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metal-organic compounds
Poly[(μ6-benzene-1,3,5-tricarboxylato-κ6O1:O1′:O3:O3′:O5:O5′)tris(N,N-dimethylformamide-κO)tris(μ3-formato-κ3O:O:O′)trizinc(II)]
aDepartment of Chemistry, Soongsil University, 369 Sangdo-Ro, Dongjak-Gu, Seoul 156-743, Republic of Korea
*Correspondence e-mail: jinkukyang@ssu.ac.kr
The 3(HCO2)3(C9H3O6)(C3H7NO)3]n, contains one Zn ion, one formate ligand, one N,N-dimethylformamide (DMF) ligand and one-third of a benzene-1,3,5-tricarboxylate (btc) ligand situated on a crystallographic 3 axis. Each ZnII atom is coordinated by one O atom from a DMF ligand, two O atoms from two btc ligands and three O atoms from three formate ligands in a distorted octahedral geometry. The ZnII atoms are connected by the formate and btc ligands, forming hexanuclear cores, which are linked by btc ligands, constructing a two-dimensional layered network along the ab plane.
of the title compound, [ZnCCDC reference: 967215
Related literature
For general background to compounds with metal-organic frameworks, see: Eddaoudi et al. (2000)·The crystal structures of isotypic compounds with NiII and MgII were reported by Maniam & Stock (2011
) and Yeh et al. (2010
), respectively.
Experimental
Crystal data
|
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: CrystalMaker (CrystalMaker, 2013
); software used to prepare material for publication: publCIF (Westrip, 2010
).
Supporting information
CCDC reference: 967215
10.1107/S1600536813028687/cv5429sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813028687/cv5429Isup2.hkl
Solvothermal reactions between ZnII ion and simple organic ligands such as benzene-1,4-dicarboxylic acid (H2BDC) and benzene-1,3,5-tricarboxylic acid (H3BTC) produce prototype metal-organic frameworks known as MOF-2, MOF-3, MOF-4, and MOF-5 (Eddaoudi et al., 2000). Among them, MOF-4 formulated as [Zn2(BTC)(NO3)](C2H5OH)5(H2O) has dinuclear zinc clusters that are held by three carboxylate groups from three distinct BTC ligands. In our trials to make a metal-organic framework composed of ZnII paddle-wheel clusters and BTC, the title compound was obtained as single crystals. During a solvothermal reaction, decomposition of N,N-dimethylformamide produced formate which became a component of the title compound.
The title compound, (I) (Fig. 1), is isostructural to the related compounds with NiII (Maniam & Stock, 2011) and MgII (Yeh et al., 2010). The crystal packing of (I) is shown in Figs. 2 & 3.
The title compound was obtained by a solvothermal reaction between zinc(II) nitrate tetrahydrate (0.157 g, 0.60 mmol) and benzene-1,3,5-tricarboxylic acid (0.084 g, 0.40 mmol) in N,N-dimethylformamide (2.0 ml). When a sealed glass tube containing the reaction mixture was heated at 130 °C and for 24 h, the title compound was produced as colorless hexagonal columnar crystals.
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: CrystalMaker (CrystalMaker, 2013); software used to prepare material for publication: publCIF (Westrip, 2010).[Zn3(HCO2)3(C9H3O6)(C3H7NO)3] | Dx = 1.888 Mg m−3 |
Mr = 757.56 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P3 | Cell parameters from 2269 reflections |
Hall symbol: -P 3 | θ = 2.4–28.2° |
a = 13.8594 (17) Å | µ = 2.76 mm−1 |
c = 8.0100 (14) Å | T = 153 K |
V = 1332.5 (4) Å3 | Column, colorless |
Z = 2 | 0.10 × 0.02 × 0.02 mm |
F(000) = 768 |
Bruker SMART APEX CCD diffractometer | 2027 independent reflections |
Radiation source: fine-focus sealed tube | 1563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.153 |
phi and ω scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −17→17 |
Tmin = 0.770, Tmax = 0.947 | k = −11→18 |
7964 measured reflections | l = −9→10 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.089 | w = 1/[σ2(Fo2) + (0.0317P)2 + 0.1686P] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max < 0.001 |
2027 reflections | Δρmax = 0.72 e Å−3 |
127 parameters | Δρmin = −0.79 e Å−3 |
[Zn3(HCO2)3(C9H3O6)(C3H7NO)3] | Z = 2 |
Mr = 757.56 | Mo Kα radiation |
Trigonal, P3 | µ = 2.76 mm−1 |
a = 13.8594 (17) Å | T = 153 K |
c = 8.0100 (14) Å | 0.10 × 0.02 × 0.02 mm |
V = 1332.5 (4) Å3 |
Bruker SMART APEX CCD diffractometer | 2027 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1563 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 0.947 | Rint = 0.153 |
7964 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.81 | Δρmax = 0.72 e Å−3 |
2027 reflections | Δρmin = −0.79 e Å−3 |
127 parameters |
Geometry. 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 > 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 | ||
Zn1 | 0.01272 (3) | 0.23313 (3) | 0.39911 (5) | 0.01217 (12) | |
O1 | −0.25265 (17) | 0.12229 (17) | 0.4805 (3) | 0.0160 (5) | |
O2 | −0.10070 (17) | 0.28429 (17) | 0.4230 (3) | 0.0149 (5) | |
O3 | −0.05005 (17) | 0.13366 (17) | 0.6162 (3) | 0.0140 (5) | |
O4 | 0.10436 (18) | 0.19215 (19) | 0.7680 (3) | 0.0162 (5) | |
C1 | −0.2019 (3) | 0.2249 (2) | 0.4582 (4) | 0.0115 (6) | |
C2 | −0.2697 (3) | 0.2816 (2) | 0.4691 (4) | 0.0113 (6) | |
C3 | −0.3856 (3) | 0.2180 (3) | 0.4700 (3) | 0.0130 (7) | |
H3 | −0.4213 | 0.1390 | 0.4712 | 0.016* | |
C4 | 0.0026 (3) | 0.1477 (3) | 0.7513 (4) | 0.0140 (7) | |
H4 | −0.0408 | 0.1214 | 0.8502 | 0.017* | |
O5 | 0.07684 (19) | 0.32946 (18) | 0.1759 (3) | 0.0198 (5) | |
N1 | 0.0391 (2) | 0.3985 (2) | −0.0540 (3) | 0.0204 (6) | |
C5 | 0.0119 (3) | 0.3253 (3) | 0.0664 (4) | 0.0203 (8) | |
H5 | −0.0626 | 0.2651 | 0.0699 | 0.024* | |
C6 | 0.1529 (3) | 0.4921 (3) | −0.0652 (5) | 0.0286 (9) | |
H6A | 0.1890 | 0.5051 | 0.0442 | 0.043* | |
H6B | 0.1514 | 0.5590 | −0.1003 | 0.043* | |
H6C | 0.1948 | 0.4749 | −0.1470 | 0.043* | |
C7 | −0.0372 (3) | 0.3837 (3) | −0.1897 (4) | 0.0294 (9) | |
H7A | −0.1092 | 0.3163 | −0.1697 | 0.044* | |
H7B | −0.0061 | 0.3762 | −0.2956 | 0.044* | |
H7C | −0.0477 | 0.4485 | −0.1951 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0082 (2) | 0.0087 (2) | 0.0197 (2) | 0.00431 (16) | 0.00015 (15) | 0.00033 (15) |
O1 | 0.0128 (12) | 0.0101 (11) | 0.0253 (13) | 0.0060 (10) | −0.0020 (10) | 0.0021 (10) |
O2 | 0.0088 (11) | 0.0097 (11) | 0.0276 (12) | 0.0056 (9) | 0.0017 (10) | −0.0001 (10) |
O3 | 0.0093 (11) | 0.0117 (11) | 0.0179 (11) | 0.0029 (9) | −0.0024 (9) | 0.0013 (9) |
O4 | 0.0109 (12) | 0.0182 (12) | 0.0194 (12) | 0.0072 (10) | −0.0014 (10) | −0.0016 (10) |
C1 | 0.0109 (16) | 0.0078 (15) | 0.0143 (16) | 0.0036 (13) | −0.0041 (13) | −0.0021 (13) |
C2 | 0.0106 (15) | 0.0107 (15) | 0.0129 (15) | 0.0056 (13) | −0.0010 (13) | 0.0011 (13) |
C3 | 0.0135 (16) | 0.0102 (16) | 0.0144 (16) | 0.0053 (13) | 0.0001 (13) | 0.0008 (13) |
C4 | 0.0128 (16) | 0.0087 (15) | 0.0205 (17) | 0.0053 (14) | 0.0010 (14) | −0.0004 (13) |
O5 | 0.0162 (12) | 0.0180 (12) | 0.0221 (13) | 0.0063 (11) | 0.0026 (10) | 0.0074 (10) |
N1 | 0.0216 (16) | 0.0224 (16) | 0.0208 (15) | 0.0137 (14) | −0.0002 (13) | 0.0020 (13) |
C5 | 0.0178 (18) | 0.0160 (18) | 0.027 (2) | 0.0084 (15) | 0.0040 (16) | 0.0004 (15) |
C6 | 0.029 (2) | 0.028 (2) | 0.028 (2) | 0.0127 (18) | 0.0057 (17) | 0.0075 (17) |
C7 | 0.036 (2) | 0.038 (2) | 0.0217 (19) | 0.025 (2) | −0.0024 (18) | −0.0004 (17) |
Zn1—O1i | 2.028 (2) | C2—C3 | 1.394 (4) |
Zn1—O2 | 2.031 (2) | C3—C2iv | 1.380 (4) |
Zn1—O4ii | 2.105 (2) | C3—H3 | 0.9500 |
Zn1—O3i | 2.108 (2) | C4—H4 | 0.9500 |
Zn1—O3 | 2.117 (2) | O5—C5 | 1.237 (4) |
Zn1—O5 | 2.140 (2) | N1—C5 | 1.311 (4) |
O1—C1 | 1.245 (3) | N1—C7 | 1.458 (4) |
O1—Zn1ii | 2.028 (2) | N1—C6 | 1.460 (5) |
O2—C1 | 1.253 (4) | C5—H5 | 0.9500 |
O3—C4 | 1.265 (4) | C6—H6A | 0.9800 |
O3—Zn1ii | 2.108 (2) | C6—H6B | 0.9800 |
O4—C4 | 1.232 (4) | C6—H6C | 0.9800 |
O4—Zn1i | 2.105 (2) | C7—H7A | 0.9800 |
C1—C2 | 1.499 (4) | C7—H7B | 0.9800 |
C2—C3iii | 1.380 (4) | C7—H7C | 0.9800 |
O1i—Zn1—O2 | 87.25 (9) | C3—C2—C1 | 119.7 (3) |
O1i—Zn1—O4ii | 168.88 (9) | C2iv—C3—C2 | 120.1 (3) |
O2—Zn1—O4ii | 93.23 (9) | C2iv—C3—H3 | 120.0 |
O1i—Zn1—O3i | 90.61 (8) | C2—C3—H3 | 120.0 |
O2—Zn1—O3i | 177.54 (9) | O4—C4—O3 | 126.7 (3) |
O4ii—Zn1—O3i | 89.09 (8) | O4—C4—H4 | 116.6 |
O1i—Zn1—O3 | 96.06 (9) | O3—C4—H4 | 116.6 |
O2—Zn1—O3 | 90.70 (8) | C5—O5—Zn1 | 119.8 (2) |
O4ii—Zn1—O3 | 95.05 (8) | C5—N1—C7 | 122.1 (3) |
O3i—Zn1—O3 | 88.32 (10) | C5—N1—C6 | 119.8 (3) |
O1i—Zn1—O5 | 85.20 (9) | C7—N1—C6 | 117.7 (3) |
O2—Zn1—O5 | 90.77 (9) | O5—C5—N1 | 124.4 (3) |
O4ii—Zn1—O5 | 83.68 (8) | O5—C5—H5 | 117.8 |
O3i—Zn1—O5 | 90.26 (9) | N1—C5—H5 | 117.8 |
O3—Zn1—O5 | 178.11 (9) | N1—C6—H6A | 109.5 |
C1—O1—Zn1ii | 135.5 (2) | N1—C6—H6B | 109.5 |
C1—O2—Zn1 | 126.83 (19) | H6A—C6—H6B | 109.5 |
C4—O3—Zn1ii | 120.2 (2) | N1—C6—H6C | 109.5 |
C4—O3—Zn1 | 125.8 (2) | H6A—C6—H6C | 109.5 |
Zn1ii—O3—Zn1 | 113.73 (10) | H6B—C6—H6C | 109.5 |
C4—O4—Zn1i | 132.5 (2) | N1—C7—H7A | 109.5 |
O1—C1—O2 | 126.2 (3) | N1—C7—H7B | 109.5 |
O1—C1—C2 | 116.5 (3) | H7A—C7—H7B | 109.5 |
O2—C1—C2 | 117.3 (3) | N1—C7—H7C | 109.5 |
C3iii—C2—C3 | 119.9 (3) | H7A—C7—H7C | 109.5 |
C3iii—C2—C1 | 120.3 (3) | H7B—C7—H7C | 109.5 |
Zn1ii—O1—C1—O2 | 42.6 (5) | C3iii—C2—C3—C2iv | 1.0 (6) |
Zn1ii—O1—C1—C2 | −139.5 (2) | C1—C2—C3—C2iv | −175.8 (2) |
Zn1—O2—C1—O1 | −2.2 (5) | Zn1i—O4—C4—O3 | −21.4 (5) |
Zn1—O2—C1—C2 | 179.99 (19) | Zn1ii—O3—C4—O4 | 159.8 (3) |
O1—C1—C2—C3iii | 170.7 (3) | Zn1—O3—C4—O4 | −26.7 (4) |
O2—C1—C2—C3iii | −11.3 (4) | Zn1—O5—C5—N1 | 163.2 (2) |
O1—C1—C2—C3 | −12.5 (4) | C7—N1—C5—O5 | 173.5 (3) |
O2—C1—C2—C3 | 165.5 (3) | C6—N1—C5—O5 | 0.5 (5) |
Symmetry codes: (i) y, −x+y, −z+1; (ii) x−y, x, −z+1; (iii) −y, x−y+1, z; (iv) −x+y−1, −x, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn3(HCO2)3(C9H3O6)(C3H7NO)3] |
Mr | 757.56 |
Crystal system, space group | Trigonal, P3 |
Temperature (K) | 153 |
a, c (Å) | 13.8594 (17), 8.0100 (14) |
V (Å3) | 1332.5 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.76 |
Crystal size (mm) | 0.10 × 0.02 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.770, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7964, 2027, 1563 |
Rint | 0.153 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.089, 0.81 |
No. of reflections | 2027 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.79 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (CrystalMaker, 2013), publCIF (Westrip, 2010).
Acknowledgements
This research was supported by the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Knowledge Economy (No. 20122010100120).
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