Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017204/sk3498sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017204/sk3498Isup2.hkl |
CCDC reference: 958841
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.
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, γC═C), 1360 (m, γC═O symmetric), 1265 (s, γC—O), 1044 (w), 1024 (s), 907 (w), 776 (s), 721 (w), 594 (m), 437 (w).
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.
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).
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.
For related literature, see: Cui et al. (2012); Karmakar & Goldberg (2011); Patra et al. (2013a, 2013b, 2013c); Wang et al. (2008).
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).
[Zn2(C16H9O7)(OH)(C3H7NO)] | Z = 2 |
Mr = 534.12 | F(000) = 540 |
Triclinic, P1 | Dx = 1.826 Mg m−3 |
a = 7.7417 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.8543 (3) Å | Cell parameters from 4319 reflections |
c = 12.5527 (3) Å | θ = 2.0–27.5° |
α = 109.463 (1)° | µ = 2.53 mm−1 |
β = 90.615 (1)° | T = 110 K |
γ = 101.884 (1)° | Plate, colourless |
V = 969.61 (4) Å3 | 0.30 × 0.25 × 0.15 mm |
Bruker APEX DUO area-detector diffractometer | 4319 independent reflections |
Radiation source: Imu Mo micro-source sealed-tube | 3474 reflections with I > 2σ(I) |
Detector resolution: 1.75 pixels mm-1 | Rint = 0.040 |
1° ω and ϕ scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→7 |
Tmin = 0.518, Tmax = 0.703 | k = −13→14 |
8513 measured reflections | l = −15→16 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H-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 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
[Zn2(C16H9O7)(OH)(C3H7NO)] | γ = 101.884 (1)° |
Mr = 534.12 | V = 969.61 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7417 (2) Å | Mo Kα radiation |
b = 10.8543 (3) Å | µ = 2.53 mm−1 |
c = 12.5527 (3) Å | T = 110 K |
α = 109.463 (1)° | 0.30 × 0.25 × 0.15 mm |
β = 90.615 (1)° |
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 = 0.703 | Rint = 0.040 |
8513 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.057 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.52 e Å−3 |
4319 reflections | Δρmin = −0.51 e Å−3 |
282 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.14134 (3) | 0.49867 (2) | 0.10074 (2) | 0.01016 (7) | |
Zn2 | 0.50942 (3) | 0.65047 (2) | 0.03857 (2) | 0.00921 (7) | |
O3 | 0.32138 (18) | 0.48139 (14) | −0.01538 (12) | 0.0090 (3) | |
H3 | 0.2569 | 0.4639 | −0.0842 | 0.011* | |
O4 | 0.2794 (2) | 0.63903 (15) | 0.24711 (13) | 0.0154 (3) | |
O5 | 0.55968 (19) | 0.69616 (15) | 0.20663 (12) | 0.0143 (3) | |
C6 | 0.4393 (3) | 0.6962 (2) | 0.27420 (18) | 0.0124 (5) | |
C7 | 0.4942 (3) | 0.7731 (2) | 0.39765 (19) | 0.0144 (5) | |
C8 | 0.6711 (3) | 0.8227 (2) | 0.43883 (19) | 0.0188 (5) | |
H8 | 0.7621 | 0.8064 | 0.3892 | 0.023* | |
C9 | 0.7139 (3) | 0.8967 (2) | 0.5541 (2) | 0.0220 (6) | |
H9 | 0.8347 | 0.9298 | 0.5828 | 0.026* | |
C10 | 0.5823 (3) | 0.9224 (2) | 0.6269 (2) | 0.0197 (5) | |
H10 | 0.6129 | 0.9733 | 0.7050 | 0.024* | |
C11 | 0.4056 (3) | 0.8736 (2) | 0.5853 (2) | 0.0172 (5) | |
C12 | 0.3619 (3) | 0.7988 (2) | 0.47147 (19) | 0.0163 (5) | |
H12 | 0.2409 | 0.7646 | 0.4434 | 0.020* | |
O13 | 0.2625 (2) | 0.89205 (17) | 0.64821 (13) | 0.0237 (4) | |
C14 | 0.2982 (3) | 0.9825 (2) | 0.76311 (18) | 0.0158 (5) | |
H14A | 0.3633 | 1.0722 | 0.7656 | 0.019* | |
H14B | 0.3705 | 0.9488 | 0.8080 | 0.019* | |
C15 | 0.1203 (3) | 0.9900 (2) | 0.80975 (18) | 0.0137 (5) | |
C16 | 0.0182 (3) | 0.8770 (2) | 0.82545 (18) | 0.0149 (5) | |
H16 | 0.0579 | 0.7956 | 0.8017 | 0.018* | |
C17 | −0.1416 (3) | 0.8809 (2) | 0.87551 (18) | 0.0124 (5) | |
C18 | −0.1999 (3) | 1.0002 (2) | 0.90958 (18) | 0.0135 (5) | |
H18 | −0.3082 | 1.0042 | 0.9441 | 0.016* | |
C19 | −0.0991 (3) | 1.1143 (2) | 0.89307 (18) | 0.0124 (5) | |
C20 | 0.0603 (3) | 1.1081 (2) | 0.84335 (18) | 0.0145 (5) | |
H20 | 0.1287 | 1.1856 | 0.8323 | 0.017* | |
C21 | −0.1670 (3) | 1.2417 (2) | 0.92897 (19) | 0.0144 (5) | |
O22 | −0.32929 (19) | 1.22689 (15) | 0.93683 (14) | 0.0173 (4) | |
O23 | −0.05636 (19) | 1.35294 (14) | 0.94505 (13) | 0.0126 (3) | |
C24 | −0.2387 (3) | 0.7582 (2) | 0.89795 (18) | 0.0110 (5) | |
O25 | −0.36216 (19) | 0.77105 (14) | 0.96256 (13) | 0.0141 (3) | |
O26 | −0.1881 (2) | 0.65203 (15) | 0.85050 (13) | 0.0161 (4) | |
O27 | −0.09392 (19) | 0.48666 (15) | 0.18739 (13) | 0.0147 (3) | |
C28 | −0.0911 (3) | 0.5199 (2) | 0.2922 (2) | 0.0176 (5) | |
H28 | 0.0165 | 0.5723 | 0.3356 | 0.021* | |
N29 | −0.2275 (3) | 0.4876 (2) | 0.34796 (16) | 0.0195 (4) | |
C30 | −0.3948 (3) | 0.4044 (3) | 0.2870 (2) | 0.0303 (6) | |
H30A | −0.4802 | 0.4607 | 0.2904 | 0.045* | |
H30B | −0.4410 | 0.3372 | 0.3219 | 0.045* | |
H30C | −0.3761 | 0.3593 | 0.2077 | 0.045* | |
C31 | −0.2192 (4) | 0.5367 (3) | 0.4717 (2) | 0.0301 (6) | |
H31A | −0.0998 | 0.5898 | 0.5026 | 0.045* | |
H31B | −0.2466 | 0.4604 | 0.4987 | 0.045* | |
H31C | −0.3055 | 0.5927 | 0.4969 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.00891 (13) | 0.00997 (13) | 0.01403 (14) | 0.00351 (10) | 0.00547 (10) | 0.00629 (10) |
Zn2 | 0.00794 (13) | 0.00748 (13) | 0.01274 (14) | 0.00159 (10) | 0.00386 (10) | 0.00415 (10) |
O3 | 0.0071 (7) | 0.0095 (7) | 0.0099 (8) | 0.0015 (6) | 0.0009 (6) | 0.0028 (6) |
O4 | 0.0139 (8) | 0.0147 (8) | 0.0139 (8) | −0.0004 (7) | 0.0055 (7) | 0.0021 (7) |
O5 | 0.0131 (8) | 0.0172 (8) | 0.0111 (8) | 0.0027 (7) | 0.0045 (7) | 0.0032 (6) |
C6 | 0.0164 (12) | 0.0095 (11) | 0.0135 (12) | 0.0046 (9) | 0.0054 (10) | 0.0056 (9) |
C7 | 0.0179 (12) | 0.0125 (11) | 0.0142 (12) | 0.0041 (9) | 0.0026 (10) | 0.0059 (9) |
C8 | 0.0179 (13) | 0.0223 (13) | 0.0176 (13) | 0.0082 (11) | 0.0056 (10) | 0.0066 (10) |
C9 | 0.0148 (13) | 0.0279 (14) | 0.0232 (14) | 0.0056 (11) | 0.0000 (10) | 0.0084 (11) |
C10 | 0.0207 (13) | 0.0222 (13) | 0.0152 (13) | 0.0038 (11) | 0.0010 (10) | 0.0056 (10) |
C11 | 0.0188 (12) | 0.0163 (12) | 0.0185 (13) | 0.0059 (10) | 0.0079 (10) | 0.0074 (10) |
C12 | 0.0177 (12) | 0.0138 (12) | 0.0150 (12) | 0.0004 (10) | 0.0034 (10) | 0.0036 (9) |
O13 | 0.0192 (9) | 0.0280 (10) | 0.0155 (9) | 0.0018 (8) | 0.0075 (7) | −0.0016 (7) |
C14 | 0.0175 (12) | 0.0158 (12) | 0.0107 (11) | 0.0011 (10) | 0.0040 (10) | 0.0015 (9) |
C15 | 0.0122 (11) | 0.0150 (12) | 0.0113 (11) | 0.0027 (9) | 0.0021 (9) | 0.0012 (9) |
C16 | 0.0171 (12) | 0.0125 (11) | 0.0143 (12) | 0.0034 (9) | 0.0012 (10) | 0.0036 (9) |
C17 | 0.0123 (11) | 0.0129 (11) | 0.0118 (11) | −0.0002 (9) | −0.0008 (9) | 0.0056 (9) |
C18 | 0.0113 (11) | 0.0151 (12) | 0.0154 (12) | 0.0030 (9) | 0.0009 (9) | 0.0071 (9) |
C19 | 0.0120 (11) | 0.0121 (11) | 0.0139 (12) | 0.0031 (9) | −0.0002 (9) | 0.0051 (9) |
C20 | 0.0174 (12) | 0.0147 (12) | 0.0127 (12) | 0.0019 (9) | 0.0014 (9) | 0.0075 (9) |
C21 | 0.0139 (12) | 0.0171 (12) | 0.0162 (12) | 0.0053 (10) | 0.0042 (10) | 0.0098 (10) |
O22 | 0.0089 (8) | 0.0118 (8) | 0.0351 (10) | 0.0039 (6) | 0.0081 (7) | 0.0119 (7) |
O23 | 0.0092 (8) | 0.0097 (8) | 0.0220 (9) | 0.0017 (6) | 0.0039 (7) | 0.0095 (7) |
C24 | 0.0082 (11) | 0.0143 (11) | 0.0115 (11) | 0.0010 (9) | −0.0016 (9) | 0.0067 (9) |
O25 | 0.0125 (8) | 0.0138 (8) | 0.0205 (9) | 0.0047 (7) | 0.0076 (7) | 0.0105 (7) |
O26 | 0.0223 (9) | 0.0137 (8) | 0.0173 (8) | 0.0096 (7) | 0.0076 (7) | 0.0084 (7) |
O27 | 0.0125 (8) | 0.0191 (9) | 0.0152 (9) | 0.0053 (7) | 0.0046 (7) | 0.0084 (7) |
C28 | 0.0147 (12) | 0.0176 (12) | 0.0228 (14) | 0.0040 (10) | 0.0024 (10) | 0.0097 (10) |
N29 | 0.0154 (11) | 0.0270 (12) | 0.0199 (11) | 0.0041 (9) | 0.0061 (9) | 0.0132 (9) |
C30 | 0.0154 (13) | 0.0428 (17) | 0.0380 (17) | 0.0007 (12) | 0.0051 (12) | 0.0240 (14) |
C31 | 0.0338 (16) | 0.0413 (17) | 0.0211 (14) | 0.0109 (14) | 0.0116 (12) | 0.0164 (12) |
Zn1—O3 | 2.0178 (13) | C14—H14B | 0.9900 |
Zn1—O26i | 2.0218 (15) | C15—C20 | 1.388 (3) |
Zn1—O4 | 2.0643 (15) | C15—C16 | 1.390 (3) |
Zn1—O23ii | 2.0982 (14) | C16—C17 | 1.395 (3) |
Zn1—O27 | 2.1346 (14) | C16—H16 | 0.9500 |
Zn1—O23iii | 2.3542 (15) | C17—C18 | 1.393 (3) |
Zn2—O25iv | 1.9821 (15) | C17—C24 | 1.504 (3) |
Zn2—O3 | 1.9990 (14) | C18—C19 | 1.401 (3) |
Zn2—O5 | 2.0133 (15) | C18—H18 | 0.9500 |
Zn2—O22ii | 2.0765 (14) | C19—C20 | 1.393 (3) |
Zn2—O3v | 2.0861 (13) | C19—C21 | 1.510 (3) |
Zn2—Zn2v | 3.0531 (5) | C20—H20 | 0.9500 |
Zn2—Zn1 | 3.2272 (3) | C21—O22 | 1.242 (3) |
O3—Zn2v | 2.0861 (13) | C21—O23 | 1.281 (3) |
O3—H3 | 0.9347 | O22—Zn2ii | 2.0765 (14) |
O4—C6 | 1.252 (3) | O23—Zn1ii | 2.0982 (14) |
O5—C6 | 1.266 (2) | O23—Zn1vi | 2.3542 (15) |
C6—C7 | 1.502 (3) | C24—O26 | 1.253 (2) |
C7—C8 | 1.389 (3) | C24—O25 | 1.260 (2) |
C7—C12 | 1.397 (3) | O25—Zn2vii | 1.9821 (15) |
C8—C9 | 1.398 (3) | O26—Zn1i | 2.0218 (15) |
C8—H8 | 0.9500 | O27—C28 | 1.242 (3) |
C9—C10 | 1.385 (3) | C28—N29 | 1.324 (3) |
C9—H9 | 0.9500 | C28—H28 | 0.9500 |
C10—C11 | 1.389 (3) | N29—C30 | 1.455 (3) |
C10—H10 | 0.9500 | N29—C31 | 1.461 (3) |
C11—O13 | 1.377 (3) | C30—H30A | 0.9800 |
C11—C12 | 1.385 (3) | C30—H30B | 0.9800 |
C12—H12 | 0.9500 | C30—H30C | 0.9800 |
O13—C14 | 1.434 (3) | C31—H31A | 0.9800 |
C14—C15 | 1.510 (3) | C31—H31B | 0.9800 |
C14—H14A | 0.9900 | C31—H31C | 0.9800 |
O3—Zn1—O26i | 95.02 (6) | C7—C12—H12 | 119.7 |
O3—Zn1—O4 | 104.27 (6) | C11—O13—C14 | 117.18 (18) |
O26i—Zn1—O4 | 90.79 (6) | O13—C14—C15 | 106.25 (18) |
O3—Zn1—O23ii | 91.68 (6) | O13—C14—H14A | 110.5 |
O26i—Zn1—O23ii | 172.05 (6) | C15—C14—H14A | 110.5 |
O4—Zn1—O23ii | 91.70 (6) | O13—C14—H14B | 110.5 |
O3—Zn1—O27 | 165.64 (6) | C15—C14—H14B | 110.5 |
O26i—Zn1—O27 | 86.77 (6) | H14A—C14—H14B | 108.7 |
O4—Zn1—O27 | 89.94 (6) | C20—C15—C16 | 119.1 (2) |
O23ii—Zn1—O27 | 85.68 (5) | C20—C15—C14 | 122.0 (2) |
O3—Zn1—O23iii | 83.70 (5) | C16—C15—C14 | 118.82 (19) |
O26i—Zn1—O23iii | 93.44 (6) | C15—C16—C17 | 121.2 (2) |
O4—Zn1—O23iii | 170.64 (5) | C15—C16—H16 | 119.4 |
O23ii—Zn1—O23iii | 83.04 (6) | C17—C16—H16 | 119.4 |
O27—Zn1—O23iii | 81.97 (5) | C18—C17—C16 | 119.2 (2) |
O25iv—Zn2—O3 | 133.57 (6) | C18—C17—C24 | 122.16 (19) |
O25iv—Zn2—O5 | 119.49 (6) | C16—C17—C24 | 118.51 (19) |
O3—Zn2—O5 | 106.93 (6) | C17—C18—C19 | 120.1 (2) |
O25iv—Zn2—O22ii | 83.93 (6) | C17—C18—H18 | 120.0 |
O3—Zn2—O22ii | 93.68 (6) | C19—C18—H18 | 120.0 |
O5—Zn2—O22ii | 92.08 (6) | C20—C19—C18 | 119.69 (19) |
O25iv—Zn2—O3v | 99.25 (6) | C20—C19—C21 | 121.3 (2) |
O3—Zn2—O3v | 83.29 (6) | C18—C19—C21 | 118.98 (19) |
O5—Zn2—O3v | 87.37 (6) | C15—C20—C19 | 120.7 (2) |
O22ii—Zn2—O3v | 176.62 (6) | C15—C20—H20 | 119.6 |
O25iv—Zn2—Zn2v | 124.13 (4) | C19—C20—H20 | 119.6 |
O3—Zn2—Zn2v | 42.73 (4) | O22—C21—O23 | 126.05 (19) |
O5—Zn2—Zn2v | 99.17 (4) | O22—C21—C19 | 115.5 (2) |
O22ii—Zn2—Zn2v | 136.39 (4) | O23—C21—C19 | 118.38 (19) |
O3v—Zn2—Zn2v | 40.56 (4) | C21—O22—Zn2ii | 135.66 (15) |
Zn2—O3—Zn1 | 106.91 (6) | C21—O23—Zn1ii | 118.31 (13) |
Zn2—O3—Zn2v | 96.71 (6) | C21—O23—Zn1vi | 132.63 (14) |
Zn1—O3—Zn2v | 122.98 (7) | Zn1ii—O23—Zn1vi | 96.96 (6) |
Zn2—O3—H3 | 116.3 | O26—C24—O25 | 125.9 (2) |
Zn1—O3—H3 | 105.1 | O26—C24—C17 | 116.45 (19) |
Zn2v—O3—H3 | 109.4 | O25—C24—C17 | 117.60 (18) |
C6—O4—Zn1 | 133.76 (14) | C24—O25—Zn2vii | 131.08 (14) |
C6—O5—Zn2 | 123.28 (14) | C24—O26—Zn1i | 134.98 (14) |
O4—C6—O5 | 125.9 (2) | C28—O27—Zn1 | 122.72 (15) |
O4—C6—C7 | 117.43 (19) | O27—C28—N29 | 124.7 (2) |
O5—C6—C7 | 116.7 (2) | O27—C28—H28 | 117.7 |
C8—C7—C12 | 119.7 (2) | N29—C28—H28 | 117.7 |
C8—C7—C6 | 121.9 (2) | C28—N29—C30 | 120.6 (2) |
C12—C7—C6 | 118.3 (2) | C28—N29—C31 | 122.1 (2) |
C7—C8—C9 | 119.3 (2) | C30—N29—C31 | 117.3 (2) |
C7—C8—H8 | 120.4 | N29—C30—H30A | 109.5 |
C9—C8—H8 | 120.4 | N29—C30—H30B | 109.5 |
C10—C9—C8 | 120.9 (2) | H30A—C30—H30B | 109.5 |
C10—C9—H9 | 119.6 | N29—C30—H30C | 109.5 |
C8—C9—H9 | 119.6 | H30A—C30—H30C | 109.5 |
C9—C10—C11 | 119.7 (2) | H30B—C30—H30C | 109.5 |
C9—C10—H10 | 120.2 | N29—C31—H31A | 109.5 |
C11—C10—H10 | 120.2 | N29—C31—H31B | 109.5 |
O13—C11—C12 | 114.6 (2) | H31A—C31—H31B | 109.5 |
O13—C11—C10 | 125.6 (2) | N29—C31—H31C | 109.5 |
C12—C11—C10 | 119.9 (2) | H31A—C31—H31C | 109.5 |
C11—C12—C7 | 120.6 (2) | H31B—C31—H31C | 109.5 |
C11—C12—H12 | 119.7 | ||
Zn1—O4—C6—O5 | 12.6 (3) | C24—C17—C18—C19 | 176.0 (2) |
Zn1—O4—C6—C7 | −167.98 (14) | C17—C18—C19—C20 | −0.5 (3) |
Zn2—O5—C6—O4 | 18.6 (3) | C17—C18—C19—C21 | 179.0 (2) |
Zn2—O5—C6—C7 | −160.84 (14) | C16—C15—C20—C19 | 0.5 (3) |
O4—C6—C7—C8 | 170.0 (2) | C14—C15—C20—C19 | −175.7 (2) |
O5—C6—C7—C8 | −10.6 (3) | C18—C19—C20—C15 | 0.1 (3) |
O4—C6—C7—C12 | −12.3 (3) | C21—C19—C20—C15 | −179.4 (2) |
O5—C6—C7—C12 | 167.2 (2) | C20—C19—C21—O22 | 157.3 (2) |
C12—C7—C8—C9 | 0.5 (3) | C18—C19—C21—O22 | −22.2 (3) |
C6—C7—C8—C9 | 178.2 (2) | C20—C19—C21—O23 | −20.6 (3) |
C7—C8—C9—C10 | −0.8 (4) | C18—C19—C21—O23 | 159.9 (2) |
C8—C9—C10—C11 | 0.3 (4) | O23—C21—O22—Zn2ii | 6.7 (4) |
C9—C10—C11—O13 | −179.9 (2) | C19—C21—O22—Zn2ii | −171.11 (15) |
C9—C10—C11—C12 | 0.4 (4) | O22—C21—O23—Zn1ii | −33.8 (3) |
O13—C11—C12—C7 | 179.6 (2) | C19—C21—O23—Zn1ii | 143.94 (16) |
C10—C11—C12—C7 | −0.7 (3) | O22—C21—O23—Zn1vi | 99.3 (3) |
C8—C7—C12—C11 | 0.2 (3) | C19—C21—O23—Zn1vi | −83.0 (2) |
C6—C7—C12—C11 | −177.6 (2) | C18—C17—C24—O26 | 170.7 (2) |
C12—C11—O13—C14 | −172.3 (2) | C16—C17—C24—O26 | −13.5 (3) |
C10—C11—O13—C14 | 8.0 (3) | C18—C17—C24—O25 | −9.6 (3) |
C11—O13—C14—C15 | 176.94 (19) | C16—C17—C24—O25 | 166.2 (2) |
O13—C14—C15—C20 | −116.2 (2) | O26—C24—O25—Zn2vii | 13.4 (3) |
O13—C14—C15—C16 | 67.5 (3) | C17—C24—O25—Zn2vii | −166.27 (14) |
C20—C15—C16—C17 | −0.8 (3) | O25—C24—O26—Zn1i | −43.2 (3) |
C14—C15—C16—C17 | 175.5 (2) | C17—C24—O26—Zn1i | 136.49 (18) |
C15—C16—C17—C18 | 0.4 (3) | Zn1—O27—C28—N29 | −164.38 (17) |
C15—C16—C17—C24 | −175.5 (2) | O27—C28—N29—C30 | 1.8 (3) |
C16—C17—C18—C19 | 0.3 (3) | O27—C28—N29—C31 | −176.2 (2) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y−1, z−1; (iv) x+1, y, z−1; (v) −x+1, −y+1, −z; (vi) x, y+1, z+1; (vii) x−1, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O27viii | 0.93 | 2.07 | 2.924 (2) | 152 |
Symmetry code: (viii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C16H9O7)(OH)(C3H7NO)] |
Mr | 534.12 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 969.61 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.53 |
Crystal size (mm) | 0.30 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Bruker APEX DUO area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.518, 0.703 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8513, 4319, 3474 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.057, 0.92 |
No. of reflections | 4319 |
No. of parameters | 282 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
Zn1—O3 | 2.0178 (13) | Zn2—O3 | 1.9990 (14) |
Zn1—O26i | 2.0218 (15) | Zn2—O5 | 2.0133 (15) |
Zn1—O4 | 2.0643 (15) | Zn2—O22ii | 2.0765 (14) |
Zn1—O23ii | 2.0982 (14) | Zn2—O3v | 2.0861 (13) |
Zn1—O27 | 2.1346 (14) | Zn2—Zn2v | 3.0531 (5) |
Zn1—O23iii | 2.3542 (15) | Zn2—Zn1 | 3.2272 (3) |
Zn2—O25iv | 1.9821 (15) | O3—Zn2v | 2.0861 (13) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1; (iii) x, y−1, z−1; (iv) x+1, y, z−1; (v) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O27vi | 0.93 | 2.07 | 2.924 (2) | 152 |
Symmetry code: (vi) −x, −y+1, −z. |
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