Acta Cryst. (2010). E66, o2622 [ doi:10.1107/S1600536810037608 ]
A new type of naphthalene-1,8-dicarboxylic anhydride, C12H6O3, was synthesized hydrothermally. Unlike the two previously reported polymorphs, which crystallize in the orthorhombic space groups P212121 [Shok et al. (1971). Kristallografiya, 16, 500-502; Grigor'eva & Chetkina (1975). Kristallografiya, 20, 1289-1290] and Pbca [Shok & Gol'der (1970). Zh. Strukt. Khim. 11, 939-940], this present structure crystallizes in the monoclinic space group P21/c. In this structure, the planar [total puckering amplitude Q = 0.0362 (15)] molecules lie parallel to each other along the a axis.
Yellow prism-shaped single crystals of Naphthalene-1,8-dicarboxylic acid anhydride were initially obtained in our attempt to prepare metal-organic coordination polymers of 1,8-NDC associated with molybdate. A mixture of 3 mmol of MoO3, 2 mmol of Mn(Ac)2, 2.0 mmol KOH and 1.5 mmol of Naphthalene-1,8-dicarboxylic anhydride, was sealed in a 25 ml Teflonlined bomb at 160°C for 5 days and then cooled to room temperature. A few single crystals suitable for X-ray diffraction analysis were obtained.
All of the H atoms were treated as riding atoms with distances C—H = 0.93 Å (CH), and Uiso(H) = 1.2 Ueq(C). The final refinement show that the highest peak in the difference electron density map equals to 0.18 e/Å3 at the distance of 0.65 Å from C5 while the deepest hole equals to -0.17 e/Å3 at the distance of 0.61 Å from C1.
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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./hg2709fig1thm.gif)
| Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. [Symmetry code: x, y, z] |
![[Figure 2]](./hg2709fig2thm.gif)
| Fig. 2. A packing diagram of the title compound viewed down the a–axis. |
| C12H6O3 | F(000) = 408 |
| Mr = 198.17 | Dx = 1.526 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1938 reflections |
| a = 3.7687 (1) Å | θ = 2.6–27.9° |
| b = 14.5269 (3) Å | µ = 0.11 mm−1 |
| c = 15.8083 (3) Å | T = 296 K |
| β = 94.752 (2)° | Prism, yellow |
| V = 862.49 (3) Å3 | 0.20 × 0.10 × 0.10 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 1964 independent reflections |
| Radiation source: fine-focus sealed tube | 1201 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| ω scans | θmax = 27.5°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −4→4 |
| Tmin = 0.875, Tmax = 0.982 | k = −17→18 |
| 7560 measured reflections | l = −20→20 |
| 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.131 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0732P)2] where P = (Fo2 + 2Fc2)/3 |
| 1964 reflections | (Δ/σ)max < 0.001 |
| 136 parameters | Δρmax = 0.18 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C12H6O3 | V = 862.49 (3) Å3 |
| Mr = 198.17 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 3.7687 (1) Å | µ = 0.11 mm−1 |
| b = 14.5269 (3) Å | T = 296 K |
| c = 15.8083 (3) Å | 0.20 × 0.10 × 0.10 mm |
| β = 94.752 (2)° |
| Bruker APEXII CCD diffractometer | 1964 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1201 reflections with I > 2σ(I) |
| Tmin = 0.875, Tmax = 0.982 | Rint = 0.027 |
| 7560 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.131 | Δρmax = 0.18 e Å−3 |
| S = 1.00 | Δρmin = −0.17 e Å−3 |
| 1964 reflections | Absolute structure: ? |
| 136 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| C5 | 0.3898 (4) | 0.64036 (9) | 0.28567 (8) | 0.0399 (4) | |
| C1 | 0.2469 (4) | 0.64100 (10) | 0.19687 (9) | 0.0486 (4) | |
| C6 | 0.5444 (4) | 0.56205 (10) | 0.32018 (9) | 0.0503 (4) | |
| H6 | 0.5618 | 0.5098 | 0.2868 | 0.060* | |
| C11 | 0.3060 (5) | 0.87580 (12) | 0.43612 (10) | 0.0588 (5) | |
| H11 | 0.2878 | 0.9279 | 0.4696 | 0.071* | |
| C4 | 0.3603 (3) | 0.72008 (9) | 0.33538 (8) | 0.0356 (4) | |
| C3 | 0.1982 (4) | 0.80075 (10) | 0.30145 (8) | 0.0397 (4) | |
| C2 | 0.0514 (4) | 0.80154 (11) | 0.21286 (9) | 0.0478 (4) | |
| C8 | 0.6540 (4) | 0.63636 (11) | 0.45452 (10) | 0.0544 (5) | |
| H8 | 0.7441 | 0.6341 | 0.5111 | 0.065* | |
| C7 | 0.6755 (4) | 0.56069 (12) | 0.40523 (10) | 0.0571 (5) | |
| H7 | 0.7788 | 0.5072 | 0.4284 | 0.068* | |
| C9 | 0.4972 (4) | 0.71882 (10) | 0.42179 (8) | 0.0429 (4) | |
| O3 | 0.0835 (3) | 0.72159 (7) | 0.16646 (6) | 0.0557 (3) | |
| C12 | 0.1693 (4) | 0.87738 (11) | 0.35104 (9) | 0.0504 (4) | |
| H12 | 0.0594 | 0.9302 | 0.3283 | 0.061* | |
| C10 | 0.4642 (4) | 0.79925 (12) | 0.47005 (9) | 0.0555 (4) | |
| H10 | 0.5534 | 0.7998 | 0.5267 | 0.067* | |
| O2 | −0.1003 (4) | 0.86395 (8) | 0.17671 (7) | 0.0747 (4) | |
| O1 | 0.2558 (4) | 0.57887 (8) | 0.14772 (7) | 0.0766 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C5 | 0.0368 (8) | 0.0459 (9) | 0.0377 (8) | −0.0059 (7) | 0.0073 (6) | 0.0044 (6) |
| C1 | 0.0597 (10) | 0.0486 (9) | 0.0376 (8) | −0.0111 (8) | 0.0043 (7) | 0.0002 (7) |
| C6 | 0.0511 (10) | 0.0467 (9) | 0.0544 (10) | −0.0002 (7) | 0.0116 (8) | 0.0037 (7) |
| C11 | 0.0618 (11) | 0.0624 (11) | 0.0531 (10) | −0.0070 (9) | 0.0104 (8) | −0.0178 (9) |
| C4 | 0.0306 (7) | 0.0447 (8) | 0.0321 (7) | −0.0061 (6) | 0.0063 (6) | 0.0035 (6) |
| C3 | 0.0357 (8) | 0.0463 (8) | 0.0376 (8) | −0.0043 (7) | 0.0053 (6) | 0.0023 (7) |
| C2 | 0.0499 (9) | 0.0539 (9) | 0.0391 (8) | 0.0002 (8) | 0.0008 (7) | 0.0061 (7) |
| C8 | 0.0447 (10) | 0.0789 (12) | 0.0387 (8) | −0.0011 (8) | −0.0020 (7) | 0.0195 (9) |
| C7 | 0.0506 (11) | 0.0605 (11) | 0.0600 (10) | 0.0071 (8) | 0.0043 (8) | 0.0210 (9) |
| C9 | 0.0345 (8) | 0.0618 (10) | 0.0325 (7) | −0.0063 (7) | 0.0033 (6) | 0.0027 (7) |
| O3 | 0.0705 (8) | 0.0593 (7) | 0.0354 (6) | −0.0055 (6) | −0.0075 (5) | 0.0030 (5) |
| C12 | 0.0495 (10) | 0.0483 (9) | 0.0545 (10) | 0.0006 (7) | 0.0103 (8) | 0.0005 (7) |
| C10 | 0.0524 (10) | 0.0797 (12) | 0.0339 (8) | −0.0086 (9) | 0.0014 (7) | −0.0075 (8) |
| O2 | 0.0918 (10) | 0.0725 (8) | 0.0572 (7) | 0.0227 (7) | −0.0100 (7) | 0.0185 (6) |
| O1 | 0.1232 (12) | 0.0586 (8) | 0.0480 (7) | −0.0138 (7) | 0.0075 (7) | −0.0131 (6) |
| C5—C6 | 1.3706 (19) | C3—C12 | 1.3710 (19) |
| C5—C4 | 1.4090 (18) | C3—C2 | 1.463 (2) |
| C5—C1 | 1.4613 (19) | C2—O2 | 1.1922 (17) |
| C1—O1 | 1.1931 (16) | C2—O3 | 1.3844 (17) |
| C1—O3 | 1.3900 (17) | C8—C7 | 1.354 (2) |
| C6—C7 | 1.394 (2) | C8—C9 | 1.4146 (19) |
| C6—H6 | 0.9300 | C8—H8 | 0.9300 |
| C11—C10 | 1.351 (2) | C7—H7 | 0.9300 |
| C11—C12 | 1.400 (2) | C9—C10 | 1.407 (2) |
| C11—H11 | 0.9300 | C12—H12 | 0.9300 |
| C4—C3 | 1.4072 (18) | C10—H10 | 0.9300 |
| C4—C9 | 1.4197 (19) | ||
| C6—C5—C4 | 120.72 (13) | O2—C2—C3 | 126.39 (15) |
| C6—C5—C1 | 119.88 (13) | O3—C2—C3 | 117.26 (13) |
| C4—C5—C1 | 119.39 (12) | C7—C8—C9 | 121.35 (14) |
| O1—C1—O3 | 116.57 (13) | C7—C8—H8 | 119.3 |
| O1—C1—C5 | 126.36 (15) | C9—C8—H8 | 119.3 |
| O3—C1—C5 | 117.07 (12) | C8—C7—C6 | 120.70 (14) |
| C5—C6—C7 | 120.05 (14) | C8—C7—H7 | 119.7 |
| C5—C6—H6 | 120.0 | C6—C7—H7 | 119.7 |
| C7—C6—H6 | 120.0 | C10—C9—C8 | 123.93 (13) |
| C10—C11—C12 | 120.65 (14) | C10—C9—C4 | 118.02 (13) |
| C10—C11—H11 | 119.7 | C8—C9—C4 | 118.05 (13) |
| C12—C11—H11 | 119.7 | C2—O3—C1 | 125.38 (11) |
| C3—C4—C5 | 121.58 (12) | C3—C12—C11 | 119.71 (14) |
| C3—C4—C9 | 119.28 (12) | C3—C12—H12 | 120.1 |
| C5—C4—C9 | 119.13 (12) | C11—C12—H12 | 120.1 |
| C12—C3—C4 | 120.72 (12) | C11—C10—C9 | 121.62 (14) |
| C12—C3—C2 | 119.96 (13) | C11—C10—H10 | 119.2 |
| C4—C3—C2 | 119.30 (13) | C9—C10—H10 | 119.2 |
| O2—C2—O3 | 116.33 (13) |
The authors acknowledge the Doctoral Foundation of Henan Polytechnic University (B2010–92, 648483) for support.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Evans, G. G. & Boeyens, J. A. (1989). Acta Cryst. B45, 581–590.
Grigor'eva, L. P. & Chetkina, L. A. (1975). Kristallografiya, 20, 1289–1290.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Shok, L. N., Chetkina, L. A., Neigauz, M. G., Gol'der, G. A., Smelyanskaya, E. M. & Fedorov, Yu. G. (1971). Kristallografiya, 16, 500–502.
Shok, L. N. & Gol'der, G. A. (1970). Zh. Strukt. Khim. 11, 939–940.
1,8-Naphthalenedicarboxylate (1,8-NDC), can be used as a rigid building blocks to design multiple metal-organic coordination polymers, as its multiple coordination sites, high symmetry and large conjugated structure. The single-crystal structure of naphthalene-1,8-dicarboxylic anhydride was firstly determined by Shok and Gol'der to be a orthorhombic space group Pbca (Shok, et al., 1970). Later a β-phase was discovered with the space group P212121 (Shok et al., 1971; Grigor'eva & Chetkina, 1975). In this paper, a new type of naphthalene-1,8-dicarboxylic acid anhydride was hydrothermally synthesized and characterized by single-crystal X-ray diffraction with the monoclinic space group P21/c.
The asymmetric unit contains only one independent molecule with the planar [total puckering amplitude Q = 0.0362 (15) (Evans & Boeyens, 1989)] molecules parallel to each other along the a-axis (Fig. 2).