Poly[(μ6-benzene-1,3,5-tricarboxyl­ato-κ6O1:O1′:O3:O3′:O5:O5′)tris­(N,N-dimethyl­formamide-κO)tris­(μ3-formato-κ2O:O′)trimagnesium(II)]

Yeh, C.-T.; Liu, H.-K.; Lin, C.-J.; Lin, C.-H.

doi:10.1107/S1600536810035907

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1289

doi:10.1107/S1600536810035907

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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-κ²O:O′)trimagnesium(II)]

Chun-Ting Yeh,^a Hsin-Kuan Liu,^a Chia-Jing Lin ^a and Chia-Her Lin ^a ^*

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
^*Correspondence e-mail: chiaher@cycu.edu.tw

(Received 21 August 2010; accepted 7 September 2010; online 25 September 2010)

The title complex, [Mg₃(CHO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]_n, exhibits a two-dimensional structure parallel to (001), which is built up from the Mg^II atoms and bridging carboxylate ligands (3 symmetry). The Mg^II atom is six-coordinated by one O atom from a dimethylformamide molecule, two O atoms from two μ₆-benzene-1,3,5-tricarboxylate ligands and three O atoms from three μ₃-formate ligands in a distorted octahedral geometry.

Related literature

For general background to the synthesis and structures of coordination polymers, see: Kitagawa et al. (2004 ); Liu et al. (2009 ). For an isotypic structure, see: He et al. (2006 ).

Experimental

Crystal data

[Mg₃(CHO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]
M_r = 211.46
Trigonal, $[P \overline 3]$
a = 13.9739 (2) Å
c = 8.1188 (1) Å
V = 1372.96 (3) Å³
Z = 6
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 295 K
0.25 × 0.25 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.954, T_max = 0.972
12089 measured reflections
2278 independent reflections
2212 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.214
S = 1.40
2278 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected bond lengths (Å)

Mg1—O1	2.008 (3)
Mg1—O2	2.132 (3)
Mg1—O2ⁱ	2.135 (3)
Mg1—O3	2.047 (3)
Mg1—O4ⁱⁱ	2.080 (3)
Mg1—O1S	2.115 (4)
Symmetry codes: (i) x-y, x-1, -z+1; (ii) -y+1, x-y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035907/hy2348sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035907/hy2348Isup2.hkl

checkCIF report

Comment top

The synthesis of coordination polymers, or so-called metal-organic frameworks (MOFs), has been a subject of intense research owing to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, luminescence. A large number of these materials have been synthesized by solvothermal reactions with organic carboxyl acids (Kitagawa et al., 2004; Liu et al., 2009). They commonly adopt three-, two- or one-dimensional structures via employed metal ions as connectors and rigid or flexible organic ligands as linkers. As a further study of such complexes, we report the title compound (Fig. 1), which is isotypic with [Co₆(C₉H₃O₆)₂(CHO₂)₆(C₃H₇NO)₆]_n (He et al., 2006) and has a two-dimensional polymeric network (Fig. 2). All the geometric parameters are within normal ranges (Table 1). The Mg^II atom is six-coordinated by one O atoms from an N,N-dimethylformamide molecule and five O atoms from the carboxylate ligands, giving a distorted octahedral geometry.

Related literature top

For general background to the synthesis and structures of coordination polymers, see: Kitagawa et al. (2004); Liu et al. (2009). For an isotypic structure, see: He et al. (2006).

Experimental top

Solvothermal reactions were carried out at 423 K for 2 d in a Teflon-lined acid digestion bomb with an internal volume of 23 ml followed by slow cooling at 6 K h^-1 to room temperature. A single-phase product consisting of transparent colorless crystals was obtained from a mixture of Mg(NO₃)₂.6H₂O (0.051 g, 0.2 mmol), benzene-1,3,5-tricarboxylic acid (0.021 g, 0.1 mmol) and formic acid (0.5 ml, 0.4 M) and N,N-dimethylformamide (5.0 ml).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the polymeric structure of the title compound, showing 50% probability displacement ellipsoids. [Symmetry codes: (i) x-y, -1+x, 1-z; (ii) 1-y, -1+x-y, z; (iii) 1-x+y, 1-x, z; (iv) 1-x, -y, 1-z; (v) 1-y, x-y, z; (vi) x-y, x, 1-z; (vii) 1+y, 1-x+y, 1-z.]
	Fig. 2. Crystal packing diagram of the title compound along the a axis.

Poly[(µ₆-benzene-1,3,5-tricarboxylato-κ⁶O¹:O^1': O³:O^3':O⁵:O^5')tris(N,N- dimethylformamide-κO)tris(µ₃-formato-κ²O:O') trimagnesium(II)] top

Crystal data top

[Mg₃(CHO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]	D_x = 1.535 Mg m⁻³
M_r = 211.46	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 9292 reflections
Hall symbol: -P 3	θ = 2.9–28.3°
a = 13.9739 (2) Å	µ = 0.19 mm⁻¹
c = 8.1188 (1) Å	T = 295 K
V = 1372.96 (3) Å³	Columnar, colorless
Z = 6	0.25 × 0.25 × 0.15 mm
F(000) = 660

Data collection top

Bruker APEXII CCD diffractometer	2278 independent reflections
Radiation source: fine-focus sealed tube	2212 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.3°, θ_min = 1.7°
ϕ and ω scans	h = −18→17
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −17→18
T_min = 0.954, T_max = 0.972	l = −10→10
12089 measured reflections

Refinement top

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H-atom parameters constrained
S = 1.40	w = 1/[σ²(F_o²) + (0.0309P)² + 6.185P] where P = (F_o² + 2F_c²)/3
2278 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Mg₃(CHO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]	Z = 6
M_r = 211.46	Mo Kα radiation
Trigonal, P3	µ = 0.19 mm⁻¹
a = 13.9739 (2) Å	T = 295 K
c = 8.1188 (1) Å	0.25 × 0.25 × 0.15 mm
V = 1372.96 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2278 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2212 reflections with I > 2σ(I)
T_min = 0.954, T_max = 0.972	R_int = 0.032
12089 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	0 restraints
wR(F²) = 0.214	H-atom parameters constrained
S = 1.40	Δρ_max = 0.47 e Å⁻³
2278 reflections	Δρ_min = −0.35 e Å⁻³
129 parameters

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

	x	y	z	U_iso*/U_eq
Mg1	0.77826 (11)	0.01439 (11)	0.39889 (18)	0.0184 (3)
O1	0.7487 (3)	0.1240 (2)	0.5146 (4)	0.0261 (7)
O2	0.9488 (2)	0.1369 (2)	0.3855 (4)	0.0220 (6)
O3	0.6145 (2)	−0.1017 (2)	0.4220 (4)	0.0256 (7)
O1S	0.7459 (3)	0.0733 (3)	0.1779 (4)	0.0327 (8)
C2	0.7301 (3)	0.2815 (3)	0.5313 (5)	0.0181 (8)
C3	0.6154 (3)	0.2191 (3)	0.5310 (5)	0.0188 (8)
H3	0.5809	0.1423	0.5307	0.023*
C4	1.0034 (3)	0.1485 (3)	0.2561 (5)	0.0223 (8)
H4A	0.9631	0.1231	0.1590	0.027*
C1	0.7986 (3)	0.2259 (3)	0.5408 (5)	0.0190 (8)
N1S	0.6441 (4)	0.0408 (4)	−0.0535 (5)	0.0363 (10)
C1S	0.6876 (4)	0.0111 (4)	0.0655 (6)	0.0328 (10)
H1S	0.6738	−0.0612	0.0656	0.039*
C2S	0.5833 (5)	−0.0326 (6)	−0.1892 (7)	0.0506 (16)
H2S1	0.5853	−0.1000	−0.1790	0.076*
H2S2	0.6165	0.0025	−0.2918	0.076*
H2S3	0.5079	−0.0488	−0.1864	0.076*
C3S	0.6642 (6)	0.1535 (6)	−0.0614 (8)	0.0498 (15)
H3S1	0.6850	0.1869	0.0456	0.075*
H3S2	0.5982	0.1525	−0.0968	0.075*
H3S3	0.7227	0.1954	−0.1383	0.075*
O4	1.1048 (3)	0.1900 (3)	0.2443 (4)	0.0261 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mg1	0.0125 (6)	0.0126 (6)	0.0301 (7)	0.0064 (5)	0.0002 (5)	0.0000 (5)
O1	0.0203 (14)	0.0149 (14)	0.0459 (19)	0.0108 (12)	0.0012 (13)	−0.0037 (13)
O2	0.0148 (13)	0.0184 (14)	0.0301 (16)	0.0063 (11)	0.0005 (11)	−0.0004 (11)
O3	0.0123 (13)	0.0136 (13)	0.0477 (19)	0.0041 (11)	0.0005 (12)	0.0017 (13)
O1S	0.0328 (18)	0.0305 (17)	0.0361 (18)	0.0169 (15)	−0.0057 (14)	0.0031 (14)
C2	0.0127 (17)	0.0148 (17)	0.029 (2)	0.0085 (14)	−0.0008 (14)	−0.0002 (14)
C3	0.0139 (17)	0.0114 (16)	0.030 (2)	0.0056 (14)	−0.0003 (14)	−0.0002 (14)
C4	0.0185 (19)	0.0194 (19)	0.027 (2)	0.0081 (16)	−0.0016 (15)	0.0009 (15)
C1	0.0179 (18)	0.0160 (17)	0.027 (2)	0.0112 (15)	0.0021 (15)	−0.0001 (15)
N1S	0.033 (2)	0.044 (3)	0.032 (2)	0.019 (2)	−0.0002 (17)	0.0045 (19)
C1S	0.028 (2)	0.033 (2)	0.039 (3)	0.016 (2)	0.003 (2)	0.006 (2)
C2S	0.039 (3)	0.067 (4)	0.034 (3)	0.018 (3)	−0.001 (2)	−0.001 (3)
C3S	0.064 (4)	0.054 (4)	0.044 (3)	0.039 (3)	−0.005 (3)	0.010 (3)
O4	0.0182 (14)	0.0281 (16)	0.0316 (17)	0.0112 (13)	0.0011 (12)	0.0005 (13)

Geometric parameters (Å, º) top

Mg1—O1	2.008 (3)	C3—H3	0.9300
Mg1—O2	2.132 (3)	C4—O4	1.238 (5)
Mg1—O2ⁱ	2.135 (3)	C4—H4A	0.9300
Mg1—O3	2.047 (3)	C1—O3^v	1.248 (5)
Mg1—O4ⁱⁱ	2.080 (3)	N1S—C1S	1.314 (6)
Mg1—O1S	2.115 (4)	N1S—C3S	1.456 (8)
O1—C1	1.251 (5)	N1S—C2S	1.455 (7)
O2—C4	1.260 (5)	C1S—H1S	0.9300
O3—C1ⁱ	1.248 (5)	C2S—H2S1	0.9600
O1S—C1S	1.243 (6)	C2S—H2S2	0.9600
C2—C3	1.390 (5)	C2S—H2S3	0.9600
C2—C3ⁱⁱⁱ	1.392 (5)	C3S—H3S1	0.9600
C2—C1	1.507 (5)	C3S—H3S2	0.9600
C3—C2^iv	1.392 (5)	C3S—H3S3	0.9600

O1—Mg1—O3	89.26 (13)	C1S—O1S—Mg1	122.9 (3)
O1—Mg1—O4ⁱⁱ	170.66 (15)	C3—C2—C3ⁱⁱⁱ	119.2 (4)
O3—Mg1—O4ⁱⁱ	93.03 (14)	C3—C2—C1	120.4 (4)
O1—Mg1—O1S	86.23 (15)	C3ⁱⁱⁱ—C2—C1	120.3 (3)
O3—Mg1—O1S	90.84 (15)	C2—C3—C2^iv	120.8 (4)
O4ⁱⁱ—Mg1—O1S	84.69 (14)	C2—C3—H3	119.6
O1—Mg1—O2	89.14 (13)	C2^iv—C3—H3	119.6
O3—Mg1—O2	177.59 (15)	O4—C4—O2	127.0 (4)
O4ⁱⁱ—Mg1—O2	88.83 (13)	O4—C4—H4A	116.5
O1S—Mg1—O2	90.85 (14)	O2—C4—H4A	116.5
O1—Mg1—O2ⁱ	96.73 (14)	O3^v—C1—O1	125.8 (4)
O3—Mg1—O2ⁱ	89.05 (13)	O3^v—C1—C2	118.0 (3)
O4ⁱⁱ—Mg1—O2ⁱ	92.36 (13)	O1—C1—C2	116.2 (4)
O1S—Mg1—O2ⁱ	177.04 (15)	C1S—N1S—C3S	120.3 (5)
O2—Mg1—O2ⁱ	89.35 (15)	C1S—N1S—C2S	122.2 (5)
O1—Mg1—Mg1ⁱ	123.18 (13)	C3S—N1S—C2S	117.3 (5)
O3—Mg1—Mg1ⁱ	72.76 (10)	O1S—C1S—N1S	124.4 (5)
O4ⁱⁱ—Mg1—Mg1ⁱ	66.10 (9)	O1S—C1S—H1S	117.8
O1S—Mg1—Mg1ⁱ	144.98 (12)	N1S—C1S—H1S	117.8
O2—Mg1—Mg1ⁱ	106.68 (9)	N1S—C2S—H2S1	109.5
O2ⁱ—Mg1—Mg1ⁱ	32.42 (8)	N1S—C2S—H2S2	109.5
O1—Mg1—Mg1^v	65.14 (11)	H2S1—C2S—H2S2	109.5
O3—Mg1—Mg1^v	145.14 (13)	N1S—C2S—H2S3	109.5
O4ⁱⁱ—Mg1—Mg1^v	116.15 (10)	H2S1—C2S—H2S3	109.5
O1S—Mg1—Mg1^v	109.51 (11)	H2S2—C2S—H2S3	109.5
O2—Mg1—Mg1^v	32.48 (8)	N1S—C3S—H3S1	109.5
O2ⁱ—Mg1—Mg1^v	72.03 (9)	N1S—C3S—H3S2	109.5
Mg1ⁱ—Mg1—Mg1^v	100.84 (5)	H3S1—C3S—H3S2	109.5
C1—O1—Mg1	137.5 (3)	N1S—C3S—H3S3	109.5
C4—O2—Mg1	120.5 (3)	H3S1—C3S—H3S3	109.5
C4—O2—Mg1^v	124.4 (3)	H3S2—C3S—H3S3	109.5
Mg1—O2—Mg1^v	115.10 (14)	C4—O4—Mg1^vi	137.3 (3)
C1ⁱ—O3—Mg1	128.3 (3)

Symmetry codes: (i) x−y, x−1, −z+1; (ii) −y+1, x−y−1, z; (iii) −y+1, x−y, z; (iv) −x+y+1, −x+1, z; (v) y+1, −x+y+1, −z+1; (vi) −x+y+2, −x+1, z.

Experimental details

Crystal data
Chemical formula	[Mg₃(CHO₂)₃(C₉H₃O₆)(C₃H₇NO)₃]
M_r	211.46
Crystal system, space group	Trigonal, P3
Temperature (K)	295
a, c (Å)	13.9739 (2), 8.1188 (1)
V (Å³)	1372.96 (3)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.25 × 0.25 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.954, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	12089, 2278, 2212
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.078, 0.214, 1.40
No. of reflections	2278
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.35

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Mg1—O1	2.008 (3)	Mg1—O3	2.047 (3)
Mg1—O2	2.132 (3)	Mg1—O4ⁱⁱ	2.080 (3)
Mg1—O2ⁱ	2.135 (3)	Mg1—O1S	2.115 (4)

Symmetry codes: (i) x−y, x−1, −z+1; (ii) −y+1, x−y−1, z.

Acknowledgements

This research was supported by National Science Council, Taiwan (NSC99–2113-M-033–005-MY2).

References

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