Crystal structure of 2-(2,4-di­chloro­phen­yl)-4-hydroxy-9-phenyl­sulfonyl-9H-carbazole-3-carbaldehyde

Umadevi, M.; Ramalingam, B.M.; Yamuna, R.; Mohanakrishnan, A.K.; Chakkaravarthi, G.

doi:10.1107/S1600536814024064

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages 466-468

doi:10.1107/S1600536814024064

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Crystal structure of 2-(2,4-dichlorophenyl)-4-hydroxy-9-phenylsulfonyl-9H-carbazole-3-carbaldehyde

M. Umadevi,^a,^b B. M. Ramalingam,^c R. Yamuna,^d ^* A. K. Mohanakrishnan ^c and G. Chakkaravarthi ^e ^*

^aResearch and Development Centre, Bharathiyar University, India, ^bDepartment of Chemistry, Pallavan College of Engineering, Kanchipuram, Tamilnadu, India, ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, ^dDepartment of Sciences, Chemistry and Materials Research Laboratory, Amrita Vishwa Vidyapeetham University, Ettimadai, Coimbatore 641 112, India, and ^eDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: ryamuna1@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 18 October 2014; accepted 31 October 2014; online 8 November 2014)

In the title compound, C₂₅H₁₅Cl₂NO₄S, the dichlorophenyl ring is twisted by 68.69 (11)° from the mean plane of the carbazole ring system [r.m.s. deviation = 0.084 (2)°]. The hydroxy group is involved in an intramolecular O—H⋯O hydrogen bond, which generates an S(6) graph-set motif. In the crystal, pairs of C—H⋯Cl hydrogen bonds link molecules into inversion dimers with an R²₂(26) motif. Weak C—H⋯O interactions further link these dimers into ribbons propagating in [100].

Keywords: crystal structure; carbazole derivative; hydrogen bonding.

CCDC reference: 1032055

1. Chemical context

In continuation of our studies of carbazole derivatives, which are found to possess various biological activities, such as anti-oxidative (Tachibana et al., 2001 ), anti-inflammatory and antimutagenic (Ramsewak et al., 1999 ), antibiotic, antifungal and cytotoxic (Chakraborty et al., 1965 , 1978 ), we report herein on the synthesis and crystal structure of the title compound (I) (Fig. 1).

Figure 1
The molecular structure of (I)

showing the atomic labelling scheme and 50% probability displacement ellipsoids.

2. Structural commentary

The geometric parameters of (I) agree well with those reported for related structures [Chakkaravarthi et al. 2008 , 2009 ]. The C1–C6 phenyl ring makes a dihedral angle of 79.76 (11)° with the carbazole ring system (C7–C18/N1). The dichlorophenyl ring (C21–C25) is twisted by 68.69 (11)° from the mean plane of the carbazole ring system and inclined at an angle of 32.22 (13)° to the phenyl ring.

Atom S1 has a distorted tetrahedral configuration. The widening of angle O1—S1—O2 [120.49 (11)°] and narrowing of angle N1—S1—C1 [105.36 (10)°] from the ideal tetrahedral values are attributed to the Thorpe–Ingold effect (Bassindale, 1984 ). As a result of the electron–withdrawing character of the phenylsulfonyl group, the bond lengths N1—C7 [1.431 (3) Å] and N1—C18 [1.414 (3) Å] in the molecule are longer than the mean value of 1.355 (14) Å (Allen et al., 1987 ; Groom & Allen et al., 2014 ).

3. Supramolecular features

The hydroxy group is involved in an intramolecular O—H⋯O hydrogen bond (Table 1), which generates an S(6) graph-set motif. In the crystal, pairs of C—H⋯Cl hydrogen bonds link molecules into inversion dimers with an R₂²(26) motif (Bernstein et al., 1995 ), and weak C—H⋯O interactions further link these dimers into ribbons propagating in [100] (Table 1 and Fig. 2) .

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O4	0.83 (1)	1.81 (2)	2.563 (3)	151 (3)
C2—H2⋯Cl1ⁱ	0.93	2.81	3.412 (2)	123
C5—H5⋯O2ⁱⁱ	0.93	2.49	3.184 (3)	131
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x+1, y, z.

Figure 2
A portion of the crystal packing of (I)

showing the hydrogen-bonded (dashed lines) ribbon [symmetry codes: (i) 1-x, 2-y, 1-z; (ii) 1 + x, y, z].

4. Synthesis and crystallization

Enamine 16 g (500 mg, 0.95 mmol) was reacted with CuBr₂ (212 mg, 0.95 mmol) in dry DMF (20 ml) at reflux for 1 h under N₂. The reaction mass was poured over crushed ice (50 ml) containing concentrated HCl (1 ml). The precipitated solid was filtered, washed with water and air-dried to obtain the crude compound, which was purified by flash column chromatography on silica gel (230–420 mesh, n-hexane/ethyl acetate, 7:3) to afford 17 g as pale-yellow crystals suitable for X-ray analysis. Yield: 368 mg (78%); m.p.: 461–463 K.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy H atom was located in a difference Fourier map and refined isotropically with a distance restraint of O—H = 0.82 (1) Å. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The components of the anisotropic displacement parameters in the direction of the bond between O4 and C19 were restrained to be equal within an effective standard deviation of 0.001 using the DELU command in SHELXL97 (Sheldrick, 2008 ).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₅H₁₅Cl₂NO₄S
M_r	496.34
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	295
a, b, c (Å)	8.0688 (4), 9.9086 (5), 14.4041 (8)
α, β, γ (°)	75.297 (3), 80.604 (2), 74.306 (3)
V (Å³)	1066.83 (10)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.44
Crystal size (mm)	0.28 × 0.24 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.887, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	35959, 6221, 3582
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.126, 1.02
No. of reflections	6221
No. of parameters	302
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.48
Computer programs: APEX2 and SAINT (Bruker, 2004 ), SHELXS97 and SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1032055

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814024064/cv5474sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024064/cv5474Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814024064/cv5474Isup3.cml

checkCIF report

Chemical context top

In continuation of our studies of carbazole derivatives, which are found to possess various biological activities, such as anti-oxidative (Tachibana et al., 2001), anti-inflammatory and antimutagenic (Ramsewak et al., 1999), antibiotic, antifungal and cytotoxic (Chakraborty et al., 1965, 1978), we report herein the synthesis and crystal structure of the title compound (I) (Fig. 1).

Structural commentary top

The geometric parameters of (I) agree well with those reported for related structures [Chakkaravarthi et al. 2008, 2009]. The C1–C6 phenyl ring makes a dihedral angle of 79.76 (11)° with the carbazole ring system (C7–C18/N1). The dichlorophenyl ring (C21–C25) is twisted by 68.69 (11)° from the mean plane of the carbazole ring system and inclined at an angle of 32.22 (13)° to the phenyl ring.

Atom S1 has a distorted tetrahedral configuration. The widening of angle O1—S1—O2 [120.49 (11)°] and narrowing of angle N1—S1—C1 [105.36 (10)°] from the ideal tetrahedral values are attributed to the Thorpe–Ingold effect (Bassindale, 1984). As a result of the electron–withdrawing character of the phenylsulfonyl group, the bond lengths N1—C7 [1.431 (3) Å] and N1—C18 [1.414 (3) Å] in the molecule are longer than the mean value of 1.355 (14) Å (Allen et al., 1987; Groom & Allen, 2014).

Supramolecular features top

The hydroxy group is involved in an intramolecular O—H···O hydrogen bond (Table 1), which generates an S(6) graph-set motif. In the crystal, pairs of C—H···Cl hydrogen bonds link molecules into centrosymmetric dimers with an R²₂(26) motif (Bernstein et al., 1995), and weak C—H···O interactions further link these dimers into ribbons propagating in [100] (Table 1 and Fig. 2 ).

Synthesis and crystallization top

The reaction of enamine 16 g (500 mg, 0.95 mmol) with CuBr₂ (212 mg, 0.95 mmol) in dry DMF (20 ml) at reflux for 1 h under N₂. The reaction mass was poured over crushed ice (50 ml) containing concentrated HCl (1 ml). The precipitated solid was filtered, washed with water and air-dried to obtain the crude compound, which was purified by flash column chromatography on silica gel (230–420 mesh, n-hexane/ethyl acetate, 7:3) to afford 17 g as pale-yellow solid crystals suitable for X-ray analysis. Yield: 368 mg (78%); m.p.: 461–463 K.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxy H atom was located in a Fourier map and refined isotropically with a distance restraint of O—H = 0.82 (1) Å. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The components of the anisotropic displacement parameters in the direction of the bond between O4 and C19 were restrained to be equal within an effective standard deviation of 0.001 using the DELU command in SHELXL97 (Sheldrick, 2008).

Related literature top

For related literature, see: Allen et al. (1987); Bassindale (1984); Bernstein et al. (1995); Chakkaravarthi et al. (2008, 2009); Chakraborty et al. (1965, 1978); Ramsewak et al. (1999); Sheldrick (2008); Tachibana et al. (2001).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic labelling scheme and 50% probability displacement ellipsoids.

Fig. 2. A portion of the crystal packing of (I) showing the hydrogen-bonded (dashed lines) ribbon [symmetry codes: (i) 1-x, 2-y, 1-z; (ii) 1+x, y, z].

2-(2,4-Dichlorophenyl)-4-hydroxy-9-phenylsulfonyl-9H-carbazole-3-carbaldehyde top

Crystal data top

C₂₅H₁₅Cl₂NO₄S	Z = 2
M_r = 496.34	F(000) = 508
Triclinic, P1	D_x = 1.545 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0688 (4) Å	Cell parameters from 9493 reflections
b = 9.9086 (5) Å	θ = 2.2–31.5°
c = 14.4041 (8) Å	µ = 0.44 mm⁻¹
α = 75.297 (3)°	T = 295 K
β = 80.604 (2)°	Block, pale yellow
γ = 74.306 (3)°	0.28 × 0.24 × 0.18 mm
V = 1066.83 (10) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	6221 independent reflections
Radiation source: fine-focus sealed tube	3582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω and ϕ scan	θ_max = 31.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.887, T_max = 0.925	k = −14→13
35959 measured reflections	l = −19→21

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0395P)² + 0.6935P] where P = (F_o² + 2F_c²)/3
6221 reflections	(Δ/σ)_max < 0.001
302 parameters	Δρ_max = 0.44 e Å⁻³
2 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₂₅H₁₅Cl₂NO₄S	γ = 74.306 (3)°
M_r = 496.34	V = 1066.83 (10) Å³
Triclinic, P1	Z = 2
a = 8.0688 (4) Å	Mo Kα radiation
b = 9.9086 (5) Å	µ = 0.44 mm⁻¹
c = 14.4041 (8) Å	T = 295 K
α = 75.297 (3)°	0.28 × 0.24 × 0.18 mm
β = 80.604 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6221 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3582 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.925	R_int = 0.044
35959 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	2 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.44 e Å⁻³
6221 reflections	Δρ_min = −0.48 e Å⁻³
302 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 > 2sigma(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
C1	1.0997 (3)	0.3850 (2)	0.70308 (15)	0.0345 (5)
C2	1.0940 (3)	0.4840 (3)	0.61674 (17)	0.0471 (6)
H2	0.9939	0.5159	0.5854	0.057*
C3	1.2388 (4)	0.5356 (3)	0.5769 (2)	0.0582 (7)
H3	1.2371	0.6018	0.5181	0.070*
C4	1.3848 (3)	0.4886 (3)	0.6244 (2)	0.0551 (7)
H4	1.4821	0.5234	0.5974	0.066*
C5	1.3893 (3)	0.3910 (3)	0.71103 (19)	0.0524 (6)
H5	1.4889	0.3607	0.7428	0.063*
C6	1.2472 (3)	0.3379 (3)	0.75090 (17)	0.0445 (5)
H6	1.2499	0.2710	0.8094	0.053*
C7	0.8949 (3)	0.3246 (2)	0.94145 (16)	0.0384 (5)
C8	1.0086 (3)	0.1961 (2)	0.97765 (19)	0.0483 (6)
H8	1.0604	0.1300	0.9395	0.058*
C9	1.0419 (3)	0.1703 (3)	1.07175 (19)	0.0530 (6)
H9	1.1187	0.0853	1.0975	0.064*
C10	0.9647 (3)	0.2669 (3)	1.12916 (19)	0.0557 (7)
H10	0.9915	0.2468	1.1924	0.067*
C11	0.8483 (3)	0.3927 (3)	1.09402 (17)	0.0487 (6)
H11	0.7938	0.4565	1.1334	0.058*
C12	0.8138 (3)	0.4224 (2)	0.99882 (16)	0.0376 (5)
C13	0.7085 (3)	0.5439 (2)	0.93908 (15)	0.0349 (5)
C14	0.5999 (3)	0.6708 (2)	0.95850 (16)	0.0387 (5)
C15	0.5169 (3)	0.7739 (2)	0.88353 (17)	0.0404 (5)
C16	0.5471 (3)	0.7497 (2)	0.78918 (17)	0.0391 (5)
C17	0.6519 (3)	0.6224 (2)	0.76991 (16)	0.0392 (5)
H17	0.6704	0.6054	0.7080	0.047*
C18	0.7289 (3)	0.5206 (2)	0.84630 (16)	0.0350 (5)
C19	0.3929 (3)	0.9054 (3)	0.9062 (2)	0.0491 (6)
H19	0.3362	0.9730	0.8567	0.059*
C20	0.4596 (3)	0.8596 (2)	0.70952 (17)	0.0415 (5)
C21	0.3271 (3)	0.8330 (3)	0.67214 (19)	0.0500 (6)
H21	0.2988	0.7447	0.6954	0.060*
C22	0.2357 (4)	0.9332 (3)	0.6016 (2)	0.0578 (7)
H22	0.1467	0.9132	0.5777	0.069*
C23	0.2786 (4)	1.0625 (3)	0.56730 (18)	0.0529 (6)
C24	0.4114 (4)	1.0926 (2)	0.60002 (19)	0.0534 (6)
H24	0.4407	1.1803	0.5752	0.064*
C25	0.5009 (3)	0.9905 (2)	0.67056 (18)	0.0478 (6)
N1	0.8388 (2)	0.38241 (18)	0.84706 (13)	0.0383 (4)
O1	0.9772 (2)	0.16411 (16)	0.78521 (13)	0.0539 (5)
O2	0.7943 (2)	0.37100 (18)	0.68385 (12)	0.0480 (4)
O3	0.5763 (2)	0.6893 (2)	1.04911 (13)	0.0545 (5)
O4	0.3634 (3)	0.9274 (2)	0.98621 (16)	0.0726 (6)
S1	0.92029 (7)	0.31431 (6)	0.75094 (4)	0.03877 (15)
Cl1	0.16251 (12)	1.19156 (9)	0.48058 (6)	0.0826 (3)
Cl2	0.66928 (11)	1.03092 (8)	0.71005 (7)	0.0781 (3)
H3A	0.512 (4)	0.7704 (18)	1.047 (2)	0.084 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0343 (11)	0.0338 (10)	0.0355 (12)	−0.0022 (9)	−0.0034 (9)	−0.0143 (9)
C2	0.0419 (13)	0.0501 (14)	0.0455 (14)	−0.0059 (11)	−0.0096 (11)	−0.0059 (11)
C3	0.0609 (17)	0.0609 (16)	0.0473 (15)	−0.0190 (14)	−0.0006 (13)	−0.0007 (12)
C4	0.0466 (15)	0.0690 (17)	0.0585 (17)	−0.0252 (13)	0.0080 (12)	−0.0257 (14)
C5	0.0367 (13)	0.0736 (18)	0.0516 (16)	−0.0115 (12)	−0.0065 (11)	−0.0229 (13)
C6	0.0376 (12)	0.0531 (14)	0.0401 (13)	−0.0060 (11)	−0.0060 (10)	−0.0093 (11)
C7	0.0346 (11)	0.0329 (11)	0.0424 (13)	−0.0066 (9)	0.0005 (9)	−0.0035 (9)
C8	0.0454 (14)	0.0340 (12)	0.0541 (15)	−0.0009 (10)	0.0008 (11)	−0.0024 (11)
C9	0.0464 (14)	0.0433 (13)	0.0551 (16)	−0.0019 (11)	−0.0061 (12)	0.0055 (12)
C10	0.0512 (15)	0.0641 (17)	0.0435 (14)	−0.0102 (13)	−0.0095 (12)	0.0017 (13)
C11	0.0479 (14)	0.0527 (14)	0.0409 (14)	−0.0082 (11)	−0.0015 (11)	−0.0082 (11)
C12	0.0344 (11)	0.0346 (11)	0.0404 (12)	−0.0089 (9)	0.0014 (9)	−0.0047 (9)
C13	0.0333 (11)	0.0311 (10)	0.0380 (12)	−0.0068 (8)	−0.0012 (9)	−0.0058 (9)
C14	0.0378 (12)	0.0394 (12)	0.0401 (12)	−0.0083 (9)	−0.0018 (10)	−0.0134 (10)
C15	0.0358 (12)	0.0334 (11)	0.0503 (14)	−0.0030 (9)	−0.0047 (10)	−0.0119 (10)
C16	0.0381 (12)	0.0313 (11)	0.0454 (13)	−0.0041 (9)	−0.0075 (10)	−0.0066 (9)
C17	0.0416 (12)	0.0350 (11)	0.0392 (12)	−0.0055 (9)	−0.0039 (10)	−0.0091 (9)
C18	0.0320 (11)	0.0286 (10)	0.0418 (12)	−0.0059 (8)	0.0001 (9)	−0.0070 (9)
C19	0.0362 (12)	0.0467 (13)	0.0581 (13)	0.0058 (10)	−0.0078 (11)	−0.0156 (11)
C20	0.0405 (12)	0.0339 (11)	0.0467 (13)	−0.0007 (9)	−0.0088 (10)	−0.0090 (10)
C21	0.0489 (14)	0.0408 (13)	0.0574 (16)	−0.0077 (11)	−0.0114 (12)	−0.0052 (11)
C22	0.0556 (16)	0.0552 (16)	0.0614 (17)	−0.0051 (13)	−0.0195 (13)	−0.0109 (13)
C23	0.0593 (16)	0.0433 (14)	0.0470 (15)	0.0084 (12)	−0.0148 (12)	−0.0099 (11)
C24	0.0685 (18)	0.0326 (12)	0.0525 (15)	−0.0043 (12)	−0.0093 (13)	−0.0040 (11)
C25	0.0506 (14)	0.0362 (12)	0.0555 (15)	−0.0057 (11)	−0.0125 (12)	−0.0085 (11)
N1	0.0386 (10)	0.0305 (9)	0.0398 (10)	−0.0009 (8)	−0.0004 (8)	−0.0074 (8)
O1	0.0599 (11)	0.0312 (8)	0.0680 (12)	−0.0069 (8)	0.0004 (9)	−0.0150 (8)
O2	0.0350 (8)	0.0574 (10)	0.0583 (11)	−0.0074 (7)	−0.0119 (8)	−0.0239 (8)
O3	0.0574 (11)	0.0555 (11)	0.0474 (10)	0.0035 (9)	−0.0069 (8)	−0.0232 (9)
O4	0.0674 (13)	0.0700 (13)	0.0780 (12)	0.0113 (10)	−0.0090 (11)	−0.0405 (11)
S1	0.0357 (3)	0.0335 (3)	0.0481 (3)	−0.0054 (2)	−0.0026 (2)	−0.0150 (2)
Cl1	0.0999 (6)	0.0621 (5)	0.0691 (5)	0.0133 (4)	−0.0379 (5)	−0.0014 (4)
Cl2	0.0858 (6)	0.0561 (4)	0.1016 (6)	−0.0308 (4)	−0.0391 (5)	−0.0005 (4)

Geometric parameters (Å, º) top

C1—C2	1.373 (3)	C14—O3	1.340 (3)
C1—C6	1.383 (3)	C14—C15	1.401 (3)
C1—S1	1.744 (2)	C15—C16	1.411 (3)
C2—C3	1.382 (3)	C15—C19	1.487 (3)
C2—H2	0.9300	C16—C17	1.380 (3)
C3—C4	1.370 (4)	C16—C20	1.488 (3)
C3—H3	0.9300	C17—C18	1.391 (3)
C4—C5	1.370 (4)	C17—H17	0.9300
C4—H4	0.9300	C18—N1	1.414 (3)
C5—C6	1.371 (3)	C19—O4	1.201 (3)
C5—H5	0.9300	C19—H19	0.9300
C6—H6	0.9300	C20—C25	1.383 (3)
C7—C8	1.386 (3)	C20—C21	1.383 (3)
C7—C12	1.392 (3)	C21—C22	1.378 (3)
C7—N1	1.431 (3)	C21—H21	0.9300
C8—C9	1.371 (4)	C22—C23	1.367 (4)
C8—H8	0.9300	C22—H22	0.9300
C9—C10	1.378 (4)	C23—C24	1.367 (4)
C9—H9	0.9300	C23—Cl1	1.731 (2)
C10—C11	1.376 (3)	C24—C25	1.379 (3)
C10—H10	0.9300	C24—H24	0.9300
C11—C12	1.386 (3)	C25—Cl2	1.730 (3)
C11—H11	0.9300	N1—S1	1.6557 (19)
C12—C13	1.439 (3)	O1—S1	1.4145 (16)
C13—C18	1.389 (3)	O2—S1	1.4211 (17)
C13—C14	1.390 (3)	O3—H3A	0.826 (10)

C2—C1—C6	120.9 (2)	C14—C15—C19	118.8 (2)
C2—C1—S1	119.29 (17)	C16—C15—C19	121.1 (2)
C6—C1—S1	119.76 (17)	C17—C16—C15	120.9 (2)
C1—C2—C3	119.3 (2)	C17—C16—C20	119.0 (2)
C1—C2—H2	120.4	C15—C16—C20	119.98 (19)
C3—C2—H2	120.4	C16—C17—C18	117.7 (2)
C4—C3—C2	119.7 (2)	C16—C17—H17	121.2
C4—C3—H3	120.2	C18—C17—H17	121.2
C2—C3—H3	120.2	C13—C18—C17	122.80 (19)
C5—C4—C3	120.9 (2)	C13—C18—N1	107.83 (18)
C5—C4—H4	119.6	C17—C18—N1	129.4 (2)
C3—C4—H4	119.6	O4—C19—C15	122.3 (2)
C4—C5—C6	120.0 (2)	O4—C19—H19	118.9
C4—C5—H5	120.0	C15—C19—H19	118.9
C6—C5—H5	120.0	C25—C20—C21	116.9 (2)
C5—C6—C1	119.2 (2)	C25—C20—C16	123.7 (2)
C5—C6—H6	120.4	C21—C20—C16	119.4 (2)
C1—C6—H6	120.4	C22—C21—C20	122.2 (2)
C8—C7—C12	121.5 (2)	C22—C21—H21	118.9
C8—C7—N1	130.3 (2)	C20—C21—H21	118.9
C12—C7—N1	108.20 (18)	C23—C22—C21	118.6 (3)
C9—C8—C7	117.5 (2)	C23—C22—H22	120.7
C9—C8—H8	121.2	C21—C22—H22	120.7
C7—C8—H8	121.2	C22—C23—C24	121.5 (2)
C8—C9—C10	121.8 (2)	C22—C23—Cl1	119.5 (2)
C8—C9—H9	119.1	C24—C23—Cl1	119.0 (2)
C10—C9—H9	119.1	C23—C24—C25	118.7 (2)
C11—C10—C9	120.8 (2)	C23—C24—H24	120.7
C11—C10—H10	119.6	C25—C24—H24	120.7
C9—C10—H10	119.6	C24—C25—C20	122.1 (2)
C10—C11—C12	118.7 (2)	C24—C25—Cl2	117.76 (19)
C10—C11—H11	120.7	C20—C25—Cl2	120.19 (19)
C12—C11—H11	120.7	C18—N1—C7	107.83 (17)
C11—C12—C7	119.8 (2)	C18—N1—S1	125.70 (15)
C11—C12—C13	132.9 (2)	C7—N1—S1	125.35 (14)
C7—C12—C13	107.26 (19)	C14—O3—H3A	106 (2)
C18—C13—C14	119.19 (19)	O1—S1—O2	120.49 (11)
C18—C13—C12	108.76 (18)	O1—S1—N1	106.41 (10)
C14—C13—C12	132.1 (2)	O2—S1—N1	106.55 (10)
O3—C14—C13	118.5 (2)	O1—S1—C1	108.93 (10)
O3—C14—C15	122.2 (2)	O2—S1—C1	108.09 (10)
C13—C14—C15	119.2 (2)	N1—S1—C1	105.36 (10)
C14—C15—C16	120.03 (19)

C6—C1—C2—C3	0.8 (4)	C16—C17—C18—C13	−2.0 (3)
S1—C1—C2—C3	−177.4 (2)	C16—C17—C18—N1	179.1 (2)
C1—C2—C3—C4	−0.7 (4)	C14—C15—C19—O4	1.2 (4)
C2—C3—C4—C5	0.0 (4)	C16—C15—C19—O4	179.0 (2)
C3—C4—C5—C6	0.6 (4)	C17—C16—C20—C25	−111.3 (3)
C4—C5—C6—C1	−0.6 (4)	C15—C16—C20—C25	71.2 (3)
C2—C1—C6—C5	−0.1 (3)	C17—C16—C20—C21	69.8 (3)
S1—C1—C6—C5	177.99 (18)	C15—C16—C20—C21	−107.7 (3)
C12—C7—C8—C9	−1.6 (3)	C25—C20—C21—C22	−2.0 (4)
N1—C7—C8—C9	178.3 (2)	C16—C20—C21—C22	176.9 (2)
C7—C8—C9—C10	0.6 (4)	C20—C21—C22—C23	0.4 (4)
C8—C9—C10—C11	1.1 (4)	C21—C22—C23—C24	1.4 (4)
C9—C10—C11—C12	−1.8 (4)	C21—C22—C23—Cl1	−178.6 (2)
C10—C11—C12—C7	0.9 (3)	C22—C23—C24—C25	−1.3 (4)
C10—C11—C12—C13	−176.5 (2)	Cl1—C23—C24—C25	178.6 (2)
C8—C7—C12—C11	0.8 (3)	C23—C24—C25—C20	−0.5 (4)
N1—C7—C12—C11	−179.09 (19)	C23—C24—C25—Cl2	179.5 (2)
C8—C7—C12—C13	178.8 (2)	C21—C20—C25—C24	2.1 (4)
N1—C7—C12—C13	−1.1 (2)	C16—C20—C25—C24	−176.8 (2)
C11—C12—C13—C18	176.4 (2)	C21—C20—C25—Cl2	−177.94 (19)
C7—C12—C13—C18	−1.2 (2)	C16—C20—C25—Cl2	3.2 (3)
C11—C12—C13—C14	−3.0 (4)	C13—C18—N1—C7	−3.7 (2)
C7—C12—C13—C14	179.4 (2)	C17—C18—N1—C7	175.4 (2)
C18—C13—C14—O3	177.4 (2)	C13—C18—N1—S1	−172.07 (15)
C12—C13—C14—O3	−3.2 (4)	C17—C18—N1—S1	7.0 (3)
C18—C13—C14—C15	−1.6 (3)	C8—C7—N1—C18	−176.9 (2)
C12—C13—C14—C15	177.8 (2)	C12—C7—N1—C18	3.0 (2)
O3—C14—C15—C16	179.6 (2)	C8—C7—N1—S1	−8.5 (3)
C13—C14—C15—C16	−1.4 (3)	C12—C7—N1—S1	171.39 (15)
O3—C14—C15—C19	−2.6 (3)	C18—N1—S1—O1	−162.99 (18)
C13—C14—C15—C19	176.4 (2)	C7—N1—S1—O1	30.6 (2)
C14—C15—C16—C17	2.9 (3)	C18—N1—S1—O2	−33.2 (2)
C19—C15—C16—C17	−174.9 (2)	C7—N1—S1—O2	160.35 (17)
C14—C15—C16—C20	−179.7 (2)	C18—N1—S1—C1	81.44 (19)
C19—C15—C16—C20	2.5 (3)	C7—N1—S1—C1	−84.97 (19)
C15—C16—C17—C18	−1.2 (3)	C2—C1—S1—O1	135.88 (19)
C20—C16—C17—C18	−178.66 (19)	C6—C1—S1—O1	−42.3 (2)
C14—C13—C18—C17	3.4 (3)	C2—C1—S1—O2	3.3 (2)
C12—C13—C18—C17	−176.1 (2)	C6—C1—S1—O2	−174.85 (17)
C14—C13—C18—N1	−177.47 (19)	C2—C1—S1—N1	−110.30 (19)
C12—C13—C18—N1	3.0 (2)	C6—C1—S1—N1	71.55 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4	0.83 (1)	1.81 (2)	2.563 (3)	151 (3)
C2—H2···Cl1ⁱ	0.93	2.81	3.412 (2)	123
C5—H5···O2ⁱⁱ	0.93	2.49	3.184 (3)	131

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O4	0.826 (10)	1.810 (18)	2.563 (3)	151 (3)
C2—H2···Cl1ⁱ	0.93	2.81	3.412 (2)	123
C5—H5···O2ⁱⁱ	0.93	2.49	3.184 (3)	131

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

Experimental details

Crystal data
Chemical formula	C₂₅H₁₅Cl₂NO₄S
M_r	496.34
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.0688 (4), 9.9086 (5), 14.4041 (8)
α, β, γ (°)	75.297 (3), 80.604 (2), 74.306 (3)
V (Å³)	1066.83 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.28 × 0.24 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.887, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	35959, 6221, 3582
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.735

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.126, 1.02
No. of reflections	6221
No. of parameters	302
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.48

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras for the data collection.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin. Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Volume 70| Part 12| December 2014| Pages 466-468

doi:10.1107/S1600536814024064

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

Crystal structure of 2-(2,4-di­chloro­phen­yl)-4-hy­droxy-9-phenyl­sulfonyl-9H-carbazole-3-carbaldehyde

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 2-(2,4-dichlorophenyl)-4-hydroxy-9-phenylsulfonyl-9H-carbazole-3-carbaldehyde

3. Supramolecular features