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 ▶; Grigor’eva & Chetkina, 1975 ▶) and Pbca (Shok & Gol’der, 1970 ▶). For puckering parameters, see: Evans & Boeyens (1989 ▶).

Experimental

Crystal data

• C₁₂H₆O₃

• M _r = 198.17

• Monoclinic,

• a = 3.7687 (1) Å

• b = 14.5269 (3) Å

• c = 15.8083 (3) Å

• β = 94.752 (2)°

• V = 862.49 (3) ų

• 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 ▶) 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

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Supplementary Material

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

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 U_iso(H) = 1.2 U_eq(C). The final refinement show that the highest peak in the difference electron density map equals to 0.18 e/ų at the distance of 0.65 Å from C5 while the deepest hole equals to -0.17 e/ų 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

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

Data collection

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

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

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 (Ų)

	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)

Atomic displacement parameters (Ų)

	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)

Geometric parameters (Å, °)

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)