Ethyl 2-[2-(2-meth-oxy-phen-yl)hydrazinyl-idene]-3-oxobutano-ate.

In the title compound, C(13)H(16)N(2)O(4), an intra-molecular N-H⋯O hydrogen bond generates an S(6) ring. The mol-ecule adopts an E configuration with respect to the central C=N double bond. In the crystal, symmetry-related mol-ecules are connected into chains along [010] via weak C-H⋯N hydrogen bonds. The crystal structure is further stabilized by weak C-H⋯π inter-actions.

Related literature

For details and applications of pyrazole derivatives, see: Rai et al. (2008 ▶); Girisha et al. (2010 ▶); Isloor et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C13H16N2O4

M = 264.28

Monoclinic,

a = 10.1885 (4) Å

b = 11.4967 (4) Å

c = 13.2492 (5) Å

β = 120.003 (3)°

V = 1343.97 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.75 × 0.27 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.931, T max = 0.981

14963 measured reflections

3909 independent reflections

3123 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.116

S = 1.03

3909 reflections

179 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034854/lh5322sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034854/lh5322Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034854/lh5322Isup3.cml

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

C13H16N2O4	F(000) = 560
Mr = 264.28	Dx = 1.306 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7354 reflections
a = 10.1885 (4) Å	θ = 2.5–30.8°
b = 11.4967 (4) Å	µ = 0.10 mm−1
c = 13.2492 (5) Å	T = 100 K
β = 120.003 (3)°	Needle, green
V = 1343.97 (9) Å3	0.75 × 0.27 × 0.20 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3909 independent reflections
Radiation source: fine-focus sealed tube	3123 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→13
Tmin = 0.931, Tmax = 0.981	k = −16→16
14963 measured reflections	l = −14→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0513P)2 + 0.4458P] where P = (Fo2 + 2Fc2)/3
3909 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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 esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.30643 (9)	0.58032 (7)	0.53563 (7)	0.02056 (18)
O2	0.61515 (9)	0.07478 (7)	0.68475 (7)	0.01987 (18)
O3	0.76423 (9)	0.37484 (7)	0.73708 (7)	0.02157 (19)
O4	0.51710 (10)	0.68753 (7)	0.63602 (7)	0.02266 (19)
N1	0.49890 (11)	0.28280 (8)	0.62667 (8)	0.01539 (19)
N2	0.44571 (10)	0.38868 (8)	0.60104 (8)	0.01477 (19)
C1	0.24246 (12)	0.20271 (10)	0.51384 (9)	0.0164 (2)
H1A	0.2010	0.2769	0.4937	0.020*
C2	0.14890 (13)	0.10570 (10)	0.47404 (10)	0.0188 (2)
H2A	0.0447	0.1147	0.4267	0.023*
C3	0.21166 (13)	−0.00471 (10)	0.50522 (10)	0.0193 (2)
H3A	0.1486	−0.0695	0.4788	0.023*
C4	0.36743 (13)	−0.02020 (10)	0.57532 (10)	0.0182 (2)
H4A	0.4082	−0.0946	0.5955	0.022*
C5	0.46119 (12)	0.07678 (9)	0.61481 (9)	0.0155 (2)
C6	0.39815 (12)	0.18864 (9)	0.58381 (9)	0.0149 (2)
C7	0.53715 (12)	0.47955 (9)	0.63721 (9)	0.0154 (2)
C8	0.45682 (13)	0.59306 (9)	0.60453 (9)	0.0160 (2)
C9	0.21993 (13)	0.68756 (10)	0.50635 (10)	0.0211 (2)
H9A	0.2528	0.7404	0.4663	0.025*
H9B	0.2336	0.7254	0.5764	0.025*
C10	0.05623 (14)	0.65495 (11)	0.42841 (12)	0.0297 (3)
H10A	−0.0054	0.7237	0.4075	0.045*
H10B	0.0255	0.6022	0.4689	0.045*
H10C	0.0442	0.6182	0.3592	0.045*
C11	0.70375 (12)	0.47143 (10)	0.70367 (9)	0.0172 (2)
C12	0.80061 (13)	0.57743 (11)	0.72907 (11)	0.0232 (2)
H12A	0.9049	0.5546	0.7633	0.035*
H12B	0.7885	0.6267	0.7823	0.035*
H12C	0.7706	0.6189	0.6579	0.035*
C13	0.68844 (14)	−0.03669 (10)	0.71190 (10)	0.0215 (2)
H13A	0.7964	−0.0261	0.7543	0.032*
H13B	0.6599	−0.0782	0.6410	0.032*
H13C	0.6581	−0.0803	0.7586	0.032*
H1N1	0.5992 (19)	0.2707 (14)	0.6701 (14)	0.037 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0175 (4)	0.0120 (4)	0.0265 (4)	0.0022 (3)	0.0067 (3)	−0.0010 (3)
O2	0.0152 (4)	0.0145 (4)	0.0242 (4)	0.0039 (3)	0.0056 (3)	0.0015 (3)
O3	0.0179 (4)	0.0180 (4)	0.0241 (4)	0.0013 (3)	0.0069 (3)	0.0013 (3)
O4	0.0229 (4)	0.0128 (4)	0.0280 (4)	−0.0026 (3)	0.0095 (4)	−0.0013 (3)
N1	0.0153 (4)	0.0113 (4)	0.0177 (4)	0.0009 (4)	0.0068 (4)	0.0009 (3)
N2	0.0182 (4)	0.0114 (4)	0.0149 (4)	0.0006 (3)	0.0084 (4)	0.0001 (3)
C1	0.0168 (5)	0.0132 (5)	0.0191 (5)	0.0030 (4)	0.0088 (4)	0.0021 (4)
C2	0.0160 (5)	0.0173 (5)	0.0224 (5)	−0.0001 (4)	0.0092 (4)	−0.0001 (4)
C3	0.0202 (5)	0.0144 (5)	0.0233 (5)	−0.0034 (4)	0.0108 (5)	−0.0019 (4)
C4	0.0224 (6)	0.0116 (5)	0.0208 (5)	0.0010 (4)	0.0111 (4)	0.0006 (4)
C5	0.0163 (5)	0.0139 (5)	0.0158 (5)	0.0021 (4)	0.0077 (4)	0.0006 (4)
C6	0.0173 (5)	0.0122 (5)	0.0163 (5)	−0.0005 (4)	0.0092 (4)	−0.0002 (4)
C7	0.0168 (5)	0.0133 (5)	0.0150 (5)	−0.0002 (4)	0.0071 (4)	0.0002 (4)
C8	0.0182 (5)	0.0140 (5)	0.0158 (5)	−0.0001 (4)	0.0085 (4)	0.0001 (4)
C9	0.0210 (6)	0.0122 (5)	0.0272 (6)	0.0038 (4)	0.0100 (5)	−0.0004 (4)
C10	0.0205 (6)	0.0212 (6)	0.0420 (7)	0.0040 (5)	0.0116 (6)	0.0000 (5)
C11	0.0170 (5)	0.0177 (5)	0.0152 (5)	−0.0010 (4)	0.0067 (4)	−0.0007 (4)
C12	0.0184 (5)	0.0204 (6)	0.0264 (6)	−0.0038 (5)	0.0078 (5)	0.0001 (5)
C13	0.0215 (6)	0.0192 (6)	0.0243 (6)	0.0081 (5)	0.0119 (5)	0.0052 (4)

O1—C8	1.3430 (14)	C4—H4A	0.9300
O1—C9	1.4510 (13)	C5—C6	1.4041 (15)
O2—C5	1.3660 (13)	C7—C11	1.4732 (16)
O2—C13	1.4355 (13)	C7—C8	1.4852 (15)
O3—C11	1.2393 (13)	C9—C10	1.5053 (17)
O4—C8	1.2143 (13)	C9—H9A	0.9700
N1—N2	1.3064 (12)	C9—H9B	0.9700
N1—C6	1.4019 (14)	C10—H10A	0.9600
N1—H1N1	0.898 (17)	C10—H10B	0.9600
N2—C7	1.3201 (14)	C10—H10C	0.9600
C1—C2	1.3885 (15)	C11—C12	1.4967 (16)
C1—C6	1.3896 (15)	C12—H12A	0.9600
C1—H1A	0.9300	C12—H12B	0.9600
C2—C3	1.3880 (16)	C12—H12C	0.9600
C2—H2A	0.9300	C13—H13A	0.9600
C3—C4	1.3925 (16)	C13—H13B	0.9600
C3—H3A	0.9300	C13—H13C	0.9600
C4—C5	1.3891 (15)
C8—O1—C9	115.03 (9)	O1—C8—C7	112.17 (9)
C5—O2—C13	117.52 (9)	O1—C9—C10	106.76 (9)
N2—N1—C6	119.32 (9)	O1—C9—H9A	110.4
N2—N1—H1N1	120.1 (11)	C10—C9—H9A	110.4
C6—N1—H1N1	120.6 (11)	O1—C9—H9B	110.4
N1—N2—C7	121.15 (9)	C10—C9—H9B	110.4
C2—C1—C6	119.85 (10)	H9A—C9—H9B	108.6
C2—C1—H1A	120.1	C9—C10—H10A	109.5
C6—C1—H1A	120.1	C9—C10—H10B	109.5
C3—C2—C1	119.66 (10)	H10A—C10—H10B	109.5
C3—C2—H2A	120.2	C9—C10—H10C	109.5
C1—C2—H2A	120.2	H10A—C10—H10C	109.5
C2—C3—C4	121.15 (10)	H10B—C10—H10C	109.5
C2—C3—H3A	119.4	O3—C11—C7	119.26 (10)
C4—C3—H3A	119.4	O3—C11—C12	119.68 (10)
C5—C4—C3	119.23 (10)	C7—C11—C12	121.05 (10)
C5—C4—H4A	120.4	C11—C12—H12A	109.5
C3—C4—H4A	120.4	C11—C12—H12B	109.5
O2—C5—C4	125.60 (10)	H12A—C12—H12B	109.5
O2—C5—C6	114.58 (9)	C11—C12—H12C	109.5
C4—C5—C6	119.81 (10)	H12A—C12—H12C	109.5
C1—C6—N1	122.73 (10)	H12B—C12—H12C	109.5
C1—C6—C5	120.29 (10)	O2—C13—H13A	109.5
N1—C6—C5	116.98 (9)	O2—C13—H13B	109.5
N2—C7—C11	124.05 (10)	H13A—C13—H13B	109.5
N2—C7—C8	113.80 (9)	O2—C13—H13C	109.5
C11—C7—C8	122.15 (10)	H13A—C13—H13C	109.5
O4—C8—O1	122.70 (10)	H13B—C13—H13C	109.5
O4—C8—C7	125.13 (10)
C6—N1—N2—C7	−178.24 (9)	C4—C5—C6—N1	179.90 (10)
C6—C1—C2—C3	0.46 (16)	N1—N2—C7—C11	2.76 (16)
C1—C2—C3—C4	−0.43 (17)	N1—N2—C7—C8	−177.39 (9)
C2—C3—C4—C5	0.18 (17)	C9—O1—C8—O4	−3.10 (15)
C13—O2—C5—C4	5.71 (15)	C9—O1—C8—C7	176.32 (9)
C13—O2—C5—C6	−174.96 (9)	N2—C7—C8—O4	174.02 (10)
C3—C4—C5—O2	179.33 (10)	C11—C7—C8—O4	−6.12 (17)
C3—C4—C5—C6	0.03 (16)	N2—C7—C8—O1	−5.37 (13)
C2—C1—C6—N1	179.86 (10)	C11—C7—C8—O1	174.48 (9)
C2—C1—C6—C5	−0.26 (15)	C8—O1—C9—C10	179.35 (10)
N2—N1—C6—C1	0.42 (15)	N2—C7—C11—O3	−6.31 (16)
N2—N1—C6—C5	−179.46 (9)	C8—C7—C11—O3	173.85 (10)
O2—C5—C6—C1	−179.36 (9)	N2—C7—C11—C12	172.36 (10)
C4—C5—C6—C1	0.01 (15)	C8—C7—C11—C12	−7.48 (15)
O2—C5—C6—N1	0.53 (13)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	0.90 (2)	1.886 (19)	2.5715 (15)	131.6 (14)
C13—H13C···N2i	0.96	2.58	3.4835 (18)	156
C12—H12B···Cg1ii	0.96	2.92	3.6620 (15)	135
C13—H13B···Cg1iii	0.96	2.66	3.4887 (14)	145

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	0.90 (2)	1.886 (19)	2.5715 (15)	131.6 (14)
C13—H13C⋯N2i	0.96	2.58	3.4835 (18)	156
C12—H12B⋯Cg1ii	0.96	2.92	3.6620 (15)	135
C13—H13B⋯Cg1iii	0.96	2.66	3.4887 (14)	145

Symmetry codes: (i) ; (ii) ; (iii) .