Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110046950/gg3245sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110046950/gg3245Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110046950/gg3245IIsup3.hkl |
CCDC references: 813469; 813470
For related literature, see: Barthelet et al. (2002); Choi et al. (2009); Eddaoudi et al. (2002); Hausdorf et al. (2008); Higuchi et al. (2009); Li et al. (1999, 2008); Loiseau et al. (2004); Luo et al. (2008); Passaniti et al. (2002); Rosi et al. (2005); Tranchemontagne et al. (2008); Wang et al. (2008); Xu et al. (2010).
All chemicals and solvents were commercially available and used without further purification. 2,5-Dimethoxyterephthalic acid was synthesized according to the procedure published by Passaniti et al. (2002).
For the synthesis of [Mn(dmt)]n, (I), MnCl2.4H2O (105 mg, 0.53 mmol) and 2,5-dimethoxyterephthalic acid (40 mg, 0.18 mmol) were dissolved in N,N-dimethyl formamide (40 ml) and heated in a sealed tube for 24 h at 373 K. Yellow crystals of (I) [Colourless given in CIF tables - please clarify] precipitated after 24 h (yield 72%).
For the synthesis of [Zn(dmt)]n, (II), the same procedure was used as for (I), using Zn(NO3)2.4H2O (140 mg, 0.53 mmol) instead of MnCl2.4H2O. Colourless crystals of (II) precipitated after 18 h (yield 79%).
For both compounds, H atoms were positioned geometrically and allowed to ride on their respective parent atoms, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H, and C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aryl H atoms.
For both compounds, 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: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
[Mn(C10H8O6)] | F(000) = 564 |
Mr = 279.10 | Dx = 1.776 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8637 reflections |
a = 16.7686 (6) Å | θ = 2.5–34.5° |
b = 8.4646 (3) Å | µ = 1.28 mm−1 |
c = 7.4464 (3) Å | T = 153 K |
β = 99.093 (1)° | Block, yellow |
V = 1043.66 (7) Å3 | 0.52 × 0.35 × 0.33 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 2156 independent reflections |
Radiation source: fine-focus sealed tube | 2084 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 34.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −26→26 |
Tmin = 0.633, Tmax = 0.747 | k = −13→13 |
11427 measured reflections | l = −11→11 |
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0264P)2 + 0.4525P] where P = (Fo2 + 2Fc2)/3 |
2156 reflections | (Δ/σ)max = 0.001 |
79 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Mn(C10H8O6)] | V = 1043.66 (7) Å3 |
Mr = 279.10 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.7686 (6) Å | µ = 1.28 mm−1 |
b = 8.4646 (3) Å | T = 153 K |
c = 7.4464 (3) Å | 0.52 × 0.35 × 0.33 mm |
β = 99.093 (1)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 2156 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 2084 reflections with I > 2σ(I) |
Tmin = 0.633, Tmax = 0.747 | Rint = 0.019 |
11427 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.052 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.42 e Å−3 |
2156 reflections | Δρmin = −0.34 e Å−3 |
79 parameters |
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 | ||
Mn1 | 1.0000 | −0.076459 (18) | 0.2500 | 0.01459 (5) | |
O1 | 0.88960 (4) | 0.05007 (7) | 0.25036 (9) | 0.02221 (11) | |
O2 | 0.96699 (3) | 0.15728 (7) | 0.48546 (7) | 0.01809 (10) | |
O3 | 0.89455 (3) | 0.29664 (7) | 0.73532 (8) | 0.02100 (11) | |
C1 | 0.82337 (4) | 0.19593 (8) | 0.45428 (9) | 0.01336 (10) | |
C2 | 0.82294 (4) | 0.27479 (8) | 0.62019 (9) | 0.01438 (10) | |
C3 | 0.74941 (4) | 0.32770 (8) | 0.66249 (9) | 0.01502 (11) | |
H3 | 0.7488 | 0.3815 | 0.7742 | 0.018* | |
C4 | 0.89808 (4) | 0.13108 (8) | 0.39354 (9) | 0.01460 (11) | |
C5 | 0.89157 (6) | 0.38382 (13) | 0.89920 (15) | 0.0369 (2) | |
H5A | 0.8689 | 0.4889 | 0.8685 | 0.055* | |
H5B | 0.9463 | 0.3945 | 0.9675 | 0.055* | |
H5C | 0.8575 | 0.3276 | 0.9736 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.00888 (7) | 0.02125 (8) | 0.01397 (7) | 0.000 | 0.00279 (4) | 0.000 |
O1 | 0.0159 (2) | 0.0270 (3) | 0.0246 (3) | 0.00280 (19) | 0.00613 (19) | −0.0088 (2) |
O2 | 0.0104 (2) | 0.0248 (2) | 0.0194 (2) | 0.00177 (17) | 0.00324 (16) | 0.00496 (18) |
O3 | 0.0127 (2) | 0.0239 (3) | 0.0241 (2) | 0.00429 (18) | −0.00405 (18) | −0.0099 (2) |
C1 | 0.0106 (2) | 0.0138 (2) | 0.0157 (2) | 0.00215 (18) | 0.00227 (18) | −0.00033 (18) |
C2 | 0.0106 (2) | 0.0149 (2) | 0.0169 (2) | 0.00198 (19) | −0.00020 (19) | −0.0019 (2) |
C3 | 0.0121 (3) | 0.0171 (3) | 0.0155 (2) | 0.0033 (2) | 0.00114 (19) | −0.0026 (2) |
C4 | 0.0123 (3) | 0.0144 (2) | 0.0179 (3) | 0.00228 (19) | 0.0048 (2) | 0.0022 (2) |
C5 | 0.0255 (4) | 0.0425 (5) | 0.0370 (5) | 0.0149 (4) | −0.0124 (3) | −0.0265 (4) |
Mn1—O2i | 2.0761 (5) | C1—C3iv | 1.3965 (9) |
Mn1—O2ii | 2.0761 (5) | C1—C2 | 1.4052 (9) |
Mn1—O1iii | 2.1391 (6) | C1—C4 | 1.5015 (9) |
Mn1—O1 | 2.1391 (6) | C2—C3 | 1.3938 (9) |
O1—C4 | 1.2567 (9) | C3—C1iv | 1.3965 (9) |
O2—C4 | 1.2660 (8) | C3—H3 | 0.9500 |
O2—Mn1ii | 2.0761 (5) | C5—H5A | 0.9800 |
O3—C2 | 1.3733 (8) | C5—H5B | 0.9800 |
O3—C5 | 1.4337 (10) | C5—H5C | 0.9800 |
O2i—Mn1—O2ii | 141.52 (3) | C3—C2—C1 | 118.61 (6) |
O2i—Mn1—O1iii | 105.36 (2) | C2—C3—C1iv | 122.04 (6) |
O2ii—Mn1—O1iii | 93.73 (2) | C2—C3—H3 | 119.0 |
O2i—Mn1—O1 | 93.73 (2) | C1iv—C3—H3 | 119.0 |
O2ii—Mn1—O1 | 105.36 (2) | O1—C4—O2 | 121.70 (6) |
O1iii—Mn1—O1 | 119.91 (4) | O1—C4—C1 | 117.85 (6) |
C4—O1—Mn1 | 107.00 (5) | O2—C4—C1 | 120.45 (6) |
C4—O2—Mn1ii | 122.61 (4) | O3—C5—H5A | 109.5 |
C2—O3—C5 | 117.13 (6) | O3—C5—H5B | 109.5 |
C3iv—C1—C2 | 119.35 (6) | H5A—C5—H5B | 109.5 |
C3iv—C1—C4 | 116.66 (6) | O3—C5—H5C | 109.5 |
C2—C1—C4 | 123.98 (6) | H5A—C5—H5C | 109.5 |
O3—C2—C3 | 122.21 (6) | H5B—C5—H5C | 109.5 |
O3—C2—C1 | 119.17 (6) | ||
O2i—Mn1—O1—C4 | −171.27 (5) | C1—C2—C3—C1iv | 0.28 (11) |
O2ii—Mn1—O1—C4 | 42.48 (5) | Mn1—O1—C4—O2 | 16.20 (8) |
O1iii—Mn1—O1—C4 | −61.16 (5) | Mn1—O1—C4—C1 | −163.40 (5) |
C5—O3—C2—C3 | −2.96 (11) | Mn1ii—O2—C4—O1 | −116.47 (7) |
C5—O3—C2—C1 | 177.31 (8) | Mn1ii—O2—C4—C1 | 63.11 (8) |
C3iv—C1—C2—O3 | 179.47 (6) | C3iv—C1—C4—O1 | −5.41 (9) |
C4—C1—C2—O3 | 0.65 (10) | C2—C1—C4—O1 | 173.44 (7) |
C3iv—C1—C2—C3 | −0.27 (11) | C3iv—C1—C4—O2 | 174.99 (6) |
C4—C1—C2—C3 | −179.09 (6) | C2—C1—C4—O2 | −6.16 (10) |
O3—C2—C3—C1iv | −179.45 (6) |
Symmetry codes: (i) x, −y, z−1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y, −z+1/2; (iv) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1iv | 0.95 | 2.37 | 2.7209 (8) | 101 |
C5—H5B···O2v | 0.98 | 2.47 | 3.0654 (11) | 119 |
Symmetry codes: (iv) −x+3/2, −y+1/2, −z+1; (v) −x+2, y, −z+3/2. |
[Zn(C10H8O6)] | F(000) = 584 |
Mr = 289.53 | Dx = 1.851 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2923 reflections |
a = 16.5936 (6) Å | θ = 2.5–26.0° |
b = 8.4438 (3) Å | µ = 2.38 mm−1 |
c = 7.4838 (3) Å | T = 153 K |
β = 97.649 (2)° | Block, colourless |
V = 1039.25 (7) Å3 | 0.21 × 0.15 × 0.13 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 1005 independent reflections |
Radiation source: fine-focus sealed tube | 898 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ϕ and ω scans | θmax = 25.8°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −19→20 |
Tmin = 0.695, Tmax = 0.746 | k = −9→10 |
6781 measured reflections | l = −9→8 |
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)] = 0.022 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0227P)2 + 0.9295P] where P = (Fo2 + 2Fc2)/3 |
1005 reflections | (Δ/σ)max < 0.001 |
79 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Zn(C10H8O6)] | V = 1039.25 (7) Å3 |
Mr = 289.53 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.5936 (6) Å | µ = 2.38 mm−1 |
b = 8.4438 (3) Å | T = 153 K |
c = 7.4838 (3) Å | 0.21 × 0.15 × 0.13 mm |
β = 97.649 (2)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 1005 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 898 reflections with I > 2σ(I) |
Tmin = 0.695, Tmax = 0.746 | Rint = 0.032 |
6781 measured reflections |
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.049 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.31 e Å−3 |
1005 reflections | Δρmin = −0.28 e Å−3 |
79 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
Zn1 | 1.0000 | −0.07765 (4) | 0.2500 | 0.01735 (12) | |
O1 | 0.89943 (8) | 0.04802 (17) | 0.27162 (18) | 0.0206 (3) | |
O2 | 0.97106 (7) | 0.16244 (16) | 0.50689 (17) | 0.0175 (3) | |
O3 | 0.88909 (8) | 0.29952 (17) | 0.74397 (19) | 0.0223 (3) | |
C1 | 0.82575 (11) | 0.1943 (2) | 0.4642 (3) | 0.0161 (4) | |
C2 | 0.81990 (11) | 0.2758 (2) | 0.6249 (3) | 0.0167 (4) | |
C3 | 0.74429 (11) | 0.3298 (2) | 0.6580 (3) | 0.0173 (4) | |
H3 | 0.7401 | 0.3848 | 0.7672 | 0.021* | |
C4 | 0.90393 (11) | 0.1308 (2) | 0.4121 (3) | 0.0157 (4) | |
C5 | 0.88121 (14) | 0.3818 (3) | 0.9077 (3) | 0.0407 (7) | |
H5A | 0.8602 | 0.4887 | 0.8795 | 0.061* | |
H5B | 0.9345 | 0.3890 | 0.9814 | 0.061* | |
H5C | 0.8435 | 0.3243 | 0.9745 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01064 (17) | 0.0276 (2) | 0.01397 (18) | 0.000 | 0.00223 (12) | 0.000 |
O1 | 0.0149 (7) | 0.0303 (9) | 0.0166 (7) | 0.0026 (6) | 0.0023 (6) | −0.0049 (6) |
O2 | 0.0116 (6) | 0.0232 (8) | 0.0177 (7) | −0.0003 (5) | 0.0020 (6) | 0.0025 (6) |
O3 | 0.0140 (7) | 0.0305 (8) | 0.0210 (8) | 0.0039 (6) | −0.0025 (6) | −0.0093 (7) |
C1 | 0.0144 (9) | 0.0172 (10) | 0.0170 (10) | 0.0000 (8) | 0.0030 (8) | 0.0027 (8) |
C2 | 0.0131 (9) | 0.0176 (10) | 0.0186 (10) | 0.0001 (8) | −0.0014 (8) | 0.0009 (8) |
C3 | 0.0165 (10) | 0.0196 (11) | 0.0157 (10) | 0.0014 (8) | 0.0024 (8) | −0.0013 (8) |
C4 | 0.0147 (10) | 0.0179 (10) | 0.0148 (10) | −0.0007 (8) | 0.0030 (8) | 0.0051 (8) |
C5 | 0.0272 (13) | 0.0553 (17) | 0.0352 (14) | 0.0159 (11) | −0.0120 (10) | −0.0260 (12) |
Zn1—O2i | 1.9547 (13) | C1—C3iv | 1.395 (3) |
Zn1—O2ii | 1.9547 (13) | C1—C2 | 1.401 (3) |
Zn1—O1iii | 2.0023 (13) | C1—C4 | 1.502 (3) |
Zn1—O1 | 2.0023 (13) | C2—C3 | 1.388 (3) |
O1—C4 | 1.256 (2) | C3—C1iv | 1.395 (3) |
O2—C4 | 1.267 (2) | C3—H3 | 0.9500 |
O2—Zn1ii | 1.9547 (13) | C5—H5A | 0.9800 |
O3—C2 | 1.371 (2) | C5—H5B | 0.9800 |
O3—C5 | 1.430 (3) | C5—H5C | 0.9800 |
O2i—Zn1—O2ii | 137.03 (8) | C3—C2—C1 | 118.85 (17) |
O2i—Zn1—O1iii | 102.89 (5) | C2—C3—C1iv | 121.94 (19) |
O2ii—Zn1—O1iii | 99.51 (5) | C2—C3—H3 | 119.0 |
O2i—Zn1—O1 | 99.51 (5) | C1iv—C3—H3 | 119.0 |
O2ii—Zn1—O1 | 102.89 (5) | O1—C4—O2 | 122.41 (17) |
O1iii—Zn1—O1 | 116.00 (8) | O1—C4—C1 | 117.28 (17) |
C4—O1—Zn1 | 113.89 (12) | O2—C4—C1 | 120.30 (17) |
C4—O2—Zn1ii | 122.20 (12) | O3—C5—H5A | 109.5 |
C2—O3—C5 | 117.63 (15) | O3—C5—H5B | 109.5 |
C3iv—C1—C2 | 119.21 (17) | H5A—C5—H5B | 109.5 |
C3iv—C1—C4 | 116.79 (18) | O3—C5—H5C | 109.5 |
C2—C1—C4 | 124.00 (17) | H5A—C5—H5C | 109.5 |
O3—C2—C3 | 122.32 (18) | H5B—C5—H5C | 109.5 |
O3—C2—C1 | 118.83 (16) | ||
O2i—Zn1—O1—C4 | −173.31 (13) | C1—C2—C3—C1iv | −0.2 (3) |
O2ii—Zn1—O1—C4 | 43.62 (14) | Zn1—O1—C4—O2 | 16.5 (2) |
O1iii—Zn1—O1—C4 | −63.84 (12) | Zn1—O1—C4—C1 | −164.29 (13) |
C5—O3—C2—C3 | 0.6 (3) | Zn1ii—O2—C4—O1 | −112.14 (18) |
C5—O3—C2—C1 | −179.4 (2) | Zn1ii—O2—C4—C1 | 68.6 (2) |
C3iv—C1—C2—O3 | −179.77 (17) | C3iv—C1—C4—O1 | −6.6 (3) |
C4—C1—C2—O3 | −0.3 (3) | C2—C1—C4—O1 | 173.91 (18) |
C3iv—C1—C2—C3 | 0.2 (3) | C3iv—C1—C4—O2 | 172.60 (17) |
C4—C1—C2—C3 | 179.64 (18) | C2—C1—C4—O2 | −6.8 (3) |
O3—C2—C3—C1iv | 179.76 (17) |
Symmetry codes: (i) x, −y, z−1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y, −z+1/2; (iv) −x+3/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1iv | 0.95 | 2.36 | 2.713 (2) | 101 |
C5—H5B···O2v | 0.98 | 2.47 | 3.071 (3) | 120 |
Symmetry codes: (iv) −x+3/2, −y+1/2, −z+1; (v) −x+2, y, −z+3/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Mn(C10H8O6)] | [Zn(C10H8O6)] |
Mr | 279.10 | 289.53 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 153 | 153 |
a, b, c (Å) | 16.7686 (6), 8.4646 (3), 7.4464 (3) | 16.5936 (6), 8.4438 (3), 7.4838 (3) |
β (°) | 99.093 (1) | 97.649 (2) |
V (Å3) | 1043.66 (7) | 1039.25 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.28 | 2.38 |
Crystal size (mm) | 0.52 × 0.35 × 0.33 | 0.21 × 0.15 × 0.13 |
Data collection | ||
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.633, 0.747 | 0.695, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11427, 2156, 2084 | 6781, 1005, 898 |
Rint | 0.019 | 0.032 |
(sin θ/λ)max (Å−1) | 0.797 | 0.613 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.052, 1.09 | 0.022, 0.049, 1.05 |
No. of reflections | 2156 | 1005 |
No. of parameters | 79 | 79 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.34 | 0.31, −0.28 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.95 | 2.37 | 2.7209 (8) | 101.3 |
C5—H5B···O2ii | 0.98 | 2.47 | 3.0654 (11) | 118.7 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.95 | 2.36 | 2.713 (2) | 101.2 |
C5—H5B···O2ii | 0.98 | 2.47 | 3.071 (3) | 119.6 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+2, y, −z+3/2. |
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Metal–organic coordination polymers (MOCPs) are crystalline frameworks composed of metal ions or clusters of metal ions called secondary building units (SBUs) and organic molecules called linkers, to form one-, two- or three-dimensional structures possessing cavities (Li et al., 1999). In specific cases, knowledge of the SBU and linker geometries, in conjunction with their interaction principles, allows the prediction of network topologies and thus supports rational framework design. It is known that specific reaction conditions such as temperature, solvent and moisture can influence SBU formation (Hausdorf et al., 2008). Nevertheless, generation of SBUs subject to linker properties has only rarely been investigated (Choi et al., 2009).
While the reaction of 2,5-dihydroxyterephthalic acid and Zn(NO3)2.4H2O [carried out under conditions (Tranchemontagne et al., 2008) comparable with those used here] leads to MOF-74 (Rosi et al., 2005) type networks, the reaction of 2,5-di-n-propoxyterephthalic acid and Zn(NO3)2.4H2O gives rise to IRMOF (Eddaoudi et al., 2002) type structures. However, three-dimensional coordination polymers containing the dmt2- anion as a linker with ZnII or MnII as metal ions for the SBU have not been reported so far. This prompted us to use the dmt2- anion as a rigid dicarboxylate with small weakly coordinating substituents for our investigations to form appropriate new types of MOCPs.
The title compounds, [Mn(dmt)]n, (I), and [Zn(dmt)]n, (II), crystallize in the monoclinic space group C2/c with asymmetric units containing one MII cation (M = Mn or Zn) and one half of a dmt2- anion (Fig. 1). Indeed, the two compounds are isomorphous, which is shown in the molecular overlay plot in Fig. 2. Besides a slight difference in the monoclinic angle β, the unit-cell dimensions do not differ significantly from each other.
As shown in Fig. 1, each of the MII cations adopts a distorted MIIO4 tetrahedral geometry, coordinated by four O atoms from four different dmt2- anions. The Mn1—O1 and Mn1—O2 bond lengths of 2.1391 (6) and 2.0761 (5) Å, respectively, in (I) are in accordance with those reported for related manganese(II) terephthalates [Mn—O = 2.100 (4)–2.188 (3) Å; Xu et al., 2010; Luo et al., 2008]. The corresponding O—Mn—O angles range from 93.73 (2) to 141.52 (3)°, thus deviating considerably from the ideal value of 109.4° for a tetrahedral coordination sphere. The Zn—O bond lengths in (II) range from 2.0023 (13) Å for Zn1—O1 to 1.9547 (13) Å for Zn1—O2 and do not vary significantly from literature values for related zinc(II) terephthalate-based MOCPs [1.935 (2)–2.104 (5) Å; Higuchi et al., 2009; Wang et al., 2008]. However, the distortion of the O—Zn—O angles from ideal tetrahedral geometry in (II), ranging from 99.51 (5) to 137.03 (8)°, is smaller than in (I). These structural differences between (I) and (II) may be caused by the different sizes of the MnII and ZnII cations (0.91 and 0.83 Å, respectively; Reference for standard values?).
The uncommon values for the O—MII—O bond angles mentioned above can be explained by the existence of a second coordination sphere formed by weak interactions between the MII cations and O atoms of the methoxy and carboxylate groups (Fig. 1). This leads to a distorted [MIIO4(O)2(OMe)2] super dodecahedron (Fig. 3), where the methoxy O atoms are located in trans positions to each other, while the two bidentate and two monodentate carboxylates coordinate in a cis position to each other (Fig. 4).
The bond lengths for M—OMe [Mn1—O3 = 2.5596 (6) Å and Zn1—O3 = 2.6224 (17) Å] and M—O2' [Mn1—O2' = 2.7570 (6) Å and Zn1—O2' = 2.8772 (16) Å] reveal that these bonds are much weaker than the M—O bonds of the inner coordination sphere. Similar coordination modes have already been reported for CdII complexes (Li et al., 2008). The MIIO8 super dodecahedra are edge-sharing, to give a one-dimensional chain along the c axis (Fig. 3). Two adjacent one-dimensional chains are interconnected by dmt2- anions to obtain a three-dimensional coordination network, with shortest Mn1A···Mn1B and Zn1A···Zn1B distances between the one-dimensional chains of 8.0793 (3) and 8.0552 (2) Å, respectively. Apart from these MII—O interactions, there are weak intermolecular C—H···O hydrogen-bonding interactions in both networks, involving C3—H3···O1i and C5—H5B···O2ii for both (I) and (II), contributing to the stabilization of the crystal structures (symmetry codes are given in Tables 1 and 2).
One dimensional rhombic channels of 9.1 × 13.1 Å in diameter (measured between atoms in opposite corners) are located along the c axis in the networks of (I) and (II). The methoxy groups point inside these channels and subdivide them into two smaller pores, shown as balls in the network structure (Fig. 5). Taking the van der Waals radii into account, their size is reduced to about 1.2 Å, which is much too small for the uptake of any solvent molecules or nitrogen. A better understanding of the network structures of (I) and (II) can be achieved by a topological investigation, reducing complex network structures to simple SBU-and-linker networks (Rosi et al., 2005) (Fig. 6). To derive the nets of (I) and (II), the SBUs were reduced to rods of shaded quadrangles linked by sharing opposite edges, which leads to a ladder-like conformation of the one-dimensional SBU chains. The linkers are represented by rungs to form a 4-connected net with parallel rungs, analogous to the Al net in SrAl2. This is called a network with sra12 topology, also found in metal–organic frameworks such as MIL-47 (Barthelet et al., 2002), MIL-53 (Loiseau et al., 2004) and MOF-71 (Rosi et al., 2005).
The main reason for the generation of the more or less unusual isomorphous structures of (I) and (II) may be the formation of metal centres with high coordination numbers. The reaction of Zn(NO3)2.4H2O and a rigid dicarboxylic acid in N,N-dimethyl formamide usually leads to an IRMOF-type framework (Eddaoudi et al., 2002) containing a four-coordinated Zn metal centre. Performing these reactions with 2,5-dihydroxyterephthalic acid instead leads to MOF-74-type frameworks, caused by the linker molecule facilitating the formation of a much more stable five-coordinated metal species. The frameworks of (I) and (II) discussed here exhibit eight-coordinated metal centres, which seems to be the most stable coordination geometry under these conditions.