metal-organic compounds
A neutral cubane with a ZnII4O4 core: tetrabenzoatotetrakis(μ3-hydroxydi-2-pyridylmethanolato)tetrazinc(II)–acetone–methanol (1/2/1)
aDepartment of Fine Chemistry, and Eco-Product and Materials Education Center, Seoul National University of Technology, Seoul 139-743, Republic of Korea, bDivision of Forest Genetic Resources, Korea Forest Research Institute, Suwon, Gyeonggi-Do 441-350, Republic of Korea, cDepartment of Forest & Environment Resources, Kyungpook National University, Sangju 742-711, Republic of Korea, and dDepartment of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Republic of Korea
*Correspondence e-mail: chealkim@sunt.ac.kr, ymeekim@ewha.ac.kr
In the title compound, [Zn4(C11H9N2O2)4(C7H5O2)4]·2(CH3)2CO·CH3OH, the tetranuclear molecule lies on a fourfold inversion axis. ZnII ions and μ3-O atoms in the cubane core occupy alternating vertices, forming two interpenetrating tetrahedra. Each ZnII ion is further coordinated by two N atoms from two different (py)2C(OH)O ligands (py is pyridyl) and one O atom from a monodentate benzoate ligand, forming a distorted octahedral environment. The (py)2C(OH)O ligand acts in an η1:η3:η1:μ3 manner, forming two five-membered ZnNCCO chelating rings with two different ZnII atoms sharing a common C—O bond, and an alkoxide-type bond to a third ZnII ion. There are four symmetry-related intramolecular O—H⋯O hydrogen bonds between the two types of ligands. In the there is a half-occupancy acetone solvent molecule and a half-occupancy methanol solvent molecule that lies on a twofold rotation axis.
Related literature
For background to transition metal ions as the major cationic contributors to the inorganic composition of natural water and biological fluids, see: Daniele et al. (2008); For related crystal structures, see: Lee et al. (2008); Park et al. (2008); Yu et al. (2008); Stoumpos et al. (2008); Papaefstathiou & Perlepes (2002); Papatriantafyllopoulou et al. (2007).
Experimental
Crystal data
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Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536809017772/lh2815sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809017772/lh2815Isup2.hkl
38.0 mg (0.125 mmol) of Zn(NO3)2.6H2O and 35.5 mg (0.25 mmol) of C6H5COONH4 were dissolved in 4 ml water and carefully layered by 4 ml solution of a mixture of acetone, methanol and ethanol (2/2/2) of di-2-pyridyl ketone ligand (46.1 mg, 0.25 mmol). Crystals of the title compound suitable for X-ray analysis were obtained in a few weeks.
H atoms were placed in calculated positions with C—H distances of 0.93–0.98 Å and O—H = 0.82 Å. They were included in the
in a riding-motion approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl and O).Data collection: SMART (Bruker, 1997); cell
SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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).[Zn4(C11H9N2O2)4(C7H5O2)4]·2C3H6O·CH4O | Dx = 1.458 Mg m−3 |
Mr = 6795.70 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42d | Cell parameters from 8208 reflections |
Hall symbol: I -4 2bw | θ = 2.8–27.0° |
a = 14.3201 (4) Å | µ = 1.30 mm−1 |
c = 37.730 (2) Å | T = 170 K |
V = 7737.1 (5) Å3 | Polyhedron, colorless |
Z = 1 | 0.10 × 0.08 × 0.05 mm |
F(000) = 3496 |
Bruker SMART CCD diffractometer | 4628 independent reflections |
Radiation source: fine-focus sealed tube | 4279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −18→18 |
Tmin = 0.883, Tmax = 0.937 | k = −9→18 |
22787 measured reflections | l = −48→48 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.110 | w = 1/[σ2(Fo2) + (0.0787P)2 + 0.4409P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
4628 reflections | Δρmax = 1.37 e Å−3 |
245 parameters | Δρmin = −0.42 e Å−3 |
5 restraints | Absolute structure: Flack (1983), 2045 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.002 (13) |
[Zn4(C11H9N2O2)4(C7H5O2)4]·2C3H6O·CH4O | Z = 1 |
Mr = 6795.70 | Mo Kα radiation |
Tetragonal, I42d | µ = 1.30 mm−1 |
a = 14.3201 (4) Å | T = 170 K |
c = 37.730 (2) Å | 0.10 × 0.08 × 0.05 mm |
V = 7737.1 (5) Å3 |
Bruker SMART CCD diffractometer | 4628 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 4279 reflections with I > 2σ(I) |
Tmin = 0.883, Tmax = 0.937 | Rint = 0.029 |
22787 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.110 | Δρmax = 1.37 e Å−3 |
S = 1.09 | Δρmin = −0.42 e Å−3 |
4628 reflections | Absolute structure: Flack (1983), 2045 Friedel pairs |
245 parameters | Absolute structure parameter: 0.002 (13) |
5 restraints |
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 | 0.61621 (2) | 0.51226 (2) | 0.470190 (8) | 0.01677 (10) | |
O1 | 0.50301 (15) | 0.59983 (13) | 0.47540 (5) | 0.0177 (4) | |
O2 | 0.53176 (14) | 0.75354 (15) | 0.45808 (6) | 0.0237 (5) | |
H2O | 0.5908 | 0.7429 | 0.4575 | 0.036* | |
O3 | 0.73924 (15) | 0.58089 (15) | 0.47172 (6) | 0.0257 (4) | |
O4 | 0.71640 (16) | 0.73233 (17) | 0.46138 (9) | 0.0390 (6) | |
N1 | 0.58789 (18) | 0.55925 (18) | 0.41603 (6) | 0.0197 (5) | |
N2 | 0.67260 (17) | 0.38313 (19) | 0.45377 (6) | 0.0204 (5) | |
C1 | 0.6300 (2) | 0.5287 (2) | 0.38641 (8) | 0.0262 (6) | |
H1 | 0.6712 | 0.4768 | 0.3881 | 0.031* | |
C2 | 0.6162 (3) | 0.5691 (3) | 0.35381 (9) | 0.0366 (8) | |
H2 | 0.6465 | 0.5455 | 0.3333 | 0.044* | |
C3 | 0.5566 (3) | 0.6455 (3) | 0.35178 (10) | 0.0404 (10) | |
H3 | 0.5448 | 0.6748 | 0.3296 | 0.049* | |
C4 | 0.5141 (3) | 0.6789 (3) | 0.38253 (8) | 0.0331 (8) | |
H4 | 0.4741 | 0.7318 | 0.3818 | 0.040* | |
C5 | 0.5320 (2) | 0.6328 (2) | 0.41431 (8) | 0.0210 (6) | |
C6 | 0.4901 (2) | 0.6676 (2) | 0.44992 (7) | 0.0187 (5) | |
C7 | 0.6154 (2) | 0.3128 (2) | 0.44535 (7) | 0.0192 (5) | |
C8 | 0.6484 (2) | 0.2278 (2) | 0.43286 (9) | 0.0256 (6) | |
H8 | 0.6064 | 0.1783 | 0.4277 | 0.031* | |
C9 | 0.7445 (3) | 0.2165 (2) | 0.42796 (10) | 0.0325 (8) | |
H9 | 0.7685 | 0.1604 | 0.4181 | 0.039* | |
C10 | 0.8032 (2) | 0.2871 (3) | 0.43751 (10) | 0.0330 (8) | |
H10 | 0.8689 | 0.2797 | 0.4353 | 0.040* | |
C11 | 0.7658 (2) | 0.3707 (2) | 0.45060 (9) | 0.0280 (7) | |
H11 | 0.8069 | 0.4197 | 0.4574 | 0.034* | |
C12 | 0.7640 (2) | 0.6651 (2) | 0.47105 (9) | 0.0227 (6) | |
C13 | 0.8626 (2) | 0.6836 (2) | 0.48381 (8) | 0.0237 (6) | |
C14 | 0.9023 (2) | 0.7726 (2) | 0.48046 (11) | 0.0341 (8) | |
H14 | 0.8676 | 0.8218 | 0.4699 | 0.041* | |
C15 | 0.9924 (3) | 0.7888 (3) | 0.49264 (12) | 0.0461 (10) | |
H15 | 1.0196 | 0.8489 | 0.4900 | 0.055* | |
C16 | 1.0423 (3) | 0.7181 (3) | 0.50846 (13) | 0.0474 (11) | |
H16 | 1.1039 | 0.7295 | 0.5168 | 0.057* | |
C17 | 1.0032 (3) | 0.6313 (3) | 0.51216 (11) | 0.0398 (8) | |
H17 | 1.0374 | 0.5829 | 0.5234 | 0.048* | |
C18 | 0.9141 (2) | 0.6138 (3) | 0.49960 (9) | 0.0306 (7) | |
H18 | 0.8882 | 0.5530 | 0.5019 | 0.037* | |
O1S | 0.9292 (16) | 1.1086 (15) | 0.3972 (6) | 0.218 (6)* | 0.50 |
C1S | 0.9466 (13) | 1.0280 (17) | 0.3923 (6) | 0.218 (6)* | 0.50 |
C2S | 0.965 (2) | 0.972 (2) | 0.4275 (8) | 0.218 (6)* | 0.50 |
H2S1 | 1.0259 | 0.9886 | 0.4372 | 0.328* | 0.50 |
H2S2 | 0.9634 | 0.9045 | 0.4224 | 0.328* | 0.50 |
H2S3 | 0.9160 | 0.9865 | 0.4448 | 0.328* | 0.50 |
C3S | 0.9503 (19) | 0.975 (2) | 0.3559 (7) | 0.218 (6)* | 0.50 |
H3S1 | 0.8956 | 0.9340 | 0.3537 | 0.328* | 0.50 |
H3S2 | 1.0073 | 0.9370 | 0.3547 | 0.328* | 0.50 |
H3S3 | 0.9504 | 1.0201 | 0.3364 | 0.328* | 0.50 |
O2S | 0.7500 | 1.0096 (11) | 0.3750 | 0.110 (5)* | 0.50 |
H2S | 0.7197 | 1.0292 | 0.3574 | 0.164* | 0.25 |
C21S | 0.7500 | 0.9049 (11) | 0.3750 | 0.139 (10)* | 0.50 |
H21A | 0.7999 | 0.8821 | 0.3595 | 0.208* | 0.25 |
H21B | 0.6896 | 0.8821 | 0.3664 | 0.208* | 0.25 |
H21C | 0.7605 | 0.8821 | 0.3992 | 0.208* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01658 (17) | 0.01739 (17) | 0.01634 (15) | 0.00064 (12) | 0.00086 (12) | 0.00068 (12) |
O1 | 0.0189 (9) | 0.0175 (9) | 0.0167 (9) | 0.0029 (8) | 0.0001 (8) | 0.0034 (7) |
O2 | 0.0206 (10) | 0.0193 (10) | 0.0311 (11) | −0.0009 (9) | 0.0009 (8) | −0.0005 (9) |
O3 | 0.0216 (11) | 0.0258 (11) | 0.0296 (11) | −0.0035 (9) | 0.0013 (9) | −0.0002 (10) |
O4 | 0.0214 (11) | 0.0262 (13) | 0.0693 (19) | −0.0015 (9) | −0.0062 (11) | 0.0019 (12) |
N1 | 0.0201 (12) | 0.0213 (12) | 0.0176 (11) | 0.0003 (9) | 0.0009 (9) | 0.0007 (9) |
N2 | 0.0182 (12) | 0.0232 (12) | 0.0199 (11) | 0.0025 (11) | 0.0015 (9) | 0.0025 (10) |
C1 | 0.0244 (15) | 0.0299 (16) | 0.0244 (14) | 0.0035 (13) | 0.0059 (12) | 0.0000 (12) |
C2 | 0.044 (2) | 0.044 (2) | 0.0218 (15) | 0.0112 (18) | 0.0101 (15) | 0.0016 (14) |
C3 | 0.050 (2) | 0.048 (2) | 0.0227 (16) | 0.0158 (19) | 0.0113 (16) | 0.0114 (15) |
C4 | 0.0378 (19) | 0.0376 (18) | 0.0238 (15) | 0.0120 (16) | 0.0058 (14) | 0.0085 (13) |
C5 | 0.0206 (14) | 0.0214 (14) | 0.0211 (14) | 0.0008 (12) | 0.0015 (10) | 0.0043 (11) |
C6 | 0.0199 (14) | 0.0168 (13) | 0.0194 (12) | 0.0026 (12) | 0.0006 (11) | 0.0040 (10) |
C7 | 0.0206 (14) | 0.0207 (13) | 0.0163 (12) | 0.0010 (12) | 0.0005 (11) | 0.0006 (10) |
C8 | 0.0267 (15) | 0.0255 (16) | 0.0245 (15) | 0.0056 (13) | −0.0002 (12) | −0.0017 (12) |
C9 | 0.0317 (18) | 0.0298 (17) | 0.0361 (18) | 0.0124 (15) | 0.0060 (15) | −0.0024 (14) |
C10 | 0.0231 (16) | 0.0371 (19) | 0.0388 (19) | 0.0086 (14) | 0.0068 (14) | 0.0018 (15) |
C11 | 0.0214 (15) | 0.0312 (17) | 0.0315 (17) | −0.0005 (13) | 0.0033 (12) | 0.0037 (14) |
C12 | 0.0192 (14) | 0.0267 (15) | 0.0221 (14) | −0.0017 (11) | 0.0049 (12) | −0.0030 (13) |
C13 | 0.0204 (15) | 0.0263 (16) | 0.0246 (14) | −0.0009 (12) | 0.0040 (12) | −0.0069 (12) |
C14 | 0.0275 (18) | 0.0260 (17) | 0.049 (2) | −0.0028 (14) | 0.0040 (14) | −0.0056 (14) |
C15 | 0.0283 (18) | 0.0291 (18) | 0.081 (3) | −0.0061 (16) | −0.001 (2) | −0.0103 (19) |
C16 | 0.0218 (17) | 0.048 (2) | 0.072 (3) | −0.0035 (16) | −0.0083 (18) | −0.020 (2) |
C17 | 0.0292 (17) | 0.038 (2) | 0.052 (2) | 0.0050 (16) | −0.0075 (17) | −0.0062 (17) |
C18 | 0.0270 (16) | 0.0290 (16) | 0.0357 (17) | −0.0039 (14) | −0.0012 (13) | −0.0028 (14) |
Zn1—O3 | 2.018 (2) | C9—C10 | 1.365 (5) |
Zn1—O1 | 2.059 (2) | C9—H9 | 0.9500 |
Zn1—O1i | 2.0776 (19) | C10—C11 | 1.401 (5) |
Zn1—N2 | 2.111 (3) | C10—H10 | 0.9500 |
Zn1—N1 | 2.189 (2) | C11—H11 | 0.9500 |
Zn1—O1ii | 2.351 (2) | C12—C13 | 1.515 (4) |
O1—C6 | 1.378 (3) | C13—C18 | 1.378 (5) |
O1—Zn1iii | 2.0777 (19) | C13—C14 | 1.401 (5) |
O1—Zn1ii | 2.352 (2) | C14—C15 | 1.389 (5) |
O2—C6 | 1.402 (4) | C14—H14 | 0.9500 |
O2—H2O | 0.8587 | C15—C16 | 1.376 (6) |
O3—C12 | 1.257 (4) | C15—H15 | 0.9500 |
O4—C12 | 1.235 (4) | C16—C17 | 1.371 (6) |
N1—C5 | 1.325 (4) | C16—H16 | 0.9500 |
N1—C1 | 1.343 (4) | C17—C18 | 1.384 (5) |
N2—C7 | 1.336 (4) | C17—H17 | 0.9500 |
N2—C11 | 1.352 (4) | C18—H18 | 0.9500 |
C1—C2 | 1.374 (5) | O1S—C1S | 1.195 (10) |
C1—H1 | 0.9500 | C1S—C2S | 1.57 (2) |
C2—C3 | 1.391 (5) | C1S—C3S | 1.57 (2) |
C2—H2 | 0.9500 | C2S—H2S1 | 0.9800 |
C3—C4 | 1.394 (5) | C2S—H2S2 | 0.9800 |
C3—H3 | 0.9500 | C2S—H2S3 | 0.9800 |
C4—C5 | 1.392 (4) | C3S—H3S1 | 0.9800 |
C4—H4 | 0.9500 | C3S—H3S2 | 0.9800 |
C5—C6 | 1.553 (4) | C3S—H3S3 | 0.9800 |
C6—C7ii | 1.546 (4) | O2S—C21S | 1.499 (2) |
C7—C8 | 1.388 (4) | O2S—H2S | 0.8400 |
C7—C6ii | 1.546 (4) | C21S—H21A | 0.9800 |
C8—C9 | 1.398 (5) | C21S—H21B | 0.9800 |
C8—H8 | 0.9500 | C21S—H21C | 0.9800 |
O3—Zn1—O1 | 112.83 (9) | C7—C8—H8 | 120.6 |
O3—Zn1—O1i | 96.98 (9) | C9—C8—H8 | 120.6 |
O1—Zn1—O1i | 83.16 (8) | C10—C9—C8 | 119.1 (3) |
O3—Zn1—N2 | 95.80 (9) | C10—C9—H9 | 120.5 |
O1—Zn1—N2 | 149.64 (9) | C8—C9—H9 | 120.5 |
O1i—Zn1—N2 | 103.94 (9) | C9—C10—C11 | 119.4 (3) |
O3—Zn1—N1 | 92.22 (9) | C9—C10—H10 | 120.3 |
O1—Zn1—N1 | 75.88 (9) | C11—C10—H10 | 120.3 |
O1i—Zn1—N1 | 159.01 (9) | N2—C11—C10 | 121.4 (3) |
N2—Zn1—N1 | 93.79 (10) | N2—C11—H11 | 119.3 |
O3—Zn1—O1ii | 164.53 (8) | C10—C11—H11 | 119.3 |
O1—Zn1—O1ii | 80.57 (8) | O4—C12—O3 | 126.7 (3) |
O1i—Zn1—O1ii | 76.33 (8) | O4—C12—C13 | 118.1 (3) |
N2—Zn1—O1ii | 72.80 (8) | O3—C12—C13 | 115.2 (3) |
N1—Zn1—O1ii | 98.82 (8) | C18—C13—C14 | 118.8 (3) |
C6—O1—Zn1 | 117.87 (17) | C18—C13—C12 | 120.6 (3) |
C6—O1—Zn1iii | 126.55 (17) | C14—C13—C12 | 120.6 (3) |
Zn1—O1—Zn1iii | 104.24 (9) | C15—C14—C13 | 119.9 (4) |
C6—O1—Zn1ii | 108.97 (17) | C15—C14—H14 | 120.0 |
Zn1—O1—Zn1ii | 98.51 (8) | C13—C14—H14 | 120.1 |
Zn1iii—O1—Zn1ii | 94.78 (7) | C16—C15—C14 | 120.2 (4) |
C6—O2—H2O | 104.9 | C16—C15—H15 | 119.9 |
C12—O3—Zn1 | 135.5 (2) | C14—C15—H15 | 119.9 |
C5—N1—C1 | 119.3 (3) | C17—C16—C15 | 119.9 (4) |
C5—N1—Zn1 | 113.71 (19) | C17—C16—H16 | 120.0 |
C1—N1—Zn1 | 126.4 (2) | C15—C16—H16 | 120.0 |
C7—N2—C11 | 119.1 (3) | C16—C17—C18 | 120.5 (4) |
C7—N2—Zn1 | 119.66 (19) | C16—C17—H17 | 119.8 |
C11—N2—Zn1 | 121.3 (2) | C18—C17—H17 | 119.8 |
N1—C1—C2 | 122.9 (3) | C13—C18—C17 | 120.6 (4) |
N1—C1—H1 | 118.6 | C13—C18—H18 | 119.7 |
C2—C1—H1 | 118.5 | C17—C18—H18 | 119.7 |
C1—C2—C3 | 118.0 (3) | O1S—C1S—C2S | 114 (2) |
C1—C2—H2 | 121.0 | O1S—C1S—C3S | 128 (2) |
C3—C2—H2 | 121.0 | C2S—C1S—C3S | 119 (2) |
C2—C3—C4 | 119.4 (3) | C1S—C2S—H2S1 | 109.5 |
C2—C3—H3 | 120.3 | C1S—C2S—H2S2 | 109.4 |
C4—C3—H3 | 120.3 | H2S1—C2S—H2S2 | 109.5 |
C5—C4—C3 | 118.3 (3) | C1S—C2S—H2S3 | 109.5 |
C5—C4—H4 | 120.9 | H2S1—C2S—H2S3 | 109.5 |
C3—C4—H4 | 120.9 | H2S2—C2S—H2S3 | 109.5 |
N1—C5—C4 | 122.0 (3) | C1S—C3S—H3S1 | 109.5 |
N1—C5—C6 | 116.5 (2) | C1S—C3S—H3S2 | 109.4 |
C4—C5—C6 | 121.4 (3) | H3S1—C3S—H3S2 | 109.5 |
O1—C6—O2 | 114.1 (2) | C1S—C3S—H3S3 | 109.5 |
O1—C6—C7ii | 109.6 (2) | H3S1—C3S—H3S3 | 109.5 |
O2—C6—C7ii | 106.3 (2) | H3S2—C3S—H3S3 | 109.5 |
O1—C6—C5 | 109.0 (2) | C21S—O2S—H2S | 109.5 |
O2—C6—C5 | 107.9 (2) | O2S—C21S—H21A | 109.00 |
C7ii—C6—C5 | 109.8 (2) | O2S—C21S—H21B | 109.00 |
N2—C7—C8 | 122.1 (3) | H21A—C21S—H21B | 110.00 |
N2—C7—C6ii | 115.9 (2) | O2S—C21S—H21C | 109.00 |
C8—C7—C6ii | 122.0 (3) | H21A—C21S—H21C | 109.00 |
C7—C8—C9 | 118.8 (3) | H21B—C21S—H21C | 109.00 |
Symmetry codes: (i) y, −x+1, −z+1; (ii) −x+1, −y+1, z; (iii) −y+1, x, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn4(C11H9N2O2)4(C7H5O2)4]·2C3H6O·CH4O |
Mr | 6795.70 |
Crystal system, space group | Tetragonal, I42d |
Temperature (K) | 170 |
a, c (Å) | 14.3201 (4), 37.730 (2) |
V (Å3) | 7737.1 (5) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.10 × 0.08 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.883, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22787, 4628, 4279 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.110, 1.09 |
No. of reflections | 4628 |
No. of parameters | 245 |
No. of restraints | 5 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.37, −0.42 |
Absolute structure | Flack (1983), 2045 Friedel pairs |
Absolute structure parameter | 0.002 (13) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
Financial support from the Korea Ministry of the Environment `ET-Human resource development Project' and the Cooperative Research Program for Agricultural Science & Technology Development (20070301–036-019–02) is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Transition metal ions have, recently, received attention as the major cationic contributors to the inorganic composition of natural water and biological fluids (Daniele, et al., 2008). While the main interest is focused on the interaction of transition metal ions with biologically active molecules such as amino acids, proteins, sugars and nucleotides, the study on the interaction of the transition metal ions with fulvic acids and humic acids, mainly found in soil, is in incipient stages. As models to examine the interaction, therefore, we have previously used copper(II) benzoate as a building block and reported the structures of copper(II) benzoates with quinoxaline, 6-methylquinoline, and 3-methylquinoline (Lee, et al., 2008; Yu, et al., 2008; Park, et al., 2008). In this work, we have employed zinc(II) benzoate as a building block and di-2-pyridyl ketone as a ligand. We report herein the structure of the product of zinc(II) benzoate with di-2-pyridyl ketone.
The crystal structure contains tetranuclear [Zn4(O2CPh)4{(py)2C(OH)O}4] molecules (Fig. 1), similar to the corresponding Mn4 cubane compound (Stoumpos, et al., 2008). The tetramolecular molecule lies on a fourfold inversion center and hence the asymmetric unit contains a quarter of a molecule. ZnII ions and µ3-O atoms in the cubane [ZnII4(µ3-OR)4]4+ core occupy alternate vertices. Thus, the molecule consists of two interpenetrating tetrahedra: one contains four µ3-O atoms originating from the (py)2C(OH)O ligands, and the other contains four ZnII atoms. Each ZnII center is coordinated by two N atoms from two different (py)2C(OH)O ligands and one O atom from a monodentate PhCO2- ligand to form a distorted octahedral geometry. The (py)2C(OH)O ligands acts as η1:η3:η1:µ3 to form two five-membered ZnNCCO chelating rings with two different ZnII ions sharing a common C—O edge and an alkoxide-type bond to a third ZnII ion. This ligation mode is common for the hydrated di-2-pyridyl ketone, (py)2C(OH)O- (Papaefstathiou & Perlepes, 2002; Papatriantafyllopoulou, et al., 2007). There are intramolecular hydrogen bonds interactions between the protonated O atom of the (py)2C(OH)O ligand and the uncoordinated O atom of the monodentate PhCO2 group.