n-Butyl 2-(3-chloro-1,2-dihydro-pyrazin-2-yl-idene)-2-cyano-acetate.

The title compound, C(11)H(12)ClN(3)O(2), is essentially planar except for the n-but-oxy group [r.m.s. deviation from the least-squares plane = 0.0131 (1) Å for 11 non-H atoms]. An intra-molecular N-H⋯O inter-action results in the formation of an S(6) ring. The n-butoxy chain in the molecule is disordered over two sets of sites of equal occupancy.

Related literature

For applications of this class of compounds, see: Matter et al. (2005); Kaliszan et al. (1985 ▶); Petrusewicz et al. (1992 ▶, 1993 ▶, 1995 ▶). For pyrazin­yl–pyrazyl­idene tautomerism, see: Pilarski et al. (1984 ▶). For related structures, see: Vishweshwar et al. (2000 ▶); Wardell et al. (2006 ▶). For the synthesis, see: Pilarski & Foks (1981 ▶, 1982 ▶).

Experimental

Crystal data

C11H12ClN3O2

M = 253.69

Monoclinic,

a = 4.918 (3) Å

b = 25.642 (7) Å

c = 10.573 (4) Å

β = 95.80 (3)°

V = 1326.7 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 120 K

0.57 × 0.11 × 0.07 mm

Data collection

Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire2 (large Be window) detector

Absorption correction: Gaussian (CrysAlis Pro; Oxford Diffraction, 2007 ▶) T min = 0.923, T max = 0.987

4629 measured reflections

1687 independent reflections

1219 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.156

S = 1.04

1687 reflections

154 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983 ▶), 466 Friedel pairs

Flack parameter: 0.05 (18)

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031870/ng2612sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031870/ng2612Isup2.hkl

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

C11H12ClN3O2	F(000) = 528
Mr = 253.69	Dx = 1.27 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1500 reflections
a = 4.918 (3) Å	θ = 2.5–32.3°
b = 25.642 (7) Å	µ = 0.28 mm−1
c = 10.573 (4) Å	T = 120 K
β = 95.80 (3)°	Block, yellow
V = 1326.7 (9) Å3	0.57 × 0.11 × 0.07 mm
Z = 4

Oxford Diffraction KM-4/Xcalibur diffractometer with a Sapphire2 (large Be window) detector	1687 independent reflections
graphite	1219 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1	Rint = 0.034
0.75° wide ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2007)	h = −3→5
Tmin = 0.923, Tmax = 0.987	k = −31→31
4629 measured reflections	l = −12→12

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.156	w = 1/[σ2(Fo2) + (0.1833P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1687 reflections	Δρmax = 0.24 e Å−3
154 parameters	Δρmin = −0.23 e Å−3
1 restraint	Absolute structure: Flack (1983), 466 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (18)

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	Occ. (<1)
Cl1	0.7083 (3)	0.42260 (5)	0.30244 (15)	0.0753 (4)
O1	0.0928 (8)	0.54438 (16)	0.6099 (3)	0.0731 (12)
N1	0.4291 (11)	0.36488 (18)	0.4525 (5)	0.0827 (13)
N2	0.1819 (9)	0.4445 (2)	0.5738 (4)	0.0612 (12)
N3	0.7225 (16)	0.55178 (17)	0.2917 (6)	0.0874 (12)
C1	0.2496 (17)	0.3549 (3)	0.5468 (7)	0.0905 (19)
H1A	0.2102	0.3199	0.5681	0.109*
C2	0.1303 (11)	0.3956 (3)	0.6086 (5)	0.0695 (16)
H2A	0.0153	0.3889	0.6737	0.083*
C3	0.3572 (10)	0.4596 (2)	0.4816 (4)	0.0548 (12)
C4	0.4796 (11)	0.4144 (2)	0.4225 (4)	0.0649 (13)
C5	0.4002 (10)	0.5136 (2)	0.4565 (4)	0.0569 (10)
C6	0.5828 (11)	0.5330 (2)	0.3632 (5)	0.0617 (11)
C7	0.2549 (12)	0.5528 (2)	0.5259 (5)	0.0626 (15)
O2	0.3471 (16)	0.6051 (3)	0.5012 (7)	0.050 (2)*	0.5
C8	0.202 (2)	0.6474 (4)	0.5635 (11)	0.056 (3)*	0.5
H8A	0.2504	0.647	0.6566	0.067*	0.5
H8B	0.0014	0.6434	0.5458	0.067*	0.5
C9	0.296 (2)	0.6977 (4)	0.5064 (9)	0.070 (3)*	0.5
H9A	0.4939	0.7017	0.5331	0.084*	0.5
H9B	0.2014	0.7269	0.5444	0.084*	0.5
C10	0.253 (3)	0.7037 (4)	0.3607 (9)	0.072 (3)*	0.5
H10A	0.3655	0.6769	0.3231	0.086*	0.5
H10B	0.0594	0.6955	0.3331	0.086*	0.5
C11	0.316 (3)	0.7546 (5)	0.3052 (16)	0.095 (4)*	0.5
H11A	0.1591	0.7664	0.248	0.143*	0.5
H11B	0.4758	0.751	0.2573	0.143*	0.5
H11C	0.3558	0.7802	0.3734	0.143*	0.5
O2A	0.268 (2)	0.6013 (4)	0.4705 (9)	0.071 (3)*	0.5
C8A	0.111 (3)	0.6434 (5)	0.5272 (13)	0.080 (4)*	0.5
H8AA	0.1828	0.6493	0.6169	0.095*	0.5
H8AB	−0.0843	0.6336	0.5246	0.095*	0.5
C9A	0.142 (3)	0.6924 (5)	0.4496 (14)	0.102 (4)*	0.5
H9A1	0.0102	0.6892	0.3728	0.122*	0.5
H9A2	0.0775	0.7217	0.4998	0.122*	0.5
C10A	0.402 (3)	0.7092 (5)	0.4057 (13)	0.092 (3)*	0.5
H10C	0.4668	0.6798	0.3559	0.11*	0.5
H10D	0.5335	0.7124	0.4827	0.11*	0.5
C11A	0.433 (4)	0.7571 (5)	0.3292 (13)	0.089 (4)*	0.5
H11D	0.6227	0.7691	0.3421	0.133*	0.5
H11E	0.3116	0.7843	0.3561	0.133*	0.5
H11F	0.3845	0.7493	0.239	0.133*	0.5
H2B	0.150 (14)	0.4691 (19)	0.627 (5)	0.10 (2)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0730 (7)	0.0881 (7)	0.0692 (6)	0.0104 (9)	0.0279 (5)	−0.0026 (8)
O1	0.085 (3)	0.067 (2)	0.073 (2)	0.003 (2)	0.035 (2)	0.0011 (18)
N1	0.098 (3)	0.070 (3)	0.085 (3)	0.007 (2)	0.036 (2)	0.001 (2)
N2	0.063 (3)	0.067 (3)	0.055 (2)	0.006 (2)	0.013 (2)	−0.003 (2)
N3	0.087 (3)	0.098 (3)	0.082 (3)	−0.002 (3)	0.034 (2)	0.021 (3)
C1	0.119 (5)	0.063 (3)	0.097 (4)	0.004 (3)	0.049 (4)	−0.001 (3)
C2	0.075 (4)	0.071 (4)	0.067 (3)	−0.004 (3)	0.028 (3)	0.002 (3)
C3	0.049 (3)	0.073 (3)	0.042 (2)	0.003 (2)	0.0044 (19)	−0.007 (2)
C4	0.063 (3)	0.080 (4)	0.053 (2)	0.009 (2)	0.014 (2)	−0.002 (2)
C5	0.055 (2)	0.065 (3)	0.052 (2)	−0.002 (2)	0.0109 (18)	0.0014 (17)
C6	0.058 (2)	0.073 (3)	0.056 (2)	0.002 (2)	0.014 (2)	0.002 (2)
C7	0.069 (3)	0.060 (4)	0.062 (3)	−0.007 (3)	0.018 (3)	0.004 (3)

Cl1—C4	1.791 (5)	C9—H9A	0.99
O1—C7	1.271 (7)	C9—H9B	0.99
N1—C4	1.338 (7)	C10—C11	1.478 (14)
N1—C1	1.421 (8)	C10—H10A	0.99
N2—C2	1.338 (9)	C10—H10B	0.99
N2—C3	1.419 (8)	C11—H11A	0.98
N2—H2B	0.87 (2)	C11—H11B	0.98
N3—C6	1.175 (8)	C11—H11C	0.98
C1—C2	1.392 (10)	O2A—C8A	1.489 (17)
C1—H1A	0.95	C8A—C9A	1.516 (14)
C2—H2A	0.95	C8A—H8AA	0.99
C3—C5	1.428 (7)	C8A—H8AB	0.99
C3—C4	1.475 (7)	C9A—C10A	1.469 (14)
C5—C7	1.472 (8)	C9A—H9A1	0.99
C5—C6	1.486 (7)	C9A—H9A2	0.99
C7—O2A	1.379 (11)	C10A—C11A	1.487 (14)
C7—O2	1.448 (10)	C10A—H10C	0.99
O2—C8	1.489 (13)	C10A—H10D	0.99
C8—C9	1.514 (12)	C11A—H11D	0.98
C8—H8A	0.99	C11A—H11E	0.98
C8—H8B	0.99	C11A—H11F	0.98
C9—C10	1.541 (12)
C4—N1—C1	118.8 (5)	C10—C9—H9A	107.8
C2—N2—C3	126.2 (5)	C8—C9—H9B	107.8
C2—N2—H2B	117 (5)	C10—C9—H9B	107.8
C3—N2—H2B	114 (5)	H9A—C9—H9B	107.2
C2—C1—N1	121.0 (6)	C11—C10—C9	118.2 (10)
C2—C1—H1A	119.5	C11—C10—H10A	107.8
N1—C1—H1A	119.5	C9—C10—H10A	107.8
N2—C2—C1	118.3 (5)	C11—C10—H10B	107.8
N2—C2—H2A	120.9	C9—C10—H10B	107.8
C1—C2—H2A	120.9	H10A—C10—H10B	107.1
N2—C3—C5	120.3 (5)	C7—O2A—C8A	115.7 (8)
N2—C3—C4	112.3 (5)	O2A—C8A—C9A	107.3 (11)
C5—C3—C4	127.5 (5)	O2A—C8A—H8AA	110.2
N1—C4—C3	123.5 (4)	C9A—C8A—H8AA	110.2
N1—C4—Cl1	115.1 (4)	O2A—C8A—H8AB	110.2
C3—C4—Cl1	121.4 (4)	C9A—C8A—H8AB	110.2
C3—C5—C7	118.7 (4)	H8AA—C8A—H8AB	108.5
C3—C5—C6	124.0 (4)	C10A—C9A—C8A	123.5 (13)
C7—C5—C6	117.3 (5)	C10A—C9A—H9A1	106.5
N3—C6—C5	175.5 (5)	C8A—C9A—H9A1	106.5
O1—C7—O2A	120.7 (6)	C10A—C9A—H9A2	106.5
O1—C7—O2	120.9 (5)	C8A—C9A—H9A2	106.5
O2A—C7—O2	19.8 (5)	H9A1—C9A—H9A2	106.5
O1—C7—C5	127.1 (5)	C9A—C10A—C11A	123.6 (13)
O2A—C7—C5	111.0 (6)	C9A—C10A—H10C	106.4
O2—C7—C5	111.5 (5)	C11A—C10A—H10C	106.4
C7—O2—C8	115.0 (7)	C9A—C10A—H10D	106.4
O2—C8—C9	105.3 (8)	C11A—C10A—H10D	106.4
O2—C8—H8A	110.7	H10C—C10A—H10D	106.5
C9—C8—H8A	110.7	C10A—C11A—H11D	109.5
O2—C8—H8B	110.7	C10A—C11A—H11E	109.5
C9—C8—H8B	110.7	H11D—C11A—H11E	109.5
H8A—C8—H8B	108.8	C10A—C11A—H11F	109.5
C8—C9—C10	117.8 (9)	H11D—C11A—H11F	109.5
C8—C9—H9A	107.8	H11E—C11A—H11F	109.5
C4—N1—C1—C2	−0.9 (10)	C6—C5—C7—O1	−179.2 (5)
C3—N2—C2—C1	−2.4 (9)	C3—C5—C7—O2A	−166.0 (6)
N1—C1—C2—N2	2.2 (11)	C6—C5—C7—O2A	13.6 (8)
C2—N2—C3—C5	−178.1 (5)	C3—C5—C7—O2	172.8 (5)
C2—N2—C3—C4	1.2 (7)	C6—C5—C7—O2	−7.6 (8)
C1—N1—C4—C3	−0.4 (8)	O1—C7—O2—C8	−10.3 (11)
C1—N1—C4—Cl1	−179.9 (5)	O2A—C7—O2—C8	85.0 (19)
N2—C3—C4—N1	0.3 (7)	C5—C7—O2—C8	177.5 (7)
C5—C3—C4—N1	179.5 (5)	C7—O2—C8—C9	−170.4 (8)
N2—C3—C4—Cl1	179.8 (3)	O2—C8—C9—C10	56.8 (12)
C5—C3—C4—Cl1	−1.0 (7)	C8—C9—C10—C11	173.4 (12)
N2—C3—C5—C7	−1.4 (6)	O1—C7—O2A—C8A	7.6 (13)
C4—C3—C5—C7	179.5 (5)	O2—C7—O2A—C8A	−89.0 (19)
N2—C3—C5—C6	179.1 (5)	C5—C7—O2A—C8A	175.8 (9)
C4—C3—C5—C6	−0.1 (8)	C7—O2A—C8A—C9A	−177.5 (10)
C3—C5—C6—N3	18E1(10)	O2A—C8A—C9A—C10A	−42.8 (19)
C7—C5—C6—N3	0(8)	C8A—C9A—C10A—C11A	179.8 (14)
C3—C5—C7—O1	1.2 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O1	0.87 (2)	1.96 (5)	2.632 (6)	133 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O1	0.87 (2)	1.96 (5)	2.632 (6)	133 (6)