5-tert-Butyl­benzene-1,3-dicarboxylic acid

In the crystal structure of the title compound, C₁₂H₁₄O₄, the carb­oxy groups are linked across centers of inversion by O—H...O hydrogen bonds; the resulting hydrogen-bonded chain adopts a zigzag motif.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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.

Related literature

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).

S2. Experimental

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.

S3. Refinement

H atoms were placed in calculated positions (C–H 0.93 – 0.96 Å) and were included in the refinement, with U_iso(H) set to 1.2 - 1.5 U_eq(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.

Computing details

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).

Figures

Fig. 1. Thermal ellipsoid plot of the hydrogen-bonded chain structure. The hydrogen bonds are shown as dashed lines. Ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radius.

5-tert-Butylbenzene-1,3-dicarboxylic acid

Crystal data

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) Å^3	0.40 × 0.34 × 0.20 mm
Z = 4

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0745P)^2 + 0.4202P] where P = (Fo^2 + 2Fc^2)/3
2055 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.21 e Å^−3
2 restraints	Δρmin = −0.19 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2^i	0.86 (1)	1.75 (1)	2.606 (2)	178 (4)
O3—H3O···O4^ii	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.