Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111037954/bm3110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111037954/bm3110Isup2.hkl |
CCDC reference: 855945
Compound (I) was synthesized by dissolving Mg(NO3)2.6H2O (99%, Sigma–Aldrich; 0.122 g, 0.47 mmol) and adamantane-1,3-dicarboxylic acid (95%, TCI-America; 0.106 g, 0.47 mmol) in a mixture of ethanol (95%, Fisher; 4.0 g) and N,N-dimethylformamide (DMF, 99%, Sigma–Aldrich; 4.0 g), and stirring the mixture for 1 h (molar ratio of metal salt–ligand–DMF–ethanol = 1:1:116:185). The resulting solution was placed in a Teflon-lined 23 ml Parr stainless steel autoclave and heated for 5 d at 453 K. The product was obtained as needle-shaped crystals (yield 0.130 g, 55% based on Mg, 0.130 g) which were washed with ethanol.
All C-bound H atoms were placed in calculated positions and treated using a riding model, with C—H = 0.97 (methylene) or 0.98 Å (methine), and with Uiso(H) = 1.2Ueq(C).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Burnett & Johnson, 1996) and CrystalMaker (Palmer, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
[Mg2(C12H14O4)2] | Z = 2 |
Mr = 246.5 | F(000) = 520 |
Triclinic, P1 | Dx = 1.452 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9034 (2) Å | Cell parameters from 9594 reflections |
b = 11.3549 (4) Å | θ = 3.1–33.0° |
c = 15.3196 (6) Å | µ = 0.15 mm−1 |
α = 70.713 (4)° | T = 293 K |
β = 83.131 (3)° | Needle, colourless |
γ = 89.141 (3)° | 0.3 × 0.1 × 0.05 mm |
V = 1124.95 (7) Å3 |
Oxford Xcalibur Atlas Gemini diffractometer | 4605 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3157 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 10.4962 pixels mm-1 | θmax = 26.4°, θmin = 3.1° |
ω scans | h = −8→8 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −14→14 |
Tmin = 0.979, Tmax = 1.000 | l = −19→19 |
28700 measured reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0797P)2] where P = (Fo2 + 2Fc2)/3 |
4605 reflections | (Δ/σ)max < 0.001 |
307 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Mg2(C12H14O4)2] | γ = 89.141 (3)° |
Mr = 246.5 | V = 1124.95 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9034 (2) Å | Mo Kα radiation |
b = 11.3549 (4) Å | µ = 0.15 mm−1 |
c = 15.3196 (6) Å | T = 293 K |
α = 70.713 (4)° | 0.3 × 0.1 × 0.05 mm |
β = 83.131 (3)° |
Oxford Xcalibur Atlas Gemini diffractometer | 4605 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 3157 reflections with I > 2σ(I) |
Tmin = 0.979, Tmax = 1.000 | Rint = 0.061 |
28700 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.154 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.46 e Å−3 |
4605 reflections | Δρmin = −0.28 e Å−3 |
307 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0787 (4) | 0.0955 (3) | 0.60973 (18) | 0.0325 (6) | |
C2 | 0.1404 (3) | 0.1959 (2) | 0.51649 (17) | 0.0280 (6) | |
C3 | −0.0342 (4) | 0.2457 (3) | 0.46362 (18) | 0.0355 (6) | |
H3A | −0.0974 | 0.1782 | 0.4511 | 0.043* | |
H3B | −0.1282 | 0.2783 | 0.5015 | 0.043* | |
C4 | 0.2380 (4) | 0.3033 (2) | 0.53668 (18) | 0.0337 (6) | |
H4A | 0.1464 | 0.3356 | 0.5758 | 0.040* | |
H4B | 0.3498 | 0.2729 | 0.5697 | 0.040* | |
C5 | 0.2896 (3) | 0.1443 (2) | 0.45653 (17) | 0.0276 (6) | |
H5A | 0.2308 | 0.0754 | 0.4440 | 0.033* | |
H5B | 0.4010 | 0.1135 | 0.4898 | 0.033* | |
C6 | 0.3038 (4) | 0.4077 (2) | 0.44481 (19) | 0.0371 (6) | |
H6 | 0.3646 | 0.4766 | 0.4578 | 0.044* | |
C7 | 0.1292 (4) | 0.4552 (3) | 0.3917 (2) | 0.0429 (7) | |
H7A | 0.0357 | 0.4901 | 0.4283 | 0.052* | |
H7B | 0.1722 | 0.5205 | 0.3335 | 0.052* | |
C8 | 0.0326 (4) | 0.3487 (3) | 0.37193 (18) | 0.0348 (6) | |
H8 | −0.0804 | 0.3796 | 0.3386 | 0.042* | |
C9 | 0.1792 (3) | 0.2962 (3) | 0.31217 (17) | 0.0308 (6) | |
H9A | 0.2199 | 0.3607 | 0.2532 | 0.037* | |
H9B | 0.1183 | 0.2281 | 0.2994 | 0.037* | |
C10 | 0.4520 (4) | 0.3551 (2) | 0.38605 (18) | 0.0319 (6) | |
H10A | 0.5625 | 0.3240 | 0.4199 | 0.038* | |
H10B | 0.4992 | 0.4207 | 0.3287 | 0.038* | |
C11 | 0.3576 (3) | 0.2489 (2) | 0.36340 (16) | 0.0261 (5) | |
C12 | 0.5037 (3) | 0.1963 (2) | 0.30560 (16) | 0.0261 (5) | |
C13 | 0.0083 (3) | 0.1980 (2) | 0.09558 (17) | 0.0265 (5) | |
C14 | 0.1581 (3) | 0.2521 (2) | 0.01134 (16) | 0.0260 (5) | |
C15 | 0.3370 (3) | 0.3017 (2) | 0.03970 (17) | 0.0302 (6) | |
H15A | 0.3931 | 0.2347 | 0.0866 | 0.036* | |
H15B | 0.2988 | 0.3665 | 0.0662 | 0.036* | |
C16 | 0.2211 (3) | 0.1476 (2) | −0.02924 (17) | 0.0262 (5) | |
H16A | 0.2753 | 0.0797 | 0.0177 | 0.031* | |
H16B | 0.1084 | 0.1153 | −0.0471 | 0.031* | |
C17 | 0.0709 (4) | 0.3569 (2) | −0.06344 (17) | 0.0314 (6) | |
H17A | 0.0277 | 0.4225 | −0.0386 | 0.038* | |
H17B | −0.0415 | 0.3249 | −0.0818 | 0.038* | |
C18 | 0.2242 (4) | 0.4104 (2) | −0.14871 (18) | 0.0342 (6) | |
H18 | 0.1679 | 0.4784 | −0.1960 | 0.041* | |
C19 | 0.2848 (4) | 0.3066 (2) | −0.18863 (18) | 0.0339 (6) | |
H19A | 0.3795 | 0.3394 | −0.2435 | 0.041* | |
H19B | 0.1718 | 0.2752 | −0.2070 | 0.041* | |
C20 | 0.4000 (4) | 0.4599 (3) | −0.11934 (19) | 0.0410 (7) | |
H20A | 0.3603 | 0.5257 | −0.0941 | 0.049* | |
H20B | 0.4965 | 0.4949 | −0.1731 | 0.049* | |
C21 | 0.3746 (3) | 0.1996 (2) | −0.11479 (17) | 0.0282 (6) | |
C22 | 0.4886 (4) | 0.3548 (2) | −0.04611 (18) | 0.0333 (6) | |
H22 | 0.6027 | 0.3871 | −0.0280 | 0.040* | |
C23 | 0.5508 (4) | 0.2512 (3) | −0.08576 (18) | 0.0342 (6) | |
H23A | 0.6082 | 0.1846 | −0.0392 | 0.041* | |
H23B | 0.6486 | 0.2838 | −0.1393 | 0.041* | |
C24 | 0.4308 (4) | 0.0980 (2) | −0.15667 (17) | 0.0319 (6) | |
O1 | −0.0981 (3) | 0.08431 (19) | 0.64206 (13) | 0.0472 (5) | |
O2 | 0.2074 (3) | 0.0308 (2) | 0.65109 (14) | 0.0557 (6) | |
O3 | 0.6788 (2) | 0.22620 (18) | 0.29161 (13) | 0.0390 (5) | |
O4 | 0.4473 (2) | 0.11580 (16) | 0.26990 (12) | 0.0307 (4) | |
O5 | 0.0584 (2) | 0.11589 (16) | 0.17021 (11) | 0.0292 (4) | |
O6 | −0.1645 (2) | 0.22741 (18) | 0.09567 (12) | 0.0383 (5) | |
O7 | 0.6078 (3) | 0.08638 (19) | −0.18251 (15) | 0.0474 (5) | |
O8 | 0.2981 (3) | 0.0323 (2) | −0.16616 (16) | 0.0545 (6) | |
Mg1 | 0.24942 (11) | 0.01551 (8) | 0.24454 (6) | 0.0287 (2) | |
Mg2 | 0.75194 (11) | 0.09054 (8) | 0.22683 (6) | 0.0269 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0308 (14) | 0.0416 (16) | 0.0247 (14) | 0.0006 (12) | 0.0020 (11) | −0.0122 (12) |
C2 | 0.0261 (13) | 0.0361 (14) | 0.0207 (13) | 0.0031 (10) | 0.0000 (10) | −0.0092 (11) |
C3 | 0.0264 (13) | 0.0488 (17) | 0.0300 (15) | 0.0070 (12) | 0.0003 (11) | −0.0127 (13) |
C4 | 0.0362 (15) | 0.0425 (16) | 0.0249 (14) | 0.0061 (12) | −0.0011 (11) | −0.0155 (12) |
C5 | 0.0236 (12) | 0.0330 (14) | 0.0252 (13) | 0.0013 (10) | 0.0015 (10) | −0.0102 (11) |
C6 | 0.0470 (16) | 0.0341 (15) | 0.0340 (15) | −0.0001 (12) | −0.0013 (12) | −0.0176 (13) |
C7 | 0.0597 (19) | 0.0325 (15) | 0.0320 (16) | 0.0149 (14) | 0.0021 (14) | −0.0077 (13) |
C8 | 0.0308 (14) | 0.0458 (16) | 0.0249 (14) | 0.0145 (12) | −0.0031 (11) | −0.0088 (12) |
C9 | 0.0289 (13) | 0.0396 (15) | 0.0238 (13) | 0.0044 (11) | −0.0012 (10) | −0.0112 (12) |
C10 | 0.0331 (14) | 0.0339 (15) | 0.0283 (14) | −0.0034 (11) | 0.0014 (11) | −0.0112 (12) |
C11 | 0.0232 (12) | 0.0346 (14) | 0.0224 (13) | 0.0026 (10) | −0.0007 (10) | −0.0128 (11) |
C12 | 0.0255 (13) | 0.0321 (14) | 0.0197 (12) | 0.0009 (10) | −0.0022 (10) | −0.0073 (11) |
C13 | 0.0256 (13) | 0.0305 (14) | 0.0266 (14) | −0.0001 (10) | −0.0026 (10) | −0.0139 (11) |
C14 | 0.0238 (12) | 0.0327 (14) | 0.0221 (13) | 0.0004 (10) | −0.0013 (10) | −0.0102 (11) |
C15 | 0.0296 (13) | 0.0371 (15) | 0.0247 (13) | −0.0051 (11) | 0.0013 (10) | −0.0128 (12) |
C16 | 0.0239 (12) | 0.0303 (14) | 0.0241 (13) | −0.0013 (10) | 0.0007 (10) | −0.0099 (11) |
C17 | 0.0334 (14) | 0.0317 (14) | 0.0282 (14) | 0.0055 (11) | −0.0028 (11) | −0.0092 (12) |
C18 | 0.0435 (15) | 0.0298 (14) | 0.0245 (14) | 0.0019 (12) | −0.0031 (12) | −0.0032 (11) |
C19 | 0.0346 (14) | 0.0421 (16) | 0.0250 (14) | −0.0038 (12) | −0.0005 (11) | −0.0121 (12) |
C20 | 0.0532 (18) | 0.0381 (16) | 0.0296 (15) | −0.0107 (13) | 0.0076 (13) | −0.0123 (13) |
C21 | 0.0243 (12) | 0.0354 (14) | 0.0250 (13) | −0.0014 (10) | 0.0013 (10) | −0.0116 (11) |
C22 | 0.0284 (13) | 0.0442 (16) | 0.0286 (14) | −0.0115 (11) | 0.0026 (11) | −0.0154 (13) |
C23 | 0.0261 (13) | 0.0465 (16) | 0.0290 (14) | −0.0039 (11) | 0.0029 (11) | −0.0132 (13) |
C24 | 0.0317 (14) | 0.0381 (15) | 0.0239 (14) | −0.0009 (11) | 0.0020 (11) | −0.0093 (12) |
O1 | 0.0326 (11) | 0.0612 (14) | 0.0349 (11) | −0.0010 (9) | 0.0069 (9) | −0.0025 (10) |
O2 | 0.0392 (12) | 0.0703 (15) | 0.0347 (12) | 0.0169 (11) | 0.0048 (9) | 0.0092 (11) |
O3 | 0.0228 (9) | 0.0539 (12) | 0.0450 (12) | −0.0026 (8) | 0.0059 (8) | −0.0259 (10) |
O4 | 0.0258 (9) | 0.0424 (11) | 0.0297 (10) | 0.0025 (7) | −0.0015 (7) | −0.0204 (8) |
O5 | 0.0242 (9) | 0.0384 (10) | 0.0207 (9) | −0.0005 (7) | −0.0005 (7) | −0.0050 (8) |
O6 | 0.0250 (10) | 0.0528 (12) | 0.0303 (10) | 0.0071 (8) | 0.0023 (8) | −0.0071 (9) |
O7 | 0.0324 (11) | 0.0628 (14) | 0.0584 (14) | 0.0056 (9) | 0.0029 (9) | −0.0384 (11) |
O8 | 0.0396 (12) | 0.0651 (14) | 0.0738 (16) | −0.0119 (10) | 0.0139 (11) | −0.0495 (13) |
Mg1 | 0.0198 (4) | 0.0404 (5) | 0.0265 (5) | 0.0014 (3) | 0.0007 (3) | −0.0131 (4) |
Mg2 | 0.0203 (4) | 0.0366 (5) | 0.0242 (5) | 0.0014 (3) | 0.0007 (3) | −0.0117 (4) |
Mg1—O1i | 1.922 (2) | C13—O6 | 1.234 (3) |
Mg1—O4 | 1.9443 (18) | C13—O5 | 1.295 (3) |
Mg1—O5 | 1.9470 (18) | C13—C14 | 1.513 (3) |
Mg1—O7ii | 1.919 (2) | C13—Mg2v | 2.502 (2) |
Mg2—O2iii | 1.971 (2) | C14—C17 | 1.528 (3) |
Mg2—O3 | 2.116 (2) | C14—C15 | 1.530 (3) |
Mg2—O4 | 2.1713 (17) | C14—C16 | 1.546 (3) |
Mg2—O5iv | 2.1739 (17) | C15—C22 | 1.534 (3) |
Mg2—O6iv | 2.1147 (19) | C15—H15A | 0.9700 |
Mg2—O8ii | 1.969 (2) | C15—H15B | 0.9700 |
C1—O2 | 1.240 (3) | C16—C21 | 1.538 (3) |
C1—O1 | 1.253 (3) | C16—H16A | 0.9700 |
C1—C2 | 1.521 (3) | C16—H16B | 0.9700 |
C2—C3 | 1.529 (3) | C17—C18 | 1.536 (3) |
C2—C5 | 1.536 (3) | C17—H17A | 0.9700 |
C2—C4 | 1.536 (4) | C17—H17B | 0.9700 |
C3—C8 | 1.526 (4) | C18—C20 | 1.520 (4) |
C3—H3A | 0.9700 | C18—C19 | 1.530 (4) |
C3—H3B | 0.9700 | C18—H18 | 0.9800 |
C4—C6 | 1.534 (4) | C19—C21 | 1.542 (4) |
C4—H4A | 0.9700 | C19—H19A | 0.9700 |
C4—H4B | 0.9700 | C19—H19B | 0.9700 |
C5—C11 | 1.551 (3) | C20—C22 | 1.522 (4) |
C5—H5A | 0.9700 | C20—H20A | 0.9700 |
C5—H5B | 0.9700 | C20—H20B | 0.9700 |
C6—C10 | 1.527 (4) | C21—C24 | 1.519 (4) |
C6—C7 | 1.527 (4) | C21—C23 | 1.531 (3) |
C6—H6 | 0.9800 | C22—C23 | 1.527 (4) |
C7—C8 | 1.521 (4) | C22—H22 | 0.9800 |
C7—H7A | 0.9700 | C23—H23A | 0.9700 |
C7—H7B | 0.9700 | C23—H23B | 0.9700 |
C8—C9 | 1.530 (3) | C24—O8 | 1.242 (3) |
C8—H8 | 0.9800 | C24—O7 | 1.257 (3) |
C9—C11 | 1.534 (3) | O1—Mg1i | 1.9223 (19) |
C9—H9A | 0.9700 | O2—Mg2iii | 1.971 (2) |
C9—H9B | 0.9700 | O5—Mg2v | 2.1739 (17) |
C10—C11 | 1.533 (3) | O6—Mg2v | 2.1147 (19) |
C10—H10A | 0.9700 | O7—Mg1ii | 1.919 (2) |
C10—H10B | 0.9700 | O8—Mg2ii | 1.969 (2) |
C11—C12 | 1.508 (3) | Mg2—C13iv | 2.502 (2) |
C12—O3 | 1.235 (3) | Mg2—Mg1 | 3.5419 (11) |
C12—O4 | 1.295 (3) | Mg2—Mg1iv | 3.5463 (11) |
C12—Mg2 | 2.497 (3) | Mg1—Mg2v | 3.5463 (11) |
O1i—Mg1—O4 | 111.03 (9) | C21—C16—C14 | 109.82 (19) |
O1i—Mg1—O5 | 104.53 (8) | C21—C16—H16A | 109.7 |
O4—Mg1—O5 | 112.92 (8) | C14—C16—H16A | 109.7 |
O7ii—Mg1—O1i | 111.52 (10) | C21—C16—H16B | 109.7 |
O7ii—Mg1—O4 | 104.95 (8) | C14—C16—H16B | 109.7 |
O7ii—Mg1—O5 | 112.07 (9) | H16A—C16—H16B | 108.2 |
O2iii—Mg2—O3 | 89.61 (9) | C14—C17—C18 | 110.0 (2) |
O2iii—Mg2—O4 | 93.73 (8) | C14—C17—H17A | 109.7 |
O2iii—Mg2—O5iv | 96.04 (8) | C18—C17—H17A | 109.7 |
O3—Mg2—O4 | 60.72 (7) | C14—C17—H17B | 109.7 |
O3—Mg2—O5iv | 108.79 (7) | C18—C17—H17B | 109.7 |
O5iv—Mg2—O6iv | 60.59 (7) | H17A—C17—H17B | 108.2 |
O6iv—Mg2—O3 | 92.72 (8) | C20—C18—C19 | 110.2 (2) |
O6iv—Mg2—O4 | 108.27 (7) | C20—C18—C17 | 109.3 (2) |
O8ii—Mg2—O2iii | 96.80 (11) | C19—C18—C17 | 108.7 (2) |
O8ii—Mg2—O4 | 95.76 (8) | C20—C18—H18 | 109.5 |
O8ii—Mg2—O5iv | 93.49 (8) | C19—C18—H18 | 109.5 |
O8ii—Mg2—O6iv | 90.71 (9) | C17—C18—H18 | 109.5 |
O2—C1—O1 | 123.2 (2) | C18—C19—C21 | 109.8 (2) |
O2—C1—C2 | 118.1 (2) | C18—C19—H19A | 109.7 |
O1—C1—C2 | 118.6 (2) | C21—C19—H19A | 109.7 |
C1—C2—C3 | 111.8 (2) | C18—C19—H19B | 109.7 |
C1—C2—C5 | 110.1 (2) | C21—C19—H19B | 109.7 |
C3—C2—C5 | 109.7 (2) | H19A—C19—H19B | 108.2 |
C1—C2—C4 | 107.3 (2) | C18—C20—C22 | 109.8 (2) |
C3—C2—C4 | 109.1 (2) | C18—C20—H20A | 109.7 |
C5—C2—C4 | 108.7 (2) | C22—C20—H20A | 109.7 |
C8—C3—C2 | 110.3 (2) | C18—C20—H20B | 109.7 |
C8—C3—H3A | 109.6 | C22—C20—H20B | 109.7 |
C2—C3—H3A | 109.6 | H20A—C20—H20B | 108.2 |
C8—C3—H3B | 109.6 | C24—C21—C23 | 112.0 (2) |
C2—C3—H3B | 109.6 | C24—C21—C16 | 109.7 (2) |
H3A—C3—H3B | 108.1 | C23—C21—C16 | 109.1 (2) |
C6—C4—C2 | 109.7 (2) | C24—C21—C19 | 108.1 (2) |
C6—C4—H4A | 109.7 | C23—C21—C19 | 109.0 (2) |
C2—C4—H4A | 109.7 | C16—C21—C19 | 108.8 (2) |
C6—C4—H4B | 109.7 | C20—C22—C23 | 109.7 (2) |
C2—C4—H4B | 109.7 | C20—C22—C15 | 109.6 (2) |
H4A—C4—H4B | 108.2 | C23—C22—C15 | 109.2 (2) |
C2—C5—C11 | 109.7 (2) | C20—C22—H22 | 109.4 |
C2—C5—H5A | 109.7 | C23—C22—H22 | 109.4 |
C11—C5—H5A | 109.7 | C15—C22—H22 | 109.4 |
C2—C5—H5B | 109.7 | C22—C23—C21 | 110.3 (2) |
C11—C5—H5B | 109.7 | C22—C23—H23A | 109.6 |
H5A—C5—H5B | 108.2 | C21—C23—H23A | 109.6 |
C10—C6—C7 | 109.4 (2) | C22—C23—H23B | 109.6 |
C10—C6—C4 | 108.5 (2) | C21—C23—H23B | 109.6 |
C7—C6—C4 | 110.2 (2) | H23A—C23—H23B | 108.1 |
C10—C6—H6 | 109.6 | O8—C24—O7 | 122.9 (3) |
C7—C6—H6 | 109.6 | O8—C24—C21 | 118.1 (2) |
C4—C6—H6 | 109.6 | O7—C24—C21 | 119.0 (2) |
C8—C7—C6 | 110.0 (2) | C1—O1—Mg1i | 135.88 (18) |
C8—C7—H7A | 109.7 | C1—O2—Mg2iii | 141.11 (18) |
C6—C7—H7A | 109.7 | C12—O3—Mg2 | 92.54 (16) |
C8—C7—H7B | 109.7 | C12—O4—Mg1 | 152.84 (16) |
C6—C7—H7B | 109.7 | C12—O4—Mg2 | 88.41 (14) |
H7A—C7—H7B | 108.2 | Mg1—O4—Mg2 | 118.67 (9) |
C7—C8—C3 | 109.6 (2) | C13—O5—Mg1 | 152.80 (16) |
C7—C8—C9 | 109.4 (2) | C13—O5—Mg2v | 88.52 (13) |
C3—C8—C9 | 109.3 (2) | Mg1—O5—Mg2v | 118.65 (8) |
C7—C8—H8 | 109.5 | C13—O6—Mg2v | 92.88 (15) |
C3—C8—H8 | 109.5 | C24—O7—Mg1ii | 135.40 (19) |
C9—C8—H8 | 109.5 | C24—O8—Mg2ii | 141.77 (19) |
C8—C9—C11 | 109.8 (2) | O2iii—Mg2—O6iv | 155.94 (9) |
C8—C9—H9A | 109.7 | O8ii—Mg2—O3 | 156.07 (9) |
C11—C9—H9A | 109.7 | O4—Mg2—O5iv | 165.66 (8) |
C8—C9—H9B | 109.7 | O8ii—Mg2—C12 | 126.99 (9) |
C11—C9—H9B | 109.7 | O2iii—Mg2—C12 | 89.87 (9) |
H9A—C9—H9B | 108.2 | O6iv—Mg2—C12 | 103.79 (8) |
C6—C10—C11 | 110.2 (2) | O3—Mg2—C12 | 29.61 (7) |
C6—C10—H10A | 109.6 | O4—Mg2—C12 | 31.23 (7) |
C11—C10—H10A | 109.6 | O5iv—Mg2—C12 | 138.13 (8) |
C6—C10—H10B | 109.6 | O8ii—Mg2—C13iv | 90.58 (9) |
C11—C10—H10B | 109.6 | O2iii—Mg2—C13iv | 127.17 (9) |
H10A—C10—H10B | 108.1 | O6iv—Mg2—C13iv | 29.53 (7) |
C12—C11—C10 | 110.42 (19) | O3—Mg2—C13iv | 103.87 (8) |
C12—C11—C9 | 110.60 (19) | O4—Mg2—C13iv | 137.56 (8) |
C10—C11—C9 | 110.1 (2) | O5iv—Mg2—C13iv | 31.17 (7) |
C12—C11—C5 | 108.78 (19) | C12—Mg2—C13iv | 125.61 (8) |
C10—C11—C5 | 108.1 (2) | O8ii—Mg2—Mg1 | 67.01 (6) |
C9—C11—C5 | 108.76 (19) | O2iii—Mg2—Mg1 | 95.26 (7) |
O3—C12—O4 | 117.9 (2) | O6iv—Mg2—Mg1 | 108.69 (6) |
O3—C12—C11 | 122.1 (2) | O3—Mg2—Mg1 | 89.51 (5) |
O4—C12—C11 | 120.1 (2) | O4—Mg2—Mg1 | 28.79 (5) |
O3—C12—Mg2 | 57.84 (13) | O5iv—Mg2—Mg1 | 158.50 (6) |
O4—C12—Mg2 | 60.36 (12) | C12—Mg2—Mg1 | 60.01 (6) |
C11—C12—Mg2 | 173.50 (17) | C13iv—Mg2—Mg1 | 134.81 (6) |
O6—C13—O5 | 117.6 (2) | O8ii—Mg2—Mg1iv | 94.73 (7) |
O6—C13—C14 | 122.2 (2) | O2iii—Mg2—Mg1iv | 67.30 (6) |
O5—C13—C14 | 120.2 (2) | O6iv—Mg2—Mg1iv | 89.38 (5) |
O6—C13—Mg2v | 57.60 (13) | O3—Mg2—Mg1iv | 108.98 (6) |
O5—C13—Mg2v | 60.31 (12) | O4—Mg2—Mg1iv | 159.29 (6) |
C14—C13—Mg2v | 173.55 (17) | O5iv—Mg2—Mg1iv | 28.80 (5) |
C13—C14—C17 | 110.6 (2) | C12—Mg2—Mg1iv | 135.26 (6) |
C13—C14—C15 | 110.06 (19) | C13iv—Mg2—Mg1iv | 59.96 (6) |
C17—C14—C15 | 109.9 (2) | Mg1—Mg2—Mg1iv | 153.78 (4) |
C13—C14—C16 | 108.55 (19) | O7ii—Mg1—Mg2 | 72.41 (6) |
C17—C14—C16 | 108.59 (19) | O1i—Mg1—Mg2 | 123.81 (7) |
C15—C14—C16 | 109.10 (19) | O4—Mg1—Mg2 | 32.54 (5) |
C14—C15—C22 | 109.5 (2) | O5—Mg1—Mg2 | 126.52 (6) |
C14—C15—H15A | 109.8 | O7ii—Mg1—Mg2v | 124.43 (7) |
C22—C15—H15A | 109.8 | O1i—Mg1—Mg2v | 71.99 (6) |
C14—C15—H15B | 109.8 | O4—Mg1—Mg2v | 126.12 (6) |
C22—C15—H15B | 109.8 | O5—Mg1—Mg2v | 32.54 (5) |
H15A—C15—H15B | 108.2 | Mg2—Mg1—Mg2v | 153.78 (4) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) x+1, y, z; (v) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mg2(C12H14O4)2] |
Mr | 246.5 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.9034 (2), 11.3549 (4), 15.3196 (6) |
α, β, γ (°) | 70.713 (4), 83.131 (3), 89.141 (3) |
V (Å3) | 1124.95 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.3 × 0.1 × 0.05 |
Data collection | |
Diffractometer | Oxford Xcalibur Atlas Gemini diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.979, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28700, 4605, 3157 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.154, 1.02 |
No. of reflections | 4605 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.28 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Burnett & Johnson, 1996) and CrystalMaker (Palmer, 2009).
Mg1—O1i | 1.922 (2) | Mg2—O3 | 2.116 (2) |
Mg1—O4 | 1.9443 (18) | Mg2—O4 | 2.1713 (17) |
Mg1—O5 | 1.9470 (18) | Mg2—O5iv | 2.1739 (17) |
Mg1—O7ii | 1.919 (2) | Mg2—O6iv | 2.1147 (19) |
Mg2—O2iii | 1.971 (2) | Mg2—O8ii | 1.969 (2) |
O1i—Mg1—O4 | 111.03 (9) | O3—Mg2—O4 | 60.72 (7) |
O1i—Mg1—O5 | 104.53 (8) | O3—Mg2—O5iv | 108.79 (7) |
O4—Mg1—O5 | 112.92 (8) | O5iv—Mg2—O6iv | 60.59 (7) |
O7ii—Mg1—O1i | 111.52 (10) | O6iv—Mg2—O3 | 92.72 (8) |
O7ii—Mg1—O4 | 104.95 (8) | O6iv—Mg2—O4 | 108.27 (7) |
O7ii—Mg1—O5 | 112.07 (9) | O8ii—Mg2—O2iii | 96.80 (11) |
O2iii—Mg2—O3 | 89.61 (9) | O8ii—Mg2—O4 | 95.76 (8) |
O2iii—Mg2—O4 | 93.73 (8) | O8ii—Mg2—O5iv | 93.49 (8) |
O2iii—Mg2—O5iv | 96.04 (8) | O8ii—Mg2—O6iv | 90.71 (9) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z; (iii) −x+1, −y, −z+1; (iv) x+1, y, z. |
Coordination polymers (CPs) or metal–organic frameworks (MOFs) (Cheetham et al., 2006) are a new class of material composed of extended arrays of metal centers, connected by organic linkers to form frameworks of various dimensionalities, tailored for specific uses such as gas storage (Murray et al., 2009), separation (Li et al., 2009), catalysis (Ma et al., 2009) and luminescence (Allendorf et al., 2009). A wide range of metal centers is used to construct MOFs or CPs. First-row transition metals are popular choices because of their well known bonding interactions with the functional groups of organic linkers. The application of alkali and alkaline earth metals to form MOFs or CPs is limited, however. The use of s-block metal centers to construct frameworks offers several advantages. Porous frameworks based on early s-block metals can provide gravimetric advantages for gas-storage applications due to the low atomic weight metal centers (Dinca & Long, 2005; Abrahams et al., 2010). In addition, nontoxic frameworks based on s-block metals (Na, K, Mg and Ca) have potential uses in biological applications (Imaz et al., 2011).
Apart from metal centers, the choice of organic linkers is critical for varying the coordination behavior of metal ions and determining the overall characteristics of the framework. For example, adamantanedicarboxylate linkers are used to form various framework topologies with first-row transition metals, lanthanides and actinides (Nazarenko et al., 2010; Nielsen et al., 2008; Millange et al., 2004; Ok & O'Hare, 2008; Xu et al., 2006). Our group is currently investigating the structure type and functionalities of different frameworks formed using s-block metal centers (Li, Mg and Ca) for potential use as gas-storage media (Banerjee et al., 2010, 2011).
In this work, we report the first example of a magnesium–adamantane-1,3-dicarboxylate [Mg(1,3-ADA)] layered polymer, namely poly[(µ4-adamantane-1,3-dicarboxylato)magnesium], (I), prepared under solvothermal conditions. Compound (I) crystallizes in the triclinic space group P1 with an asymmetric unit comprising two MgII ions and two complete dianionic 1,3-ADA2- ligands (Fig. 1). There are two types of crystallographically independent Mg site, viz. Mg1 with a tetrahedral MgO4 environment and Mg2 with a distorted octahedral MgO6 environment.
Atom Mg1 is coordinated to four bridging bidentate 1,3-ADA2- ligands, with Mg—O bond lengths and internal O—Mg—O angles of 1.919 (2)–1.947 (2) Å and 104.53 (8)–112.92 (8)°, respectively (Table 1). Tetrahedral coordination of magnesium is well established in magnesium-based organometallic compounds (Cambridge Structural Database, Version 5.32, update of November 2010; Allen 2002), but to the best of our knowledge this is the first time that such coordination has been seen in a magnesium-based polymer. Atom Mg2 is also coordinated by four 1,3-ADA2- ligands, where two of these act as bidentate chelating ligands donating four O atoms [O3, O4, O5iv and O6iv; symmetry code: (iv) x + 1, y, z] which occupy two axial and two equatorial sites. The other equatorial O atoms [O2iii and O8ii; symmetry codes: (iii) -x + 1, -y, -z + 3; (ii) -x + 1, -y, -z + 2] are donated by two different bridging bidentate 1,3-ADA2- ligands. The coordination octahedron is highly distorted, with two narrow O—Mg—O angles [O3—Mg2—O4 = 60.72 (7)° and O5iv—Mg2—O6iv = 60.59 (7)°; symmetry code: (iv) x + 1, y, z] from chelating carboxylate groups (Table 1). The Mg2—O bond lengths lie in the range 1.969 (2)–2.174 (2) Å.
Atoms O4 and O5 bridge adjacent Mg1 and Mg2 centers, leading to the formation of ···Mg1···Mg2···Mg1··· chains running parallel to the a axis (Fig. 2); the Mg1···Mg2 and Mg2···Mg1iv [symmetry code: (iv) x + 1, y, z] distances are 3.5419 (11) and 3.5463 (11) Å, respectively. The Mg1···Mg2 chains are crosslinked by 1,3-ADA2- ligands. The carboxylate groups of the 1,3-ADA2- linkers display two different coordination behaviors, bidentate-chelating (O3/O4 and O5/O6) and bidentate-bridging (O1/O2 and O7/O8) (Fig. 1), with atoms O4 and O5 shared between atoms Mg1 and Mg2. Hence, each of the organic linkers connects four metal ions to produce two-dimensional layers in the ac plane (Fig. 3).