Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012981/bm1431sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012981/bm1431IIsup2.hkl |
CCDC reference: 156143
Complexation of Zn(ClO4)2·6H2O by 2 molar equivalents of L (Solanki et al., 1998) in CH3NO2 yielded a pale yellow solution, which was filtered and concentrated in vacuo. Vapour diffusion of Et2O into this solution afforded colourless blocks of (II) of diffraction quality. Elemental analysis: found: C 65.1, H 6.6, N 7.5%; calculated for C58H58Cl2N10O4Zn·2CH3NO2: C 65.3, H 6.6, N 7.6%.
Methyl H atoms were located in difference Fourier syntheses, while sp2 H atoms were placed geometrically. All sp2 H atoms were refined with C—H 0.925 Å and Uiso = 1.2Ueq(C), while for methyl groups the corresponding values were 0.98 Å and 1.5 Ueq(C). The slightly high Rint value for the structure reflects a very large dataset containing a great deal of redundancy, collected from a sample of only moderate quality.
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 and local software.
Fig. 1. The molecular structure of the cation of (II) with 35% probability displacement ellipsoids, showing the atom-numbering scheme employed. For clarity, H atoms have been removed. |
[Zn(C29H29N5)2](ClO4)2·2CH3NO2 | F(000) = 2672 |
Mr = 1281.50 | Dx = 1.441 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9913 (2) Å | Cell parameters from 86756 reflections |
b = 19.8605 (3) Å | θ = 1.6–27.5° |
c = 25.1833 (3) Å | µ = 0.58 mm−1 |
β = 100.0240 (9)° | T = 150 K |
V = 5905.93 (15) Å3 | Block, colourless |
Z = 4 | 0.54 × 0.42 × 0.28 mm |
Nonius KappaCCD area-detector diffractometer | 13519 independent reflections |
Radiation source: fine-focus sealed tube | 9275 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.100 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 1.6° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −25→25 |
Tmin = 0.745, Tmax = 0.854 | l = −32→32 |
86756 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0718P)2 + 1.2064P] where P = (Fo2 + 2Fc2)/3 |
13519 reflections | (Δ/σ)max = 0.001 |
784 parameters | Δρmax = 0.51 e Å−3 |
0 restraints | Δρmin = −0.96 e Å−3 |
[Zn(C29H29N5)2](ClO4)2·2CH3NO2 | V = 5905.93 (15) Å3 |
Mr = 1281.50 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.9913 (2) Å | µ = 0.58 mm−1 |
b = 19.8605 (3) Å | T = 150 K |
c = 25.1833 (3) Å | 0.54 × 0.42 × 0.28 mm |
β = 100.0240 (9)° |
Nonius KappaCCD area-detector diffractometer | 13519 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 9275 reflections with I > 2σ(I) |
Tmin = 0.745, Tmax = 0.854 | Rint = 0.100 |
86756 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.51 e Å−3 |
13519 reflections | Δρmin = −0.96 e Å−3 |
784 parameters |
Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings |
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. Structure solution was achieved by direct methods using SHELXS97 (Sheldrick, 1990), while least squares refinement used SHELXL97 (Sheldrick, 1997). No disorder was detected during refinement, and no restraints were applied. All non-H atoms were refined anisotropically, while H atoms were placed in calculated positions and refined using a riding model. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.25188 (2) | 0.135096 (14) | 0.221358 (10) | 0.02305 (9) | |
N2 | 0.23192 (16) | 0.10188 (10) | 0.29666 (8) | 0.0241 (4) | |
C3 | 0.2317 (2) | 0.14607 (12) | 0.33649 (9) | 0.0248 (5) | |
C4 | 0.2117 (2) | 0.12758 (14) | 0.38686 (10) | 0.0324 (6) | |
H4 | 0.2107 | 0.1592 | 0.4139 | 0.039* | |
C5 | 0.1919 (2) | 0.05971 (14) | 0.39458 (10) | 0.0356 (6) | |
H5 | 0.1803 | 0.0452 | 0.4281 | 0.043* | |
C6 | 0.1930 (2) | 0.01284 (13) | 0.35415 (10) | 0.0312 (6) | |
H6 | 0.1804 | −0.0327 | 0.3597 | 0.037* | |
C7 | 0.2130 (2) | 0.03688 (13) | 0.30523 (9) | 0.0265 (5) | |
N8 | 0.25111 (17) | 0.21324 (10) | 0.32173 (8) | 0.0265 (4) | |
N9 | 0.25170 (16) | 0.22712 (10) | 0.26826 (7) | 0.0237 (4) | |
C10 | 0.2573 (2) | 0.29429 (12) | 0.26476 (10) | 0.0267 (5) | |
C11 | 0.2618 (3) | 0.32293 (14) | 0.31634 (11) | 0.0385 (7) | |
H11 | 0.2678 | 0.3688 | 0.3242 | 0.046* | |
C12 | 0.2560 (2) | 0.27083 (13) | 0.35087 (10) | 0.0355 (6) | |
H12 | 0.2542 | 0.2752 | 0.3872 | 0.043* | |
C13 | 0.2521 (2) | 0.32558 (12) | 0.21062 (10) | 0.0281 (5) | |
C14 | 0.3500 (2) | 0.32899 (12) | 0.18694 (10) | 0.0300 (6) | |
C15 | 0.3408 (2) | 0.35056 (13) | 0.13390 (11) | 0.0346 (6) | |
H15 | 0.4064 | 0.3538 | 0.1194 | 0.041* | |
C16 | 0.2367 (2) | 0.36844 (14) | 0.10340 (11) | 0.0369 (6) | |
C17 | 0.1428 (2) | 0.36878 (14) | 0.12845 (11) | 0.0360 (6) | |
H17 | 0.0743 | 0.3814 | 0.1080 | 0.043* | |
C18 | 0.1483 (2) | 0.34901 (13) | 0.18202 (11) | 0.0313 (6) | |
C19 | 0.4644 (2) | 0.31224 (14) | 0.21895 (11) | 0.0376 (6) | |
H19A | 0.4617 | 0.2677 | 0.2354 | 0.056* | |
H19B | 0.4853 | 0.3461 | 0.2473 | 0.056* | |
H19C | 0.5207 | 0.3120 | 0.1950 | 0.056* | |
C20 | 0.2273 (3) | 0.39009 (18) | 0.04545 (12) | 0.0511 (8) | |
H20A | 0.2088 | 0.3510 | 0.0218 | 0.077* | |
H20B | 0.2996 | 0.4094 | 0.0398 | 0.077* | |
H20C | 0.1675 | 0.4240 | 0.0371 | 0.077* | |
C21 | 0.0427 (2) | 0.35688 (15) | 0.20654 (12) | 0.0398 (7) | |
H21A | 0.0614 | 0.3496 | 0.2456 | 0.060* | |
H21B | −0.0139 | 0.3237 | 0.1906 | 0.060* | |
H21C | 0.0121 | 0.4024 | 0.1994 | 0.060* | |
N22 | 0.21654 (17) | −0.00361 (10) | 0.25928 (8) | 0.0261 (4) | |
N23 | 0.23673 (16) | 0.02669 (10) | 0.21282 (8) | 0.0251 (4) | |
C24 | 0.2401 (2) | −0.02316 (13) | 0.17746 (10) | 0.0279 (5) | |
C25 | 0.2221 (2) | −0.08545 (14) | 0.20130 (11) | 0.0365 (6) | |
H25 | 0.2177 | −0.1273 | 0.1845 | 0.044* | |
C26 | 0.2082 (2) | −0.07178 (13) | 0.25287 (11) | 0.0331 (6) | |
H26 | 0.1949 | −0.1031 | 0.2784 | 0.040* | |
C27 | 0.2586 (2) | −0.00694 (12) | 0.12194 (10) | 0.0278 (5) | |
C28 | 0.1660 (2) | 0.01270 (13) | 0.08261 (10) | 0.0311 (6) | |
C29 | 0.1844 (2) | 0.03229 (14) | 0.03216 (10) | 0.0345 (6) | |
H29 | 0.1232 | 0.0448 | 0.0064 | 0.041* | |
C30 | 0.2921 (2) | 0.03306 (14) | 0.01853 (10) | 0.0337 (6) | |
C31 | 0.3820 (2) | 0.01139 (14) | 0.05731 (10) | 0.0346 (6) | |
H31 | 0.4542 | 0.0105 | 0.0490 | 0.042* | |
C32 | 0.3680 (2) | −0.00917 (13) | 0.10885 (10) | 0.0319 (6) | |
C33 | 0.0474 (2) | 0.01174 (15) | 0.09475 (11) | 0.0380 (6) | |
H33A | 0.0471 | 0.0319 | 0.1302 | 0.057* | |
H33B | 0.0206 | −0.0349 | 0.0947 | 0.057* | |
H33C | −0.0027 | 0.0376 | 0.0672 | 0.057* | |
C34 | 0.3091 (3) | 0.05579 (16) | −0.03660 (11) | 0.0449 (7) | |
H34A | 0.3202 | 0.0164 | −0.0585 | 0.067* | |
H34B | 0.3759 | 0.0849 | −0.0331 | 0.067* | |
H34C | 0.2422 | 0.0808 | −0.0540 | 0.067* | |
C35 | 0.4696 (2) | −0.03141 (16) | 0.14910 (11) | 0.0430 (7) | |
H35A | 0.5277 | 0.0037 | 0.1528 | 0.065* | |
H35B | 0.5001 | −0.0731 | 0.1365 | 0.065* | |
H35C | 0.4469 | −0.0393 | 0.1841 | 0.065* | |
N36 | 0.27249 (16) | 0.16691 (10) | 0.14625 (8) | 0.0241 (4) | |
C37 | 0.3748 (2) | 0.17057 (12) | 0.13305 (9) | 0.0258 (5) | |
C38 | 0.3939 (2) | 0.19174 (13) | 0.08331 (10) | 0.0305 (6) | |
H38 | 0.4657 | 0.1922 | 0.0745 | 0.037* | |
C39 | 0.2992 (2) | 0.21033 (14) | 0.04640 (10) | 0.0322 (6) | |
H39 | 0.3074 | 0.2239 | 0.0122 | 0.039* | |
C40 | 0.1916 (2) | 0.20829 (13) | 0.05927 (10) | 0.0298 (6) | |
H40 | 0.1284 | 0.2213 | 0.0350 | 0.036* | |
C41 | 0.1825 (2) | 0.18510 (12) | 0.10997 (9) | 0.0243 (5) | |
N42 | 0.46307 (16) | 0.15183 (11) | 0.17565 (8) | 0.0272 (5) | |
N43 | 0.43613 (16) | 0.13750 (10) | 0.22510 (8) | 0.0262 (4) | |
C44 | 0.5351 (2) | 0.13201 (12) | 0.25860 (10) | 0.0276 (5) | |
C45 | 0.6248 (2) | 0.14277 (15) | 0.23018 (11) | 0.0370 (6) | |
H45 | 0.7018 | 0.1413 | 0.2431 | 0.044* | |
C46 | 0.5766 (2) | 0.15579 (15) | 0.17853 (11) | 0.0355 (6) | |
H46 | 0.6122 | 0.1652 | 0.1496 | 0.043* | |
C47 | 0.5358 (2) | 0.12010 (13) | 0.31711 (10) | 0.0300 (6) | |
C48 | 0.5084 (2) | 0.05632 (14) | 0.33536 (10) | 0.0321 (6) | |
C49 | 0.4966 (2) | 0.04885 (16) | 0.38919 (11) | 0.0391 (7) | |
H49 | 0.4760 | 0.0070 | 0.4011 | 0.047* | |
C50 | 0.5124 (2) | 0.10200 (18) | 0.42526 (11) | 0.0455 (8) | |
C51 | 0.5473 (3) | 0.16296 (18) | 0.40722 (12) | 0.0476 (8) | |
H51 | 0.5649 | 0.1985 | 0.4312 | 0.057* | |
C52 | 0.5615 (2) | 0.17350 (14) | 0.35396 (11) | 0.0383 (7) | |
C53 | 0.4957 (2) | −0.00390 (14) | 0.29854 (11) | 0.0381 (6) | |
H53A | 0.5666 | −0.0114 | 0.2851 | 0.057* | |
H53B | 0.4343 | 0.0042 | 0.2681 | 0.057* | |
H53C | 0.4779 | −0.0437 | 0.3185 | 0.057* | |
C54 | 0.4938 (3) | 0.0939 (2) | 0.48266 (13) | 0.0717 (12) | |
H54A | 0.4126 | 0.0895 | 0.4831 | 0.108* | |
H54B | 0.5235 | 0.1335 | 0.5037 | 0.108* | |
H54C | 0.5333 | 0.0535 | 0.4984 | 0.108* | |
C55 | 0.6033 (3) | 0.24092 (16) | 0.33919 (13) | 0.0570 (9) | |
H55A | 0.6170 | 0.2396 | 0.3020 | 0.086* | |
H55B | 0.6739 | 0.2519 | 0.3635 | 0.086* | |
H55C | 0.5462 | 0.2753 | 0.3424 | 0.086* | |
N56 | 0.07836 (16) | 0.17746 (10) | 0.12830 (7) | 0.0253 (4) | |
N57 | 0.07650 (16) | 0.15035 (10) | 0.17828 (7) | 0.0230 (4) | |
C58 | −0.0332 (2) | 0.14385 (12) | 0.18158 (10) | 0.0258 (5) | |
C59 | −0.1009 (2) | 0.16743 (14) | 0.13377 (10) | 0.0315 (6) | |
H59 | −0.1792 | 0.1693 | 0.1262 | 0.038* | |
C60 | −0.0284 (2) | 0.18787 (14) | 0.10107 (10) | 0.0321 (6) | |
H60 | −0.0477 | 0.2060 | 0.0669 | 0.039* | |
C61 | −0.0707 (2) | 0.11603 (13) | 0.23065 (10) | 0.0267 (5) | |
C62 | −0.0634 (2) | 0.15634 (13) | 0.27712 (10) | 0.0281 (5) | |
C63 | −0.0994 (2) | 0.13056 (14) | 0.32232 (10) | 0.0319 (6) | |
H63 | −0.0927 | 0.1577 | 0.3538 | 0.038* | |
C64 | −0.1448 (2) | 0.06649 (14) | 0.32325 (10) | 0.0320 (6) | |
C65 | −0.1555 (2) | 0.02854 (14) | 0.27646 (11) | 0.0359 (6) | |
H65 | −0.1839 | −0.0152 | 0.2761 | 0.043* | |
C66 | −0.1197 (2) | 0.05181 (14) | 0.22986 (11) | 0.0329 (6) | |
C67 | −0.0279 (2) | 0.22861 (14) | 0.27643 (11) | 0.0385 (6) | |
H67A | −0.0929 | 0.2562 | 0.2603 | 0.058* | |
H67B | 0.0326 | 0.2331 | 0.2551 | 0.058* | |
H67C | −0.0004 | 0.2438 | 0.3134 | 0.058* | |
C68 | −0.1852 (3) | 0.04075 (16) | 0.37298 (11) | 0.0438 (7) | |
H68A | −0.2351 | 0.0743 | 0.3852 | 0.066* | |
H68B | −0.1199 | 0.0327 | 0.4015 | 0.066* | |
H68C | −0.2269 | −0.0014 | 0.3645 | 0.066* | |
C69 | −0.1427 (3) | 0.00802 (17) | 0.18013 (13) | 0.0569 (9) | |
H69A | −0.0875 | −0.0288 | 0.1836 | 0.085* | |
H69B | −0.1362 | 0.0351 | 0.1483 | 0.085* | |
H69C | −0.2194 | −0.0107 | 0.1763 | 0.085* | |
Cl70 | −0.00754 (5) | 0.19456 (3) | −0.07600 (2) | 0.03230 (15) | |
O71 | −0.01943 (17) | 0.15782 (11) | −0.02791 (7) | 0.0448 (5) | |
O72 | −0.11652 (17) | 0.21764 (13) | −0.10213 (9) | 0.0556 (6) | |
O73 | 0.06568 (18) | 0.25182 (11) | −0.06190 (8) | 0.0483 (5) | |
O74 | 0.0402 (2) | 0.15169 (11) | −0.11171 (9) | 0.0561 (6) | |
Cl75 | −0.29084 (6) | 0.31741 (3) | 0.11716 (3) | 0.03563 (16) | |
O76 | −0.2692 (2) | 0.28740 (12) | 0.17002 (9) | 0.0567 (6) | |
O77 | −0.37365 (19) | 0.36966 (12) | 0.11554 (9) | 0.0563 (6) | |
O78 | −0.3295 (2) | 0.26673 (12) | 0.07827 (10) | 0.0671 (7) | |
O79 | −0.18724 (17) | 0.34644 (12) | 0.10737 (9) | 0.0548 (6) | |
C80 | −0.1349 (4) | 0.34720 (19) | −0.00958 (16) | 0.0790 (13) | |
H80A | −0.2005 | 0.3358 | −0.0352 | 0.119* | |
H80B | −0.1253 | 0.3149 | 0.0191 | 0.119* | |
H80C | −0.0697 | 0.3466 | −0.0267 | 0.119* | |
N81 | −0.1442 (2) | 0.41736 (13) | 0.00974 (10) | 0.0457 (6) | |
O82 | −0.2376 (2) | 0.44344 (13) | 0.00165 (9) | 0.0588 (6) | |
O83 | −0.0606 (2) | 0.44538 (14) | 0.03337 (11) | 0.0685 (7) | |
C84 | −0.2679 (3) | 0.15195 (18) | −0.01551 (13) | 0.0499 (8) | |
H84A | −0.2163 | 0.1171 | −0.0009 | 0.075* | |
H84B | −0.2368 | 0.1953 | −0.0042 | 0.075* | |
H84C | −0.2806 | 0.1495 | −0.0539 | 0.075* | |
N85 | −0.3764 (2) | 0.14521 (13) | 0.00379 (11) | 0.0422 (6) | |
O87 | −0.4603 (2) | 0.17022 (14) | −0.02297 (10) | 0.0656 (7) | |
O86 | −0.3762 (2) | 0.11557 (12) | 0.04645 (10) | 0.0575 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02420 (15) | 0.02458 (15) | 0.02087 (15) | −0.00018 (11) | 0.00532 (11) | 0.00108 (11) |
N2 | 0.0237 (10) | 0.0259 (11) | 0.0227 (10) | 0.0006 (8) | 0.0042 (8) | 0.0006 (8) |
C3 | 0.0235 (12) | 0.0271 (13) | 0.0236 (12) | 0.0020 (10) | 0.0037 (9) | 0.0016 (10) |
C4 | 0.0405 (15) | 0.0349 (15) | 0.0229 (13) | 0.0034 (12) | 0.0087 (11) | −0.0005 (11) |
C5 | 0.0425 (16) | 0.0407 (16) | 0.0261 (13) | 0.0038 (13) | 0.0124 (11) | 0.0079 (12) |
C6 | 0.0356 (14) | 0.0277 (13) | 0.0317 (14) | 0.0001 (11) | 0.0102 (11) | 0.0076 (11) |
C7 | 0.0245 (12) | 0.0281 (13) | 0.0274 (13) | 0.0012 (10) | 0.0055 (10) | 0.0022 (10) |
N8 | 0.0321 (11) | 0.0255 (11) | 0.0218 (10) | 0.0033 (9) | 0.0047 (8) | −0.0004 (8) |
N9 | 0.0267 (10) | 0.0244 (10) | 0.0206 (10) | 0.0002 (8) | 0.0061 (8) | 0.0014 (8) |
C10 | 0.0257 (13) | 0.0259 (13) | 0.0284 (13) | 0.0010 (10) | 0.0044 (10) | −0.0005 (10) |
C11 | 0.0570 (18) | 0.0239 (13) | 0.0343 (15) | 0.0014 (13) | 0.0072 (13) | −0.0042 (11) |
C12 | 0.0501 (17) | 0.0316 (14) | 0.0248 (13) | 0.0039 (13) | 0.0067 (12) | −0.0053 (11) |
C13 | 0.0334 (14) | 0.0210 (12) | 0.0294 (13) | −0.0018 (10) | 0.0044 (11) | 0.0010 (10) |
C14 | 0.0341 (14) | 0.0222 (13) | 0.0346 (14) | 0.0006 (11) | 0.0089 (11) | −0.0006 (11) |
C15 | 0.0398 (15) | 0.0264 (14) | 0.0407 (15) | −0.0022 (12) | 0.0159 (12) | 0.0022 (11) |
C16 | 0.0470 (17) | 0.0298 (14) | 0.0350 (15) | 0.0023 (12) | 0.0103 (12) | 0.0046 (12) |
C17 | 0.0378 (15) | 0.0342 (15) | 0.0340 (14) | −0.0007 (12) | 0.0010 (12) | 0.0059 (12) |
C18 | 0.0323 (14) | 0.0257 (13) | 0.0359 (14) | −0.0010 (11) | 0.0061 (11) | 0.0032 (11) |
C19 | 0.0330 (15) | 0.0344 (15) | 0.0466 (16) | 0.0029 (12) | 0.0100 (12) | 0.0037 (13) |
C20 | 0.062 (2) | 0.057 (2) | 0.0358 (16) | 0.0020 (17) | 0.0139 (15) | 0.0118 (15) |
C21 | 0.0314 (15) | 0.0437 (17) | 0.0454 (17) | 0.0011 (12) | 0.0095 (12) | 0.0122 (13) |
N22 | 0.0290 (11) | 0.0246 (11) | 0.0263 (10) | −0.0004 (9) | 0.0088 (8) | 0.0016 (9) |
N23 | 0.0243 (10) | 0.0253 (11) | 0.0259 (10) | 0.0003 (8) | 0.0049 (8) | 0.0014 (8) |
C24 | 0.0253 (12) | 0.0264 (13) | 0.0325 (13) | −0.0003 (10) | 0.0065 (10) | −0.0028 (11) |
C25 | 0.0459 (16) | 0.0244 (13) | 0.0402 (15) | −0.0003 (12) | 0.0102 (12) | −0.0042 (12) |
C26 | 0.0387 (15) | 0.0210 (13) | 0.0414 (15) | −0.0029 (11) | 0.0121 (12) | 0.0005 (11) |
C27 | 0.0312 (13) | 0.0246 (13) | 0.0282 (13) | −0.0015 (10) | 0.0064 (10) | −0.0053 (10) |
C28 | 0.0307 (14) | 0.0278 (13) | 0.0348 (14) | 0.0000 (11) | 0.0061 (11) | −0.0090 (11) |
C29 | 0.0379 (15) | 0.0327 (15) | 0.0301 (14) | 0.0046 (12) | −0.0015 (11) | −0.0046 (11) |
C30 | 0.0418 (15) | 0.0298 (14) | 0.0303 (13) | −0.0002 (12) | 0.0083 (11) | −0.0041 (11) |
C31 | 0.0327 (14) | 0.0368 (15) | 0.0361 (15) | −0.0006 (12) | 0.0110 (11) | −0.0044 (12) |
C32 | 0.0321 (14) | 0.0312 (14) | 0.0317 (14) | 0.0013 (11) | 0.0036 (11) | −0.0061 (11) |
C33 | 0.0290 (14) | 0.0428 (16) | 0.0418 (16) | 0.0005 (12) | 0.0049 (12) | −0.0113 (13) |
C34 | 0.0520 (18) | 0.0511 (19) | 0.0326 (15) | 0.0027 (15) | 0.0103 (13) | 0.0044 (14) |
C35 | 0.0335 (15) | 0.0566 (19) | 0.0393 (16) | 0.0083 (14) | 0.0073 (12) | −0.0011 (14) |
N36 | 0.0232 (10) | 0.0270 (11) | 0.0224 (10) | 0.0002 (8) | 0.0044 (8) | −0.0003 (8) |
C37 | 0.0254 (13) | 0.0263 (13) | 0.0265 (12) | 0.0003 (10) | 0.0064 (10) | 0.0013 (10) |
C38 | 0.0304 (14) | 0.0341 (14) | 0.0305 (13) | −0.0004 (11) | 0.0153 (11) | 0.0012 (11) |
C39 | 0.0403 (15) | 0.0345 (15) | 0.0233 (13) | −0.0009 (12) | 0.0094 (11) | 0.0032 (11) |
C40 | 0.0334 (14) | 0.0317 (14) | 0.0237 (12) | 0.0000 (11) | 0.0033 (10) | 0.0017 (10) |
C41 | 0.0249 (12) | 0.0240 (12) | 0.0241 (12) | −0.0002 (10) | 0.0043 (10) | −0.0011 (10) |
N42 | 0.0227 (10) | 0.0324 (12) | 0.0279 (11) | 0.0015 (9) | 0.0086 (8) | 0.0037 (9) |
N43 | 0.0259 (11) | 0.0270 (11) | 0.0259 (11) | −0.0002 (9) | 0.0054 (8) | 0.0038 (9) |
C44 | 0.0226 (12) | 0.0259 (13) | 0.0334 (13) | 0.0020 (10) | 0.0028 (10) | 0.0038 (11) |
C45 | 0.0204 (13) | 0.0464 (17) | 0.0432 (16) | 0.0033 (12) | 0.0032 (11) | 0.0075 (13) |
C46 | 0.0244 (13) | 0.0433 (16) | 0.0412 (16) | 0.0018 (12) | 0.0124 (11) | 0.0073 (13) |
C47 | 0.0222 (12) | 0.0355 (15) | 0.0313 (14) | 0.0036 (11) | 0.0018 (10) | 0.0025 (11) |
C48 | 0.0241 (13) | 0.0384 (15) | 0.0334 (14) | 0.0018 (11) | 0.0041 (10) | 0.0037 (12) |
C49 | 0.0306 (14) | 0.0516 (18) | 0.0348 (15) | −0.0012 (13) | 0.0046 (11) | 0.0086 (13) |
C50 | 0.0337 (15) | 0.069 (2) | 0.0328 (15) | 0.0054 (15) | 0.0025 (12) | −0.0009 (15) |
C51 | 0.0454 (18) | 0.057 (2) | 0.0364 (16) | 0.0086 (15) | −0.0052 (13) | −0.0132 (15) |
C52 | 0.0348 (15) | 0.0373 (16) | 0.0382 (16) | 0.0053 (12) | −0.0067 (12) | −0.0020 (12) |
C53 | 0.0381 (15) | 0.0323 (15) | 0.0427 (16) | 0.0011 (12) | 0.0035 (12) | 0.0064 (12) |
C54 | 0.062 (2) | 0.117 (4) | 0.0371 (18) | 0.002 (2) | 0.0115 (16) | −0.001 (2) |
C55 | 0.069 (2) | 0.0400 (18) | 0.053 (2) | −0.0062 (17) | −0.0136 (17) | −0.0024 (15) |
N56 | 0.0229 (10) | 0.0316 (11) | 0.0212 (10) | −0.0004 (9) | 0.0032 (8) | 0.0034 (8) |
N57 | 0.0228 (10) | 0.0259 (11) | 0.0210 (10) | 0.0003 (8) | 0.0055 (8) | 0.0015 (8) |
C58 | 0.0231 (12) | 0.0253 (13) | 0.0293 (13) | −0.0022 (10) | 0.0052 (10) | −0.0025 (10) |
C59 | 0.0204 (12) | 0.0391 (15) | 0.0339 (14) | 0.0023 (11) | 0.0020 (10) | 0.0053 (12) |
C60 | 0.0253 (13) | 0.0397 (15) | 0.0292 (13) | 0.0023 (11) | −0.0011 (10) | 0.0059 (11) |
C61 | 0.0220 (12) | 0.0280 (13) | 0.0300 (13) | 0.0022 (10) | 0.0046 (10) | 0.0016 (10) |
C62 | 0.0253 (13) | 0.0303 (13) | 0.0287 (13) | −0.0020 (11) | 0.0046 (10) | −0.0012 (11) |
C63 | 0.0306 (14) | 0.0381 (15) | 0.0265 (13) | −0.0020 (12) | 0.0035 (10) | 0.0001 (11) |
C64 | 0.0291 (13) | 0.0345 (14) | 0.0333 (14) | 0.0027 (11) | 0.0078 (11) | 0.0083 (12) |
C65 | 0.0400 (15) | 0.0250 (13) | 0.0462 (16) | −0.0008 (12) | 0.0174 (13) | 0.0039 (12) |
C66 | 0.0314 (14) | 0.0320 (14) | 0.0378 (14) | −0.0015 (11) | 0.0135 (11) | −0.0037 (12) |
C67 | 0.0452 (16) | 0.0350 (15) | 0.0379 (15) | −0.0110 (13) | 0.0144 (13) | −0.0059 (12) |
C68 | 0.0490 (18) | 0.0470 (18) | 0.0377 (16) | 0.0004 (14) | 0.0137 (13) | 0.0117 (14) |
C69 | 0.081 (2) | 0.0422 (18) | 0.056 (2) | −0.0224 (17) | 0.0356 (18) | −0.0164 (16) |
Cl70 | 0.0337 (3) | 0.0351 (3) | 0.0283 (3) | −0.0018 (3) | 0.0058 (3) | 0.0025 (3) |
O71 | 0.0442 (12) | 0.0576 (13) | 0.0324 (10) | −0.0101 (10) | 0.0060 (9) | 0.0132 (9) |
O72 | 0.0395 (12) | 0.0737 (17) | 0.0511 (13) | 0.0063 (11) | 0.0007 (10) | 0.0195 (12) |
O73 | 0.0589 (13) | 0.0428 (12) | 0.0431 (12) | −0.0191 (10) | 0.0086 (10) | 0.0002 (10) |
O74 | 0.0751 (16) | 0.0441 (13) | 0.0583 (14) | 0.0007 (11) | 0.0369 (12) | −0.0070 (11) |
Cl75 | 0.0357 (4) | 0.0320 (3) | 0.0397 (4) | −0.0015 (3) | 0.0082 (3) | −0.0017 (3) |
O76 | 0.0733 (16) | 0.0534 (14) | 0.0461 (13) | 0.0096 (12) | 0.0183 (11) | 0.0138 (11) |
O77 | 0.0541 (14) | 0.0526 (14) | 0.0633 (15) | 0.0208 (11) | 0.0135 (11) | 0.0021 (11) |
O78 | 0.0718 (16) | 0.0554 (15) | 0.0673 (16) | −0.0050 (13) | −0.0070 (13) | −0.0288 (13) |
O79 | 0.0378 (12) | 0.0576 (14) | 0.0703 (15) | −0.0079 (10) | 0.0136 (10) | 0.0145 (12) |
C80 | 0.132 (4) | 0.050 (2) | 0.059 (2) | 0.022 (2) | 0.025 (2) | −0.0066 (18) |
N81 | 0.0570 (17) | 0.0443 (15) | 0.0369 (14) | 0.0088 (14) | 0.0108 (12) | 0.0047 (12) |
O82 | 0.0584 (15) | 0.0613 (15) | 0.0555 (14) | 0.0128 (12) | 0.0062 (11) | −0.0002 (12) |
O83 | 0.0543 (15) | 0.0724 (18) | 0.0759 (17) | −0.0039 (13) | 0.0032 (13) | 0.0069 (14) |
C84 | 0.0414 (17) | 0.057 (2) | 0.0556 (19) | −0.0111 (15) | 0.0210 (15) | −0.0082 (16) |
N85 | 0.0408 (15) | 0.0376 (14) | 0.0516 (16) | −0.0062 (11) | 0.0176 (12) | −0.0101 (12) |
O87 | 0.0430 (14) | 0.0776 (19) | 0.0764 (17) | −0.0005 (13) | 0.0107 (12) | 0.0010 (14) |
O86 | 0.0739 (16) | 0.0465 (13) | 0.0614 (15) | −0.0039 (12) | 0.0375 (12) | 0.0003 (12) |
Zn1—N2 | 2.0607 (19) | C38—C39 | 1.386 (4) |
Zn1—N9 | 2.176 (2) | C39—C40 | 1.385 (4) |
Zn1—N23 | 2.168 (2) | C40—C41 | 1.379 (3) |
Zn1—N36 | 2.0497 (19) | C41—N56 | 1.413 (3) |
Zn1—N43 | 2.195 (2) | N42—C46 | 1.353 (3) |
Zn1—N57 | 2.2130 (19) | N42—N43 | 1.370 (3) |
N2—C3 | 1.333 (3) | N43—C44 | 1.335 (3) |
N2—C7 | 1.335 (3) | C44—C45 | 1.408 (4) |
C3—C4 | 1.381 (3) | C44—C47 | 1.491 (4) |
C3—N8 | 1.415 (3) | C45—C46 | 1.353 (4) |
C4—C5 | 1.388 (4) | C47—C48 | 1.406 (4) |
C5—C6 | 1.381 (4) | C47—C52 | 1.408 (4) |
C6—C7 | 1.381 (3) | C48—C49 | 1.395 (4) |
C7—N22 | 1.416 (3) | C48—C53 | 1.505 (4) |
N8—C12 | 1.355 (3) | C49—C50 | 1.384 (4) |
N8—N9 | 1.376 (3) | C50—C51 | 1.383 (5) |
N9—C10 | 1.339 (3) | C50—C54 | 1.509 (4) |
C10—C11 | 1.410 (3) | C51—C52 | 1.397 (4) |
C10—C13 | 1.490 (3) | C52—C55 | 1.499 (4) |
C11—C12 | 1.361 (4) | N56—C60 | 1.359 (3) |
C13—C18 | 1.404 (4) | N56—N57 | 1.373 (3) |
C13—C14 | 1.408 (4) | N57—C58 | 1.339 (3) |
C14—C15 | 1.389 (4) | C58—C59 | 1.410 (3) |
C14—C19 | 1.502 (4) | C58—C61 | 1.492 (3) |
C15—C16 | 1.392 (4) | C59—C60 | 1.360 (4) |
C16—C17 | 1.384 (4) | C61—C66 | 1.403 (4) |
C16—C20 | 1.507 (4) | C61—C62 | 1.408 (3) |
C17—C18 | 1.396 (4) | C62—C63 | 1.384 (4) |
C18—C21 | 1.510 (4) | C62—C67 | 1.498 (4) |
N22—C26 | 1.365 (3) | C63—C64 | 1.386 (4) |
N22—N23 | 1.374 (3) | C64—C65 | 1.386 (4) |
N23—C24 | 1.337 (3) | C64—C68 | 1.509 (4) |
C24—C25 | 1.408 (4) | C65—C66 | 1.397 (4) |
C24—C27 | 1.489 (3) | C66—C69 | 1.510 (4) |
C25—C26 | 1.365 (4) | Cl70—O74 | 1.428 (2) |
C27—C28 | 1.408 (4) | Cl70—O72 | 1.432 (2) |
C27—C32 | 1.408 (4) | Cl70—O71 | 1.4420 (19) |
C28—C29 | 1.383 (4) | Cl70—O73 | 1.443 (2) |
C28—C33 | 1.506 (4) | Cl75—O78 | 1.424 (2) |
C29—C30 | 1.393 (4) | Cl75—O79 | 1.429 (2) |
C30—C31 | 1.391 (4) | Cl75—O77 | 1.432 (2) |
C30—C34 | 1.507 (4) | Cl75—O76 | 1.440 (2) |
C31—C32 | 1.399 (4) | C80—N81 | 1.486 (4) |
C32—C35 | 1.509 (4) | N81—O83 | 1.209 (3) |
N36—C37 | 1.327 (3) | N81—O82 | 1.218 (3) |
N36—C41 | 1.337 (3) | C84—N85 | 1.472 (4) |
C37—C38 | 1.378 (3) | N85—O87 | 1.215 (3) |
C37—N42 | 1.420 (3) | N85—O86 | 1.225 (3) |
N2—Zn1—N9 | 76.01 (8) | C41—N36—Zn1 | 120.08 (16) |
N2—Zn1—N23 | 75.65 (8) | N36—C37—C38 | 123.5 (2) |
N2—Zn1—N36 | 179.25 (8) | N36—C37—N42 | 113.4 (2) |
N2—Zn1—N43 | 104.16 (7) | C38—C37—N42 | 123.2 (2) |
N2—Zn1—N57 | 104.02 (7) | C37—C38—C39 | 116.4 (2) |
N9—Zn1—N23 | 151.62 (7) | C40—C39—C38 | 121.5 (2) |
N9—Zn1—N36 | 104.69 (8) | C41—C40—C39 | 117.0 (2) |
N9—Zn1—N43 | 93.12 (7) | N36—C41—C40 | 122.6 (2) |
N9—Zn1—N57 | 93.47 (7) | N36—C41—N56 | 113.7 (2) |
N23—Zn1—N36 | 103.65 (8) | C40—C41—N56 | 123.7 (2) |
N23—Zn1—N43 | 95.29 (7) | C46—N42—N43 | 111.0 (2) |
N23—Zn1—N57 | 91.79 (7) | C46—N42—C37 | 129.5 (2) |
N36—Zn1—N43 | 75.57 (7) | N43—N42—C37 | 118.60 (19) |
N36—Zn1—N57 | 76.25 (7) | C44—N43—N42 | 105.49 (19) |
N43—Zn1—N57 | 151.82 (7) | C44—N43—Zn1 | 143.36 (17) |
C3—N2—C7 | 119.5 (2) | N42—N43—Zn1 | 111.12 (14) |
C3—N2—Zn1 | 119.82 (16) | N43—C44—C45 | 109.9 (2) |
C7—N2—Zn1 | 120.59 (16) | N43—C44—C47 | 119.3 (2) |
N2—C3—C4 | 122.6 (2) | C45—C44—C47 | 130.7 (2) |
N2—C3—N8 | 113.6 (2) | C46—C45—C44 | 106.4 (2) |
C4—C3—N8 | 123.7 (2) | C45—C46—N42 | 107.3 (2) |
C3—C4—C5 | 116.6 (2) | C48—C47—C52 | 120.0 (2) |
C6—C5—C4 | 121.8 (2) | C48—C47—C44 | 120.3 (2) |
C7—C6—C5 | 116.7 (2) | C52—C47—C44 | 119.7 (2) |
N2—C7—C6 | 122.7 (2) | C49—C48—C47 | 118.8 (3) |
N2—C7—N22 | 112.8 (2) | C49—C48—C53 | 119.9 (3) |
C6—C7—N22 | 124.6 (2) | C47—C48—C53 | 121.3 (2) |
C12—N8—N9 | 110.7 (2) | C50—C49—C48 | 122.1 (3) |
C12—N8—C3 | 130.3 (2) | C51—C50—C49 | 117.8 (3) |
N9—N8—C3 | 118.37 (19) | C51—C50—C54 | 120.8 (3) |
C10—N9—N8 | 105.83 (19) | C49—C50—C54 | 121.4 (3) |
C10—N9—Zn1 | 142.75 (16) | C50—C51—C52 | 122.8 (3) |
N8—N9—Zn1 | 111.32 (14) | C51—C52—C47 | 118.1 (3) |
N9—C10—C11 | 109.6 (2) | C51—C52—C55 | 118.3 (3) |
N9—C10—C13 | 118.7 (2) | C47—C52—C55 | 123.6 (3) |
C11—C10—C13 | 131.6 (2) | C60—N56—N57 | 110.99 (19) |
C12—C11—C10 | 106.5 (2) | C60—N56—C41 | 128.9 (2) |
N8—C12—C11 | 107.3 (2) | N57—N56—C41 | 119.87 (18) |
C18—C13—C14 | 119.8 (2) | C58—N57—N56 | 105.53 (18) |
C18—C13—C10 | 120.0 (2) | C58—N57—Zn1 | 144.75 (16) |
C14—C13—C10 | 120.2 (2) | N56—N57—Zn1 | 109.73 (13) |
C15—C14—C13 | 119.3 (2) | N57—C58—C59 | 109.9 (2) |
C15—C14—C19 | 119.8 (2) | N57—C58—C61 | 121.8 (2) |
C13—C14—C19 | 120.8 (2) | C59—C58—C61 | 128.2 (2) |
C14—C15—C16 | 121.5 (3) | C60—C59—C58 | 106.4 (2) |
C17—C16—C15 | 118.2 (3) | N56—C60—C59 | 107.1 (2) |
C17—C16—C20 | 120.7 (3) | C66—C61—C62 | 119.6 (2) |
C15—C16—C20 | 121.1 (3) | C66—C61—C58 | 120.7 (2) |
C16—C17—C18 | 122.3 (3) | C62—C61—C58 | 119.6 (2) |
C17—C18—C13 | 118.6 (2) | C63—C62—C61 | 119.3 (2) |
C17—C18—C21 | 117.6 (2) | C63—C62—C67 | 119.6 (2) |
C13—C18—C21 | 123.8 (2) | C61—C62—C67 | 120.8 (2) |
C26—N22—N23 | 110.7 (2) | C62—C63—C64 | 122.2 (2) |
C26—N22—C7 | 130.4 (2) | C65—C64—C63 | 117.6 (2) |
N23—N22—C7 | 118.82 (19) | C65—C64—C68 | 121.7 (2) |
C24—N23—N22 | 105.85 (19) | C63—C64—C68 | 120.6 (2) |
C24—N23—Zn1 | 142.16 (17) | C64—C65—C66 | 122.5 (2) |
N22—N23—Zn1 | 111.99 (14) | C65—C66—C61 | 118.6 (2) |
N23—C24—C25 | 110.0 (2) | C65—C66—C69 | 117.9 (2) |
N23—C24—C27 | 119.5 (2) | C61—C66—C69 | 123.4 (2) |
C25—C24—C27 | 130.5 (2) | O74—Cl70—O72 | 109.57 (15) |
C26—C25—C24 | 106.5 (2) | O74—Cl70—O71 | 109.65 (14) |
C25—C26—N22 | 106.9 (2) | O72—Cl70—O71 | 109.40 (13) |
C28—C27—C32 | 119.8 (2) | O74—Cl70—O73 | 109.36 (14) |
C28—C27—C24 | 119.5 (2) | O72—Cl70—O73 | 109.16 (14) |
C32—C27—C24 | 120.7 (2) | O71—Cl70—O73 | 109.69 (12) |
C29—C28—C27 | 119.5 (2) | O78—Cl75—O79 | 110.77 (16) |
C29—C28—C33 | 119.8 (2) | O78—Cl75—O77 | 110.59 (15) |
C27—C28—C33 | 120.7 (2) | O79—Cl75—O77 | 108.79 (14) |
C28—C29—C30 | 122.2 (2) | O78—Cl75—O76 | 109.14 (15) |
C31—C30—C29 | 117.5 (2) | O79—Cl75—O76 | 107.71 (14) |
C31—C30—C34 | 121.8 (2) | O77—Cl75—O76 | 109.79 (14) |
C29—C30—C34 | 120.7 (2) | O83—N81—O82 | 123.1 (3) |
C30—C31—C32 | 122.6 (2) | O83—N81—C80 | 119.3 (3) |
C31—C32—C27 | 118.4 (2) | O82—N81—C80 | 117.6 (3) |
C31—C32—C35 | 119.7 (2) | O87—N85—O86 | 123.9 (3) |
C27—C32—C35 | 121.9 (2) | O87—N85—C84 | 118.3 (3) |
C37—N36—C41 | 119.0 (2) | O86—N85—C84 | 117.8 (3) |
C37—N36—Zn1 | 120.87 (16) |
Experimental details
Crystal data | |
Chemical formula | [Zn(C29H29N5)2](ClO4)2·2CH3NO2 |
Mr | 1281.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.9913 (2), 19.8605 (3), 25.1833 (3) |
β (°) | 100.0240 (9) |
V (Å3) | 5905.93 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.54 × 0.42 × 0.28 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.745, 0.854 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 86756, 13519, 9275 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.136, 1.04 |
No. of reflections | 13519 |
No. of parameters | 784 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.96 |
Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1996), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), SHELXL97 and local software.
Zn1—N2 | 2.0607 (19) | Zn1—N36 | 2.0497 (19) |
Zn1—N9 | 2.176 (2) | Zn1—N43 | 2.195 (2) |
Zn1—N23 | 2.168 (2) | Zn1—N57 | 2.2130 (19) |
N2—Zn1—N9 | 76.01 (8) | N9—Zn1—N57 | 93.47 (7) |
N2—Zn1—N23 | 75.65 (8) | N23—Zn1—N36 | 103.65 (8) |
N2—Zn1—N36 | 179.25 (8) | N23—Zn1—N43 | 95.29 (7) |
N2—Zn1—N43 | 104.16 (7) | N23—Zn1—N57 | 91.79 (7) |
N2—Zn1—N57 | 104.02 (7) | N36—Zn1—N43 | 75.57 (7) |
N9—Zn1—N23 | 151.62 (7) | N36—Zn1—N57 | 76.25 (7) |
N9—Zn1—N36 | 104.69 (8) | N43—Zn1—N57 | 151.82 (7) |
N9—Zn1—N43 | 93.12 (7) |
Ring A | Ring B | Interplanar spacing | Dihedral Angle | Offset |
N2-C7 | C47-C52 | 3.56 | 8.2 (2) | 1.2 |
N2-C7 | C61-C66 | 3.89 | 14.4 (2) | 0.7 |
N36-C41 | C13-C18 | 3.47 | 5.6 (2) | 1.0 |
N36-C41 | C27-C32 | 3.52 | 2.8 (2) | 0.6 |
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We have recently described the complex [CuL2](ClO4)2·2CH3NO2, (I) {L is 2,6-bis[3-(2,4,6-trimethylphenyl)pyrazol-1-yl]pyridine}, which exhibits a rhombic six-coordinate stereochemistry in the crystal (Solanki et al., 1998). This complex exhibits an unusual {dz2}1 electronic ground state, which is imposed by intramolecular steric repulsions at the metal ion between the mesityl substituents of one ligand and the pyridine ring of the other (Solanki et al., 1998; Bridgeman et al., 1999). We were interested in comparing the molecular structure of (I) with an analogue containing a metal ion with a spherical d shell, to determine the extent to which the {dz2}1 unpaired electron dictates the stereochemistry of the CuII ion. We have therefore determined the crystal structure of the title compound, [ZnL2](ClO4)2·2CH3NO2, (II). \sch
Compound (II) is isomorphous with its CuII congener (Solanki et al., 1998), also crystallizing in space group P212121. The asymmetric unit contains one formula unit, with the cation and all anions and solvent molecules in general positions. The ZnII ion adopts a rhombic coordination geometry, with the Zn—Npyrazole bonds to one ligand (Zn1—N9 and Zn1—N23) being shorter than the corresponding bonds to the other ligand (Zn1—N43 and Zn1—N57) by 0.027 (3)–0.037 (3) Å. This is a lower rhombicity than is exhibited by the CuII complex, however, where the Cu—Npyrazole bonds to one ligand are 0.091 (8)–0.114 (8) Å shorter than to the other. Interestingly, although one ligand (N2—C35) is bound symmetrically to the ZnII ion, the other (N36—C69) is slightly asymmetrically coordinated, with Zn1—N43 being 0.018 (3) Å shorter than Zn—N57. Since space-filling models show no steric contacts that could impose these small distortions from ideal D2 d symmetry, both the rhombicity of the coordination sphere and the asymmetric binding of ligand N36—C69 are probably imposed by the local lattice environment. Overall, the coordination geometry in this complex closely resembles those of stereochemically similar ZnII complexes containing two terpyridyl derivatives as ligands (Whittle et al., 1998; Alcock et al., 2000). The small rhombicity exhibited by (II) suggests that the more rhombic stereochemistry adopted by (I) is largely driven by the electronic preferences of the CuII ion.
The mesityl rings of each ligand in (II) sandwich the pyridine ring of the coligand, forming two perpendicular triple π-π stacks. The metric parameters for these π-π interactions are given in Table 2. For comparison, the Cu—Npyrazole bonds in (I) range from 2.136 (6)–2.256 (6) Å, while the π-π interplanar distances are in the range 3.5–3.7 Å and the dihedral angles in the range 2.0 (2)–13.2 (2)° (Solanki et al., 1998). The small horizontal offsets of these interacting rings are consistent with these being electrostatically repulsive π-π interactions (Hunter & Sanders, 1990). There are no close intermolecular contacts within the crystal lattice.