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

In the title mol-ecule, C(11)H(11)ClN(2)O, 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 chloro-ethyl side chain is in a synclinal conformation, nearly orthogonal to the pyrimidine ring, with a dihedral angle between the chloro-ethyl side chain and the pyrimidine ring of 88.5 (1)°. Weak inter-molecular C-H⋯N and C-H⋯Cl hydrogen bonds along with π-π inter-actions 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 = 222.67

Orthorhombic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.181

S = 1.11

3089 reflections

138 parameters

H-atom parameters constrained

Δρmax = 0.99 e Å−3

Δρmin = −0.52 e Å−3

Absolute structure: Flack (1983 ▶), 1103 Friedel pairs

Flack parameter: 0.32 (12)

Data collection: CrysAlisPro (Oxford Diffraction, 2007 ▶); 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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H11ClN2O	F(000) = 464
Mr = 222.67	Dx = 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

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

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(Fo2) + (0.1108P)2 + 0.2652P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
3089 reflections	Δρmax = 0.99 e Å−3
138 parameters	Δρmin = −0.51 e Å−3
0 restraints	Absolute structure: Flack (1983), 1103 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.32 (12)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) .