organic compounds
H-carbazole-2,7-dicarboxylate
of dimethyl 9aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA, and bDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
*Correspondence e-mail: dmanke@umassd.edu
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.
CCDC reference: 1426074
1. 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).
2. Experimental
2.1. Crystal data
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2.3. Refinement
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Data collection: APEX2 (Bruker, 2005); cell 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).
Supporting information
CCDC reference: 1426074
10.1107/S2056989015017557/su5208sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017557/su5208Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017557/su5208Isup3.cml
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
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].
The compound was prepared by a literature procedure (Olkhovik et al. 2008). Crystals suitable for X-ray
were grown by slow evaporation of a solution in ethanol.Crystal data, data collection and structure
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 Uiso(H) = 1.2Ueq(N). The C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.95-0.98 Å with Uiso(H) =1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 (Sheldrick, 2008), PLATON (Spek (2009) and publCIF (Westrip, 2010).C16H13NO4 | F(000) = 1184 |
Mr = 283.27 | Dx = 1.419 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5867 reflections |
a = 29.684 (2) Å | θ = 3.1–26.3° |
b = 5.8264 (4) Å | µ = 0.10 mm−1 |
c = 15.4210 (11) Å | T = 100 K |
β = 96.252 (3)° | Block, yellow |
V = 2651.2 (3) Å3 | 0.28 × 0.18 × 0.10 mm |
Z = 8 |
Bruker CMOS detector diffractometer | 2716 independent reflections |
Radiation source: fine-focus sealed tube | 2141 reflections with I > 2σ(I) |
Doubly curved mirrors monochromator | Rint = 0.042 |
φ and ω scans | θmax = 26.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −36→36 |
Tmin = 0.972, Tmax = 0.990 | k = −7→7 |
16278 measured reflections | l = −19→19 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0509P)2 + 1.5495P] where P = (Fo2 + 2Fc2)/3 |
2716 reflections | (Δ/σ)max = 0.001 |
195 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.22 e Å−3 |
C16H13NO4 | V = 2651.2 (3) Å3 |
Mr = 283.27 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.684 (2) Å | µ = 0.10 mm−1 |
b = 5.8264 (4) Å | T = 100 K |
c = 15.4210 (11) Å | 0.28 × 0.18 × 0.10 mm |
β = 96.252 (3)° |
Bruker CMOS detector diffractometer | 2716 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2141 reflections with I > 2σ(I) |
Tmin = 0.972, Tmax = 0.990 | Rint = 0.042 |
16278 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.22 e Å−3 |
2716 reflections | Δρmin = −0.22 e Å−3 |
195 parameters |
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 | ||
O1 | 0.46191 (4) | 0.66773 (19) | 0.82835 (7) | 0.0330 (3) | |
O2 | 0.47499 (4) | 0.3231 (2) | 0.88997 (8) | 0.0435 (3) | |
O3 | 0.15036 (3) | 0.56249 (18) | 0.46010 (7) | 0.0281 (3) | |
O4 | 0.12301 (3) | 0.23787 (18) | 0.51083 (7) | 0.0287 (3) | |
N1 | 0.31090 (4) | 0.5801 (2) | 0.63776 (8) | 0.0206 (3) | |
H1N | 0.3176 (5) | 0.703 (2) | 0.6095 (10) | 0.025* | |
C1 | 0.34155 (4) | 0.4608 (2) | 0.69505 (8) | 0.0193 (3) | |
C2 | 0.38361 (5) | 0.5315 (2) | 0.73472 (9) | 0.0214 (3) | |
H2A | 0.3958 | 0.6769 | 0.7221 | 0.026* | |
C3 | 0.40714 (5) | 0.3814 (2) | 0.79351 (9) | 0.0224 (3) | |
C4 | 0.38949 (5) | 0.1642 (3) | 0.81051 (10) | 0.0250 (3) | |
H4A | 0.4066 | 0.0629 | 0.8496 | 0.030* | |
C5 | 0.34764 (5) | 0.0959 (2) | 0.77109 (9) | 0.0217 (3) | |
H5A | 0.3358 | −0.0508 | 0.7831 | 0.026* | |
C6 | 0.32293 (5) | 0.2456 (2) | 0.71332 (9) | 0.0185 (3) | |
C7 | 0.27864 (5) | 0.2357 (2) | 0.66416 (8) | 0.0179 (3) | |
C8 | 0.24369 (5) | 0.0734 (2) | 0.65636 (9) | 0.0196 (3) | |
H8A | 0.2472 | −0.0684 | 0.6868 | 0.024* | |
C9 | 0.20400 (5) | 0.1208 (2) | 0.60415 (9) | 0.0195 (3) | |
H9A | 0.1802 | 0.0107 | 0.5982 | 0.023* | |
C10 | 0.19859 (4) | 0.3317 (2) | 0.55960 (9) | 0.0190 (3) | |
C11 | 0.23263 (4) | 0.4955 (2) | 0.56654 (9) | 0.0189 (3) | |
H11A | 0.2287 | 0.6376 | 0.5365 | 0.023* | |
C12 | 0.27267 (4) | 0.4461 (2) | 0.61861 (9) | 0.0183 (3) | |
C13 | 0.45135 (5) | 0.4484 (3) | 0.84215 (10) | 0.0271 (3) | |
C14 | 0.50435 (5) | 0.7491 (3) | 0.87314 (12) | 0.0371 (4) | |
H14A | 0.5076 | 0.9135 | 0.8620 | 0.056* | |
H14B | 0.5296 | 0.6655 | 0.8518 | 0.056* | |
H14C | 0.5046 | 0.7233 | 0.9360 | 0.056* | |
C15 | 0.15579 (5) | 0.3916 (2) | 0.50484 (9) | 0.0205 (3) | |
C16 | 0.08012 (5) | 0.2876 (3) | 0.46017 (11) | 0.0348 (4) | |
H16A | 0.0590 | 0.1609 | 0.4661 | 0.052* | |
H16B | 0.0849 | 0.3058 | 0.3986 | 0.052* | |
H16C | 0.0675 | 0.4298 | 0.4815 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0263 (6) | 0.0291 (6) | 0.0403 (7) | −0.0047 (5) | −0.0108 (5) | 0.0021 (5) |
O2 | 0.0376 (7) | 0.0349 (7) | 0.0522 (8) | 0.0020 (5) | −0.0209 (6) | 0.0067 (6) |
O3 | 0.0248 (6) | 0.0295 (6) | 0.0291 (6) | −0.0003 (4) | −0.0013 (4) | 0.0094 (5) |
O4 | 0.0209 (5) | 0.0290 (6) | 0.0346 (6) | −0.0051 (4) | −0.0045 (5) | 0.0051 (5) |
N1 | 0.0205 (6) | 0.0176 (6) | 0.0229 (6) | −0.0017 (5) | −0.0012 (5) | 0.0058 (5) |
C1 | 0.0210 (7) | 0.0189 (7) | 0.0182 (7) | 0.0032 (5) | 0.0024 (5) | 0.0010 (5) |
C2 | 0.0213 (7) | 0.0200 (7) | 0.0227 (7) | 0.0007 (6) | 0.0014 (6) | 0.0001 (6) |
C3 | 0.0219 (7) | 0.0236 (7) | 0.0212 (7) | 0.0026 (6) | 0.0003 (6) | −0.0012 (6) |
C4 | 0.0276 (8) | 0.0240 (7) | 0.0225 (7) | 0.0054 (6) | −0.0008 (6) | 0.0038 (6) |
C5 | 0.0267 (8) | 0.0182 (7) | 0.0201 (7) | 0.0012 (6) | 0.0022 (6) | 0.0022 (6) |
C6 | 0.0218 (7) | 0.0182 (7) | 0.0157 (7) | 0.0007 (5) | 0.0035 (5) | −0.0022 (5) |
C7 | 0.0219 (7) | 0.0187 (7) | 0.0135 (6) | 0.0025 (5) | 0.0040 (5) | −0.0010 (5) |
C8 | 0.0253 (7) | 0.0163 (6) | 0.0180 (7) | 0.0006 (5) | 0.0053 (6) | 0.0011 (5) |
C9 | 0.0219 (7) | 0.0175 (7) | 0.0198 (7) | −0.0027 (5) | 0.0046 (6) | −0.0025 (5) |
C10 | 0.0206 (7) | 0.0200 (7) | 0.0167 (7) | 0.0002 (6) | 0.0036 (5) | −0.0017 (6) |
C11 | 0.0222 (7) | 0.0165 (6) | 0.0182 (7) | 0.0013 (5) | 0.0034 (5) | 0.0020 (5) |
C12 | 0.0204 (7) | 0.0173 (6) | 0.0173 (6) | −0.0009 (5) | 0.0032 (5) | −0.0010 (5) |
C13 | 0.0265 (8) | 0.0267 (8) | 0.0270 (8) | 0.0041 (6) | −0.0025 (6) | −0.0021 (6) |
C14 | 0.0266 (9) | 0.0372 (9) | 0.0446 (10) | −0.0064 (7) | −0.0093 (7) | −0.0028 (8) |
C15 | 0.0212 (7) | 0.0213 (7) | 0.0192 (7) | −0.0016 (6) | 0.0031 (6) | −0.0015 (6) |
C16 | 0.0218 (8) | 0.0428 (10) | 0.0374 (9) | −0.0036 (7) | −0.0068 (7) | 0.0025 (8) |
O1—C13 | 1.3382 (19) | C5—H5A | 0.9500 |
O1—C14 | 1.4490 (18) | C6—C7 | 1.445 (2) |
O2—C13 | 1.2070 (18) | C7—C8 | 1.3992 (19) |
O3—C15 | 1.2119 (17) | C7—C12 | 1.4145 (19) |
O4—C15 | 1.3333 (17) | C8—C9 | 1.381 (2) |
O4—C16 | 1.4487 (18) | C8—H8A | 0.9500 |
N1—C12 | 1.3824 (17) | C9—C10 | 1.409 (2) |
N1—C1 | 1.3842 (17) | C9—H9A | 0.9500 |
N1—H1N | 0.870 (13) | C10—C11 | 1.3852 (19) |
C1—C2 | 1.3915 (19) | C10—C15 | 1.4884 (19) |
C1—C6 | 1.4112 (19) | C11—C12 | 1.3902 (19) |
C2—C3 | 1.391 (2) | C11—H11A | 0.9500 |
C2—H2A | 0.9500 | C14—H14A | 0.9800 |
C3—C4 | 1.406 (2) | C14—H14B | 0.9800 |
C3—C13 | 1.491 (2) | C14—H14C | 0.9800 |
C4—C5 | 1.381 (2) | C16—H16A | 0.9800 |
C4—H4A | 0.9500 | C16—H16B | 0.9800 |
C5—C6 | 1.3963 (19) | C16—H16C | 0.9800 |
C13—O1—C14 | 116.30 (12) | C8—C9—H9A | 119.9 |
C15—O4—C16 | 115.68 (12) | C10—C9—H9A | 119.9 |
C12—N1—C1 | 108.67 (11) | C11—C10—C9 | 121.32 (13) |
C12—N1—H1N | 125.6 (10) | C11—C10—C15 | 116.91 (12) |
C1—N1—H1N | 124.2 (10) | C9—C10—C15 | 121.75 (12) |
N1—C1—C2 | 128.90 (13) | C10—C11—C12 | 118.22 (12) |
N1—C1—C6 | 109.20 (12) | C10—C11—H11A | 120.9 |
C2—C1—C6 | 121.84 (12) | C12—C11—H11A | 120.9 |
C1—C2—C3 | 117.59 (13) | N1—C12—C11 | 129.57 (12) |
C1—C2—H2A | 121.2 | N1—C12—C7 | 109.14 (12) |
C3—C2—H2A | 121.2 | C11—C12—C7 | 121.27 (12) |
C2—C3—C4 | 121.10 (13) | O2—C13—O1 | 122.98 (14) |
C2—C3—C13 | 121.01 (13) | O2—C13—C3 | 124.78 (14) |
C4—C3—C13 | 117.87 (13) | O1—C13—C3 | 112.24 (12) |
C5—C4—C3 | 120.86 (13) | O1—C14—H14A | 109.5 |
C5—C4—H4A | 119.6 | O1—C14—H14B | 109.5 |
C3—C4—H4A | 119.6 | H14A—C14—H14B | 109.5 |
C4—C5—C6 | 119.08 (13) | O1—C14—H14C | 109.5 |
C4—C5—H5A | 120.5 | H14A—C14—H14C | 109.5 |
C6—C5—H5A | 120.5 | H14B—C14—H14C | 109.5 |
C5—C6—C1 | 119.49 (13) | O3—C15—O4 | 122.58 (13) |
C5—C6—C7 | 133.96 (13) | O3—C15—C10 | 124.62 (13) |
C1—C6—C7 | 106.53 (12) | O4—C15—C10 | 112.79 (12) |
C8—C7—C12 | 119.44 (13) | O4—C16—H16A | 109.5 |
C8—C7—C6 | 134.08 (13) | O4—C16—H16B | 109.5 |
C12—C7—C6 | 106.46 (12) | H16A—C16—H16B | 109.5 |
C9—C8—C7 | 119.52 (13) | O4—C16—H16C | 109.5 |
C9—C8—H8A | 120.2 | H16A—C16—H16C | 109.5 |
C7—C8—H8A | 120.2 | H16B—C16—H16C | 109.5 |
C8—C9—C10 | 120.24 (13) | ||
C12—N1—C1—C2 | −177.05 (13) | C8—C9—C10—C15 | −178.18 (12) |
C12—N1—C1—C6 | 0.08 (15) | C9—C10—C11—C12 | 0.28 (19) |
N1—C1—C2—C3 | 177.00 (13) | C15—C10—C11—C12 | 178.78 (12) |
C6—C1—C2—C3 | 0.2 (2) | C1—N1—C12—C11 | 177.91 (13) |
C1—C2—C3—C4 | 1.5 (2) | C1—N1—C12—C7 | −0.13 (15) |
C1—C2—C3—C13 | −176.94 (13) | C10—C11—C12—N1 | −178.41 (13) |
C2—C3—C4—C5 | −1.8 (2) | C10—C11—C12—C7 | −0.58 (19) |
C13—C3—C4—C5 | 176.68 (13) | C8—C7—C12—N1 | 178.58 (12) |
C3—C4—C5—C6 | 0.4 (2) | C6—C7—C12—N1 | 0.13 (15) |
C4—C5—C6—C1 | 1.3 (2) | C8—C7—C12—C11 | 0.35 (19) |
C4—C5—C6—C7 | −177.33 (14) | C6—C7—C12—C11 | −178.10 (12) |
N1—C1—C6—C5 | −178.98 (12) | C14—O1—C13—O2 | 1.1 (2) |
C2—C1—C6—C5 | −1.6 (2) | C14—O1—C13—C3 | 179.87 (13) |
N1—C1—C6—C7 | −0.01 (14) | C2—C3—C13—O2 | −175.23 (15) |
C2—C1—C6—C7 | 177.37 (12) | C4—C3—C13—O2 | 6.3 (2) |
C5—C6—C7—C8 | 0.6 (3) | C2—C3—C13—O1 | 6.0 (2) |
C1—C6—C7—C8 | −178.20 (14) | C4—C3—C13—O1 | −172.48 (13) |
C5—C6—C7—C12 | 178.69 (14) | C16—O4—C15—O3 | 0.0 (2) |
C1—C6—C7—C12 | −0.07 (14) | C16—O4—C15—C10 | 179.05 (12) |
C12—C7—C8—C9 | 0.20 (19) | C11—C10—C15—O3 | 7.1 (2) |
C6—C7—C8—C9 | 178.13 (14) | C9—C10—C15—O3 | −174.35 (13) |
C7—C8—C9—C10 | −0.49 (19) | C11—C10—C15—O4 | −171.85 (12) |
C8—C9—C10—C11 | 0.3 (2) | C9—C10—C15—O4 | 6.65 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O3i | 0.87 (1) | 2.04 (1) | 2.8834 (16) | 164 (1) |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O3i | 0.872 (13) | 2.036 (14) | 2.8834 (16) | 163.6 (13) |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
Acknowledgements
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).
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