Crystal structure of dimethyl 9H-carbazole-2,7-di­carb­oxy­late

Ryan L Lehane; James A Golen; Arnold L Rheingold; David R Manke

doi:10.1107/S2056989015017557

. 2015 Sep 26;71(Pt 10):o784–o785. doi: 10.1107/S2056989015017557

Crystal structure of dimethyl 9H-carbazole-2,7-dicarboxylate

Ryan L Lehane ^a, James A Golen ^b, Arnold L Rheingold ^b, David R Manke ^a,^*

PMCID: PMC4647360 PMID: 26594478

Abstract

In the title compound, C₁₆H₁₃NO₄, the carbazole ring system is almost planar with non-H atoms possessing a mean deviation from planarity of 0.037 Å. The two ester groups are orientated trans to one another and tilted slightly from the mean plane of the carbazole ring system, making dihedral angles of 8.12 (6) and 8.21 (5)°. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds forming inversion dimers. The dimers are linked by parallel slipped π–π interactions, forming slabs propagating along the b-axis direction [inter-centroid distance = 3.6042 (8) Å, inter-planar distance = 3.3437 (5) Å, slippage = 1.345 Å].

Keywords: crystal structure, carbazoles, hydrogen bonding, π–π interactions

Related literature

For the synthesis of the title compound, see: Olkhovik et al. (2008 ▸). For the crystal structures of some carbazoles, see: Clarke & Spink (1969 ▸); Gajda et al. (2014 ▸). For the structure of 9H-carbazole-3,6-dicarboxylic acid, see: Weseliński et al. (2014 ▸). For coordination polymers featuring the dicarboxylate of the parent compound, see: Yi et al. (2013 ▸, 2014 ▸, 2015 ▸). graphic file with name e-71-0o784-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₃NO₄
M _r = 283.27
Monoclinic,
a = 29.684 (2) Å
b = 5.8264 (4) Å
c = 15.4210 (11) Å
β = 96.252 (3)°
V = 2651.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.28 × 0.18 × 0.10 mm

Data collection

Bruker CMOS detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.972, T _max = 0.990
16278 measured reflections
2716 independent reflections
2141 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.03
2716 reflections
195 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▸); cell refinement: SAINT (Bruker, 2005 ▸); 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: SHELXL97, PLATON (Spek (2009 ▸) and publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015017557/su5208sup1.cif

e-71-0o784-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017557/su5208Isup2.hkl

e-71-0o784-Isup2.hkl^{(133.5KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015017557/su5208Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015017557/su5208fig1.tif

Molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.9MB, tif)}

b . DOI: 10.1107/S2056989015017557/su5208fig2.tif

A view along the b axis of the crystal packing of the title compound, with hydrogen bonds shown as dashed lines (ee Table 1).

CCDC reference: 1426074

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1NO3ⁱ	0.87(1)	2.04(1)	2.8834(16)	164(1)

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Symmetry code: (i) Inline graphic .

Acknowledgments

RLL thanks the Jean Dreyfus Boissevain Lectureship for Undergraduate Institutions, the UMass Dartmouth Office of Undergraduate Research Award and the UMass Dartmouth Honors Summer Research Grant for funding. DRM gratefully acknowledges support from the National Science Foundation (CHE-1229339 and CHE-1429086).

supplementary crystallographic information

S1. Comment

Biphenyl-4,4'-dicarboxylate and its derivatives are widely used in metal-organic frameworks (MOFs) as linkers. One derivative that is being explored in coordination polymers is 9H-carbazole-2,7-dicarboxylate (Yi et al., 2013, 2014, 2015). Herein, we report on the crystal structure of the previously synthesized 9H-carbazole-2,7-dicarboxylic acid dimethyl ester (Olkhovik et al., 2008).

The molecular structure of the title compound is shown in Fig. 1. The bond distances and angles are similar to those observed in some carbazole derivatives (Clarke & Spink, 1969; Gajda et al., 2014,) and a structurally characterized carbazole dicarboxylic acid (Weseliński et al., 2014). The carbazole unit is nearly planar with a mean deviation from planarity of 0.037 Å. The carboxylate groups are trans to one another and skewed slightly from the mean plane of the carbazole unit, with carbazole-ester dihedral angles of 8.12 (6) and 8.21 (5)°, involving ester groups O1/O2/C3/C13/C14 and O3/O4/C10/C15/C16, respectively.

In the crystal, molecules are linked by a pair of N—H···O hydrogen bonds forming inversion dimers (Fig. 2 and Table 1). The dimers are linked by parallel slipped π-π interactions forming slabs propagating along the b axis direction [Cg3···Cg3ⁱ = 3.6042 (8) Å, interplanar distance = 3.3437 (5) Å, slippage 1.345 Å; Cg3 is the centroid of ring C7—C12; symmetry code: (i) -x+1/2, -y+1/2, -z+1].

S2. Synthesis and crystallization

The compound was prepared by a literature procedure (Olkhovik et al. 2008). Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a solution in ethanol.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atom H1N was located in a difference Fourier map and refined with a distance restraint: N—H = 0.87 (2) Å with U_iso(H) = 1.2U_eq(N). The C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.95-0.98 Å with U_iso(H) =1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.