Acta Cryst. (2009). E65, m237 [ doi:10.1107/S1600536809002864 ]
![[mu]](/logos/entities/mu_rmgif.gif)
4-biphenyl-4,4'-dicarboxylato-magnesium(II)]The solvothermal reaction of magnesium nitrate with biphenyl-4,4'-dicarboxylic acid in N,N-dimethylformamide and water leads to the formation of crystals of the title complex, [Mg(C14H8O4)(H2O)2]n. In the crystal structure, the Mg cations are coordinated by six O atoms from two water molecules and four symmetry-related biphenyl-4,4'-dicarboxylate anions within slightly distorted octahedra. The Mg cations are located on a center of inversion, the biphenyl-4,4'-dicarboxylate anions around a twofold rotation axis and the water molecule in a general position. The Mg cations are linked by the anions into a three-dimensional framework.
The reaction was carried out under solvothermal conditions in a teflon-lined autoclav with an inner volume of 23 ml. A single-phase product consisting of transparent colorless crystals was obtained by heating a mixture of Mg(NO3)2˙6H2O, (0.1281 g, 0.5 mmol), biphenyl-4,4'-dicarboxylic acid (C14H10O4, 0.0290 g, 0.125 mmol), N,N-dimethylformamide (10.0 ml), and H2O (2.0 ml)at 423 K for 2 d followed by slow cooling at 6 K/h to room temperature.
The C—H H atoms were positioned with idealized geometry and were refined isotropic using a riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms at the water molecule were found in difference map and were refined with varying coordinates isotropic.
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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./nc2132fig1thm.gif)
| Fig. 1. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. [symmetry codes: (i) -x + 2,-y + 1,-z; (ii) -x + 3/2,y - 1/2,z; (iii) x + 1/2,-y + 3/2,-z; (iv) -x + 2,y,-z + 1/2.]. |
![[Figure 2]](./nc2132fig2thm.gif)
| Fig. 2. Crystal structure of the title compound with view along the a axis. |
| [Mg(C14H8O4)(H2O)2] | Dx = 1.553 Mg m−3 |
| Mr = 150.27 | Mo Kα radiation, λ = 0.71073 Å |
| Orthorhombic, Pbcn | Cell parameters from 1007 reflections |
| a = 6.5913 (10) Å | θ = 3.1–25.2° |
| b = 7.2900 (9) Å | µ = 0.16 mm−1 |
| c = 26.759 (4) Å | T = 295 K |
| V = 1285.8 (3) Å3 | Lamellar, colorless |
| Z = 8 | 0.15 × 0.10 × 0.05 mm |
| F(000) = 624 |
| Bruker APEXII CCD diffractometer | 1589 independent reflections |
| Radiation source: fine-focus sealed tube | 1048 reflections with I > 2σ(I) |
| graphite | Rint = 0.048 |
| φ and ω scans | θmax = 28.4°, θmin = 1.5° |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −7→8 |
| Tmin = 0.976, Tmax = 0.995 | k = −9→9 |
| 5950 measured reflections | l = −22→35 |
| 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0448P)2 + 0.3401P] where P = (Fo2 + 2Fc2)/3 |
| 1589 reflections | (Δ/σ)max < 0.001 |
| 97 parameters | Δρmax = 0.30 e Å−3 |
| 0 restraints | Δρmin = −0.30 e Å−3 |
| [Mg(C14H8O4)(H2O)2] | V = 1285.8 (3) Å3 |
| Mr = 150.27 | Z = 8 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 6.5913 (10) Å | µ = 0.16 mm−1 |
| b = 7.2900 (9) Å | T = 295 K |
| c = 26.759 (4) Å | 0.15 × 0.10 × 0.05 mm |
| Bruker APEXII CCD diffractometer | 1589 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1048 reflections with I > 2σ(I) |
| Tmin = 0.976, Tmax = 0.995 | Rint = 0.048 |
| 5950 measured reflections | θmax = 28.4° |
| R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
| wR(F2) = 0.106 | Δρmax = 0.30 e Å−3 |
| S = 1.01 | Δρmin = −0.30 e Å−3 |
| 1589 reflections | Absolute structure: ? |
| 97 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > σ(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 | ||
| Mg1 | 1.0000 | 0.5000 | 0.0000 | 0.0159 (2) | |
| C1 | 0.7888 (3) | 0.7850 (2) | 0.06884 (7) | 0.0162 (4) | |
| C2 | 0.8503 (3) | 0.7715 (3) | 0.12262 (7) | 0.0184 (4) | |
| C3 | 0.7124 (3) | 0.8132 (3) | 0.16000 (7) | 0.0245 (5) | |
| H3 | 0.5796 | 0.8440 | 0.1517 | 0.029* | |
| C4 | 0.7715 (4) | 0.8092 (3) | 0.20963 (7) | 0.0259 (5) | |
| H4 | 0.6775 | 0.8380 | 0.2343 | 0.031* | |
| C5 | 0.9691 (3) | 0.7629 (3) | 0.22334 (7) | 0.0211 (5) | |
| C6 | 1.1051 (3) | 0.7183 (3) | 0.18550 (7) | 0.0261 (5) | |
| H6 | 1.2372 | 0.6854 | 0.1938 | 0.031* | |
| C7 | 1.0476 (3) | 0.7220 (3) | 0.13581 (8) | 0.0242 (5) | |
| H7 | 1.1409 | 0.6915 | 0.1111 | 0.029* | |
| O1 | 0.9201 (2) | 0.74253 (17) | 0.03552 (5) | 0.0194 (3) | |
| O1W | 0.7228 (2) | 0.48848 (18) | −0.03619 (5) | 0.0221 (3) | |
| H1WA | 0.6306 | 0.5799 | −0.0412 | 0.080* | |
| H1WB | 0.6335 | 0.4082 | −0.0293 | 0.080* | |
| O2 | 0.6164 (2) | 0.8454 (2) | 0.05857 (5) | 0.0233 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mg1 | 0.0166 (5) | 0.0205 (4) | 0.0107 (4) | 0.0010 (4) | 0.0010 (4) | −0.0006 (4) |
| C1 | 0.0195 (11) | 0.0161 (9) | 0.0129 (9) | 0.0000 (8) | 0.0000 (8) | 0.0002 (7) |
| C2 | 0.0214 (12) | 0.0218 (10) | 0.0121 (9) | 0.0017 (8) | −0.0020 (8) | 0.0004 (8) |
| C3 | 0.0214 (12) | 0.0352 (12) | 0.0171 (10) | 0.0075 (10) | −0.0001 (9) | 0.0004 (9) |
| C4 | 0.0271 (13) | 0.0388 (11) | 0.0116 (9) | 0.0057 (10) | 0.0022 (9) | −0.0003 (9) |
| C5 | 0.0240 (12) | 0.0272 (10) | 0.0120 (10) | 0.0006 (9) | −0.0017 (9) | −0.0002 (8) |
| C6 | 0.0202 (12) | 0.0416 (12) | 0.0166 (10) | 0.0029 (10) | −0.0037 (9) | 0.0012 (9) |
| C7 | 0.0216 (12) | 0.0369 (12) | 0.0141 (10) | 0.0042 (10) | 0.0010 (8) | −0.0005 (9) |
| O1 | 0.0221 (8) | 0.0232 (7) | 0.0129 (7) | 0.0025 (6) | 0.0012 (6) | −0.0015 (6) |
| O1W | 0.0165 (8) | 0.0279 (7) | 0.0221 (7) | 0.0001 (6) | −0.0011 (6) | 0.0012 (6) |
| O2 | 0.0200 (8) | 0.0346 (8) | 0.0152 (7) | 0.0065 (7) | −0.0015 (7) | 0.0041 (6) |
| Mg1—O1Wi | 2.0696 (14) | C3—H3 | 0.9300 |
| Mg1—O1W | 2.0696 (14) | C4—C5 | 1.395 (3) |
| Mg1—O1 | 2.0753 (12) | C4—H4 | 0.9300 |
| Mg1—O1i | 2.0753 (12) | C5—C6 | 1.391 (3) |
| Mg1—O2ii | 2.0774 (13) | C5—C5iv | 1.484 (4) |
| Mg1—O2iii | 2.0774 (13) | C6—C7 | 1.383 (3) |
| C1—O2 | 1.249 (2) | C6—H6 | 0.9300 |
| C1—O1 | 1.281 (2) | C7—H7 | 0.9300 |
| C1—C2 | 1.498 (3) | O1W—H1WA | 0.9119 |
| C2—C3 | 1.385 (3) | O1W—H1WB | 0.8502 |
| C2—C7 | 1.395 (3) | O2—Mg1v | 2.0774 (13) |
| C3—C4 | 1.384 (3) | ||
| O1Wi—Mg1—O1W | 180.00 (10) | C4—C3—C2 | 120.2 (2) |
| O1Wi—Mg1—O1 | 88.58 (5) | C4—C3—H3 | 119.9 |
| O1W—Mg1—O1 | 91.42 (5) | C2—C3—H3 | 119.9 |
| O1Wi—Mg1—O1i | 91.42 (5) | C3—C4—C5 | 121.3 (2) |
| O1W—Mg1—O1i | 88.58 (5) | C3—C4—H4 | 119.3 |
| O1—Mg1—O1i | 180.00 (6) | C5—C4—H4 | 119.3 |
| O1Wi—Mg1—O2ii | 89.72 (5) | C6—C5—C4 | 117.84 (18) |
| O1W—Mg1—O2ii | 90.28 (5) | C6—C5—C5iv | 121.5 (2) |
| O1—Mg1—O2ii | 91.31 (5) | C4—C5—C5iv | 120.6 (2) |
| O1i—Mg1—O2ii | 88.69 (5) | C7—C6—C5 | 121.3 (2) |
| O1Wi—Mg1—O2iii | 90.28 (5) | C7—C6—H6 | 119.4 |
| O1W—Mg1—O2iii | 89.72 (5) | C5—C6—H6 | 119.4 |
| O1—Mg1—O2iii | 88.69 (5) | C6—C7—C2 | 120.2 (2) |
| O1i—Mg1—O2iii | 91.31 (5) | C6—C7—H7 | 119.9 |
| O2ii—Mg1—O2iii | 180.00 (8) | C2—C7—H7 | 119.9 |
| O2—C1—O1 | 123.14 (17) | C1—O1—Mg1 | 134.15 (12) |
| O2—C1—C2 | 118.73 (17) | Mg1—O1W—H1WA | 128.9 |
| O1—C1—C2 | 118.03 (17) | Mg1—O1W—H1WB | 122.5 |
| C3—C2—C7 | 119.06 (18) | H1WA—O1W—H1WB | 94.2 |
| C3—C2—C1 | 120.10 (18) | C1—O2—Mg1v | 133.89 (13) |
| C7—C2—C1 | 120.82 (18) |
| Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, z; (iii) x+1/2, −y+3/2, −z; (iv) −x+2, y, −z+1/2; (v) x−1/2, −y+3/2, −z. |
This research was supported by the National Science Council, Taiwan (grant No. NSC97-2113-M-033–003-MY2), and Chung-Yuan Christian University, Taiwan, under grant No. CYCU-97-CR-CH.
Bruker (2007). SADABS, SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
The synthesis of coordination polymers, or so-called metal-organic frameworks (MOF), 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 compounds have been synthesized by solvothermal reactions with organic carboxyl acids (Kitagawa et al., 2004). Here we report on the new metal organic framework bis(aqua)-biphenyl-4,4'-dicarboxylate magnesium (II). In the crystal structure the Mg cations are sorrounded by two O atoms from two symmetry related water molecules and four O atoms of four symmetry related anions (Fig. 1). The coordination polyhedron around the Mg cations can be described as a slightly distorted octahedron. The Mg cations are linked via the anions into a three-dimensional network (Fig. 2).