Crystal structure of dimethyl 3,3′-[(3-nitro­phen­yl)methyl­ene]bis­(1H-indole-2-carboxyl­ate) ethanol monosolvate

Sun, H.-S.; Li, Y.-L.; Jiang, H.; Xu, N.; Xu, H.

doi:10.1107/S1600536814022296

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 370-372

doi:10.1107/S1600536814022296

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Crystal structure of dimethyl 3,3′-[(3-nitrophenyl)methylene]bis(1H-indole-2-carboxylate) ethanol monosolvate

Hong-Shun Sun,^a ^* Yu-Long Li,^a Hong Jiang,^a Ning Xu ^a and Hong Xu ^a

^aChemical Engineering Department, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: njutshs@126.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 25 September 2014; accepted 9 October 2014; online 24 October 2014)

In the title compound, C₂₇H₂₁N₃O₆·C₂H₅OH, the indole ring systems are approximately perpendicular to each other, with a dihedral angle of 89.3 (5)°; the plane of the benzene ring is oriented with respect to the indole ring systems at 49.9 (5) and 73.4 (3)°. In the crystal, molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds and weak C—H⋯π interactions into a three-dimensional supramolecular architecture. A void of 33.0 (7) Å³ is observed in the crystal structure. The solvent ethanol molecule acts as a donor, forming an O—H⋯O hydrogen bond, reinforcing the framework structure.

Keywords: indole; crystal structure; MRI contrast agent.

CCDC reference: 1028397

1. Chemical context

Indole derivatives are found abundantly in a variety of natural plants and exhibit various physiological properties (Poter et al., 1977 ; Sundberg, 1996 ). Among them, bis-indolymethane derivatives are found to be potentially bioactive compounds (Chang et al., 1999 ; Ge et al., 1999 ). In recent years, the synthesis and application of bis-indolymethane derivatives have been widely studied. The title compound is one of the bis-indolymethane derivatives as a precursor for MRI contrast agents (Ni, 2008 ). We report herein the synthesis and crystal structure of the title compound.

2. Structural commentary

The molecular structure of the title compound is shown in Fig. 1. The two indole ring systems are nearly perpendicular to each other [dihedral angle = 89.3 (5)°] while the benzene ring (C1–C6) is twisted to the N1/C8–C15 and N2/C18–C25 indole ring systems with dihedral angles of 49.9 (5) and 73.4 (3)°, respectively. The carboxyl groups are approximately coplanar with the attached indole ring systems, the dihedral angles between the carboxyl groups and the mean plane of attached indole ring system are 10.0 (3) and 4.0 (4)°. The nitro group is also nearly coplanar with the attached benzene ring, the dihedral angle being 7.7 (7)°. A void of 33.0 (7) Å³ is observed in the crystal structure. The solvent ethanol molecule acts as a donor, forming an O—H⋯O hydrogen bond, reinforcing the framework structure.

Figure 1
The molecular structure of the title molecule. showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the hydrogen bond between the main molecule and the ethanol solvent molecule.

3. Supramolecular features

In the crystal, the organic molecules and ethanol solvent molecules are linked by classic N—H⋯O and O—H⋯O hydrogen bonds and weak C—H⋯π interactions involved the benzene rings, forming the three-dimensional supramolecular architecture (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3, Cg4 and Cg5 are the centroids of the C1-ring, C10-ring and C20-ring, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O7ⁱ	0.86	2.17	2.924 (3)	146
N3—H3A⋯O4ⁱⁱ	0.86	2.02	2.861 (4)	166
O7—H7B⋯O5	0.82	2.13	2.892 (4)	154
C10—H10A⋯Cg3	0.93	2.87	3.633 (4)	140
C11—H11A⋯Cg5ⁱⁱⁱ	0.93	2.76	3.634 (4)	156
C17—H17B⋯Cg4ⁱ	0.96	2.89	3.813 (5)	163
C27—H27B⋯Cg5ⁱⁱ	0.96	2.75	3.496 (4)	135
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x+2, -y+1, -z+1; (iii) -x+2, -y, -z.

4. Database survey

Several similar structures have been reported previously, i.e. diethyl 3,3′-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2012 ) and dimethyl 3,3′-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2013 ). In those structures, the two indole ring systems are also nearly perpendicular to each other, the dihedral angles are 82.0 (5) and 84.5 (5)°, respectively.

5. Synthesis and crystallization

Methyl indole-2-carboxylate (17.5 g, 100 mmol) was dissolved in 200 ml methanol; commercially available 3-nitrobenzaldehyde (7.6 g, 50 mmol) was added and the mixture was heated to reflux temperature. Concentrated HCl (3.7 ml) was added and the reaction was left for 1 h. After cooling the white product was filtered off and washed thoroughly with methanol. The reaction can be followed by thin-layer chromatography (CHCl₃–hexane = 1:1 v/v). The yield was 90%. Crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

6. Refinement

H atoms were positioned geometrically, with N—H = 0.86Å and O—H = 0.82Å, and C—H = 0.93, 0.96, 0.97 or 0.98 Å for aromatic, methyl, methene and methine H atom, respectively, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,N,O), where x = 1.5 for methyl and hydroxy, and x = 1.2 for all other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₇H₂₁N₃O₆·C₂H₆O
M_r	529.54
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	11.074 (2), 11.585 (2), 12.898 (3)
α, β, γ (°)	114.09 (3), 106.68 (3), 99.20 (3)
V (Å³)	1372.5 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968 )
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5313, 5032, 3254
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.166, 1.04
No. of reflections	5032
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.26
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994 ), XCAD4 (Harms & Wocadlo, 1995 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1028397

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814022296/xu5823sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022296/xu5823Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814022296/xu5823Isup3.cml

checkCIF report

Chemical context top

Indole derivatives are found abundantly in a variety of natural plants and exhibit various physiological properties (Poter et al., 1977; Sundberg, 1996). Among them, bis-indolymethane derivatives are found to be potentially bioactive compounds (Chang et al., 1999; Ge et al., 1999). In recent years, the synthesis and application of bis-indolymethane derivatives have been widely studied. The title compound is one of bis-indolymethane derivatives as a precursor for MRI Contrast Agents (Ni, 2008). We report herein the synthesis and crystal structure of the title compound.

Structural commentary top

Supramolecular features top

In the crystal, the organic molecules and crystalline water molecules are linked by classic N—H···O and O—H···O hydrogen bonds and weak C—H···π interactions involved the benzene rings, forming the three-dimensional supramolecular architecture (Table 1).

Database survey top

Several similar structures have been reported previously, i.e. diethyl 3,3'-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2012) and dimethyl 3,3'-(phenylmethylene)bis(1H-indole-2-carboxylate) (Sun et al., 2013). In those structures, the two indole ring systems are also nearly perpendicular to each other, the dihedral angles are 82.0 (5) and 84.5 (5)°, respectively.

Synthesis and crystallization top

Refinement top

H atoms were positioned geometrically, with N—H = 0.86Å and O—H = 0.82Å, and C—H = 0.93, 0.96, 0.97 or 0.98 Å for aromatic, methyl, methene and methine H atom , respectively, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,N,O), where x = 1.5 for methyl and hydroxy, and x = 1.2 for all other H atoms.

Related literature top

For related literature, see: Chang et al. (1999); Ge et al. (1999); Ni (2008); Poter et al. (1977); Sun et al. (2012, 2013); Sundberg (1996).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

The molecular structure of the title molecule. showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the hydrogen bond.

3,3'-[(3-Nitrophenyl)methylene]bis(1H-indole-2-carboxylate) ethanol monosolvate top

Crystal data top

C₂₇H₂₁N₃O₆·C₂H₆O	Z = 2
M_r = 529.54	F(000) = 556
Triclinic, P1	D_x = 1.281 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.074 (2) Å	Cell parameters from 25 reflections
b = 11.585 (2) Å	θ = 9–13°
c = 12.898 (3) Å	µ = 0.09 mm⁻¹
α = 114.09 (3)°	T = 293 K
β = 106.68 (3)°	Block, colorless
γ = 99.20 (3)°	0.30 × 0.20 × 0.10 mm
V = 1372.5 (5) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	3254 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 25.4°, θ_min = 1.9°
ω/2θ scans	h = 0→13
Absorption correction: ψ scan (North et al., 1968)	k = −13→13
T_min = 0.973, T_max = 0.991	l = −15→14
5313 measured reflections	3 standard reflections every 200 reflections
5032 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0769P)² + 0.4188P] where P = (F_o² + 2F_c²)/3
5032 reflections	(Δ/σ)_max = 0.001
352 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₇H₂₁N₃O₆·C₂H₆O	γ = 99.20 (3)°
M_r = 529.54	V = 1372.5 (5) Å³
Triclinic, P1	Z = 2
a = 11.074 (2) Å	Mo Kα radiation
b = 11.585 (2) Å	µ = 0.09 mm⁻¹
c = 12.898 (3) Å	T = 293 K
α = 114.09 (3)°	0.30 × 0.20 × 0.10 mm
β = 106.68 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3254 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.029
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
5313 measured reflections	intensity decay: 1%
5032 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
5032 reflections	Δρ_min = −0.25 e Å⁻³
352 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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) top

	x	y	z	U_iso*/U_eq
N1	0.4712 (3)	−0.2518 (3)	0.0074 (4)	0.0901 (11)
N2	1.1545 (2)	0.0075 (2)	0.4249 (2)	0.0438 (6)
H2A	1.2151	0.0123	0.4870	0.053*
N3	0.9859 (2)	0.4742 (2)	0.3448 (2)	0.0414 (5)
H3A	0.9740	0.5507	0.3650	0.050*
O1	0.4711 (3)	−0.2634 (3)	0.0977 (4)	0.1266 (13)
O2	0.3872 (3)	−0.3273 (3)	−0.0959 (3)	0.1360 (14)
O3	1.1911 (2)	0.21184 (19)	0.64357 (18)	0.0599 (6)
O4	1.0053 (2)	0.25277 (18)	0.55999 (17)	0.0506 (5)
O5	0.71167 (19)	0.2865 (2)	0.36509 (19)	0.0548 (5)
O6	0.77081 (18)	0.49394 (18)	0.39092 (18)	0.0504 (5)
O7	0.6624 (2)	0.0902 (2)	0.4450 (2)	0.0733 (7)
H7B	0.7018	0.1489	0.4354	0.110*
C1	0.6788 (3)	−0.0661 (3)	0.1405 (3)	0.0490 (7)
H1A	0.6817	−0.0846	0.2047	0.059*
C2	0.5754 (3)	−0.1429 (3)	0.0248 (3)	0.0565 (8)
C3	0.5662 (3)	−0.1189 (3)	−0.0723 (3)	0.0616 (9)
H3B	0.4956	−0.1715	−0.1484	0.074*
C4	0.6637 (3)	−0.0153 (3)	−0.0543 (3)	0.0607 (9)
H4A	0.6603	0.0025	−0.1190	0.073*
C5	0.7674 (3)	0.0629 (3)	0.0598 (3)	0.0497 (7)
H5A	0.8323	0.1337	0.0710	0.060*
C6	0.7767 (3)	0.0382 (2)	0.1580 (2)	0.0395 (6)
C7	0.8906 (2)	0.1240 (2)	0.2847 (2)	0.0361 (6)
H7A	0.8495	0.1390	0.3451	0.043*
C8	0.9896 (2)	0.0532 (2)	0.3134 (2)	0.0354 (6)
C9	1.0194 (3)	−0.0546 (2)	0.2304 (2)	0.0389 (6)
C10	0.9715 (3)	−0.1346 (3)	0.1015 (3)	0.0484 (7)
H10A	0.9044	−0.1207	0.0497	0.058*
C11	1.0243 (3)	−0.2330 (3)	0.0530 (3)	0.0598 (8)
H11A	0.9910	−0.2870	−0.0321	0.072*
C12	1.1276 (3)	−0.2544 (3)	0.1288 (3)	0.0609 (9)
H12A	1.1624	−0.3211	0.0930	0.073*
C13	1.1778 (3)	−0.1789 (3)	0.2542 (3)	0.0524 (8)
H13A	1.2462	−0.1931	0.3044	0.063*
C14	1.1231 (3)	−0.0798 (3)	0.3043 (2)	0.0410 (6)
C15	1.0733 (3)	0.0872 (2)	0.4314 (2)	0.0390 (6)
C16	1.0840 (3)	0.1913 (3)	0.5490 (2)	0.0425 (7)
C17	1.2112 (4)	0.3165 (3)	0.7644 (3)	0.0695 (10)
H17A	1.2900	0.3234	0.8255	0.104*
H17B	1.1360	0.2952	0.7838	0.104*
H17C	1.2208	0.3999	0.7635	0.104*
C18	0.9553 (2)	0.2606 (2)	0.3046 (2)	0.0359 (6)
C19	1.0709 (3)	0.3062 (2)	0.2854 (2)	0.0378 (6)
C20	1.1640 (3)	0.2491 (3)	0.2473 (3)	0.0477 (7)
H20A	1.1577	0.1615	0.2292	0.057*
C21	1.2643 (3)	0.3253 (3)	0.2377 (3)	0.0624 (9)
H21A	1.3258	0.2880	0.2123	0.075*
C22	1.2763 (3)	0.4570 (3)	0.2648 (3)	0.0631 (9)
H22A	1.3456	0.5054	0.2570	0.076*
C23	1.1893 (3)	0.5166 (3)	0.3023 (3)	0.0529 (8)
H23A	1.1980	0.6047	0.3208	0.064*
C24	1.0863 (3)	0.4401 (3)	0.3120 (2)	0.0399 (6)
C25	0.9066 (2)	0.3671 (2)	0.3405 (2)	0.0366 (6)
C26	0.7876 (3)	0.3752 (3)	0.3664 (2)	0.0394 (6)
C27	0.6529 (3)	0.5128 (3)	0.4122 (3)	0.0663 (9)
H27A	0.6516	0.6011	0.4285	0.099*
H27B	0.6530	0.5013	0.4819	0.099*
H27C	0.5757	0.4485	0.3405	0.099*
C28	0.5250 (4)	0.0591 (4)	0.3849 (4)	0.0870 (12)
H28A	0.4800	−0.0202	0.3845	0.104*
H28B	0.5049	0.0384	0.2998	0.104*
C29	0.4715 (4)	0.1671 (5)	0.4421 (5)	0.1096 (17)
H29A	0.3772	0.1388	0.3969	0.164*
H29B	0.5131	0.2452	0.4404	0.164*
H29C	0.4894	0.1872	0.5260	0.164*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.062 (2)	0.059 (2)	0.101 (3)	−0.0028 (16)	0.000 (2)	0.025 (2)
N2	0.0404 (13)	0.0425 (13)	0.0432 (14)	0.0130 (11)	0.0046 (10)	0.0235 (11)
N3	0.0425 (13)	0.0313 (11)	0.0503 (14)	0.0153 (10)	0.0173 (11)	0.0187 (10)
O1	0.096 (2)	0.107 (3)	0.129 (3)	−0.0288 (19)	0.014 (2)	0.057 (2)
O2	0.102 (2)	0.087 (2)	0.109 (3)	−0.0398 (19)	−0.024 (2)	0.0179 (19)
O3	0.0643 (14)	0.0489 (12)	0.0396 (12)	0.0150 (10)	−0.0031 (10)	0.0140 (10)
O4	0.0582 (13)	0.0395 (11)	0.0457 (12)	0.0168 (10)	0.0147 (10)	0.0163 (9)
O5	0.0454 (12)	0.0523 (12)	0.0729 (15)	0.0170 (10)	0.0255 (11)	0.0333 (11)
O6	0.0448 (11)	0.0443 (11)	0.0645 (13)	0.0227 (9)	0.0227 (10)	0.0243 (10)
O7	0.0597 (14)	0.0859 (17)	0.0859 (17)	0.0228 (13)	0.0164 (13)	0.0598 (15)
C1	0.0440 (16)	0.0369 (15)	0.0531 (18)	0.0118 (13)	0.0097 (14)	0.0166 (13)
C2	0.0388 (16)	0.0382 (16)	0.064 (2)	0.0084 (13)	0.0055 (15)	0.0110 (15)
C3	0.0479 (19)	0.054 (2)	0.0476 (19)	0.0224 (16)	−0.0033 (15)	0.0054 (15)
C4	0.060 (2)	0.065 (2)	0.0404 (17)	0.0271 (18)	0.0054 (15)	0.0173 (15)
C5	0.0463 (17)	0.0507 (17)	0.0430 (17)	0.0149 (14)	0.0090 (14)	0.0203 (14)
C6	0.0372 (14)	0.0332 (14)	0.0385 (15)	0.0163 (12)	0.0081 (12)	0.0114 (12)
C7	0.0359 (14)	0.0326 (13)	0.0357 (14)	0.0115 (11)	0.0112 (11)	0.0142 (11)
C8	0.0331 (14)	0.0305 (13)	0.0385 (15)	0.0076 (11)	0.0090 (11)	0.0171 (11)
C9	0.0396 (15)	0.0355 (14)	0.0413 (15)	0.0124 (12)	0.0117 (12)	0.0207 (12)
C10	0.0544 (18)	0.0459 (16)	0.0425 (17)	0.0196 (14)	0.0143 (14)	0.0208 (14)
C11	0.077 (2)	0.0561 (19)	0.0492 (18)	0.0301 (18)	0.0282 (17)	0.0225 (15)
C12	0.073 (2)	0.0516 (18)	0.071 (2)	0.0364 (17)	0.0347 (19)	0.0298 (17)
C13	0.0521 (18)	0.0464 (17)	0.063 (2)	0.0234 (14)	0.0187 (16)	0.0296 (16)
C14	0.0419 (15)	0.0367 (14)	0.0438 (16)	0.0112 (12)	0.0134 (13)	0.0215 (13)
C15	0.0394 (15)	0.0315 (13)	0.0419 (15)	0.0086 (12)	0.0096 (12)	0.0189 (12)
C16	0.0462 (16)	0.0325 (14)	0.0395 (16)	0.0052 (13)	0.0062 (13)	0.0185 (12)
C17	0.086 (3)	0.0516 (19)	0.0377 (18)	0.0107 (18)	−0.0004 (17)	0.0122 (15)
C18	0.0348 (14)	0.0337 (13)	0.0319 (14)	0.0104 (11)	0.0062 (11)	0.0141 (11)
C19	0.0365 (14)	0.0350 (14)	0.0348 (14)	0.0113 (12)	0.0090 (12)	0.0139 (12)
C20	0.0458 (17)	0.0403 (15)	0.0557 (18)	0.0156 (13)	0.0210 (14)	0.0205 (14)
C21	0.053 (2)	0.063 (2)	0.074 (2)	0.0243 (17)	0.0356 (18)	0.0269 (18)
C22	0.0520 (19)	0.056 (2)	0.083 (2)	0.0128 (16)	0.0345 (18)	0.0313 (18)
C23	0.0534 (18)	0.0423 (16)	0.065 (2)	0.0129 (15)	0.0245 (16)	0.0278 (15)
C24	0.0390 (15)	0.0374 (14)	0.0397 (15)	0.0115 (12)	0.0118 (12)	0.0179 (12)
C25	0.0358 (14)	0.0320 (13)	0.0357 (14)	0.0108 (11)	0.0088 (11)	0.0141 (11)
C26	0.0351 (14)	0.0378 (15)	0.0394 (15)	0.0115 (12)	0.0085 (12)	0.0174 (12)
C27	0.0509 (19)	0.071 (2)	0.085 (3)	0.0347 (17)	0.0318 (18)	0.035 (2)
C28	0.062 (2)	0.098 (3)	0.091 (3)	0.010 (2)	0.005 (2)	0.059 (3)
C29	0.070 (3)	0.117 (4)	0.187 (5)	0.039 (3)	0.061 (3)	0.103 (4)

Geometric parameters (Å, º) top

N1—O2	1.218 (4)	C10—C11	1.369 (4)
N1—O1	1.226 (5)	C10—H10A	0.9300
N1—C2	1.459 (5)	C11—C12	1.404 (4)
N2—C14	1.362 (3)	C11—H11A	0.9300
N2—C15	1.383 (3)	C12—C13	1.364 (4)
N2—H2A	0.8600	C12—H12A	0.9300
N3—C24	1.358 (3)	C13—C14	1.395 (4)
N3—C25	1.372 (3)	C13—H13A	0.9300
N3—H3A	0.8600	C15—C16	1.458 (4)
O3—C16	1.339 (3)	C17—H17A	0.9600
O3—C17	1.456 (4)	C17—H17B	0.9600
O4—C16	1.214 (3)	C17—H17C	0.9600
O5—C26	1.211 (3)	C18—C25	1.385 (3)
O6—C26	1.337 (3)	C18—C19	1.433 (4)
O6—C27	1.441 (3)	C19—C20	1.409 (4)
O7—C28	1.402 (4)	C19—C24	1.414 (4)
O7—H7B	0.8200	C20—C21	1.372 (4)
C1—C6	1.380 (4)	C20—H20A	0.9300
C1—C2	1.393 (4)	C21—C22	1.393 (4)
C1—H1A	0.9300	C21—H21A	0.9300
C2—C3	1.370 (5)	C22—C23	1.359 (4)
C3—C4	1.369 (5)	C22—H22A	0.9300
C3—H3B	0.9300	C23—C24	1.397 (4)
C4—C5	1.384 (4)	C23—H23A	0.9300
C4—H4A	0.9300	C25—C26	1.457 (4)
C5—C6	1.388 (4)	C27—H27A	0.9600
C5—H5A	0.9300	C27—H27B	0.9600
C6—C7	1.529 (4)	C27—H27C	0.9600
C7—C18	1.511 (3)	C28—C29	1.482 (6)
C7—C8	1.521 (3)	C28—H28A	0.9700
C7—H7A	0.9800	C28—H28B	0.9700
C8—C15	1.384 (3)	C29—H29A	0.9600
C8—C9	1.435 (4)	C29—H29B	0.9600
C9—C10	1.408 (4)	C29—H29C	0.9600
C9—C14	1.420 (4)

O2—N1—O1	122.4 (4)	N2—C15—C8	109.5 (2)
O2—N1—C2	118.9 (4)	N2—C15—C16	121.9 (2)
O1—N1—C2	118.7 (3)	C8—C15—C16	128.6 (2)
C14—N2—C15	109.2 (2)	O4—C16—O3	123.8 (3)
C14—N2—H2A	125.4	O4—C16—C15	123.9 (2)
C15—N2—H2A	125.4	O3—C16—C15	112.2 (2)
C24—N3—C25	109.1 (2)	O3—C17—H17A	109.5
C24—N3—H3A	125.4	O3—C17—H17B	109.5
C25—N3—H3A	125.4	H17A—C17—H17B	109.5
C16—O3—C17	115.9 (2)	O3—C17—H17C	109.5
C26—O6—C27	117.0 (2)	H17A—C17—H17C	109.5
C28—O7—H7B	109.5	H17B—C17—H17C	109.5
C6—C1—C2	118.6 (3)	C25—C18—C19	105.9 (2)
C6—C1—H1A	120.7	C25—C18—C7	124.8 (2)
C2—C1—H1A	120.7	C19—C18—C7	129.2 (2)
C3—C2—C1	122.8 (3)	C20—C19—C24	117.8 (2)
C3—C2—N1	118.8 (3)	C20—C19—C18	135.2 (2)
C1—C2—N1	118.3 (3)	C24—C19—C18	107.0 (2)
C4—C3—C2	118.2 (3)	C21—C20—C19	118.7 (3)
C4—C3—H3B	120.9	C21—C20—H20A	120.6
C2—C3—H3B	120.9	C19—C20—H20A	120.6
C3—C4—C5	120.2 (3)	C20—C21—C22	121.8 (3)
C3—C4—H4A	119.9	C20—C21—H21A	119.1
C5—C4—H4A	119.9	C22—C21—H21A	119.1
C4—C5—C6	121.5 (3)	C23—C22—C21	121.6 (3)
C4—C5—H5A	119.2	C23—C22—H22A	119.2
C6—C5—H5A	119.2	C21—C22—H22A	119.2
C1—C6—C5	118.6 (3)	C22—C23—C24	117.3 (3)
C1—C6—C7	119.3 (2)	C22—C23—H23A	121.4
C5—C6—C7	122.1 (2)	C24—C23—H23A	121.4
C18—C7—C8	113.3 (2)	N3—C24—C23	129.1 (2)
C18—C7—C6	112.2 (2)	N3—C24—C19	108.2 (2)
C8—C7—C6	113.1 (2)	C23—C24—C19	122.8 (3)
C18—C7—H7A	105.8	N3—C25—C18	109.9 (2)
C8—C7—H7A	105.8	N3—C25—C26	120.3 (2)
C6—C7—H7A	105.8	C18—C25—C26	129.7 (2)
C15—C8—C9	106.5 (2)	O5—C26—O6	123.4 (2)
C15—C8—C7	124.1 (2)	O5—C26—C25	125.2 (2)
C9—C8—C7	129.4 (2)	O6—C26—C25	111.4 (2)
C10—C9—C14	117.5 (2)	O6—C27—H27A	109.5
C10—C9—C8	135.7 (2)	O6—C27—H27B	109.5
C14—C9—C8	106.8 (2)	H27A—C27—H27B	109.5
C11—C10—C9	119.5 (3)	O6—C27—H27C	109.5
C11—C10—H10A	120.3	H27A—C27—H27C	109.5
C9—C10—H10A	120.3	H27B—C27—H27C	109.5
C10—C11—C12	121.5 (3)	O7—C28—C29	114.0 (4)
C10—C11—H11A	119.2	O7—C28—H28A	108.8
C12—C11—H11A	119.2	C29—C28—H28A	108.8
C13—C12—C11	121.1 (3)	O7—C28—H28B	108.8
C13—C12—H12A	119.4	C29—C28—H28B	108.8
C11—C12—H12A	119.4	H28A—C28—H28B	107.7
C12—C13—C14	117.7 (3)	C28—C29—H29A	109.5
C12—C13—H13A	121.2	C28—C29—H29B	109.5
C14—C13—H13A	121.2	H29A—C29—H29B	109.5
N2—C14—C13	129.2 (3)	C28—C29—H29C	109.5
N2—C14—C9	108.1 (2)	H29A—C29—H29C	109.5
C13—C14—C9	122.7 (3)	H29B—C29—H29C	109.5

C6—C1—C2—C3	−0.5 (4)	C7—C8—C15—N2	−177.3 (2)
C6—C1—C2—N1	−179.1 (3)	C9—C8—C15—C16	179.5 (3)
O2—N1—C2—C3	8.1 (5)	C7—C8—C15—C16	1.0 (4)
O1—N1—C2—C3	−171.5 (4)	C17—O3—C16—O4	−1.0 (4)
O2—N1—C2—C1	−173.3 (3)	C17—O3—C16—C15	178.6 (2)
O1—N1—C2—C1	7.1 (5)	N2—C15—C16—O4	−171.1 (2)
C1—C2—C3—C4	0.6 (5)	C8—C15—C16—O4	10.7 (4)
N1—C2—C3—C4	179.1 (3)	N2—C15—C16—O3	9.3 (4)
C2—C3—C4—C5	−0.7 (5)	C8—C15—C16—O3	−168.9 (3)
C3—C4—C5—C6	0.9 (5)	C8—C7—C18—C25	−149.2 (2)
C2—C1—C6—C5	0.6 (4)	C6—C7—C18—C25	81.3 (3)
C2—C1—C6—C7	179.7 (2)	C8—C7—C18—C19	34.6 (4)
C4—C5—C6—C1	−0.8 (4)	C6—C7—C18—C19	−95.0 (3)
C4—C5—C6—C7	−179.9 (2)	C25—C18—C19—C20	−178.9 (3)
C1—C6—C7—C18	−157.0 (2)	C7—C18—C19—C20	−2.1 (5)
C5—C6—C7—C18	22.1 (3)	C25—C18—C19—C24	0.5 (3)
C1—C6—C7—C8	73.4 (3)	C7—C18—C19—C24	177.3 (2)
C5—C6—C7—C8	−107.6 (3)	C24—C19—C20—C21	−0.2 (4)
C18—C7—C8—C15	73.3 (3)	C18—C19—C20—C21	179.1 (3)
C6—C7—C8—C15	−157.5 (2)	C19—C20—C21—C22	0.2 (5)
C18—C7—C8—C9	−104.8 (3)	C20—C21—C22—C23	0.0 (5)
C6—C7—C8—C9	24.3 (4)	C21—C22—C23—C24	−0.4 (5)
C15—C8—C9—C10	179.2 (3)	C25—N3—C24—C23	179.3 (3)
C7—C8—C9—C10	−2.4 (5)	C25—N3—C24—C19	0.2 (3)
C15—C8—C9—C14	−0.7 (3)	C22—C23—C24—N3	−178.7 (3)
C7—C8—C9—C14	177.7 (2)	C22—C23—C24—C19	0.4 (4)
C14—C9—C10—C11	0.8 (4)	C20—C19—C24—N3	179.1 (2)
C8—C9—C10—C11	−179.1 (3)	C18—C19—C24—N3	−0.4 (3)
C9—C10—C11—C12	−1.4 (5)	C20—C19—C24—C23	−0.1 (4)
C10—C11—C12—C13	1.1 (5)	C18—C19—C24—C23	−179.6 (3)
C11—C12—C13—C14	−0.1 (5)	C24—N3—C25—C18	0.1 (3)
C15—N2—C14—C13	−179.4 (3)	C24—N3—C25—C26	−177.3 (2)
C15—N2—C14—C9	0.8 (3)	C19—C18—C25—N3	−0.4 (3)
C12—C13—C14—N2	179.7 (3)	C7—C18—C25—N3	−177.4 (2)
C12—C13—C14—C9	−0.5 (4)	C19—C18—C25—C26	176.8 (2)
C10—C9—C14—N2	−180.0 (2)	C7—C18—C25—C26	−0.2 (4)
C8—C9—C14—N2	−0.1 (3)	C27—O6—C26—O5	−2.3 (4)
C10—C9—C14—C13	0.2 (4)	C27—O6—C26—C25	177.0 (2)
C8—C9—C14—C13	−179.9 (3)	N3—C25—C26—O5	−179.9 (2)
C14—N2—C15—C8	−1.2 (3)	C18—C25—C26—O5	3.2 (4)
C14—N2—C15—C16	−179.7 (2)	N3—C25—C26—O6	0.8 (3)
C9—C8—C15—N2	1.2 (3)	C18—C25—C26—O6	−176.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg3, Cg4 and Cg5 are the centroids of the C1-ring, C10-ring and C20-ring, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7ⁱ	0.86	2.17	2.924 (3)	146
N3—H3A···O4ⁱⁱ	0.86	2.02	2.861 (4)	166
O7—H7B···O5	0.82	2.13	2.892 (4)	154
C10—H10A···Cg3	0.93	2.87	3.633 (4)	140
C11—H11A···Cg5ⁱⁱⁱ	0.93	2.76	3.634 (4)	156
C17—H17B···Cg4ⁱ	0.96	2.89	3.813 (5)	163
C27—H27B···Cg5ⁱⁱ	0.96	2.75	3.496 (4)	135

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg3, Cg4 and Cg5 are the centroids of the C1-ring, C10-ring and C20-ring, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O7ⁱ	0.86	2.17	2.924 (3)	146
N3—H3A···O4ⁱⁱ	0.86	2.02	2.861 (4)	166
O7—H7B···O5	0.82	2.13	2.892 (4)	154
C10—H10A···Cg3	0.93	2.87	3.633 (4)	140
C11—H11A···Cg5ⁱⁱⁱ	0.93	2.76	3.634 (4)	156
C17—H17B···Cg4ⁱ	0.96	2.89	3.813 (5)	163
C27—H27B···Cg5ⁱⁱ	0.96	2.75	3.496 (4)	135

Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₇H₂₁N₃O₆·C₂H₆O
M_r	529.54
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.074 (2), 11.585 (2), 12.898 (3)
α, β, γ (°)	114.09 (3), 106.68 (3), 99.20 (3)
V (Å³)	1372.5 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5313, 5032, 3254
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.166, 1.04
No. of reflections	5032
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.25

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXTL (Sheldrick, 2008).

Acknowledgements

Diffraction data were collected in the Center of Testing and Analysis, Nanjing University. The work was supported by the Funding of Nanjing College of Chemical Technology, China (NHKY-2013–02).

References

Chang, Y.-C., Riby, J., Grace, H. F., Peng, G.-F. & Bieldanes, L. F. (1999). Biochem. Pharmacol. 58, 825–834. Web of Science CrossRef PubMed CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Ge, X., Fares, F. A. & Fares, S. Y. (1999). Anticancer Res. 19, 3199–3203. Web of Science PubMed CAS Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Ni, Y.-C. (2008). Curr. Med. Imaging Rev. 4, 96–112. Web of Science CrossRef CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Poter, J. K., Bacon, C. W., Robins, J. D., Himmelsbach, D. S. & Higman, H. C. (1977). J. Agric. Food Chem. 25, 88–93. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, H.-S., Li, Y.-L., Xu, N., Xu, H. & Zhang, J.-D. (2012). Acta Cryst. E68, o2764. CSD CrossRef IUCr Journals Google Scholar
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Sundberg, R. J. (1996). The Chemistry of Indoles, p. 113. New York: Academic Press. Google Scholar

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Volume 70| Part 11| November 2014| Pages 370-372

doi:10.1107/S1600536814022296

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of di­methyl 3,3′-[(3-nitro­phen­yl)methyl­ene]bis­­(1H-indole-2-carboxyl­ate) ethanol monosolvate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of dimethyl 3,3′-[(3-nitrophenyl)methylene]bis(1H-indole-2-carboxylate) ethanol monosolvate

3. Supramolecular features