The crystal structures of 2,6-naphthalenedicarboxylic acid (NDA) and dimethyl 2,6-naphthalenedicarboxylate (NDC) have been solved ab initio using a combination of X-ray powder diffraction and computational chemistry techniques. These two crystal structures, and that of 2,6-dimethylnaphthalene (DMN), have been refined by the Rietveld technique. DMN crystallizes in the orthorhombic space group Pbca, with a = 7.4544 (4), b = 6.0826 (6), c = 20.0946 (12) Å, V = 911.1 (1) Å3 and Z = 4. The structure consists of a herringbone stacking parallel to a, resulting in loosely bound layers perpendicular to c. NDA crystallizes in the triclinic space group P1, with a = 3.7061 (8), b = 7.4688 (14), c = 8.5352 (22) Å, α = 86.62 (2), β = 85.49 (2), γ = 87.99 (2)°, V = 235.00 (6) Å3 and Z = 1. The structure consists of loosely packed hydrogen-bonded chains along [111]. NDC crystallizes in the monoclinic space group P21/c, with a = 13.41931 (14), b = 6.14869 (5), c = 7.15257 (5) Å, β = 100.400 (1)°, V = 580.47 (1) Å3 at 300 K and Z = 2. The structure consists of layers of NDC molecules perpendicular to a. The ester group is twisted 20° out of the mean ring plane in NDC. The conformations of the carboxyl groups in NDA and NDC differ. MP2 calculations suggest that the observed twist in NDC corresponds to an increase in conformational energy of 9 kJ mol−1.
Supporting information
| Crystallographic Information File (CIF) Contains datablocks text, dmn, nda, ndc |
| Rietveld powder data file (CIF format) Contains datablocks kadu216, _overall, KADU216_phase_1, KADU216_phase_2, KADU216_phase_3 |
| Rietveld powder data file (CIF format) Contains datablocks edlu06, _overall, EDLU06_phase_1 |
| Rietveld powder data file (CIF format) Contains datablocks publ, _overall, YMC_phase_1, YMC_phase_2 |
CCDC references: 131744; 131745; 131746
Crystal data top
C12H12 | c = 20.0946 (12) Å |
Mr = 156 | V = 911.12 (11) Å3 |
Orthorhombic, Pbca | Z = 4 |
Hall symbol: -P 2ac 2ab | Cu radiation, λ = 1.5406 Å |
a = 7.4544 (4) Å | × × mm |
b = 6.0826 (6) Å | |
Crystal data top
C12H12 | c = 20.0946 (12) Å |
Mr = 156 | V = 911.12 (11) Å3 |
Orthorhombic, Pbca | Z = 4 |
a = 7.4544 (4) Å | Cu radiation, λ = 1.5406 Å |
b = 6.0826 (6) Å | × × mm |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.0747 (7) | −0.2245 (5) | 0.05524 (16) | 0.0327 (14) | |
C2 | 0.0291 (7) | −0.1401 (7) | 0.11735 (10) | 0.0327 (14) | |
C3 | −0.0501 (8) | 0.0665 (7) | 0.12223 (11) | 0.0327 (14) | |
C4 | −0.0836 (5) | 0.1887 (5) | 0.06499 (17) | 0.0327 (14) | |
C5 | −0.0379 (8) | 0.1043 (6) | 0.00288 (12) | 0.0327 (14) | |
C6 | 0.0691 (9) | −0.2765 (11) | 0.1796 (2) | 0.0327 (14) | |
H1 | 0.13727 | −0.36194 | 0.05223 | 0.05 | |
H3 | −0.08499 | 0.12338 | 0.16486 | 0.05 | |
H4 | −0.14077 | 0.32956 | 0.06804 | 0.05 | |
H6a | 0.02582 | −0.19759 | 0.21882 | 0.05 | |
H6b | 0.00317 | −0.41330 | 0.17655 | 0.05 | |
H6c | 0.19233 | −0.30354 | 0.18314 | 0.05 | |
Geometric parameters (Å, º) top
C2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C6 | 1.530 (3) | C3—C4 | 1.392 |
C4—C5 | 1.392 | C5—C5i | 1.394 (4) |
C5—C1i | 1.405 (3) | | |
| | | |
C3—C2—C1 | 120 | C3—C2—C6 | 121.0 (3) |
C1—C2—C6 | 119.0 (3) | C2—C3—C4 | 120 |
C3—C4—C5 | 120 | C4—C5—C5i | 120.6 (1) |
C4—C5—C1i | 120.4 (2) | C5—C5i—C1 | 119.0 (2) |
C2—C1—C5i | 120.4 (2) | | |
Symmetry code: (i) −x, −y, −z. |
Crystal data top
C12H8O4 | α = 86.62 (2)° |
Mr = 216 | β = 85.49 (2)° |
Triclinic, P1 | γ = 87.99 (2)° |
Hall symbol: -P 1 | V = 235.00 (6) Å3 |
a = 3.7061 (8) Å | Z = 1 |
b = 7.4688 (14) Å | Cu radiation, λ = 1.5406 Å |
c = 8.535 (2) Å | × × mm |
Crystal data top
C12H8O4 | β = 85.49 (2)° |
Mr = 216 | γ = 87.99 (2)° |
Triclinic, P1 | V = 235.00 (6) Å3 |
a = 3.7061 (8) Å | Z = 1 |
b = 7.4688 (14) Å | Cu radiation, λ = 1.5406 Å |
c = 8.535 (2) Å | × × mm |
α = 86.62 (2)° | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.619 (5) | 0.2666 (5) | 0.5718 (10) | 0.05 | |
C2 | 0.663 (4) | 0.2945 (9) | 0.7289 (8) | 0.05 | |
C3 | 0.636 (4) | 0.4675 (12) | 0.7819 (6) | 0.05 | |
C4 | 0.564 (3) | 0.6126 (8) | 0.6779 (8) | 0.05 | |
C5 | 0.520 (5) | 0.5848 (5) | 0.5208 (9) | 0.05 | |
C7 | 0.763 (5) | 0.1425 (12) | 0.8485 (11) | 0.05 | |
O1 | 0.915 (4) | 0.0095 (13) | 0.8015 (12) | 0.05 | |
O2 | 0.889 (4) | 0.2036 (11) | 0.9812 (11) | 0.05 | |
H1 | 0.69502 | 0.15599 | 0.52971 | 0.08 | |
H2 | 0.9539 | 0.1334 | 1.0558 | 0.08 | |
H3 | 0.67204 | 0.49483 | 0.88873 | 0.08 | |
H4 | 0.54191 | 0.73661 | 0.71097 | 0.08 | |
Geometric parameters (Å, º) top
C2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C7 | 1.537 (6) | C1—C5i | 1.428 (7) |
C3—C4 | 1.392 | C4—C5 | 1.392 |
C5—C5i | 1.351 (8) | C7—O1 | 1.198 (9) |
C7—O2 | 1.366 (9) | | |
| | | |
C2—C1—C5i | 116.8 (5) | C1—C2—C3 | 120 |
C1—C2—C7 | 123.0 (5) | C3—C2—C7 | 116.9 (6) |
C2—C3—C4 | 120 | C3—C4—C5 | 120 |
C4—C5—C5i | 118.4 (5) | C4—C5—C1i | 120.3 (5) |
C2—C7—O1 | 119.0 (9) | C2—C7—O2 | 113.0 (9) |
O1—C7—O2 | 115.1 (9) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Crystal data top
C14H12O4 | c = 7.15257 (5) Å |
Mr = 244 | β = 100.400 (1)° |
Monoclinic, P21/c | V = 580.47 (1) Å3 |
Hall symbol: -P 2ybc | Z = 2 |
a = 13.41931 (14) Å | Synchrotron radiation, λ = 1.15023 Å |
b = 6.14869 (5) Å | × × mm |
Crystal data top
C14H12O4 | β = 100.400 (1)° |
Mr = 244 | V = 580.47 (1) Å3 |
Monoclinic, P21/c | Z = 2 |
a = 13.41931 (14) Å | Synchrotron radiation, λ = 1.15023 Å |
b = 6.14869 (5) Å | × × mm |
c = 7.15257 (5) Å | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | −0.1040 (2) | −0.1874 (4) | −0.1007 (5) | 0.018 (1) | |
C2 | −0.1894 (1) | −0.0634 (6) | −0.0889 (5) | 0.018 (1) | |
C3 | −0.1786 (2) | 0.1450 (6) | −0.0118 (5) | 0.018 (1) | |
C4 | −0.0824 (2) | 0.2294 (3) | 0.0536 (3) | 0.018 (1) | |
C5 | 0.0030 (2) | 0.1054 (5) | 0.0418 (6) | 0.018 (1) | |
C7 | −0.2961 (4) | −0.1447 (9) | −0.1564 (9) | 0.065 (1) | |
C8 | −0.3995 (5) | −0.4521 (8) | −0.2158 (9) | 0.065 (1) | |
O1 | −0.3679 (4) | −0.0283 (5) | −0.1824 (6) | 0.065 (1) | |
O2 | −0.2968 (4) | −0.3610 (6) | −0.1662 (6) | 0.065 (1) | |
H1 | −0.10988 | −0.32732 | −0.16292 | 0.08 | |
H3 | −0.23656 | 0.22009 | 0.00727 | 0.08 | |
H4 | −0.07469 | 0.36332 | 0.11918 | 0.08 | |
H8a | −0.39678 | −0.60428 | −0.22005 | 0.08 | |
H8b | −0.43334 | −0.40741 | −0.11185 | 0.08 | |
H8c | −0.43400 | −0.39121 | −0.33000 | 0.08 | |
Geometric parameters (Å, º) top
C2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C7 | 1.510 (5) | C3—C4 | 1.392 |
C4—C5 | 1.392 | C5—C5i | 1.423 (5) |
C5—C1i | 1.436 (4) | C7—O1 | 1.188 (5) |
C7—O2 | 1.332 (5) | O2—C8 | 1.470 (5) |
| | | |
C1—C2—C3 | 120 | C1—C2—C7 | 122.9 (2) |
C3—C2—C7 | 117.1 (2) | C2—C3—C4 | 120 |
C3—C4—C5 | 120 | C4—C5—C5i | 122.6 (1) |
C4—C5—C1i | 122.3 (3) | C1i—C5—C5i | 114.9 (3) |
C2—C1—C5i | 122.3 (2) | C2—C7—O1 | 123.1 (5) |
C2—C7—O2 | 110.2 (5) | O1—C7—O2 | 126.5 (5) |
C7—O2—C8 | 113.0 (5) | | |
Symmetry code: (i) −x, −y, −z. |
Experimental details
| (dmn) | (nda) | (ndc) |
Crystal data |
Chemical formula | C12H12 | C12H8O4 | C14H12O4 |
Mr | 156 | 216 | 244 |
Crystal system, space group | Orthorhombic, Pbca | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | ? | ? | ? |
a, b, c (Å) | 7.4544 (4), 6.0826 (6), 20.0946 (12) | 3.7061 (8), 7.4688 (14), 8.535 (2) | 13.41931 (14), 6.14869 (5), 7.15257 (5) |
α, β, γ (°) | 90, 90, 90 | 86.62 (2), 85.49 (2), 87.99 (2) | 90, 100.400 (1), 90 |
V (Å3) | 911.12 (11) | 235.00 (6) | 580.47 (1) |
Z | 4 | 1 | 2 |
Radiation type | Cu, λ = 1.5406 Å | Cu, λ = 1.5406 Å | Synchrotron, λ = 1.15023 Å |
µ (mm−1) | ? | ? | ? |
Crystal size (mm) | × × | × × | × × |
|
Data collection |
Diffractometer | ? | ? | ? |
Absorption correction | ? | ? | ? |
No. of measured, independent and observed (?) reflections | ?, ?, ? | ?, ?, ? | ?, ?, ? |
Rint | ? | ? | ? |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | ?, ?, ? | ?, ?, ? | ?, ?, ? |
No. of reflections | ? | ? | ? |
No. of parameters | ? | ? | ? |
No. of restraints | ? | ? | ? |
Δρmax, Δρmin (e Å−3) | ?, ? | ?, ? | ?, ? |
Selected geometric parameters (Å, º) for (dmn) topC2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C6 | 1.530 (3) | C3—C4 | 1.392 |
C4—C5 | 1.392 | C5—C5i | 1.394 (4) |
C5—C1i | 1.405 (3) | | |
| | | |
C3—C2—C1 | 120 | C3—C2—C6 | 121.0 (3) |
C1—C2—C6 | 119.0 (3) | C2—C3—C4 | 120 |
C3—C4—C5 | 120 | C4—C5—C5i | 120.6 (1) |
C4—C5—C1i | 120.4 (2) | C5—C5i—C1 | 119.0 (2) |
C2—C1—C5i | 120.4 (2) | | |
Symmetry code: (i) −x, −y, −z. |
Selected geometric parameters (Å, º) for (nda) topC2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C7 | 1.537 (6) | C1—C5i | 1.428 (7) |
C3—C4 | 1.392 | C4—C5 | 1.392 |
C5—C5i | 1.351 (8) | C7—O1 | 1.198 (9) |
C7—O2 | 1.366 (9) | | |
| | | |
C2—C1—C5i | 116.8 (5) | C1—C2—C3 | 120 |
C1—C2—C7 | 123.0 (5) | C3—C2—C7 | 116.9 (6) |
C2—C3—C4 | 120 | C3—C4—C5 | 120 |
C4—C5—C5i | 118.4 (5) | C4—C5—C1i | 120.3 (5) |
C2—C7—O1 | 119.0 (9) | C2—C7—O2 | 113.0 (9) |
O1—C7—O2 | 115.1 (9) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (ndc) topC2—C1 | 1.392 | C2—C3 | 1.392 |
C2—C7 | 1.510 (5) | C3—C4 | 1.392 |
C4—C5 | 1.392 | C5—C5i | 1.423 (5) |
C5—C1i | 1.436 (4) | C7—O1 | 1.188 (5) |
C7—O2 | 1.332 (5) | O2—C8 | 1.470 (5) |
| | | |
C1—C2—C3 | 120 | C1—C2—C7 | 122.9 (2) |
C3—C2—C7 | 117.1 (2) | C2—C3—C4 | 120 |
C3—C4—C5 | 120 | C4—C5—C5i | 122.6 (1) |
C4—C5—C1i | 122.3 (3) | C1i—C5—C5i | 114.9 (3) |
C2—C1—C5i | 122.3 (2) | C2—C7—O1 | 123.1 (5) |
C2—C7—O2 | 110.2 (5) | O1—C7—O2 | 126.5 (5) |
C7—O2—C8 | 113.0 (5) | | |
Symmetry code: (i) −x, −y, −z. |