7.17 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Zn PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4
Alert level G REFLT03_ALERT_4_G WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure From the CIF: _diffrn_reflns_theta_max 27.07 From the CIF: _reflns_number_total 3379 Count of symmetry unique reflns 3284 Completeness (_total/calc) 102.89% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 95 Fraction of Friedel pairs measured 0.029 Are heavy atom types Z>Si present yes PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn (2) 1.99 PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni (2) 1.99
0 ALERT level A = In general: serious problem 6 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 9 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
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.