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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2622.
Published online 2010 September 25. doi:  10.1107/S1600536810037608
PMCID: PMC2983304

Naphthalene-1,8-dicarb­oxy­lic anhydride: a monoclinic polymorph

Abstract

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.

Related literature

The previously reported polymorphs crystallize in P212121 (Shok et al., 1971 [triangle]; Grigor’eva & Chetkina, 1975 [triangle]) and Pbca (Shok & Gol’der, 1970 [triangle]). For puckering parameters, see: Evans & Boeyens (1989 [triangle]).

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Object name is e-66-o2622-scheme1.jpg

Experimental

Crystal data

  • C12H6O3
  • M r = 198.17
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2622-efi1.jpg
  • a = 3.7687 (1) Å
  • b = 14.5269 (3) Å
  • c = 15.8083 (3) Å
  • β = 94.752 (2)°
  • V = 862.49 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 296 K
  • 0.20 × 0.10 × 0.10 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.875, T max = 0.982
  • 7560 measured reflections
  • 1964 independent reflections
  • 1201 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.131
  • S = 1.00
  • 1964 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037608/hg2709sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037608/hg2709Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the Doctoral Foundation of Henan Polytechnic University (B2010–92, 648483) for support.

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

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.

Figures

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]
Fig. 2.
A packing diagram of the title compound viewed down the a–axis.

Crystal data

C12H6O3F(000) = 408
Mr = 198.17Dx = 1.526 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1938 reflections
a = 3.7687 (1) Åθ = 2.6–27.9°
b = 14.5269 (3) ŵ = 0.11 mm1
c = 15.8083 (3) ÅT = 296 K
β = 94.752 (2)°Prism, yellow
V = 862.49 (3) Å30.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer1964 independent reflections
Radiation source: fine-focus sealed tube1201 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −4→4
Tmin = 0.875, Tmax = 0.982k = −17→18
7560 measured reflectionsl = −20→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0732P)2] where P = (Fo2 + 2Fc2)/3
1964 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = −0.17 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C50.3898 (4)0.64036 (9)0.28567 (8)0.0399 (4)
C10.2469 (4)0.64100 (10)0.19687 (9)0.0486 (4)
C60.5444 (4)0.56205 (10)0.32018 (9)0.0503 (4)
H60.56180.50980.28680.060*
C110.3060 (5)0.87580 (12)0.43612 (10)0.0588 (5)
H110.28780.92790.46960.071*
C40.3603 (3)0.72008 (9)0.33538 (8)0.0356 (4)
C30.1982 (4)0.80075 (10)0.30145 (8)0.0397 (4)
C20.0514 (4)0.80154 (11)0.21286 (9)0.0478 (4)
C80.6540 (4)0.63636 (11)0.45452 (10)0.0544 (5)
H80.74410.63410.51110.065*
C70.6755 (4)0.56069 (12)0.40523 (10)0.0571 (5)
H70.77880.50720.42840.068*
C90.4972 (4)0.71882 (10)0.42179 (8)0.0429 (4)
O30.0835 (3)0.72159 (7)0.16646 (6)0.0557 (3)
C120.1693 (4)0.87738 (11)0.35104 (9)0.0504 (4)
H120.05940.93020.32830.061*
C100.4642 (4)0.79925 (12)0.47005 (9)0.0555 (4)
H100.55340.79980.52670.067*
O2−0.1003 (4)0.86395 (8)0.17671 (7)0.0747 (4)
O10.2558 (4)0.57887 (8)0.14772 (7)0.0766 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C50.0368 (8)0.0459 (9)0.0377 (8)−0.0059 (7)0.0073 (6)0.0044 (6)
C10.0597 (10)0.0486 (9)0.0376 (8)−0.0111 (8)0.0043 (7)0.0002 (7)
C60.0511 (10)0.0467 (9)0.0544 (10)−0.0002 (7)0.0116 (8)0.0037 (7)
C110.0618 (11)0.0624 (11)0.0531 (10)−0.0070 (9)0.0104 (8)−0.0178 (9)
C40.0306 (7)0.0447 (8)0.0321 (7)−0.0061 (6)0.0063 (6)0.0035 (6)
C30.0357 (8)0.0463 (8)0.0376 (8)−0.0043 (7)0.0053 (6)0.0023 (7)
C20.0499 (9)0.0539 (9)0.0391 (8)0.0002 (8)0.0008 (7)0.0061 (7)
C80.0447 (10)0.0789 (12)0.0387 (8)−0.0011 (8)−0.0020 (7)0.0195 (9)
C70.0506 (11)0.0605 (11)0.0600 (10)0.0071 (8)0.0043 (8)0.0210 (9)
C90.0345 (8)0.0618 (10)0.0325 (7)−0.0063 (7)0.0033 (6)0.0027 (7)
O30.0705 (8)0.0593 (7)0.0354 (6)−0.0055 (6)−0.0075 (5)0.0030 (5)
C120.0495 (10)0.0483 (9)0.0545 (10)0.0006 (7)0.0103 (8)0.0005 (7)
C100.0524 (10)0.0797 (12)0.0339 (8)−0.0086 (9)0.0014 (7)−0.0075 (8)
O20.0918 (10)0.0725 (8)0.0572 (7)0.0227 (7)−0.0100 (7)0.0185 (6)
O10.1232 (12)0.0586 (8)0.0480 (7)−0.0138 (7)0.0075 (7)−0.0131 (6)

Geometric parameters (Å, °)

C5—C61.3706 (19)C3—C121.3710 (19)
C5—C41.4090 (18)C3—C21.463 (2)
C5—C11.4613 (19)C2—O21.1922 (17)
C1—O11.1931 (16)C2—O31.3844 (17)
C1—O31.3900 (17)C8—C71.354 (2)
C6—C71.394 (2)C8—C91.4146 (19)
C6—H60.9300C8—H80.9300
C11—C101.351 (2)C7—H70.9300
C11—C121.400 (2)C9—C101.407 (2)
C11—H110.9300C12—H120.9300
C4—C31.4072 (18)C10—H100.9300
C4—C91.4197 (19)
C6—C5—C4120.72 (13)O2—C2—C3126.39 (15)
C6—C5—C1119.88 (13)O3—C2—C3117.26 (13)
C4—C5—C1119.39 (12)C7—C8—C9121.35 (14)
O1—C1—O3116.57 (13)C7—C8—H8119.3
O1—C1—C5126.36 (15)C9—C8—H8119.3
O3—C1—C5117.07 (12)C8—C7—C6120.70 (14)
C5—C6—C7120.05 (14)C8—C7—H7119.7
C5—C6—H6120.0C6—C7—H7119.7
C7—C6—H6120.0C10—C9—C8123.93 (13)
C10—C11—C12120.65 (14)C10—C9—C4118.02 (13)
C10—C11—H11119.7C8—C9—C4118.05 (13)
C12—C11—H11119.7C2—O3—C1125.38 (11)
C3—C4—C5121.58 (12)C3—C12—C11119.71 (14)
C3—C4—C9119.28 (12)C3—C12—H12120.1
C5—C4—C9119.13 (12)C11—C12—H12120.1
C12—C3—C4120.72 (12)C11—C10—C9121.62 (14)
C12—C3—C2119.96 (13)C11—C10—H10119.2
C4—C3—C2119.30 (13)C9—C10—H10119.2
O2—C2—O3116.33 (13)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2709).

References

  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Evans, D. G. & Boeyens, J. C. 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. [PubMed]
  • 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.

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