Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100019983/ta1298sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100019983/ta1298Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100019983/ta1298sup3.pdf |
CCDC reference: 162557
N,N'-Bis(salicylidene)-1,3-propanediamine (0.564 g, 2 mmol) was dissolved in methanol (250 ml) by heating to boiling point. A solution of Zn(CH3COO)2·2H2O (0.660 g, 3 mmol) in hot methanol (100 ml) was added to the solution. The resulting mixture was set aside for 1 d and the colourless prismatic crystals of (I) which formed were filtered off and dried in air.
The H atoms of C19 were taken from a difference map, while the other H atoms were placed geometrically 0.95 Å from their parent atoms. For all H atoms a riding model was used, with Ueq(H) = 1.3Ueq(C).
Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: MolEN; program(s) used to refine structure: MolEN; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: MolEN and PLATON99 (Spek, 1990).
[Zn{Zn(CH3COO)(C17H16N2O2)}2] | F(000) = 896 |
Mr = 874.91 | Dx = 1.640 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.4243 (14) Å | Cell parameters from 25 reflections |
b = 20.3334 (18) Å | θ = 8.6–11.4° |
c = 8.3832 (11) Å | µ = 2.07 mm−1 |
β = 85.639 (13)° | T = 295 K |
V = 1771.8 (4) Å3 | Prismatic, colourless |
Z = 2 | 0.20 × 0.10 × 0.05 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.033 |
ω/2θ scans | θmax = 26.7° |
Absorption correction: ψ-scan (MolEN; Fair, 1990) | h = 0→13 |
Tmin = 0.798, Tmax = 0.902 | k = 0→25 |
4101 measured reflections | l = −10→10 |
3724 independent reflections | 3 standard reflections every 120 min |
2514 reflections with I > 2σ(I) | intensity decay: 0.036% |
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | Weighting scheme based on measured s.u.'s w = 1/[σ2(F) + (0.02F)2 + 0.25] |
wR(F2) = 0.056 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.84 e Å−3 |
2514 reflections | Δρmin = −0.23 e Å−3 |
241 parameters |
[Zn{Zn(CH3COO)(C17H16N2O2)}2] | V = 1771.8 (4) Å3 |
Mr = 874.91 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.4243 (14) Å | µ = 2.07 mm−1 |
b = 20.3334 (18) Å | T = 295 K |
c = 8.3832 (11) Å | 0.20 × 0.10 × 0.05 mm |
β = 85.639 (13)° |
Enraf-Nonius CAD-4 diffractometer | 2514 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (MolEN; Fair, 1990) | Rint = 0.033 |
Tmin = 0.798, Tmax = 0.902 | 3 standard reflections every 120 min |
4101 measured reflections | intensity decay: 0.036% |
3724 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 241 parameters |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.84 e Å−3 |
2514 reflections | Δρmin = −0.23 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0 | 0 | 0 | 0.0331 (3) | |
Zn2 | 0.20732 (6) | −0.10627 (3) | −0.01408 (8) | 0.0318 (2) | |
O1 | 0.1971 (3) | −0.0079 (2) | −0.0694 (5) | 0.0371 (12) | |
O2 | 0.0194 (3) | −0.1004 (2) | −0.0623 (5) | 0.0375 (12) | |
O3 | 0.0485 (4) | −0.0264 (2) | 0.2330 (5) | 0.0414 (12) | |
O4 | 0.1920 (4) | −0.1076 (2) | 0.2222 (5) | 0.0403 (12) | |
N1 | 0.4031 (4) | −0.0999 (2) | −0.0678 (5) | 0.0357 (14) | |
N2 | 0.2087 (4) | −0.2043 (2) | −0.0812 (6) | 0.0344 (12) | |
C1 | 0.2764 (5) | 0.0260 (3) | −0.1667 (6) | 0.0337 (16) | |
C2 | 0.2396 (6) | 0.0872 (3) | −0.2279 (7) | 0.0417 (17) | |
C3 | 0.3210 (7) | 0.1228 (3) | −0.3307 (8) | 0.0488 (19) | |
C4 | 0.4429 (6) | 0.1007 (3) | −0.3766 (8) | 0.0529 (19) | |
C5 | 0.4846 (6) | 0.0440 (3) | −0.3142 (8) | 0.0487 (19) | |
C6 | 0.4047 (5) | 0.0053 (3) | −0.2089 (7) | 0.0368 (17) | |
C7 | 0.4598 (5) | −0.0535 (3) | −0.1464 (7) | 0.0409 (18) | |
C8 | 0.4799 (5) | −0.1548 (3) | −0.0147 (8) | 0.0453 (17) | |
C9 | 0.4490 (5) | −0.2178 (3) | −0.0981 (8) | 0.0469 (19) | |
C10 | 0.3184 (6) | −0.2473 (3) | −0.0455 (8) | 0.0459 (19) | |
C11 | 0.1204 (5) | −0.2324 (3) | −0.1555 (7) | 0.0368 (17) | |
C12 | 0.0010 (5) | −0.2032 (3) | −0.2001 (6) | 0.0335 (17) | |
C13 | −0.0726 (6) | −0.2437 (3) | −0.2937 (7) | 0.0431 (17) | |
C14 | −0.1892 (6) | −0.2228 (3) | −0.3416 (7) | 0.051 (2) | |
C15 | −0.2337 (6) | −0.1621 (3) | −0.2938 (7) | 0.0476 (19) | |
C16 | −0.1652 (5) | −0.1210 (3) | −0.2007 (7) | 0.0420 (17) | |
C17 | −0.0447 (5) | −0.1405 (3) | −0.1523 (6) | 0.0305 (12) | |
C18 | 0.1187 (6) | −0.0673 (3) | 0.2970 (7) | 0.0410 (17) | |
C19 | 0.1194 (9) | −0.0697 (5) | 0.4764 (8) | 0.088 (3) | |
H2 | 0.156 | 0.104 | −0.197 | 0.0532 | |
H3 | 0.292 | 0.163 | −0.372 | 0.0646 | |
H4 | 0.497 | 0.125 | −0.451 | 0.0671 | |
H5 | 0.570 | 0.029 | −0.343 | 0.0633 | |
H7 | 0.550 | −0.058 | −0.166 | 0.0519 | |
H11 | 0.135 | −0.277 | −0.185 | 0.0494 | |
H13 | −0.041 | −0.286 | −0.324 | 0.0557 | |
H14 | −0.238 | −0.250 | −0.407 | 0.0659 | |
H15 | −0.315 | −0.148 | −0.326 | 0.0633 | |
H16 | −0.199 | −0.079 | −0.169 | 0.0545 | |
H81 | 0.462 | −0.160 | 0.097 | 0.0595 | |
H82 | 0.569 | −0.145 | −0.037 | 0.0595 | |
H91 | 0.513 | −0.249 | −0.078 | 0.0621 | |
H92 | 0.451 | −0.209 | −0.210 | 0.0621 | |
H101 | 0.310 | −0.288 | −0.099 | 0.0595 | |
H102 | 0.315 | −0.255 | 0.067 | 0.0595 | |
H191 | 0.176 | −0.104 | 0.505 | 0.1039 | |
H192 | 0.146 | −0.029 | 0.512 | 0.1039 | |
H193 | 0.034 | −0.079 | 0.522 | 0.1039 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0265 (4) | 0.0290 (4) | 0.0434 (5) | 0.0062 (4) | 0.0009 (4) | −0.0026 (4) |
Zn2 | 0.0265 (2) | 0.0285 (3) | 0.0399 (3) | 0.0057 (3) | 0.0002 (2) | −0.0019 (3) |
O1 | 0.028 (2) | 0.029 (2) | 0.053 (2) | 0.008 (2) | 0.006 (2) | 0.006 (2) |
O2 | 0.030 (2) | 0.032 (2) | 0.051 (2) | 0.006 (2) | −0.006 (2) | −0.013 (2) |
O3 | 0.043 (2) | 0.040 (2) | 0.041 (2) | 0.004 (2) | −0.001 (2) | 0.001 (2) |
O4 | 0.042 (2) | 0.033 (2) | 0.045 (2) | 0.010 (2) | 0.003 (2) | 0.001 (2) |
N1 | 0.030 (2) | 0.032 (2) | 0.044 (2) | 0.003 (2) | −0.003 (2) | −0.003 (2) |
N2 | 0.029 (2) | 0.027 (2) | 0.047 (2) | 0.007 (2) | −0.001 (2) | −0.002 (2) |
C1 | 0.031 (2) | 0.035 (3) | 0.035 (3) | −0.004 (2) | −0.002 (2) | −0.003 (2) |
C2 | 0.040 (3) | 0.037 (3) | 0.048 (3) | 0.003 (3) | −0.002 (3) | 0.003 (3) |
C3 | 0.058 (4) | 0.039 (3) | 0.050 (3) | −0.006 (3) | −0.008 (3) | 0.005 (3) |
C4 | 0.054 (3) | 0.051 (4) | 0.051 (3) | −0.013 (3) | 0.013 (3) | 0.003 (3) |
C5 | 0.038 (3) | 0.043 (3) | 0.063 (4) | −0.006 (3) | 0.009 (3) | −0.006 (3) |
C6 | 0.034 (3) | 0.035 (3) | 0.041 (3) | −0.003 (2) | −0.001 (2) | −0.009 (2) |
C7 | 0.021 (2) | 0.047 (3) | 0.054 (3) | −0.001 (2) | 0.000 (2) | −0.012 (3) |
C8 | 0.030 (3) | 0.049 (3) | 0.057 (3) | 0.009 (3) | −0.010 (3) | −0.000 (3) |
C9 | 0.033 (3) | 0.040 (3) | 0.068 (4) | 0.014 (3) | −0.005 (3) | −0.005 (3) |
C10 | 0.040 (3) | 0.037 (3) | 0.061 (4) | 0.008 (3) | −0.006 (3) | 0.002 (3) |
C11 | 0.037 (3) | 0.026 (3) | 0.046 (3) | 0.004 (2) | 0.006 (2) | −0.003 (2) |
C12 | 0.038 (3) | 0.028 (3) | 0.035 (3) | −0.003 (2) | 0.000 (2) | 0.001 (2) |
C13 | 0.045 (3) | 0.038 (3) | 0.046 (3) | −0.005 (3) | −0.002 (3) | −0.005 (3) |
C14 | 0.051 (3) | 0.055 (4) | 0.047 (3) | −0.004 (3) | −0.012 (3) | −0.012 (3) |
C15 | 0.035 (3) | 0.061 (4) | 0.047 (3) | 0.001 (3) | −0.011 (2) | −0.007 (3) |
C16 | 0.032 (3) | 0.042 (3) | 0.050 (3) | 0.005 (2) | −0.003 (2) | −0.006 (3) |
C17 | 0.030 (2) | 0.030 (2) | 0.031 (2) | −0.005 (2) | −0.000 (2) | 0.003 (2) |
C18 | 0.041 (3) | 0.042 (3) | 0.039 (3) | 0.004 (3) | 0.003 (2) | 0.001 (3) |
C19 | 0.107 (6) | 0.113 (6) | 0.043 (4) | 0.059 (5) | 0.000 (4) | −0.002 (4) |
Zn1—Zn2 | 3.0520 (8) | C6—C7 | 1.442 (8) |
Zn1—O1 | 2.098 (3) | C7—H7 | 0.95 |
Zn1—O2 | 2.113 (4) | C8—C9 | 1.507 (9) |
Zn1—O3 | 2.124 (4) | C8—H81 | 0.95 |
Zn2—O1 | 2.057 (4) | C8—H82 | 0.95 |
Zn2—O2 | 2.034 (4) | C9—C10 | 1.522 (8) |
Zn2—O4 | 1.975 (4) | C9—H91 | 0.95 |
Zn2—N1 | 2.060 (4) | C9—H92 | 0.95 |
Zn2—N2 | 2.071 (4) | C10—H101 | 0.95 |
O1—C1 | 1.312 (6) | C10—H102 | 0.95 |
O2—C17 | 1.325 (6) | C11—C12 | 1.453 (8) |
O3—C18 | 1.254 (7) | C11—H11 | 0.95 |
O4—C18 | 1.256 (7) | C12—C13 | 1.405 (8) |
N1—C7 | 1.271 (7) | C12—C17 | 1.409 (7) |
N1—C8 | 1.463 (7) | C13—C14 | 1.376 (9) |
N2—C10 | 1.487 (7) | C13—H13 | 0.95 |
N2—C11 | 1.284 (7) | C14—C15 | 1.369 (9) |
C1—C2 | 1.410 (8) | C14—H14 | 0.95 |
C1—C6 | 1.421 (7) | C15—C16 | 1.379 (9) |
C2—C3 | 1.369 (9) | C15—H15 | 0.95 |
C2—H2 | 0.95 | C16—C17 | 1.407 (8) |
C3—C4 | 1.376 (9) | C16—H16 | 0.95 |
C3—H3 | 0.95 | C18—C19 | 1.505 (9) |
C4—C5 | 1.351 (9) | C19—H191 | 0.947 |
C4—H4 | 0.95 | C19—H192 | 0.934 |
C5—C6 | 1.407 (8) | C19—H193 | 0.959 |
C5—H5 | 0.95 | ||
O1—Zn1—O2 | 77.5 (1) | C1—C6—C5 | 119.5 (5) |
O1—Zn1—O3 | 86.5 (1) | C1—C6—C7 | 123.2 (5) |
O2—Zn1—O3 | 87.6 (2) | C5—C6—C7 | 117.2 (5) |
O1—Zn1—O1i | 180.0 | N1—C7—C6 | 128.4 (5) |
O1—Zn1—O2i | 102.5 (1) | N1—C7—H7 | 115.8 |
O1—Zn1—O3i | 93.5 (2) | C6—C7—H7 | 115.8 |
O2—Zn1—O2i | 180.0 | N1—C8—C9 | 111.5 (5) |
O2—Zn1—O3i | 92.4 (2) | N1—C8—H81 | 108.9 |
O3—Zn1—O3i | 180.0 | N1—C8—H82 | 109.0 |
O1—Zn2—O2 | 80.3 (1) | C9—C8—H81 | 108.9 |
O1—Zn2—O4 | 103.7 (2) | C9—C8—H82 | 109.0 |
O1—Zn2—N1 | 87.5 (2) | H81—C8—H82 | 109.5 |
O1—Zn2—N2 | 150.9 (2) | C8—C9—C10 | 114.8 (5) |
O2—Zn2—O4 | 101.2 (2) | C8—C9—H91 | 108.1 |
O2—Zn2—N1 | 155.0 (2) | C8—C9—H92 | 108.1 |
O2—Zn2—N2 | 89.4 (2) | C10—C9—H91 | 108.2 |
O4—Zn2—N1 | 102.9 (2) | C10—C9—H92 | 108.2 |
O4—Zn2—N2 | 104.9 (2) | H91—C9—H92 | 109.5 |
N1—Zn2—N2 | 90.9 (2) | N2—C10—C9 | 113.3 (5) |
Zn1—O1—Zn2 | 94.5 (1) | N2—C10—H101 | 108.5 |
Zn1—O1—C1 | 133.6 (3) | N2—C10—H102 | 108.6 |
Zn2—O1—C1 | 127.6 (3) | C9—C10—H101 | 108.4 |
Zn1—O2—Zn2 | 94.8 (2) | C9—C10—H102 | 108.5 |
Zn1—O2—C17 | 133.8 (3) | H101—C10—H102 | 109.5 |
Zn2—O2—C17 | 127.7 (3) | N2—C11—C12 | 127.1 (5) |
Zn1—O3—C18 | 138.4 (4) | N2—C11—H11 | 116.5 |
Zn2—O4—C18 | 119.5 (4) | C12—C11—H11 | 116.4 |
O3—C18—O4 | 124.9 (5) | C11—C12—C13 | 114.7 (5) |
O3—C18—C19 | 119.7 (6) | C11—C12—C17 | 125.1 (5) |
O4—C18—C19 | 115.4 (6) | C13—C12—C17 | 120.2 (5) |
Zn2—N1—C7 | 125.0 (4) | C12—C13—C14 | 120.9 (6) |
Zn2—N1—C8 | 116.2 (3) | C12—C13—H13 | 119.4 |
C7—N1—C8 | 118.7 (4) | C14—C13—H13 | 119.7 |
Zn2—N2—C10 | 120.0 (4) | C13—C14—C15 | 118.7 (6) |
Zn2—N2—C11 | 124.7 (4) | C13—C14—H14 | 120.7 |
C10—N2—C11 | 115.3 (5) | C15—C14—H14 | 120.6 |
O1—C1—C2 | 121.0 (5) | C14—C15—C16 | 122.3 (6) |
O1—C1—C6 | 122.4 (5) | C14—C15—H15 | 118.8 |
C2—C1—C6 | 116.5 (5) | C16—C15—H15 | 119.0 |
C1—C2—C3 | 121.6 (5) | C15—C16—C17 | 120.3 (5) |
C1—C2—H2 | 118.8 | C15—C16—H16 | 120.1 |
C3—C2—H2 | 119.6 | C17—C16—H16 | 119.6 |
C2—C3—C4 | 121.2 (6) | O2—C17—C12 | 123.0 (5) |
C2—C3—H3 | 119.3 | O2—C17—C16 | 119.4 (5) |
C4—C3—H3 | 119.5 | C12—C17—C16 | 117.6 (5) |
C3—C4—C5 | 119.3 (6) | C18—C19—H191 | 108.9 |
C3—C4—H4 | 120.3 | C18—C19—H192 | 108.5 |
C5—C4—H4 | 120.4 | C18—C19—H193 | 109.3 |
C4—C5—C6 | 121.8 (6) | H191—C19—H192 | 111.1 |
C4—C5—H5 | 119.4 | H191—C19—H193 | 109.0 |
C6—C5—H5 | 118.9 | H192—C19—H193 | 110.1 |
O2—Zn1—O1—Zn2 | −26.4 (1) | O1—Zn2—N2—C10 | 123.6 (4) |
O2—Zn1—O1—C1 | 130.5 (5) | O1—Zn2—N2—C11 | −55.6 (6) |
O3—Zn1—O1—Zn2 | 61.9 (2) | O2—Zn2—N2—C10 | −167.9 (4) |
O3—Zn1—O1—C1 | −141.2 (5) | O2—Zn2—N2—C11 | 12.9 (5) |
O1—Zn1—O2—Zn2 | 26.7 (2) | O4—Zn2—N2—C10 | −66.5 (4) |
O1—Zn1—O2—C17 | −131.8 (5) | O4—Zn2—N2—C11 | 114.4 (5) |
O3—Zn1—O2—Zn2 | −60.2 (2) | N1—Zn2—N2—C10 | 37.1 (4) |
O3—Zn1—O2—C17 | 141.3 (5) | N1—Zn2—N2—C11 | −142.1 (5) |
O1—Zn1—O3—C18 | −43.8 (6) | Zn1—O1—C1—C2 | 11.6 (8) |
O2—Zn1—O3—C18 | 33.8 (6) | Zn1—O1—C1—C6 | −171.9 (4) |
O2—Zn2—O1—Zn1 | 27.2 (2) | Zn2—O1—C1—C2 | 161.9 (4) |
O2—Zn2—O1—C1 | −131.7 (4) | Zn2—O1—C1—C6 | −21.5 (7) |
O4—Zn2—O1—Zn1 | −72.1 (2) | Zn1—O2—C17—C12 | 167.9 (4) |
O4—Zn2—O1—C1 | 129.0 (4) | Zn1—O2—C17—C16 | −13.5 (7) |
N1—Zn2—O1—Zn1 | −174.7 (2) | Zn2—O2—C17—C12 | 15.3 (7) |
N1—Zn2—O1—C1 | 26.3 (4) | Zn2—O2—C17—C16 | −166.0 (4) |
N2—Zn2—O1—Zn1 | 97.9 (3) | Zn1—O3—C18—C19 | −177.8 (5) |
N2—Zn2—O1—C1 | −61.0 (6) | Zn2—O4—C18—C19 | −176.7 (5) |
O1—Zn2—O2—Zn1 | −27.0 (2) | C8—N1—C7—C6 | −179.3 (6) |
O1—Zn2—O2—C17 | 133.4 (4) | Zn2—N1—C8—C9 | 64.7 (6) |
O4—Zn2—O2—Zn1 | 75.2 (2) | C7—N1—C8—C9 | −113.3 (6) |
O4—Zn2—O2—C17 | −124.3 (4) | Zn2—N2—C10—C9 | −50.1 (6) |
N1—Zn2—O2—Zn1 | −89.0 (4) | C11—N2—C10—C9 | 129.2 (6) |
N1—Zn2—O2—C17 | 71.5 (6) | C10—N2—C11—C12 | 177.6 (5) |
N2—Zn2—O2—Zn1 | −179.7 (2) | O1—C1—C2—C3 | −179.4 (5) |
N2—Zn2—O2—C17 | −19.2 (4) | O1—C1—C6—C5 | 179.9 (5) |
O1—Zn2—O4—C18 | 36.6 (4) | C2—C1—C6—C7 | 175.2 (5) |
O2—Zn2—O4—C18 | −46.0 (4) | C4—C5—C6—C7 | −178.6 (6) |
N1—Zn2—O4—C18 | 127.2 (4) | C1—C6—C7—N1 | 11.4 (9) |
N2—Zn2—O4—C18 | −138.4 (4) | C5—C6—C7—N1 | −169.9 (6) |
O1—Zn2—N1—C7 | −16.6 (5) | N1—C8—C9—C10 | −71.8 (7) |
O1—Zn2—N1—C8 | 165.6 (4) | C8—C9—C10—N2 | 63.1 (7) |
O2—Zn2—N1—C7 | 43.9 (7) | N2—C11—C12—C13 | 174.5 (6) |
O2—Zn2—N1—C8 | −133.9 (4) | N2—C11—C12—C17 | −7.7 (9) |
O4—Zn2—N1—C7 | −120.2 (5) | C11—C12—C13—C14 | 178.6 (6) |
O4—Zn2—N1—C8 | 62.1 (4) | C11—C12—C17—C16 | −177.3 (5) |
N2—Zn2—N1—C7 | 134.3 (5) | C13—C12—C17—O2 | 179.1 (5) |
N2—Zn2—N1—C8 | −43.5 (4) | C15—C16—C17—O2 | −179.7 (5) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn{Zn(CH3COO)(C17H16N2O2)}2] |
Mr | 874.91 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.4243 (14), 20.3334 (18), 8.3832 (11) |
β (°) | 85.639 (13) |
V (Å3) | 1771.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.07 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ-scan (MolEN; Fair, 1990) |
Tmin, Tmax | 0.798, 0.902 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4101, 3724, 2514 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.632 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.056, 1.01 |
No. of reflections | 2514 |
No. of parameters | 241 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.84, −0.23 |
Computer programs: MolEN (Fair, 1990), ORTEP-3 for Windows (Farrugia, 1997), MolEN and PLATON99 (Spek, 1990).
Zn1—Zn2 | 3.0520 (8) | Zn2—O4 | 1.975 (4) |
Zn1—O1 | 2.098 (3) | Zn2—N1 | 2.060 (4) |
Zn1—O2 | 2.113 (4) | Zn2—N2 | 2.071 (4) |
Zn1—O3 | 2.124 (4) | O3—C18 | 1.254 (7) |
Zn2—O1 | 2.057 (4) | O4—C18 | 1.256 (7) |
Zn2—O2 | 2.034 (4) | ||
O1—Zn1—O2 | 77.5 (1) | O2—Zn2—O4 | 101.2 (2) |
O1—Zn1—O3 | 86.5 (1) | O2—Zn2—N1 | 155.0 (2) |
O2—Zn1—O3 | 87.6 (2) | O2—Zn2—N2 | 89.4 (2) |
O1—Zn1—O1i | 180.0 | O4—Zn2—N1 | 102.9 (2) |
O1—Zn1—O2i | 102.5 (1) | O4—Zn2—N2 | 104.9 (2) |
O1—Zn1—O3i | 93.5 (2) | N1—Zn2—N2 | 90.9 (2) |
O2—Zn1—O2i | 180.0 | Zn1—O1—Zn2 | 94.5 (1) |
O2—Zn1—O3i | 92.4 (2) | Zn1—O2—Zn2 | 94.8 (2) |
O3—Zn1—O3i | 180.0 | Zn1—O3—C18 | 138.4 (4) |
O1—Zn2—O2 | 80.3 (1) | Zn2—O4—C18 | 119.5 (4) |
O1—Zn2—O4 | 103.7 (2) | O3—C18—O4 | 124.9 (5) |
O1—Zn2—N1 | 87.5 (2) | O3—C18—C19 | 119.7 (6) |
O1—Zn2—N2 | 150.9 (2) | O4—C18—C19 | 115.4 (6) |
Symmetry code: (i) −x, −y, −z. |
Structural studies and the magnetic properties of trinuclear complexes prepared with the deprotonated N,N'-bis(salicylidene)-1,3-propanediamine (SALPD2-, C17H16N2O2) ligand have been the subject of considerable interest in our laboratory. In these complexes, acetate or nitrite anions constitute the µ-bridging between the three metal ions, which are also doubly oxygen bridged, so that the metal ions used in the synthesis (M is Zn2+, Ni2+, Cd2+, Cu2+ or Co2+) are all triply bridged (Ülkü et al., 1999; Atakol, Arici, Ercan & Ülkü, 1999; Atakol, Arici, Tahir et al., 1999; Atakol, Tatar et al., 1999; Tahir et al., 1998; Ülkü, Ercan et al., 1997; Ülkü, Tahir et al., 1997, and references therein). Since there are three metal ions in these linear complexes, various combinations of metallic ions are possible in the central and terminal locations, so that homonuclear as well as heteronuclear compounds can be synthesized. When the synthesis involves a paramagnetic ion, then the magnetic properties of the compound become interesting, due to the superexchange interaction between the diamagnetic ions of the bridges. The ligand stereochemistry around the metal ions and the structure of the O-atom bridges influence these magnetic exchange interactions, and therefore the structural parameters are important.
The synthesis of similar trinuclear complexes of the general formulae [MCu2(SALPD)2(CH3COO)2] (M is Mn2+, Co2+, Ni2+, Cu2+ or Zn2+) and [MNi2(SALPD)2(CH3COO)2] (M is Mg2+, Mn2+, Co2+ or Ni2+) were reported by Fukuhara et al. (1990). Only the structure of [ZnCu2(SALPD)2(CH3COO)2] in this group of compounds has been determined by X-ray diffraction to date (Fukuhara et al., 1990). Gerli et al. (1991) reported trinuclear structures formulated as [M3{(SALPN)(CH3COO)[(CH3)2NCHO]}2] [M is Co2+ or Fe2+; SALPN is N,N'-bis(salicylidene)-2,2-dimethylpropylenediamine]. We report here a new member of the linear homometallic trinuclear compound family, the title compound, (I), in which the central as well as the terminal metal ion locations are occupied by zinc atoms. \sch
Among the trinuclear complexes cited above, this complex resembles the complex of [Zn{Cu(CH3COO)(C17H16N2O2)}2], (II) (Fukuhara et al., 1990), more than any other trinuclear complex, so that the two are almost identical molecules. In both molecules, the central Zn2+ ion, located on an inversion centre, has as its nearest neighbours four bridging O atoms from two SALPD2- ligands (O1, O2, O1i and O2i) and two O atoms from two bridging acetate groups (O3 and O3i) [symmetry code: (i) -x, -y, -z]. This environment constitutes an irregular octahedral geometry around the Zn ion. The Zn—O bond lengths around the central Zn ion in both complexes have equal values within experimental error.
The coordination polyhedra around the inversion-related terminal ions, Zn in (I) and Cu in (II), are slightly distorted square-pyramids, whose basal plane is made up of the two bridging O atoms and two N atoms of the SALPD2- ligand, while the apical positions are occupied by an O atom of the acetate group. The corresponding M—O and M—N distances within the coordination polyhedra around the terminal ions are different in these two complexes, so that the square pyramid around the Cu ion in (II) is slightly elongated when compared with the square pyramid around the Zn ion in (I).
These two almost identical molecules of (I) and (II) crystallize in the space groups P21/c and P21/a, respectively, and have almost the same unit-cell volume [1771.8 (4) and 1766.7 (9) Å3, respectively]. However, the unit-cell parameters of the Cu—Zn—Cu trimer, (II) [a = 16.228 (5), b = 11.971 (2) and c = 9.239 (3) Å, and β = 100.15 (3)°], are considerably different from the corresponding values of the Zn—Zn—Zn trimer, (I), especially with respect to a and b. This results in different molecular packing, as can be seen in Fig. 2. For clarity reasons H atoms have been omitted and the least overlapping projections are shown in the drawing.
An intermolecular interaction analysis shows that in the Zn—Zn—Zn trimer there is one intermolecular hydrogen bond between atoms C11 and O4ii [symmetry code: (ii) x, -1/2 - y, z - 1/2], with a donor-acceptor distance of 3.475 (7) Å. Several weaker interactions with intermolecular distances of less than 3.5 Å are observed in both structures. In the Zn—Zn—Zn trimer four such interactions exist, between O3 and C16ii [3.238 (7) Å], and O3 and C2ii [3.251 (8) Å]. Two additional interactions are found between C3 and C15iii [3.437 (9) Å; symmetry code: (iii) -x, -y, -1 - z] and between C7 and C7iv [3.431 (8) Å; symmetry code: (iv) 1 - x, -y, -z].
In the Cu—Zn—Cu trimer, the number of intermolecular contacts of less than 3.5 Å is almost twice as many as the number of interactions observed in (I). They are as follows: O2···C2i [3.398 (18) Å], O3···C2i [2.83 (3) Å], C2···C17i [3.49 (2) Å], Cu···C4v [3.287 (17) Å], N1···C4i [3.43 (2) Å], C1···C5v [3.47 (2) Å] and C6···C6v [3.39 (2) Å]. [Symmetry code: (v) -x, -y, 1 - z].
These two almost identical molecules of (I) and (II) crystallize so that they seem to be polymorphs.
NB Each symop definition must be used only once so as not to cause confusion. There were two different definitions of (i) in the original CIF and two of (ii). They have been renumbered, but please check them all carefully.