[(E)-(1-Phenyl­ethyl­idene)amino]­urea methanol monosolvate

Liu, G.-B.; Chen, P.-S.; Liu, C.-X.; Fu, L.; Nie, X.-L.

doi:10.1107/S1600536811000225

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o345

doi:10.1107/S1600536811000225

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[(E)-(1-Phenylethylidene)amino]urea methanol monosolvate

Guang-Bin Liu,^a Peng-Sheng Chen,^b Chang-Xiang Liu,^a Ling Fu ^a and Xu-Liang Nie ^a ^*

^aDepartment of Chemistry, Jiangxi Agricultural University, Nanchang 330045, People's Republic of China, and ^bGuanlian Middle School of Wuning, Jiangxi Wuning 332302, People's Republic of China
^*Correspondence e-mail: niexuliang1981@163.com

(Received 28 December 2010; accepted 4 January 2011; online 12 January 2011)

In the title compound, C₉H₁₁N₃O·CH₄O, the semicarbazone moiety is nearly planar [maximum deviation = 0.017 (2) Å] and is twisted by a dihedral angle of 29.40 (13)° with respect to the phenyl ring. The semicarbazone moiety and phenyl ring are located on opposite sides of the C=N bond, showing the E configuration. An intermolecular O—H⋯O and N—H⋯O hydrogen-bonding network occurs in the crystal structure.

Related literature

For general background and applications of semicarbazone derivatives, see: Chandra & Gupta (2005 ). For related structures, see: Fun et al. (2009a ,b ).

Experimental

Crystal data

C₉H₁₁N₃O·CH₄O
M_r = 209.25
Monoclinic, P 2₁ /n
a = 6.629 (3) Å
b = 8.371 (4) Å
c = 20.329 (9) Å
β = 99.181 (5)°
V = 1113.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.24 × 0.22 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
8148 measured reflections
2057 independent reflections
1617 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.128
S = 1.07
2057 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.26 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
O2—H2A⋯O1ⁱ	0.82	1.93	2.745 (2)	177
N2—H8⋯O1ⁱⁱ	0.86	2.10	2.936 (2)	164
N3—H3A⋯O2ⁱⁱⁱ	0.86	2.12	2.953 (2)	164
N3—H3B⋯O2	0.86	2.36	3.042 (2)	137
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z+2; (iii) -x+1, -y, -z+2.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000225/xu5132sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000225/xu5132Isup2.hkl

checkCIF report

Comment top

The semicarbazone is a derivative of an aldehyde or ketone formed by a condensation between a ketone or aldehyde and semicarbazide. It is widely used in field of organometalics (Chandra & Gupta, 2005). Several crystal structures have recently reported by Fun et al., 2009a,b. Here we report the crystal structure of the title compound, (I).

In (I) (Fig. 1), the semicarbazone group is nearly planar, with the maximum deviation of 0.017 (2) Å. The mean plane of semicarbazone group and the benzene ring makes a dihedral angle of 29.40 (13)°. In the crystal structure there is also a methanol molecular which is stabilized by N—H···O hydrogen bond with the semicarbazone group. The methanol molecular further linked the semicarbazone group adjacent into a one-dimensional chain by N—H···O hydrogen bonds formed along the b axis. These chains are further linked via pairs of O—H···O hydrogen bonds involving the methanol O atoms and semicarbazone O atoms to a two-dimensional hydrogen bonds framework (Fig. 3).

Related literature top

For general background and applications of semicarbazone derivatives, see: Chandra & Gupta (2005). For related structures, see: Fun et al. (2009a,b).

Experimental top

Semicarbazide hydrochloride (11 g, 0.1 mol) was dissolved in water (100 ml), and sodium acetate (16.4 g, 0.2 mol) was added and dissolved by stirring at room temperature. To this, acetophenone (11.4 g, 0.095 mol) in ethanol (60 ml) was then added, and the mixture stirred well for 2 h at 323 K using a modified Vilsmeier-Haak reaction. The separated crystals were filtered, washed with cold water and recrystallized from methanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. The crystal packing of (I), showing a one-dimensional chain down the b axis; H-bonds are shown as dashed lines.
	Fig. 3. The crystal packing of (I), showing a two-dimensional sheet; H-bonds are shown as dashed lines.

[(E)-(1-Phenylethylidene)amino]urea methanol monosolvate top

Crystal data top

C₉H₁₁N₃O·CH₄O	F(000) = 448
M_r = 209.25	D_x = 1.248 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2808 reflections
a = 6.629 (3) Å	θ = 2.6–28.2°
b = 8.371 (4) Å	µ = 0.09 mm⁻¹
c = 20.329 (9) Å	T = 296 K
β = 99.181 (5)°	Block, colourless
V = 1113.6 (8) Å³	0.24 × 0.22 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1617 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.027
Graphite monochromator	θ_max = 25.5°, θ_min = 2.6°
ϕ and ω scans	h = −8→8
8148 measured reflections	k = −9→10
2057 independent reflections	l = −24→24

Refinement top

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0583P)² + 0.3389P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
2057 reflections	Δρ_max = 0.26 e Å⁻³
140 parameters	Δρ_min = −0.18 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (4)

Crystal data top

C₉H₁₁N₃O·CH₄O	V = 1113.6 (8) Å³
M_r = 209.25	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.629 (3) Å	µ = 0.09 mm⁻¹
b = 8.371 (4) Å	T = 296 K
c = 20.329 (9) Å	0.24 × 0.22 × 0.18 mm
β = 99.181 (5)°

Data collection top

Bruker APEXII CCD diffractometer	1617 reflections with I > 2σ(I)
8148 measured reflections	R_int = 0.027
2057 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.07	Δρ_max = 0.26 e Å⁻³
2057 reflections	Δρ_min = −0.18 e Å⁻³
140 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
C1	0.0487 (3)	0.6825 (3)	0.73837 (11)	0.0636 (6)
H1	0.0233	0.7479	0.7010	0.076*
C2	−0.0980 (3)	0.5772 (3)	0.75182 (11)	0.0630 (6)
H2	−0.2233	0.5717	0.7238	0.076*
C3	−0.0590 (3)	0.4793 (3)	0.80720 (10)	0.0550 (6)
H3	−0.1582	0.4076	0.8163	0.066*
C4	0.1262 (3)	0.4875 (2)	0.84901 (9)	0.0438 (5)
H4	0.1504	0.4216	0.8863	0.053*
C5	0.2773 (2)	0.5931 (2)	0.83614 (8)	0.0371 (4)
C6	0.2342 (3)	0.6916 (2)	0.78033 (10)	0.0521 (5)
H6	0.3319	0.7645	0.7712	0.063*
C7	0.6059 (3)	0.7470 (2)	0.88452 (10)	0.0509 (5)
H7A	0.6457	0.7752	0.9305	0.076*
H7B	0.5268	0.8322	0.8617	0.076*
H7C	0.7257	0.7294	0.8645	0.076*
C8	0.4800 (2)	0.5973 (2)	0.87964 (8)	0.0362 (4)
C9	0.7858 (2)	0.3143 (2)	0.97715 (8)	0.0361 (4)
C10	0.0959 (4)	0.0359 (3)	0.89062 (11)	0.0673 (6)
H10A	−0.0277	0.0967	0.8798	0.101*
H10B	0.0627	−0.0746	0.8957	0.101*
H10C	0.1762	0.0466	0.8555	0.101*
N1	0.5332 (2)	0.46585 (17)	0.91022 (7)	0.0362 (4)
N2	0.7209 (2)	0.45770 (17)	0.95027 (7)	0.0398 (4)
H8	0.7957	0.5416	0.9582	0.048*
O1	0.96431 (17)	0.30074 (14)	1.00688 (6)	0.0458 (4)
N3	0.6552 (2)	0.19317 (18)	0.96944 (9)	0.0526 (5)
H3A	0.6927	0.1007	0.9853	0.063*
H3B	0.5330	0.2071	0.9486	0.063*
O2	0.20857 (19)	0.09309 (17)	0.95077 (7)	0.0544 (4)
H2A	0.1370	0.1538	0.9688	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0641 (14)	0.0727 (15)	0.0482 (12)	0.0140 (12)	−0.0092 (10)	0.0110 (11)
C2	0.0449 (11)	0.0791 (16)	0.0569 (13)	0.0150 (11)	−0.0162 (10)	−0.0122 (12)
C3	0.0361 (10)	0.0651 (13)	0.0613 (13)	−0.0020 (9)	0.0001 (9)	−0.0118 (11)
C4	0.0392 (9)	0.0484 (11)	0.0427 (10)	0.0015 (8)	0.0032 (8)	0.0004 (8)
C5	0.0372 (9)	0.0385 (9)	0.0344 (9)	0.0060 (7)	0.0021 (7)	−0.0030 (7)
C6	0.0502 (11)	0.0547 (12)	0.0484 (11)	0.0029 (9)	−0.0009 (9)	0.0092 (9)
C7	0.0467 (10)	0.0442 (11)	0.0569 (12)	−0.0038 (8)	−0.0063 (9)	0.0047 (9)
C8	0.0360 (9)	0.0400 (10)	0.0319 (9)	0.0005 (7)	0.0030 (7)	0.0003 (7)
C9	0.0318 (8)	0.0383 (9)	0.0365 (9)	−0.0005 (7)	0.0008 (7)	0.0000 (7)
C10	0.0706 (14)	0.0675 (15)	0.0605 (14)	−0.0034 (12)	0.0005 (12)	−0.0025 (11)
N1	0.0310 (7)	0.0409 (8)	0.0346 (8)	−0.0004 (6)	−0.0012 (6)	0.0024 (6)
N2	0.0334 (7)	0.0370 (8)	0.0450 (9)	−0.0043 (6)	−0.0058 (6)	0.0042 (6)
O1	0.0337 (7)	0.0422 (7)	0.0562 (8)	0.0000 (5)	−0.0085 (6)	0.0011 (6)
N3	0.0356 (8)	0.0401 (9)	0.0758 (12)	−0.0042 (7)	−0.0096 (8)	0.0125 (8)
O2	0.0420 (7)	0.0510 (9)	0.0658 (9)	0.0044 (6)	−0.0047 (6)	−0.0037 (7)

Geometric parameters (Å, º) top

C1—C2	1.372 (3)	C7—H7C	0.9600
C1—C6	1.382 (3)	C8—N1	1.285 (2)
C1—H1	0.9300	C9—O1	1.2453 (19)
C2—C3	1.383 (3)	C9—N3	1.326 (2)
C2—H2	0.9300	C9—N2	1.360 (2)
C3—C4	1.379 (2)	C10—O2	1.411 (2)
C3—H3	0.9300	C10—H10A	0.9600
C4—C5	1.391 (3)	C10—H10B	0.9600
C4—H4	0.9300	C10—H10C	0.9600
C5—C6	1.395 (3)	N1—N2	1.3757 (18)
C5—C8	1.486 (2)	N2—H8	0.8600
C6—H6	0.9300	N3—H3A	0.8600
C7—C8	1.500 (3)	N3—H3B	0.8600
C7—H7A	0.9600	O2—H2A	0.8200
C7—H7B	0.9600

C2—C1—C6	120.1 (2)	H7A—C7—H7C	109.5
C2—C1—H1	120.0	H7B—C7—H7C	109.5
C6—C1—H1	120.0	N1—C8—C5	114.83 (15)
C1—C2—C3	119.75 (18)	N1—C8—C7	125.18 (15)
C1—C2—H2	120.1	C5—C8—C7	119.98 (15)
C3—C2—H2	120.1	O1—C9—N3	122.64 (15)
C4—C3—C2	120.3 (2)	O1—C9—N2	119.38 (15)
C4—C3—H3	119.8	N3—C9—N2	117.96 (14)
C2—C3—H3	119.8	O2—C10—H10A	109.5
C3—C4—C5	120.83 (18)	O2—C10—H10B	109.5
C3—C4—H4	119.6	H10A—C10—H10B	109.5
C5—C4—H4	119.6	O2—C10—H10C	109.5
C4—C5—C6	117.92 (16)	H10A—C10—H10C	109.5
C4—C5—C8	120.83 (15)	H10B—C10—H10C	109.5
C6—C5—C8	121.22 (16)	C8—N1—N2	118.77 (14)
C1—C6—C5	121.1 (2)	C9—N2—N1	118.67 (13)
C1—C6—H6	119.5	C9—N2—H8	120.7
C5—C6—H6	119.5	N1—N2—H8	120.7
C8—C7—H7A	109.5	C9—N3—H3A	120.0
C8—C7—H7B	109.5	C9—N3—H3B	120.0
H7A—C7—H7B	109.5	H3A—N3—H3B	120.0
C8—C7—H7C	109.5	C10—O2—H2A	109.5

C6—C1—C2—C3	−0.5 (3)	C6—C5—C8—N1	−152.23 (17)
C1—C2—C3—C4	0.2 (3)	C4—C5—C8—C7	−154.55 (18)
C2—C3—C4—C5	−0.4 (3)	C6—C5—C8—C7	27.1 (3)
C3—C4—C5—C6	0.9 (3)	C5—C8—N1—N2	178.39 (14)
C3—C4—C5—C8	−177.47 (17)	C7—C8—N1—N2	−0.9 (3)
C2—C1—C6—C5	1.0 (3)	O1—C9—N2—N1	171.57 (15)
C4—C5—C6—C1	−1.2 (3)	N3—C9—N2—N1	−7.4 (2)
C8—C5—C6—C1	177.18 (18)	C8—N1—N2—C9	−173.38 (16)
C4—C5—C8—N1	26.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.93	2.745 (2)	177
N2—H8···O1ⁱⁱ	0.86	2.10	2.936 (2)	164
N3—H3A···O2ⁱⁱⁱ	0.86	2.12	2.953 (2)	164
N3—H3B···O2	0.86	2.36	3.042 (2)	137

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O·CH₄O
M_r	209.25
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	6.629 (3), 8.371 (4), 20.329 (9)
β (°)	99.181 (5)
V (Å³)	1113.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.24 × 0.22 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8148, 2057, 1617
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.128, 1.07
No. of reflections	2057
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.18

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.82	1.93	2.745 (2)	177
N2—H8···O1ⁱⁱ	0.86	2.10	2.936 (2)	164
N3—H3A···O2ⁱⁱⁱ	0.86	2.12	2.953 (2)	164
N3—H3B···O2	0.86	2.36	3.042 (2)	137

Symmetry codes: (i) x−1, y, z; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y, −z+2.

Acknowledgements

This work was supported by the Research Foundation of Educational Department of Jiangxi Province [GJJ10421] and the Natural Science Foundation of Jiangxi Agricultural University, China (09003321).

References

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