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ISSN: 2056-9890

4-(4-Bromo­phen­yl)-2-oxo-1,2,5,6-tetra­hydro­benzo[h]quinoline-3-carbo­nitrile

aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 7 August 2011; accepted 19 August 2011; online 27 August 2011)

In the mol­ecule of the title compound, C20H13BrN2O, the tetra­hydro­benzo[h]quinoline fused-ring system is buckled owing to the ethyl­ene –CH2CH2– fragment, the benzene ring and the pyridine ring being twisted by 17.7 (1)°. The 4-substituted aromatic ring is bent away from the pyridine ring by 82.3 (1)° in order to avoid crowding the cyanide substituent. Two mol­ecules are linked by a pair of N—H⋯O hydrogen bonds to form a centrosymmetric dimer.

Related literature

For background to the anti­cancer properties of this class of compounds, see: Rostom et al. (2011[Rostom, S. A. F., Faidallah, H. M. & Al-Saadi, M. S. (2011). Med. Chem. Res. 20 (DOI: 10.1007/s00044-010-9469-0). ]).

[Scheme 1]

Experimental

Crystal data
  • C20H13BrN2O

  • Mr = 377.23

  • Monoclinic, C 2/c

  • a = 22.6906 (5) Å

  • b = 8.5060 (2) Å

  • c = 17.6112 (5) Å

  • β = 106.498 (3)°

  • V = 3259.13 (14) Å3

  • Z = 8

  • Cu Kα radiation

  • μ = 3.50 mm−1

  • T = 100 K

  • 0.30 × 0.25 × 0.20 mm

Data collection
  • Agilent SuperNova Dual diffractometer with Atlas detector

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]) Tmin = 0.420, Tmax = 0.541

  • 6063 measured reflections

  • 3244 independent reflections

  • 3132 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.094

  • S = 1.06

  • 3244 reflections

  • 221 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.57 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 (3) 1.96 (3) 2.807 (2) 172 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: CrysAlis PRO (Agilent, 2010[Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The compound (Scheme I) belongs to a series of cyano-pyridinones that have been evaluated for their anticancer properties (Rostom et al., 2011). The tetrahydrobenzo[h]quinoline fused-ring system is buckled owing to the ethylene –CH2CH2– fragment, the benzene ring and the pyridine ring being twisted by 17.7 (1)°. The 4-subsituted aromatic ring is bent away from the pyridine ring by 83.2 (1) ° in order to avoid crowding the cyanide substituent (Fig. 1). Two molecules are linked by an N—H···O hydrogen bonds to form a centrosymmetric dimer (Table 1).

Related literature top

For background to the anticancer properties of this class of compounds, see: Rostom et al. (2011).

Experimental top

A mixture of p-bromobenzaldehyde (1.85 g, 10 mmol), 1-tetralone (1.46 g, 10 mmol), ethyl cyanoacetate (1.1 g, 10 mmol) and ammonium acetate (6.2 g, 80 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction mixture was allowed to cool, and the orange precipitate that formed was filtered, washed with water, dried and recrystallized from ethanol; m.p. >630 K.

Refinement top

Carbon- and nitrogen-bound H atoms were placed in calculated positions [C—H 0.95 to 0.99 Å, Uiso(H) = 1.2Ueq(C)] and were included in the refinement in the riding model approximation.

The amino H atom was located in a difference Fourier map and was freely refined.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C20H13BrN2O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
4-(4-Bromophenyl)-2-oxo-1,2,5,6-tetrahydrobenzo[h]quinoline- 3-carbonitrile top
Crystal data top
C20H13BrN2OF(000) = 1520
Mr = 377.23Dx = 1.538 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -C 2ycCell parameters from 4349 reflections
a = 22.6906 (5) Åθ = 4.2–74.3°
b = 8.5060 (2) ŵ = 3.50 mm1
c = 17.6112 (5) ÅT = 100 K
β = 106.498 (3)°Octahedron, yellow
V = 3259.13 (14) Å30.30 × 0.25 × 0.20 mm
Z = 8
Data collection top
Agilent SuperNova Dual
diffractometer with Atlas detector
3244 independent reflections
Radiation source: SuperNova (Cu) X-ray Source3132 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.022
Detector resolution: 10.4041 pixels mm-1θmax = 74.4°, θmin = 5.2°
ω scansh = 2727
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
k = 710
Tmin = 0.420, Tmax = 0.541l = 1421
6063 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0634P)2 + 3.4873P]
where P = (Fo2 + 2Fc2)/3
3244 reflections(Δ/σ)max = 0.001
221 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
C20H13BrN2OV = 3259.13 (14) Å3
Mr = 377.23Z = 8
Monoclinic, C2/cCu Kα radiation
a = 22.6906 (5) ŵ = 3.50 mm1
b = 8.5060 (2) ÅT = 100 K
c = 17.6112 (5) Å0.30 × 0.25 × 0.20 mm
β = 106.498 (3)°
Data collection top
Agilent SuperNova Dual
diffractometer with Atlas detector
3244 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2010)
3132 reflections with I > 2σ(I)
Tmin = 0.420, Tmax = 0.541Rint = 0.022
6063 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.094H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.56 e Å3
3244 reflectionsΔρmin = 0.57 e Å3
221 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.918537 (8)0.05660 (2)0.742895 (12)0.02179 (11)
O10.57369 (7)0.53089 (18)0.51145 (10)0.0241 (3)
N10.53722 (7)0.3095 (2)0.55547 (10)0.0172 (3)
N20.73458 (8)0.5190 (3)0.57289 (12)0.0264 (4)
C10.54467 (9)0.1682 (2)0.59371 (11)0.0167 (4)
C20.48982 (9)0.0824 (2)0.60012 (12)0.0175 (4)
C30.43270 (9)0.1549 (2)0.58744 (12)0.0195 (4)
H30.42840.26380.57510.023*
C40.38190 (10)0.0686 (2)0.59274 (14)0.0223 (4)
H40.34320.11870.58480.027*
C50.38810 (10)0.0913 (3)0.60971 (13)0.0244 (4)
H50.35330.15100.61230.029*
C60.44492 (10)0.1637 (3)0.62285 (13)0.0240 (4)
H60.44870.27280.63490.029*
C70.49638 (10)0.0790 (2)0.61870 (12)0.0203 (4)
C80.55804 (9)0.1564 (3)0.63177 (14)0.0253 (4)
H8A0.56290.19120.58030.030*
H8B0.56020.25050.66550.030*
C90.61001 (10)0.0444 (2)0.67123 (14)0.0240 (5)
H9A0.60960.02410.72640.029*
H9B0.64990.09320.67280.029*
C100.60314 (9)0.1088 (2)0.62645 (11)0.0181 (4)
C110.65406 (9)0.1960 (2)0.61906 (11)0.0179 (4)
C120.64485 (9)0.3399 (2)0.58053 (11)0.0177 (4)
C130.58428 (9)0.4025 (2)0.54653 (12)0.0178 (4)
C140.69504 (10)0.4366 (2)0.57531 (13)0.0193 (4)
C150.71808 (8)0.1347 (2)0.65091 (11)0.0176 (4)
C160.74530 (10)0.0579 (3)0.59968 (13)0.0252 (5)
H160.72280.04480.54560.030*
C170.80490 (10)0.0000 (3)0.62658 (12)0.0251 (4)
H170.82320.05320.59160.030*
C180.83693 (9)0.0216 (2)0.70531 (12)0.0182 (4)
C190.81110 (9)0.0985 (2)0.75721 (12)0.0194 (4)
H190.83400.11270.81100.023*
C200.75125 (9)0.1550 (2)0.72992 (12)0.0200 (4)
H200.73300.20730.76520.024*
H10.5015 (13)0.349 (3)0.5343 (15)0.026 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.01372 (15)0.02727 (16)0.02247 (15)0.00536 (7)0.00206 (10)0.00254 (7)
O10.0149 (7)0.0195 (7)0.0366 (9)0.0000 (6)0.0050 (6)0.0078 (6)
N10.0119 (7)0.0173 (8)0.0211 (8)0.0001 (6)0.0026 (6)0.0008 (6)
N20.0188 (9)0.0326 (10)0.0289 (10)0.0042 (8)0.0084 (8)0.0001 (8)
C10.0157 (9)0.0182 (9)0.0154 (8)0.0006 (7)0.0032 (7)0.0010 (7)
C20.0176 (9)0.0195 (9)0.0147 (9)0.0015 (8)0.0034 (7)0.0000 (7)
C30.0160 (9)0.0202 (9)0.0217 (9)0.0007 (8)0.0043 (7)0.0011 (8)
C40.0161 (10)0.0266 (11)0.0242 (11)0.0010 (8)0.0054 (8)0.0009 (8)
C50.0209 (10)0.0280 (11)0.0241 (10)0.0076 (9)0.0063 (8)0.0018 (9)
C60.0237 (10)0.0210 (10)0.0257 (10)0.0040 (8)0.0046 (8)0.0032 (8)
C70.0217 (10)0.0198 (10)0.0184 (10)0.0014 (8)0.0039 (8)0.0011 (7)
C80.0214 (10)0.0193 (10)0.0340 (11)0.0006 (8)0.0062 (9)0.0048 (9)
C90.0172 (10)0.0245 (11)0.0278 (11)0.0024 (8)0.0023 (9)0.0085 (8)
C100.0153 (9)0.0193 (10)0.0186 (9)0.0012 (8)0.0028 (7)0.0019 (8)
C110.0155 (9)0.0210 (9)0.0162 (8)0.0011 (8)0.0028 (7)0.0020 (7)
C120.0133 (8)0.0214 (9)0.0180 (9)0.0001 (7)0.0037 (7)0.0006 (7)
C130.0148 (9)0.0187 (9)0.0192 (9)0.0006 (8)0.0037 (7)0.0014 (8)
C140.0147 (10)0.0237 (11)0.0187 (10)0.0035 (7)0.0036 (8)0.0009 (7)
C150.0133 (8)0.0186 (9)0.0193 (9)0.0003 (7)0.0024 (7)0.0027 (7)
C160.0190 (10)0.0354 (13)0.0176 (10)0.0066 (8)0.0008 (8)0.0028 (8)
C170.0216 (10)0.0333 (12)0.0193 (10)0.0065 (9)0.0039 (8)0.0027 (9)
C180.0128 (8)0.0210 (9)0.0199 (9)0.0019 (8)0.0032 (7)0.0038 (8)
C190.0157 (9)0.0216 (9)0.0181 (9)0.0007 (8)0.0004 (7)0.0005 (8)
C200.0177 (9)0.0225 (10)0.0195 (9)0.0018 (8)0.0050 (8)0.0018 (8)
Geometric parameters (Å, º) top
Br1—C181.9009 (19)C8—H8A0.9900
O1—C131.244 (3)C8—H8B0.9900
N1—C11.365 (3)C9—C101.508 (3)
N1—C131.374 (3)C9—H9A0.9900
N1—H10.86 (3)C9—H9B0.9900
N2—C141.149 (3)C10—C111.410 (3)
C1—C101.383 (3)C11—C121.387 (3)
C1—C21.474 (3)C11—C151.494 (3)
C2—C31.395 (3)C12—C141.429 (3)
C2—C71.410 (3)C12—C131.436 (3)
C3—C41.392 (3)C15—C201.392 (3)
C3—H30.9500C15—C161.393 (3)
C4—C51.391 (3)C16—C171.390 (3)
C4—H40.9500C16—H160.9500
C5—C61.388 (3)C17—C181.383 (3)
C5—H50.9500C17—H170.9500
C6—C71.392 (3)C18—C191.382 (3)
C6—H60.9500C19—C201.391 (3)
C7—C81.504 (3)C19—H190.9500
C8—C91.522 (3)C20—H200.9500
C1—N1—C13124.93 (17)C8—C9—H9B109.5
C1—N1—H1121.9 (19)H9A—C9—H9B108.1
C13—N1—H1113.2 (18)C1—C10—C11118.91 (18)
N1—C1—C10119.81 (18)C1—C10—C9118.56 (18)
N1—C1—C2118.98 (17)C11—C10—C9122.49 (18)
C10—C1—C2121.20 (18)C12—C11—C10119.75 (18)
C3—C2—C7119.98 (19)C12—C11—C15119.14 (17)
C3—C2—C1122.38 (18)C10—C11—C15121.11 (18)
C7—C2—C1117.64 (18)C11—C12—C14121.83 (18)
C4—C3—C2120.39 (19)C11—C12—C13121.65 (18)
C4—C3—H3119.8C14—C12—C13116.48 (18)
C2—C3—H3119.8O1—C13—N1121.05 (18)
C5—C4—C3119.7 (2)O1—C13—C12124.01 (18)
C5—C4—H4120.2N1—C13—C12114.94 (18)
C3—C4—H4120.2N2—C14—C12177.1 (2)
C6—C5—C4120.2 (2)C20—C15—C16119.48 (18)
C6—C5—H5119.9C20—C15—C11121.61 (18)
C4—C5—H5119.9C16—C15—C11118.89 (18)
C5—C6—C7121.0 (2)C17—C16—C15120.9 (2)
C5—C6—H6119.5C17—C16—H16119.6
C7—C6—H6119.5C15—C16—H16119.6
C6—C7—C2118.8 (2)C18—C17—C16118.6 (2)
C6—C7—C8121.56 (19)C18—C17—H17120.7
C2—C7—C8119.62 (19)C16—C17—H17120.7
C7—C8—C9111.25 (18)C17—C18—C19121.67 (18)
C7—C8—H8A109.4C17—C18—Br1119.04 (16)
C9—C8—H8A109.4C19—C18—Br1119.29 (15)
C7—C8—H8B109.4C18—C19—C20119.37 (19)
C9—C8—H8B109.4C18—C19—H19120.3
H8A—C8—H8B108.0C20—C19—H19120.3
C10—C9—C8110.52 (18)C15—C20—C19120.03 (18)
C10—C9—H9A109.5C15—C20—H20120.0
C8—C9—H9A109.5C19—C20—H20120.0
C10—C9—H9B109.5
C13—N1—C1—C100.5 (3)C9—C10—C11—C12176.75 (19)
C13—N1—C1—C2178.78 (18)C1—C10—C11—C15177.91 (18)
N1—C1—C2—C316.9 (3)C9—C10—C11—C154.3 (3)
C10—C1—C2—C3162.37 (19)C10—C11—C12—C14176.52 (19)
N1—C1—C2—C7162.20 (18)C15—C11—C12—C144.5 (3)
C10—C1—C2—C718.5 (3)C10—C11—C12—C130.9 (3)
C7—C2—C3—C40.2 (3)C15—C11—C12—C13178.03 (18)
C1—C2—C3—C4178.85 (19)C1—N1—C13—O1179.27 (19)
C2—C3—C4—C50.9 (3)C1—N1—C13—C120.6 (3)
C3—C4—C5—C61.3 (3)C11—C12—C13—O1179.99 (19)
C4—C5—C6—C70.6 (3)C14—C12—C13—O12.4 (3)
C5—C6—C7—C20.6 (3)C11—C12—C13—N10.1 (3)
C5—C6—C7—C8179.2 (2)C14—C12—C13—N1177.43 (17)
C3—C2—C7—C60.9 (3)C12—C11—C15—C2096.8 (2)
C1—C2—C7—C6178.17 (18)C10—C11—C15—C2084.2 (3)
C3—C2—C7—C8179.62 (19)C12—C11—C15—C1682.1 (2)
C1—C2—C7—C80.5 (3)C10—C11—C15—C1696.8 (2)
C6—C7—C8—C9146.7 (2)C20—C15—C16—C170.6 (3)
C2—C7—C8—C934.7 (3)C11—C15—C16—C17179.5 (2)
C7—C8—C9—C1051.9 (2)C15—C16—C17—C180.6 (4)
N1—C1—C10—C110.4 (3)C16—C17—C18—C190.1 (3)
C2—C1—C10—C11179.60 (18)C16—C17—C18—Br1179.90 (17)
N1—C1—C10—C9177.51 (18)C17—C18—C19—C200.4 (3)
C2—C1—C10—C91.7 (3)Br1—C18—C19—C20179.60 (16)
C8—C9—C10—C137.1 (3)C16—C15—C20—C190.0 (3)
C8—C9—C10—C11145.1 (2)C11—C15—C20—C19178.99 (19)
C1—C10—C11—C121.0 (3)C18—C19—C20—C150.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.86 (3)1.96 (3)2.807 (2)172 (3)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC20H13BrN2O
Mr377.23
Crystal system, space groupMonoclinic, C2/c
Temperature (K)100
a, b, c (Å)22.6906 (5), 8.5060 (2), 17.6112 (5)
β (°) 106.498 (3)
V3)3259.13 (14)
Z8
Radiation typeCu Kα
µ (mm1)3.50
Crystal size (mm)0.30 × 0.25 × 0.20
Data collection
DiffractometerAgilent SuperNova Dual
diffractometer with Atlas detector
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2010)
Tmin, Tmax0.420, 0.541
No. of measured, independent and
observed [I > 2σ(I)] reflections
6063, 3244, 3132
Rint0.022
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.094, 1.06
No. of reflections3244
No. of parameters221
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.56, 0.57

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.86 (3)1.96 (3)2.807 (2)172 (3)
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

The authors thank King Abdulaziz University and the University of Malaya for supporting this study.

References

First citationAgilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.  Google Scholar
First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationRostom, S. A. F., Faidallah, H. M. & Al-Saadi, M. S. (2011). Med. Chem. Res. 20 (DOI: 10.1007/s00044-010-9469-0).  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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