Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113008111/ky3027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113008111/ky3027Isup2.hkl |
CCDC reference: 950352
N,N'-Bis(pyridin-3-ylmethyl)-[1,1'-biphenyl]-4,4'-dicarboxamide (L) was synthesized according to the literature method of Luo et al. (2007). For the preparation of (I), L (84.50 mg, 0.2 mmol), [1,1'-biphenyl]-4,4'-dicarboxylic acid (48.45 mg, 0.2 mmol) and ZnCl2 (27.26 mg, 0.2 mmol) were mixed with deionized water (6 ml) in a 25 ml Teflon-lined reactor, and heated to 433 K for 3 d. The mixture was cooled to room temperature at a rate of 3 K h-1. Finally, block-shaped crystals were obtained in 63% yield based on ZnCl2.
H atoms bonded to N atoms were found by difference synthesis and refined with the N—H distances restrained to approximate 0.86 (1) Å. H atoms bonded to C atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å for CH and CH2 groups, respectively, and treated using a riding-model approximation. For all H atoms, Uiso(H) = 1.2Ueq(N,C).
The [1,1'-biphenyl]-4,4'-dicarboxylate ligand was treated as disordered over two sites with occupancies refined to 0.854 (6) and 0.146 (6). To obtain a sensible stable model, the geometry of the minor component needed to be set to that of a regular hexagon (AFIX 66 for the aryl ring) and restraints were placed on the C1A—C2A and C1A—O1A distances. Displacement parameters for the minor disorder component were set to equal those of the major component for those pairs of atom sites which were spacially close. The displacement parameters of the major disorder component were restrained to act as a single body using DELU and SIMU instructions. Removal of any group of restraints or constraints gave unacceptable results for the model of the minor disorder component.
Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Zn2(C14H8O4)Cl2(C26H22N4O2)3] | Z = 2 |
Mr = 854.64 | F(000) = 884 |
Triclinic, P1 | Dx = 1.473 Mg m−3 |
a = 8.9365 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7815 (2) Å | Cell parameters from 2336 reflections |
c = 22.3819 (5) Å | θ = 2.3–18.5° |
α = 86.696 (2)° | µ = 0.77 mm−1 |
β = 80.675 (2)° | T = 296 K |
γ = 89.888 (2)° | Block, colourless |
V = 1927.34 (7) Å3 | 0.15 × 0.12 × 0.10 mm |
Bruker APEXII CCD area-detector diffractometer | 7549 independent reflections |
Radiation source: fine-focus sealed tube | 4948 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
phi and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.894, Tmax = 0.927 | k = −12→12 |
28062 measured reflections | l = −27→27 |
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)] = 0.050 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.P)2 + 0.6236P] where P = (Fo2 + 2Fc2)/3 |
7549 reflections | (Δ/σ)max = 0.001 |
563 parameters | Δρmax = 0.31 e Å−3 |
194 restraints | Δρmin = −0.31 e Å−3 |
[Zn2(C14H8O4)Cl2(C26H22N4O2)3] | γ = 89.888 (2)° |
Mr = 854.64 | V = 1927.34 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9365 (2) Å | Mo Kα radiation |
b = 9.7815 (2) Å | µ = 0.77 mm−1 |
c = 22.3819 (5) Å | T = 296 K |
α = 86.696 (2)° | 0.15 × 0.12 × 0.10 mm |
β = 80.675 (2)° |
Bruker APEXII CCD area-detector diffractometer | 7549 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4948 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 0.927 | Rint = 0.074 |
28062 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 194 restraints |
wR(F2) = 0.114 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.31 e Å−3 |
7549 reflections | Δρmin = −0.31 e Å−3 |
563 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.46048 (4) | 1.00700 (4) | 0.159609 (16) | 0.04135 (13) | |
Cl1 | 0.64713 (10) | 0.91677 (10) | 0.09384 (4) | 0.0607 (3) | |
O3 | −0.0106 (3) | 0.6055 (2) | 0.27051 (9) | 0.0489 (6) | |
O4 | 0.0703 (3) | 0.8903 (2) | 0.75252 (10) | 0.0629 (7) | |
O5 | 0.6003 (3) | 1.5671 (3) | 0.23920 (12) | 0.0754 (8) | |
N1 | 0.2719 (3) | 0.9229 (2) | 0.13485 (11) | 0.0394 (6) | |
N2 | −0.1050 (3) | 0.8185 (3) | 0.26520 (11) | 0.0386 (6) | |
H2N | −0.107 (4) | 0.8968 (14) | 0.2810 (13) | 0.046* | |
N3 | 0.1274 (4) | 0.6679 (3) | 0.76251 (12) | 0.0500 (7) | |
H3N | 0.128 (4) | 0.5885 (15) | 0.7479 (14) | 0.060* | |
N4 | −0.1384 (5) | 0.5545 (4) | 0.94168 (19) | 0.0962 (13) | |
N5 | 0.4646 (3) | 1.2132 (3) | 0.13051 (11) | 0.0426 (6) | |
N6 | 0.3498 (3) | 1.5240 (3) | 0.25551 (13) | 0.0533 (7) | |
H6N | 0.267 (2) | 1.533 (4) | 0.2805 (12) | 0.064* | |
C8 | 0.2768 (4) | 0.8878 (4) | 0.07740 (14) | 0.0542 (9) | |
H8 | 0.3658 | 0.9036 | 0.0499 | 0.065* | |
C9 | 0.1560 (4) | 0.8299 (4) | 0.05788 (16) | 0.0618 (10) | |
H9 | 0.1624 | 0.8084 | 0.0176 | 0.074* | |
C10 | 0.0243 (4) | 0.8035 (3) | 0.09841 (14) | 0.0467 (8) | |
H10 | −0.0586 | 0.7631 | 0.0859 | 0.056* | |
C11 | 0.0168 (3) | 0.8375 (3) | 0.15774 (13) | 0.0347 (7) | |
C12 | 0.1430 (3) | 0.8967 (3) | 0.17348 (13) | 0.0375 (7) | |
H12 | 0.1387 | 0.9200 | 0.2134 | 0.045* | |
C13 | −0.1259 (4) | 0.8131 (3) | 0.20278 (13) | 0.0439 (8) | |
H13A | −0.2000 | 0.8813 | 0.1945 | 0.053* | |
H13B | −0.1670 | 0.7240 | 0.1971 | 0.053* | |
C14 | −0.0471 (3) | 0.7139 (3) | 0.29471 (13) | 0.0363 (7) | |
C15 | −0.0309 (3) | 0.7308 (3) | 0.35912 (13) | 0.0347 (7) | |
C16 | 0.0432 (4) | 0.6284 (3) | 0.38814 (13) | 0.0420 (8) | |
H16 | 0.0830 | 0.5544 | 0.3667 | 0.050* | |
C17 | 0.0586 (4) | 0.6344 (3) | 0.44823 (13) | 0.0430 (8) | |
H17 | 0.1111 | 0.5655 | 0.4662 | 0.052* | |
C18 | −0.0027 (3) | 0.7416 (3) | 0.48267 (13) | 0.0365 (7) | |
C19 | −0.0767 (4) | 0.8433 (3) | 0.45316 (14) | 0.0468 (8) | |
H19 | −0.1183 | 0.9167 | 0.4746 | 0.056* | |
C20 | −0.0900 (4) | 0.8383 (3) | 0.39274 (14) | 0.0455 (8) | |
H20 | −0.1397 | 0.9086 | 0.3743 | 0.055* | |
C21 | 0.0136 (4) | 0.7453 (3) | 0.54748 (13) | 0.0365 (7) | |
C22 | 0.1281 (4) | 0.6734 (3) | 0.57057 (14) | 0.0422 (8) | |
H22 | 0.1943 | 0.6210 | 0.5449 | 0.051* | |
C23 | 0.1459 (4) | 0.6775 (3) | 0.63012 (14) | 0.0432 (8) | |
H23 | 0.2225 | 0.6268 | 0.6443 | 0.052* | |
C24 | 0.0516 (4) | 0.7560 (3) | 0.66939 (13) | 0.0379 (7) | |
C25 | −0.0627 (4) | 0.8285 (3) | 0.64705 (14) | 0.0475 (8) | |
H25 | −0.1264 | 0.8831 | 0.6726 | 0.057* | |
C26 | −0.0837 (4) | 0.8211 (3) | 0.58778 (14) | 0.0449 (8) | |
H26 | −0.1642 | 0.8674 | 0.5744 | 0.054* | |
C27 | 0.0818 (4) | 0.7759 (3) | 0.73184 (13) | 0.0414 (8) | |
C28 | 0.1805 (4) | 0.6795 (4) | 0.82043 (14) | 0.0547 (9) | |
H28A | 0.2394 | 0.7632 | 0.8187 | 0.066* | |
H28B | 0.2469 | 0.6033 | 0.8268 | 0.066* | |
C29 | 0.0537 (4) | 0.6804 (3) | 0.87331 (14) | 0.0432 (8) | |
C30 | 0.0125 (5) | 0.7962 (4) | 0.90363 (16) | 0.0584 (10) | |
H30 | 0.0624 | 0.8789 | 0.8912 | 0.070* | |
C31 | −0.1026 (5) | 0.7891 (5) | 0.95226 (18) | 0.0700 (11) | |
H31 | −0.1315 | 0.8668 | 0.9732 | 0.084* | |
C32 | −0.1740 (5) | 0.6679 (6) | 0.96960 (19) | 0.0765 (12) | |
H32 | −0.2517 | 0.6645 | 1.0028 | 0.092* | |
C33 | −0.0260 (6) | 0.5640 (4) | 0.8950 (2) | 0.0783 (13) | |
H33 | 0.0009 | 0.4844 | 0.8752 | 0.094* | |
C34 | 0.5504 (4) | 1.2548 (4) | 0.07776 (14) | 0.0508 (9) | |
H34 | 0.5951 | 1.1890 | 0.0524 | 0.061* | |
C35 | 0.5749 (4) | 1.3903 (4) | 0.05970 (15) | 0.0602 (10) | |
H35 | 0.6360 | 1.4160 | 0.0231 | 0.072* | |
C36 | 0.5066 (4) | 1.4877 (4) | 0.09710 (16) | 0.0587 (10) | |
H36 | 0.5220 | 1.5802 | 0.0857 | 0.070* | |
C37 | 0.4165 (4) | 1.4489 (4) | 0.15082 (15) | 0.0494 (9) | |
C38 | 0.3997 (4) | 1.3105 (3) | 0.16597 (14) | 0.0466 (8) | |
H38 | 0.3402 | 1.2830 | 0.2027 | 0.056* | |
C39 | 0.3387 (5) | 1.5546 (4) | 0.19178 (16) | 0.0621 (10) | |
H39A | 0.3840 | 1.6437 | 0.1790 | 0.075* | |
H39B | 0.2325 | 1.5591 | 0.1874 | 0.075* | |
C40 | 0.4827 (4) | 1.5423 (3) | 0.27464 (17) | 0.0526 (9) | |
C41 | 0.4820 (4) | 1.5276 (3) | 0.34165 (15) | 0.0461 (8) | |
C42 | 0.5764 (4) | 1.6100 (4) | 0.36657 (17) | 0.0584 (10) | |
H42 | 0.6380 | 1.6736 | 0.3415 | 0.070* | |
C43 | 0.5822 (4) | 1.6008 (4) | 0.42775 (17) | 0.0572 (9) | |
H43 | 0.6454 | 1.6602 | 0.4433 | 0.069* | |
C44 | 0.4961 (4) | 1.5049 (3) | 0.46688 (15) | 0.0458 (8) | |
C45 | 0.4033 (4) | 1.4213 (4) | 0.44062 (18) | 0.0616 (10) | |
H45 | 0.3434 | 1.3557 | 0.4651 | 0.074* | |
C46 | 0.3969 (4) | 1.4320 (4) | 0.37978 (17) | 0.0608 (10) | |
H46 | 0.3335 | 1.3732 | 0.3640 | 0.073* | |
O1 | 0.4818 (5) | 1.0340 (5) | 0.24193 (18) | 0.0679 (12) | 0.854 (6) |
O2 | 0.3458 (4) | 0.8502 (4) | 0.27173 (13) | 0.0812 (14) | 0.854 (6) |
C1 | 0.4197 (9) | 0.9480 (8) | 0.2828 (3) | 0.0492 (14) | 0.854 (6) |
C2 | 0.4415 (8) | 0.9685 (8) | 0.3472 (3) | 0.0385 (13) | 0.854 (6) |
C3 | 0.5425 (7) | 1.0610 (9) | 0.3619 (3) | 0.0642 (17) | 0.854 (6) |
H3 | 0.5975 | 1.1175 | 0.3313 | 0.077* | 0.854 (6) |
C4 | 0.5645 (8) | 1.0725 (10) | 0.4208 (4) | 0.0672 (19) | 0.854 (6) |
H4 | 0.6347 | 1.1363 | 0.4288 | 0.081* | 0.854 (6) |
C5 | 0.4863 (10) | 0.9926 (10) | 0.4688 (3) | 0.0356 (11) | 0.854 (6) |
C6 | 0.3835 (8) | 0.9014 (6) | 0.4533 (3) | 0.0452 (15) | 0.854 (6) |
H6 | 0.3268 | 0.8459 | 0.4838 | 0.054* | 0.854 (6) |
C7 | 0.3617 (8) | 0.8894 (6) | 0.3941 (3) | 0.0493 (15) | 0.854 (6) |
H7 | 0.2913 | 0.8262 | 0.3859 | 0.059* | 0.854 (6) |
O1A | 0.551 (3) | 1.013 (3) | 0.2393 (13) | 0.0679 (12) | 0.146 (6) |
O2A | 0.310 (2) | 0.970 (3) | 0.2675 (8) | 0.074 (4) | 0.146 (6) |
C1A | 0.440 (5) | 0.979 (6) | 0.2785 (15) | 0.0492 (14) | 0.146 (6) |
C2A | 0.467 (5) | 0.986 (5) | 0.3423 (16) | 0.0385 (13) | 0.146 (6) |
C3A | 0.590 (5) | 1.056 (5) | 0.357 (2) | 0.0642 (17) | 0.146 (6) |
H3A | 0.6616 | 1.0966 | 0.3262 | 0.077* | 0.146 (6) |
C4A | 0.606 (5) | 1.066 (6) | 0.417 (2) | 0.0672 (19) | 0.146 (6) |
H4A | 0.6884 | 1.1125 | 0.4270 | 0.081* | 0.146 (6) |
C5A | 0.499 (6) | 1.005 (6) | 0.4631 (17) | 0.0356 (11) | 0.146 (6) |
C6A | 0.375 (5) | 0.935 (5) | 0.4485 (19) | 0.0452 (15) | 0.146 (6) |
H6A | 0.3038 | 0.8951 | 0.4792 | 0.054* | 0.146 (6) |
C7A | 0.359 (5) | 0.926 (4) | 0.388 (2) | 0.0493 (15) | 0.146 (6) |
H7A | 0.2769 | 0.8791 | 0.3784 | 0.059* | 0.146 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0429 (2) | 0.0530 (3) | 0.0285 (2) | −0.00346 (17) | −0.00603 (15) | −0.00476 (16) |
Cl1 | 0.0494 (5) | 0.0850 (7) | 0.0478 (5) | 0.0179 (5) | −0.0063 (4) | −0.0100 (5) |
O3 | 0.0716 (16) | 0.0393 (13) | 0.0372 (13) | 0.0047 (11) | −0.0102 (11) | −0.0089 (10) |
O4 | 0.105 (2) | 0.0411 (14) | 0.0469 (15) | 0.0059 (13) | −0.0221 (14) | −0.0118 (11) |
O5 | 0.0608 (18) | 0.095 (2) | 0.0641 (18) | −0.0148 (15) | 0.0129 (14) | −0.0131 (15) |
N1 | 0.0433 (16) | 0.0457 (16) | 0.0304 (14) | −0.0018 (12) | −0.0082 (12) | −0.0054 (12) |
N2 | 0.0482 (16) | 0.0389 (15) | 0.0293 (14) | −0.0015 (13) | −0.0077 (12) | −0.0027 (12) |
N3 | 0.080 (2) | 0.0412 (17) | 0.0329 (16) | 0.0118 (16) | −0.0185 (14) | −0.0076 (13) |
N4 | 0.112 (3) | 0.087 (3) | 0.082 (3) | −0.036 (3) | 0.006 (3) | −0.004 (2) |
N5 | 0.0460 (16) | 0.0536 (17) | 0.0268 (14) | −0.0001 (13) | −0.0013 (12) | −0.0034 (12) |
N6 | 0.052 (2) | 0.0574 (19) | 0.0469 (19) | 0.0049 (15) | 0.0047 (14) | −0.0097 (15) |
C8 | 0.047 (2) | 0.084 (3) | 0.0299 (19) | −0.0057 (19) | 0.0011 (15) | −0.0110 (17) |
C9 | 0.054 (2) | 0.097 (3) | 0.036 (2) | −0.007 (2) | −0.0078 (18) | −0.0224 (19) |
C10 | 0.045 (2) | 0.057 (2) | 0.041 (2) | −0.0015 (16) | −0.0143 (16) | −0.0122 (16) |
C11 | 0.0411 (18) | 0.0323 (17) | 0.0325 (17) | 0.0020 (14) | −0.0114 (14) | −0.0027 (13) |
C12 | 0.0428 (19) | 0.0455 (19) | 0.0238 (16) | 0.0000 (15) | −0.0044 (14) | −0.0016 (13) |
C13 | 0.048 (2) | 0.050 (2) | 0.0349 (18) | −0.0068 (16) | −0.0108 (15) | 0.0016 (15) |
C14 | 0.0377 (18) | 0.0370 (18) | 0.0323 (17) | −0.0063 (14) | −0.0004 (13) | −0.0003 (14) |
C15 | 0.0397 (18) | 0.0331 (17) | 0.0293 (16) | −0.0056 (14) | 0.0005 (13) | −0.0006 (13) |
C16 | 0.052 (2) | 0.0370 (18) | 0.0350 (18) | 0.0021 (15) | −0.0015 (15) | −0.0025 (14) |
C17 | 0.051 (2) | 0.0422 (19) | 0.0345 (18) | 0.0061 (16) | −0.0066 (15) | 0.0026 (14) |
C18 | 0.0439 (18) | 0.0336 (17) | 0.0303 (17) | −0.0041 (14) | −0.0021 (14) | 0.0010 (13) |
C19 | 0.066 (2) | 0.0359 (18) | 0.039 (2) | 0.0087 (16) | −0.0085 (17) | −0.0075 (15) |
C20 | 0.066 (2) | 0.0338 (18) | 0.0386 (19) | 0.0065 (16) | −0.0158 (16) | −0.0022 (14) |
C21 | 0.0460 (19) | 0.0307 (16) | 0.0314 (17) | −0.0057 (14) | −0.0021 (14) | −0.0012 (13) |
C22 | 0.051 (2) | 0.0396 (18) | 0.0355 (18) | 0.0045 (15) | −0.0041 (15) | −0.0056 (14) |
C23 | 0.050 (2) | 0.0401 (18) | 0.0412 (19) | 0.0048 (15) | −0.0134 (16) | −0.0027 (15) |
C24 | 0.052 (2) | 0.0296 (16) | 0.0320 (17) | −0.0045 (15) | −0.0067 (15) | −0.0004 (13) |
C25 | 0.061 (2) | 0.047 (2) | 0.0344 (19) | 0.0095 (17) | −0.0052 (16) | −0.0087 (15) |
C26 | 0.052 (2) | 0.0452 (19) | 0.0377 (19) | 0.0051 (16) | −0.0105 (16) | 0.0007 (15) |
C27 | 0.052 (2) | 0.0392 (19) | 0.0329 (18) | 0.0005 (15) | −0.0051 (15) | −0.0070 (15) |
C28 | 0.061 (2) | 0.066 (2) | 0.041 (2) | 0.0110 (19) | −0.0186 (18) | −0.0089 (17) |
C29 | 0.053 (2) | 0.044 (2) | 0.0354 (19) | 0.0042 (16) | −0.0166 (15) | −0.0026 (15) |
C30 | 0.085 (3) | 0.049 (2) | 0.043 (2) | 0.004 (2) | −0.015 (2) | −0.0027 (17) |
C31 | 0.086 (3) | 0.074 (3) | 0.051 (3) | 0.016 (3) | −0.009 (2) | −0.014 (2) |
C32 | 0.062 (3) | 0.113 (4) | 0.053 (3) | −0.011 (3) | −0.002 (2) | −0.007 (3) |
C33 | 0.108 (4) | 0.058 (3) | 0.066 (3) | −0.003 (3) | −0.001 (3) | −0.015 (2) |
C34 | 0.057 (2) | 0.063 (2) | 0.0300 (18) | 0.0004 (18) | 0.0014 (16) | −0.0061 (16) |
C35 | 0.079 (3) | 0.055 (2) | 0.040 (2) | 0.000 (2) | 0.0107 (18) | 0.0074 (18) |
C36 | 0.067 (3) | 0.054 (2) | 0.051 (2) | −0.0004 (19) | −0.0016 (19) | 0.0087 (18) |
C37 | 0.054 (2) | 0.052 (2) | 0.043 (2) | 0.0105 (17) | −0.0115 (17) | −0.0017 (17) |
C38 | 0.046 (2) | 0.059 (2) | 0.0330 (18) | 0.0022 (17) | 0.0002 (15) | −0.0013 (16) |
C39 | 0.071 (3) | 0.062 (2) | 0.052 (2) | 0.018 (2) | −0.0059 (19) | −0.0052 (19) |
C40 | 0.050 (2) | 0.047 (2) | 0.058 (2) | 0.0018 (17) | 0.0010 (19) | −0.0096 (17) |
C41 | 0.0422 (19) | 0.044 (2) | 0.049 (2) | 0.0049 (16) | 0.0024 (16) | −0.0086 (16) |
C42 | 0.050 (2) | 0.062 (2) | 0.059 (3) | −0.0101 (19) | 0.0038 (18) | −0.0011 (19) |
C43 | 0.053 (2) | 0.060 (2) | 0.058 (2) | −0.0112 (18) | −0.0058 (18) | −0.0061 (19) |
C44 | 0.0368 (19) | 0.0396 (19) | 0.059 (2) | 0.0064 (15) | −0.0020 (17) | −0.0040 (17) |
C45 | 0.061 (2) | 0.062 (2) | 0.060 (3) | −0.018 (2) | −0.005 (2) | −0.0009 (19) |
C46 | 0.062 (2) | 0.064 (2) | 0.056 (2) | −0.018 (2) | −0.0086 (19) | −0.0077 (19) |
O1 | 0.096 (3) | 0.078 (2) | 0.0321 (15) | −0.023 (3) | −0.018 (2) | 0.0038 (14) |
O2 | 0.128 (3) | 0.077 (3) | 0.0477 (19) | −0.030 (2) | −0.0393 (19) | −0.0029 (17) |
C1 | 0.063 (3) | 0.055 (4) | 0.0316 (19) | 0.008 (2) | −0.0135 (19) | −0.005 (2) |
C2 | 0.045 (3) | 0.042 (3) | 0.0298 (19) | 0.005 (2) | −0.009 (2) | −0.0048 (18) |
C3 | 0.086 (5) | 0.075 (3) | 0.030 (2) | −0.035 (4) | −0.009 (3) | 0.0075 (19) |
C4 | 0.090 (5) | 0.076 (3) | 0.037 (2) | −0.042 (4) | −0.016 (3) | 0.0024 (19) |
C5 | 0.045 (3) | 0.036 (3) | 0.026 (2) | 0.0022 (18) | −0.0065 (18) | −0.0031 (18) |
C6 | 0.052 (2) | 0.051 (4) | 0.031 (2) | −0.012 (3) | −0.0047 (17) | 0.004 (2) |
C7 | 0.053 (2) | 0.058 (4) | 0.038 (2) | −0.013 (3) | −0.0127 (17) | −0.003 (2) |
O1A | 0.096 (3) | 0.078 (2) | 0.0321 (15) | −0.023 (3) | −0.018 (2) | 0.0038 (14) |
O2A | 0.084 (6) | 0.099 (10) | 0.048 (7) | −0.005 (8) | −0.035 (6) | −0.019 (7) |
C1A | 0.063 (3) | 0.055 (4) | 0.0316 (19) | 0.008 (2) | −0.0135 (19) | −0.005 (2) |
C2A | 0.045 (3) | 0.042 (3) | 0.0298 (19) | 0.005 (2) | −0.009 (2) | −0.0048 (18) |
C3A | 0.086 (5) | 0.075 (3) | 0.030 (2) | −0.035 (4) | −0.009 (3) | 0.0075 (19) |
C4A | 0.090 (5) | 0.076 (3) | 0.037 (2) | −0.042 (4) | −0.016 (3) | 0.0024 (19) |
C5A | 0.045 (3) | 0.036 (3) | 0.026 (2) | 0.0022 (18) | −0.0065 (18) | −0.0031 (18) |
C6A | 0.052 (2) | 0.051 (4) | 0.031 (2) | −0.012 (3) | −0.0047 (17) | 0.004 (2) |
C7A | 0.053 (2) | 0.058 (4) | 0.038 (2) | −0.013 (3) | −0.0127 (17) | −0.003 (2) |
Zn1—O1 | 1.916 (4) | C29—C33 | 1.366 (5) |
Zn1—N1 | 2.045 (2) | C29—C30 | 1.373 (4) |
Zn1—O1A | 2.08 (3) | C30—C31 | 1.370 (5) |
Zn1—N5 | 2.082 (3) | C30—H30 | 0.9300 |
Zn1—Cl1 | 2.2531 (9) | C31—C32 | 1.354 (6) |
O3—C14 | 1.237 (3) | C31—H31 | 0.9300 |
O4—C27 | 1.233 (3) | C32—H32 | 0.9300 |
O5—C40 | 1.225 (4) | C33—H33 | 0.9300 |
N1—C12 | 1.339 (4) | C34—C35 | 1.371 (5) |
N1—C8 | 1.344 (4) | C34—H34 | 0.9300 |
N2—C14 | 1.335 (4) | C35—C36 | 1.379 (5) |
N2—C13 | 1.443 (4) | C35—H35 | 0.9300 |
N2—H2N | 0.8600 (10) | C36—C37 | 1.369 (5) |
N3—C27 | 1.327 (4) | C36—H36 | 0.9300 |
N3—C28 | 1.461 (4) | C37—C38 | 1.379 (4) |
N3—H3N | 0.8600 (10) | C37—C39 | 1.514 (5) |
N4—C32 | 1.318 (5) | C38—H38 | 0.9300 |
N4—C33 | 1.327 (5) | C39—H39A | 0.9700 |
N5—C34 | 1.342 (4) | C39—H39B | 0.9700 |
N5—C38 | 1.345 (4) | C40—C41 | 1.497 (5) |
N6—C40 | 1.341 (5) | C41—C42 | 1.371 (5) |
N6—C39 | 1.460 (4) | C41—C46 | 1.372 (5) |
N6—H6N | 0.8600 (11) | C42—C43 | 1.377 (5) |
C8—C9 | 1.364 (5) | C42—H42 | 0.9300 |
C8—H8 | 0.9300 | C43—C44 | 1.389 (5) |
C9—C10 | 1.380 (5) | C43—H43 | 0.9300 |
C9—H9 | 0.9300 | C44—C45 | 1.384 (5) |
C10—C11 | 1.379 (4) | C44—C44i | 1.493 (6) |
C10—H10 | 0.9300 | C45—C46 | 1.370 (5) |
C11—C12 | 1.373 (4) | C45—H45 | 0.9300 |
C11—C13 | 1.502 (4) | C46—H46 | 0.9300 |
C12—H12 | 0.9300 | O1—C1 | 1.266 (6) |
C13—H13A | 0.9700 | O2—C1 | 1.223 (7) |
C13—H13B | 0.9700 | C1—C2 | 1.510 (5) |
C14—C15 | 1.491 (4) | C2—C7 | 1.368 (5) |
C15—C20 | 1.382 (4) | C2—C3 | 1.370 (6) |
C15—C16 | 1.387 (4) | C3—C4 | 1.375 (5) |
C16—C17 | 1.379 (4) | C3—H3 | 0.9300 |
C16—H16 | 0.9300 | C4—C5 | 1.383 (5) |
C17—C18 | 1.395 (4) | C4—H4 | 0.9300 |
C17—H17 | 0.9300 | C5—C6 | 1.379 (5) |
C18—C19 | 1.388 (4) | C5—C5ii | 1.473 (13) |
C18—C21 | 1.484 (4) | C6—C7 | 1.381 (5) |
C19—C20 | 1.380 (4) | C6—H6 | 0.9300 |
C19—H19 | 0.9300 | C7—H7 | 0.9300 |
C20—H20 | 0.9300 | O1A—C1A | 1.25 (2) |
C21—C22 | 1.391 (4) | O2A—C1A | 1.23 (5) |
C21—C26 | 1.393 (4) | C1A—C2A | 1.492 (10) |
C22—C23 | 1.371 (4) | C2A—C3A | 1.3900 |
C22—H22 | 0.9300 | C2A—C7A | 1.3900 |
C23—C24 | 1.381 (4) | C3A—C4A | 1.3900 |
C23—H23 | 0.9300 | C3A—H3A | 0.9300 |
C24—C25 | 1.385 (4) | C4A—C5A | 1.3900 |
C24—C27 | 1.489 (4) | C4A—H4A | 0.9300 |
C25—C26 | 1.376 (4) | C5A—C6A | 1.3900 |
C25—H25 | 0.9300 | C5A—C5Aii | 1.65 (7) |
C26—H26 | 0.9300 | C6A—C7A | 1.3900 |
C28—C29 | 1.501 (5) | C6A—H6A | 0.9300 |
C28—H28A | 0.9700 | C7A—H7A | 0.9300 |
C28—H28B | 0.9700 | ||
O1—Zn1—N1 | 123.74 (15) | C31—C30—C29 | 119.5 (4) |
O1—Zn1—O1A | 18.0 (8) | C31—C30—H30 | 120.2 |
N1—Zn1—O1A | 135.9 (8) | C29—C30—H30 | 120.2 |
O1—Zn1—N5 | 96.69 (15) | C32—C31—C30 | 119.4 (4) |
N1—Zn1—N5 | 106.72 (10) | C32—C31—H31 | 120.3 |
O1A—Zn1—N5 | 101.6 (9) | C30—C31—H31 | 120.3 |
O1—Zn1—Cl1 | 122.04 (14) | N4—C32—C31 | 123.1 (4) |
N1—Zn1—Cl1 | 101.51 (7) | N4—C32—H32 | 118.5 |
O1A—Zn1—Cl1 | 104.1 (8) | C31—C32—H32 | 118.5 |
N5—Zn1—Cl1 | 103.27 (7) | N4—C33—C29 | 125.8 (4) |
C12—N1—C8 | 117.3 (3) | N4—C33—H33 | 117.1 |
C12—N1—Zn1 | 123.4 (2) | C29—C33—H33 | 117.1 |
C8—N1—Zn1 | 119.2 (2) | N5—C34—C35 | 122.7 (3) |
C14—N2—C13 | 122.0 (3) | N5—C34—H34 | 118.6 |
C14—N2—H2N | 117 (2) | C35—C34—H34 | 118.6 |
C13—N2—H2N | 119 (2) | C34—C35—C36 | 118.4 (3) |
C27—N3—C28 | 122.0 (3) | C34—C35—H35 | 120.8 |
C27—N3—H3N | 120 (2) | C36—C35—H35 | 120.8 |
C28—N3—H3N | 118 (2) | C37—C36—C35 | 120.4 (3) |
C32—N4—C33 | 116.3 (4) | C37—C36—H36 | 119.8 |
C34—N5—C38 | 117.4 (3) | C35—C36—H36 | 119.8 |
C34—N5—Zn1 | 119.6 (2) | C36—C37—C38 | 117.4 (3) |
C38—N5—Zn1 | 122.5 (2) | C36—C37—C39 | 121.0 (3) |
C40—N6—C39 | 119.5 (3) | C38—C37—C39 | 121.6 (3) |
C40—N6—H6N | 119 (2) | N5—C38—C37 | 123.6 (3) |
C39—N6—H6N | 115 (2) | N5—C38—H38 | 118.2 |
N1—C8—C9 | 122.4 (3) | C37—C38—H38 | 118.2 |
N1—C8—H8 | 118.8 | N6—C39—C37 | 112.7 (3) |
C9—C8—H8 | 118.8 | N6—C39—H39A | 109.0 |
C8—C9—C10 | 119.4 (3) | C37—C39—H39A | 109.0 |
C8—C9—H9 | 120.3 | N6—C39—H39B | 109.0 |
C10—C9—H9 | 120.3 | C37—C39—H39B | 109.0 |
C11—C10—C9 | 119.3 (3) | H39A—C39—H39B | 107.8 |
C11—C10—H10 | 120.4 | O5—C40—N6 | 122.0 (4) |
C9—C10—H10 | 120.4 | O5—C40—C41 | 121.1 (3) |
C12—C11—C10 | 117.6 (3) | N6—C40—C41 | 116.9 (3) |
C12—C11—C13 | 121.7 (3) | C42—C41—C46 | 117.4 (3) |
C10—C11—C13 | 120.8 (3) | C42—C41—C40 | 118.7 (3) |
N1—C12—C11 | 124.0 (3) | C46—C41—C40 | 123.9 (3) |
N1—C12—H12 | 118.0 | C41—C42—C43 | 121.5 (3) |
C11—C12—H12 | 118.0 | C41—C42—H42 | 119.2 |
N2—C13—C11 | 114.1 (3) | C43—C42—H42 | 119.2 |
N2—C13—H13A | 108.7 | C42—C43—C44 | 121.6 (4) |
C11—C13—H13A | 108.7 | C42—C43—H43 | 119.2 |
N2—C13—H13B | 108.7 | C44—C43—H43 | 119.2 |
C11—C13—H13B | 108.7 | C45—C44—C43 | 115.9 (3) |
H13A—C13—H13B | 107.6 | C45—C44—C44i | 122.9 (4) |
O3—C14—N2 | 122.0 (3) | C43—C44—C44i | 121.2 (4) |
O3—C14—C15 | 120.6 (3) | C46—C45—C44 | 122.3 (4) |
N2—C14—C15 | 117.4 (3) | C46—C45—H45 | 118.9 |
C20—C15—C16 | 117.7 (3) | C44—C45—H45 | 118.9 |
C20—C15—C14 | 124.6 (3) | C45—C46—C41 | 121.3 (4) |
C16—C15—C14 | 117.6 (3) | C45—C46—H46 | 119.3 |
C17—C16—C15 | 121.1 (3) | C41—C46—H46 | 119.3 |
C17—C16—H16 | 119.4 | C1—O1—Zn1 | 118.2 (4) |
C15—C16—H16 | 119.4 | O2—C1—O1 | 122.5 (6) |
C16—C17—C18 | 121.5 (3) | O2—C1—C2 | 120.0 (5) |
C16—C17—H17 | 119.3 | O1—C1—C2 | 117.5 (5) |
C18—C17—H17 | 119.3 | C7—C2—C3 | 116.9 (3) |
C19—C18—C17 | 116.8 (3) | C7—C2—C1 | 119.9 (5) |
C19—C18—C21 | 122.5 (3) | C3—C2—C1 | 123.2 (5) |
C17—C18—C21 | 120.7 (3) | C2—C3—C4 | 121.6 (4) |
C20—C19—C18 | 121.6 (3) | C2—C3—H3 | 119.2 |
C20—C19—H19 | 119.2 | C4—C3—H3 | 119.2 |
C18—C19—H19 | 119.2 | C3—C4—C5 | 122.5 (4) |
C19—C20—C15 | 121.2 (3) | C3—C4—H4 | 118.7 |
C19—C20—H20 | 119.4 | C5—C4—H4 | 118.7 |
C15—C20—H20 | 119.4 | C6—C5—C4 | 115.1 (3) |
C22—C21—C26 | 117.0 (3) | C6—C5—C5ii | 124.0 (8) |
C22—C21—C18 | 121.2 (3) | C4—C5—C5ii | 120.9 (9) |
C26—C21—C18 | 121.8 (3) | C5—C6—C7 | 122.4 (3) |
C23—C22—C21 | 121.8 (3) | C5—C6—H6 | 118.8 |
C23—C22—H22 | 119.1 | C7—C6—H6 | 118.8 |
C21—C22—H22 | 119.1 | C2—C7—C6 | 121.5 (4) |
C22—C23—C24 | 120.8 (3) | C2—C7—H7 | 119.3 |
C22—C23—H23 | 119.6 | C6—C7—H7 | 119.3 |
C24—C23—H23 | 119.6 | C1A—O1A—Zn1 | 102 (2) |
C23—C24—C25 | 118.0 (3) | O2A—C1A—O1A | 123 (3) |
C23—C24—C27 | 121.3 (3) | O2A—C1A—C2A | 120 (3) |
C25—C24—C27 | 120.2 (3) | O1A—C1A—C2A | 115 (4) |
C26—C25—C24 | 121.2 (3) | C3A—C2A—C7A | 120.0 |
C26—C25—H25 | 119.4 | C3A—C2A—C1A | 122 (3) |
C24—C25—H25 | 119.4 | C7A—C2A—C1A | 118 (3) |
C25—C26—C21 | 121.0 (3) | C4A—C3A—C2A | 120.0 |
C25—C26—H26 | 119.5 | C4A—C3A—H3A | 120.0 |
C21—C26—H26 | 119.5 | C2A—C3A—H3A | 120.0 |
O4—C27—N3 | 122.1 (3) | C3A—C4A—C5A | 120.0 |
O4—C27—C24 | 120.4 (3) | C3A—C4A—H4A | 120.0 |
N3—C27—C24 | 117.4 (3) | C5A—C4A—H4A | 120.0 |
N3—C28—C29 | 113.1 (3) | C6A—C5A—C4A | 120.0 |
N3—C28—H28A | 109.0 | C6A—C5A—C5Aii | 112 (6) |
C29—C28—H28A | 109.0 | C4A—C5A—C5Aii | 128 (6) |
N3—C28—H28B | 109.0 | C5A—C6A—C7A | 120.0 |
C29—C28—H28B | 109.0 | C5A—C6A—H6A | 120.0 |
H28A—C28—H28B | 107.8 | C7A—C6A—H6A | 120.0 |
C33—C29—C30 | 115.9 (3) | C6A—C7A—C2A | 120.0 |
C33—C29—C28 | 121.5 (3) | C6A—C7A—H7A | 120.0 |
C30—C29—C28 | 122.6 (3) | C2A—C7A—H7A | 120.0 |
O1—Zn1—N1—C12 | 8.7 (3) | C32—N4—C33—C29 | −0.7 (7) |
O1A—Zn1—N1—C12 | 26.1 (13) | C30—C29—C33—N4 | 0.5 (7) |
N5—Zn1—N1—C12 | −101.6 (2) | C28—C29—C33—N4 | 179.2 (4) |
Cl1—Zn1—N1—C12 | 150.6 (2) | C38—N5—C34—C35 | 0.9 (5) |
O1—Zn1—N1—C8 | −169.3 (3) | Zn1—N5—C34—C35 | −170.9 (3) |
O1A—Zn1—N1—C8 | −151.9 (13) | N5—C34—C35—C36 | −0.9 (6) |
N5—Zn1—N1—C8 | 80.4 (2) | C34—C35—C36—C37 | −0.2 (6) |
Cl1—Zn1—N1—C8 | −27.4 (2) | C35—C36—C37—C38 | 1.1 (5) |
O1—Zn1—N5—C34 | 134.5 (3) | C35—C36—C37—C39 | −178.9 (3) |
N1—Zn1—N5—C34 | −97.2 (3) | C34—N5—C38—C37 | 0.2 (5) |
O1A—Zn1—N5—C34 | 117.0 (8) | Zn1—N5—C38—C37 | 171.7 (2) |
Cl1—Zn1—N5—C34 | 9.3 (3) | C36—C37—C38—N5 | −1.2 (5) |
O1—Zn1—N5—C38 | −36.8 (3) | C39—C37—C38—N5 | 178.9 (3) |
N1—Zn1—N5—C38 | 91.4 (3) | C40—N6—C39—C37 | 73.3 (4) |
O1A—Zn1—N5—C38 | −54.4 (8) | C36—C37—C39—N6 | −135.8 (4) |
Cl1—Zn1—N5—C38 | −162.0 (2) | C38—C37—C39—N6 | 44.2 (5) |
C12—N1—C8—C9 | 1.1 (5) | C39—N6—C40—O5 | −9.5 (5) |
Zn1—N1—C8—C9 | 179.2 (3) | C39—N6—C40—C41 | 171.9 (3) |
N1—C8—C9—C10 | −1.3 (6) | O5—C40—C41—C42 | 36.4 (5) |
C8—C9—C10—C11 | 0.7 (5) | N6—C40—C41—C42 | −145.0 (3) |
C9—C10—C11—C12 | −0.1 (5) | O5—C40—C41—C46 | −140.6 (4) |
C9—C10—C11—C13 | 178.6 (3) | N6—C40—C41—C46 | 37.9 (5) |
C8—N1—C12—C11 | −0.5 (4) | C46—C41—C42—C43 | −2.2 (5) |
Zn1—N1—C12—C11 | −178.5 (2) | C40—C41—C42—C43 | −179.4 (3) |
C10—C11—C12—N1 | 0.0 (4) | C41—C42—C43—C44 | 1.9 (5) |
C13—C11—C12—N1 | −178.7 (3) | C42—C43—C44—C45 | −0.9 (5) |
C14—N2—C13—C11 | −78.8 (4) | C42—C43—C44—C44i | 179.6 (3) |
C12—C11—C13—N2 | −17.3 (4) | C43—C44—C45—C46 | 0.2 (5) |
C10—C11—C13—N2 | 164.1 (3) | C44i—C44—C45—C46 | 179.7 (4) |
C13—N2—C14—O3 | −1.3 (5) | C44—C45—C46—C41 | −0.5 (6) |
C13—N2—C14—C15 | −179.9 (3) | C42—C41—C46—C45 | 1.5 (5) |
O3—C14—C15—C20 | −169.3 (3) | C40—C41—C46—C45 | 178.6 (3) |
N2—C14—C15—C20 | 9.3 (4) | N1—Zn1—O1—C1 | 33.3 (7) |
O3—C14—C15—C16 | 7.7 (4) | O1A—Zn1—O1—C1 | −104 (3) |
N2—C14—C15—C16 | −173.6 (3) | N5—Zn1—O1—C1 | 148.6 (6) |
C20—C15—C16—C17 | −0.7 (5) | Cl1—Zn1—O1—C1 | −101.2 (6) |
C14—C15—C16—C17 | −178.0 (3) | Zn1—O1—C1—O2 | −0.9 (11) |
C15—C16—C17—C18 | 1.7 (5) | Zn1—O1—C1—C2 | 178.2 (6) |
C16—C17—C18—C19 | −1.5 (5) | O2—C1—C2—C7 | −9.1 (12) |
C16—C17—C18—C21 | 179.3 (3) | O1—C1—C2—C7 | 171.7 (7) |
C17—C18—C19—C20 | 0.5 (5) | O2—C1—C2—C3 | 168.7 (7) |
C21—C18—C19—C20 | 179.6 (3) | O1—C1—C2—C3 | −10.4 (12) |
C18—C19—C20—C15 | 0.5 (5) | C7—C2—C3—C4 | 1.0 (7) |
C16—C15—C20—C19 | −0.4 (5) | C1—C2—C3—C4 | −176.9 (8) |
C14—C15—C20—C19 | 176.7 (3) | C2—C3—C4—C5 | −0.4 (8) |
C19—C18—C21—C22 | −157.4 (3) | C3—C4—C5—C6 | −0.5 (7) |
C17—C18—C21—C22 | 21.7 (4) | C3—C4—C5—C5ii | 179.7 (13) |
C19—C18—C21—C26 | 22.3 (5) | C4—C5—C6—C7 | 0.8 (6) |
C17—C18—C21—C26 | −158.6 (3) | C5ii—C5—C6—C7 | −179.4 (13) |
C26—C21—C22—C23 | −0.7 (5) | C3—C2—C7—C6 | −0.8 (6) |
C18—C21—C22—C23 | 179.0 (3) | C1—C2—C7—C6 | 177.2 (8) |
C21—C22—C23—C24 | −1.2 (5) | C5—C6—C7—C2 | −0.2 (6) |
C22—C23—C24—C25 | 1.0 (5) | O1—Zn1—O1A—C1A | 37 (3) |
C22—C23—C24—C27 | −171.9 (3) | N1—Zn1—O1A—C1A | −17 (4) |
C23—C24—C25—C26 | 1.0 (5) | N5—Zn1—O1A—C1A | 113 (4) |
C27—C24—C25—C26 | 174.1 (3) | Cl1—Zn1—O1A—C1A | −140 (4) |
C24—C25—C26—C21 | −2.9 (5) | Zn1—O1A—C1A—O2A | −11 (7) |
C22—C21—C26—C25 | 2.7 (5) | Zn1—O1A—C1A—C2A | −175 (4) |
C18—C21—C26—C25 | −177.0 (3) | O2A—C1A—C2A—C3A | −150 (4) |
C28—N3—C27—O4 | −5.8 (5) | O1A—C1A—C2A—C3A | 15 (7) |
C28—N3—C27—C24 | 171.3 (3) | O2A—C1A—C2A—C7A | 27 (7) |
C23—C24—C27—O4 | 136.0 (3) | O1A—C1A—C2A—C7A | −168 (4) |
C25—C24—C27—O4 | −36.9 (5) | C7A—C2A—C3A—C4A | 0.0 |
C23—C24—C27—N3 | −41.2 (4) | C1A—C2A—C3A—C4A | 177 (5) |
C25—C24—C27—N3 | 146.0 (3) | C2A—C3A—C4A—C5A | 0.0 |
C27—N3—C28—C29 | 83.0 (4) | C3A—C4A—C5A—C6A | 0.0 |
N3—C28—C29—C33 | 73.6 (4) | C3A—C4A—C5A—C5Aii | 175 (10) |
N3—C28—C29—C30 | −107.8 (4) | C4A—C5A—C6A—C7A | 0.0 |
C33—C29—C30—C31 | −0.1 (5) | C5Aii—C5A—C6A—C7A | −176 (9) |
C28—C29—C30—C31 | −178.8 (3) | C5A—C6A—C7A—C2A | 0.0 |
C29—C30—C31—C32 | 0.0 (6) | C3A—C2A—C7A—C6A | 0.0 |
C33—N4—C32—C31 | 0.5 (7) | C1A—C2A—C7A—C6A | −177 (5) |
C30—C31—C32—N4 | −0.2 (7) |
Symmetry codes: (i) −x+1, −y+3, −z+1; (ii) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O3iii | 0.86 (1) | 2.26 (2) | 3.046 (4) | 152 (3) |
N2—H2N···O4iv | 0.86 (1) | 2.18 (2) | 2.863 (3) | 136 (3) |
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C14H8O4)Cl2(C26H22N4O2)3] |
Mr | 854.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.9365 (2), 9.7815 (2), 22.3819 (5) |
α, β, γ (°) | 86.696 (2), 80.675 (2), 89.888 (2) |
V (Å3) | 1927.34 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.15 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.894, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28062, 7549, 4948 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.114, 1.03 |
No. of reflections | 7549 |
No. of parameters | 563 |
No. of restraints | 194 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.31 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005).
Zn1—O1 | 1.916 (4) | Zn1—N5 | 2.082 (3) |
Zn1—N1 | 2.045 (2) | Zn1—Cl1 | 2.2531 (9) |
O1—Zn1—N1 | 123.74 (15) | O1—Zn1—Cl1 | 122.04 (14) |
O1—Zn1—N5 | 96.69 (15) | N1—Zn1—Cl1 | 101.51 (7) |
N1—Zn1—N5 | 106.72 (10) | N5—Zn1—Cl1 | 103.27 (7) |
O1A—Zn1—N5 | 101.6 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3N···O3i | 0.8600 (10) | 2.260 (17) | 3.046 (4) | 152 (3) |
N2—H2N···O4ii | 0.8600 (10) | 2.18 (2) | 2.863 (3) | 136 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
Metal–organic framework (MOF) materials have been widely studied by chemists due to their potential applications in areas such as gas storage, luminescence and catalysis, and because they often have intrinsically interesting structures, such as interpenetrating nets or polyrotaxane or polycatenane topological matrices (Sumida et al., 2012; Cui et al., 2012; Blatov & Prosperio, 2011; Ockwig et al., 2005). It is well known that MOFs are made by the combination of metals or metal clusters and organic ligands. The nature of the organic ligand has thus played an important role in designing special metal–organic frameworks. For example, high-symmetry multicarboxylate or multipyridine ligands are employed to construct porous MOFs (Heine et al., 2011; Sumida et al., 2012); V-shaped ligands are encountered in polyrotaxane and polycatenane systems (Cao et al., 2009) and ligands with enlarged conjugate π–π systems are used to build luminescent MOFs (Cui et al., 2012). Recently, the new field of carboxylate-assisted pyridineacylamide MOFs has been found and studied. For example, N,N'-bis(pyridin-4-yl)phthalamide was employed to construct eightfold interpenetrated three-dimensional diamondoid nets (Gong, Li et al., 2011; Gong, Zhou et al., 2011) and N,N'-bis(pyridin-4-yl)isophthalamide was used to build novel 65.8-mok topological MOFs and reversible colour change MOFs by desolvation and solvation (Gong, Zhou et al., 2011; Gong et al. 2010). For N,N'-bis(pyridin-4-yl)biphenyl-4,4'-dicarboxamide, it was possible to build porous and luminescent MOFs which exhibited excellent selectivity for CO2 adsoption and tunable photoluminescence properties (Luo et al., 2012). Finally, the V-shaped ligand N,N'-bis(pyridin-3-ylmethyl)naphthalene-1,4-dicarboxamide, gave a novel entwining structure with a polycatenane array through combining ZnII and 1,3,5-trimesic acid (Sun et al., 2012). Because carboxylate-assisted pyridineacylamide systems have such noteworthy features, we have turned our attention to this field. Herein, we report a novel one-dimensional pyridineacylamide compound, (I), formed by combining ZnCl2, N,N'-bis(pyridin-3-ylmethyl)-[1,1'-biphenyl]-4,4'-dicarboxamide (denoted L) and [1,1'-biphenyl]-4,4'-dicarboxylic acid. Furthermore, the synthesis, structure, thermostability and solid-state photoluminescence properties of (I) are reported.
The asymmetric unit of (I) contains a ZnCl unit, half of a [1,1'-biphenyl]-4,4'-dicarboxylate ligand and one and a half independent pyridineacylamide L ligands. Both the dicarboxylate ligands and one of pyridineacylamide ligands thus lie on special positions with crystallographic inversion centres at the mid-points of their central C—C bonds. Notably, the dicarboxylate anions are somewhat disordered by a small rotation about the C1···C5 axis and are refined with each atom split over two sites with refined occupancies of 0.854 (6) and 0.146 (6). Details of the modelling of this fragment are given in the refinement section, below. In (I), each ZnII centre is coordinated in a distorted tetrahedral manner by two pyridine N atoms of two L ligands, one carboxylate O atom of L1 ligand and one terminal chloride ligand (Fig. 1). The bond lengths involving the Zn1 atom are given in Table 1. These bond lengths are in the normal range observed in the literature (Sun et al., 2012). The centrosymmetric [1,1'-biphenyl]-4,4'-dicarboxylate ligand acts in a bidentate mode connecting two metal centers with a span of approximately 15.36 Å. The pyridineacylamide L ligands have trans Z-shaped conformations. Interestingly, two kinds of coordination mode are observed for the L ligands. The centrosymmetric ligand plays a bridging role connecting two ZnII centres, whilst the ligand in the general position only bonds to one ZnII centre and is thus a terminal ligand with one uncoordinated pyridine N atom (N4). Fig. 2 shows that the ZnII centres linked by [1,1'-biphenyl]-4,4'-dicarboxylate bridges are separated approximately along the c direction. Each dicarboxylate bridge alternates with one based on an L ligand, resulting in a one-dimensional chain with a bow-like shape that propagates along the b direction. In (I), the [1,1'-biphenyl]-4,4'-dicarboxylate ligand shows negligible distortion from linearity; thus it is the flexible Z-shaped nature of the L ligand that is responsible for the formation of this bow-like chain.
As shown in Fig. 3 and Table 2, N—H···O hydrogen-bond interactions between the acylamide groups of the monodentate nonbridging L ligands extend these one-dimensional chains into a two-dimensional supramolecular net lying within the ab plane. The two-dimensional net is further connected by numerous weak nontraditional hydrogen-bond interactions, such as C—H···O, C—H···N and C—H···Cl. The three-dimensional structure results through the ···AA··· stacking of the two-dimensional nets in the c direction (Fig. 4). To the best of our knowledge, there is only one complex described in the literature that is based on the L ligand (Xu et al., 2012). This complex is [Cd(L)(L1)(bdc)0.5] {L1 is 4'-[(pyridin-3-ylmethyl)carbamoyl]-[1,1'-biphenyl]-4-carboxylate and bdc is benzenedicarboxylate}. Here the combination of L1- and Cd2+ constructs a 34-membered ring and the role of the L ligands is to link the 34-membered rings to give two-dimensional layers. The dicarboxylate bdc2- ligands further link these two-dimensional layers to construct a three-dimensional framework, which can be simplified into a 6-connected alfa-Po topological net. This contrasts sharply with (I), where combining the two organic ligands gives a one-dimensional coordination structure. Finally, it is noted that in previously reported pyridineacylamide complexes, the co-existence of pyridineacylamide and halogen ligands, or pyridineacylamide and carboxylate ligands, are known (Gong, Li et al., 2011; Gong et al. 2010; Luo et al., 2012; Sun et al., 2012; Li & Li, 2013), but the co-existence of all three components, viz. pyridineacylamide, halogen and carboxylate, as observed in (I), has not been previously encountered.
Thermogravimetric analysis (TGA) of (I) was carried out under a nitrogen atmosphere from 308 to 1073 K at a heating rate of 10 K min-1. As shown in Fig. 5, compound (I) is stable to heating to over 473 K, but displays a sharp weight loss from approximately 603 K, indicating decomposition. In addition, the solid-state photoluminescence properties of (I) were measured. As shown in Fig. 6, an intense emission occurs at 368 nm with the excitation wavelength at 332 nm. Comparatively, the free [1,1'-biphenyl]-4,4'-dicarboxylic acid ligand shows an emission at 400 nm (Han et al., 2008), and the free L ligand shows emission at 344 nm with excitation at 300 nm. Moreover, the emission of carboxylate ligands originating from the pi*–n transition is normally weak. Thus, it is believed that the photoluminescence emission of (I) is derived from L.