Poly[(μ₆-benzene-1,3,5-tricarboxyl­ato-κ⁶ O ¹:O ^1′:O ³:O ^3′:O ⁵:O ^5′)tris­(N,N-dimethyl­formamide-κO)tris­(μ₃-formato-κ² O:O′)trimagnesium(II)]

Abstract

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,

• a = 13.9739 (2) Å

• c = 8.1188 (1) Å

• V = 1372.96 (3) ų

• 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[F ² > 2σ(F ²)] = 0.078

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

H atoms were constrained to ideal geometries, with C—H = 0.93 (CH) and 0.96 (CH₃) Å and U_iso(H) = 1.2(1.5 for methyl)U_eq(C).

Figures

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.

Crystal data

[Mg3(CHO2)3(C9H3O6)(C3H7NO)3]	Dx = 1.535 Mg m−3
Mr = 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

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

Refinement

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(Fo2) + (0.0309P)2 + 6.185P] where P = (Fo2 + 2Fc2)/3
2278 reflections	(Δ/σ)max < 0.001
129 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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—O3v	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—C2iv	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—C2iv	120.8 (4)
O4ii—Mg1—O1S	84.69 (14)	C2—C3—H3	119.6
O1—Mg1—O2	89.14 (13)	C2iv—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)	O3v—C1—O1	125.8 (4)
O3—Mg1—O2i	89.05 (13)	O3v—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—Mg1v	65.14 (11)	H2S1—C2S—H2S2	109.5
O3—Mg1—Mg1v	145.14 (13)	N1S—C2S—H2S3	109.5
O4ii—Mg1—Mg1v	116.15 (10)	H2S1—C2S—H2S3	109.5
O1S—Mg1—Mg1v	109.51 (11)	H2S2—C2S—H2S3	109.5
O2—Mg1—Mg1v	32.48 (8)	N1S—C3S—H3S1	109.5
O2i—Mg1—Mg1v	72.03 (9)	N1S—C3S—H3S2	109.5
Mg1i—Mg1—Mg1v	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—Mg1v	124.4 (3)	H3S2—C3S—H3S3	109.5
Mg1—O2—Mg1v	115.10 (14)	C4—O4—Mg1vi	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.