3-(2-Chloro­ethyl)-2-methyl-4H-pyrido[1,2-a]pyrimidin-4-one

Jasinski, J.P.; Butcher, R.J.; Hakim Al-Arique, Q.N.M.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536809027548

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages o1987-o1988

doi:10.1107/S1600536809027548

Open

access

3-(2-Chloroethyl)-2-methyl-4H-pyrido[1,2-a]pyrimidin-4-one

Jerry P. Jasinski,^a Ray J. Butcher,^b ^* Q. N. M. Hakim Al-Arique,^c H. S. Yathirajan ^c and B. Narayana ^d

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington DC 20059, USA, ^cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^dDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 11 June 2009; accepted 13 July 2009; online 25 July 2009)

In the title molecule, C₁₁H₁₁ClN₂O, the pyrido[1,2-a]pyrimidine ring system is planar (maximum deviation = 0.0148 Å) and the methyl C and carbonyl O atoms are nearly coplanar to it. The chloroethyl side chain is in a synclinal conformation, nearly orthogonal to the pyrimidine ring, with a dihedral angle between the chloroethyl side chain and the pyrimidine ring of 88.5 (1)°. Weak intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds along with π–π interactions between the pyrimidine and pyridine rings [centroid–centroid distance is 3.538 (2) Å] form a three-dimensional network. The crystal is a racemic twin with a 0.68 (12):0.32 (12) domain ratio. MOPAC AM1 and density functional theory (DFT) theoretical calculations at the B3-LYP/6–311+G(d,p) level support these observations.

Related literature

For related structures, see: Blaton et al. (1995 ); Chen & He (2006 ); Elotmani et al. (2002 ); Jottier et al. (1992 ); Koval'chukova et al. (2004 ); Peeters et al. (1993 ); Ravikumar & Sridhar, (2006 ); Yu et al. (2007 ). For general background to heterofused pyrimidines, see: Baraldi et al. (2002 ); Bookser et al. (2005 ); Chen et al. (2004 ); La Motta et al. (2007 ); Gabbert & Giannini (1997 ); Goodacre et al. (2006 ); Hossain et al. (1997 ); Joseph & Burke (1993 ); Nikitin & Smirnov (1994 ); Sabnis & Rangnekar (1990 ); Wang et al. (2004 ); White et al. (2004 ). For the synthesis, see: Toche et al. (2008 ). For GAUSSIAN03 theoretical calculations, see: Becke (1988 , 1993 ); Frisch et al. (2004 ); Hehre et al. (1986 ); Lee et al. (1988 ); Schmidt & Polik (2007 ).

Experimental

Crystal data

C₁₁H₁₁ClN₂O
M_r = 222.67
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.2546 (4) Å
b = 11.6274 (10) Å
c = 20.604 (2) Å
V = 1019.27 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 110 K
0.51 × 0.35 × 0.12 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.835, T_max = 0.959
4613 measured reflections
3089 independent reflections
2607 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.181
S = 1.11
3089 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 1103 Friedel pairs
Flack parameter: 0.32 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯N2ⁱ	0.95	2.50	3.394 (3)	157
C2—H2A⋯Clⁱⁱ	0.95	2.90	3.559 (3)	128
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlisPro (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027548/ci2827sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027548/ci2827Isup2.hkl

checkCIF report

Comment top

Heterofused pyrimidines exhibit promising antiviral (Hossain et al. 1997), antibacterial (Sabnis & Rangnekar, 1990), anti-AIDS (Joseph & Burke, 1993), and antinociceptive (Bookser et al. 2005) activities. Fused pyrimidines are extensively used in neurology, particularly in the treatment of neurodegenerative disorders such as Parkinson's disease (Baraldi et al. 2002), antianxiety disorders (Goodacre et al. 2006) and depression (Chen et al. 2004). Fused pyrimidines are selective inhibitors for multidrug resistance (MDR) (Wang et al. 2004). A review on the synthesis, chemical and biological properties of pyrido[1,2-a]pyrimidines is described (Nikitin & Smirnov, 1994). Pyrido[1,2-a]pyrimidin-4-one derivatives as a novel class of selective aldose reductase inhibitors exhibiting antioxidant activity has been reported (La Motta et al. 2007). The synthesis and anticonvulsant evaluation of some new 2-substituted-3-arylpyrido[2,3-d]pyrimidinones have also been reported (White et al. 2004). The crystal structures of 3-{2-[4-(6-fluoro-1,2-benzisoxazol-3-yl)piperidino]ethyl}-6,7,8,9- tetrahydro-2-methyl-4H-pyrido[1,2-a]pyrimidin-4-one (risperidone) (Peeters et al. 1993), 3-{2-[4-(4-fluorobenzoyl)piperidino]ethyl}-2-methyl-4H-pyrido[1,2-a]pyrimidin-4-one (Pirenperone) (Blaton et al. 1995), 5-methyl-2-morpholino-3-p-tolyl-8,9,10,11-tetrahydro-2-benzothieno[2', 3':6,5]pyrido[4,3-d]pyrimidin-4(3H)-one (Chen & He, 2006), 3-{2-[4-(6-fluoro-1,2-benzisoxazol-3-yl)-1-piperidinyl]ethyl}-2,9- dimethyl-4H-pyrido[1,2-a]pyrimidin-4-one (Ocaperidone) (Jottier et al. 1992), 2-methyl-3-(3-methyl-1H-pyrazol-5-yl)pyrido[1,2-a]pyrimidin-4-one (Elotmani et al. 2002), 2-methyl-3-chloro-9-hydroxypyrido[1,2-a]pyrimidin-4-one and bis(2-methyl-3-chloro-9-hydroxypyrido[1,2-a]pyrimidin-4-onium) perchlorate (Koval'chukova et al. 2004), 3-(2-chloroethyl)-2-methyl-4-oxo-6,7,8,9-tetrahydro-4H-pyrido[1,2-a] pyrimidin-1-ium chloride (Ravikumar & Sridhar, 2006) and 9-(4-methoxybenzoyl)-1,2,3,4-tetrahydro-6H-pyrido[1,2-a]pyrimidin-6-one (Yu et al. 2007) have also been reported.

The title compound, (I), is an intermediate in the synthesis of risperidone, which is a potent antipsychotic agent, especially useful for treating schizophrenia (Gabbert & Giannini, 1997). In view of the importance of (I), the present paper describes its crystal structure.

The overall molecular geometry of (I), including bond distances and angles, is in good agreement with related structures (Blaton et al. 1995; Jottier et al. 1992; Peeters et al. 1993; Ravikumar & Sridhar, 2006). It consists of a pyridine ring fused to a substituted pyrimidine ring creating a planar ring system (maximum deviation, C1, = -0.0148Å) with the methyl C and carbonyl O atoms nearly coplanar to the pyrimidine ring (Torsion angles C1-C9-C7-C8 = 177.6 (3)° ; C2-N1-C1-O = -2.5 (4)° (Fig. 1). The sum of the angles aroumd N1 is 360.0 (5)° indicating sp² hybridization. The chloroethyl side chain is in a synclinal (-sc) conformation (C1—C9—C10—C11 torsion angle = -86.6 (3)°), nearly orthogonal to the pyrimidine ring, with a dihedral angle separation between the C10/C11/Cl group and the pyrimidine ring of 88.5 (1)°.

While no classic hydrogen bonds are observed, a weak intermolecular hydrogen bond interaction exists between atom C5 from the pyridine ring and N2 from a nearby pyrimidine ring (Table 1 and Fig. 2). In addition, a weak intermolecular interaction between atom C2 from the pyrimidine ring and Cl from the substituted pyrimidine group also occurs, each influencing crystal packing and, therefore, resulting in a three-dimensional network (Fig. 2). In addition, π-π interactions between N1/C1/C9/C7/N2/C6 (centroid Cg1) and N1/C2-C6 (centroid Cg2) rings of molecules at (x, y, z) and (1+x, y, z), with a Cg1···Cg2 distance of 3.538 (2) Å, provide additional stability to the crystal packing. The crystal is a racemic twin with domains of 0.68 (12) and 0.32 (12).

In support of these observations, a MOPAC AM1 (Schmidt & Polik, 2007) and density functional theory (DFT) geometry optimized theoretical calculation (Schmidt & Polik, 2007) with the GAUSSIAN03 program package (Frisch et al. 2004) employing the B3-LYP (Becke 3 parameter Lee-Yang-Parr) exchange correlation functional, which combines the hybrid exchange functional of Becke (Becke, 1988, 1993) with the gradient-correlation functional of Lee, Yang and Parr (Lee et al. 1988) and the 6–311+G(d,p) basis set (Hehre et al. 1986), was performed on (I) utilizing starting geometries taken from the X-ray refinement data. In both calculations the resulting bond distances and angles remained relatively constant. However, the C9—C10—C11—Cl torsion angle decreased by 3.2 (1)° to 175.4 (3)° (MOPAC) and 0.07° to 178.5 (7)° (DFT) and the dihedral angle between the C10/C11/Cl group and the pyrimidine ring decreased by 2.3 (8)° to 86.1 (3)° (MOPAC) and by 8.3 (6)° to 80.1 (5)° (DFT), respectively.

In summary, it is clear that the collection of weak intermolecular hydrogen bond interactions and π-π intermolecular interactions do play a role in stabilizing crystal packing of (I).

Related literature top

For related structures, see: Blaton et al. (1995); Chen & He (2006); Elotmani et al. (2002); Jottier et al. (1992); Koval'chukova et al. (2004); Peeters et al. (1993); Ravikumar & Sridhar, (2006); Yu et al. (2007). For general background to heterofused pyrimidines, see: Baraldi et al. (2002); Bookser et al. (2005); Chen et al. (2004); La Motta et al. (2007); Gabbert & Giannini (1997); Goodacre et al. (2006); Hossain et al. (1997); Joseph & Burke (1993); Nikitin & Smirnov (1994); Sabnis & Rangnekar (1990); Wang et al. (2004); White et al. (2004). For the synthesis, see: Toche et al. (2008). For GAUSSIAN03 theoretical calculations, see: Becke (1988, 1993); Frisch et al. (2004); Hehre et al. (1986); Lee et al. (1988); Schmidt & Polik (2007).

Experimental top

The title compound was synthesized following the reported procedure (Toche et al. 2008). Pale yellow crystals of compound (I) were obtained by slow evaporation from ethyl acetate solution (m.p. 405–408 K). Analytical data: Found (calculated): C %: 59.28 (59.33); H%: 4.97 (4.98); N%: 12.54 (12.58).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of (I), viewed down the b axis. Dashed lines indicate weak C5—H5A···N2 and C2—H2A···Cl intermolecular interactions.

3-(2-Chloroethyl)-2-methyl-4H-pyrido[1,2-a]pyrimidin-4-one top

Crystal data top

C₁₁H₁₁ClN₂O	F(000) = 464
M_r = 222.67	D_x = 1.451 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2755 reflections
a = 4.2546 (4) Å	θ = 4.8–32.6°
b = 11.6274 (10) Å	µ = 0.35 mm⁻¹
c = 20.604 (2) Å	T = 110 K
V = 1019.27 (17) Å³	Plate, colorless
Z = 4	0.51 × 0.35 × 0.12 mm

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	3089 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2607 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.6°, θ_min = 4.9°
ϕ and ω scans	h = −3→6
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −17→16
T_min = 0.835, T_max = 0.959	l = −30→27
4613 measured reflections

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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.181	w = 1/[σ²(F_o²) + (0.1108P)² + 0.2652P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
3089 reflections	Δρ_max = 0.99 e Å⁻³
138 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1103 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.32 (12)

Crystal data top

C₁₁H₁₁ClN₂O	V = 1019.27 (17) Å³
M_r = 222.67	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.2546 (4) Å	µ = 0.35 mm⁻¹
b = 11.6274 (10) Å	T = 110 K
c = 20.604 (2) Å	0.51 × 0.35 × 0.12 mm

Data collection top

Oxford Diffraction Gemini R CCD diffractometer	3089 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	2607 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.959	R_int = 0.054
4613 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.181	Δρ_max = 0.99 e Å⁻³
S = 1.11	Δρ_min = −0.52 e Å⁻³
3089 reflections	Absolute structure: Flack (1983), 1103 Friedel pairs
138 parameters	Absolute structure parameter: 0.32 (12)
0 restraints

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
Cl	0.49448 (19)	0.87358 (6)	0.12093 (3)	0.02056 (18)
O	0.1937 (6)	1.09071 (18)	0.30555 (10)	0.0240 (5)
N1	−0.0403 (6)	0.9961 (2)	0.39118 (10)	0.0150 (4)
N2	0.0097 (7)	0.79306 (19)	0.40322 (11)	0.0172 (4)
C1	0.1541 (7)	0.9982 (2)	0.33357 (13)	0.0151 (5)
C2	−0.1616 (9)	1.0994 (2)	0.41318 (14)	0.0207 (6)
H2A	−0.1116	1.1685	0.3909	0.025*
C3	−0.3506 (8)	1.1032 (3)	0.46596 (15)	0.0231 (6)
H3A	−0.4354	1.1744	0.4803	0.028*
C4	−0.4212 (7)	0.9999 (3)	0.49970 (14)	0.0211 (6)
H4A	−0.5530	1.0019	0.5369	0.025*
C5	−0.3006 (8)	0.8986 (2)	0.47886 (13)	0.0191 (5)
H5A	−0.3477	0.8299	0.5019	0.023*
C6	−0.1033 (7)	0.8935 (2)	0.42262 (13)	0.0147 (5)
C7	0.1973 (8)	0.7917 (2)	0.34977 (13)	0.0155 (5)
C8	0.3087 (9)	0.6735 (2)	0.33069 (16)	0.0239 (6)
H8A	0.2581	0.6188	0.3653	0.036*
H8B	0.5366	0.6750	0.3238	0.036*
H8C	0.2038	0.6499	0.2905	0.036*
C9	0.2748 (7)	0.8891 (2)	0.31499 (12)	0.0146 (5)
C10	0.4766 (9)	0.8869 (2)	0.25437 (12)	0.0182 (5)
H10A	0.6268	0.8220	0.2567	0.022*
H10B	0.5983	0.9592	0.2511	0.022*
C11	0.2671 (7)	0.8733 (3)	0.19491 (13)	0.0201 (5)
H11A	0.1130	0.9371	0.1936	0.024*
H11B	0.1489	0.8002	0.1982	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0233 (3)	0.0253 (3)	0.0132 (3)	−0.0031 (3)	0.0030 (3)	−0.0001 (2)
O	0.0323 (13)	0.0185 (9)	0.0214 (10)	−0.0029 (9)	0.0024 (10)	0.0048 (8)
N1	0.0188 (11)	0.0144 (8)	0.0118 (9)	0.0013 (9)	−0.0009 (9)	0.0005 (7)
N2	0.0200 (10)	0.0157 (8)	0.0160 (10)	−0.0002 (12)	−0.0001 (11)	0.0019 (7)
C1	0.0168 (12)	0.0163 (11)	0.0122 (11)	−0.0028 (11)	−0.0005 (10)	0.0002 (9)
C2	0.0286 (15)	0.0163 (11)	0.0173 (13)	0.0039 (12)	0.0000 (12)	−0.0001 (9)
C3	0.0259 (15)	0.0235 (13)	0.0198 (14)	0.0058 (13)	−0.0013 (12)	−0.0054 (10)
C4	0.0198 (14)	0.0300 (14)	0.0135 (12)	0.0026 (12)	0.0017 (10)	−0.0019 (10)
C5	0.0196 (13)	0.0234 (12)	0.0142 (12)	−0.0029 (12)	0.0018 (11)	0.0028 (10)
C6	0.0178 (11)	0.0146 (11)	0.0118 (11)	−0.0013 (9)	−0.0029 (9)	0.0017 (8)
C7	0.0194 (13)	0.0125 (10)	0.0146 (11)	0.0001 (11)	−0.0022 (11)	−0.0001 (9)
C8	0.0282 (16)	0.0167 (11)	0.0267 (15)	0.0015 (13)	0.0028 (14)	−0.0022 (10)
C9	0.0133 (11)	0.0183 (11)	0.0124 (12)	−0.0020 (10)	−0.0004 (9)	0.0005 (9)
C10	0.0164 (12)	0.0245 (12)	0.0138 (11)	−0.0008 (13)	0.0011 (10)	0.0003 (9)
C11	0.0178 (12)	0.0305 (13)	0.0119 (11)	−0.0035 (12)	0.0019 (10)	−0.0012 (11)

Geometric parameters (Å, º) top

Cl—C11	1.805 (3)	C5—C6	1.432 (4)
O—C1	1.232 (3)	C5—H5A	0.95
N1—C2	1.383 (4)	C7—C9	1.381 (4)
N1—C6	1.384 (3)	C7—C8	1.505 (4)
N1—C1	1.447 (3)	C8—H8A	0.98
N2—C6	1.325 (3)	C8—H8B	0.98
N2—C7	1.360 (4)	C8—H8C	0.98
C1—C9	1.421 (4)	C9—C10	1.516 (4)
C2—C3	1.353 (5)	C10—C11	1.523 (4)
C2—H2A	0.95	C10—H10A	0.99
C3—C4	1.420 (5)	C10—H10B	0.99
C3—H3A	0.95	C11—H11A	0.99
C4—C5	1.355 (4)	C11—H11B	0.99
C4—H4A	0.95

C2—N1—C6	121.5 (2)	N2—C7—C8	114.0 (2)
C2—N1—C1	117.9 (2)	C9—C7—C8	122.6 (3)
C6—N1—C1	120.6 (2)	C7—C8—H8A	109.5
C6—N2—C7	117.9 (2)	C7—C8—H8B	109.5
O—C1—C9	127.1 (3)	H8A—C8—H8B	109.5
O—C1—N1	118.5 (3)	C7—C8—H8C	109.5
C9—C1—N1	114.4 (2)	H8A—C8—H8C	109.5
C3—C2—N1	120.9 (3)	H8B—C8—H8C	109.5
C3—C2—H2A	119.5	C7—C9—C1	120.4 (2)
N1—C2—H2A	119.5	C7—C9—C10	123.3 (2)
C2—C3—C4	119.4 (3)	C1—C9—C10	116.3 (2)
C2—C3—H3A	120.3	C9—C10—C11	109.5 (3)
C4—C3—H3A	120.3	C9—C10—H10A	109.8
C5—C4—C3	120.0 (3)	C11—C10—H10A	109.8
C5—C4—H4A	120.0	C9—C10—H10B	109.8
C3—C4—H4A	120.0	C11—C10—H10B	109.8
C4—C5—C6	120.9 (3)	H10A—C10—H10B	108.2
C4—C5—H5A	119.5	C10—C11—Cl	111.4 (2)
C6—C5—H5A	119.5	C10—C11—H11A	109.3
N2—C6—N1	123.3 (2)	Cl—C11—H11A	109.3
N2—C6—C5	119.6 (2)	C10—C11—H11B	109.3
N1—C6—C5	117.2 (2)	Cl—C11—H11B	109.3
N2—C7—C9	123.4 (2)	H11A—C11—H11B	108.0

C2—N1—C1—O	−2.5 (4)	C4—C5—C6—N2	−179.6 (3)
C6—N1—C1—O	177.1 (3)	C4—C5—C6—N1	0.5 (4)
C2—N1—C1—C9	178.7 (3)	C6—N2—C7—C9	−0.1 (4)
C6—N1—C1—C9	−1.8 (4)	C6—N2—C7—C8	−178.8 (3)
C6—N1—C2—C3	−0.9 (5)	N2—C7—C9—C1	−1.0 (4)
C1—N1—C2—C3	178.6 (3)	C8—C7—C9—C1	177.6 (3)
N1—C2—C3—C4	1.0 (5)	N2—C7—C9—C10	−178.2 (3)
C2—C3—C4—C5	−0.3 (5)	C8—C7—C9—C10	0.4 (5)
C3—C4—C5—C6	−0.5 (5)	O—C1—C9—C7	−176.9 (3)
C7—N2—C6—N1	0.2 (4)	N1—C1—C9—C7	1.8 (4)
C7—N2—C6—C5	−179.7 (3)	O—C1—C9—C10	0.6 (4)
C2—N1—C6—N2	−179.7 (3)	N1—C1—C9—C10	179.3 (2)
C1—N1—C6—N2	0.8 (4)	C7—C9—C10—C11	90.7 (3)
C2—N1—C6—C5	0.2 (4)	C1—C9—C10—C11	−86.6 (3)
C1—N1—C6—C5	−179.3 (3)	C9—C10—C11—Cl	178.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···N2ⁱ	0.95	2.50	3.394 (3)	157
C2—H2A···Clⁱⁱ	0.95	2.90	3.559 (3)	128

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁ClN₂O
M_r	222.67
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	110
a, b, c (Å)	4.2546 (4), 11.6274 (10), 20.604 (2)
V (Å³)	1019.27 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.51 × 0.35 × 0.12

Data collection
Diffractometer	Oxford Diffraction Gemini R CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.835, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	4613, 3089, 2607
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.181, 1.11
No. of reflections	3089
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.99, −0.52
Absolute structure	Flack (1983), 1103 Friedel pairs
Absolute structure parameter	0.32 (12)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···N2ⁱ	0.95	2.50	3.394 (3)	157
C2—H2A···Clⁱⁱ	0.95	2.90	3.559 (3)	128

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x, y+1/2, −z+1/2.

Acknowledgements

QNMHA thanks the University of Mysore for use of its research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

References

Baraldi, P. G., Cacciari, B., Romagnoli, R., Spalluto, G., Monopoli, A., Ongini, E., Varani, K. & Borea, P. A. (2002). J. Med. Chem. 45, 115–126. Web of Science CrossRef PubMed CAS Google Scholar
Becke, A. D. (1988). Phys. Rev. A38, 3098–100. CrossRef Google Scholar
Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652. CrossRef CAS Web of Science Google Scholar
Blaton, N. M., Peeters, O. M. & De Ranter, C. J. (1995). Acta Cryst. C51, 533–535. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Bookser, B. C., Ugarkar, B. G., Matelich, M. C., Lemus, R. H., Alla, M., Tsuchiya, M., Nakane, M., Nagahisa, A., Wiesner, J. B. & Erion, M. D. (2005). J. Med. Chem. 48, 7808–7820. Web of Science CrossRef PubMed CAS Google Scholar
Chen, C., Chen, C., Wilcoxen, K. M., Huang, C. Q., Xie, Y.-F., McCarthy, J. R., Webb, T. R., Zhu, Y.-F., Saunders, J., Liu, X.-J., Chen, T.-K., Bozigian, H. & Grigoriadis, D. E. (2004). J. Med. Chem. 47, 4787–4798. Web of Science CrossRef PubMed CAS Google Scholar
Chen, H.-L. & He, H.-W. (2006). Acta Cryst. E62, o1226–o1227. Web of Science CSD CrossRef IUCr Journals Google Scholar
Elotmani, B., Elmahi, M., Essassi, E. M. & Pierrot, M. (2002). Acta Cryst. E58, o388–o389. Web of Science CSD CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Frisch, M. J., et al. (2004). GAUSSIAN03. Gaussian Inc., Wallingford, CT 06492, USA. Google Scholar
Gabbert, J. F. & Giannini, A. J. (1997). Am. J. Ther. 4, 159–164. CrossRef PubMed CAS Google Scholar
Goodacre, S. C., Street, L. J., Hallett, D., Crawforth, J. M., Kelly, S., Owens, A. P., Blackaby, W. P., Lewis, R. T., Stanley, J., Smith, A. J., Ferris, P., Sohal, B., Cook, S. M., Pike, A., Brown, N., Wafford, K. A., Marshall, G., Castro, J. L. & Atack, J. R. (2006). J. Med. Chem. 49, 35–38. Web of Science CrossRef PubMed CAS Google Scholar
Hehre, W. J., Random, L., von Schleyer, P. R. & Pople, J. A. (1986). In Ab Initio Molecular Orbital Theory. New York: Wiley. Google Scholar
Hossain, N., Rozenski, J., De Clercq, E. & Herdewijn, P. (1997). J. Org. Chem. 62, 2442–2447. CrossRef PubMed CAS Web of Science Google Scholar
Joseph, S. & Burke, J. M. (1993). J. Biol. Chem. 268, 24515–24518. CAS PubMed Web of Science Google Scholar
Jottier, W. I., De Winter, H. L., Peeters, O. M., Blaton, N. M. & De Ranter, C. J. (1992). Acta Cryst. C48, 1827–1830. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Koval'chukova, O. V., Mordovina, N. I., Kuz'mina, N. E., Nikitin, S. V., Zaitsev, B. E., Strashnova, S. B. & Palkina, K. K. (2004). Crystallogr. Rep. 49, 792–797. CAS Google Scholar
La Motta, C., Sartinit, S., Mugnaini, L., Simorini, F., Taliani, S., Salerno, S., Marini, A. M., Da Settimo, F., Lavecchia, A., Novellino, E., Cantore, M., Failli, P. & Ciuffi, M. (2007). J. Med. Chem. 50, 4917–4927. Web of Science CrossRef PubMed CAS Google Scholar
Lee, C., Yang, W. & Parr, R. G. (1988). Phys. Rev. B, 37, 785–789. CrossRef CAS Web of Science Google Scholar
Nikitin, S. V. & Smirnov, L. D. (1994). Chem. Heter. Copm. 30, 507–522. CrossRef Google Scholar
Oxford Diffraction (2007). CrysAlisPro and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Google Scholar
Peeters, O. M., Blaton, N. M. & De Ranter, C. J. (1993). Acta Cryst. C49, 1698–1700. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Ravikumar, K. & Sridhar, B. (2006). Acta Cryst. E62, o3730–o3731. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sabnis, R. W. & Rangnekar, D. W. (1990). Indian J. Technol. 28, 54–58. CAS Google Scholar
Schmidt, J. R. & Polik, W. F. (2007). WebMO Pro. WebMO, LLC: Holland, MI, USA. URL: http://www.webmo.net. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Toche, R. B., Ghotekar, B. K., Kazi, M. A., Patil, S. P. & Jachak, M. N. (2008). Schol. Res. Exch. doi:10.3814/2008/434329, 1–5. Google Scholar
Wang, S., Folkes, A., Chuckowree, I., Cockcroft, X., Sohal, S., Miller, W., Milton, J., Wren, S. P., Vicker, N., Depledge, P., Scott, J., Smith, L., Jones, H., Mistry, P., Faint, R., Thompson, D. & Cocks, S. (2004). J. Med. Chem. 47, 1329–1338. Web of Science CrossRef PubMed CAS Google Scholar
White, D. C., Greenwood, D. C., Downey, A. L., Bloomquis, J. R. & Wolfe, J. F. (2004). Bioorg. Med. Chem. 12, 5711–5717. Web of Science CrossRef PubMed CAS Google Scholar
Yu, C.-Y., Yuan, X.-N. & Huang, Z.-T. (2007). Acta Cryst. E63, o3186. Web of Science CSD CrossRef IUCr Journals Google Scholar