Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014487/da1133sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014487/da1133Isup2.hkl |
CCDC reference: 158233
To a solution of N,N'-bis-salicylidene-1,3-propanediamine (0.840 g, 3 mmol) in hot ethanol (50 ml), ammonia solution (10 ml) was added and the mixture was heated to boiling. A solution of NiBr2·6H2O (0.715 g, 3 mmol) in hot water (20 ml) was added, and the resulting mixture was left to stand in air. After 2 h, the light blue Ni complex was filtered, and dried at 423 K for 3 h. This complex (0.339 g, 1 mmol) was dissolved in hot DMF (10 mmol) and dioxane (30 mmol). Dropwise addition of ZnBr2 (0.225 g, 1 mmol) in hot methanol (10 ml) was added. The resulting mixture was set aside for 3 d and the light blue crystals which formed were filtered off and dried in air.
All non-H atoms were refined with anisotropic displacement parameters. H atoms bonded to C atoms were placed geometrically from their parent atoms.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON99 (Spek, 1999); software used to prepare material for publication: SHELXL97.
[NiZnBr2(C3H7NO)2(C17H16N2O2)] | Z = 4 |
Mr = 710.39 | Dx = 1.698 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 25 reflections |
a = 10.518 (3) Å | θ = 2.8–12.7° |
b = 15.180 (8) Å | µ = 4.45 mm−1 |
c = 17.618 (6) Å | T = 295 K |
β = 98.85 (2)° | Prism, light blue |
V = 2779.5 (19) Å3 | 0.45 × 0.35 × 0.18 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.000 |
ω/2θ scans | θmax = 27.5° |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | h = −13→13 |
Tmin = 0.138, Tmax = 0.459 | k = −20→19 |
3265 measured reflections | l = −23→22 |
3265 independent reflections | 3 standard reflections every 120 min |
2965 reflections with I > 2σ(I) | intensity decay: 1.8% |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.039 | Calculated w = 1/[σ2(Fo2) + (0.0884P)2 + 1.4211P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.108 | (Δ/σ)max = 0.003 |
S = 1.03 | Δρmax = 0.67 e Å−3 |
3265 reflections | Δρmin = −0.69 e Å−3 |
329 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.0026 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.022 (15) |
Hydrogen site location: inferred from neighbouring sites |
[NiZnBr2(C3H7NO)2(C17H16N2O2)] | V = 2779.5 (19) Å3 |
Mr = 710.39 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.518 (3) Å | µ = 4.45 mm−1 |
b = 15.180 (8) Å | T = 295 K |
c = 17.618 (6) Å | 0.45 × 0.35 × 0.18 mm |
β = 98.85 (2)° |
Enraf-Nonius CAD-4 diffractometer | 2965 reflections with I > 2σ(I) |
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) | Rint = 0.000 |
Tmin = 0.138, Tmax = 0.459 | 3 standard reflections every 120 min |
3265 measured reflections | intensity decay: 1.8% |
3265 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.108 | Δρmax = 0.67 e Å−3 |
S = 1.03 | Δρmin = −0.69 e Å−3 |
3265 reflections | Absolute structure: Flack (1983) |
329 parameters | Absolute structure parameter: −0.022 (15) |
2 restraints |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni | 0.64193 (7) | 0.91396 (5) | 0.77186 (4) | 0.0396 (2) | |
Zn | 0.79252 (7) | 0.81928 (5) | 0.65962 (4) | 0.0446 (2) | |
Br1 | 0.91548 (10) | 0.90540 (7) | 0.58790 (5) | 0.0800 (3) | |
Br2 | 0.79871 (9) | 0.66467 (5) | 0.64511 (5) | 0.0710 (3) | |
O1 | 0.6151 (4) | 0.8620 (3) | 0.6653 (3) | 0.0457 (10) | |
O2 | 0.8143 (5) | 0.8580 (3) | 0.7688 (2) | 0.0454 (10) | |
O3 | 0.7040 (6) | 1.0340 (3) | 0.7270 (3) | 0.0574 (12) | |
O4 | 0.5741 (5) | 0.7978 (3) | 0.8213 (3) | 0.0544 (11) | |
N1 | 0.7040 (7) | 0.9582 (4) | 0.8796 (3) | 0.0531 (14) | |
N2 | 0.4576 (6) | 0.9561 (4) | 0.7579 (4) | 0.0534 (13) | |
N3 | 0.6839 (7) | 1.1356 (4) | 0.6319 (4) | 0.061 (2) | |
N4 | 0.5303 (6) | 0.6523 (4) | 0.8212 (4) | 0.0503 (13) | |
C1 | 0.9189 (7) | 0.8569 (4) | 0.8206 (4) | 0.0462 (14) | |
C2 | 1.0312 (9) | 0.8186 (6) | 0.8040 (6) | 0.069 (2) | |
C3 | 1.1428 (11) | 0.8190 (8) | 0.8592 (7) | 0.091 (3) | |
C4 | 1.1453 (11) | 0.8578 (9) | 0.9282 (6) | 0.090 (3) | |
C5 | 1.0365 (10) | 0.8951 (7) | 0.9466 (5) | 0.073 (2) | |
C6 | 0.9197 (8) | 0.8969 (5) | 0.8930 (4) | 0.053 (2) | |
C7 | 0.8141 (8) | 0.9425 (5) | 0.9179 (4) | 0.056 (2) | |
C8 | 0.6115 (10) | 1.0097 (6) | 0.9166 (6) | 0.072 (2) | |
C9 | 0.4781 (10) | 0.9760 (6) | 0.8999 (5) | 0.072 (2) | |
C10 | 0.4093 (10) | 1.0030 (7) | 0.8205 (5) | 0.075 (2) | |
C11 | 0.3761 (8) | 0.9422 (5) | 0.6977 (5) | 0.061 (2) | |
C12 | 0.3945 (7) | 0.9007 (4) | 0.6267 (4) | 0.051 (2) | |
C13 | 0.2887 (9) | 0.8975 (6) | 0.5682 (7) | 0.073 (3) | |
C14 | 0.2951 (10) | 0.8574 (6) | 0.4976 (6) | 0.075 (3) | |
C15 | 0.4067 (11) | 0.8192 (6) | 0.4865 (5) | 0.072 (3) | |
C16 | 0.5134 (9) | 0.8201 (4) | 0.5412 (4) | 0.055 (2) | |
C17 | 0.5101 (7) | 0.8610 (4) | 0.6121 (4) | 0.0441 (14) | |
C18 | 0.5848 (7) | 0.7228 (5) | 0.7965 (4) | 0.051 (2) | |
C19 | 0.6484 (7) | 1.0667 (5) | 0.6678 (4) | 0.054 (2) | |
C20A | 0.8243 (3) | 1.1555 (4) | 0.6412 (3) | 0.076 (13) | 0.41 (8) |
C20B | 0.7722 (7) | 1.1948 (3) | 0.6711 (3) | 0.130 (2) | 0.59 (8) |
C21 | 0.6097 (11) | 1.1721 (6) | 0.5622 (6) | 0.077 (2)* | |
C22 | 0.5507 (11) | 0.5661 (5) | 0.7894 (7) | 0.081 (3)* | |
C23 | 0.4509 (10) | 0.6556 (6) | 0.8796 (6) | 0.073 (2) | |
H2 | 1.0326 | 0.7926 | 0.7563 | 0.0830* | |
H3 | 1.2169 | 0.7918 | 0.8479 | 0.1090* | |
H4 | 1.2212 | 0.8591 | 0.9631 | 0.1070* | |
H5 | 1.0381 | 0.9200 | 0.9950 | 0.0870* | |
H7 | 0.8279 | 0.9632 | 0.9682 | 0.0670* | |
H11 | 0.2929 | 0.9617 | 0.6999 | 0.0730* | |
H13 | 0.2115 | 0.9228 | 0.5766 | 0.0880* | |
H14 | 0.2241 | 0.8570 | 0.4590 | 0.0900* | |
H15 | 0.4109 | 0.7913 | 0.4400 | 0.0860* | |
H16 | 0.5888 | 0.7934 | 0.5314 | 0.0660* | |
H18 | 0.6347 | 0.7154 | 0.7578 | 0.0610* | |
H19 | 0.5723 | 1.0395 | 0.6459 | 0.0640* | |
H81 | 0.6127 | 1.0704 | 0.8993 | 0.0860* | |
H82 | 0.6389 | 1.0093 | 0.9717 | 0.0860* | |
H91 | 0.4297 | 0.9978 | 0.9386 | 0.0860* | |
H92 | 0.4798 | 0.9122 | 0.9032 | 0.0860* | |
H101 | 0.3180 | 0.9915 | 0.8175 | 0.0900* | |
H102 | 0.4203 | 1.0659 | 0.8139 | 0.0900* | |
H201 | 0.8525 | 1.1538 | 0.5919 | 0.0910* | 0.41 (8) |
H202 | 0.8611 | 1.1149 | 0.6750 | 0.0910* | 0.41 (8) |
H203 | 0.8310 | 1.2151 | 0.6631 | 0.0910* | 0.41 (8) |
H204 | 0.7287 | 1.2483 | 0.6807 | 0.1550* | 0.59 (8) |
H205 | 0.8379 | 1.2075 | 0.6405 | 0.1550* | 0.59 (8) |
H206 | 0.8106 | 1.1692 | 0.7190 | 0.1550* | 0.59 (8) |
H211 | 0.6538 | 1.2224 | 0.5459 | 0.0920* | |
H212 | 0.5263 | 1.1896 | 0.5724 | 0.0920* | |
H213 | 0.6002 | 1.1283 | 0.5224 | 0.0920* | |
H221 | 0.5044 | 0.5226 | 0.8137 | 0.0970* | |
H222 | 0.6409 | 0.5524 | 0.7984 | 0.0970* | |
H223 | 0.5204 | 0.5664 | 0.7352 | 0.0970* | |
H231 | 0.4212 | 0.5974 | 0.8889 | 0.0880* | |
H232 | 0.3784 | 0.6932 | 0.8634 | 0.0880* | |
H233 | 0.4995 | 0.6785 | 0.9260 | 0.0880* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0392 (4) | 0.0380 (3) | 0.0424 (4) | 0.0006 (3) | 0.0091 (3) | 0.0014 (3) |
Zn | 0.0451 (4) | 0.0500 (4) | 0.0394 (3) | 0.0040 (3) | 0.0090 (3) | 0.0100 (3) |
Br1 | 0.0813 (7) | 0.0903 (6) | 0.0766 (5) | 0.0343 (5) | 0.0382 (5) | 0.0150 (5) |
Br2 | 0.0907 (7) | 0.0521 (4) | 0.0723 (5) | −0.0017 (3) | 0.0195 (5) | 0.0196 (4) |
O1 | 0.038 (2) | 0.054 (2) | 0.045 (2) | −0.001 (2) | 0.002 (2) | 0.007 (2) |
O2 | 0.040 (2) | 0.059 (2) | 0.036 (2) | 0.000 (2) | 0.005 (2) | 0.006 (2) |
O3 | 0.066 (3) | 0.045 (2) | 0.060 (3) | 0.011 (2) | 0.007 (3) | −0.006 (2) |
O4 | 0.061 (3) | 0.044 (2) | 0.060 (3) | 0.002 (2) | 0.016 (2) | −0.008 (2) |
N1 | 0.065 (4) | 0.045 (3) | 0.053 (3) | −0.005 (2) | 0.021 (3) | −0.009 (3) |
N2 | 0.039 (3) | 0.055 (3) | 0.069 (4) | 0.004 (3) | 0.019 (3) | 0.008 (3) |
N3 | 0.066 (4) | 0.047 (3) | 0.068 (4) | 0.018 (3) | 0.000 (3) | −0.006 (3) |
N4 | 0.040 (3) | 0.043 (3) | 0.068 (4) | 0.007 (2) | 0.005 (3) | −0.003 (2) |
C1 | 0.043 (4) | 0.048 (3) | 0.046 (3) | 0.014 (3) | 0.002 (3) | −0.001 (3) |
C2 | 0.049 (5) | 0.088 (6) | 0.067 (5) | 0.010 (4) | 0.001 (4) | 0.019 (4) |
C3 | 0.052 (5) | 0.117 (9) | 0.096 (8) | 0.014 (6) | −0.014 (6) | 0.016 (5) |
C4 | 0.056 (6) | 0.138 (9) | 0.064 (6) | 0.022 (6) | −0.024 (5) | −0.012 (6) |
C5 | 0.066 (6) | 0.091 (6) | 0.055 (4) | 0.010 (4) | −0.011 (4) | −0.022 (5) |
C6 | 0.050 (4) | 0.056 (4) | 0.050 (4) | 0.008 (3) | 0.000 (3) | −0.012 (3) |
C7 | 0.063 (5) | 0.055 (4) | 0.046 (3) | −0.003 (3) | 0.002 (3) | −0.018 (4) |
C8 | 0.082 (6) | 0.065 (5) | 0.072 (5) | −0.025 (4) | 0.023 (5) | −0.009 (5) |
C9 | 0.082 (6) | 0.071 (5) | 0.071 (5) | −0.010 (4) | 0.040 (5) | 0.003 (5) |
C10 | 0.066 (5) | 0.088 (6) | 0.077 (5) | −0.011 (4) | 0.030 (4) | 0.025 (5) |
C11 | 0.040 (4) | 0.048 (3) | 0.096 (6) | 0.016 (4) | 0.016 (4) | 0.007 (3) |
C12 | 0.042 (4) | 0.045 (3) | 0.063 (4) | 0.010 (3) | −0.002 (3) | −0.005 (3) |
C13 | 0.044 (4) | 0.067 (4) | 0.105 (7) | 0.025 (5) | −0.002 (5) | −0.003 (4) |
C14 | 0.069 (6) | 0.071 (5) | 0.073 (5) | 0.016 (4) | −0.029 (5) | −0.019 (5) |
C15 | 0.088 (7) | 0.065 (5) | 0.055 (4) | 0.001 (3) | −0.014 (5) | −0.018 (5) |
C16 | 0.064 (5) | 0.049 (3) | 0.048 (4) | 0.001 (3) | −0.008 (4) | −0.001 (3) |
C17 | 0.045 (4) | 0.034 (3) | 0.051 (3) | 0.004 (2) | −0.001 (3) | −0.008 (3) |
C18 | 0.048 (4) | 0.049 (3) | 0.056 (4) | 0.013 (3) | 0.009 (3) | 0.001 (3) |
C19 | 0.053 (4) | 0.049 (3) | 0.058 (4) | −0.001 (3) | 0.007 (3) | −0.006 (3) |
C20A | 0.062 (16) | 0.08 (3) | 0.081 (18) | 0.034 (18) | 0.004 (13) | −0.027 (13) |
C20B | 0.17 (4) | 0.085 (18) | 0.11 (2) | 0.035 (18) | −0.05 (3) | −0.06 (2) |
C21 | 0.077 (6) | 0.081 (5) | 0.069 (5) | 0.021 (4) | 0.004 (5) | −0.001 (5) |
C22 | 0.075 (6) | 0.045 (4) | 0.128 (9) | −0.002 (5) | 0.030 (6) | −0.007 (4) |
C23 | 0.067 (6) | 0.068 (5) | 0.088 (6) | 0.015 (4) | 0.024 (5) | −0.010 (4) |
Ni—Zn | 3.0738 (19) | C13—C14 | 1.40 (2) |
Br1—Zn | 2.3412 (18) | C14—C15 | 1.350 (2) |
Br2—Zn | 2.3628 (16) | C15—C16 | 1.362 (12) |
Zn—O1 | 1.993 (5) | C16—C17 | 1.400 (11) |
Zn—O2 | 1.991 (4) | C2—H2 | 0.9300 |
Ni—O1 | 2.016 (5) | C3—H3 | 0.9300 |
Ni—O2 | 2.010 (5) | C4—H4 | 0.9300 |
Ni—O3 | 2.128 (5) | C5—H5 | 0.9300 |
Ni—O4 | 2.137 (5) | C7—H7 | 0.9300 |
Ni—N1 | 2.025 (6) | C8—H81 | 0.9700 |
Ni—N2 | 2.020 (7) | C8—H82 | 0.9700 |
O1—C17 | 1.334 (9) | C9—H91 | 0.9700 |
O2—C1 | 1.317 (9) | C9—H92 | 0.9700 |
O3—C19 | 1.220 (9) | C10—H101 | 0.9700 |
O4—C18 | 1.231 (9) | C10—H102 | 0.9700 |
N1—C7 | 1.270 (11) | C11—H11 | 0.9300 |
N1—C8 | 1.476 (12) | C13—H13 | 0.9300 |
N2—C10 | 1.468 (12) | C14—H14 | 0.9300 |
N2—C11 | 1.275 (11) | C15—H15 | 0.9300 |
N3—C19 | 1.306 (10) | C16—H16 | 0.9300 |
N3—C21 | 1.459 (13) | C18—H18 | 0.9300 |
N3—C20A | 1.49 (3) | C19—H19 | 0.9300 |
N3—C20B | 1.40 (6) | C21—H211 | 0.9600 |
N4—C18 | 1.319 (10) | C21—H212 | 0.9600 |
N4—C22 | 1.452 (11) | C21—H213 | 0.9600 |
N4—C23 | 1.422 (13) | C22—H221 | 0.9600 |
C1—C2 | 1.387 (12) | C22—H222 | 0.9600 |
C1—C6 | 1.411 (11) | C22—H223 | 0.9600 |
C2—C3 | 1.406 (14) | C23—H231 | 0.9600 |
C3—C4 | 1.350 (2) | C23—H232 | 0.9600 |
C4—C5 | 1.360 (2) | C23—H233 | 0.9600 |
C5—C6 | 1.431 (12) | C20A—H201 | 0.9600 |
C6—C7 | 1.435 (12) | C20A—H202 | 0.9600 |
C8—C9 | 1.480 (14) | C20A—H203 | 0.9600 |
C9—C10 | 1.528 (13) | C20B—H204 | 0.9600 |
C11—C12 | 1.440 (11) | C20B—H205 | 0.9600 |
C12—C13 | 1.396 (13) | C20B—H206 | 0.9600 |
C12—C17 | 1.415 (11) | ||
Br1—Zn—Br2 | 118.01 (5) | C1—C2—H2 | 120.0 |
Br1—Zn—O1 | 116.41 (15) | C3—C2—H2 | 120.0 |
Br1—Zn—O2 | 111.45 (15) | C2—C3—H3 | 119.2 |
Br2—Zn—O1 | 111.73 (14) | C4—C3—H3 | 119.1 |
Br2—Zn—O2 | 113.38 (14) | C3—C4—H4 | 120.1 |
O1—Zn—O2 | 79.9 (2) | C5—C4—H4 | 120.1 |
O1—Ni—O2 | 78.89 (17) | C4—C5—H5 | 119.4 |
O1—Ni—O3 | 89.78 (19) | C6—C5—H5 | 119.3 |
O1—Ni—O4 | 92.81 (19) | N1—C7—H7 | 116.0 |
O1—Ni—N1 | 169.0 (2) | C6—C7—H7 | 116.1 |
O1—Ni—N2 | 90.9 (2) | N1—C8—H81 | 108.8 |
O2—Ni—O3 | 91.3 (2) | N1—C8—H82 | 108.9 |
O2—Ni—O4 | 91.22 (19) | C9—C8—H81 | 108.9 |
O2—Ni—N1 | 90.2 (2) | C9—C8—H82 | 108.9 |
O2—Ni—N2 | 169.4 (2) | H81—C8—H82 | 107.7 |
O3—Ni—O4 | 176.7 (2) | C8—C9—H91 | 109.1 |
O3—Ni—N1 | 89.5 (2) | C8—C9—H92 | 109.0 |
O3—Ni—N2 | 91.6 (2) | C10—C9—H91 | 109.0 |
O4—Ni—N1 | 88.4 (2) | C10—C9—H92 | 108.9 |
O4—Ni—N2 | 86.4 (2) | H91—C9—H92 | 107.8 |
N1—Ni—N2 | 100.0 (3) | N2—C10—H101 | 109.0 |
Zn—O1—Ni | 100.1 (2) | N2—C10—H102 | 109.0 |
Zn—O1—C17 | 129.9 (4) | C9—C10—H101 | 109.1 |
Ni—O1—C17 | 129.9 (4) | C9—C10—H102 | 109.0 |
Zn—O2—Ni | 100.4 (2) | H101—C10—H102 | 107.8 |
Zn—O2—C1 | 128.7 (4) | N2—C11—H11 | 115.4 |
Ni—O2—C1 | 130.3 (4) | C12—C11—H11 | 115.4 |
Ni—O3—C19 | 122.1 (5) | C12—C13—H13 | 119.0 |
Ni—O4—C18 | 124.3 (5) | C14—C13—H13 | 119.0 |
Ni—N1—C7 | 124.9 (5) | C13—C14—H14 | 120.8 |
Ni—N1—C8 | 116.8 (6) | C15—C14—H14 | 120.6 |
C7—N1—C8 | 118.3 (7) | C14—C15—H15 | 118.9 |
Ni—N2—C10 | 119.9 (6) | C16—C15—H15 | 118.8 |
Ni—N2—C11 | 124.0 (6) | C15—C16—H16 | 119.8 |
C10—N2—C11 | 116.1 (7) | C17—C16—H16 | 119.8 |
C19—N3—C21 | 123.8 (7) | O4—C18—H18 | 117.7 |
C19—N3—C20B | 120.0 (2) | N4—C18—H18 | 117.9 |
C19—N3—C20A | 118.0 (2) | O3—C19—H19 | 116.3 |
C21—N3—C20B | 113.0 (2) | N3—C19—H19 | 116.5 |
C21—N3—C20A | 114.0 (2) | N3—C21—H211 | 109.5 |
C18—N4—C22 | 120.4 (7) | N3—C21—H212 | 109.5 |
C18—N4—C23 | 122.9 (7) | N3—C21—H213 | 109.5 |
C22—N4—C23 | 116.7 (7) | H211—C21—H212 | 109.5 |
O2—C1—C2 | 120.4 (7) | H211—C21—H213 | 109.5 |
O2—C1—C6 | 120.6 (7) | H212—C21—H213 | 109.5 |
C2—C1—C6 | 118.9 (7) | N4—C22—H221 | 109.4 |
C1—C2—C3 | 120.0 (9) | N4—C22—H222 | 109.4 |
C2—C3—C4 | 121.7 (11) | N4—C22—H223 | 109.5 |
C3—C4—C5 | 119.8 (10) | H221—C22—H222 | 109.5 |
C4—C5—C6 | 121.3 (8) | H221—C22—H223 | 109.5 |
C1—C6—C5 | 118.3 (8) | H222—C22—H223 | 109.5 |
C1—C6—C7 | 125.9 (7) | N4—C23—H231 | 109.5 |
C5—C6—C7 | 115.8 (7) | N4—C23—H232 | 109.5 |
N1—C7—C6 | 127.9 (7) | N4—C23—H233 | 109.5 |
N1—C8—C9 | 113.5 (8) | H231—C23—H232 | 109.5 |
C8—C9—C10 | 113.0 (8) | H231—C23—H233 | 109.4 |
N2—C10—C9 | 112.8 (8) | H232—C23—H233 | 109.4 |
N2—C11—C12 | 129.2 (8) | N3—C20A—H202 | 109.0 |
C11—C12—C13 | 117.3 (7) | N3—C20A—H203 | 110.0 |
C11—C12—C17 | 125.3 (7) | H201—C20A—H202 | 108.0 |
C13—C12—C17 | 117.4 (7) | H201—C20A—H203 | 110.0 |
C12—C13—C14 | 122.1 (9) | H202—C20A—H203 | 110.0 |
C13—C14—C15 | 118.6 (9) | N3—C20A—H201 | 110.0 |
C14—C15—C16 | 122.2 (9) | H205—C20B—H206 | 109.0 |
C15—C16—C17 | 120.3 (8) | N3—C20B—H204 | 110.0 |
O1—C17—C12 | 120.6 (6) | N3—C20B—H205 | 110.0 |
O1—C17—C16 | 120.0 (7) | N3—C20B—H206 | 109.0 |
C12—C17—C16 | 119.4 (7) | H204—C20B—H205 | 110.0 |
O4—C18—N4 | 124.4 (7) | H204—C20B—H206 | 109.0 |
O3—C19—N3 | 127.2 (8) | ||
Br1—Zn—O1—Ni | −102.85 (17) | O4—Ni—N1—C8 | −89.1 (6) |
Br2—Zn—O1—Ni | 117.48 (15) | O1—Ni—N2—C10 | 179.4 (7) |
O2—Zn—O1—Ni | 6.20 (19) | O3—Ni—N2—C10 | −90.8 (6) |
Br1—Zn—O1—C17 | 73.8 (5) | O4—Ni—N2—C10 | 86.7 (6) |
Br2—Zn—O1—C17 | −65.9 (5) | O3—Ni—N2—C11 | 91.6 (6) |
O2—Zn—O1—C17 | −177.2 (5) | O4—Ni—N2—C11 | −91.0 (6) |
O1—Zn—O2—Ni | −6.22 (19) | N1—Ni—N2—C11 | −178.7 (6) |
Br1—Zn—O2—Ni | 108.33 (17) | Zn—O1—C17—C12 | −175.6 (4) |
Br2—Zn—O2—Ni | −115.66 (15) | Ni—O1—C17—C16 | −179.6 (5) |
O1—Zn—O2—C1 | −178.4 (5) | Zn—O2—C1—C2 | −5.7 (9) |
Br1—Zn—O2—C1 | −63.9 (5) | Ni—O2—C1—C2 | −175.7 (6) |
Br2—Zn—O2—C1 | 72.1 (5) | Zn—O2—C1—C6 | 172.4 (5) |
O2—Ni—O1—Zn | −6.16 (19) | Ni—O3—C19—N3 | −173.9 (6) |
O3—Ni—O1—Zn | 85.2 (2) | Ni—O4—C18—N4 | −171.8 (5) |
O4—Ni—O1—Zn | −96.8 (2) | Ni—N1—C8—C9 | 38.6 (9) |
N2—Ni—O1—Zn | 176.7 (2) | C7—N1—C8—C9 | −139.2 (8) |
O2—Ni—O1—C17 | 177.2 (5) | C8—N1—C7—C6 | −177.7 (8) |
O3—Ni—O1—C17 | −91.4 (5) | Ni—N1—C7—C6 | 4.7 (12) |
O4—Ni—O1—C17 | 86.5 (5) | Ni—N2—C10—C9 | −28.8 (10) |
O1—Ni—O2—Zn | 6.17 (19) | C10—N2—C11—C12 | 178.1 (8) |
O3—Ni—O2—Zn | −83.4 (2) | C11—N2—C10—C9 | 149.0 (8) |
O4—Ni—O2—Zn | 98.8 (2) | Ni—N2—C11—C12 | −4.2 (12) |
N1—Ni—O2—Zn | −172.8 (2) | C20B—N3—C19—O3 | −19 (3) |
O1—Ni—O2—C1 | 178.2 (6) | C21—N3—C19—O3 | −178.2 (8) |
O3—Ni—O2—C1 | 88.7 (5) | C22—N4—C18—O4 | −178.7 (8) |
O4—Ni—O2—C1 | −89.2 (5) | O2—C1—C6—C5 | −178.9 (7) |
O1—Ni—O3—C19 | 43.4 (6) | O2—C1—C2—C3 | 179.0 (8) |
O2—Ni—O3—C19 | 122.3 (6) | C2—C1—C6—C7 | 177.1 (8) |
N1—Ni—O3—C19 | −147.5 (6) | C4—C5—C6—C7 | −176.6 (10) |
N2—Ni—O3—C19 | −47.5 (6) | C5—C6—C7—N1 | 175.1 (8) |
O1—Ni—O4—C18 | 30.2 (6) | N1—C8—C9—C10 | −78.7 (10) |
O2—Ni—O4—C18 | −48.7 (6) | C8—C9—C10—N2 | 72.1 (10) |
N1—Ni—O4—C18 | −138.9 (6) | N2—C11—C12—C17 | 4.5 (13) |
N2—Ni—O4—C18 | 121.0 (6) | N2—C11—C12—C13 | −177.2 (8) |
O3—Ni—N1—C7 | −93.9 (6) | C11—C12—C17—C16 | 177.7 (7) |
O4—Ni—N1—C7 | 88.6 (6) | C13—C12—C17—O1 | 179.7 (6) |
N2—Ni—N1—C7 | 174.6 (6) | C11—C12—C13—C14 | −178.8 (8) |
O2—Ni—N1—C8 | 179.7 (6) | C15—C16—C17—O1 | −179.7 (7) |
O3—Ni—N1—C8 | 88.4 (6) |
Experimental details
Crystal data | |
Chemical formula | [NiZnBr2(C3H7NO)2(C17H16N2O2)] |
Mr | 710.39 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 295 |
a, b, c (Å) | 10.518 (3), 15.180 (8), 17.618 (6) |
β (°) | 98.85 (2) |
V (Å3) | 2779.5 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.45 |
Crystal size (mm) | 0.45 × 0.35 × 0.18 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990) |
Tmin, Tmax | 0.138, 0.459 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3265, 3265, 2965 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.108, 1.03 |
No. of reflections | 3265 |
No. of parameters | 329 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.69 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.022 (15) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1993), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON99 (Spek, 1999), SHELXL97.
Ni—Zn | 3.0738 (19) | Ni—O3 | 2.128 (5) |
Br1—Zn | 2.3412 (18) | Ni—O4 | 2.137 (5) |
Br2—Zn | 2.3628 (16) | Ni—N1 | 2.025 (6) |
Zn—O1 | 1.993 (5) | Ni—N2 | 2.020 (7) |
Zn—O2 | 1.991 (4) | N3—C20A | 1.49 (3) |
Ni—O1 | 2.016 (5) | N3—C20B | 1.40 (6) |
Ni—O2 | 2.010 (5) | ||
Br1—Zn—Br2 | 118.01 (5) | Ni—O3—C19 | 122.1 (5) |
Br1—Zn—O1 | 116.41 (15) | Ni—O4—C18 | 124.3 (5) |
Br1—Zn—O2 | 111.45 (15) | Ni—N1—C7 | 124.9 (5) |
Br2—Zn—O1 | 111.73 (14) | Ni—N1—C8 | 116.8 (6) |
Br2—Zn—O2 | 113.38 (14) | C7—N1—C8 | 118.3 (7) |
O1—Zn—O2 | 79.9 (2) | Ni—N2—C10 | 119.9 (6) |
O1—Ni—O2 | 78.89 (17) | Ni—N2—C11 | 124.0 (6) |
O1—Ni—O3 | 89.78 (19) | C10—N2—C11 | 116.1 (7) |
O1—Ni—O4 | 92.81 (19) | C19—N3—C21 | 123.8 (7) |
O1—Ni—N1 | 169.0 (2) | C19—N3—C20B | 120.0 (2) |
O1—Ni—N2 | 90.9 (2) | C19—N3—C20A | 118.0 (2) |
O2—Ni—O3 | 91.3 (2) | C21—N3—C20B | 113.0 (2) |
O2—Ni—O4 | 91.22 (19) | C21—N3—C20A | 114.0 (2) |
O2—Ni—N1 | 90.2 (2) | C18—N4—C22 | 120.4 (7) |
O2—Ni—N2 | 169.4 (2) | C18—N4—C23 | 122.9 (7) |
O3—Ni—O4 | 176.7 (2) | C22—N4—C23 | 116.7 (7) |
O3—Ni—N1 | 89.5 (2) | O2—C1—C2 | 120.4 (7) |
O3—Ni—N2 | 91.6 (2) | O2—C1—C6 | 120.6 (7) |
O4—Ni—N1 | 88.4 (2) | N1—C7—C6 | 127.9 (7) |
O4—Ni—N2 | 86.4 (2) | N1—C8—C9 | 113.5 (8) |
N1—Ni—N2 | 100.0 (3) | N2—C10—C9 | 112.8 (8) |
Zn—O1—Ni | 100.1 (2) | N2—C11—C12 | 129.2 (8) |
Zn—O1—C17 | 129.9 (4) | O1—C17—C12 | 120.6 (6) |
Ni—O1—C17 | 129.9 (4) | O1—C17—C16 | 120.0 (7) |
Zn—O2—Ni | 100.4 (2) | O4—C18—N4 | 124.4 (7) |
Zn—O2—C1 | 128.7 (4) | O3—C19—N3 | 127.2 (8) |
Ni—O2—C1 | 130.3 (4) |
N,N'-bis(salicylidene)-1,3-propanediamine is quite an interesting ligand, and has appeared in the literature of coordination chemistry for 50 years. The complexes formed between this ligand and first row transition metals tend toward µ-bridging in nonaqueous media with Lewis acids. Consequently di-, tri- and even polynuclear complexes are formed.
At present, the magnetic properties of homo- and heteropolynuclear compounds are not clearly understood, but these properties are currently under investigation (Meenakumari et al., 1993; Tuna et al., 1999).
Nickel often exhibits interesting magnetic properties, and Zn has biological importance and is an essential element for living beings. In this study, ZnBr2 was added to the square-planar complex of N,N'-bis-(salicylidene)-1,3-propanediamine and nickel(II) (Drew et al., 1985) to form a heterodinuclear complex. In a previous study, we prepared a similar Ni—Zn complex via the reaction of N,N'-bis(salicylidene)-1,3-propanediaminato nickel(II) as a Lewis acid with 3,5-dimethylpyridine and ZnI2, and the resulting molecular structure was reported (Arıcı et al., 1999). This previous dinuclear complex included two 3,5-dimethylpyridine molecules coordinated to the nickel(II) at the axial position to complete the octahedral coordination. The present structure, (I), is very similar to the aforesaid complex, except that no pyridine derivatives are added and the six-coordination of NiII is completed by dimethylformamide solvent molecules. \sch
As seen in Fig.1, the coordination environments of the metals are common ones, i.e. octahedral for NiII and tetrahedral for ZnII, even though the NiII starting material was a square-planar complex (Sogo et al., 1988; Greenwood et al., 1994). The transformation is aided by the Lewis basicity of the ZnII bromide, such that electron density is drawn away from the phenolic O atoms. The reduced electron density at the NiII center thus promotes axial coordination of solvent molecules such as 3,5-dimethylpyridine in the previous case or the DMF solvent in the present one. In each case the structure includes one octahedron and one tetrahedron which share one edge.
The distances from Ni to atoms N1 and N2 are essentially the same as those in the 3,5-dimethylpyridine complex (within 1σ), but the Ni–O1 and Ni–O2 distances [2.016 (5) and 2.010 (5) Å] are significantly shorter than the corresponding distances in the 3,5-dimethylpyridine complex [2.039 (3) and 2.030 (3) Å], probably due to the difference in the halide bonded to Zn. The coordination around the nickel and zinc atoms are quite distorted from ideal octahedral and ideal tetrahedral geometries due to the constraints imposed by the chelating ligands. The Ni—O(axial) distances are 2.128 (5) and 2.137 (5) Å. The distances between the two metals is 3.0738 (19) Å, which is shorter in comparison to some similar complexes (Ercan et al., 1998).
The complex is stable up to 423 K (the approximate boiling point of N,N-dimethylformamide). Thermogravimetric analysis results indicate a loss of dimethylformamide at this temperature, followed by irregular decomposition with increasing temperature.
The average Ni—O, Ni—N, and Zn—Br bond lengths are 2.07 (3), 2.023 (4) and 2.35 (1) Å, respectively, which are in agreement with values reported previously for NiII complexes (Ercan et al., 1998). Atom Ni is 0.0188 (3) Å out of the least-squares plane defined by O1, O2, N1, and N2. The dihedral angle between the planes of the two chelating moieties (O2, C1, C6, C7, N1 and O1, C17, C12, C11, N2) is 3.2 (3)°. Atom C20 is disordered; the atom with suffix A has occupancy 0.41 (8).
All the chelate rings around Ni, except for one, are planar. The Ni—N1—C8—C9—C10—N2 ring is in a half-chair conformation. The Ni—O1—Zn—O2 ring is planar within 0.05 Å, as it is in similar complexes.