2-Eth­oxy­ethyl (Z)-2-cyano-3-[(N-phenyl­carbamo­yl)amino]­prop-2-enoate

Zhong, S.; Wei, D.; Liu, J.; Liu, B.

doi:10.1107/S1600536811055000

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o267

doi:10.1107/S1600536811055000

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2-Ethoxyethyl (Z)-2-cyano-3-[(N-phenylcarbamoyl)amino]prop-2-enoate

Shihua Zhong,^a Dongmei Wei,^a Jianbing Liu ^a ^* and Bingyu Liu ^a

^aCollege of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, Hunan, People's Republic of China
^*Correspondence e-mail: hunansdljb@163.com

(Received 1 December 2011; accepted 21 December 2011; online 7 January 2012)

The crystal structure of the title compound, C₁₅H₁₇N₃O₄, is stabilized by intermolecular N—H⋯N hydrogen bonds. An intramolecular N—H⋯O hydrogen bond also occurs.

Related literature

The title compound was synthesized as a possible novel herbicide. For details of the synthesis, see: Wang et al. (2004 ); Senda et al. (1972 ). For reviews of cyanoacrylate derivatives as bioactive agents, see: Zhang et al. (2008 ); Liu et al. (1998 ).

Experimental

Crystal data

C₁₅H₁₇N₃O₄
M_r = 303.32
Monoclinic, C 2/c
a = 25.102 (7) Å
b = 12.013 (3) Å
c = 10.436 (3) Å
β = 96.248 (4)°
V = 3128.4 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 K
0.48 × 0.44 × 0.09 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.956, T_max = 0.992
16240 measured reflections
4149 independent reflections
2994 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.116
S = 1.00
4149 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3	0.910 (15)	2.068 (15)	2.7543 (14)	131.2 (12)
N1—H1N⋯N3ⁱ	0.867 (15)	2.050 (15)	2.9120 (15)	172.6 (14)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055000/hg5148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055000/hg5148Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811055000/hg5148Isup3.cml

checkCIF report

Comment top

Previous studies have shown that cyanoacrylate derivatives are an important class of compounds with high bioactivities and can be applied as herbicide (Zhang et al., 2008), urea derivatives also exhibit good herbicidal activities (Liu et al., 1998), both kinds of compounds are inhibitors of photosystem II electron transport and inhibit the growth of weeds by disrupting photosynthetic electron transport. A novel cyanoacrylate compound (C₁₅H₁₇N₃O₄) which bears a phenyl urea unit was synthesized and investigated for its ability to inhibit PSII electron transport, its crystal structure is reported here.

The crystal structure of title compound is stabilized by inter-molecular N—H···N hydrogen bonds, the orientation of phenylurea and ester carbonyl is cis and an intramolecular N—H···O hydrogen bond was generated to stabilize the conformation.

Related literature top

The title compound was synthesized as a possible novel herbicide. For details of the synthesis, see: Wang et al. (2004); Senda et al. (1972). For reviews of cyanoacrylate derivatives as bioactive agents, see: Zhang et al. (2008); Liu et al. (1998).

Experimental top

The title compound was prepared according to the reported method (Wang et al., 2004; Senda et al., 1972). A mixture of 2-ethoxyethyl cyanoacetate (0.55 g, 3.5 mmol), Phenylurea (0.39 g 2.9 mmol) and triethyl orthoformate (0.59 ml, 3.5 mmol) was heated at 378 K for 2 hr, cooled to room temperature, the precipitation was filtered off, washed with hexane and recrystallized from ethanol to give white solid (yield 37%), mp: 458 K. Crystals of (I) suitable for XRD were obtained by slow evaporation of a mixture solution of ethanol and acetone in a ratio of 1:2 at 293 K.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of compound shows displacement ellipsoids drawn at the 50% probability level, all H atoms have been omitted for clarity.
	Fig. 2. The crystal packing of the title compound with hydrogen bonds drawn as dashed lines.

2-Ethoxyethyl (Z)-2-cyano-3-[(N-phenylcarbamoyl)amino]prop-2-enoate top

Crystal data top

C₁₅H₁₇N₃O₄	F(000) = 1280
M_r = 303.32	D_x = 1.288 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4353 reflections
a = 25.102 (7) Å	θ = 2.7–29.1°
b = 12.013 (3) Å	µ = 0.10 mm⁻¹
c = 10.436 (3) Å	T = 153 K
β = 96.248 (4)°	Platelet, colorless
V = 3128.4 (16) Å³	0.48 × 0.44 × 0.09 mm
Z = 8

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	4149 independent reflections
Radiation source: Rotating Anode	2994 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 28.5714 pixels mm^-1	θ_max = 29.1°, θ_min = 2.7°
phi and ω scans	h = −34→32
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
T_min = 0.956, T_max = 0.992	l = −13→14
16240 measured reflections

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0616P)² + 0.136P] where P = (F_o² + 2F_c²)/3
4149 reflections	(Δ/σ)_max < 0.001
208 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₅H₁₇N₃O₄	V = 3128.4 (16) Å³
M_r = 303.32	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.102 (7) Å	µ = 0.10 mm⁻¹
b = 12.013 (3) Å	T = 153 K
c = 10.436 (3) Å	0.48 × 0.44 × 0.09 mm
β = 96.248 (4)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	4149 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2994 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.992	R_int = 0.038
16240 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.28 e Å⁻³
4149 reflections	Δρ_min = −0.18 e Å⁻³
208 parameters

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
O1	0.15659 (4)	0.22114 (7)	0.47309 (9)	0.0364 (2)
O2	0.32432 (3)	0.36646 (7)	0.09862 (8)	0.0255 (2)
O3	0.27763 (4)	0.46231 (7)	0.23556 (8)	0.0306 (2)
O4	0.42663 (4)	0.39232 (8)	−0.00208 (9)	0.0364 (2)
N1	0.16467 (4)	0.40528 (8)	0.53128 (10)	0.0250 (2)
N2	0.21226 (4)	0.33631 (8)	0.37397 (9)	0.0240 (2)
N3	0.28465 (4)	0.09868 (8)	0.07213 (10)	0.0289 (3)
C1	0.11615 (5)	0.52205 (11)	0.66349 (12)	0.0307 (3)
H1	0.1298	0.5844	0.6216	0.037*
C2	0.08347 (6)	0.53787 (13)	0.76109 (13)	0.0375 (3)
H2	0.0747	0.6112	0.7858	0.045*
C3	0.06367 (6)	0.44733 (14)	0.82240 (13)	0.0396 (3)
H3	0.0416	0.4583	0.8896	0.047*
C4	0.07616 (5)	0.34066 (13)	0.78556 (13)	0.0362 (3)
H4	0.0625	0.2785	0.8278	0.043*
C5	0.10845 (5)	0.32346 (11)	0.68761 (12)	0.0282 (3)
H5	0.1165	0.2500	0.6622	0.034*
C6	0.12894 (5)	0.41423 (10)	0.62707 (11)	0.0232 (3)
C7	0.17519 (5)	0.31405 (9)	0.46344 (12)	0.0242 (3)
C8	0.22843 (5)	0.25503 (9)	0.29863 (11)	0.0227 (3)
H8	0.2142	0.1827	0.3086	0.027*
C9	0.26364 (5)	0.26801 (9)	0.20886 (11)	0.0221 (2)
C10	0.28862 (5)	0.37541 (10)	0.18432 (11)	0.0229 (3)
C11	0.34591 (5)	0.47118 (10)	0.05780 (13)	0.0291 (3)
H11A	0.3684	0.5062	0.1306	0.035*
H11B	0.3164	0.5229	0.0284	0.035*
C12	0.37881 (5)	0.44736 (11)	−0.05006 (12)	0.0306 (3)
H12A	0.3581	0.4000	−0.1153	0.037*
H12B	0.3876	0.5179	−0.0921	0.037*
C13	0.45942 (7)	0.36769 (16)	−0.10075 (16)	0.0567 (5)
H13A	0.4701	0.4375	−0.1414	0.068*
H13B	0.4393	0.3214	−0.1680	0.068*
C14	0.50822 (8)	0.30642 (17)	−0.0432 (2)	0.0745 (6)
H14A	0.5255	0.3486	0.0303	0.112*
H14B	0.5333	0.2978	−0.1082	0.112*
H14C	0.4978	0.2328	−0.0140	0.112*
C15	0.27583 (5)	0.17378 (9)	0.13389 (11)	0.0225 (2)
H2N	0.2248 (6)	0.4059 (13)	0.3597 (14)	0.038 (4)*
H1N	0.1787 (6)	0.4663 (13)	0.5061 (13)	0.035 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0471 (6)	0.0169 (4)	0.0493 (6)	−0.0065 (4)	0.0241 (5)	−0.0041 (4)
O2	0.0295 (5)	0.0150 (4)	0.0342 (5)	0.0004 (3)	0.0134 (4)	0.0003 (3)
O3	0.0400 (5)	0.0168 (4)	0.0375 (5)	−0.0024 (4)	0.0153 (4)	−0.0060 (4)
O4	0.0314 (5)	0.0425 (6)	0.0375 (5)	0.0078 (4)	0.0141 (4)	0.0064 (4)
N1	0.0334 (6)	0.0155 (5)	0.0278 (5)	−0.0017 (4)	0.0116 (5)	0.0003 (4)
N2	0.0296 (6)	0.0155 (5)	0.0285 (5)	−0.0011 (4)	0.0100 (4)	−0.0003 (4)
N3	0.0372 (6)	0.0178 (5)	0.0324 (6)	0.0009 (4)	0.0075 (5)	−0.0013 (4)
C1	0.0371 (7)	0.0251 (6)	0.0304 (7)	0.0022 (5)	0.0059 (6)	−0.0027 (5)
C2	0.0379 (8)	0.0414 (8)	0.0337 (7)	0.0084 (6)	0.0059 (6)	−0.0101 (6)
C3	0.0309 (7)	0.0592 (10)	0.0302 (7)	0.0019 (7)	0.0106 (6)	−0.0055 (7)
C4	0.0303 (7)	0.0464 (9)	0.0330 (7)	−0.0043 (6)	0.0084 (6)	0.0058 (6)
C5	0.0283 (7)	0.0285 (6)	0.0283 (6)	−0.0019 (5)	0.0057 (5)	0.0028 (5)
C6	0.0235 (6)	0.0252 (6)	0.0212 (6)	0.0009 (4)	0.0031 (5)	−0.0007 (5)
C7	0.0271 (6)	0.0182 (6)	0.0282 (6)	0.0003 (4)	0.0070 (5)	0.0011 (5)
C8	0.0265 (6)	0.0161 (5)	0.0256 (6)	0.0003 (4)	0.0030 (5)	−0.0002 (4)
C9	0.0259 (6)	0.0146 (5)	0.0261 (6)	0.0014 (4)	0.0045 (5)	−0.0008 (4)
C10	0.0254 (6)	0.0181 (6)	0.0258 (6)	0.0011 (4)	0.0049 (5)	−0.0009 (4)
C11	0.0336 (7)	0.0165 (6)	0.0391 (7)	−0.0024 (5)	0.0123 (6)	0.0018 (5)
C12	0.0333 (7)	0.0263 (6)	0.0337 (7)	0.0011 (5)	0.0101 (6)	0.0050 (5)
C13	0.0563 (10)	0.0660 (12)	0.0536 (10)	0.0232 (9)	0.0333 (8)	0.0157 (8)
C14	0.0570 (12)	0.0897 (16)	0.0838 (14)	0.0342 (11)	0.0399 (11)	0.0275 (12)
C15	0.0255 (6)	0.0172 (5)	0.0251 (6)	0.0001 (4)	0.0046 (5)	0.0030 (4)

Geometric parameters (Å, º) top

O1—C7	1.2183 (14)	C4—C5	1.3875 (18)
O2—C10	1.3376 (14)	C4—H4	0.9500
O2—C11	1.4520 (14)	C5—C6	1.3869 (17)
O3—C10	1.2181 (14)	C5—H5	0.9500
O4—C12	1.4135 (15)	C8—C9	1.3650 (16)
O4—C13	1.4177 (17)	C8—H8	0.9500
N1—C7	1.3465 (15)	C9—C15	1.4281 (16)
N1—C6	1.4179 (15)	C9—C10	1.4691 (16)
N1—H1N	0.867 (15)	C11—C12	1.4943 (18)
N2—C8	1.3439 (15)	C11—H11A	0.9900
N2—C7	1.4136 (15)	C11—H11B	0.9900
N2—H2N	0.910 (15)	C12—H12A	0.9900
N3—C15	1.1443 (15)	C12—H12B	0.9900
C1—C2	1.3887 (18)	C13—C14	1.498 (2)
C1—C6	1.3970 (17)	C13—H13A	0.9900
C1—H1	0.9500	C13—H13B	0.9900
C2—C3	1.382 (2)	C14—H14A	0.9800
C2—H2	0.9500	C14—H14B	0.9800
C3—C4	1.384 (2)	C14—H14C	0.9800
C3—H3	0.9500

C10—O2—C11	115.17 (9)	C8—C9—C15	118.61 (11)
C12—O4—C13	112.22 (11)	C8—C9—C10	122.71 (10)
C7—N1—C6	127.43 (10)	C15—C9—C10	118.66 (10)
C7—N1—H1N	114.8 (10)	O3—C10—O2	124.24 (11)
C6—N1—H1N	117.3 (10)	O3—C10—C9	123.70 (11)
C8—N2—C7	120.76 (10)	O2—C10—C9	112.06 (10)
C8—N2—H2N	116.1 (9)	O2—C11—C12	108.04 (10)
C7—N2—H2N	123.0 (9)	O2—C11—H11A	110.1
C2—C1—C6	119.87 (13)	C12—C11—H11A	110.1
C2—C1—H1	120.1	O2—C11—H11B	110.1
C6—C1—H1	120.1	C12—C11—H11B	110.1
C3—C2—C1	120.20 (13)	H11A—C11—H11B	108.4
C3—C2—H2	119.9	O4—C12—C11	109.89 (10)
C1—C2—H2	119.9	O4—C12—H12A	109.7
C2—C3—C4	119.78 (13)	C11—C12—H12A	109.7
C2—C3—H3	120.1	O4—C12—H12B	109.7
C4—C3—H3	120.1	C11—C12—H12B	109.7
C3—C4—C5	120.72 (13)	H12A—C12—H12B	108.2
C3—C4—H4	119.6	O4—C13—C14	108.98 (14)
C5—C4—H4	119.6	O4—C13—H13A	109.9
C6—C5—C4	119.60 (13)	C14—C13—H13A	109.9
C6—C5—H5	120.2	O4—C13—H13B	109.9
C4—C5—H5	120.2	C14—C13—H13B	109.9
C5—C6—C1	119.82 (12)	H13A—C13—H13B	108.3
C5—C6—N1	123.78 (11)	C13—C14—H14A	109.5
C1—C6—N1	116.35 (11)	C13—C14—H14B	109.5
O1—C7—N1	127.11 (12)	H14A—C14—H14B	109.5
O1—C7—N2	120.92 (11)	C13—C14—H14C	109.5
N1—C7—N2	111.98 (10)	H14A—C14—H14C	109.5
N2—C8—C9	125.30 (11)	H14B—C14—H14C	109.5
N2—C8—H8	117.3	N3—C15—C9	178.57 (13)
C9—C8—H8	117.3

C6—C1—C2—C3	0.1 (2)	C7—N2—C8—C9	179.49 (11)
C1—C2—C3—C4	−0.5 (2)	N2—C8—C9—C15	−178.46 (11)
C2—C3—C4—C5	0.1 (2)	N2—C8—C9—C10	0.22 (19)
C3—C4—C5—C6	0.8 (2)	C11—O2—C10—O3	−6.56 (17)
C4—C5—C6—C1	−1.16 (18)	C11—O2—C10—C9	172.90 (10)
C4—C5—C6—N1	176.29 (11)	C8—C9—C10—O3	−4.72 (19)
C2—C1—C6—C5	0.71 (19)	C15—C9—C10—O3	173.95 (11)
C2—C1—C6—N1	−176.93 (11)	C8—C9—C10—O2	175.81 (10)
C7—N1—C6—C5	15.9 (2)	C15—C9—C10—O2	−5.52 (16)
C7—N1—C6—C1	−166.53 (12)	C10—O2—C11—C12	−172.26 (10)
C6—N1—C7—O1	−1.3 (2)	C13—O4—C12—C11	180.00 (13)
C6—N1—C7—N2	178.81 (11)	O2—C11—C12—O4	−71.42 (13)
C8—N2—C7—O1	−0.93 (18)	C12—O4—C13—C14	−178.18 (14)
C8—N2—C7—N1	178.97 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.910 (15)	2.068 (15)	2.7543 (14)	131.2 (12)
N1—H1N···N3ⁱ	0.867 (15)	2.050 (15)	2.9120 (15)	172.6 (14)

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇N₃O₄
M_r	303.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	153
a, b, c (Å)	25.102 (7), 12.013 (3), 10.436 (3)
β (°)	96.248 (4)
V (Å³)	3128.4 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.48 × 0.44 × 0.09

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.956, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	16240, 4149, 2994
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.116, 1.00
No. of reflections	4149
No. of parameters	208
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.18

Computer programs: CrystalClear (Rigaku, 2008), 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
N2—H2N···O3	0.910 (15)	2.068 (15)	2.7543 (14)	131.2 (12)
N1—H1N···N3ⁱ	0.867 (15)	2.050 (15)	2.9120 (15)	172.6 (14)

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

We are grateful to Hunan Normal University for financial support and thank Mr Kai-bei Yu of Beijing Institute of Technology for the X-ray crystallographic data collection and structure determination.

References

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