(E)-1-(4-Methoxy­benzyl­idene)­semicarbazide

Liang, Z.-P.; Li, J.; Wang, H.-L.; Wang, H.-Q.

doi:10.1107/S1600536807023240

(E)-1-(4-Methoxybenzylidene)semicarbazide

Z.-P. Liang, J. Li, H.-L. Wang and H.-Q. Wang

In the crystal structure of the title compound, C₉H₁₁N₃O₂, the almost planar molecules interact by way of N—H

O hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023240/hb2409sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023240/hb2409Isup2.hkl Contains datablock I

CCDC reference: 651464

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.043
wR factor = 0.131
Data-to-parameter ratio = 12.1

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT731_ALERT_1_C Bond    Calc   0.888(19), Rep    0.886(9) ......       2.11 su-Ra
              N3   -H3B     1.555   1.555

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In this paper, the structure of the title compound, (I), is reported. The bond lengths and angles agree with those in a similar compound (E)-1-(4-Hydroxybenzylidene)semicarbazide hemihydrate (Tai et al., 2007). The molecule is essentially planar, with a maximum deviation from the mean plane of 0.033 (4) Å for the non-hydrogen atoms. The crystal structure is stabilized by N—H···O hydrogen bonds (Fig. 2 and Table 2).

Related literature top

For a related structure, see Tai et al. (2007).

Experimental top

A mixture of 4-methoxybenzaldehyde (0.01 mol) and semicarbazide hydrochloride (0.01 mol) in ethanol (10 ml) was refluxed for 1 h. After cooling, filtration and drying, the title compound was obtained. 10 mg of this compound was dissolved in ethanol (12 ml), and the solution was then allowed to evaporate at room temperature; light yellow single crystals of (I) were formed after 8 d.

Structure description top

For a related structure, see Tai et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. The crystal packing of (I), viewed along the b axis. Hydrogen bonds are indicated by dashed lines.

(E)-1-(4-Methoxybenzylidene)semicarbazide top

Crystal data top

C₉H₁₁N₃O₂	F(000) = 408
M_r = 193.21	D_x = 1.335 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1284 reflections
a = 13.811 (11) Å	θ = 3.0–24.6°
b = 5.443 (4) Å	µ = 0.10 mm⁻¹
c = 12.912 (10) Å	T = 294 K
β = 97.933 (13)°	Block, light yellow
V = 961.4 (13) Å³	0.22 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1698 independent reflections
Radiation source: fine-focus sealed tube	1080 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −16→15
T_min = 0.979, T_max = 0.990	k = −4→6
4626 measured reflections	l = −15→13

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: difmap and geom
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.072P)² + 0.0049P] where P = (F_o² + 2F_c²)/3
1698 reflections	(Δ/σ)_max = 0.004
140 parameters	Δρ_max = 0.14 e Å⁻³
4 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₁₁N₃O₂	V = 961.4 (13) Å³
M_r = 193.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.811 (11) Å	µ = 0.10 mm⁻¹
b = 5.443 (4) Å	T = 294 K
c = 12.912 (10) Å	0.22 × 0.20 × 0.10 mm
β = 97.933 (13)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1698 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1080 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.990	R_int = 0.034
4626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	4 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.14 e Å⁻³
1698 reflections	Δρ_min = −0.19 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
O1	0.41747 (12)	1.0943 (3)	0.72911 (13)	0.0620 (5)
O2	−0.00139 (11)	0.1030 (2)	1.13605 (10)	0.0443 (4)
N1	0.14797 (13)	0.4422 (3)	0.98921 (12)	0.0376 (5)
N2	0.08994 (13)	0.2555 (3)	1.01916 (13)	0.0408 (5)
N3	0.07790 (15)	0.4668 (3)	1.17129 (13)	0.0435 (5)
C1	0.26768 (16)	0.8148 (4)	0.90565 (16)	0.0426 (6)
H1	0.2498	0.8496	0.9709	0.051*
C2	0.32882 (17)	0.9721 (4)	0.86267 (17)	0.0463 (6)
H2	0.3522	1.1117	0.8994	0.056*
C3	0.35624 (16)	0.9253 (4)	0.76477 (17)	0.0420 (6)
C4	0.32198 (15)	0.7166 (4)	0.71071 (16)	0.0444 (6)
H4	0.3401	0.6826	0.6455	0.053*
C5	0.26042 (16)	0.5587 (4)	0.75450 (15)	0.0418 (6)
H5	0.2373	0.4189	0.7177	0.050*
C6	0.23206 (16)	0.6034 (3)	0.85243 (15)	0.0356 (5)
C7	0.16913 (15)	0.4259 (3)	0.89599 (15)	0.0377 (5)
H7	0.1434	0.2958	0.8542	0.045*
C8	0.05186 (15)	0.2709 (3)	1.11155 (14)	0.0345 (5)
C9	0.4390 (2)	1.0650 (6)	0.62403 (19)	0.0804 (10)
H9A	0.4745	0.9148	0.6189	0.121*
H9B	0.4779	1.2010	0.6064	0.121*
H9C	0.3790	1.0597	0.5766	0.121*
H3A	0.0485 (14)	0.501 (4)	1.2275 (12)	0.062 (7)*
H2A	0.0686 (14)	0.140 (3)	0.9726 (13)	0.047 (6)*
H3B	0.1138 (15)	0.586 (3)	1.1490 (16)	0.064 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0656 (13)	0.0628 (11)	0.0611 (11)	−0.0215 (8)	0.0210 (9)	0.0056 (8)
O2	0.0615 (11)	0.0435 (8)	0.0312 (8)	−0.0086 (7)	0.0183 (7)	0.0022 (6)
N1	0.0484 (12)	0.0398 (9)	0.0264 (9)	−0.0026 (8)	0.0117 (8)	0.0017 (7)
N2	0.0585 (13)	0.0401 (10)	0.0272 (9)	−0.0102 (9)	0.0179 (9)	−0.0034 (8)
N3	0.0603 (14)	0.0452 (11)	0.0274 (10)	−0.0055 (10)	0.0146 (9)	−0.0046 (8)
C1	0.0552 (15)	0.0431 (12)	0.0306 (11)	0.0027 (11)	0.0101 (11)	−0.0006 (9)
C2	0.0548 (16)	0.0401 (12)	0.0442 (13)	−0.0058 (11)	0.0080 (11)	−0.0054 (10)
C3	0.0430 (15)	0.0428 (12)	0.0417 (13)	−0.0028 (10)	0.0107 (11)	0.0085 (9)
C4	0.0513 (15)	0.0548 (14)	0.0295 (12)	−0.0043 (11)	0.0137 (10)	0.0023 (10)
C5	0.0497 (15)	0.0458 (12)	0.0311 (12)	−0.0046 (10)	0.0099 (10)	−0.0024 (9)
C6	0.0421 (14)	0.0383 (11)	0.0269 (11)	0.0020 (9)	0.0067 (10)	0.0038 (8)
C7	0.0451 (14)	0.0412 (11)	0.0275 (11)	−0.0006 (9)	0.0081 (10)	0.0010 (8)
C8	0.0443 (13)	0.0360 (11)	0.0239 (10)	0.0055 (9)	0.0072 (9)	0.0046 (8)
C9	0.086 (2)	0.104 (2)	0.0543 (18)	−0.0391 (18)	0.0217 (16)	0.0196 (15)

Geometric parameters (Å, º) top

O1—C3	1.372 (2)	C2—C3	1.392 (3)
O1—C9	1.437 (3)	C2—H2	0.9300
O2—C8	1.241 (2)	C3—C4	1.382 (3)
N1—C7	1.280 (3)	C4—C5	1.383 (3)
N1—N2	1.382 (2)	C4—H4	0.9300
N2—C8	1.371 (3)	C5—C6	1.396 (3)
N2—H2A	0.893 (9)	C5—H5	0.9300
N3—C8	1.336 (3)	C6—C7	1.463 (3)
N3—H3A	0.899 (9)	C7—H7	0.9300
N3—H3B	0.886 (9)	C9—H9A	0.9600
C1—C2	1.372 (3)	C9—H9B	0.9600
C1—C6	1.395 (3)	C9—H9C	0.9600
C1—H1	0.9300

C3—O1—C9	117.38 (18)	C5—C4—H4	120.3
C7—N1—N2	115.36 (17)	C4—C5—C6	121.8 (2)
C8—N2—N1	120.35 (16)	C4—C5—H5	119.1
C8—N2—H2A	119.9 (14)	C6—C5—H5	119.1
N1—N2—H2A	118.7 (13)	C1—C6—C5	117.78 (19)
C8—N3—H3A	121.1 (13)	C1—C6—C7	122.91 (19)
C8—N3—H3B	120.9 (13)	C5—C6—C7	119.29 (18)
H3A—N3—H3B	116.4 (14)	N1—C7—C6	122.71 (19)
C2—C1—C6	120.7 (2)	N1—C7—H7	118.6
C2—C1—H1	119.7	C6—C7—H7	118.6
C6—C1—H1	119.7	O2—C8—N3	124.21 (18)
C1—C2—C3	120.8 (2)	O2—C8—N2	119.26 (17)
C1—C2—H2	119.6	N3—C8—N2	116.50 (19)
C3—C2—H2	119.6	O1—C9—H9A	109.5
O1—C3—C4	124.45 (19)	O1—C9—H9B	109.5
O1—C3—C2	116.09 (19)	H9A—C9—H9B	109.5
C4—C3—C2	119.46 (19)	O1—C9—H9C	109.5
C3—C4—C5	119.4 (2)	H9A—C9—H9C	109.5
C3—C4—H4	120.3	H9B—C9—H9C	109.5

C7—N1—N2—C8	−171.16 (19)	C2—C1—C6—C5	−0.2 (3)
C6—C1—C2—C3	0.4 (3)	C2—C1—C6—C7	178.11 (19)
C9—O1—C3—C4	6.8 (3)	C4—C5—C6—C1	0.2 (3)
C9—O1—C3—C2	−173.7 (2)	C4—C5—C6—C7	−178.21 (19)
C1—C2—C3—O1	179.93 (19)	N2—N1—C7—C6	−178.17 (17)
C1—C2—C3—C4	−0.5 (3)	C1—C6—C7—N1	−5.3 (3)
O1—C3—C4—C5	180.0 (2)	C5—C6—C7—N1	173.0 (2)
C2—C3—C4—C5	0.5 (3)	N1—N2—C8—O2	178.81 (18)
C3—C4—C5—C6	−0.3 (3)	N1—N2—C8—N3	−3.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱ	0.90 (1)	2.04 (1)	2.929 (3)	171 (2)
N2—H2A···O2ⁱⁱ	0.89 (1)	2.05 (1)	2.940 (3)	172 (2)

Symmetry codes: (i) −x, y+1/2, −z+5/2; (ii) −x, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁N₃O₂
M_r	193.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	13.811 (11), 5.443 (4), 12.912 (10)
β (°)	97.933 (13)
V (Å³)	961.4 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.979, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	4626, 1698, 1080
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.131, 1.03
No. of reflections	1698
No. of parameters	140
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.