6-(4-Bromo­phen­yl)-2-eth­oxy-4-(4-ethoxy­phen­yl)nicotinonitrile

Chantrapromma, S.; Fun, H.-K.; Suwunwong, T.; Padaki, M.; Isloor, A.M.

doi:10.1107/S1600536809051861

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages o79-o80

doi:10.1107/S1600536809051861

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6-(4-Bromophenyl)-2-ethoxy-4-(4-ethoxyphenyl)nicotinonitrile

Suchada Chantrapromma,^a ^*‡ Hoong-Kun Fun,^b § Thitipone Suwunwong,^a Mahesh Padaki ^c and Arun M. Isloor ^c

^aCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cDepartment of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 12 November 2009; accepted 2 December 2009; online 9 December 2009)

The molecule of the title nicotinonitrile derivative, C₂₂H₁₉BrN₂O₂, is non-planar, the central pyridine ring making dihedral angles of 7.34 (14) and 43.56 (15)° with the 4-bromophenyl and 4-ethoxyphenyl rings, respectively. The ethoxy group of the 4-ethoxyphenyl is slightly twisted from the attached benzene ring [C—O—C—C = 174.2 (3)°], whereas the ethoxy group attached to the pyridine ring is in a (+)syn-clinal conformation [C—O—C—C = 83.0 (3)°]. A weak intramolecular C—H⋯N interaction generates an S(5) ring motif. In the crystal structure, the molecules are linked by weak intermolecular C—H⋯N interactions into screw chains along the b axis. These chains stacked along the a axis. π–π interactions with centroid–centroid distances of 3.8724 (16) and 3.8727 (16) Å are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For the synthesis and applications of nicotinonitrile derivatives, see: Borgna et al. (1993 ); Fun et al. (2008 ); Goda et al. (2004 ); Kamal et al. (2007 ); Malinka et al. (1998 ). For related structures, see: Chantrapromma et al. (2009 ). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₂H₁₉BrN₂O₂
M_r = 423.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.3414 (2) Å
b = 14.7392 (6) Å
c = 29.4409 (13) Å
V = 1883.89 (14) Å³
Z = 4
Mo Kα radiation
μ = 2.20 mm⁻¹
T = 100 K
0.57 × 0.05 × 0.03 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.368, T_max = 0.931
18389 measured reflections
5477 independent reflections
4081 reflections with I > 2σ(I)
R_int = 0.076

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.084
S = 0.99
5477 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.54 e Å⁻³
Absolute structure: Flack (1983 ), 2269 Friedel pairs
Flack parameter: 0.008 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N1	0.93	2.41	2.758 (4)	102
C5—H5A⋯N2ⁱ	0.93	2.58	3.446 (4)	156
C13—H13A⋯N2ⁱⁱ	0.93	2.53	3.206 (4)	130
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051861/sj2683sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051861/sj2683Isup2.hkl

checkCIF report

Comment top

A large number of substituted pyridines have been claimed to exhibit biological activities in a number of areas (Borgna et al., 1993; Goda et al., 2004; Kamal et al., 2007; Malinka et al., 1998). The pyridine ring is among the most common heterocyclic compounds found in the naturally occurring heterocycles and in various therapeutic agents. Our research is aimed at the synthesis and preliminary pharmacological screening (in vivo) of the nicotinonitrile derivatives. Therefore the title nicotinonitrile derivative, which is a substituted pyridine compound, was synthesized by cyclization of a chalcone derivative (Fun et al., 2008) and malononitrile in order to investigate its analgesic and anti-inflammatory activities. Our results of these pharmacological studies showed that the title compound is a promising candidate for analgesic and anti-inflammatory activities. The analgesic and anti-inflammatory profiles of the title compound together with some other related nicotinonitrile derivatives will be reported elsewhere.

The title compound (I), C₂₂H₁₉BrN₂O₂ is a non-planar molecule (Fig. 1). The central pyridine ring is nearly coplanar with the 4-bromophenyl ring with the dihedral angle of 7.34 (14)° whereas it is inclined to the 4-ethoxyphenyl unit with the dihedral angle of 43.56 (15)°. The ethoxy substituent of the 4-ethoxyphenyl is slightly twisted from the mean plane of the attached benzene ring with the torsion angle C15–O2–C20–C21 = 174.2 (3)° whereas the ethoxy group attached to the pyridine ring is in a (+)syn-clinal conformation with a C11–O1–C18–C19 torsion angle of 83.0 (3)°. The orientation of the cyano group can be indicated by the torsion angle C8–C9–C10–C22 = 177.0 (3)°. A weak intramolecular C1—H1A···N1 interaction generates an S(5) ring motif (Bernstein et al., 1995). The bond distances agree with the literature values (Allen et al., 1987) and are comparable with those for a related structure (Chantrapromma et al., 2009).

In the crystal structure (Fig. 2), the molecules are linked by weak intermolecular C—H···N interactions (Table 1) into screw chains along the b axis. These chains stacked along the a axis. The crystal is further stabilized by π···π interactions with the Cg₁···Cg₂ distances of 3.8724 (16) Å (symmetry code: -1 + x, y, z) and 3.8727 (16) Å (symmetry code: 1 + x, y, z); Cg₁ and Cg₂ are the centroids of C7–C11/N1 and C1–C6 rings, respectively.

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the synthesis and applications of nicotinonitrile derivatives, see: Borgna et al. (1993); Fun et al. (2008); Goda et al. (2004); Kamal et al. (2007); Malinka et al. (1998). For related structures, see: Chantrapromma et al. (2009). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986).

Experimental top

(E-1-(4-Bromophenyl)-3-(4-ethoxyphenyl)prop-2-en-1-one (0.50 g, 0.0015 mole) were added with continuous stirring to a freshly prepared sodium alkoxide (0.0014 mole of sodium in 100 ml of ethanol). Malononitrile (1.30 g, 0.02 mol) was then added with continuous stirring at room temperature until the precipitate separated out. The resulting solid was filtered (yield 65%). Colorless needle-shaped single crystals of the title compound suitable for x-ray structure determination were recrystalized from acetone/ethanol (1:1 v/v) by the slow evaporation of the solvent at room temperature over several days, Mp. 418–419 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound viewed along the a axis, showing chains stacked down the a axis. Hydrogen bonds are shown as dashed lines.

6-(4-Bromophenyl)-2-ethoxy-4-(4-ethoxyphenyl)nicotinonitrile top

Crystal data top

C₂₂H₁₉BrN₂O₂	D_x = 1.492 Mg m⁻³
M_r = 423.29	Melting point = 418–419 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5478 reflections
a = 4.3414 (2) Å	θ = 1.4–30.0°
b = 14.7392 (6) Å	µ = 2.20 mm⁻¹
c = 29.4409 (13) Å	T = 100 K
V = 1883.89 (14) Å³	Needle, colourless
Z = 4	0.57 × 0.05 × 0.03 mm
F(000) = 864

Data collection top

Bruker APEXII CCD area detector diffractometer	5477 independent reflections
Radiation source: sealed tube	4081 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.368, T_max = 0.931	k = −20→20
18389 measured reflections	l = −41→41

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0276P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
5477 reflections	Δρ_max = 0.58 e Å⁻³
246 parameters	Δρ_min = −0.54 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2269 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (9)

Crystal data top

C₂₂H₁₉BrN₂O₂	V = 1883.89 (14) Å³
M_r = 423.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.3414 (2) Å	µ = 2.20 mm⁻¹
b = 14.7392 (6) Å	T = 100 K
c = 29.4409 (13) Å	0.57 × 0.05 × 0.03 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	5477 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4081 reflections with I > 2σ(I)
T_min = 0.368, T_max = 0.931	R_int = 0.076
18389 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.084	Δρ_max = 0.58 e Å⁻³
S = 0.99	Δρ_min = −0.54 e Å⁻³
5477 reflections	Absolute structure: Flack (1983), 2269 Friedel pairs
246 parameters	Absolute structure parameter: 0.008 (9)
0 restraints

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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
Br1	1.58148 (8)	0.282863 (19)	0.048491 (10)	0.02362 (8)
O1	0.4205 (6)	0.74788 (11)	0.14589 (6)	0.0216 (4)
O2	−0.0548 (6)	0.47728 (13)	0.40035 (6)	0.0252 (5)
N2	0.0125 (7)	0.76955 (17)	0.24500 (8)	0.0298 (7)
N1	0.7019 (6)	0.61534 (15)	0.14495 (8)	0.0196 (5)
C1	1.0999 (8)	0.50365 (18)	0.09800 (9)	0.0197 (6)
H1A	1.0551	0.5618	0.0877	0.024*
C2	1.2818 (8)	0.44749 (19)	0.07176 (10)	0.0214 (7)
H2A	1.3606	0.4679	0.0442	0.026*
C3	1.3459 (7)	0.36055 (18)	0.08677 (9)	0.0191 (7)
C4	1.2361 (8)	0.32993 (19)	0.12783 (10)	0.0220 (7)
H4A	1.2821	0.2716	0.1377	0.026*
C5	1.0564 (8)	0.38691 (17)	0.15427 (9)	0.0204 (6)
H5A	0.9838	0.3665	0.1822	0.025*
C6	0.9818 (7)	0.47489 (18)	0.13976 (9)	0.0185 (7)
C7	0.7817 (7)	0.53544 (18)	0.16580 (10)	0.0178 (6)
C8	0.6704 (7)	0.51430 (19)	0.20904 (10)	0.0195 (7)
H8A	0.7262	0.4597	0.2226	0.023*
C9	0.4766 (7)	0.57403 (18)	0.23214 (9)	0.0170 (6)
C10	0.3912 (8)	0.65388 (18)	0.20974 (9)	0.0189 (6)
C11	0.5132 (7)	0.67004 (18)	0.16607 (9)	0.0186 (7)
C12	0.3562 (8)	0.55145 (19)	0.27789 (9)	0.0189 (7)
C13	0.2478 (8)	0.46338 (18)	0.28616 (10)	0.0197 (7)
H13A	0.2680	0.4192	0.2638	0.024*
C14	0.1114 (9)	0.44126 (18)	0.32705 (9)	0.0200 (7)
H14A	0.0369	0.3829	0.3318	0.024*
C15	0.0855 (9)	0.50606 (18)	0.36103 (9)	0.0199 (6)
C16	0.1977 (8)	0.5937 (2)	0.35411 (10)	0.0230 (7)
H16A	0.1834	0.6371	0.3769	0.028*
C17	0.3314 (7)	0.61494 (19)	0.31246 (10)	0.0222 (7)
H17A	0.4061	0.6733	0.3077	0.027*
C18	0.5818 (8)	0.7761 (2)	0.10480 (8)	0.0230 (6)
H18A	0.7994	0.7626	0.1081	0.028*
H18B	0.5605	0.8412	0.1012	0.028*
C19	0.4616 (8)	0.7296 (2)	0.06258 (9)	0.0284 (7)
H19A	0.5543	0.7564	0.0362	0.043*
H19B	0.2420	0.7366	0.0610	0.043*
H19C	0.5123	0.6662	0.0637	0.043*
C20	−0.1371 (8)	0.5444 (2)	0.43323 (10)	0.0243 (8)
H20A	−0.2638	0.5911	0.4195	0.029*
H20B	0.0460	0.5726	0.4458	0.029*
C21	−0.3148 (8)	0.4952 (2)	0.46998 (11)	0.0306 (8)
H21A	−0.3648	0.5368	0.4939	0.046*
H21B	−0.1911	0.4467	0.4819	0.046*
H21C	−0.5011	0.4707	0.4574	0.046*
C22	0.1818 (7)	0.7186 (2)	0.22906 (9)	0.0210 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02481 (15)	0.02126 (12)	0.02480 (13)	0.00135 (15)	−0.00071 (16)	−0.00381 (13)
O1	0.0280 (11)	0.0181 (9)	0.0186 (9)	0.0039 (10)	0.0014 (12)	0.0043 (7)
O2	0.0376 (14)	0.0207 (9)	0.0173 (9)	0.0022 (11)	0.0044 (11)	−0.0004 (8)
N2	0.040 (2)	0.0236 (13)	0.0260 (12)	0.0087 (13)	−0.0018 (12)	0.0006 (10)
N1	0.0204 (14)	0.0189 (11)	0.0195 (12)	−0.0008 (11)	−0.0024 (11)	0.0008 (9)
C1	0.0211 (16)	0.0187 (12)	0.0192 (13)	0.0005 (15)	−0.0017 (15)	0.0004 (10)
C2	0.0186 (16)	0.0227 (15)	0.0229 (15)	−0.0008 (14)	−0.0008 (14)	0.0022 (12)
C3	0.0169 (18)	0.0196 (13)	0.0209 (14)	−0.0009 (12)	−0.0019 (13)	−0.0023 (11)
C4	0.0259 (18)	0.0154 (13)	0.0246 (16)	0.0012 (13)	−0.0041 (15)	0.0017 (11)
C5	0.0233 (17)	0.0196 (13)	0.0184 (13)	0.0003 (15)	−0.0004 (15)	0.0035 (10)
C6	0.0169 (18)	0.0186 (13)	0.0199 (14)	−0.0010 (12)	−0.0061 (13)	0.0020 (11)
C7	0.0172 (16)	0.0152 (13)	0.0210 (15)	−0.0022 (12)	−0.0055 (13)	0.0014 (11)
C8	0.0186 (19)	0.0190 (14)	0.0208 (15)	0.0006 (13)	−0.0027 (13)	0.0010 (12)
C9	0.0161 (17)	0.0181 (12)	0.0167 (13)	−0.0037 (12)	−0.0049 (12)	0.0021 (10)
C10	0.0219 (16)	0.0165 (12)	0.0182 (13)	0.0004 (14)	−0.0045 (14)	−0.0016 (10)
C11	0.0203 (19)	0.0141 (12)	0.0213 (13)	−0.0008 (12)	−0.0040 (12)	0.0016 (10)
C12	0.023 (2)	0.0186 (13)	0.0157 (14)	−0.0007 (13)	−0.0018 (13)	0.0008 (10)
C13	0.0243 (17)	0.0159 (13)	0.0191 (15)	0.0034 (13)	−0.0033 (14)	−0.0017 (11)
C14	0.0243 (18)	0.0157 (13)	0.0199 (14)	0.0017 (14)	−0.0019 (15)	0.0015 (10)
C15	0.0240 (16)	0.0215 (13)	0.0140 (13)	0.0030 (16)	0.0007 (15)	0.0007 (10)
C16	0.0288 (19)	0.0214 (14)	0.0188 (15)	0.0010 (14)	−0.0027 (15)	−0.0025 (12)
C17	0.0260 (19)	0.0169 (13)	0.0237 (15)	−0.0011 (13)	−0.0053 (14)	0.0001 (11)
C18	0.0266 (15)	0.0221 (13)	0.0204 (13)	−0.0010 (18)	0.0012 (15)	0.0036 (11)
C19	0.0302 (19)	0.0321 (16)	0.0230 (13)	0.0023 (17)	0.0012 (14)	0.0030 (12)
C20	0.029 (2)	0.0276 (15)	0.0165 (13)	0.0029 (15)	0.0022 (14)	−0.0077 (11)
C21	0.033 (2)	0.0360 (18)	0.0228 (16)	−0.0011 (17)	0.0033 (15)	−0.0058 (14)
C22	0.0264 (17)	0.0196 (12)	0.0171 (13)	−0.0023 (16)	−0.0042 (12)	0.0026 (13)

Geometric parameters (Å, º) top

Br1—C3	1.905 (3)	C10—C11	1.411 (4)
O1—C11	1.353 (3)	C10—C22	1.435 (4)
O1—C18	1.458 (3)	C12—C17	1.387 (4)
O2—C15	1.375 (3)	C12—C13	1.402 (4)
O2—C20	1.429 (3)	C13—C14	1.380 (4)
N2—C22	1.151 (4)	C13—H13A	0.9300
N1—C11	1.307 (4)	C14—C15	1.388 (4)
N1—C7	1.372 (3)	C14—H14A	0.9300
C1—C2	1.380 (4)	C15—C16	1.395 (4)
C1—C6	1.398 (4)	C16—C17	1.392 (4)
C1—H1A	0.9300	C16—H16A	0.9300
C2—C3	1.384 (4)	C17—H17A	0.9300
C2—H2A	0.9300	C18—C19	1.512 (4)
C3—C4	1.376 (4)	C18—H18A	0.9700
C4—C5	1.386 (4)	C18—H18B	0.9700
C4—H4A	0.9300	C19—H19A	0.9600
C5—C6	1.403 (4)	C19—H19B	0.9600
C5—H5A	0.9300	C19—H19C	0.9600
C6—C7	1.462 (4)	C20—C21	1.514 (4)
C7—C8	1.397 (4)	C20—H20A	0.9700
C8—C9	1.395 (4)	C20—H20B	0.9700
C8—H8A	0.9300	C21—H21A	0.9600
C9—C10	1.399 (4)	C21—H21B	0.9600
C9—C12	1.483 (4)	C21—H21C	0.9600

C11—O1—C18	117.6 (2)	C14—C13—H13A	119.5
C15—O2—C20	117.9 (2)	C12—C13—H13A	119.5
C11—N1—C7	118.4 (3)	C13—C14—C15	120.1 (3)
C2—C1—C6	121.4 (3)	C13—C14—H14A	120.0
C2—C1—H1A	119.3	C15—C14—H14A	120.0
C6—C1—H1A	119.3	O2—C15—C14	115.5 (2)
C1—C2—C3	119.4 (3)	O2—C15—C16	124.3 (2)
C1—C2—H2A	120.3	C14—C15—C16	120.2 (3)
C3—C2—H2A	120.3	C17—C16—C15	118.8 (3)
C4—C3—C2	121.0 (3)	C17—C16—H16A	120.6
C4—C3—Br1	120.6 (2)	C15—C16—H16A	120.6
C2—C3—Br1	118.4 (2)	C12—C17—C16	121.8 (3)
C3—C4—C5	119.3 (3)	C12—C17—H17A	119.1
C3—C4—H4A	120.3	C16—C17—H17A	119.1
C5—C4—H4A	120.3	O1—C18—C19	112.8 (3)
C4—C5—C6	121.3 (3)	O1—C18—H18A	109.0
C4—C5—H5A	119.4	C19—C18—H18A	109.0
C6—C5—H5A	119.4	O1—C18—H18B	109.0
C1—C6—C5	117.6 (3)	C19—C18—H18B	109.0
C1—C6—C7	119.6 (2)	H18A—C18—H18B	107.8
C5—C6—C7	122.8 (3)	C18—C19—H19A	109.5
N1—C7—C8	120.8 (3)	C18—C19—H19B	109.5
N1—C7—C6	116.1 (3)	H19A—C19—H19B	109.5
C8—C7—C6	123.2 (2)	C18—C19—H19C	109.5
C9—C8—C7	120.8 (3)	H19A—C19—H19C	109.5
C9—C8—H8A	119.6	H19B—C19—H19C	109.5
C7—C8—H8A	119.6	O2—C20—C21	106.2 (2)
C8—C9—C10	117.5 (3)	O2—C20—H20A	110.5
C8—C9—C12	120.9 (3)	C21—C20—H20A	110.5
C10—C9—C12	121.6 (3)	O2—C20—H20B	110.5
C9—C10—C11	118.2 (3)	C21—C20—H20B	110.5
C9—C10—C22	122.7 (3)	H20A—C20—H20B	108.7
C11—C10—C22	119.1 (2)	C20—C21—H21A	109.5
N1—C11—O1	120.1 (2)	C20—C21—H21B	109.5
N1—C11—C10	124.4 (3)	H21A—C21—H21B	109.5
O1—C11—C10	115.6 (2)	C20—C21—H21C	109.5
C17—C12—C13	118.1 (3)	H21A—C21—H21C	109.5
C17—C12—C9	122.9 (2)	H21B—C21—H21C	109.5
C13—C12—C9	118.9 (2)	N2—C22—C10	179.0 (3)
C14—C13—C12	120.9 (3)

C6—C1—C2—C3	0.8 (5)	C7—N1—C11—C10	1.9 (4)
C1—C2—C3—C4	−1.3 (5)	C18—O1—C11—N1	−11.6 (4)
C1—C2—C3—Br1	177.1 (2)	C18—O1—C11—C10	168.9 (3)
C2—C3—C4—C5	0.6 (5)	C9—C10—C11—N1	−0.1 (5)
Br1—C3—C4—C5	−177.8 (2)	C22—C10—C11—N1	−179.0 (3)
C3—C4—C5—C6	0.6 (5)	C9—C10—C11—O1	179.4 (3)
C2—C1—C6—C5	0.4 (5)	C22—C10—C11—O1	0.5 (4)
C2—C1—C6—C7	−178.0 (3)	C8—C9—C12—C17	140.0 (3)
C4—C5—C6—C1	−1.1 (5)	C10—C9—C12—C17	−42.6 (5)
C4—C5—C6—C7	177.2 (3)	C8—C9—C12—C13	−43.3 (4)
C11—N1—C7—C8	−1.7 (4)	C10—C9—C12—C13	134.0 (3)
C11—N1—C7—C6	177.2 (3)	C17—C12—C13—C14	2.0 (5)
C1—C6—C7—N1	5.4 (4)	C9—C12—C13—C14	−174.8 (3)
C5—C6—C7—N1	−173.0 (3)	C12—C13—C14—C15	−1.3 (5)
C1—C6—C7—C8	−175.7 (3)	C20—O2—C15—C14	−169.1 (3)
C5—C6—C7—C8	5.9 (5)	C20—O2—C15—C16	10.8 (5)
N1—C7—C8—C9	−0.3 (4)	C13—C14—C15—O2	179.8 (3)
C6—C7—C8—C9	−179.1 (3)	C13—C14—C15—C16	−0.2 (5)
C7—C8—C9—C10	2.0 (4)	O2—C15—C16—C17	−179.1 (3)
C7—C8—C9—C12	179.5 (3)	C14—C15—C16—C17	0.9 (5)
C8—C9—C10—C11	−1.9 (4)	C13—C12—C17—C16	−1.3 (5)
C12—C9—C10—C11	−179.3 (3)	C9—C12—C17—C16	175.4 (3)
C8—C9—C10—C22	177.0 (3)	C15—C16—C17—C12	−0.1 (5)
C12—C9—C10—C22	−0.4 (5)	C11—O1—C18—C19	83.0 (3)
C7—N1—C11—O1	−177.6 (3)	C15—O2—C20—C21	174.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1	0.93	2.41	2.758 (4)	102
C5—H5A···N2ⁱ	0.93	2.58	3.446 (4)	156
C13—H13A···N2ⁱⁱ	0.93	2.53	3.206 (4)	130

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

Experimental details

Crystal data
Chemical formula	C₂₂H₁₉BrN₂O₂
M_r	423.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	4.3414 (2), 14.7392 (6), 29.4409 (13)
V (Å³)	1883.89 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.20
Crystal size (mm)	0.57 × 0.05 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.368, 0.931
No. of measured, independent and observed [I > 2σ(I)] reflections	18389, 5477, 4081
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.084, 0.99
No. of reflections	5477
No. of parameters	246
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.54
Absolute structure	Flack (1983), 2269 Friedel pairs
Absolute structure parameter	0.008 (9)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1	0.93	2.41	2.758 (4)	102
C5—H5A···N2ⁱ	0.93	2.58	3.446 (4)	156
C13—H13A···N2ⁱⁱ	0.93	2.53	3.206 (4)	130

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

Footnotes

‡Thomson Reuters ResearcherID: A-5085-2009.

§Thomson Reuters ResearcherID: A-3561-2009. Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

The authors thank the Thailand Research Fund (TRF) for a research grant (RSA 5280033) and Prince of Songkla University for financial support. AMI is grateful to the Director, NITK-Surathkal, India, for providing research facilities and the Head of the Department of Chemistry and Dean R&D, NITK-Surathkal, for their encouragement. The authors also thank the Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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