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The synthesis is reported of the tri­carb­oxy­lic acid 3-(3,5-di­­carb­oxy­benzyl­oxy)benzoic acid (H3L) and the product of its reaction under solvothermal conditions with ZnII cations, namely poly[[[mu]6-3-(3,5-di­carboxyl­ato­benzyl­oxy)benzo­ato](di­methyl­formamide)-[mu]3-hydroxido-dizinc(II)], [Zn2(C16H9O7)(OH)(C3H7NO)]n, the formation of which is associated with complete deprotonation of H3L. Its crystal structure consists of a single-framework coordination polymer of the organic L3- ligand with ZnII cations in a 1:2 ratio, with additional hydroxide and di­methyl­formamide (DMF) ligands coordinated to the ZnII centres. The ZnII cations are characterized by coordination numbers of 5 and 6, being bridged to each other by hydroxide ligands. In the polymeric framework, the carboxyl­ate- and hy­droxy-bridged ZnII cations are arranged in ­coordination-tessellated columns, which propagate along the a axis of the crystal structure, and each L3- ligand links to seven different ZnII centres via Zn-O bonds of two different columns. The coordination framework, composed of [Zn2(L)(OH)(DMF)]n units, forms an open architecture, the channel voids within it being filled by the zinc-coordinating DMF ligands. This report provides the first structural evidence for the formation of coordination polymers with H3L via multiple metal-ligand bonds through its carboxyl­ate groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017204/sk3498sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017204/sk3498Isup2.hkl
Contains datablock I

CCDC reference: 958841

Introduction top

This communication is part of a recent series of studies on the coordination chemistry of newly synthesized multidentate ligands with a flexible backbone, which can adjust their conformation in a given reaction with metal ions in order to optimize the coordination process. These ligands are functionalized with various combinations of carb­oxy­lic acids and pyridyl substituents, placed on the ligand periphery and oriented in diverging directions (Patra et al., 2013a,b,c; Karmakar & Goldberg, 2011). Our efforts are aimed primarily at the synthesis of metal–organic frameworks with three-dimensional connectivity features and the evaluation of their potential applications.

Experimental top

Experimental details are summarized in Table 1.

Synthesis and crystallization top

All chemicals used for the syntheses were commercially available reagents of analytical grade and were used without further purification. The FT–IR spectra were recorded from KBr pellets in the 4000–400 cm-1 range on a Nicolet 5DX spectrometer. H3L was synthesized according to reported procedures (Patra et al., 2013a,b). Polymer (I) was obtained in the following manner. A mixture of Zn(NO3)2.6H2O (5.8 mg, 0.02 mmol) and H3L (3.2 mg, 0.01 mmol) was dissolved in DMF–water (4 ml, 1:1 v/v). The mixture was then heated for 48 h in a bath reactor at 373 K and, after cooling to room temperature, colourless crystals were obtained. These were separated by filtration, washed with water and dried in air (yield 45%, based on metal salt). FT–IR (KBr, ν, cm-1): 3290 (br, γO—H) 2987 (mb, γC—H), 1612 (s, γC O asymmetric), 1543 (s, γCC), 1360 (m, γCO symmetric), 1265 (s, γC—O), 1044 (w), 1024 (s), 907 (w), 776 (s), 721 (w), 594 (m), 437 (w).

Refinement top

All H atoms were located in calculated positions and constrained to ride on their parent C atoms, with Csp2—H = 0.95 Å and Csp3—H = 0.98 or 0.99 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H or 1.5Ueq(C) otherwise. The H atom of the bridging hydroxide ligand was located in a difference Fourier map but was not refined. It was constrained to ride on its parent O atom, with Uiso(H) = 1.2Ueq(O). The intensity of a single reflection, 001, which was affected by the beam-stop, could not be estimated reliably and was omitted from the refinement calculations.

Comment top

In this paper, we describe the unique supra­molecular coordination pattern obtained by reacting 3-(3,5-di­carb­oxy­benzyl­oxy)benzoic acid (H3L) with zinc nitrate hexahydrate. The organic ligand has three molecular recognition sites for metal coordination (the carb­oxy­lic acid groups), oriented in diverging directions. This provides the driving force for simultaneous coordination (after complete deprotonation) to several metal-ion connectors and the formation of the coordination-driven polymeric framework poly[[µ6-3-(3,5-di­carboxyl­ato­benzyl­oxy)benzoato](di­methyl­formamide)-µ-hydroxido-dizinc(II)], (I) (Fig. 1).

The molecular shape of the organic ligand of (I) is characterized by a bent shape around the central CH2—O bond. The two benzene rings of L3- are roughly perpendicular to one another, the dihedral angle between their mean planes (defined by atoms C7–C12 and C15–C20) being 72.77 (7)°. The carboxyl­ate groups C6/O4/O5 and C24/O25/O26 coordinate to two different ZnII cations each in a µ2-η1-η1 mode, while the C21/O22/O23 carboxyl­ate group binds simultaneously to three ZnII cations in a µ3-η2-η1 mode (Fig. 2 and Table 2). The coordination scheme in (I) represents a continuous inter­action synthon that propagates throughout the crystal structure. The organic L3- linkers are tessellated to one another by periodically spaced polymeric [Zn2(L)(OH)(DMF)]n arrays, that propagate along the a direction and act as construction pillars of the metal–organic framework (Fig. 2).

The Zn1···Zn2 distance in the asymmetric unit is 3.2272 (3) Å, and that between proximate Zn2 atoms related by an inversion centre at (1/2,1/2,0) is 3.0531 (5) Å. Atom Zn1 is six-coordinate with approximate o­cta­hedral geometry, connected to four different carboxyl­ate groups, the DMF ligand and the metal-bridging hydroxide group. Atom Zn2 is located near an inversion centre and is five-coordinate in a square-pyramidal fashion, linked to three carboxyl­ates and two inversion-related hydroxides (the presence of the latter accounts for charge balance). The multiple coordination of the ligand spacers and the metal-ion connectors invokes the formation of a supra­molecular network of three-dimensional topology (Fig. 3). The hydroxide ligand bridges between three adjacent ZnII cations and is hydrogen-bonded to one of the neighbouring carboxyl­ate groups (Table 3).

Conclusions top

In summary, we report here on the synthesis of a new tri­carb­oxy­lic acid ligand and demonstrate its capacity to engage in extended coordination polymerization with ZnII cations. The resulting structure represents a three-dimensional single-framework polymer sustained by pillars of hy­droxy- and carboxyl­ate-bridged multi-nuclear coordination synthons. Similarly shaped flexible organic ligands with four carb­oxy­lic acid functions and cadmium, copper, cobalt and manganese cation connectors were found to form polymeric structures as well (Patra et al., 2013a). Polymeric assemblies of yet another ligand with one pyridyl and three carb­oxy­lic acid functions with divalent cadmium, copper, cobalt, manganese and nickel cations have also been characterized (Patra et al., 2013b). Coordination polymers based on related tri- and tetra­carb­oxy­lic acid (tripodal and tetra­podal) ligands crosslinked by various metal ions, which represent microporous solids with attractive gas sorption features, have also been reported (e.g. Wang et al., 2008; Cui et al., 2012). In the above context, efforts will be made to replace the DMF component in (I) by a noncoordinating species, and then examine the potential porosity (sorption/desorption) features of the resulting material.

Related literature top

For related literature, see: Cui et al. (2012); Karmakar & Goldberg (2011); Patra et al. (2013a, 2013b, 2013c); Wang et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2012 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2012 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level at 110 (2) K.
[Figure 2] Fig. 2. A view of the coordination pattern around the ZnII cations of (I), along the `construction pillars' along the a axis of the crystal structure. H atoms have been omitted and only the carboxylate residues of the organic ligand are shown for clarity. The DMF species are represented by their O atoms only. Note the square-pyramidal five-coordinate environment around atom Zn1 and the square-bipyramidal six-coordinate shell around atom Zn2. An inversion centre at (1/2, 1/2, 0) is indicated by a black dot.
[Figure 3] Fig. 3. A view of the crystal structure, approximately down the a axis. Note the intrachannel voids, which are occupied by the zinc-bound DMF molecules. The ZnII cations are denoted by small spheres.
Poly[[µ6-3-(3,5-dicarboxylatobenzyloxy)benzoato](dimethylformamide)-µ-hydroxido-dizinc(II)] top
Crystal data top
[Zn2(C16H9O7)(OH)(C3H7NO)]Z = 2
Mr = 534.12F(000) = 540
Triclinic, P1Dx = 1.826 Mg m3
a = 7.7417 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.8543 (3) ÅCell parameters from 4319 reflections
c = 12.5527 (3) Åθ = 2.0–27.5°
α = 109.463 (1)°µ = 2.53 mm1
β = 90.615 (1)°T = 110 K
γ = 101.884 (1)°Plate, colourless
V = 969.61 (4) Å30.30 × 0.25 × 0.15 mm
Data collection top
Bruker APEX DUO area-detector
diffractometer
4319 independent reflections
Radiation source: Imu Mo micro-source sealed-tube3474 reflections with I > 2σ(I)
Detector resolution: 1.75 pixels mm-1Rint = 0.040
ω and ϕ scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 107
Tmin = 0.518, Tmax = 0.703k = 1314
8513 measured reflectionsl = 1516
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters constrained
S = 0.92 w = 1/[σ2(Fo2) + (0.0265P)2]
where P = (Fo2 + 2Fc2)/3
4319 reflections(Δ/σ)max < 0.001
282 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
[Zn2(C16H9O7)(OH)(C3H7NO)]γ = 101.884 (1)°
Mr = 534.12V = 969.61 (4) Å3
Triclinic, P1Z = 2
a = 7.7417 (2) ÅMo Kα radiation
b = 10.8543 (3) ŵ = 2.53 mm1
c = 12.5527 (3) ÅT = 110 K
α = 109.463 (1)°0.30 × 0.25 × 0.15 mm
β = 90.615 (1)°
Data collection top
Bruker APEX DUO area-detector
diffractometer
4319 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
3474 reflections with I > 2σ(I)
Tmin = 0.518, Tmax = 0.703Rint = 0.040
8513 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.057H-atom parameters constrained
S = 0.92Δρmax = 0.52 e Å3
4319 reflectionsΔρmin = 0.51 e Å3
282 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.14134 (3)0.49867 (2)0.10074 (2)0.01016 (7)
Zn20.50942 (3)0.65047 (2)0.03857 (2)0.00921 (7)
O30.32138 (18)0.48139 (14)0.01538 (12)0.0090 (3)
H30.25690.46390.08420.011*
O40.2794 (2)0.63903 (15)0.24711 (13)0.0154 (3)
O50.55968 (19)0.69616 (15)0.20663 (12)0.0143 (3)
C60.4393 (3)0.6962 (2)0.27420 (18)0.0124 (5)
C70.4942 (3)0.7731 (2)0.39765 (19)0.0144 (5)
C80.6711 (3)0.8227 (2)0.43883 (19)0.0188 (5)
H80.76210.80640.38920.023*
C90.7139 (3)0.8967 (2)0.5541 (2)0.0220 (6)
H90.83470.92980.58280.026*
C100.5823 (3)0.9224 (2)0.6269 (2)0.0197 (5)
H100.61290.97330.70500.024*
C110.4056 (3)0.8736 (2)0.5853 (2)0.0172 (5)
C120.3619 (3)0.7988 (2)0.47147 (19)0.0163 (5)
H120.24090.76460.44340.020*
O130.2625 (2)0.89205 (17)0.64821 (13)0.0237 (4)
C140.2982 (3)0.9825 (2)0.76311 (18)0.0158 (5)
H14A0.36331.07220.76560.019*
H14B0.37050.94880.80800.019*
C150.1203 (3)0.9900 (2)0.80975 (18)0.0137 (5)
C160.0182 (3)0.8770 (2)0.82545 (18)0.0149 (5)
H160.05790.79560.80170.018*
C170.1416 (3)0.8809 (2)0.87551 (18)0.0124 (5)
C180.1999 (3)1.0002 (2)0.90958 (18)0.0135 (5)
H180.30821.00420.94410.016*
C190.0991 (3)1.1143 (2)0.89307 (18)0.0124 (5)
C200.0603 (3)1.1081 (2)0.84335 (18)0.0145 (5)
H200.12871.18560.83230.017*
C210.1670 (3)1.2417 (2)0.92897 (19)0.0144 (5)
O220.32929 (19)1.22689 (15)0.93683 (14)0.0173 (4)
O230.05636 (19)1.35294 (14)0.94505 (13)0.0126 (3)
C240.2387 (3)0.7582 (2)0.89795 (18)0.0110 (5)
O250.36216 (19)0.77105 (14)0.96256 (13)0.0141 (3)
O260.1881 (2)0.65203 (15)0.85050 (13)0.0161 (4)
O270.09392 (19)0.48666 (15)0.18739 (13)0.0147 (3)
C280.0911 (3)0.5199 (2)0.2922 (2)0.0176 (5)
H280.01650.57230.33560.021*
N290.2275 (3)0.4876 (2)0.34796 (16)0.0195 (4)
C300.3948 (3)0.4044 (3)0.2870 (2)0.0303 (6)
H30A0.48020.46070.29040.045*
H30B0.44100.33720.32190.045*
H30C0.37610.35930.20770.045*
C310.2192 (4)0.5367 (3)0.4717 (2)0.0301 (6)
H31A0.09980.58980.50260.045*
H31B0.24660.46040.49870.045*
H31C0.30550.59270.49690.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.00891 (13)0.00997 (13)0.01403 (14)0.00351 (10)0.00547 (10)0.00629 (10)
Zn20.00794 (13)0.00748 (13)0.01274 (14)0.00159 (10)0.00386 (10)0.00415 (10)
O30.0071 (7)0.0095 (7)0.0099 (8)0.0015 (6)0.0009 (6)0.0028 (6)
O40.0139 (8)0.0147 (8)0.0139 (8)0.0004 (7)0.0055 (7)0.0021 (7)
O50.0131 (8)0.0172 (8)0.0111 (8)0.0027 (7)0.0045 (7)0.0032 (6)
C60.0164 (12)0.0095 (11)0.0135 (12)0.0046 (9)0.0054 (10)0.0056 (9)
C70.0179 (12)0.0125 (11)0.0142 (12)0.0041 (9)0.0026 (10)0.0059 (9)
C80.0179 (13)0.0223 (13)0.0176 (13)0.0082 (11)0.0056 (10)0.0066 (10)
C90.0148 (13)0.0279 (14)0.0232 (14)0.0056 (11)0.0000 (10)0.0084 (11)
C100.0207 (13)0.0222 (13)0.0152 (13)0.0038 (11)0.0010 (10)0.0056 (10)
C110.0188 (12)0.0163 (12)0.0185 (13)0.0059 (10)0.0079 (10)0.0074 (10)
C120.0177 (12)0.0138 (12)0.0150 (12)0.0004 (10)0.0034 (10)0.0036 (9)
O130.0192 (9)0.0280 (10)0.0155 (9)0.0018 (8)0.0075 (7)0.0016 (7)
C140.0175 (12)0.0158 (12)0.0107 (11)0.0011 (10)0.0040 (10)0.0015 (9)
C150.0122 (11)0.0150 (12)0.0113 (11)0.0027 (9)0.0021 (9)0.0012 (9)
C160.0171 (12)0.0125 (11)0.0143 (12)0.0034 (9)0.0012 (10)0.0036 (9)
C170.0123 (11)0.0129 (11)0.0118 (11)0.0002 (9)0.0008 (9)0.0056 (9)
C180.0113 (11)0.0151 (12)0.0154 (12)0.0030 (9)0.0009 (9)0.0071 (9)
C190.0120 (11)0.0121 (11)0.0139 (12)0.0031 (9)0.0002 (9)0.0051 (9)
C200.0174 (12)0.0147 (12)0.0127 (12)0.0019 (9)0.0014 (9)0.0075 (9)
C210.0139 (12)0.0171 (12)0.0162 (12)0.0053 (10)0.0042 (10)0.0098 (10)
O220.0089 (8)0.0118 (8)0.0351 (10)0.0039 (6)0.0081 (7)0.0119 (7)
O230.0092 (8)0.0097 (8)0.0220 (9)0.0017 (6)0.0039 (7)0.0095 (7)
C240.0082 (11)0.0143 (11)0.0115 (11)0.0010 (9)0.0016 (9)0.0067 (9)
O250.0125 (8)0.0138 (8)0.0205 (9)0.0047 (7)0.0076 (7)0.0105 (7)
O260.0223 (9)0.0137 (8)0.0173 (8)0.0096 (7)0.0076 (7)0.0084 (7)
O270.0125 (8)0.0191 (9)0.0152 (9)0.0053 (7)0.0046 (7)0.0084 (7)
C280.0147 (12)0.0176 (12)0.0228 (14)0.0040 (10)0.0024 (10)0.0097 (10)
N290.0154 (11)0.0270 (12)0.0199 (11)0.0041 (9)0.0061 (9)0.0132 (9)
C300.0154 (13)0.0428 (17)0.0380 (17)0.0007 (12)0.0051 (12)0.0240 (14)
C310.0338 (16)0.0413 (17)0.0211 (14)0.0109 (14)0.0116 (12)0.0164 (12)
Geometric parameters (Å, º) top
Zn1—O32.0178 (13)C14—H14B0.9900
Zn1—O26i2.0218 (15)C15—C201.388 (3)
Zn1—O42.0643 (15)C15—C161.390 (3)
Zn1—O23ii2.0982 (14)C16—C171.395 (3)
Zn1—O272.1346 (14)C16—H160.9500
Zn1—O23iii2.3542 (15)C17—C181.393 (3)
Zn2—O25iv1.9821 (15)C17—C241.504 (3)
Zn2—O31.9990 (14)C18—C191.401 (3)
Zn2—O52.0133 (15)C18—H180.9500
Zn2—O22ii2.0765 (14)C19—C201.393 (3)
Zn2—O3v2.0861 (13)C19—C211.510 (3)
Zn2—Zn2v3.0531 (5)C20—H200.9500
Zn2—Zn13.2272 (3)C21—O221.242 (3)
O3—Zn2v2.0861 (13)C21—O231.281 (3)
O3—H30.9347O22—Zn2ii2.0765 (14)
O4—C61.252 (3)O23—Zn1ii2.0982 (14)
O5—C61.266 (2)O23—Zn1vi2.3542 (15)
C6—C71.502 (3)C24—O261.253 (2)
C7—C81.389 (3)C24—O251.260 (2)
C7—C121.397 (3)O25—Zn2vii1.9821 (15)
C8—C91.398 (3)O26—Zn1i2.0218 (15)
C8—H80.9500O27—C281.242 (3)
C9—C101.385 (3)C28—N291.324 (3)
C9—H90.9500C28—H280.9500
C10—C111.389 (3)N29—C301.455 (3)
C10—H100.9500N29—C311.461 (3)
C11—O131.377 (3)C30—H30A0.9800
C11—C121.385 (3)C30—H30B0.9800
C12—H120.9500C30—H30C0.9800
O13—C141.434 (3)C31—H31A0.9800
C14—C151.510 (3)C31—H31B0.9800
C14—H14A0.9900C31—H31C0.9800
O3—Zn1—O26i95.02 (6)C7—C12—H12119.7
O3—Zn1—O4104.27 (6)C11—O13—C14117.18 (18)
O26i—Zn1—O490.79 (6)O13—C14—C15106.25 (18)
O3—Zn1—O23ii91.68 (6)O13—C14—H14A110.5
O26i—Zn1—O23ii172.05 (6)C15—C14—H14A110.5
O4—Zn1—O23ii91.70 (6)O13—C14—H14B110.5
O3—Zn1—O27165.64 (6)C15—C14—H14B110.5
O26i—Zn1—O2786.77 (6)H14A—C14—H14B108.7
O4—Zn1—O2789.94 (6)C20—C15—C16119.1 (2)
O23ii—Zn1—O2785.68 (5)C20—C15—C14122.0 (2)
O3—Zn1—O23iii83.70 (5)C16—C15—C14118.82 (19)
O26i—Zn1—O23iii93.44 (6)C15—C16—C17121.2 (2)
O4—Zn1—O23iii170.64 (5)C15—C16—H16119.4
O23ii—Zn1—O23iii83.04 (6)C17—C16—H16119.4
O27—Zn1—O23iii81.97 (5)C18—C17—C16119.2 (2)
O25iv—Zn2—O3133.57 (6)C18—C17—C24122.16 (19)
O25iv—Zn2—O5119.49 (6)C16—C17—C24118.51 (19)
O3—Zn2—O5106.93 (6)C17—C18—C19120.1 (2)
O25iv—Zn2—O22ii83.93 (6)C17—C18—H18120.0
O3—Zn2—O22ii93.68 (6)C19—C18—H18120.0
O5—Zn2—O22ii92.08 (6)C20—C19—C18119.69 (19)
O25iv—Zn2—O3v99.25 (6)C20—C19—C21121.3 (2)
O3—Zn2—O3v83.29 (6)C18—C19—C21118.98 (19)
O5—Zn2—O3v87.37 (6)C15—C20—C19120.7 (2)
O22ii—Zn2—O3v176.62 (6)C15—C20—H20119.6
O25iv—Zn2—Zn2v124.13 (4)C19—C20—H20119.6
O3—Zn2—Zn2v42.73 (4)O22—C21—O23126.05 (19)
O5—Zn2—Zn2v99.17 (4)O22—C21—C19115.5 (2)
O22ii—Zn2—Zn2v136.39 (4)O23—C21—C19118.38 (19)
O3v—Zn2—Zn2v40.56 (4)C21—O22—Zn2ii135.66 (15)
Zn2—O3—Zn1106.91 (6)C21—O23—Zn1ii118.31 (13)
Zn2—O3—Zn2v96.71 (6)C21—O23—Zn1vi132.63 (14)
Zn1—O3—Zn2v122.98 (7)Zn1ii—O23—Zn1vi96.96 (6)
Zn2—O3—H3116.3O26—C24—O25125.9 (2)
Zn1—O3—H3105.1O26—C24—C17116.45 (19)
Zn2v—O3—H3109.4O25—C24—C17117.60 (18)
C6—O4—Zn1133.76 (14)C24—O25—Zn2vii131.08 (14)
C6—O5—Zn2123.28 (14)C24—O26—Zn1i134.98 (14)
O4—C6—O5125.9 (2)C28—O27—Zn1122.72 (15)
O4—C6—C7117.43 (19)O27—C28—N29124.7 (2)
O5—C6—C7116.7 (2)O27—C28—H28117.7
C8—C7—C12119.7 (2)N29—C28—H28117.7
C8—C7—C6121.9 (2)C28—N29—C30120.6 (2)
C12—C7—C6118.3 (2)C28—N29—C31122.1 (2)
C7—C8—C9119.3 (2)C30—N29—C31117.3 (2)
C7—C8—H8120.4N29—C30—H30A109.5
C9—C8—H8120.4N29—C30—H30B109.5
C10—C9—C8120.9 (2)H30A—C30—H30B109.5
C10—C9—H9119.6N29—C30—H30C109.5
C8—C9—H9119.6H30A—C30—H30C109.5
C9—C10—C11119.7 (2)H30B—C30—H30C109.5
C9—C10—H10120.2N29—C31—H31A109.5
C11—C10—H10120.2N29—C31—H31B109.5
O13—C11—C12114.6 (2)H31A—C31—H31B109.5
O13—C11—C10125.6 (2)N29—C31—H31C109.5
C12—C11—C10119.9 (2)H31A—C31—H31C109.5
C11—C12—C7120.6 (2)H31B—C31—H31C109.5
C11—C12—H12119.7
Zn1—O4—C6—O512.6 (3)C24—C17—C18—C19176.0 (2)
Zn1—O4—C6—C7167.98 (14)C17—C18—C19—C200.5 (3)
Zn2—O5—C6—O418.6 (3)C17—C18—C19—C21179.0 (2)
Zn2—O5—C6—C7160.84 (14)C16—C15—C20—C190.5 (3)
O4—C6—C7—C8170.0 (2)C14—C15—C20—C19175.7 (2)
O5—C6—C7—C810.6 (3)C18—C19—C20—C150.1 (3)
O4—C6—C7—C1212.3 (3)C21—C19—C20—C15179.4 (2)
O5—C6—C7—C12167.2 (2)C20—C19—C21—O22157.3 (2)
C12—C7—C8—C90.5 (3)C18—C19—C21—O2222.2 (3)
C6—C7—C8—C9178.2 (2)C20—C19—C21—O2320.6 (3)
C7—C8—C9—C100.8 (4)C18—C19—C21—O23159.9 (2)
C8—C9—C10—C110.3 (4)O23—C21—O22—Zn2ii6.7 (4)
C9—C10—C11—O13179.9 (2)C19—C21—O22—Zn2ii171.11 (15)
C9—C10—C11—C120.4 (4)O22—C21—O23—Zn1ii33.8 (3)
O13—C11—C12—C7179.6 (2)C19—C21—O23—Zn1ii143.94 (16)
C10—C11—C12—C70.7 (3)O22—C21—O23—Zn1vi99.3 (3)
C8—C7—C12—C110.2 (3)C19—C21—O23—Zn1vi83.0 (2)
C6—C7—C12—C11177.6 (2)C18—C17—C24—O26170.7 (2)
C12—C11—O13—C14172.3 (2)C16—C17—C24—O2613.5 (3)
C10—C11—O13—C148.0 (3)C18—C17—C24—O259.6 (3)
C11—O13—C14—C15176.94 (19)C16—C17—C24—O25166.2 (2)
O13—C14—C15—C20116.2 (2)O26—C24—O25—Zn2vii13.4 (3)
O13—C14—C15—C1667.5 (3)C17—C24—O25—Zn2vii166.27 (14)
C20—C15—C16—C170.8 (3)O25—C24—O26—Zn1i43.2 (3)
C14—C15—C16—C17175.5 (2)C17—C24—O26—Zn1i136.49 (18)
C15—C16—C17—C180.4 (3)Zn1—O27—C28—N29164.38 (17)
C15—C16—C17—C24175.5 (2)O27—C28—N29—C301.8 (3)
C16—C17—C18—C190.3 (3)O27—C28—N29—C31176.2 (2)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iii) x, y1, z1; (iv) x+1, y, z1; (v) x+1, y+1, z; (vi) x, y+1, z+1; (vii) x1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O27viii0.932.072.924 (2)152
Symmetry code: (viii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Zn2(C16H9O7)(OH)(C3H7NO)]
Mr534.12
Crystal system, space groupTriclinic, P1
Temperature (K)110
a, b, c (Å)7.7417 (2), 10.8543 (3), 12.5527 (3)
α, β, γ (°)109.463 (1), 90.615 (1), 101.884 (1)
V3)969.61 (4)
Z2
Radiation typeMo Kα
µ (mm1)2.53
Crystal size (mm)0.30 × 0.25 × 0.15
Data collection
DiffractometerBruker APEX DUO area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.518, 0.703
No. of measured, independent and
observed [I > 2σ(I)] reflections
8513, 4319, 3474
Rint0.040
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.057, 0.92
No. of reflections4319
No. of parameters282
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.52, 0.51

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS2012 (Sheldrick, 2008), SHELXL2012 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2008).

Selected bond lengths (Å) top
Zn1—O32.0178 (13)Zn2—O31.9990 (14)
Zn1—O26i2.0218 (15)Zn2—O52.0133 (15)
Zn1—O42.0643 (15)Zn2—O22ii2.0765 (14)
Zn1—O23ii2.0982 (14)Zn2—O3v2.0861 (13)
Zn1—O272.1346 (14)Zn2—Zn2v3.0531 (5)
Zn1—O23iii2.3542 (15)Zn2—Zn13.2272 (3)
Zn2—O25iv1.9821 (15)O3—Zn2v2.0861 (13)
Symmetry codes: (i) x, y+1, z+1; (ii) x, y+2, z+1; (iii) x, y1, z1; (iv) x+1, y, z1; (v) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O27vi0.932.072.924 (2)152
Symmetry code: (vi) x, y+1, z.
 

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