A neutral cubane with a Zn(4)O(4) core: tetra-benzoato-tetra-kis(μ(3)-hydroxydi-2-pyridylmethano-lato)tetra-zinc(II)-acetone-methanol (1/2/1).

In the title compound, [Zn(4)(C(11)H(9)N(2)O(2))(4)(C(7)H(5)O(2))(4)]·2(CH(3))(2)CO·CH(3)OH, the tetra-nuclear mol-ecule lies on a fourfold inversion axis. Zn(II) ions and μ(3)-O atoms in the cubane core occupy alternating vertices, forming two inter-penetrating tetra-hedra. Each Zn(II) ion is further coordinated by two N atoms from two different (py)(2)C(OH)O ligands (py is pyrid-yl) and one O atom from a monodentate benzoate ligand, forming a distorted octa-hedral environment. The (py)(2)C(OH)O ligand acts in an η(1):η(3):η(1):μ(3) manner, forming two five-membered ZnNCCO chelating rings with two different Zn(II) atoms sharing a common C-O bond, and an alkoxide-type bond to a third Zn(II) ion. There are four symmetry-related intra-molecular O-H⋯O hydrogen bonds between the two types of ligands. In the asymmetric unit, there is a half-occupancy acetone solvent mol-ecule 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

[Zn4(C11H9N2O2)4(C7H5O2)4]·2C3H6O·CH4O

M = 6795.70

Tetragonal,

a = 14.3201 (4) Å

c = 37.730 (2) Å

V = 7737.1 (5) Å3

Z = 1

Mo Kα radiation

μ = 1.30 mm−1

T = 170 K

0.10 × 0.08 × 0.05 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.883, T max = 0.937

22787 measured reflections

4628 independent reflections

4279 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.110

S = 1.09

4628 reflections

245 parameters

5 restraints

H-atom parameters constrained

Δρmax = 1.37 e Å−3

Δρmin = −0.42 e Å−3

Absolute structure: Flack (1983 ▶), 2045 Friedel pairs

Flack parameter: 0.002 (13)

Data collection: SMART (Bruker, 1997 ▶); cell refinement: 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809017772/lh2815sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809017772/lh2815Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[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	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	Flack parameter: 0.002 (13)

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	0.98000
C8—C9	1.398 (5)	C21S—H21B	0.98000
C8—H8	0.9500	C21S—H21C	0.98000
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

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O4	0.86	1.81	2.664 (3)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2O⋯O4	0.86	1.81	2.664 (3)	172