Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680200209X/na6136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680200209X/na6136Isup2.hkl |
CCDC reference: 182589
The title complex was obtained as a minor product in the synthesis of a dimeric zinc complex with benzoate bridges (Necefolglu, 2002). The two products could be distinguished by their different crystal habits. The minor product has its origin in the presence of calcium ions in the unpurified tap water used in the synthesis.
Since this was an early experiment with one of the first commercial CCD diffractometers, operating parameters were not yet optimized. One consequence is the rather low maximum θ, as a result of a crystal-to-detector distance of approximately 6 cm. Data are essentially complete, however, to θ = 24°. H atoms were placed geometrically and refined with a riding model (including free rotation about C—C bonds), and with Uiso constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom.
Data collection: SMART (Siemens, 1995); cell refinement: local programs; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Fig. 1. The molecular structure of (I) with atom labels and 50% probability ellipsoids for non-H atoms. |
[CaZn2(C7H5O2)6(C10H14N2O)2] | F(000) = 1300 |
Mr = 1253.94 | Dx = 1.403 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.347 (2) Å | Cell parameters from 7387 reflections |
b = 10.7691 (13) Å | θ = 2.0–25.4° |
c = 17.647 (2) Å | µ = 0.96 mm−1 |
β = 107.207 (3)° | T = 160 K |
V = 2967.6 (6) Å3 | Block, colourless |
Z = 2 | 0.30 × 0.20 × 0.16 mm |
Siemens SMART 1K CCD diffractometer | 4938 independent reflections |
Radiation source: sealed tube | 4193 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 8.192 pixels mm-1 | θmax = 25.5°, θmin = 1.5° |
ω rotation with narrow frames scans | h = −17→18 |
Absorption correction: multi-scan (SHELXTL; Sheldrick, 1997) | k = −12→12 |
Tmin = 0.860, Tmax = 0.925 | l = −20→15 |
12317 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0348P)2 + 2.7427P] where P = (Fo2 + 2Fc2)/3 |
4938 reflections | (Δ/σ)max < 0.001 |
376 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[CaZn2(C7H5O2)6(C10H14N2O)2] | V = 2967.6 (6) Å3 |
Mr = 1253.94 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.347 (2) Å | µ = 0.96 mm−1 |
b = 10.7691 (13) Å | T = 160 K |
c = 17.647 (2) Å | 0.30 × 0.20 × 0.16 mm |
β = 107.207 (3)° |
Siemens SMART 1K CCD diffractometer | 4938 independent reflections |
Absorption correction: multi-scan (SHELXTL; Sheldrick, 1997) | 4193 reflections with I > 2σ(I) |
Tmin = 0.860, Tmax = 0.925 | Rint = 0.039 |
12317 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.41 e Å−3 |
4938 reflections | Δρmin = −0.48 e Å−3 |
376 parameters |
x | y | z | Uiso*/Ueq | ||
Zn | 0.20197 (2) | 0.19710 (3) | 0.04078 (2) | 0.02835 (11) | |
Ca | 0.0000 | 0.0000 | 0.0000 | 0.02526 (19) | |
N1 | 0.31448 (15) | 0.2969 (2) | 0.05654 (15) | 0.0326 (6) | |
C1 | 0.3254 (2) | 0.4128 (3) | 0.0858 (2) | 0.0402 (8) | |
H1 | 0.2846 | 0.4472 | 0.1087 | 0.048* | |
C2 | 0.4010 (2) | 0.4774 (3) | 0.0961 (2) | 0.0494 (9) | |
H2 | 0.4008 | 0.5642 | 0.1054 | 0.059* | |
C3 | 0.4671 (2) | 0.4218 (3) | 0.0753 (2) | 0.0457 (9) | |
H3 | 0.5205 | 0.4637 | 0.0862 | 0.055* | |
C4 | 0.45723 (18) | 0.3021 (3) | 0.04543 (18) | 0.0331 (7) | |
C5 | 0.37961 (18) | 0.2441 (3) | 0.03646 (18) | 0.0326 (7) | |
H5 | 0.3727 | 0.1613 | 0.0171 | 0.039* | |
C6 | 0.52377 (18) | 0.2415 (3) | 0.01435 (18) | 0.0329 (7) | |
O1 | 0.52052 (14) | 0.2591 (2) | −0.05501 (13) | 0.0457 (6) | |
N2 | 0.58412 (15) | 0.1708 (2) | 0.06381 (15) | 0.0336 (6) | |
C7 | 0.64967 (18) | 0.1126 (3) | 0.03345 (19) | 0.0368 (7) | |
H7A | 0.6241 | 0.0942 | −0.0237 | 0.044* | |
H7B | 0.6681 | 0.0330 | 0.0613 | 0.044* | |
C8 | 0.72458 (19) | 0.1991 (3) | 0.0403 (2) | 0.0421 (8) | |
H8A | 0.7680 | 0.1551 | 0.0224 | 0.063* | |
H8B | 0.7484 | 0.2208 | 0.0965 | 0.063* | |
H8C | 0.7075 | 0.2750 | 0.0090 | 0.063* | |
C9 | 0.5898 (2) | 0.1471 (3) | 0.14682 (18) | 0.0415 (8) | |
H9A | 0.5614 | 0.2180 | 0.1645 | 0.050* | |
H9B | 0.6505 | 0.1459 | 0.1796 | 0.050* | |
C10 | 0.5496 (2) | 0.0237 (4) | 0.1576 (2) | 0.0596 (11) | |
H10A | 0.4962 | 0.0128 | 0.1146 | 0.089* | |
H10B | 0.5370 | 0.0271 | 0.2085 | 0.089* | |
H10C | 0.5880 | −0.0464 | 0.1579 | 0.089* | |
O2 | 0.13990 (12) | 0.32848 (19) | 0.07535 (12) | 0.0331 (5) | |
O3 | 0.02892 (14) | 0.2024 (2) | 0.03401 (14) | 0.0445 (6) | |
C11 | 0.06069 (19) | 0.3030 (3) | 0.06260 (17) | 0.0305 (7) | |
C12 | 0.00513 (17) | 0.3999 (3) | 0.08220 (16) | 0.0285 (6) | |
C13 | 0.0394 (2) | 0.5109 (3) | 0.11757 (19) | 0.0364 (7) | |
H13 | 0.0994 | 0.5250 | 0.1315 | 0.044* | |
C14 | −0.0128 (2) | 0.5995 (3) | 0.1358 (2) | 0.0462 (8) | |
H14 | 0.0083 | 0.6770 | 0.1593 | 0.055* | |
C15 | −0.1001 (2) | 0.5788 (3) | 0.1178 (2) | 0.0454 (9) | |
H15 | −0.1370 | 0.6380 | 0.1307 | 0.054* | |
C16 | −0.1344 (2) | 0.4694 (3) | 0.0823 (2) | 0.0429 (8) | |
H16 | −0.1947 | 0.4582 | 0.0672 | 0.051* | |
C17 | −0.08257 (19) | 0.3798 (3) | 0.06443 (18) | 0.0371 (7) | |
H17 | −0.1057 | 0.3010 | 0.0450 | 0.044* | |
O4 | 0.18972 (12) | 0.14893 (19) | −0.06907 (12) | 0.0352 (5) | |
O5 | 0.07706 (14) | 0.0230 (2) | −0.09016 (13) | 0.0449 (6) | |
C18 | 0.13757 (18) | 0.0683 (3) | −0.10940 (17) | 0.0306 (7) | |
C19 | 0.15360 (17) | 0.0265 (3) | −0.18477 (17) | 0.0292 (6) | |
C20 | 0.11088 (19) | −0.0769 (3) | −0.22417 (19) | 0.0399 (8) | |
H20 | 0.0714 | −0.1190 | −0.2031 | 0.048* | |
C21 | 0.1268 (2) | −0.1202 (3) | −0.2926 (2) | 0.0473 (9) | |
H21 | 0.0957 | −0.1897 | −0.3197 | 0.057* | |
C22 | 0.1856 (2) | −0.0579 (4) | −0.3216 (2) | 0.0487 (9) | |
H22 | 0.2004 | −0.0875 | −0.3665 | 0.058* | |
C23 | 0.2278 (2) | 0.0450 (3) | −0.28328 (19) | 0.0453 (8) | |
H23 | 0.2673 | 0.0891 | −0.3034 | 0.054* | |
C24 | 0.21239 (19) | 0.0873 (3) | −0.21453 (18) | 0.0369 (7) | |
H24 | 0.2407 | 0.1601 | −0.1895 | 0.044* | |
O6 | 0.25188 (13) | 0.0520 (2) | 0.10273 (12) | 0.0367 (5) | |
O7 | 0.12999 (13) | −0.0504 (2) | 0.09010 (13) | 0.0442 (6) | |
C25 | 0.20928 (18) | −0.0414 (3) | 0.11458 (17) | 0.0319 (7) | |
C26 | 0.26071 (18) | −0.1454 (3) | 0.16197 (16) | 0.0309 (7) | |
C27 | 0.2201 (2) | −0.2521 (3) | 0.17617 (19) | 0.0435 (8) | |
H27 | 0.1595 | −0.2584 | 0.1561 | 0.052* | |
C28 | 0.2677 (2) | −0.3484 (3) | 0.2199 (2) | 0.0521 (9) | |
H28 | 0.2403 | −0.4241 | 0.2259 | 0.063* | |
C29 | 0.3555 (2) | −0.3397 (3) | 0.24893 (19) | 0.0463 (9) | |
H29 | 0.3871 | −0.4007 | 0.2846 | 0.056* | |
C30 | 0.3963 (2) | −0.2341 (3) | 0.23457 (19) | 0.0419 (8) | |
H30 | 0.4571 | −0.2315 | 0.2496 | 0.050* | |
C31 | 0.34922 (18) | −0.1373 (3) | 0.19134 (17) | 0.0340 (7) | |
H31 | 0.3776 | −0.0633 | 0.1838 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.02146 (18) | 0.02655 (19) | 0.0385 (2) | −0.00234 (14) | 0.01103 (14) | −0.00277 (15) |
Ca | 0.0171 (4) | 0.0261 (4) | 0.0337 (4) | −0.0032 (3) | 0.0093 (3) | −0.0029 (3) |
N1 | 0.0243 (12) | 0.0295 (14) | 0.0447 (15) | −0.0023 (11) | 0.0111 (11) | −0.0059 (11) |
C1 | 0.0341 (17) | 0.0354 (18) | 0.057 (2) | −0.0060 (14) | 0.0237 (15) | −0.0112 (16) |
C2 | 0.0422 (19) | 0.036 (2) | 0.077 (3) | −0.0135 (16) | 0.0285 (18) | −0.0182 (18) |
C3 | 0.0315 (17) | 0.045 (2) | 0.064 (2) | −0.0150 (15) | 0.0195 (16) | −0.0185 (17) |
C4 | 0.0253 (15) | 0.0350 (17) | 0.0377 (17) | −0.0031 (13) | 0.0071 (13) | −0.0023 (14) |
C5 | 0.0279 (15) | 0.0276 (16) | 0.0431 (18) | 0.0001 (13) | 0.0117 (13) | −0.0038 (14) |
C6 | 0.0249 (15) | 0.0328 (17) | 0.0403 (18) | −0.0048 (13) | 0.0088 (14) | −0.0050 (14) |
O1 | 0.0388 (13) | 0.0568 (16) | 0.0432 (14) | 0.0108 (11) | 0.0147 (11) | 0.0046 (11) |
N2 | 0.0275 (13) | 0.0364 (15) | 0.0370 (14) | 0.0006 (11) | 0.0097 (11) | −0.0024 (12) |
C7 | 0.0283 (16) | 0.0382 (19) | 0.0432 (18) | 0.0051 (14) | 0.0098 (14) | −0.0066 (15) |
C8 | 0.0278 (16) | 0.046 (2) | 0.054 (2) | 0.0000 (15) | 0.0147 (15) | −0.0032 (16) |
C9 | 0.0349 (17) | 0.052 (2) | 0.0353 (17) | 0.0007 (16) | 0.0062 (14) | −0.0033 (16) |
C10 | 0.053 (2) | 0.077 (3) | 0.045 (2) | −0.020 (2) | 0.0097 (18) | 0.006 (2) |
O2 | 0.0273 (11) | 0.0330 (12) | 0.0402 (12) | −0.0004 (9) | 0.0122 (9) | −0.0036 (9) |
O3 | 0.0447 (13) | 0.0304 (13) | 0.0613 (15) | −0.0049 (11) | 0.0199 (11) | −0.0100 (11) |
C11 | 0.0327 (16) | 0.0280 (17) | 0.0329 (16) | −0.0021 (13) | 0.0129 (13) | 0.0006 (13) |
C12 | 0.0281 (15) | 0.0284 (16) | 0.0316 (15) | 0.0018 (13) | 0.0130 (12) | 0.0039 (13) |
C13 | 0.0316 (16) | 0.0325 (17) | 0.0487 (19) | −0.0025 (14) | 0.0174 (14) | −0.0032 (15) |
C14 | 0.052 (2) | 0.0306 (18) | 0.063 (2) | 0.0003 (16) | 0.0291 (18) | −0.0047 (17) |
C15 | 0.050 (2) | 0.038 (2) | 0.059 (2) | 0.0131 (16) | 0.0325 (18) | 0.0108 (17) |
C16 | 0.0306 (17) | 0.050 (2) | 0.052 (2) | 0.0053 (16) | 0.0186 (15) | 0.0083 (17) |
C17 | 0.0304 (16) | 0.0379 (19) | 0.0449 (18) | −0.0047 (14) | 0.0142 (14) | 0.0001 (15) |
O4 | 0.0333 (11) | 0.0318 (12) | 0.0418 (12) | −0.0026 (10) | 0.0132 (10) | −0.0040 (10) |
O5 | 0.0376 (12) | 0.0562 (15) | 0.0486 (14) | −0.0097 (11) | 0.0245 (11) | −0.0083 (12) |
C18 | 0.0253 (15) | 0.0306 (17) | 0.0371 (17) | 0.0023 (13) | 0.0110 (13) | 0.0012 (13) |
C19 | 0.0226 (14) | 0.0313 (17) | 0.0320 (16) | 0.0019 (12) | 0.0055 (12) | 0.0000 (13) |
C20 | 0.0286 (16) | 0.047 (2) | 0.0427 (18) | −0.0037 (15) | 0.0091 (14) | −0.0061 (16) |
C21 | 0.0410 (19) | 0.051 (2) | 0.0421 (19) | 0.0030 (17) | 0.0001 (16) | −0.0146 (17) |
C22 | 0.046 (2) | 0.066 (3) | 0.0339 (18) | 0.0181 (19) | 0.0103 (15) | −0.0015 (17) |
C23 | 0.0437 (19) | 0.058 (2) | 0.0395 (18) | 0.0077 (17) | 0.0212 (16) | 0.0072 (17) |
C24 | 0.0358 (17) | 0.0373 (18) | 0.0406 (18) | 0.0014 (14) | 0.0160 (14) | 0.0032 (15) |
O6 | 0.0315 (11) | 0.0323 (12) | 0.0452 (13) | 0.0007 (10) | 0.0097 (10) | 0.0053 (10) |
O7 | 0.0243 (11) | 0.0497 (15) | 0.0519 (14) | 0.0000 (10) | 0.0007 (10) | 0.0043 (11) |
C25 | 0.0294 (16) | 0.0376 (18) | 0.0283 (15) | 0.0005 (14) | 0.0077 (13) | −0.0051 (13) |
C26 | 0.0312 (15) | 0.0338 (17) | 0.0259 (15) | −0.0014 (13) | 0.0057 (12) | −0.0033 (13) |
C27 | 0.0372 (18) | 0.046 (2) | 0.0435 (19) | −0.0085 (16) | 0.0062 (15) | 0.0065 (16) |
C28 | 0.060 (2) | 0.043 (2) | 0.047 (2) | −0.0087 (18) | 0.0058 (18) | 0.0133 (17) |
C29 | 0.058 (2) | 0.043 (2) | 0.0325 (18) | 0.0128 (18) | 0.0050 (16) | 0.0059 (15) |
C30 | 0.0329 (17) | 0.049 (2) | 0.0415 (18) | 0.0106 (16) | 0.0083 (15) | −0.0015 (16) |
C31 | 0.0290 (16) | 0.0360 (18) | 0.0357 (17) | 0.0020 (14) | 0.0073 (13) | −0.0001 (14) |
Zn—N1 | 2.077 (2) | C23—C24 | 1.387 (4) |
Zn—O2 | 1.942 (2) | O6—C25 | 1.275 (4) |
Zn—O4 | 1.959 (2) | O7—C25 | 1.243 (3) |
Zn—O6 | 1.943 (2) | C25—C26 | 1.498 (4) |
Ca—O3 | 2.273 (2) | C26—C27 | 1.387 (4) |
Ca—O3i | 2.273 (2) | C26—C31 | 1.388 (4) |
Ca—O5 | 2.316 (2) | C27—C28 | 1.386 (5) |
Ca—O5i | 2.316 (2) | C28—C29 | 1.378 (5) |
Ca—O7 | 2.311 (2) | C29—C30 | 1.379 (5) |
Ca—O7i | 2.311 (2) | C30—C31 | 1.384 (4) |
N1—C1 | 1.342 (4) | C1—H1 | 0.950 |
N1—C5 | 1.343 (4) | C2—H2 | 0.950 |
C1—C2 | 1.382 (4) | C3—H3 | 0.950 |
C2—C3 | 1.377 (5) | C5—H5 | 0.950 |
C3—C4 | 1.384 (4) | C7—H7A | 0.990 |
C4—C5 | 1.380 (4) | C7—H7B | 0.990 |
C4—C6 | 1.505 (4) | C8—H8A | 0.980 |
C6—O1 | 1.224 (4) | C8—H8B | 0.980 |
C6—N2 | 1.344 (4) | C8—H8C | 0.980 |
N2—C7 | 1.472 (4) | C9—H9A | 0.990 |
N2—C9 | 1.463 (4) | C9—H9B | 0.990 |
C7—C8 | 1.515 (4) | C10—H10A | 0.980 |
C9—C10 | 1.519 (5) | C10—H10B | 0.980 |
O2—C11 | 1.277 (3) | C10—H10C | 0.980 |
O3—C11 | 1.242 (3) | C13—H13 | 0.950 |
C11—C12 | 1.489 (4) | C14—H14 | 0.950 |
C12—C13 | 1.388 (4) | C15—H15 | 0.950 |
C12—C17 | 1.391 (4) | C16—H16 | 0.950 |
C13—C14 | 1.380 (4) | C17—H17 | 0.950 |
C14—C15 | 1.386 (5) | C20—H20 | 0.950 |
C15—C16 | 1.374 (5) | C21—H21 | 0.950 |
C16—C17 | 1.381 (4) | C22—H22 | 0.950 |
O4—C18 | 1.276 (3) | C23—H23 | 0.950 |
O5—C18 | 1.238 (3) | C24—H24 | 0.950 |
C18—C19 | 1.499 (4) | C27—H27 | 0.950 |
C19—C20 | 1.387 (4) | C28—H28 | 0.950 |
C19—C24 | 1.388 (4) | C29—H29 | 0.950 |
C20—C21 | 1.390 (4) | C30—H30 | 0.950 |
C21—C22 | 1.388 (5) | C31—H31 | 0.950 |
C22—C23 | 1.373 (5) | ||
N1—Zn—O2 | 96.04 (9) | O7—C25—C26 | 119.4 (3) |
N1—Zn—O4 | 95.55 (9) | C25—C26—C27 | 120.1 (3) |
N1—Zn—O6 | 97.64 (9) | C25—C26—C31 | 120.8 (3) |
O2—Zn—O4 | 126.44 (9) | C27—C26—C31 | 119.1 (3) |
O2—Zn—O6 | 125.51 (9) | C26—C27—C28 | 120.1 (3) |
O4—Zn—O6 | 104.28 (9) | C27—C28—C29 | 120.5 (3) |
O3—Ca—O3i | 180.00 (12) | C28—C29—C30 | 119.7 (3) |
O3—Ca—O5 | 88.06 (8) | C29—C30—C31 | 120.2 (3) |
O3i—Ca—O5i | 88.06 (8) | C26—C31—C30 | 120.4 (3) |
O3—Ca—O5i | 91.94 (8) | N1—C1—H1 | 119.7 |
O3i—Ca—O5 | 91.94 (8) | C2—C1—H1 | 117.4 |
O3—Ca—O7 | 88.09 (8) | C3—C2—H2 | 121.1 |
O3i—Ca—O7i | 88.09 (8) | C1—C2—H2 | 118.0 |
O3—Ca—O7i | 91.91 (8) | C2—C3—H3 | 119.1 |
O3i—Ca—O7 | 91.91 (8) | C4—C3—H3 | 121.1 |
O5—Ca—O5i | 180.00 (7) | N1—C5—H5 | 118.2 |
O5—Ca—O7 | 85.49 (8) | C4—C5—H5 | 118.2 |
O5i—Ca—O7i | 85.49 (8) | N2—C7—H7A | 108.8 |
O5i—Ca—O7 | 94.51 (8) | C8—C7—H7A | 107.0 |
O5—Ca—O7i | 94.51 (8) | N2—C7—H7B | 109.5 |
O7—Ca—O7i | 180.00 (18) | C8—C7—H7B | 111.9 |
Zn—N1—C1 | 123.0 (2) | H7A—C7—H7B | 107.9 |
Zn—N1—C5 | 119.0 (2) | C7—C8—H8A | 108.8 |
C1—N1—C5 | 118.0 (3) | C7—C8—H8B | 107.3 |
N1—C1—C2 | 122.0 (3) | H8A—C8—H8B | 109.5 |
C1—C2—C3 | 119.2 (3) | C7—C8—H8C | 112.3 |
C2—C3—C4 | 119.6 (3) | H8A—C8—H8C | 109.5 |
C3—C4—C5 | 117.7 (3) | H8B—C8—H8C | 109.5 |
C3—C4—C6 | 121.8 (3) | N2—C9—H9A | 106.6 |
C5—C4—C6 | 120.1 (3) | C10—C9—H9A | 112.0 |
N1—C5—C4 | 123.5 (3) | N2—C9—H9B | 110.0 |
C4—C6—O1 | 118.3 (3) | C10—C9—H9B | 108.1 |
C4—C6—N2 | 118.7 (3) | H9A—C9—H9B | 107.9 |
O1—C6—N2 | 123.0 (3) | C9—C10—H10A | 109.0 |
C6—N2—C7 | 118.6 (3) | C9—C10—H10B | 107.3 |
C6—N2—C9 | 124.5 (3) | H10A—C10—H10B | 109.5 |
C7—N2—C9 | 117.0 (2) | C9—C10—H10C | 112.0 |
N2—C7—C8 | 111.6 (3) | H10A—C10—H10C | 109.5 |
N2—C9—C10 | 112.1 (3) | H10B—C10—H10C | 109.5 |
Zn—O2—C11 | 112.66 (18) | C14—C13—H13 | 119.4 |
Ca—O3—C11 | 166.6 (2) | C12—C13—H13 | 120.2 |
O2—C11—O3 | 122.6 (3) | C13—C14—H14 | 122.7 |
O2—C11—C12 | 117.7 (3) | C15—C14—H14 | 117.2 |
O3—C11—C12 | 119.6 (3) | C16—C15—H15 | 118.9 |
C11—C12—C13 | 121.0 (3) | C14—C15—H15 | 121.4 |
C11—C12—C17 | 119.8 (3) | C15—C16—H16 | 119.1 |
C13—C12—C17 | 119.2 (3) | C17—C16—H16 | 120.3 |
C12—C13—C14 | 120.3 (3) | C16—C17—H17 | 120.0 |
C13—C14—C15 | 120.1 (3) | C12—C17—H17 | 119.6 |
C14—C15—C16 | 119.7 (3) | C19—C20—H20 | 119.1 |
C15—C16—C17 | 120.6 (3) | C21—C20—H20 | 120.2 |
C12—C17—C16 | 120.0 (3) | C22—C21—H21 | 121.5 |
Zn—O4—C18 | 126.02 (19) | C20—C21—H21 | 119.4 |
Ca—O5—C18 | 150.7 (2) | C23—C22—H22 | 117.8 |
O4—C18—O5 | 124.9 (3) | C21—C22—H22 | 121.3 |
O4—C18—C19 | 115.9 (2) | C22—C23—H23 | 121.2 |
O5—C18—C19 | 119.2 (3) | C24—C23—H23 | 118.8 |
C18—C19—C20 | 119.5 (3) | C23—C24—H24 | 119.2 |
C18—C19—C24 | 121.1 (3) | C19—C24—H24 | 120.7 |
C20—C19—C24 | 119.4 (3) | C28—C27—H27 | 120.4 |
C19—C20—C21 | 120.6 (3) | C26—C27—H27 | 119.6 |
C20—C21—C22 | 119.1 (3) | C29—C28—H28 | 119.4 |
C21—C22—C23 | 120.7 (3) | C27—C28—H28 | 119.9 |
C22—C23—C24 | 120.0 (3) | C28—C29—H29 | 120.2 |
C19—C24—C23 | 120.1 (3) | C30—C29—H29 | 119.6 |
Zn—O6—C25 | 124.59 (19) | C29—C30—H30 | 119.7 |
Ca—O7—C25 | 150.8 (2) | C31—C30—H30 | 119.8 |
O6—C25—O7 | 124.7 (3) | C30—C31—H31 | 119.6 |
O6—C25—C26 | 115.9 (2) | C26—C31—H31 | 119.9 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [CaZn2(C7H5O2)6(C10H14N2O)2] |
Mr | 1253.94 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 160 |
a, b, c (Å) | 16.347 (2), 10.7691 (13), 17.647 (2) |
β (°) | 107.207 (3) |
V (Å3) | 2967.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.30 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART 1K CCD diffractometer |
Absorption correction | Multi-scan (SHELXTL; Sheldrick, 1997) |
Tmin, Tmax | 0.860, 0.925 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12317, 4938, 4193 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.097, 1.12 |
No. of reflections | 4938 |
No. of parameters | 376 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.48 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXTL (Sheldrick, 1997), SHELXTL and local programs.
Zn—N1 | 2.077 (2) | O2—C11 | 1.277 (3) |
Zn—O2 | 1.942 (2) | O3—C11 | 1.242 (3) |
Zn—O4 | 1.959 (2) | O4—C18 | 1.276 (3) |
Zn—O6 | 1.943 (2) | O5—C18 | 1.238 (3) |
Ca—O3 | 2.273 (2) | O6—C25 | 1.275 (4) |
Ca—O5 | 2.316 (2) | O7—C25 | 1.243 (3) |
Ca—O7 | 2.311 (2) | ||
N1—Zn—O2 | 96.04 (9) | O5—Ca—O7 | 85.49 (8) |
N1—Zn—O4 | 95.55 (9) | Zn—O2—C11 | 112.66 (18) |
N1—Zn—O6 | 97.64 (9) | Ca—O3—C11 | 166.6 (2) |
O2—Zn—O4 | 126.44 (9) | Zn—O4—C18 | 126.02 (19) |
O2—Zn—O6 | 125.51 (9) | Ca—O5—C18 | 150.7 (2) |
O4—Zn—O6 | 104.28 (9) | Zn—O6—C25 | 124.59 (19) |
O3—Ca—O5 | 88.06 (8) | Ca—O7—C25 | 150.8 (2) |
O3—Ca—O7 | 88.09 (8) |
The title compound, (I), was obtained as a minor product in the preparation of the bridged dimeric complex [Zn2(benzoate)4(DENA)2], where DENA is N,N'-diethylnicotinamide. The calcium is derived from impurities in the reagents. Crystals of (I) were separated manually from those of the major product, which has also been crystallographically characterized (Necefoglu et al., 2002).
The molecule (Fig. 1) has crystallographic inversion symmetry. Six benzoate bridges link the central calcium ion with the two zinc ions, the three metal ions forming a symmetrical linear array. Each zinc ion is additionally coordinated by a monodentate DENA ligand to give somewhat distorted tetrahedral coordination by one N and three O atoms. Coordination of calcium is reasonably close to ideal octahedral (Table 1). There are no significant intermolecular interactions.
The benzoate ligands are not symmetrical. Each has one short C—O bond, which coordinates to Ca, and one longer C—O bond, coordinated to Zn; there is thus some localization of double and single bonds in the carboxylate groups. The Ca—O—C angles are considerably greater than Zn—O—C. These features are similar to those of a previously reported CaZn2 complex with crotonate bridging ligands, which has been compared in detail with other MZn2 analogous complexes having a range of transition and main-group metals M (Clegg et al., 1988).