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)]

Sim, J.; Kim, T.; Yang, J.K.

doi:10.1107/S1600536813028687

metal-organic compounds

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doi:10.1107/S1600536813028687

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Poly[(μ₆-benzene-1,3,5-tricarboxylato-κ⁶O¹:O^1′:O³:O^3′:O⁵:O^5′)tris(N,N-dimethylformamide-κO)tris(μ₃-formato-κ³O:O:O′)trizinc(II)]

Jaeung Sim,^a Taemin Kim ^a and Jin Kuk Yang ^a ^*

^aDepartment of Chemistry, Soongsil University, 369 Sangdo-Ro, Dongjak-Gu, Seoul 156-743, Republic of Korea
^*Correspondence e-mail: jinkukyang@ssu.ac.kr

(Received 20 September 2013; accepted 18 October 2013; online 26 October 2013)

The asymmetric unit of the title compound, [Zn₃(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 Zn^II 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 Zn^II 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.

CCDC 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 Ni^II and Mg^II were reported by Maniam & Stock (2011 ) and Yeh et al. (2010 ), respectively.

Experimental

Crystal data

[Zn₃(HCO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]
M_r = 757.56
Trigonal, $[P \overline 3]$
a = 13.8594 (17) Å
c = 8.0100 (14) Å
V = 1332.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 2.76 mm⁻¹
T = 153 K
0.10 × 0.02 × 0.02 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.770, T_max = 0.947
7964 measured reflections
2027 independent reflections
1563 reflections with I > 2σ(I)
R_int = 0.153

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.089
S = 0.81
2027 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.79 e Å⁻³

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: CrystalMaker (CrystalMaker, 2013 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 967215

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813028687/cv5429sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028687/cv5429Isup2.hkl

checkCIF report

Comment top

Solvothermal reactions between Zn^II 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 Zn^II 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 Ni^II (Maniam & Stock, 2011) and Mg^II (Yeh et al., 2010). The crystal packing of (I) is shown in Figs. 2 & 3.

Experimental top

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.

Refinement top

Hydrogen atoms were placed at calculated positions (C—H = 0.95–0.98 Å) and refined as riding, with U_iso(H) = 1.2–1.5 U_eq(C).

Related literature top

For general background to compounds with metal-organic framework structures, see: Eddaoudi et al. (2000).The crystal structures of isotypic compounds with Ni^II and Mg^II were reported by Maniam & Stock (2011) and Yeh et al. (2010), respectively.

Computing details top

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

Figures top

	Fig. 1. A content of the asymmetric unit of (I) showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are represented with empty balls without labels.
	Fig. 2. A portion of the packing diagram of (I) viewed along the c aixs.
	Fig. 3. A portion of the packing diagram of (I) viewed along the a aixs.

Poly[(µ₆-benzene-1,3,5-tricarboxylato-κ⁶O¹:O^1':O³:O^3':O⁵:O^5')tris(N,N-dimethylformamide-κO)tris(µ₃-formato-κ³O:O:O')trizinc(II)] top

Crystal data top

[Zn₃(HCO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]	D_x = 1.888 Mg m⁻³
M_r = 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

Data collection top

Bruker SMART APEX CCD diffractometer	2027 independent reflections
Radiation source: fine-focus sealed tube	1563 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.153
phi and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
T_min = 0.770, T_max = 0.947	k = −11→18
7964 measured reflections	l = −9→10

Refinement top

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(F_o²) + (0.0317P)² + 0.1686P] where P = (F_o² + 2F_c²)/3
S = 0.81	(Δ/σ)_max < 0.001
2027 reflections	Δρ_max = 0.72 e Å⁻³
127 parameters	Δρ_min = −0.79 e Å⁻³

Crystal data top

[Zn₃(HCO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]	Z = 2
M_r = 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

Data collection top

Bruker SMART APEX CCD diffractometer	2027 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1563 reflections with I > 2σ(I)
T_min = 0.770, T_max = 0.947	R_int = 0.153
7964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 0.81	Δρ_max = 0.72 e Å⁻³
2027 reflections	Δρ_min = −0.79 e Å⁻³
127 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Zn1—O1ⁱ	2.028 (2)	C2—C3	1.394 (4)
Zn1—O2	2.031 (2)	C3—C2^iv	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)	C2^iv—C3—C2	120.1 (3)
O2—Zn1—O4ⁱⁱ	93.23 (9)	C2^iv—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—C2^iv	1.0 (6)
Zn1ⁱⁱ—O1—C1—C2	−139.5 (2)	C1—C2—C3—C2^iv	−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]
M_r	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)
T_min, T_max	0.770, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	7964, 2027, 1563
R_int	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
Δρ_max, Δρ_min (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).

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
CrystalMaker (2013). CrystalMaker. CrystalMaker Software Ltd, Yarnton, Oxfordshire, England. Google Scholar
Eddaoudi, M., Li, H. & Yaghi, O. M. (2000). J. Am. Chem. Soc. 122, 1391–1397. Web of Science CrossRef CAS Google Scholar
Maniam, P. & Stock, N. (2011). Inorg. Chem. 50, 5085–5097. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yeh, C.-T., Liu, H.-K., Lin, C.-J. & Lin, C.-H. (2010). Acta Cryst. E66, m1289. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page m619

doi:10.1107/S1600536813028687

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