(E)-1-[4-(Dimethyl­amino)benzyl­idene]­semicarbazide–acetic acid (1/2)

Liang, Z.-P.; Li, J.; Wang, H.-L.; Zhang, Y.-C.

doi:10.1107/S1600536807024956

(E)-1-[4-(Dimethylamino)benzylidene]semicarbazide–acetic acid (1/2)

Z.-P. Liang, J. Li, H.-L. Wang and Y.-C. Zhang

In the crystal structure of the title compound, C₁₀H₁₆N₄O·2C₂H₄O₂, the molecules interact by way of O—H

O and N—H

O hydrogen bonds, resulting in [010] chains built up from the 1-[4-(dimethylamino)benzylidene]semicarbazide molecule and one of the acetic acid molecules. The other acetic acid molecule forms isolated centrosymmetric dimers.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024956/hb2411sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024956/hb2411Isup2.hkl Contains datablock I

CCDC reference: 651488

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.006 Å
R factor = 0.062
wR factor = 0.202
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         44 Perc.
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.04 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C11
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C13
PLAT245_ALERT_2_C U(iso) H4A     Smaller than U(eq) N4      by ...       0.02 AngSq
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          6
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.897(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.897(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.01(3), Rep   2.017(11) ......       2.73 su-Ra
              H3A  -O1      1.555   2.566

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

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

Comment top

Their preparation, properties and applications od Schiff bases are important in the development of coordination chemistry. The asymmetric unit of the title compound, (I), contains one (E)-1-(4-(dimethylamino)benzylidene)semicarbazide molecule and two acetic acid molecules (Fig. 1). The bond lengths and angles of the Schiff base in (I) agree with those in the related (E)-1-(4-hydroxybenzylidene)semicarbazide hemihydrate (Tai et al., 2007). The main molecule in (I) is essentially planar, with a maximum deviation from the mean plane for the non-hydrogen atoms of 0.042 (2) Å. The crystal structure of (I) is stabilized by O—H···O and N—H···O hydrogen bonds (Fig. 2 and Table 1), to result in a chains built up from the C₁₀H₁₆N₄0 molecule and the C13-containing acetic acid molecule. Conversely, the C11 acetic acid molecule forms isolated inversion dimers.

Related literature top

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

Experimental top

A mixture of 4-(dimethylamino)benzaldehyde (0.01 mol) and semicarbazide hydrochloride (0.01 mol) in ethanol (10 ml) was refluxed for 1 h. After cooling, filtration and drying, the compound (E)-1-(4-(dimethylamino)benzylidene)semicarbazide was obtained. 10 mg of this compound was dissolved in acetic acid (8 ml), and the solution was then allowed to evaporate at room temperature; light yellow blocks of (I) were formed after 12 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 a axis. Hydrogen bonds are indicated by dashed lines.

(E)-1-[4-(Dimethylamino)benzylidene]semicarbazide–acetic acid (1/2) top

Crystal data top

C₁₀H₁₄N₄O·2C₂H₄O₂	Z = 2
M_r = 326.36	F(000) = 348
Triclinic, P1	D_x = 1.239 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2931 (2) Å	Cell parameters from 886 reflections
b = 10.7952 (8) Å	θ = 2.9–23.5°
c = 12.2472 (7) Å	µ = 0.10 mm⁻¹
α = 71.422 (17)°	T = 294 K
β = 80.020 (4)°	Block, light yellow
γ = 73.947 (4)°	0.16 × 0.14 × 0.12 mm
V = 874.49 (12) Å³

Data collection top

Bruker SMART CCD diffractometer	3064 independent reflections
Radiation source: fine-focus sealed tube	1351 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −8→7
T_min = 0.985, T_max = 0.989	k = −12→12
4441 measured reflections	l = −14→6

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.202	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0848P)² + 0.1483P] where P = (F_o² + 2F_c²)/3
3064 reflections	(Δ/σ)_max = 0.005
225 parameters	Δρ_max = 0.19 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₄N₄O·2C₂H₄O₂	γ = 73.947 (4)°
M_r = 326.36	V = 874.49 (12) Å³
Triclinic, P1	Z = 2
a = 7.2931 (2) Å	Mo Kα radiation
b = 10.7952 (8) Å	µ = 0.10 mm⁻¹
c = 12.2472 (7) Å	T = 294 K
α = 71.422 (17)°	0.16 × 0.14 × 0.12 mm
β = 80.020 (4)°

Data collection top

Bruker SMART CCD diffractometer	3064 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1351 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.989	R_int = 0.040
4441 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	1 restraint
wR(F²) = 0.202	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.19 e Å⁻³
3064 reflections	Δρ_min = −0.21 e Å⁻³
225 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	−0.0214 (4)	0.6237 (2)	0.5764 (2)	0.0645 (9)
N1	0.3989 (6)	0.9089 (3)	−0.2633 (3)	0.0756 (12)
N2	0.1380 (5)	0.7164 (3)	0.2810 (3)	0.0543 (9)
N3	0.0888 (5)	0.6399 (3)	0.3916 (3)	0.0609 (10)
N4	0.0405 (6)	0.8213 (4)	0.4616 (4)	0.0686 (12)
C1	0.2324 (6)	0.8560 (4)	0.0449 (3)	0.0593 (12)
H1	0.1941	0.9067	0.0972	0.071*
C2	0.2830 (6)	0.9184 (4)	−0.0688 (3)	0.0621 (13)
H2	0.2769	1.0101	−0.0915	0.074*
C3	0.3434 (6)	0.8470 (4)	−0.1512 (3)	0.0540 (11)
C4	0.3461 (6)	0.7089 (4)	−0.1113 (3)	0.0549 (12)
H4	0.3838	0.6576	−0.1631	0.066*
C5	0.2941 (6)	0.6479 (3)	0.0034 (3)	0.0526 (11)
H5	0.2977	0.5565	0.0268	0.063*
C6	0.2366 (5)	0.7196 (3)	0.0842 (3)	0.0470 (10)
C7	0.1849 (6)	0.6532 (4)	0.2048 (3)	0.0537 (11)
H7	0.1862	0.5622	0.2267	0.064*
C8	0.0324 (6)	0.6951 (4)	0.4796 (3)	0.0520 (11)
C9	0.3996 (8)	1.0509 (4)	−0.3013 (4)	0.0873 (17)
H9A	0.2720	1.1034	−0.2895	0.131*
H9B	0.4438	1.0761	−0.3820	0.131*
H9C	0.4833	1.0670	−0.2575	0.131*
C10	0.4361 (8)	0.8414 (5)	−0.3535 (4)	0.0910 (17)
H10A	0.5516	0.7714	−0.3415	0.137*
H10B	0.4506	0.9053	−0.4278	0.137*
H10C	0.3308	0.8030	−0.3508	0.137*
O2	0.4506 (5)	0.5408 (3)	0.6268 (3)	0.0902 (12)
O3	0.4009 (5)	0.3657 (3)	0.5886 (3)	0.0960 (12)
H3	0.4495	0.4040	0.5221	0.115*
C11	0.3914 (7)	0.4363 (5)	0.6571 (5)	0.0765 (14)
C12	0.3084 (8)	0.3842 (5)	0.7785 (5)	0.0920 (16)
H12A	0.4089	0.3254	0.8251	0.138*
H12B	0.2162	0.3355	0.7789	0.138*
H12C	0.2468	0.4583	0.8096	0.138*
O4	0.9048 (5)	0.8908 (3)	0.6896 (3)	0.0806 (10)
O5	0.8966 (5)	0.6762 (3)	0.7728 (2)	0.0788 (10)
H5A	0.9164	0.6733	0.7056	0.118*
C13	0.8785 (6)	0.8016 (4)	0.7749 (4)	0.0606 (12)
C14	0.8229 (7)	0.8142 (5)	0.8945 (4)	0.0776 (15)
H14A	0.9334	0.8155	0.9264	0.116*
H14B	0.7724	0.7390	0.9418	0.116*
H14C	0.7270	0.8961	0.8924	0.116*
H4A	0.070 (5)	0.872 (3)	0.393 (3)	0.046 (11)*
H3A	0.070 (5)	0.558 (2)	0.400 (3)	0.070 (13)*
H4B	0.000 (8)	0.857 (6)	0.523 (5)	0.14 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.102 (2)	0.0522 (15)	0.0443 (17)	−0.0302 (15)	0.0101 (16)	−0.0185 (13)
N1	0.121 (4)	0.064 (2)	0.047 (2)	−0.036 (2)	0.012 (2)	−0.0201 (18)
N2	0.068 (2)	0.0523 (18)	0.047 (2)	−0.0230 (17)	0.0054 (18)	−0.0180 (17)
N3	0.091 (3)	0.0506 (19)	0.047 (2)	−0.0283 (19)	0.0085 (19)	−0.0198 (17)
N4	0.109 (4)	0.054 (2)	0.046 (2)	−0.033 (2)	0.002 (2)	−0.012 (2)
C1	0.080 (3)	0.047 (2)	0.053 (3)	−0.014 (2)	0.005 (2)	−0.023 (2)
C2	0.089 (4)	0.044 (2)	0.056 (3)	−0.022 (2)	0.009 (3)	−0.019 (2)
C3	0.066 (3)	0.054 (2)	0.044 (2)	−0.018 (2)	0.002 (2)	−0.0173 (19)
C4	0.073 (3)	0.047 (2)	0.049 (2)	−0.015 (2)	0.003 (2)	−0.0227 (19)
C5	0.066 (3)	0.0389 (19)	0.053 (3)	−0.0144 (19)	−0.001 (2)	−0.0133 (18)
C6	0.051 (3)	0.047 (2)	0.043 (2)	−0.0113 (19)	0.000 (2)	−0.0166 (18)
C7	0.061 (3)	0.046 (2)	0.056 (3)	−0.017 (2)	0.001 (2)	−0.017 (2)
C8	0.066 (3)	0.045 (2)	0.048 (3)	−0.018 (2)	−0.002 (2)	−0.014 (2)
C9	0.129 (5)	0.066 (3)	0.057 (3)	−0.032 (3)	0.011 (3)	−0.006 (2)
C10	0.135 (5)	0.102 (4)	0.049 (3)	−0.047 (3)	0.013 (3)	−0.035 (3)
O2	0.106 (3)	0.067 (2)	0.113 (3)	−0.038 (2)	−0.008 (2)	−0.0342 (19)
O3	0.125 (3)	0.074 (2)	0.104 (3)	−0.041 (2)	−0.011 (2)	−0.030 (2)
C11	0.067 (4)	0.068 (3)	0.098 (4)	−0.010 (3)	−0.020 (3)	−0.026 (3)
C12	0.085 (4)	0.095 (4)	0.101 (4)	−0.026 (3)	−0.011 (3)	−0.031 (3)
O4	0.116 (3)	0.0558 (18)	0.075 (2)	−0.0313 (18)	0.005 (2)	−0.0225 (16)
O5	0.130 (3)	0.0568 (17)	0.0556 (19)	−0.0280 (17)	0.006 (2)	−0.0264 (15)
C13	0.067 (3)	0.055 (2)	0.067 (3)	−0.017 (2)	−0.002 (3)	−0.027 (2)
C14	0.095 (4)	0.085 (3)	0.072 (3)	−0.029 (3)	0.002 (3)	−0.047 (3)

Geometric parameters (Å, º) top

O1—C8	1.256 (4)	C7—H7	0.9300
N1—C3	1.367 (5)	C9—H9A	0.9600
N1—C9	1.454 (5)	C9—H9B	0.9600
N1—C10	1.458 (5)	C9—H9C	0.9600
N2—C7	1.273 (4)	C10—H10A	0.9600
N2—N3	1.388 (4)	C10—H10B	0.9600
N3—C8	1.344 (5)	C10—H10C	0.9600
N3—H3A	0.897 (10)	O2—C11	1.243 (5)
N4—C8	1.325 (5)	O3—C11	1.284 (5)
N4—H4A	0.87 (4)	O3—H3	0.8522
N4—H4B	0.91 (6)	C11—C12	1.496 (7)
C1—C2	1.375 (5)	C12—H12A	0.9600
C1—C6	1.389 (5)	C12—H12B	0.9600
C1—H1	0.9300	C12—H12C	0.9600
C2—C3	1.401 (5)	O4—C13	1.203 (5)
C2—H2	0.9300	O5—C13	1.331 (5)
C3—C4	1.409 (5)	O5—H5A	0.8200
C4—C5	1.384 (5)	C13—C14	1.490 (6)
C4—H4	0.9300	C14—H14A	0.9600
C5—C6	1.386 (5)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600
C6—C7	1.455 (5)

C3—N1—C9	121.4 (3)	N4—C8—N3	118.8 (4)
C3—N1—C10	121.8 (4)	N1—C9—H9A	109.5
C9—N1—C10	116.4 (4)	N1—C9—H9B	109.5
C7—N2—N3	114.9 (3)	H9A—C9—H9B	109.5
C8—N3—N2	120.9 (3)	N1—C9—H9C	109.5
C8—N3—H3A	119 (3)	H9A—C9—H9C	109.5
N2—N3—H3A	119 (3)	H9B—C9—H9C	109.5
C8—N4—H4A	122 (2)	N1—C10—H10A	109.5
C8—N4—H4B	117 (4)	N1—C10—H10B	109.5
H4A—N4—H4B	121 (4)	H10A—C10—H10B	109.5
C2—C1—C6	122.1 (3)	N1—C10—H10C	109.5
C2—C1—H1	118.9	H10A—C10—H10C	109.5
C6—C1—H1	118.9	H10B—C10—H10C	109.5
C1—C2—C3	121.6 (4)	C11—O3—H3	108.8
C1—C2—H2	119.2	O2—C11—O3	122.9 (5)
C3—C2—H2	119.2	O2—C11—C12	120.9 (5)
N1—C3—C2	121.2 (4)	O3—C11—C12	116.3 (5)
N1—C3—C4	122.6 (3)	C11—C12—H12A	109.5
C2—C3—C4	116.2 (4)	C11—C12—H12B	109.5
C5—C4—C3	121.4 (3)	H12A—C12—H12B	109.5
C5—C4—H4	119.3	C11—C12—H12C	109.5
C3—C4—H4	119.3	H12A—C12—H12C	109.5
C4—C5—C6	121.7 (3)	H12B—C12—H12C	109.5
C4—C5—H5	119.2	C13—O5—H5A	109.5
C6—C5—H5	119.2	O4—C13—O5	122.9 (4)
C5—C6—C1	117.0 (3)	O4—C13—C14	125.9 (4)
C5—C6—C7	120.8 (3)	O5—C13—C14	111.2 (4)
C1—C6—C7	122.2 (3)	C13—C14—H14A	109.5
N2—C7—C6	121.7 (3)	C13—C14—H14B	109.5
N2—C7—H7	119.1	H14A—C14—H14B	109.5
C6—C7—H7	119.1	C13—C14—H14C	109.5
O1—C8—N4	122.7 (3)	H14A—C14—H14C	109.5
O1—C8—N3	118.5 (3)	H14B—C14—H14C	109.5

C7—N2—N3—C8	−178.5 (4)	C3—C4—C5—C6	0.1 (7)
C6—C1—C2—C3	−0.6 (7)	C4—C5—C6—C1	0.4 (6)
C9—N1—C3—C2	0.7 (7)	C4—C5—C6—C7	−179.1 (4)
C10—N1—C3—C2	−171.2 (4)	C2—C1—C6—C5	−0.1 (6)
C9—N1—C3—C4	−178.3 (4)	C2—C1—C6—C7	179.4 (4)
C10—N1—C3—C4	9.8 (7)	N3—N2—C7—C6	178.7 (4)
C1—C2—C3—N1	−178.0 (4)	C5—C6—C7—N2	177.6 (4)
C1—C2—C3—C4	1.0 (7)	C1—C6—C7—N2	−1.9 (6)
N1—C3—C4—C5	178.3 (4)	N2—N3—C8—O1	175.8 (4)
C2—C3—C4—C5	−0.8 (6)	N2—N3—C8—N4	−5.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.85	1.82	2.658 (6)	170
O5—H5A···O1ⁱⁱ	0.82	1.78	2.579 (4)	166
N4—H4A···O4ⁱⁱⁱ	0.87 (4)	2.48 (4)	3.164 (6)	135 (3)
N3—H3A···O1^iv	0.90 (1)	2.02 (1)	2.913 (5)	178 (4)
N4—H4B···O4^v	0.91 (6)	2.16 (6)	3.051 (6)	166 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₄O·2C₂H₄O₂
M_r	326.36
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.2931 (2), 10.7952 (8), 12.2472 (7)
α, β, γ (°)	71.422 (17), 80.020 (4), 73.947 (4)
V (Å³)	874.49 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.16 × 0.14 × 0.12

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.985, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	4441, 3064, 1351
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.202, 1.01
No. of reflections	3064
No. of parameters	225
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.21

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