2-(4-Chloro-2-nitro­phen­yl)-9-phenyl­sulfonyl-9H-carbazole-3-carbaldehyde

Gopinath, S.; Sethusankar, K.; Ramalingam, B.M.; Mohanakrishnan, A.K.

doi:10.1107/S1600536813022253

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1420-o1421

doi:10.1107/S1600536813022253

Open

access

2-(4-Chloro-2-nitrophenyl)-9-phenylsulfonyl-9H-carbazole-3-carbaldehyde

S. Gopinath,^a K. Sethusankar,^a ^* Bose Muthu Ramalingam ^b and Arasambattu K. Mohanakrishnan ^b

^aDepartment of Physics, RKM Vivekananda College (Autonomous), Chennai 600 004, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: ksethusankar@yahoo.co.in

(Received 1 August 2013; accepted 8 August 2013; online 14 August 2013)

In the title compound, C₂₅H₁₅ClN₂O₆S, the carbazole ring system is essentially planar, with a maximum deviation of 0.152 (3) Å for the C atom to which the 4-chloro-2-nitrophenyl ring is attached. Its mean plane is almost orthogonal to the phenylsulfonyl and nitrophenyl rings, making dihedral angles of 82.64 (14) and 79.89 (13)°, respectively. The N atom of the nitro group deviates by 0.032 (3) Å from the benzene ring to which it is attached. The molecular structure features intramolecular O—H⋯O and C—H⋯O hydrogen bonds, which generate three S(6) ring motifs. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, which generate C(6) and C(9) chains running in the [100] and [010] directions, respectively, forming a two-dimensional network lying parallel to (001). There are also R₄³(28) supramolecular graph-set ring motifs enclosed within these networks.

Related literature

For the biological activity and uses of carbazole derivatives, see: Itoigawa et al. (2000 ); Ramsewak et al. (1999 ). For their electronic properties and applications, see: Friend et al. (1999 ); Zhang et al. (2004 ). For related structures, see: Chakkaravarthi et al. (2008 ). For bond-length distortions, see: Allen et al. (1987 ). For graph-set notation, see: Bernstein et al. (1995 ). For the Thorpe–Ingold effect, see: Bassindale et al. (1984 ).

Experimental

Crystal data

C₂₅H₁₅ClN₂O₆S
M_r = 506.91
Monoclinic, P 2₁ /c
a = 8.1947 (15) Å
b = 14.384 (3) Å
c = 18.795 (3) Å
β = 90.963 (9)°
V = 2215.2 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.910, T_max = 0.939
16586 measured reflections
3893 independent reflections
2809 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.172
S = 1.05
3893 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	1.91	2.629 (4)	146
C2—H2⋯O3	0.93	2.36	2.949 (5)	121
C9—H9⋯O4	0.93	2.31	2.910 (4)	122
C13—H13⋯O4ⁱ	0.93	2.56	3.411 (4)	153
C18—H18⋯O4ⁱⁱ	0.93	2.53	3.287 (4)	139
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813022253/su2632sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813022253/su2632Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813022253/su2632Isup3.cml

checkCIF report

Comment top

Carbazole and its derivative have become quite attractive compounds owing to their applications in pharmacy and molecular electronics. It has been reported that carbazole derivatives exhibit various biological activities such as antitumor and antioxidative (Itoigawa et al., 2000), and anti-inflammatory and antimutagenic (Ramsewak et al., 1999). They also exhibit electroactivity and luminenscence and are considered to be potential candidates for electronic applications such as colour displays, organic, semiconductors, laser and solar cells (Friend et al., 1999; Zhang et al., 2004).

The title compound, Fig. 1, comprises a carbazole ring system which is attached to a phenyl-sulfonyl ring, a chloro substituted nitro-phenyl ring, a carbaldehyde group and a hydroxyl group. The carbazole ring system is essentially planar with maximum deviation of -0.152 (3) Å for atom C10 to which is attached the 4-chloro-2-nitro-phenyl ring. Atom O1 significantly deviates from the carbazole ring mean plane by -0.1921 (24) Å. The carbazole ring system is almost orthogonal to the phenyl ring attached to sulfonyl group and to the 4-chloro-2-nitro-phenyl ring with dihedral angles of 82.64 (14)° and 79.89 (13)°, respectively.

As a result of electron-withdrawing character of the phenylsulfonyl group the bond lengths N1–C1 = 1.429 (4) Å and N1–C8 = 1.408 (4) Å are longer than the mean value of 1.355 (14) Å (Allen et al., 1987). Atom S1 has a distorted tetrahedral configuration. The widening of angle O3—S1—O4 [120.14 (14) °] and the narrowing of angle N1—S1—C11 [103.36 (13)°] from the ideal tetrahedral value are attributed to the Thorpe-Ingold effect (Bassindale et al., 1984).

The sum of the bond angles around atom N1 [355.1°] indicate sp² hybridization. Atom N2 and chlorine atom Cl1 deviate significantly, by 0.0319 (31) Å and -0.0240 (13) Å, respectively, from the phenyl ring.

The molecular structure is stabilized by O-H···O and C-H···O hydrogen bonds (Table 1 and Fig. 1), which generate three S(6) ring motifs (Bernstein et al., 1995).

In the crystal, molecules are linked by C-H···O hydrogen bonds, which generate C(6) and C(9) chains running in directions [100] and [010], respectively (Table 1 and Fig. 2), and forming a two-dimensional network lying parallel to (001). There are also R³₄(28) supramolecular graph-set ring motifs enclosed within these networks.

Related literature top

For the biological activity and uses of carbazole derivatives, see: Itoigawa et al. (2000); Ramsewak et al. (1999). For their electronic properties and applications, see: Friend et al. (1999); Zhang et al. (2004). For related structures, see: Chakkaravarthi et al. (2008). For bond-length distortions, see: Allen et al. (1987). For graph-set notation, see: Bernstein et al. (1995). For the Thorpe–Ingold effect, see: Bassindale et al. (1984).

Experimental top

The enamine, (2E)-1-[1-(phenylsulfonyl)-2-[(E)-2-(4-cholro-2-nitrophenyl)ethenyl]-2,3 -dihydro-1H-indol-3-yl]-3-dimethylamino)prop-2-en-1-one (0.500 g, 0.93 mmol), with CuBr₂ (0.209 g, 0.93 mmol) in dry DMF (20 ml) was refluxed under N₂ for 1 h. The mixture was then poured over crushed ice (50 g) containing conc. HCl (1 ml). The crude product was filtered and dried. It was then purified by flash column chromatography on silica gel (230–420 mesh, n-hexane/ethyl acetate, 7:3) to afford the title compound as a pale yellow solid [Yield= 91%]. Yellow block-like crystal were obtained by slow evaporation of a solution in CHCl₃.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at 30% probability level. The intramolecular O-H···O and C-H···O hydrogen bonds are shown as dashed lines (see Table 1 for details).
	Fig. 2. The crystal packing of the title compound viewed along the c axis. The dashed lines indicate C—H···O hydrogen bonds [see Table 1 for details; symmetry codes: (i) x+1, y, z; (ii) -x, y-1/2, -z+1/2].

2-(4-Chloro-2-nitrophenyl)-9-phenylsulfonyl-9H-carbazole-3-carbaldehyde top

Crystal data top

C₂₅H₁₅ClN₂O₆S	F(000) = 1040
M_r = 506.91	D_x = 1.520 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3893 reflections
a = 8.1947 (15) Å	θ = 1.8–25.0°
b = 14.384 (3) Å	µ = 0.31 mm⁻¹
c = 18.795 (3) Å	T = 296 K
β = 90.963 (9)°	Block, yellow
V = 2215.2 (7) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	3893 independent reflections
Radiation source: fine-focus sealed tube	2809 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω & ϕ scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
T_min = 0.910, T_max = 0.939	k = −17→15
16586 measured reflections	l = −22→22

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0933P)² + 0.9326P] where P = (F_o² + 2F_c²)/3
3893 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

C₂₅H₁₅ClN₂O₆S	V = 2215.2 (7) Å³
M_r = 506.91	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1947 (15) Å	µ = 0.31 mm⁻¹
b = 14.384 (3) Å	T = 296 K
c = 18.795 (3) Å	0.30 × 0.25 × 0.20 mm
β = 90.963 (9)°

Data collection top

Bruker SMART APEXII CCD diffractometer	3893 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2809 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.939	R_int = 0.056
16586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	Δρ_max = 0.42 e Å⁻³
3893 reflections	Δρ_min = −0.40 e Å⁻³
316 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2551 (3)	0.6180 (2)	0.50926 (15)	0.0528 (8)
C2	0.3370 (4)	0.6615 (3)	0.56478 (17)	0.0671 (9)
H2	0.3374	0.7259	0.5694	0.081*
C3	0.4184 (4)	0.6050 (4)	0.61323 (19)	0.0788 (12)
H3	0.4772	0.6323	0.6505	0.095*
C4	0.4150 (5)	0.5097 (4)	0.60796 (19)	0.0780 (11)
H4	0.4717	0.4740	0.6414	0.094*
C5	0.3290 (4)	0.4662 (3)	0.55391 (19)	0.0685 (9)
H5	0.3241	0.4017	0.5512	0.082*
C6	0.2497 (3)	0.5214 (2)	0.50362 (16)	0.0536 (8)
C7	0.1606 (3)	0.4993 (2)	0.43898 (16)	0.0505 (7)
C8	0.1173 (3)	0.5826 (2)	0.40603 (16)	0.0469 (7)
C9	0.0421 (3)	0.5859 (2)	0.33864 (16)	0.0494 (7)
H9	0.0132	0.6421	0.3175	0.059*
C10	0.0132 (3)	0.5029 (2)	0.30519 (16)	0.0501 (7)
C11	0.0462 (4)	0.4168 (2)	0.33792 (18)	0.0561 (8)
C12	0.1204 (4)	0.4155 (2)	0.40598 (18)	0.0569 (8)
C13	0.0128 (5)	0.3305 (3)	0.3022 (2)	0.0770 (11)
H13	−0.0318	0.3342	0.2565	0.092*
C14	0.3698 (3)	0.7616 (2)	0.37430 (17)	0.0493 (7)
C15	0.3674 (4)	0.7328 (2)	0.3047 (2)	0.0622 (9)
H15	0.2690	0.7201	0.2813	0.075*
C16	0.5117 (5)	0.7232 (3)	0.2703 (2)	0.0809 (11)
H16	0.5125	0.7035	0.2232	0.097*
C17	0.6562 (5)	0.7428 (3)	0.3057 (3)	0.0918 (14)
H17	0.7546	0.7355	0.2824	0.110*
C18	0.6566 (5)	0.7726 (3)	0.3743 (3)	0.0935 (14)
H18	0.7549	0.7870	0.3971	0.112*
C19	0.5137 (4)	0.7815 (3)	0.4098 (2)	0.0722 (10)
H19	0.5135	0.8007	0.4571	0.087*
C20	−0.0564 (3)	0.5080 (2)	0.23145 (16)	0.0503 (7)
C21	−0.2215 (4)	0.5008 (3)	0.21838 (19)	0.0681 (9)
H21	−0.2892	0.4855	0.2558	0.082*
C22	−0.2902 (4)	0.5152 (3)	0.1522 (2)	0.0718 (10)
H22	−0.4023	0.5092	0.1451	0.086*
C23	−0.1919 (4)	0.5385 (3)	0.09668 (19)	0.0658 (9)
C24	−0.0268 (4)	0.5468 (2)	0.10637 (17)	0.0592 (8)
H24	0.0399	0.5635	0.0689	0.071*
C25	0.0376 (3)	0.5298 (2)	0.17300 (16)	0.0519 (7)
Cl1	−0.27788 (15)	0.55884 (9)	0.01388 (6)	0.1018 (4)
N1	0.1664 (3)	0.65682 (17)	0.45026 (13)	0.0503 (6)
N2	0.2158 (3)	0.5375 (2)	0.18092 (15)	0.0664 (8)
O1	0.1583 (3)	0.33589 (17)	0.43974 (14)	0.0784 (7)
H1	0.1286	0.2916	0.4153	0.118*
O2	0.0370 (5)	0.25321 (19)	0.32590 (17)	0.1032 (10)
O3	0.2092 (3)	0.82164 (17)	0.48325 (13)	0.0717 (7)
O4	0.0573 (2)	0.78288 (15)	0.37344 (12)	0.0569 (6)
O5	0.2857 (3)	0.4869 (2)	0.22158 (17)	0.0960 (9)
O6	0.2834 (3)	0.5962 (3)	0.14560 (17)	0.1149 (12)
S1	0.18862 (9)	0.76577 (5)	0.42149 (4)	0.0504 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0501 (15)	0.063 (2)	0.0456 (16)	−0.0008 (13)	0.0061 (13)	0.0019 (15)
C2	0.071 (2)	0.081 (3)	0.0489 (19)	−0.0099 (18)	0.0001 (16)	−0.0027 (17)
C3	0.071 (2)	0.116 (4)	0.049 (2)	−0.006 (2)	−0.0034 (17)	0.004 (2)
C4	0.076 (2)	0.108 (4)	0.051 (2)	0.013 (2)	0.0055 (18)	0.022 (2)
C5	0.073 (2)	0.077 (2)	0.057 (2)	0.0105 (18)	0.0189 (17)	0.0186 (19)
C6	0.0520 (16)	0.065 (2)	0.0445 (16)	−0.0013 (14)	0.0122 (13)	0.0055 (15)
C7	0.0482 (15)	0.0523 (19)	0.0514 (17)	−0.0029 (13)	0.0147 (13)	0.0056 (15)
C8	0.0425 (13)	0.0495 (18)	0.0490 (16)	−0.0033 (12)	0.0080 (12)	−0.0036 (14)
C9	0.0498 (15)	0.0492 (18)	0.0492 (17)	−0.0020 (13)	0.0025 (13)	−0.0023 (14)
C10	0.0496 (15)	0.0516 (19)	0.0494 (17)	−0.0076 (13)	0.0112 (13)	−0.0078 (15)
C11	0.0650 (18)	0.0476 (19)	0.0564 (19)	−0.0101 (14)	0.0183 (15)	−0.0057 (15)
C12	0.0645 (18)	0.048 (2)	0.0587 (19)	−0.0016 (14)	0.0212 (15)	0.0053 (16)
C13	0.106 (3)	0.059 (2)	0.068 (2)	−0.011 (2)	0.024 (2)	−0.0087 (19)
C14	0.0473 (15)	0.0424 (17)	0.0580 (18)	−0.0019 (12)	−0.0019 (13)	0.0068 (14)
C15	0.0558 (17)	0.062 (2)	0.069 (2)	0.0010 (15)	0.0040 (16)	0.0054 (17)
C16	0.080 (3)	0.083 (3)	0.080 (3)	0.008 (2)	0.025 (2)	0.015 (2)
C17	0.059 (2)	0.099 (3)	0.118 (4)	0.007 (2)	0.030 (2)	0.031 (3)
C18	0.051 (2)	0.109 (4)	0.121 (4)	−0.011 (2)	−0.002 (2)	0.025 (3)
C19	0.0564 (18)	0.077 (3)	0.083 (3)	−0.0145 (16)	−0.0066 (17)	0.010 (2)
C20	0.0544 (15)	0.0457 (18)	0.0511 (17)	−0.0051 (13)	0.0080 (13)	−0.0111 (14)
C21	0.0545 (17)	0.083 (3)	0.068 (2)	−0.0100 (16)	0.0110 (16)	−0.0126 (19)
C22	0.0532 (18)	0.084 (3)	0.078 (3)	0.0019 (16)	−0.0033 (18)	−0.017 (2)
C23	0.070 (2)	0.060 (2)	0.067 (2)	0.0141 (16)	−0.0138 (18)	−0.0133 (18)
C24	0.0674 (19)	0.058 (2)	0.0519 (19)	0.0037 (15)	0.0072 (15)	−0.0045 (15)
C25	0.0532 (16)	0.0508 (19)	0.0519 (18)	−0.0011 (13)	0.0042 (14)	−0.0087 (14)
Cl1	0.1052 (8)	0.1192 (10)	0.0800 (7)	0.0313 (7)	−0.0284 (6)	−0.0017 (6)
N1	0.0544 (13)	0.0517 (16)	0.0449 (13)	−0.0047 (11)	0.0020 (11)	−0.0015 (12)
N2	0.0553 (15)	0.093 (2)	0.0514 (16)	−0.0074 (15)	0.0070 (13)	−0.0066 (16)
O1	0.1124 (19)	0.0498 (15)	0.0736 (16)	0.0026 (13)	0.0212 (14)	0.0123 (12)
O2	0.174 (3)	0.0460 (17)	0.091 (2)	−0.0101 (17)	0.026 (2)	−0.0035 (15)
O3	0.0860 (15)	0.0605 (15)	0.0685 (15)	−0.0006 (12)	−0.0026 (12)	−0.0224 (12)
O4	0.0465 (10)	0.0543 (14)	0.0696 (14)	0.0067 (9)	−0.0036 (10)	−0.0058 (11)
O5	0.0603 (14)	0.134 (3)	0.093 (2)	0.0160 (15)	0.0053 (14)	0.0219 (19)
O6	0.0769 (17)	0.171 (3)	0.097 (2)	−0.045 (2)	0.0073 (16)	0.041 (2)
S1	0.0506 (4)	0.0452 (5)	0.0552 (5)	0.0003 (3)	−0.0015 (3)	−0.0074 (3)

Geometric parameters (Å, º) top

C1—C2	1.381 (4)	C14—S1	1.743 (3)
C1—C6	1.394 (5)	C15—C16	1.364 (5)
C1—N1	1.429 (4)	C15—H15	0.9300
C2—C3	1.384 (5)	C16—C17	1.378 (6)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.375 (6)	C17—C18	1.359 (7)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.377 (5)	C18—C19	1.364 (6)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.388 (5)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.374 (4)
C6—C7	1.442 (4)	C20—C25	1.388 (4)
C7—C12	1.392 (5)	C21—C22	1.373 (5)
C7—C8	1.392 (4)	C21—H21	0.9300
C8—C9	1.400 (4)	C22—C23	1.370 (5)
C8—N1	1.408 (4)	C22—H22	0.9300
C9—C10	1.369 (4)	C23—C24	1.367 (5)
C9—H9	0.9300	C23—Cl1	1.723 (4)
C10—C11	1.406 (4)	C24—C25	1.373 (4)
C10—C20	1.492 (4)	C24—H24	0.9300
C11—C12	1.407 (5)	C25—N2	1.469 (4)
C11—C13	1.435 (5)	N1—S1	1.669 (3)
C12—O1	1.343 (4)	N2—O5	1.196 (4)
C13—O2	1.213 (5)	N2—O6	1.213 (4)
C13—H13	0.9300	O1—H1	0.8200
C14—C15	1.372 (5)	O3—S1	1.420 (2)
C14—C19	1.375 (4)	O4—S1	1.415 (2)

C2—C1—C6	121.6 (3)	C14—C15—H15	120.5
C2—C1—N1	130.1 (3)	C15—C16—C17	119.7 (4)
C6—C1—N1	108.4 (3)	C15—C16—H16	120.2
C1—C2—C3	117.0 (4)	C17—C16—H16	120.2
C1—C2—H2	121.5	C18—C17—C16	120.7 (4)
C3—C2—H2	121.5	C18—C17—H17	119.6
C4—C3—C2	122.0 (4)	C16—C17—H17	119.6
C4—C3—H3	119.0	C17—C18—C19	120.4 (4)
C2—C3—H3	119.0	C17—C18—H18	119.8
C3—C4—C5	121.0 (4)	C19—C18—H18	119.8
C3—C4—H4	119.5	C18—C19—C14	118.6 (4)
C5—C4—H4	119.5	C18—C19—H19	120.7
C4—C5—C6	118.0 (4)	C14—C19—H19	120.7
C4—C5—H5	121.0	C21—C20—C25	115.7 (3)
C6—C5—H5	121.0	C21—C20—C10	121.5 (3)
C5—C6—C1	120.3 (3)	C25—C20—C10	122.5 (3)
C5—C6—C7	132.2 (3)	C22—C21—C20	122.6 (3)
C1—C6—C7	107.4 (3)	C22—C21—H21	118.7
C12—C7—C8	119.3 (3)	C20—C21—H21	118.7
C12—C7—C6	132.8 (3)	C23—C22—C21	119.3 (3)
C8—C7—C6	107.8 (3)	C23—C22—H22	120.4
C7—C8—C9	122.5 (3)	C21—C22—H22	120.4
C7—C8—N1	108.8 (3)	C24—C23—C22	120.9 (3)
C9—C8—N1	128.7 (3)	C24—C23—Cl1	119.6 (3)
C10—C9—C8	117.1 (3)	C22—C23—Cl1	119.5 (3)
C10—C9—H9	121.4	C23—C24—C25	118.1 (3)
C8—C9—H9	121.4	C23—C24—H24	121.0
C9—C10—C11	122.4 (3)	C25—C24—H24	121.0
C9—C10—C20	116.4 (3)	C24—C25—C20	123.5 (3)
C11—C10—C20	121.2 (3)	C24—C25—N2	116.5 (3)
C10—C11—C12	119.1 (3)	C20—C25—N2	120.1 (3)
C10—C11—C13	121.5 (3)	C8—N1—C1	107.4 (2)
C12—C11—C13	119.3 (3)	C8—N1—S1	123.5 (2)
O1—C12—C7	118.5 (3)	C1—N1—S1	124.1 (2)
O1—C12—C11	122.2 (3)	O5—N2—O6	123.7 (3)
C7—C12—C11	119.3 (3)	O5—N2—C25	118.9 (3)
O2—C13—C11	126.4 (4)	O6—N2—C25	117.4 (3)
O2—C13—H13	116.8	C12—O1—H1	109.5
C11—C13—H13	116.8	O4—S1—O3	120.14 (14)
C15—C14—C19	121.6 (3)	O4—S1—N1	106.50 (13)
C15—C14—S1	119.8 (2)	O3—S1—N1	106.18 (14)
C19—C14—S1	118.5 (3)	O4—S1—C14	109.06 (14)
C16—C15—C14	119.0 (3)	O3—S1—C14	110.19 (15)
C16—C15—H15	120.5	N1—S1—C14	103.37 (13)

C6—C1—C2—C3	2.3 (5)	C15—C14—C19—C18	0.3 (5)
N1—C1—C2—C3	−177.4 (3)	S1—C14—C19—C18	175.9 (3)
C1—C2—C3—C4	−1.8 (5)	C9—C10—C20—C21	−95.9 (4)
C2—C3—C4—C5	−0.3 (6)	C11—C10—C20—C21	83.9 (4)
C3—C4—C5—C6	1.9 (5)	C9—C10—C20—C25	77.3 (4)
C4—C5—C6—C1	−1.4 (5)	C11—C10—C20—C25	−102.9 (4)
C4—C5—C6—C7	175.0 (3)	C25—C20—C21—C22	−0.8 (5)
C2—C1—C6—C5	−0.7 (4)	C10—C20—C21—C22	172.9 (3)
N1—C1—C6—C5	179.0 (3)	C20—C21—C22—C23	−0.6 (6)
C2—C1—C6—C7	−177.9 (3)	C21—C22—C23—C24	0.5 (6)
N1—C1—C6—C7	1.8 (3)	C21—C22—C23—Cl1	−178.7 (3)
C5—C6—C7—C12	1.8 (5)	C22—C23—C24—C25	0.9 (5)
C1—C6—C7—C12	178.6 (3)	Cl1—C23—C24—C25	−179.8 (3)
C5—C6—C7—C8	−175.4 (3)	C23—C24—C25—C20	−2.5 (5)
C1—C6—C7—C8	1.4 (3)	C23—C24—C25—N2	178.8 (3)
C12—C7—C8—C9	−3.6 (4)	C21—C20—C25—C24	2.4 (5)
C6—C7—C8—C9	174.1 (2)	C10—C20—C25—C24	−171.2 (3)
C12—C7—C8—N1	178.3 (2)	C21—C20—C25—N2	−178.9 (3)
C6—C7—C8—N1	−4.0 (3)	C10—C20—C25—N2	7.5 (5)
C7—C8—C9—C10	−0.5 (4)	C7—C8—N1—C1	5.1 (3)
N1—C8—C9—C10	177.2 (2)	C9—C8—N1—C1	−172.9 (3)
C8—C9—C10—C11	4.2 (4)	C7—C8—N1—S1	161.01 (19)
C8—C9—C10—C20	−175.9 (2)	C9—C8—N1—S1	−16.9 (4)
C9—C10—C11—C12	−3.7 (4)	C2—C1—N1—C8	175.5 (3)
C20—C10—C11—C12	176.4 (3)	C6—C1—N1—C8	−4.2 (3)
C9—C10—C11—C13	179.1 (3)	C2—C1—N1—S1	19.7 (4)
C20—C10—C11—C13	−0.7 (4)	C6—C1—N1—S1	−160.0 (2)
C8—C7—C12—O1	−177.8 (3)	C24—C25—N2—O5	−145.9 (3)
C6—C7—C12—O1	5.2 (5)	C20—C25—N2—O5	35.2 (5)
C8—C7—C12—C11	4.0 (4)	C24—C25—N2—O6	34.5 (5)
C6—C7—C12—C11	−173.0 (3)	C20—C25—N2—O6	−144.3 (3)
C10—C11—C12—O1	−178.7 (3)	C8—N1—S1—O4	40.4 (2)
C13—C11—C12—O1	−1.5 (5)	C1—N1—S1—O4	−167.7 (2)
C10—C11—C12—C7	−0.5 (4)	C8—N1—S1—O3	169.5 (2)
C13—C11—C12—C7	176.7 (3)	C1—N1—S1—O3	−38.5 (3)
C10—C11—C13—O2	179.9 (4)	C8—N1—S1—C14	−74.5 (2)
C12—C11—C13—O2	2.8 (6)	C1—N1—S1—C14	77.5 (2)
C19—C14—C15—C16	0.5 (5)	C15—C14—S1—O4	−29.1 (3)
S1—C14—C15—C16	−175.0 (3)	C19—C14—S1—O4	155.3 (3)
C14—C15—C16—C17	−0.3 (6)	C15—C14—S1—O3	−162.9 (3)
C15—C16—C17—C18	−0.7 (6)	C19—C14—S1—O3	21.4 (3)
C16—C17—C18—C19	1.6 (7)	C15—C14—S1—N1	84.0 (3)
C17—C18—C19—C14	−1.3 (6)	C19—C14—S1—N1	−91.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.91	2.629 (4)	146
C2—H2···O3	0.93	2.36	2.949 (5)	121
C9—H9···O4	0.93	2.31	2.910 (4)	122
C13—H13···O4ⁱ	0.93	2.56	3.411 (4)	153
C18—H18···O4ⁱⁱ	0.93	2.53	3.287 (4)	139

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.91	2.629 (4)	146
C2—H2···O3	0.93	2.36	2.949 (5)	121
C9—H9···O4	0.93	2.31	2.910 (4)	122
C13—H13···O4ⁱ	0.93	2.56	3.411 (4)	153
C18—H18···O4ⁱⁱ	0.93	2.53	3.287 (4)	139

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

Acknowledgements

The authors thank Mr T. Srinivasan and Dr D. Velmurugan the Technology Business Incubator (TBI), CAS in Crystallography and Biophysics, University of Madras, Maraimalai Campus, Chennai, and the Department of Science and Technology (DST) 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
Bassindale, A. (1984). The Third Dimension in Organic Chemistry, ch. 1, p. 11. New York: John Wiley and Sons. Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chakkaravarthi, G., Dhayalan, V., Mohanakrishnan, A. K. & Manivannan, V. (2008). Acta Cryst. E64, o1667–o1668. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Friend, R. H., Gymer, R. W., Holmes, A. B., Burroughes, J. H., Mark, R. N., Taliani, C., Bradley, D. D. C., Dos Santos, D. A., Bredas, J. L., Logdlund, M. & Salaneck, W. R. (1999). Nature (London), 397, 121–127. Web of Science CrossRef CAS Google Scholar
Itoigawa, M., Kashiwada, Y., Ito, C., Furukawa, H., Tachibana, Y., Bastow, K. F. & Lee, K. H. (2000). J. Nat. Prod. 63, 893–897. Web of Science CrossRef PubMed CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ramsewak, R. S., Nair, M. G., Strasburg, G. M., DeWitt, D. L. & Nitiss, J. L. (1999). J. Agric. Food Chem. 47, 444–447. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Q., Chen, J., Cheng, Y., Wang, L., Ma, D., Jing, X. & Wang, F. (2004). J. Mater. Chem. 14, 895–900. Web of Science CrossRef CAS Google Scholar