Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113007075/dt3018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113007075/dt3018Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113007075/dt3018IIsup3.hkl |
CCDC references: 950347; 950348
3,4-Dimethoxy-trans-cinnamic acid (Dmca) was synthesized according to the literature method of Qian et al. (2012) (see Scheme 1). Malonic acid (10.5 g, 0.1 mol) and 3,4-dimethoxybenzaldehyde (16.6 g, 0.1 mol) in ethanol (50 ml) were added to a 500 ml round-bottomed flask fitted with a reflux condenser and thermometer. Pyridine (5 ml) was then added. The mixture was heated under reflux for 12 h and then cooled to 273 K. Colourless crystals precipitated and were separated by filtration and washed with cold water (4 × 20 ml). The product was dried at 333–343 K (yield 16.6 g, 80%; m.p. 559.8–561.0 K) and was used without further purification in the syntheses of the title metal complexes.
For the synthesis of (I), Dmca (0.1 mmol, 20.8 mg), zinc sulfate (0.05 mmol, 14.4 mg) and 4-(1H-pyrazol-3-yl)pyridine (L1; 0.1 mmol, 14.5 mg) were sealed in a Teflon-lined autoclave (10 ml) and heated at 433 K for 3 d to give colourless block-shaped crystals of (I).
Complex (II) was synthesized in an analogous manner, but using 4,4'-bipyridine (L2) instead of L1.
Water H atoms were located in difference Fourier maps and included as riding atoms, with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). Other H atoms were placed in idealized positions and treated as riding, with C—H = 0.93 Å (CH) and Uiso(H) = 1.2Ueq(C).
The elongated displacement ellipsoids of the F atoms in the trifluoromethanesulfonate anion (OTf-) indicate possible disorder, but attempts to refine this with split F-atom positions were unsuccessful. In order to keep the OTf- anion stable in the refinement, a series of C—F [1.40 (1) Å], C—S [1.65 (2) Å] and F···F [2.20 (2) Å] distance restraints were used.
For both compounds, data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Zn2(C11H11O4)4(C8H7N3)2]·7H2O | F(000) = 2872 |
Mr = 1376.02 | Dx = 1.410 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6010 reflections |
a = 25.1037 (8) Å | θ = 2.7–25.5° |
b = 17.2675 (8) Å | µ = 0.82 mm−1 |
c = 14.9338 (6) Å | T = 293 K |
β = 90.042 (2)° | Block, colourless |
V = 6473.5 (4) Å3 | 0.23 × 0.20 × 0.16 mm |
Z = 4 |
Bruker D8 Venture Photon diffractometer | 6010 independent reflections |
Radiation source: fine-focus sealed tube | 5030 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 25.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −28→30 |
Tmin = 0.833, Tmax = 0.880 | k = −20→20 |
33253 measured reflections | l = −18→18 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0626P)2 + 8.0375P] where P = (Fo2 + 2Fc2)/3 |
6010 reflections | (Δ/σ)max = 0.002 |
436 parameters | Δρmax = 0.74 e Å−3 |
13 restraints | Δρmin = −0.28 e Å−3 |
[Zn2(C11H11O4)4(C8H7N3)2]·7H2O | V = 6473.5 (4) Å3 |
Mr = 1376.02 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.1037 (8) Å | µ = 0.82 mm−1 |
b = 17.2675 (8) Å | T = 293 K |
c = 14.9338 (6) Å | 0.23 × 0.20 × 0.16 mm |
β = 90.042 (2)° |
Bruker D8 Venture Photon diffractometer | 6010 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5030 reflections with I > 2σ(I) |
Tmin = 0.833, Tmax = 0.880 | Rint = 0.033 |
33253 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 13 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.74 e Å−3 |
6010 reflections | Δρmin = −0.28 e Å−3 |
436 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) | |
O5 | 0.58140 (10) | 0.75328 (14) | 0.8611 (2) | 0.0783 (8) | |
C1 | 0.32715 (11) | 0.65652 (16) | 0.46089 (17) | 0.0416 (6) | |
C2 | 0.36894 (11) | 0.59985 (16) | 0.43752 (18) | 0.0440 (6) | |
H2 | 0.3590 | 0.5485 | 0.4292 | 0.053* | |
C3 | 0.41941 (10) | 0.61807 (15) | 0.42788 (17) | 0.0419 (6) | |
H3 | 0.4281 | 0.6696 | 0.4385 | 0.050* | |
C4 | 0.46358 (10) | 0.56758 (15) | 0.40256 (17) | 0.0383 (6) | |
C5 | 0.45753 (10) | 0.48734 (15) | 0.39626 (17) | 0.0393 (6) | |
H5 | 0.4247 | 0.4651 | 0.4090 | 0.047* | |
C6 | 0.49921 (10) | 0.44090 (14) | 0.37160 (17) | 0.0386 (6) | |
C7 | 0.54889 (10) | 0.47401 (15) | 0.35110 (18) | 0.0413 (6) | |
C8 | 0.55514 (11) | 0.55329 (16) | 0.35754 (19) | 0.0473 (6) | |
H8 | 0.5879 | 0.5758 | 0.3447 | 0.057* | |
C9 | 0.51270 (11) | 0.59910 (16) | 0.38301 (19) | 0.0473 (6) | |
H9 | 0.5173 | 0.6524 | 0.3871 | 0.057* | |
C10 | 0.44772 (13) | 0.32548 (17) | 0.3772 (3) | 0.0635 (9) | |
H10A | 0.4350 | 0.3352 | 0.4368 | 0.095* | |
H10B | 0.4516 | 0.2707 | 0.3683 | 0.095* | |
H10C | 0.4227 | 0.3457 | 0.3346 | 0.095* | |
C11 | 0.63862 (12) | 0.4534 (2) | 0.3080 (3) | 0.0802 (12) | |
H11A | 0.6360 | 0.4907 | 0.2606 | 0.120* | |
H11B | 0.6619 | 0.4122 | 0.2900 | 0.120* | |
H11C | 0.6527 | 0.4779 | 0.3607 | 0.120* | |
C12 | 0.35825 (13) | 0.93060 (19) | 0.5886 (2) | 0.0631 (8) | |
H12 | 0.3436 | 0.9098 | 0.6405 | 0.076* | |
C13 | 0.39590 (15) | 0.9886 (2) | 0.5968 (3) | 0.0707 (10) | |
H13 | 0.4062 | 1.0058 | 0.6533 | 0.085* | |
C14 | 0.41826 (11) | 1.02102 (16) | 0.5211 (2) | 0.0544 (8) | |
C15 | 0.40035 (13) | 0.99383 (19) | 0.4398 (3) | 0.0629 (8) | |
H15 | 0.4135 | 1.0150 | 0.3870 | 0.075* | |
C16 | 0.36291 (13) | 0.93516 (18) | 0.4364 (2) | 0.0580 (8) | |
H16 | 0.3518 | 0.9172 | 0.3808 | 0.070* | |
C17 | 0.45941 (12) | 1.08121 (17) | 0.5285 (3) | 0.0618 (9) | |
N3 | 0.48003 (11) | 1.11337 (16) | 0.4546 (3) | 0.0792 (9) | |
N2 | 0.51663 (12) | 1.16377 (17) | 0.4867 (3) | 0.0889 (12) | |
H2N | 0.5362 | 1.1925 | 0.4532 | 0.107* | |
C20 | 0.23439 (11) | 0.77561 (16) | 0.33199 (18) | 0.0436 (6) | |
C21 | 0.22632 (11) | 0.79081 (18) | 0.23574 (18) | 0.0473 (6) | |
H21 | 0.2455 | 0.8313 | 0.2102 | 0.057* | |
C22 | 0.19432 (12) | 0.75171 (17) | 0.18372 (19) | 0.0496 (7) | |
H22 | 0.1758 | 0.7111 | 0.2101 | 0.060* | |
C23 | 0.18448 (11) | 0.76485 (17) | 0.08839 (18) | 0.0468 (6) | |
C24 | 0.15298 (12) | 0.71382 (18) | 0.0408 (2) | 0.0534 (7) | |
H24 | 0.1383 | 0.6713 | 0.0700 | 0.064* | |
C25 | 0.14273 (12) | 0.72470 (18) | −0.05071 (19) | 0.0517 (7) | |
H25 | 0.1213 | 0.6897 | −0.0813 | 0.062* | |
C26 | 0.16406 (11) | 0.78635 (16) | −0.09488 (17) | 0.0425 (6) | |
C27 | 0.19627 (11) | 0.83883 (16) | −0.04645 (18) | 0.0448 (6) | |
C28 | 0.20587 (12) | 0.82744 (16) | 0.04350 (19) | 0.0471 (6) | |
H28 | 0.2271 | 0.8625 | 0.0745 | 0.056* | |
C29 | 0.24901 (15) | 0.9534 (2) | −0.0511 (2) | 0.0715 (10) | |
H29A | 0.2297 | 0.9754 | −0.0018 | 0.107* | |
H29B | 0.2589 | 0.9937 | −0.0921 | 0.107* | |
H29C | 0.2805 | 0.9282 | −0.0292 | 0.107* | |
C30 | 0.12583 (15) | 0.7519 (2) | −0.2349 (2) | 0.0719 (10) | |
H30A | 0.1408 | 0.7009 | −0.2311 | 0.108* | |
H30B | 0.1257 | 0.7686 | −0.2963 | 0.108* | |
H30C | 0.0900 | 0.7512 | −0.2126 | 0.108* | |
H5A | 0.6129 (8) | 0.749 (2) | 0.880 (3) | 0.086* | |
H6A | 0.2380 (17) | 0.922 (2) | 0.7727 (12) | 0.086* | |
H5B | 0.5664 (13) | 0.7097 (14) | 0.860 (3) | 0.086* | |
H6B | 0.2392 (17) | 0.9035 (17) | 0.6801 (17) | 0.086* | |
N1 | 0.34200 (8) | 0.90327 (12) | 0.51022 (15) | 0.0419 (5) | |
C18 | 0.48261 (15) | 1.1115 (2) | 0.6057 (3) | 0.0804 (11) | |
H18 | 0.4748 | 1.0984 | 0.6647 | 0.097* | |
C19 | 0.51897 (17) | 1.1640 (2) | 0.5769 (4) | 0.0929 (15) | |
H19 | 0.5412 | 1.1942 | 0.6124 | 0.111* | |
O1 | 0.20728 (10) | 0.72376 (13) | 0.36834 (13) | 0.0652 (6) | |
O2 | 0.34037 (8) | 0.72572 (12) | 0.47361 (16) | 0.0621 (6) | |
O3 | 0.28029 (8) | 0.63211 (12) | 0.46419 (16) | 0.0591 (5) | |
O4 | 0.26762 (9) | 0.81782 (13) | 0.37178 (13) | 0.0570 (5) | |
O6 | 0.23775 (16) | 0.9384 (2) | 0.7179 (2) | 0.1125 (11) | |
O7 | 0.58735 (7) | 0.42290 (11) | 0.32691 (14) | 0.0533 (5) | |
O8 | 0.49778 (8) | 0.36230 (11) | 0.36520 (15) | 0.0559 (5) | |
O9 | 0.21647 (9) | 0.89884 (13) | −0.09573 (14) | 0.0622 (6) | |
O10 | 0.15731 (9) | 0.80455 (13) | −0.18233 (14) | 0.0593 (6) | |
Zn1 | 0.289143 (11) | 0.814009 (16) | 0.502212 (19) | 0.03508 (11) | |
O1W | 0.6926 (3) | 0.9436 (4) | 0.2585 (5) | 0.120 (2) | 0.50 |
O2W | 0.5701 (4) | 0.8765 (4) | 0.7276 (4) | 0.205 (4) | 0.70 |
O3W | 0.5000 | 0.9583 (6) | 0.7500 | 0.192 (5) | 0.60 |
H2A | 0.5500 | 0.8752 | 0.6838 | 0.288* | 0.70 |
H2B | 0.5805 | 0.8349 | 0.7524 | 0.288* | 0.70 |
H1B | 0.7180 | 0.9587 | 0.2942 | 0.288* | 0.50 |
H3A | 0.5007 | 0.9461 | 0.6935 | 0.288* | 0.60 |
H1A | 0.7104 | 0.9187 | 0.2180 | 0.288* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O5 | 0.0521 (14) | 0.0501 (13) | 0.133 (2) | −0.0032 (11) | −0.0171 (14) | −0.0116 (15) |
C1 | 0.0405 (15) | 0.0417 (15) | 0.0427 (14) | 0.0097 (12) | 0.0015 (11) | 0.0017 (12) |
C2 | 0.0425 (15) | 0.0361 (14) | 0.0534 (16) | 0.0082 (11) | 0.0039 (12) | −0.0031 (12) |
C3 | 0.0433 (15) | 0.0334 (13) | 0.0489 (15) | 0.0064 (11) | 0.0034 (11) | 0.0015 (11) |
C4 | 0.0361 (13) | 0.0376 (13) | 0.0413 (14) | 0.0055 (10) | 0.0012 (10) | 0.0007 (11) |
C5 | 0.0322 (13) | 0.0377 (13) | 0.0482 (15) | 0.0003 (10) | 0.0036 (10) | 0.0016 (11) |
C6 | 0.0385 (14) | 0.0335 (13) | 0.0438 (14) | 0.0024 (10) | 0.0013 (11) | 0.0005 (11) |
C7 | 0.0350 (13) | 0.0438 (14) | 0.0451 (14) | 0.0051 (11) | 0.0022 (11) | −0.0017 (12) |
C8 | 0.0363 (14) | 0.0449 (15) | 0.0606 (17) | −0.0054 (12) | 0.0094 (12) | 0.0001 (13) |
C9 | 0.0456 (15) | 0.0336 (13) | 0.0626 (18) | −0.0014 (12) | 0.0070 (13) | 0.0010 (12) |
C10 | 0.0519 (18) | 0.0382 (16) | 0.101 (3) | −0.0079 (13) | −0.0038 (17) | 0.0019 (16) |
C11 | 0.0361 (17) | 0.070 (2) | 0.134 (4) | 0.0047 (16) | 0.0205 (19) | −0.018 (2) |
C12 | 0.0589 (19) | 0.063 (2) | 0.067 (2) | −0.0174 (16) | 0.0027 (15) | −0.0026 (17) |
C13 | 0.069 (2) | 0.063 (2) | 0.081 (2) | −0.0185 (18) | −0.0074 (18) | −0.0092 (18) |
C14 | 0.0355 (15) | 0.0388 (15) | 0.089 (2) | 0.0022 (12) | −0.0021 (15) | −0.0017 (15) |
C15 | 0.0536 (19) | 0.0517 (18) | 0.083 (2) | −0.0076 (15) | 0.0086 (16) | 0.0115 (17) |
C16 | 0.0519 (18) | 0.0559 (18) | 0.0663 (19) | −0.0084 (14) | 0.0002 (15) | 0.0036 (16) |
C17 | 0.0408 (16) | 0.0354 (15) | 0.109 (3) | 0.0034 (12) | −0.0036 (17) | 0.0022 (17) |
N3 | 0.0514 (16) | 0.0472 (16) | 0.139 (3) | −0.0091 (13) | −0.0068 (17) | 0.0137 (18) |
N2 | 0.0489 (17) | 0.0430 (16) | 0.175 (4) | −0.0115 (13) | −0.012 (2) | 0.017 (2) |
C20 | 0.0426 (15) | 0.0456 (15) | 0.0425 (14) | 0.0099 (12) | 0.0014 (12) | −0.0002 (12) |
C21 | 0.0459 (16) | 0.0538 (16) | 0.0422 (15) | 0.0012 (13) | 0.0002 (12) | 0.0065 (13) |
C22 | 0.0516 (16) | 0.0497 (16) | 0.0474 (16) | 0.0051 (13) | 0.0050 (13) | 0.0064 (13) |
C23 | 0.0431 (15) | 0.0504 (16) | 0.0469 (15) | 0.0044 (12) | −0.0017 (12) | 0.0002 (13) |
C24 | 0.0548 (18) | 0.0519 (17) | 0.0535 (17) | −0.0051 (14) | 0.0011 (14) | 0.0041 (14) |
C25 | 0.0506 (17) | 0.0529 (17) | 0.0516 (17) | −0.0057 (13) | −0.0032 (13) | −0.0024 (14) |
C26 | 0.0399 (14) | 0.0483 (15) | 0.0392 (14) | 0.0056 (12) | 0.0015 (11) | 0.0041 (12) |
C27 | 0.0450 (15) | 0.0437 (15) | 0.0458 (15) | 0.0036 (12) | 0.0002 (12) | 0.0048 (12) |
C28 | 0.0468 (16) | 0.0464 (16) | 0.0480 (16) | 0.0034 (12) | −0.0020 (12) | 0.0002 (13) |
C29 | 0.082 (2) | 0.058 (2) | 0.074 (2) | −0.0167 (18) | −0.0153 (19) | 0.0047 (17) |
C30 | 0.074 (2) | 0.082 (2) | 0.059 (2) | −0.012 (2) | −0.0113 (17) | −0.0028 (18) |
N1 | 0.0321 (11) | 0.0359 (11) | 0.0576 (14) | 0.0001 (9) | 0.0002 (10) | 0.0006 (10) |
C18 | 0.058 (2) | 0.059 (2) | 0.124 (3) | −0.0099 (18) | −0.014 (2) | −0.010 (2) |
C19 | 0.064 (3) | 0.052 (2) | 0.163 (5) | −0.0095 (18) | −0.030 (3) | −0.004 (3) |
O1 | 0.0890 (17) | 0.0639 (14) | 0.0426 (11) | −0.0219 (13) | −0.0107 (11) | 0.0135 (10) |
O2 | 0.0439 (12) | 0.0426 (12) | 0.0998 (17) | 0.0127 (9) | 0.0025 (11) | −0.0116 (11) |
O3 | 0.0398 (11) | 0.0482 (12) | 0.0895 (16) | 0.0071 (9) | 0.0144 (10) | −0.0078 (11) |
O4 | 0.0547 (13) | 0.0740 (15) | 0.0422 (11) | −0.0113 (11) | −0.0065 (9) | 0.0036 (10) |
O6 | 0.133 (3) | 0.119 (3) | 0.086 (2) | 0.003 (2) | 0.018 (2) | −0.033 (2) |
O7 | 0.0349 (10) | 0.0469 (11) | 0.0780 (14) | 0.0056 (8) | 0.0110 (9) | −0.0082 (10) |
O8 | 0.0410 (11) | 0.0344 (10) | 0.0922 (16) | 0.0009 (8) | 0.0063 (10) | −0.0055 (10) |
O9 | 0.0728 (15) | 0.0572 (13) | 0.0565 (12) | −0.0167 (11) | −0.0091 (10) | 0.0085 (10) |
O10 | 0.0642 (14) | 0.0653 (14) | 0.0483 (12) | −0.0053 (11) | −0.0059 (10) | 0.0026 (10) |
Zn1 | 0.03140 (17) | 0.03075 (17) | 0.04309 (19) | 0.00042 (11) | −0.00039 (12) | 0.00036 (12) |
O1W | 0.131 (6) | 0.092 (5) | 0.136 (6) | 0.004 (4) | 0.013 (5) | −0.023 (4) |
O2W | 0.347 (12) | 0.149 (6) | 0.118 (5) | −0.088 (7) | −0.044 (6) | 0.015 (4) |
O3W | 0.253 (15) | 0.155 (10) | 0.168 (10) | 0.000 | −0.094 (10) | 0.000 |
O5—H5A | 0.845 (18) | C20—O4 | 1.257 (3) |
O5—H5B | 0.840 (18) | C20—C21 | 1.475 (4) |
C1—O3 | 1.251 (3) | C21—C22 | 1.305 (4) |
C1—O2 | 1.255 (3) | C21—H21 | 0.9300 |
C1—C2 | 1.476 (4) | C22—C23 | 1.462 (4) |
C2—C3 | 1.314 (4) | C22—H22 | 0.9300 |
C2—H2 | 0.9300 | C23—C24 | 1.381 (4) |
C3—C4 | 1.460 (3) | C23—C28 | 1.381 (4) |
C3—H3 | 0.9300 | C24—C25 | 1.403 (4) |
C4—C9 | 1.379 (4) | C24—H24 | 0.9300 |
C4—C5 | 1.397 (4) | C25—C26 | 1.362 (4) |
C5—C6 | 1.369 (3) | C25—H25 | 0.9300 |
C5—H5 | 0.9300 | C26—O10 | 1.354 (3) |
C6—O8 | 1.361 (3) | C26—C27 | 1.413 (4) |
C6—C7 | 1.406 (4) | C27—O9 | 1.369 (3) |
C7—O7 | 1.357 (3) | C27—C28 | 1.379 (4) |
C7—C8 | 1.381 (4) | C28—H28 | 0.9300 |
C8—C9 | 1.381 (4) | C29—O9 | 1.413 (4) |
C8—H8 | 0.9300 | C29—H29A | 0.9600 |
C9—H9 | 0.9300 | C29—H29B | 0.9600 |
C10—O8 | 1.420 (4) | C29—H29C | 0.9600 |
C10—H10A | 0.9600 | C30—O10 | 1.437 (4) |
C10—H10B | 0.9600 | C30—H30A | 0.9600 |
C10—H10C | 0.9600 | C30—H30B | 0.9600 |
C11—O7 | 1.419 (4) | C30—H30C | 0.9600 |
C11—H11A | 0.9600 | N1—Zn1 | 2.037 (2) |
C11—H11B | 0.9600 | C18—C19 | 1.357 (6) |
C11—H11C | 0.9600 | C18—H18 | 0.9300 |
C12—N1 | 1.326 (4) | C19—H19 | 0.9300 |
C12—C13 | 1.383 (4) | O1—Zn1i | 2.042 (2) |
C12—H12 | 0.9300 | O2—Zn1 | 2.0399 (19) |
C13—C14 | 1.381 (5) | O3—Zn1i | 2.0389 (19) |
C13—H13 | 0.9300 | O4—Zn1 | 2.022 (2) |
C14—C15 | 1.376 (5) | O6—H6A | 0.868 (18) |
C14—C17 | 1.469 (4) | O6—H6B | 0.826 (18) |
C15—C16 | 1.383 (4) | Zn1—O3i | 2.0389 (19) |
C15—H15 | 0.9300 | Zn1—O1i | 2.042 (2) |
C16—N1 | 1.339 (4) | Zn1—Zn1i | 2.9585 (5) |
C16—H16 | 0.9300 | O1W—H1B | 0.8712 |
C17—N3 | 1.339 (5) | O1W—H1A | 0.8671 |
C17—C18 | 1.393 (5) | O2W—H2A | 0.8261 |
N3—N2 | 1.353 (4) | O2W—H2B | 0.8498 |
N2—C19 | 1.349 (6) | O3W—H3A | 0.8695 |
N2—H2N | 0.8600 | O3W—H3A | 0.8695 |
C20—O1 | 1.249 (3) | ||
H5A—O5—H5B | 111 (3) | C21—C22—C23 | 127.1 (3) |
O3—C1—O2 | 124.3 (2) | C21—C22—H22 | 116.5 |
O3—C1—C2 | 117.0 (2) | C23—C22—H22 | 116.5 |
O2—C1—C2 | 118.6 (2) | C24—C23—C28 | 118.2 (3) |
C3—C2—C1 | 123.6 (3) | C24—C23—C22 | 119.9 (3) |
C3—C2—H2 | 118.2 | C28—C23—C22 | 121.9 (3) |
C1—C2—H2 | 118.2 | C23—C24—C25 | 121.4 (3) |
C2—C3—C4 | 128.2 (3) | C23—C24—H24 | 119.3 |
C2—C3—H3 | 115.9 | C25—C24—H24 | 119.3 |
C4—C3—H3 | 115.9 | C26—C25—C24 | 120.3 (3) |
C9—C4—C5 | 118.3 (2) | C26—C25—H25 | 119.9 |
C9—C4—C3 | 119.9 (2) | C24—C25—H25 | 119.9 |
C5—C4—C3 | 121.8 (2) | O10—C26—C25 | 126.8 (3) |
C6—C5—C4 | 121.1 (2) | O10—C26—C27 | 114.6 (2) |
C6—C5—H5 | 119.5 | C25—C26—C27 | 118.6 (2) |
C4—C5—H5 | 119.5 | O9—C27—C28 | 124.6 (3) |
O8—C6—C5 | 125.7 (2) | O9—C27—C26 | 115.0 (2) |
O8—C6—C7 | 114.4 (2) | C28—C27—C26 | 120.4 (3) |
C5—C6—C7 | 119.9 (2) | C27—C28—C23 | 121.1 (3) |
O7—C7—C8 | 125.6 (2) | C27—C28—H28 | 119.4 |
O7—C7—C6 | 115.1 (2) | C23—C28—H28 | 119.4 |
C8—C7—C6 | 119.2 (2) | O9—C29—H29A | 109.5 |
C9—C8—C7 | 120.0 (2) | O9—C29—H29B | 109.5 |
C9—C8—H8 | 120.0 | H29A—C29—H29B | 109.5 |
C7—C8—H8 | 120.0 | O9—C29—H29C | 109.5 |
C4—C9—C8 | 121.5 (2) | H29A—C29—H29C | 109.5 |
C4—C9—H9 | 119.3 | H29B—C29—H29C | 109.5 |
C8—C9—H9 | 119.3 | O10—C30—H30A | 109.5 |
O8—C10—H10A | 109.5 | O10—C30—H30B | 109.5 |
O8—C10—H10B | 109.5 | H30A—C30—H30B | 109.5 |
H10A—C10—H10B | 109.5 | O10—C30—H30C | 109.5 |
O8—C10—H10C | 109.5 | H30A—C30—H30C | 109.5 |
H10A—C10—H10C | 109.5 | H30B—C30—H30C | 109.5 |
H10B—C10—H10C | 109.5 | C12—N1—C16 | 117.3 (3) |
O7—C11—H11A | 109.5 | C12—N1—Zn1 | 121.4 (2) |
O7—C11—H11B | 109.5 | C16—N1—Zn1 | 121.2 (2) |
H11A—C11—H11B | 109.5 | C19—C18—C17 | 105.6 (4) |
O7—C11—H11C | 109.5 | C19—C18—H18 | 127.2 |
H11A—C11—H11C | 109.5 | C17—C18—H18 | 127.2 |
H11B—C11—H11C | 109.5 | N2—C19—C18 | 106.6 (4) |
N1—C12—C13 | 123.1 (3) | N2—C19—H19 | 126.7 |
N1—C12—H12 | 118.4 | C18—C19—H19 | 126.7 |
C13—C12—H12 | 118.4 | C20—O1—Zn1i | 128.08 (19) |
C14—C13—C12 | 119.9 (3) | C1—O2—Zn1 | 125.23 (18) |
C14—C13—H13 | 120.0 | C1—O3—Zn1i | 131.32 (19) |
C12—C13—H13 | 120.0 | C20—O4—Zn1 | 127.83 (19) |
C15—C14—C13 | 116.8 (3) | H6A—O6—H6B | 113 (3) |
C15—C14—C17 | 122.5 (3) | C7—O7—C11 | 117.2 (2) |
C13—C14—C17 | 120.7 (3) | C6—O8—C10 | 117.4 (2) |
C14—C15—C16 | 120.3 (3) | C27—O9—C29 | 117.8 (2) |
C14—C15—H15 | 119.9 | C26—O10—C30 | 116.7 (2) |
C16—C15—H15 | 119.9 | O4—Zn1—N1 | 101.86 (9) |
N1—C16—C15 | 122.5 (3) | O4—Zn1—O3i | 89.68 (9) |
N1—C16—H16 | 118.7 | N1—Zn1—O3i | 101.37 (8) |
C15—C16—H16 | 118.7 | O4—Zn1—O2 | 89.46 (9) |
N3—C17—C18 | 111.4 (3) | N1—Zn1—O2 | 99.62 (9) |
N3—C17—C14 | 120.2 (3) | O3i—Zn1—O2 | 158.71 (9) |
C18—C17—C14 | 128.4 (4) | O4—Zn1—O1i | 159.04 (9) |
C17—N3—N2 | 103.8 (4) | N1—Zn1—O1i | 99.08 (9) |
C19—N2—N3 | 112.6 (4) | O3i—Zn1—O1i | 87.12 (10) |
C19—N2—H2N | 123.7 | O2—Zn1—O1i | 86.12 (10) |
N3—N2—H2N | 123.7 | O4—Zn1—Zn1i | 79.97 (6) |
O1—C20—O4 | 124.9 (3) | N1—Zn1—Zn1i | 177.72 (7) |
O1—C20—C21 | 118.5 (3) | O3i—Zn1—Zn1i | 77.20 (6) |
O4—C20—C21 | 116.6 (3) | O2—Zn1—Zn1i | 81.71 (6) |
C22—C21—C20 | 124.9 (3) | O1i—Zn1—Zn1i | 79.12 (6) |
C22—C21—H21 | 117.6 | H1B—O1W—H1A | 101.4 |
C20—C21—H21 | 117.6 | H2A—O2W—H2B | 120.5 |
O3—C1—C2—C3 | 177.0 (3) | C26—C27—C28—C23 | 0.1 (4) |
O2—C1—C2—C3 | −1.1 (4) | C24—C23—C28—C27 | −0.2 (4) |
C1—C2—C3—C4 | −178.1 (2) | C22—C23—C28—C27 | 179.8 (3) |
C2—C3—C4—C9 | 170.5 (3) | C13—C12—N1—C16 | −1.2 (5) |
C2—C3—C4—C5 | −8.6 (4) | C13—C12—N1—Zn1 | 176.9 (3) |
C9—C4—C5—C6 | 0.2 (4) | C15—C16—N1—C12 | 0.6 (5) |
C3—C4—C5—C6 | 179.4 (2) | C15—C16—N1—Zn1 | −177.5 (2) |
C4—C5—C6—O8 | 178.6 (3) | N3—C17—C18—C19 | −0.2 (4) |
C4—C5—C6—C7 | −0.8 (4) | C14—C17—C18—C19 | 178.7 (3) |
O8—C6—C7—O7 | 0.9 (3) | N3—N2—C19—C18 | 0.2 (5) |
C5—C6—C7—O7 | −179.6 (2) | C17—C18—C19—N2 | 0.0 (4) |
O8—C6—C7—C8 | −178.5 (3) | O4—C20—O1—Zn1i | −4.3 (4) |
C5—C6—C7—C8 | 1.0 (4) | C21—C20—O1—Zn1i | 177.4 (2) |
O7—C7—C8—C9 | −180.0 (3) | O3—C1—O2—Zn1 | −0.1 (4) |
C6—C7—C8—C9 | −0.6 (4) | C2—C1—O2—Zn1 | 177.81 (18) |
C5—C4—C9—C8 | 0.2 (4) | O2—C1—O3—Zn1i | −4.9 (4) |
C3—C4—C9—C8 | −179.0 (3) | C2—C1—O3—Zn1i | 177.15 (19) |
C7—C8—C9—C4 | 0.1 (4) | O1—C20—O4—Zn1 | 1.9 (4) |
N1—C12—C13—C14 | 0.2 (6) | C21—C20—O4—Zn1 | −179.85 (18) |
C12—C13—C14—C15 | 1.3 (5) | C8—C7—O7—C11 | 1.1 (4) |
C12—C13—C14—C17 | −178.3 (3) | C6—C7—O7—C11 | −178.3 (3) |
C13—C14—C15—C16 | −1.9 (5) | C5—C6—O8—C10 | 6.0 (4) |
C17—C14—C15—C16 | 177.7 (3) | C7—C6—O8—C10 | −174.6 (3) |
C14—C15—C16—N1 | 1.0 (5) | C28—C27—O9—C29 | −0.7 (4) |
C15—C14—C17—N3 | 1.8 (4) | C26—C27—O9—C29 | 180.0 (3) |
C13—C14—C17—N3 | −178.6 (3) | C25—C26—O10—C30 | −2.3 (4) |
C15—C14—C17—C18 | −177.1 (3) | C27—C26—O10—C30 | 178.6 (3) |
C13—C14—C17—C18 | 2.5 (5) | C20—O4—Zn1—N1 | −178.2 (2) |
C18—C17—N3—N2 | 0.3 (4) | C20—O4—Zn1—O3i | −76.6 (2) |
C14—C17—N3—N2 | −178.7 (3) | C20—O4—Zn1—O2 | 82.1 (2) |
C17—N3—N2—C19 | −0.3 (4) | C20—O4—Zn1—O1i | 4.5 (4) |
O1—C20—C21—C22 | −3.1 (4) | C20—O4—Zn1—Zn1i | 0.4 (2) |
O4—C20—C21—C22 | 178.5 (3) | C12—N1—Zn1—O4 | 166.8 (2) |
C20—C21—C22—C23 | 179.3 (3) | C16—N1—Zn1—O4 | −15.1 (2) |
C21—C22—C23—C24 | 174.1 (3) | C12—N1—Zn1—O3i | 74.8 (2) |
C21—C22—C23—C28 | −5.9 (5) | C16—N1—Zn1—O3i | −107.2 (2) |
C28—C23—C24—C25 | 0.0 (4) | C12—N1—Zn1—O2 | −101.7 (2) |
C22—C23—C24—C25 | 180.0 (3) | C16—N1—Zn1—O2 | 76.3 (2) |
C23—C24—C25—C26 | 0.3 (5) | C12—N1—Zn1—O1i | −14.1 (2) |
C24—C25—C26—O10 | −179.4 (3) | C16—N1—Zn1—O1i | 163.9 (2) |
C24—C25—C26—C27 | −0.3 (4) | C1—O2—Zn1—O4 | −77.3 (2) |
O10—C26—C27—O9 | −1.3 (4) | C1—O2—Zn1—N1 | −179.2 (2) |
C25—C26—C27—O9 | 179.6 (3) | C1—O2—Zn1—O3i | 10.5 (4) |
O10—C26—C27—C28 | 179.3 (2) | C1—O2—Zn1—O1i | 82.2 (2) |
C25—C26—C27—C28 | 0.2 (4) | C1—O2—Zn1—Zn1i | 2.7 (2) |
O9—C27—C28—C23 | −179.3 (3) |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H3A···N3ii | 0.87 | 2.49 | 3.336 (5) | 165 |
O5—H5B···O8iii | 0.84 (2) | 2.12 (2) | 2.897 (3) | 152 (4) |
O6—H6A···O9iv | 0.86 (2) | 2.10 (2) | 2.916 (4) | 163 (4) |
O6—H6B···O3i | 0.83 (2) | 2.28 (2) | 3.011 (4) | 147 (3) |
O5—H5A···O1v | 0.84 (2) | 2.42 (2) | 3.186 (4) | 152 (3) |
O5—H5A···O2vi | 0.84 (2) | 2.52 (3) | 3.189 (4) | 137 (3) |
O5—H5B···O7iii | 0.84 (2) | 2.40 (3) | 3.088 (3) | 139 (3) |
O1W—H1A···O4vii | 0.87 | 2.27 | 3.083 (8) | 157 |
O1W—H1B···O6ii | 0.87 | 2.10 | 2.708 (8) | 126 |
O2W—H2A···N3ii | 0.83 | 2.21 | 3.002 (8) | 161 |
O2W—H2B···O5 | 0.85 | 2.15 | 2.929 (7 | 152 |
N2—H2N···O5viii | 0.86 | 2.01 | 2.867 (5) | 171 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x, −y+1, z+1/2; (iv) x, y, z+1; (v) x+1/2, −y+3/2, z+1/2; (vi) −x+1, y, −z+3/2; (vii) −x+1, y, −z+1/2; (viii) x, −y+2, z−1/2. |
[Zn(C11H11O4)2(C10H8N2)] | F(000) = 1320 |
Mr = 635.97 | Dx = 1.492 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2804 reflections |
a = 26.6175 (11) Å | θ = 2.3–26.1° |
b = 6.0635 (3) Å | µ = 0.93 mm−1 |
c = 18.7796 (9) Å | T = 293 K |
β = 110.954 (2)° | Block, colourless |
V = 2830.5 (2) Å3 | 0.24 × 0.20 × 0.18 mm |
Z = 4 |
Bruker D8 Venture Photon diffractometer | 2804 independent reflections |
Radiation source: fine-focus sealed tube | 2473 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 26.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −32→31 |
Tmin = 0.801, Tmax = 0.847 | k = −6→7 |
15758 measured reflections | l = −23→23 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0521P)2 + 5.2961P] where P = (Fo2 + 2Fc2)/3 |
2804 reflections | (Δ/σ)max < 0.001 |
197 parameters | Δρmax = 0.82 e Å−3 |
13 restraints | Δρmin = −0.58 e Å−3 |
[Zn(C11H11O4)2(C10H8N2)] | V = 2830.5 (2) Å3 |
Mr = 635.97 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.6175 (11) Å | µ = 0.93 mm−1 |
b = 6.0635 (3) Å | T = 293 K |
c = 18.7796 (9) Å | 0.24 × 0.20 × 0.18 mm |
β = 110.954 (2)° |
Bruker D8 Venture Photon diffractometer | 2804 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2473 reflections with I > 2σ(I) |
Tmin = 0.801, Tmax = 0.847 | Rint = 0.033 |
15758 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 13 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.82 e Å−3 |
2804 reflections | Δρmin = −0.58 e Å−3 |
197 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
C1 | 0.70862 (10) | 1.2295 (4) | 0.63512 (14) | 0.0324 (5) | |
C2 | 1.00075 (10) | 0.0676 (4) | 0.96740 (14) | 0.0310 (5) | |
C3 | 0.75587 (10) | 1.1146 (4) | 0.65099 (15) | 0.0333 (6) | |
H3 | 0.7611 | 0.9845 | 0.6790 | 0.040* | |
C4 | 0.91399 (11) | 0.7744 (5) | 0.68978 (17) | 0.0431 (6) | |
C5 | 0.79649 (10) | 1.1908 (4) | 0.62552 (15) | 0.0340 (6) | |
C6 | 0.84658 (11) | 1.0676 (5) | 0.64012 (16) | 0.0379 (6) | |
H6 | 0.8700 | 1.1250 | 0.6182 | 0.045* | |
C7 | 0.70055 (11) | 1.4278 (5) | 0.59293 (15) | 0.0352 (6) | |
C8 | 0.86246 (11) | 0.8876 (5) | 0.67996 (16) | 0.0403 (6) | |
H8 | 0.8403 | 0.8270 | 0.7035 | 0.048* | |
C9 | 0.63889 (14) | 1.7147 (5) | 0.53058 (19) | 0.0532 (8) | |
H9A | 0.6663 | 1.8256 | 0.5491 | 0.080* | |
H9B | 0.6050 | 1.7740 | 0.5287 | 0.080* | |
H9C | 0.6363 | 1.6697 | 0.4804 | 0.080* | |
C10 | 0.96471 (12) | 0.0337 (5) | 0.89359 (16) | 0.0414 (7) | |
H10 | 0.9384 | −0.0748 | 0.8841 | 0.050* | |
C11 | 0.78791 (12) | 1.3861 (5) | 0.58533 (17) | 0.0435 (7) | |
H11 | 0.8146 | 1.4404 | 0.5689 | 0.052* | |
C12 | 1.03855 (13) | 0.2323 (5) | 0.97580 (16) | 0.0491 (8) | |
H12 | 1.0638 | 0.2626 | 1.0238 | 0.059* | |
C13 | 1.03899 (12) | 0.3512 (5) | 0.91370 (16) | 0.0477 (7) | |
H13 | 1.0650 | 0.4599 | 0.9213 | 0.057* | |
C14 | 0.96792 (12) | 0.1606 (5) | 0.83463 (15) | 0.0430 (7) | |
H14 | 0.9433 | 0.1339 | 0.7859 | 0.052* | |
C15 | 0.74044 (13) | 1.5033 (5) | 0.56893 (18) | 0.0437 (7) | |
H15 | 0.7356 | 1.6341 | 0.5414 | 0.052* | |
C16 | 0.67560 (13) | 0.9839 (5) | 0.70686 (19) | 0.0455 (7) | |
H16A | 0.6824 | 0.8543 | 0.6823 | 0.068* | |
H16B | 0.6443 | 0.9606 | 0.7200 | 0.068* | |
H16C | 0.7061 | 1.0132 | 0.7523 | 0.068* | |
N1 | 1.00409 (8) | 0.3189 (4) | 0.84324 (12) | 0.0320 (5) | |
O1 | 0.92764 (9) | 0.6198 (4) | 0.73752 (14) | 0.0585 (6) | |
O2 | 0.94172 (9) | 0.8319 (4) | 0.65310 (14) | 0.0574 (5) | |
O3 | 0.66668 (8) | 1.1677 (3) | 0.65616 (12) | 0.0438 (5) | |
O4 | 0.65248 (9) | 1.5292 (3) | 0.58049 (13) | 0.0460 (5) | |
Zn1 | 1.0000 | 0.51729 (7) | 0.7500 | 0.02977 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0341 (13) | 0.0318 (13) | 0.0320 (13) | −0.0002 (11) | 0.0125 (11) | −0.0015 (11) |
C2 | 0.0304 (13) | 0.0333 (13) | 0.0286 (13) | 0.0009 (11) | 0.0097 (10) | 0.0002 (11) |
C3 | 0.0366 (14) | 0.0282 (12) | 0.0346 (13) | 0.0035 (11) | 0.0120 (11) | 0.0020 (11) |
C4 | 0.0381 (12) | 0.0457 (13) | 0.0468 (13) | 0.0033 (11) | 0.0168 (10) | −0.0058 (11) |
C5 | 0.0342 (13) | 0.0342 (13) | 0.0334 (13) | 0.0001 (11) | 0.0119 (11) | −0.0046 (11) |
C6 | 0.0360 (14) | 0.0371 (14) | 0.0453 (16) | −0.0038 (12) | 0.0202 (12) | −0.0055 (12) |
C7 | 0.0378 (14) | 0.0327 (13) | 0.0329 (14) | 0.0049 (11) | 0.0101 (11) | 0.0007 (11) |
C8 | 0.0310 (13) | 0.0482 (16) | 0.0430 (15) | 0.0029 (13) | 0.0147 (12) | 0.0034 (13) |
C9 | 0.0604 (19) | 0.0442 (17) | 0.0511 (18) | 0.0173 (15) | 0.0154 (15) | 0.0138 (14) |
C10 | 0.0419 (15) | 0.0478 (16) | 0.0314 (14) | −0.0165 (13) | 0.0094 (12) | 0.0000 (12) |
C11 | 0.0491 (17) | 0.0405 (15) | 0.0495 (17) | −0.0017 (13) | 0.0283 (14) | 0.0056 (13) |
C12 | 0.0541 (18) | 0.0519 (18) | 0.0289 (14) | −0.0205 (15) | −0.0002 (12) | 0.0008 (13) |
C13 | 0.0486 (17) | 0.0479 (17) | 0.0375 (15) | −0.0195 (14) | 0.0043 (13) | 0.0044 (13) |
C14 | 0.0444 (16) | 0.0516 (17) | 0.0266 (13) | −0.0138 (14) | 0.0049 (11) | −0.0016 (12) |
C15 | 0.0536 (18) | 0.0347 (15) | 0.0472 (17) | 0.0060 (13) | 0.0234 (14) | 0.0102 (12) |
C16 | 0.0523 (18) | 0.0419 (16) | 0.0504 (17) | 0.0026 (13) | 0.0283 (15) | 0.0089 (13) |
N1 | 0.0328 (11) | 0.0337 (11) | 0.0284 (11) | −0.0004 (9) | 0.0095 (9) | 0.0015 (9) |
O1 | 0.0434 (12) | 0.0704 (16) | 0.0682 (15) | 0.0215 (12) | 0.0279 (11) | 0.0250 (13) |
O2 | 0.0530 (9) | 0.0602 (9) | 0.0654 (9) | 0.0030 (7) | 0.0290 (7) | 0.0025 (8) |
O3 | 0.0385 (10) | 0.0429 (11) | 0.0556 (12) | 0.0069 (9) | 0.0237 (9) | 0.0138 (9) |
O4 | 0.0424 (11) | 0.0408 (11) | 0.0543 (13) | 0.0134 (9) | 0.0166 (10) | 0.0149 (9) |
Zn1 | 0.0253 (2) | 0.0360 (3) | 0.0288 (2) | 0.000 | 0.01061 (16) | 0.000 |
C1—O3 | 1.363 (3) | C9—H9C | 0.9600 |
C1—C3 | 1.374 (4) | C10—C14 | 1.376 (4) |
C1—C7 | 1.414 (4) | C10—H10 | 0.9300 |
C2—C12 | 1.386 (4) | C11—C15 | 1.385 (4) |
C2—C10 | 1.390 (4) | C11—H11 | 0.9300 |
C2—C2i | 1.486 (5) | C12—C13 | 1.375 (4) |
C3—C5 | 1.408 (4) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—N1 | 1.332 (3) |
C4—O2 | 1.227 (4) | C13—H13 | 0.9300 |
C4—O1 | 1.258 (4) | C14—N1 | 1.328 (3) |
C4—C8 | 1.485 (4) | C14—H14 | 0.9300 |
C5—C11 | 1.379 (4) | C15—H15 | 0.9300 |
C5—C6 | 1.466 (4) | C16—O3 | 1.430 (3) |
C6—C8 | 1.305 (4) | C16—H16A | 0.9600 |
C6—H6 | 0.9300 | C16—H16B | 0.9600 |
C7—O4 | 1.362 (4) | C16—H16C | 0.9600 |
C7—C15 | 1.372 (4) | N1—Zn1 | 2.095 (2) |
C8—H8 | 0.9300 | O1—Zn1 | 1.957 (2) |
C9—O4 | 1.426 (3) | Zn1—O1ii | 1.957 (2) |
C9—H9A | 0.9600 | Zn1—N1ii | 2.095 (2) |
C9—H9B | 0.9600 | ||
O3—C1—C3 | 125.4 (2) | C5—C11—C15 | 121.5 (3) |
O3—C1—C7 | 114.8 (2) | C5—C11—H11 | 119.3 |
C3—C1—C7 | 119.8 (2) | C15—C11—H11 | 119.3 |
C12—C2—C10 | 115.7 (2) | C13—C12—C2 | 120.5 (3) |
C12—C2—C2i | 122.4 (3) | C13—C12—H12 | 119.8 |
C10—C2—C2i | 121.9 (3) | C2—C12—H12 | 119.8 |
C1—C3—C5 | 121.0 (2) | N1—C13—C12 | 123.4 (3) |
C1—C3—H3 | 119.5 | N1—C13—H13 | 118.3 |
C5—C3—H3 | 119.5 | C12—C13—H13 | 118.3 |
O2—C4—O1 | 122.2 (3) | N1—C14—C10 | 123.9 (2) |
O2—C4—C8 | 120.9 (3) | N1—C14—H14 | 118.1 |
O1—C4—C8 | 116.9 (3) | C10—C14—H14 | 118.1 |
C11—C5—C3 | 118.1 (2) | C7—C15—C11 | 120.5 (3) |
C11—C5—C6 | 120.1 (3) | C7—C15—H15 | 119.7 |
C3—C5—C6 | 121.8 (2) | C11—C15—H15 | 119.7 |
C8—C6—C5 | 128.3 (3) | O3—C16—H16A | 109.5 |
C8—C6—H6 | 115.9 | O3—C16—H16B | 109.5 |
C5—C6—H6 | 115.9 | H16A—C16—H16B | 109.5 |
O4—C7—C15 | 125.7 (3) | O3—C16—H16C | 109.5 |
O4—C7—C1 | 115.2 (2) | H16A—C16—H16C | 109.5 |
C15—C7—C1 | 119.2 (3) | H16B—C16—H16C | 109.5 |
C6—C8—C4 | 123.6 (3) | C14—N1—C13 | 116.4 (2) |
C6—C8—H8 | 118.2 | C14—N1—Zn1 | 119.64 (17) |
C4—C8—H8 | 118.2 | C13—N1—Zn1 | 123.73 (19) |
O4—C9—H9A | 109.5 | C4—O1—Zn1 | 110.08 (19) |
O4—C9—H9B | 109.5 | C1—O3—C16 | 116.7 (2) |
H9A—C9—H9B | 109.5 | C7—O4—C9 | 118.1 (2) |
O4—C9—H9C | 109.5 | O1ii—Zn1—O1 | 142.94 (16) |
H9A—C9—H9C | 109.5 | O1ii—Zn1—N1ii | 92.13 (9) |
H9B—C9—H9C | 109.5 | O1—Zn1—N1ii | 109.13 (10) |
C14—C10—C2 | 120.0 (3) | O1ii—Zn1—N1 | 109.13 (10) |
C14—C10—H10 | 120.0 | O1—Zn1—N1 | 92.13 (9) |
C2—C10—H10 | 120.0 | N1ii—Zn1—N1 | 109.91 (12) |
O3—C1—C3—C5 | 178.9 (2) | C1—C7—C15—C11 | 0.4 (4) |
C7—C1—C3—C5 | −0.3 (4) | C5—C11—C15—C7 | 0.4 (5) |
C1—C3—C5—C11 | 1.1 (4) | C10—C14—N1—C13 | 0.6 (5) |
C1—C3—C5—C6 | −178.4 (2) | C10—C14—N1—Zn1 | −174.7 (2) |
C11—C5—C6—C8 | 176.3 (3) | C12—C13—N1—C14 | −0.7 (5) |
C3—C5—C6—C8 | −4.3 (5) | C12—C13—N1—Zn1 | 174.3 (3) |
O3—C1—C7—O4 | 0.9 (3) | O2—C4—O1—Zn1 | 6.0 (4) |
C3—C1—C7—O4 | −179.8 (2) | C8—C4—O1—Zn1 | −173.5 (2) |
O3—C1—C7—C15 | −179.8 (3) | C3—C1—O3—C16 | 8.3 (4) |
C3—C1—C7—C15 | −0.5 (4) | C7—C1—O3—C16 | −172.4 (2) |
C5—C6—C8—C4 | 178.9 (3) | C15—C7—O4—C9 | 8.3 (4) |
O2—C4—C8—C6 | −8.5 (5) | C1—C7—O4—C9 | −172.4 (2) |
O1—C4—C8—C6 | 170.9 (3) | C4—O1—Zn1—O1ii | 44.4 (2) |
C12—C2—C10—C14 | −0.3 (4) | C4—O1—Zn1—N1ii | −77.3 (2) |
C2i—C2—C10—C14 | −179.1 (3) | C4—O1—Zn1—N1 | 170.8 (2) |
C3—C5—C11—C15 | −1.2 (4) | C14—N1—Zn1—O1ii | −151.6 (2) |
C6—C5—C11—C15 | 178.3 (3) | C13—N1—Zn1—O1ii | 33.5 (3) |
C10—C2—C12—C13 | 0.1 (5) | C14—N1—Zn1—O1 | 59.3 (2) |
C2i—C2—C12—C13 | 179.0 (3) | C13—N1—Zn1—O1 | −115.6 (3) |
C2—C12—C13—N1 | 0.4 (5) | C14—N1—Zn1—N1ii | −51.9 (2) |
C2—C10—C14—N1 | −0.1 (5) | C13—N1—Zn1—N1ii | 133.2 (3) |
O4—C7—C15—C11 | 179.7 (3) |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Zn2(C11H11O4)4(C8H7N3)2]·7H2O | [Zn(C11H11O4)2(C10H8N2)] |
Mr | 1376.02 | 635.97 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 25.1037 (8), 17.2675 (8), 14.9338 (6) | 26.6175 (11), 6.0635 (3), 18.7796 (9) |
β (°) | 90.042 (2) | 110.954 (2) |
V (Å3) | 6473.5 (4) | 2830.5 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.82 | 0.93 |
Crystal size (mm) | 0.23 × 0.20 × 0.16 | 0.24 × 0.20 × 0.18 |
Data collection | ||
Diffractometer | Bruker D8 Venture Photon diffractometer | Bruker D8 Venture Photon diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.833, 0.880 | 0.801, 0.847 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33253, 6010, 5030 | 15758, 2804, 2473 |
Rint | 0.033 | 0.033 |
(sin θ/λ)max (Å−1) | 0.606 | 0.619 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.05 | 0.039, 0.105, 1.05 |
No. of reflections | 6010 | 2804 |
No. of parameters | 436 | 197 |
No. of restraints | 13 | 13 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.28 | 0.82, −0.58 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
N1—Zn1 | 2.037 (2) | O3—Zn1i | 2.0389 (19) |
O1—Zn1i | 2.042 (2) | O4—Zn1 | 2.022 (2) |
O2—Zn1 | 2.0399 (19) |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3W—H3A···N3ii | 0.87 | 2.49 | 3.336 (5) | 165.3 |
O5—H5B···O8iii | 0.843 (18) | 2.12 (2) | 2.897 (3) | 152 (4) |
O6—H6A···O9iv | 0.862 (18) | 2.10 (2) | 2.916 (4) | 163 (4) |
O6—H6B···O3i | 0.832 (18) | 2.28 (2) | 3.011 (4) | 147 (3) |
O5—H5A···O1v | 0.844 (18) | 2.42 (2) | 3.186 (4) | 152 (3) |
O5—H5A···O2vi | 0.844 (18) | 2.52 (3) | 3.189 (4) | 137 (3) |
O5—H5B···O7iii | 0.843 (18) | 2.40 (3) | 3.088 (3) | 139 (3) |
O1W—H1A···O4vii | 0.87 | 2.27 | 3.083 (8) | 157 |
O1W—H1B···O6ii | 0.87 | 2.10 | 2.708 (8) | 126 |
O2W—H2A···N3ii | 0.83 | 2.21 | 3.002 (8) | 161 |
O2W—H2B···O5 | 0.85 | 2.15 | 2.929(7 | 152 |
N2—H2N···O5viii | 0.86 | 2.01 | 2.867 (5) | 171 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) x, −y+1, z+1/2; (iv) x, y, z+1; (v) x+1/2, −y+3/2, z+1/2; (vi) −x+1, y, −z+3/2; (vii) −x+1, y, −z+1/2; (viii) x, −y+2, z−1/2. |
Considerable attention has been devoted to metal–organic frameworks (MOFs) because of their potential applications as functional solid materials (Ghosh et al., 2013; Liu et al., 2010; Qin et al., 2011) and intriguing structural topologies (Zhang et al., 2011; Xu & Raymond, 2000). Although the principles of the rational design and synthesis MOFs still need to be classified, the selection of appropriate organic ligands is considered one of the most effective ways of manipulating the structure of target MOFs (Farha et al., 2010). Among the various organic ligands, carboxylate ligands, especially aromatic carboxylate ligands, are often selected as useful building blocks, due to their various coordination modes to metal cations (Mahata et al., 2013; Zhao et al., 2009) and their ability to act as both hydrogen-bond acceptors and donors to assemble intriguing supramolecular structures (Das & Bharadwaj, 2006; Weyna et al., 2012). The introduction of additional auxiliary N-donor ligands to the synthetic systems can satisfy and even mediate the coordination needs of the metal centres and consequently generate more meaningful architectures (Lan et al., 2009). Cinnamic acid and its derivatives are well known for their biological activities, such as antioxidant (Chung & Shin, 2007) and antimicrobial (Qian et al., 2012) properties, yet little attention has been paid to this system in supramolecular and materials chemistry to date, especially based on 3,4-dimethoxy-trans-cinnamic acid (Dmca; see Scheme 1) (Drew et al., 1994). In this contribution, we investigated the self-assembly reaction of Dmca with 4-(1H-pyrazol-3-yl)pyridine (L1), 4,4'-bipyridine (L2) and ZnSO4 under hydrothermal reaction conditions. Two coordination complexes, [Zn2(Dmca)4(L1)2].7H2O, (I), and [Zn(Dmca)2(L2)]n, (II), were isolated (see Scheme 2).
Complex (I) crystallizes in the monoclinic space group C2/c, with one half of a [Zn2(Dmca)4(L1)2].7H2O unit (the ZnII cation is on a centre of inversion) in the asymmetric unit. Complex (I) consists of a dinuclear paddle-wheel-type framework, wherein the pair of ZnII cations is bridged by four syn–syn bidentate bridging carboxylate groups (Fig. 1). The nonbonded Zn···Zn separation of 2.9585 (6) Å is shorter than that observed in the structurally related compound [Zn2(MeCH═ CHCO2)4(quinoline)2] [2.976(su?) Å; Clegg et al., 1986]. Ligand L1 is coordinated to each ZnII cation along the Zn···Zn axis and thus the ZnII centre attains a square-pyramidal geometry. The Zn—O and Zn—N bond lengths (Table 1) are all within the normal ranges (Kumar et al., 2011; Olmo et al., 2006). The pyrazole group of L1 is uncoordinated, which limits the further extension of the structure.
Given the strong hydrogen-bond capability of the water molecules and the uncoordinated pyrazole groups, it is not surprising that complex (I) displays a robust hydrogen-bonding framework. The dinuclear units are linked into a one-dimensional chain-like structure extending along the crystallographic c axis via O6—H6B···O3i and O6—H6A···O9ii hydrogen bonds (Fig. 2) [symmetry codes: (i) -x + 1/2, -y + 3/2, -z + 1; (ii) x, y, z + 1]. The uncoordinated pyrazole groups act as hydrogen-bond acceptors and link the chains into a two-dimensional network in the ac plane via O3W—H3A···N3iii hydrogen bonds (Fig. 3) [symmetry code: (iii) x + 1, -y + 2, -z + 1]. These two-dimensional layers are stacked in an ···AA··· fashion, and are further linked into a three-dimensional framework via hydrongen-bonding interactions involving the solvent water molecules and Dmca ligands [O5—H5B···O7iv, O5—H5B···O8iv, O5—H5A···O2v and O5—H5A···O1vi; symmetry codes: (iv) x, -y + 1, z + 1/2; (v) -x + 1, y, -z + 3/2; (vi) x + 1/2, -y + 3/2, z + 1/2; Fig. 4].
When ligand L2 was used instead of L1 in the reaction, complex (II) was obtained. The asymmetric unit of (II) contains one crystallographically independent ZnII centre, one Dmca ligand and one half of an L2 ligand. As shown in Fig. 5, the ZnII centre possesses a distorted tetrahedral geometry, coordinated by two O atoms from the carboxylate groups and two N atoms from the L2 ligand. The Zn—O and Zn—N bond lengths [1.957 (2)–2.095 (2) Å] are comparable with those reported for complex (I). The ZnII cations are bridged by the L2 ligand to form an infinite chain structure extending along the crystallographic c axis (Fig. 6). Pairs of adjacent L2 ligands are almost perpendicular to each other [dihedral angle = 83.48 (5)°]. The carboxylate group of the Dmca ligand is monodentate, which prevents the structure from attaining a higher dimensionality. No hydrogen-bonding or π–π interactions are observed in the crystal structure of (II).
In summary, two mixed-ligand coordination complexes have been synthesized based on zinc(II), Dmca and two kinds of pyridine derivatives under hydrothermal conditions. The results show that the N-donor coligands have a significant effect on the formation of the complex structure.