metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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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)]

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 MgII atoms and bridging carboxyl­ate ligands (3 symmetry). The MgII 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[Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334-2375.]); Liu et al. (2009[Liu, H. K., Tsao, T. H., Zhang, Y. T. & Lin, C. H. (2009). CrystEngComm, 11, 1462-1468.]). For an isotypic structure, see: He et al. (2006[He, J., Zhang, Y., Pan, Q., Yu, J., Ding, H. & Xu, R. (2006). Micropor. Mesopor. Mater. 90, 145-152.]).

[Scheme 1]

Experimental

Crystal data
  • [Mg3(CHO2)3(C9H3O6)(C3H7NO)3]

  • Mr = 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[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.954, Tmax = 0.972

  • 12089 measured reflections

  • 2278 independent reflections

  • 2212 reflections with I > 2σ(I)

  • Rint = 0.032

Refinement
  • R[F2 > 2σ(F2)] = 0.078

  • wR(F2) = 0.214

  • S = 1.40

  • 2278 reflections

  • 129 parameters

  • H-atom parameters constrained

  • Δρmax = 0.47 e Å−3

  • Δρmin = −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[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information


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 MgII 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).

Refinement top

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

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
[Figure 1] 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.]
[Figure 2] Fig. 2. Crystal packing diagram of the title compound along the a axis.
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)] top
Crystal data top
[Mg3(CHO2)3(C9H3O6)(C3H7NO)3]Dx = 1.535 Mg m3
Mr = 211.46Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3Cell parameters from 9292 reflections
Hall symbol: -P 3θ = 2.9–28.3°
a = 13.9739 (2) ŵ = 0.19 mm1
c = 8.1188 (1) ÅT = 295 K
V = 1372.96 (3) Å3Columnar, colorless
Z = 60.25 × 0.25 × 0.15 mm
F(000) = 660
Data collection top
Bruker APEXII CCD
diffractometer
2278 independent reflections
Radiation source: fine-focus sealed tube2212 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 8.3333 pixels mm-1θmax = 28.3°, θmin = 1.7°
ϕ and ω scansh = 1817
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
k = 1718
Tmin = 0.954, Tmax = 0.972l = 1010
12089 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.078Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.214H-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 parametersΔρmax = 0.47 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Mg3(CHO2)3(C9H3O6)(C3H7NO)3]Z = 6
Mr = 211.46Mo Kα radiation
Trigonal, P3µ = 0.19 mm1
a = 13.9739 (2) ÅT = 295 K
c = 8.1188 (1) Å0.25 × 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)
Tmin = 0.954, Tmax = 0.972Rint = 0.032
12089 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0780 restraints
wR(F2) = 0.214H-atom parameters constrained
S = 1.40Δρmax = 0.47 e Å3
2278 reflectionsΔρmin = 0.35 e Å3
129 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mg10.77826 (11)0.01439 (11)0.39889 (18)0.0184 (3)
O10.7487 (3)0.1240 (2)0.5146 (4)0.0261 (7)
O20.9488 (2)0.1369 (2)0.3855 (4)0.0220 (6)
O30.6145 (2)0.1017 (2)0.4220 (4)0.0256 (7)
O1S0.7459 (3)0.0733 (3)0.1779 (4)0.0327 (8)
C20.7301 (3)0.2815 (3)0.5313 (5)0.0181 (8)
C30.6154 (3)0.2191 (3)0.5310 (5)0.0188 (8)
H30.58090.14230.53070.023*
C41.0034 (3)0.1485 (3)0.2561 (5)0.0223 (8)
H4A0.96310.12310.15900.027*
C10.7986 (3)0.2259 (3)0.5408 (5)0.0190 (8)
N1S0.6441 (4)0.0408 (4)0.0535 (5)0.0363 (10)
C1S0.6876 (4)0.0111 (4)0.0655 (6)0.0328 (10)
H1S0.67380.06120.06560.039*
C2S0.5833 (5)0.0326 (6)0.1892 (7)0.0506 (16)
H2S10.58530.10000.17900.076*
H2S20.61650.00250.29180.076*
H2S30.50790.04880.18640.076*
C3S0.6642 (6)0.1535 (6)0.0614 (8)0.0498 (15)
H3S10.68500.18690.04560.075*
H3S20.59820.15250.09680.075*
H3S30.72270.19540.13830.075*
O41.1048 (3)0.1900 (3)0.2443 (4)0.0261 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mg10.0125 (6)0.0126 (6)0.0301 (7)0.0064 (5)0.0002 (5)0.0000 (5)
O10.0203 (14)0.0149 (14)0.0459 (19)0.0108 (12)0.0012 (13)0.0037 (13)
O20.0148 (13)0.0184 (14)0.0301 (16)0.0063 (11)0.0005 (11)0.0004 (11)
O30.0123 (13)0.0136 (13)0.0477 (19)0.0041 (11)0.0005 (12)0.0017 (13)
O1S0.0328 (18)0.0305 (17)0.0361 (18)0.0169 (15)0.0057 (14)0.0031 (14)
C20.0127 (17)0.0148 (17)0.029 (2)0.0085 (14)0.0008 (14)0.0002 (14)
C30.0139 (17)0.0114 (16)0.030 (2)0.0056 (14)0.0003 (14)0.0002 (14)
C40.0185 (19)0.0194 (19)0.027 (2)0.0081 (16)0.0016 (15)0.0009 (15)
C10.0179 (18)0.0160 (17)0.027 (2)0.0112 (15)0.0021 (15)0.0001 (15)
N1S0.033 (2)0.044 (3)0.032 (2)0.019 (2)0.0002 (17)0.0045 (19)
C1S0.028 (2)0.033 (2)0.039 (3)0.016 (2)0.003 (2)0.006 (2)
C2S0.039 (3)0.067 (4)0.034 (3)0.018 (3)0.001 (2)0.001 (3)
C3S0.064 (4)0.054 (4)0.044 (3)0.039 (3)0.005 (3)0.010 (3)
O40.0182 (14)0.0281 (16)0.0316 (17)0.0112 (13)0.0011 (12)0.0005 (13)
Geometric parameters (Å, º) top
Mg1—O12.008 (3)C3—H30.9300
Mg1—O22.132 (3)C4—O41.238 (5)
Mg1—O2i2.135 (3)C4—H4A0.9300
Mg1—O32.047 (3)C1—O3v1.248 (5)
Mg1—O4ii2.080 (3)N1S—C1S1.314 (6)
Mg1—O1S2.115 (4)N1S—C3S1.456 (8)
O1—C11.251 (5)N1S—C2S1.455 (7)
O2—C41.260 (5)C1S—H1S0.9300
O3—C1i1.248 (5)C2S—H2S10.9600
O1S—C1S1.243 (6)C2S—H2S20.9600
C2—C31.390 (5)C2S—H2S30.9600
C2—C3iii1.392 (5)C3S—H3S10.9600
C2—C11.507 (5)C3S—H3S20.9600
C3—C2iv1.392 (5)C3S—H3S30.9600
O1—Mg1—O389.26 (13)C1S—O1S—Mg1122.9 (3)
O1—Mg1—O4ii170.66 (15)C3—C2—C3iii119.2 (4)
O3—Mg1—O4ii93.03 (14)C3—C2—C1120.4 (4)
O1—Mg1—O1S86.23 (15)C3iii—C2—C1120.3 (3)
O3—Mg1—O1S90.84 (15)C2—C3—C2iv120.8 (4)
O4ii—Mg1—O1S84.69 (14)C2—C3—H3119.6
O1—Mg1—O289.14 (13)C2iv—C3—H3119.6
O3—Mg1—O2177.59 (15)O4—C4—O2127.0 (4)
O4ii—Mg1—O288.83 (13)O4—C4—H4A116.5
O1S—Mg1—O290.85 (14)O2—C4—H4A116.5
O1—Mg1—O2i96.73 (14)O3v—C1—O1125.8 (4)
O3—Mg1—O2i89.05 (13)O3v—C1—C2118.0 (3)
O4ii—Mg1—O2i92.36 (13)O1—C1—C2116.2 (4)
O1S—Mg1—O2i177.04 (15)C1S—N1S—C3S120.3 (5)
O2—Mg1—O2i89.35 (15)C1S—N1S—C2S122.2 (5)
O1—Mg1—Mg1i123.18 (13)C3S—N1S—C2S117.3 (5)
O3—Mg1—Mg1i72.76 (10)O1S—C1S—N1S124.4 (5)
O4ii—Mg1—Mg1i66.10 (9)O1S—C1S—H1S117.8
O1S—Mg1—Mg1i144.98 (12)N1S—C1S—H1S117.8
O2—Mg1—Mg1i106.68 (9)N1S—C2S—H2S1109.5
O2i—Mg1—Mg1i32.42 (8)N1S—C2S—H2S2109.5
O1—Mg1—Mg1v65.14 (11)H2S1—C2S—H2S2109.5
O3—Mg1—Mg1v145.14 (13)N1S—C2S—H2S3109.5
O4ii—Mg1—Mg1v116.15 (10)H2S1—C2S—H2S3109.5
O1S—Mg1—Mg1v109.51 (11)H2S2—C2S—H2S3109.5
O2—Mg1—Mg1v32.48 (8)N1S—C3S—H3S1109.5
O2i—Mg1—Mg1v72.03 (9)N1S—C3S—H3S2109.5
Mg1i—Mg1—Mg1v100.84 (5)H3S1—C3S—H3S2109.5
C1—O1—Mg1137.5 (3)N1S—C3S—H3S3109.5
C4—O2—Mg1120.5 (3)H3S1—C3S—H3S3109.5
C4—O2—Mg1v124.4 (3)H3S2—C3S—H3S3109.5
Mg1—O2—Mg1v115.10 (14)C4—O4—Mg1vi137.3 (3)
C1i—O3—Mg1128.3 (3)
Symmetry codes: (i) xy, x1, z+1; (ii) y+1, xy1, z; (iii) y+1, xy, 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]
Mr211.46
Crystal system, space groupTrigonal, P3
Temperature (K)295
a, c (Å)13.9739 (2), 8.1188 (1)
V3)1372.96 (3)
Z6
Radiation typeMo Kα
µ (mm1)0.19
Crystal size (mm)0.25 × 0.25 × 0.15
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.954, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
12089, 2278, 2212
Rint0.032
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.078, 0.214, 1.40
No. of reflections2278
No. of parameters129
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—O12.008 (3)Mg1—O32.047 (3)
Mg1—O22.132 (3)Mg1—O4ii2.080 (3)
Mg1—O2i2.135 (3)Mg1—O1S2.115 (4)
Symmetry codes: (i) xy, x1, z+1; (ii) y+1, xy1, z.
 

Acknowledgements

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

References

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHe, J., Zhang, Y., Pan, Q., Yu, J., Ding, H. & Xu, R. (2006). Micropor. Mesopor. Mater. 90, 145–152.  Web of Science CSD CrossRef CAS Google Scholar
First citationKitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375.  Web of Science CrossRef CAS Google Scholar
First citationLiu, H. K., Tsao, T. H., Zhang, Y. T. & Lin, C. H. (2009). CrystEngComm, 11, 1462–1468.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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