Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038408/sj2322sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038408/sj2322Isup2.hkl |
CCDC reference: 660241
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.059
- wR factor = 0.171
- Data-to-parameter ratio = 13.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT242_ALERT_2_B Check Low Ueq as Compared to Neighbors for C9
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.87 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.45 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for C9 - C10 .. 5.01 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C9 - C11 .. 5.46 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.21 PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.855(10) ...... 3.00 su-Ra O1 -H1O 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.85(4), Rep 0.859(10) ...... 4.00 su-Ra O3 -H3O 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.85(3), Rep 0.860(10) ...... 3.00 su-Ra O1 -H1O 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.85(4), Rep 0.860(10) ...... 4.00 su-Ra O3 -H3O 1.555 1.555 PLAT736_ALERT_1_C H...A Calc 1.76(3), Rep 1.750(10) ...... 3.00 su-Ra H1O -O2 1.555 3.556 PLAT736_ALERT_1_C H...A Calc 1.74(4), Rep 1.730(10) ...... 4.00 su-Ra H3O -O4 1.555 3.766
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For the microporous nickel derivative of 5-tert-butyl-1,3-benzenedicarboxylic acid, see Ma et al. (2007), and for the microporous copper derivative, see Pan et al. (2006).
The compound was returned unchanged in an attempt to synthesize the copper derivative. 5-tert-Butyl-benzene-1,3-dicarboxylic acid (0.5 mmol) was dissolved in DMF (5 ml); the solution was layered over silica gel (5 ml) containing copper nitrate (0.5 mmol). Colorless crystals were found at the interface between the solution and the gel after several days.
H atoms were placed in calculated positions (C–H 0.93 – 0.96 Å) and were included in the refinement, with Uiso(H) set to 1.2 - 1.5 Ueq(C). The H atoms of the carboxylate OH groups were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.85±0.01 Å; their temperature factors were freely refined.
The nickel (Ma et al., 2007) and zinc (Pan et al., 2006) derivatives of 5-tertbutyl-1,3-benzenedicarboxylic acid have a microporous framework and can be used for gas separation. Attempt to synthesize a similar copper derivative returned the starting reactants. In the crystal structure, the carboxy –CO2H groups are linked across different centers-of-inversion by O–H···O hydrogen bonds. Because the groups are at the 1,3-positions, the resulting chain adopts a zigzag motif.
For the microporous nickel derivative of 5-tert-butyl-1,3-benzenedicarboxylic acid, see Ma et al. (2007), and for the microporous copper derivative, see Pan et al. (2006).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
C12H14O4 | F(000) = 472 |
Mr = 222.23 | Dx = 1.252 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1901 reflections |
a = 6.2917 (5) Å | θ = 2.4–25.5° |
b = 10.5847 (9) Å | µ = 0.09 mm−1 |
c = 17.838 (2) Å | T = 293 K |
β = 97.137 (1)° | Block, colorless |
V = 1178.7 (2) Å3 | 0.40 × 0.34 × 0.20 mm |
Z = 4 |
Bruker APEX diffractometer | 1711 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
φ and ω scans | h = −7→7 |
5746 measured reflections | k = −9→12 |
2055 independent reflections | l = −20→21 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0745P)2 + 0.4202P] where P = (Fo2 + 2Fc2)/3 |
2055 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.21 e Å−3 |
2 restraints | Δρmin = −0.19 e Å−3 |
C12H14O4 | V = 1178.7 (2) Å3 |
Mr = 222.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.2917 (5) Å | µ = 0.09 mm−1 |
b = 10.5847 (9) Å | T = 293 K |
c = 17.838 (2) Å | 0.40 × 0.34 × 0.20 mm |
β = 97.137 (1)° |
Bruker APEX diffractometer | 1711 reflections with I > 2σ(I) |
5746 measured reflections | Rint = 0.019 |
2055 independent reflections |
R[F2 > 2σ(F2)] = 0.059 | 2 restraints |
wR(F2) = 0.171 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2055 reflections | Δρmin = −0.19 e Å−3 |
156 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.1901 (3) | 0.11648 (18) | 0.51399 (10) | 0.0684 (6) | |
H1O | 0.089 (5) | 0.084 (4) | 0.535 (2) | 0.152 (17)* | |
O2 | 0.1249 (3) | −0.02278 (17) | 0.42164 (9) | 0.0663 (5) | |
O3 | 0.7687 (3) | 0.41928 (19) | 0.51110 (10) | 0.0748 (6) | |
H3O | 0.842 (7) | 0.482 (3) | 0.530 (3) | 0.18 (2)* | |
O4 | 0.9974 (3) | 0.39797 (17) | 0.42778 (9) | 0.0648 (5) | |
C1 | 0.2288 (3) | 0.0675 (2) | 0.45294 (12) | 0.0473 (5) | |
C2 | 0.4090 (3) | 0.1196 (2) | 0.41733 (11) | 0.0447 (5) | |
C3 | 0.4595 (3) | 0.0712 (2) | 0.35009 (12) | 0.0470 (5) | |
H3 | 0.3767 | 0.0058 | 0.3272 | 0.056* | |
C4 | 0.6285 (3) | 0.1162 (2) | 0.31544 (11) | 0.0456 (5) | |
C5 | 0.7481 (3) | 0.2123 (2) | 0.35179 (11) | 0.0441 (5) | |
H5 | 0.8647 | 0.2441 | 0.3305 | 0.053* | |
C6 | 0.6994 (3) | 0.26268 (19) | 0.41898 (11) | 0.0423 (5) | |
C7 | 0.5287 (3) | 0.2176 (2) | 0.45191 (11) | 0.0453 (5) | |
H7 | 0.4942 | 0.2525 | 0.4967 | 0.054* | |
C8 | 0.8324 (3) | 0.3665 (2) | 0.45451 (11) | 0.0466 (5) | |
C9 | 0.6793 (4) | 0.0612 (2) | 0.24053 (13) | 0.0573 (7) | |
C10 | 0.7336 (7) | −0.0771 (3) | 0.2514 (2) | 0.1065 (12) | |
H10A | 0.7691 | −0.1118 | 0.2049 | 0.160* | |
H10B | 0.6125 | −0.1212 | 0.2665 | 0.160* | |
H10C | 0.8536 | −0.0861 | 0.2899 | 0.160* | |
C11 | 0.4867 (5) | 0.0735 (4) | 0.18159 (16) | 0.0911 (10) | |
H11A | 0.5203 | 0.0400 | 0.1345 | 0.137* | |
H11B | 0.4484 | 0.1610 | 0.1753 | 0.137* | |
H11C | 0.3688 | 0.0274 | 0.1975 | 0.137* | |
C12 | 0.8677 (6) | 0.1269 (4) | 0.2130 (2) | 0.1218 (17) | |
H12A | 0.8957 | 0.0899 | 0.1661 | 0.183* | |
H12B | 0.9916 | 0.1175 | 0.2498 | 0.183* | |
H12C | 0.8358 | 0.2150 | 0.2056 | 0.183* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0706 (12) | 0.0808 (13) | 0.0595 (10) | −0.0314 (10) | 0.0312 (9) | −0.0120 (9) |
O2 | 0.0623 (10) | 0.0750 (12) | 0.0641 (10) | −0.0342 (9) | 0.0181 (8) | −0.0107 (9) |
O3 | 0.0834 (13) | 0.0877 (14) | 0.0602 (11) | −0.0446 (11) | 0.0361 (9) | −0.0355 (10) |
O4 | 0.0670 (11) | 0.0749 (12) | 0.0576 (10) | −0.0362 (9) | 0.0280 (8) | −0.0205 (8) |
C1 | 0.0475 (12) | 0.0528 (13) | 0.0425 (11) | −0.0120 (10) | 0.0092 (9) | −0.0007 (10) |
C2 | 0.0432 (11) | 0.0475 (12) | 0.0444 (11) | −0.0096 (9) | 0.0094 (9) | 0.0012 (9) |
C3 | 0.0449 (11) | 0.0465 (12) | 0.0500 (12) | −0.0112 (9) | 0.0082 (9) | −0.0087 (9) |
C4 | 0.0446 (11) | 0.0498 (13) | 0.0435 (11) | −0.0068 (9) | 0.0096 (9) | −0.0086 (9) |
C5 | 0.0419 (11) | 0.0494 (12) | 0.0427 (11) | −0.0090 (9) | 0.0117 (8) | −0.0036 (9) |
C6 | 0.0456 (11) | 0.0442 (11) | 0.0381 (10) | −0.0093 (9) | 0.0092 (8) | −0.0015 (9) |
C7 | 0.0484 (11) | 0.0491 (13) | 0.0402 (10) | −0.0092 (9) | 0.0123 (9) | −0.0041 (9) |
C8 | 0.0536 (12) | 0.0514 (13) | 0.0369 (10) | −0.0163 (10) | 0.0140 (9) | −0.0044 (9) |
C9 | 0.0530 (13) | 0.0671 (16) | 0.0542 (13) | −0.0117 (11) | 0.0161 (10) | −0.0250 (11) |
C10 | 0.132 (3) | 0.092 (2) | 0.098 (2) | 0.028 (2) | 0.023 (2) | −0.036 (2) |
C11 | 0.087 (2) | 0.132 (3) | 0.0554 (16) | 0.0004 (19) | 0.0119 (14) | −0.0316 (18) |
C12 | 0.106 (2) | 0.179 (4) | 0.093 (2) | −0.068 (3) | 0.066 (2) | −0.080 (3) |
O1—C1 | 1.257 (3) | C6—C7 | 1.372 (3) |
O1—H1O | 0.855 (10) | C6—C8 | 1.476 (3) |
O2—C1 | 1.250 (3) | C7—H7 | 0.9300 |
O3—C8 | 1.261 (3) | C9—C12 | 1.508 (4) |
O3—H3O | 0.859 (10) | C9—C11 | 1.508 (4) |
O4—C8 | 1.241 (2) | C9—C10 | 1.510 (4) |
C1—C2 | 1.474 (3) | C10—H10A | 0.9600 |
C2—C3 | 1.377 (3) | C10—H10B | 0.9600 |
C2—C7 | 1.382 (3) | C10—H10C | 0.9600 |
C3—C4 | 1.379 (3) | C11—H11A | 0.9600 |
C3—H3 | 0.9300 | C11—H11B | 0.9600 |
C4—C5 | 1.379 (3) | C11—H11C | 0.9600 |
C4—C9 | 1.527 (3) | C12—H12A | 0.9600 |
C5—C6 | 1.380 (3) | C12—H12B | 0.9600 |
C5—H5 | 0.9300 | C12—H12C | 0.9600 |
C1—O1—H1O | 117 (3) | O3—C8—C6 | 116.99 (18) |
C8—O3—H3O | 117 (3) | C12—C9—C11 | 109.2 (3) |
O2—C1—O1 | 123.7 (2) | C12—C9—C10 | 108.3 (3) |
O2—C1—C2 | 118.8 (2) | C11—C9—C10 | 108.8 (3) |
O1—C1—C2 | 117.47 (19) | C12—C9—C4 | 111.58 (19) |
C3—C2—C7 | 119.74 (19) | C11—C9—C4 | 109.9 (2) |
C3—C2—C1 | 120.62 (19) | C10—C9—C4 | 109.0 (2) |
C7—C2—C1 | 119.63 (19) | C9—C10—H10A | 109.5 |
C2—C3—C4 | 122.41 (19) | C9—C10—H10B | 109.5 |
C2—C3—H3 | 118.8 | H10A—C10—H10B | 109.5 |
C4—C3—H3 | 118.8 | C9—C10—H10C | 109.5 |
C5—C4—C3 | 116.75 (19) | H10A—C10—H10C | 109.5 |
C5—C4—C9 | 122.10 (19) | H10B—C10—H10C | 109.5 |
C3—C4—C9 | 121.15 (19) | C9—C11—H11A | 109.5 |
C4—C5—C6 | 121.75 (18) | C9—C11—H11B | 109.5 |
C4—C5—H5 | 119.1 | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 119.1 | C9—C11—H11C | 109.5 |
C7—C6—C5 | 120.50 (18) | H11A—C11—H11C | 109.5 |
C7—C6—C8 | 120.47 (18) | H11B—C11—H11C | 109.5 |
C5—C6—C8 | 119.02 (17) | C9—C12—H12A | 109.5 |
C6—C7—C2 | 118.82 (19) | C9—C12—H12B | 109.5 |
C6—C7—H7 | 120.6 | H12A—C12—H12B | 109.5 |
C2—C7—H7 | 120.6 | C9—C12—H12C | 109.5 |
O4—C8—O3 | 123.57 (19) | H12A—C12—H12C | 109.5 |
O4—C8—C6 | 119.44 (18) | H12B—C12—H12C | 109.5 |
O2—C1—C2—C3 | 1.1 (3) | C8—C6—C7—C2 | −179.47 (19) |
O1—C1—C2—C3 | −179.5 (2) | C3—C2—C7—C6 | −1.5 (3) |
O2—C1—C2—C7 | −178.6 (2) | C1—C2—C7—C6 | 178.25 (19) |
O1—C1—C2—C7 | 0.8 (3) | C7—C6—C8—O4 | 173.3 (2) |
C7—C2—C3—C4 | 0.6 (3) | C5—C6—C8—O4 | −7.3 (3) |
C1—C2—C3—C4 | −179.1 (2) | C7—C6—C8—O3 | −7.1 (3) |
C2—C3—C4—C5 | 0.6 (3) | C5—C6—C8—O3 | 172.3 (2) |
C2—C3—C4—C9 | −179.5 (2) | C5—C4—C9—C12 | −1.2 (4) |
C3—C4—C5—C6 | −1.0 (3) | C3—C4—C9—C12 | 178.9 (3) |
C9—C4—C5—C6 | 179.1 (2) | C5—C4—C9—C11 | −122.5 (3) |
C4—C5—C6—C7 | 0.1 (3) | C3—C4—C9—C11 | 57.6 (3) |
C4—C5—C6—C8 | −179.27 (19) | C5—C4—C9—C10 | 118.4 (3) |
C5—C6—C7—C2 | 1.1 (3) | C3—C4—C9—C10 | −61.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.86 (1) | 1.75 (1) | 2.606 (2) | 178 (4) |
O3—H3O···O4ii | 0.86 (1) | 1.73 (1) | 2.588 (2) | 176 (5) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H14O4 |
Mr | 222.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.2917 (5), 10.5847 (9), 17.838 (2) |
β (°) | 97.137 (1) |
V (Å3) | 1178.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.34 × 0.20 |
Data collection | |
Diffractometer | Bruker APEX |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5746, 2055, 1711 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.171, 1.05 |
No. of reflections | 2055 |
No. of parameters | 156 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.19 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O2i | 0.86 (1) | 1.75 (1) | 2.606 (2) | 178 (4) |
O3—H3O···O4ii | 0.86 (1) | 1.73 (1) | 2.588 (2) | 176 (5) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+2, −y+1, −z+1. |
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The nickel (Ma et al., 2007) and zinc (Pan et al., 2006) derivatives of 5-tertbutyl-1,3-benzenedicarboxylic acid have a microporous framework and can be used for gas separation. Attempt to synthesize a similar copper derivative returned the starting reactants. In the crystal structure, the carboxy –CO2H groups are linked across different centers-of-inversion by O–H···O hydrogen bonds. Because the groups are at the 1,3-positions, the resulting chain adopts a zigzag motif.