Diethyl 2-{[(4-meth-oxy-3-pyrid-yl)amino]-methyl-idene}malonate.

In the title mol-ecule, C(14)H(8)N(2)O(5), the amino group is involved in the formation an intra-molecular N-H⋯O hydrogen bond. In the crystal, weak inter-molecular C-H⋯O and C-H⋯N hydrogen bonds link the mol-ecules into ribbons along the b axis.

Related literature

For details of the synthesis, see: Brown & Dewar (1978 ▶). For related structures, see: Thenmozhi et al. (2009 ▶); Feng et al. (2010 ▶). For potential applications of metal complexes with β-diketone derivatives, see: Nishihama et al. (2001 ▶); Soldatov et al. (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C14H18N2O5

M = 294.30

Monoclinic,

a = 19.012 (4) Å

b = 8.6620 (17) Å

c = 9.1600 (18) Å

β = 94.08 (3)°

V = 1504.7 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 295 K

0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.971, T max = 0.990

2843 measured reflections

2758 independent reflections

1452 reflections with I > 2σ(I)

R int = 0.034

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.142

S = 1.01

2758 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.14 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811026353/cv5129sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811026353/cv5129Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811026353/cv5129Isup3.cml

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

C14H18N2O5	F(000) = 624
Mr = 294.30	Dx = 1.299 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 19.012 (4) Å	θ = 10–13°
b = 8.6620 (17) Å	µ = 0.10 mm−1
c = 9.1600 (18) Å	T = 295 K
β = 94.08 (3)°	Block, colourless
V = 1504.7 (5) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1452 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
graphite	θmax = 25.4°, θmin = 1.1°
ω/2θ scans	h = −22→0
Absorption correction: ψ scan (North et al., 1968)	k = 0→10
Tmin = 0.971, Tmax = 0.990	l = −10→11
2843 measured reflections	3 standard reflections every 200 reflections
2758 independent reflections	intensity decay: 1%

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.056P)2] where P = (Fo2 + 2Fc2)/3
2758 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.16 e Å−3
0 restraints	Δρmin = −0.14 e Å−3

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
O1	0.15081 (10)	0.3780 (2)	0.5511 (2)	0.0649 (6)
C1	0.11221 (14)	0.4906 (3)	0.4828 (3)	0.0502 (7)
N1	0.03465 (13)	0.7408 (3)	0.3671 (3)	0.0668 (7)
N2	0.17585 (11)	0.6573 (2)	0.6532 (2)	0.0527 (6)
H2A	0.1916	0.5742	0.6954	0.063*
O2	0.25551 (12)	1.0765 (2)	0.7731 (2)	0.0826 (8)
C2	0.06290 (15)	0.4714 (3)	0.3677 (3)	0.0591 (8)
H2B	0.0543	0.3744	0.3268	0.071*
O3	0.31389 (12)	0.9837 (2)	0.9718 (2)	0.0868 (8)
C3	0.02656 (15)	0.5984 (4)	0.3142 (3)	0.0645 (9)
H3A	−0.0062	0.5840	0.2350	0.077*
O4	0.26443 (12)	0.5409 (2)	0.8621 (2)	0.0804 (7)
C4	0.08378 (14)	0.7576 (3)	0.4773 (3)	0.0590 (8)
H4A	0.0916	0.8563	0.5150	0.071*
O5	0.34811 (10)	0.6944 (2)	0.9616 (2)	0.0662 (6)
C5	0.12345 (14)	0.6392 (3)	0.5386 (3)	0.0463 (7)
C6	0.14403 (17)	0.2247 (3)	0.4922 (4)	0.0776 (10)
H6A	0.1740	0.1558	0.5503	0.116*
H6B	0.1576	0.2245	0.3933	0.116*
H6C	0.0959	0.1913	0.4937	0.116*
C7	0.20362 (14)	0.7889 (3)	0.7033 (3)	0.0528 (7)
H7A	0.1854	0.8789	0.6601	0.063*
C8	0.25623 (14)	0.8065 (3)	0.8119 (3)	0.0484 (7)
C9	0.27475 (15)	0.9670 (3)	0.8476 (3)	0.0591 (8)
C10	0.3349 (2)	1.1375 (4)	1.0158 (5)	0.1076 (14)
H10A	0.3393	1.2015	0.9301	0.129*
H10B	0.2996	1.1831	1.0739	0.129*
C11	0.4004 (2)	1.1295 (4)	1.0990 (5)	0.1279 (16)
H11A	0.4144	1.2313	1.1305	0.192*
H11B	0.4353	1.0869	1.0399	0.192*
H11C	0.3958	1.0649	1.1829	0.192*
C12	0.28810 (15)	0.6696 (3)	0.8807 (3)	0.0526 (7)
C13	0.38151 (16)	0.5613 (3)	1.0303 (3)	0.0721 (9)
H13A	0.4013	0.4961	0.9576	0.087*
H13B	0.3475	0.5014	1.0804	0.087*
C14	0.43854 (18)	0.6193 (4)	1.1373 (4)	0.0959 (12)
H14A	0.4621	0.5333	1.1855	0.144*
H14B	0.4183	0.6836	1.2086	0.144*
H14C	0.4719	0.6781	1.0864	0.144*

	U11	U22	U33	U12	U13	U23
O1	0.0708 (14)	0.0499 (12)	0.0701 (13)	0.0029 (10)	−0.0218 (11)	−0.0015 (10)
C1	0.0463 (16)	0.0575 (17)	0.0455 (15)	0.0011 (14)	−0.0067 (13)	0.0004 (13)
N1	0.0626 (17)	0.0728 (17)	0.0629 (16)	0.0032 (14)	−0.0106 (13)	0.0104 (14)
N2	0.0607 (15)	0.0465 (14)	0.0490 (13)	0.0003 (12)	−0.0088 (11)	−0.0020 (11)
O2	0.1070 (19)	0.0537 (13)	0.0823 (16)	0.0006 (12)	−0.0257 (14)	0.0033 (11)
C2	0.0626 (19)	0.0608 (19)	0.0523 (17)	−0.0071 (16)	−0.0065 (15)	−0.0006 (15)
O3	0.1061 (18)	0.0546 (13)	0.0922 (17)	−0.0018 (12)	−0.0465 (14)	−0.0092 (11)
C3	0.060 (2)	0.080 (2)	0.0512 (18)	−0.0070 (17)	−0.0126 (15)	0.0049 (16)
O4	0.0954 (17)	0.0519 (13)	0.0881 (16)	−0.0083 (12)	−0.0342 (13)	0.0069 (11)
C4	0.0562 (19)	0.0590 (18)	0.0601 (18)	−0.0002 (15)	−0.0084 (15)	0.0010 (15)
O5	0.0625 (13)	0.0543 (12)	0.0786 (14)	−0.0005 (10)	−0.0184 (11)	0.0023 (10)
C5	0.0471 (16)	0.0533 (17)	0.0379 (14)	−0.0012 (14)	−0.0017 (12)	0.0030 (12)
C6	0.086 (2)	0.0476 (19)	0.096 (3)	0.0027 (17)	−0.0172 (19)	−0.0094 (17)
C7	0.0563 (18)	0.0485 (17)	0.0533 (17)	0.0021 (15)	0.0018 (14)	−0.0020 (14)
C8	0.0485 (16)	0.0480 (16)	0.0482 (15)	−0.0025 (14)	0.0003 (13)	−0.0016 (13)
C9	0.0544 (19)	0.059 (2)	0.0629 (19)	−0.0010 (16)	−0.0062 (15)	−0.0029 (16)
C10	0.115 (3)	0.055 (2)	0.142 (3)	−0.004 (2)	−0.063 (3)	−0.021 (2)
C11	0.120 (3)	0.090 (3)	0.164 (4)	−0.022 (3)	−0.063 (3)	−0.002 (3)
C12	0.0569 (19)	0.0520 (18)	0.0481 (16)	−0.0066 (15)	−0.0020 (15)	−0.0035 (14)
C13	0.071 (2)	0.069 (2)	0.073 (2)	0.0150 (18)	−0.0134 (18)	0.0041 (17)
C14	0.078 (2)	0.110 (3)	0.095 (3)	0.014 (2)	−0.028 (2)	0.000 (2)

O1—C1	1.348 (3)	C6—H6A	0.9600
O1—C6	1.436 (3)	C6—H6B	0.9600
C1—C2	1.370 (3)	C6—H6C	0.9600
C1—C5	1.396 (3)	C7—C8	1.368 (3)
N1—C3	1.330 (4)	C7—H7A	0.9300
N1—C4	1.333 (3)	C8—C12	1.455 (4)
N2—C7	1.325 (3)	C8—C9	1.465 (4)
N2—C5	1.404 (3)	C10—C11	1.414 (4)
N2—H2A	0.8600	C10—H10A	0.9700
O2—C9	1.210 (3)	C10—H10B	0.9700
C2—C3	1.371 (4)	C11—H11A	0.9600
C2—H2B	0.9300	C11—H11B	0.9600
O3—C9	1.323 (3)	C11—H11C	0.9600
O3—C10	1.440 (3)	C13—C14	1.495 (4)
C3—H3A	0.9300	C13—H13A	0.9700
O4—C12	1.209 (3)	C13—H13B	0.9700
C4—C5	1.370 (3)	C14—H14A	0.9600
C4—H4A	0.9300	C14—H14B	0.9600
O5—C12	1.333 (3)	C14—H14C	0.9600
O5—C13	1.440 (3)
C1—O1—C6	117.6 (2)	C7—C8—C9	114.8 (2)
O1—C1—C2	126.1 (3)	C12—C8—C9	126.2 (2)
O1—C1—C5	115.6 (2)	O2—C9—O3	121.9 (3)
C2—C1—C5	118.2 (3)	O2—C9—C8	124.0 (3)
C3—N1—C4	115.7 (3)	O3—C9—C8	114.1 (3)
C7—N2—C5	126.8 (2)	C11—C10—O3	108.8 (3)
C7—N2—H2A	116.6	C11—C10—H10A	109.9
C5—N2—H2A	116.6	O3—C10—H10A	109.9
C1—C2—C3	118.5 (3)	C11—C10—H10B	109.9
C1—C2—H2B	120.7	O3—C10—H10B	109.9
C3—C2—H2B	120.7	H10A—C10—H10B	108.3
C9—O3—C10	118.0 (2)	C10—C11—H11A	109.5
N1—C3—C2	124.9 (3)	C10—C11—H11B	109.5
N1—C3—H3A	117.6	H11A—C11—H11B	109.5
C2—C3—H3A	117.6	C10—C11—H11C	109.5
N1—C4—C5	124.4 (3)	H11A—C11—H11C	109.5
N1—C4—H4A	117.8	H11B—C11—H11C	109.5
C5—C4—H4A	117.8	O4—C12—O5	121.5 (3)
C12—O5—C13	116.6 (2)	O4—C12—C8	123.4 (3)
C4—C5—C1	118.3 (2)	O5—C12—C8	115.0 (2)
C4—C5—N2	124.3 (2)	O5—C13—C14	107.1 (3)
C1—C5—N2	117.3 (2)	O5—C13—H13A	110.3
O1—C6—H6A	109.5	C14—C13—H13A	110.3
O1—C6—H6B	109.5	O5—C13—H13B	110.3
H6A—C6—H6B	109.5	C14—C13—H13B	110.3
O1—C6—H6C	109.5	H13A—C13—H13B	108.5
H6A—C6—H6C	109.5	C13—C14—H14A	109.5
H6B—C6—H6C	109.5	C13—C14—H14B	109.5
N2—C7—C8	126.9 (3)	H14A—C14—H14B	109.5
N2—C7—H7A	116.5	C13—C14—H14C	109.5
C8—C7—H7A	116.5	H14A—C14—H14C	109.5
C7—C8—C12	119.0 (2)	H14B—C14—H14C	109.5
C6—O1—C1—C2	5.0 (4)	N2—C7—C8—C12	1.7 (4)
C6—O1—C1—C5	−176.5 (2)	N2—C7—C8—C9	−178.1 (3)
O1—C1—C2—C3	177.8 (3)	C10—O3—C9—O2	−1.4 (5)
C5—C1—C2—C3	−0.7 (4)	C10—O3—C9—C8	179.8 (3)
C4—N1—C3—C2	2.2 (4)	C7—C8—C9—O2	−12.7 (4)
C1—C2—C3—N1	−1.1 (5)	C12—C8—C9—O2	167.5 (3)
C3—N1—C4—C5	−1.7 (4)	C7—C8—C9—O3	166.0 (3)
N1—C4—C5—C1	0.1 (4)	C12—C8—C9—O3	−13.8 (4)
N1—C4—C5—N2	179.1 (3)	C9—O3—C10—C11	−150.4 (4)
O1—C1—C5—C4	−177.5 (2)	C13—O5—C12—O4	−2.5 (4)
C2—C1—C5—C4	1.1 (4)	C13—O5—C12—C8	−179.5 (2)
O1—C1—C5—N2	3.4 (4)	C7—C8—C12—O4	−10.7 (4)
C2—C1—C5—N2	−177.9 (2)	C9—C8—C12—O4	169.1 (3)
C7—N2—C5—C4	−12.2 (4)	C7—C8—C12—O5	166.2 (2)
C7—N2—C5—C1	166.8 (3)	C9—C8—C12—O5	−14.0 (4)
C5—N2—C7—C8	−177.8 (3)	C12—O5—C13—C14	−168.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4	0.86	2.01	2.656 (3)	131
C6—H6A···O2i	0.96	2.57	3.462 (4)	155
C2—H2B···N1ii	0.93	2.63	3.389 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4	0.86	2.01	2.656 (3)	131
C6—H6A⋯O2i	0.96	2.57	3.462 (4)	155
C2—H2B⋯N1ii	0.93	2.63	3.389 (3)	139

Symmetry codes: (i) ; (ii) .