Ethyl 3-(3-eth­oxy-2-hydroxy­benzyl­idene)carbazate

Li, Y.-F.; Liu, H.-X.; Jian, F.-F.

doi:10.1107/S1600536809044626

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2934

https://doi.org/10.1107/S1600536809044626

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Ethyl 3-(3-ethoxy-2-hydroxybenzylidene)carbazate

Yu-Feng Li,^a Hai-Xing Liu ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 19 October 2009; accepted 27 October 2009; online 31 October 2009)

In the title compound, C₁₂H₁₆N₂O₄, an intramolecular O—H⋯O hydrogen bond occurs. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming chains propagating in the [010] direction.

Related literature

For background to Schiff bases, see: Cimerman et al. (1997 ).

Experimental

Crystal data

C₁₂H₁₆N₂O₄
M_r = 252.27
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.1140 (14) Å
b = 9.6010 (19) Å
c = 18.570 (4) Å
V = 1268.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.19 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
11976 measured reflections
2917 independent reflections
2680 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.07
2917 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.14 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
O4—H4A⋯N2	0.82	1.91	2.6290 (15)	145
N1—H1A⋯O2ⁱ	0.86	2.31	2.9633 (15)	132
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809044626/hb5155sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044626/hb5155Isup2.hkl

checkCIF report

Related literature top

For background to Schiff bases, see: Cimerman et al. (1997).

Experimental top

A mixture of 3-ethoxy-2-hydroxybenzaldehyde (0.1 mol), and ethyl carbazate (0.1 mol) was stirred in refluxing ethanol (20 ml) for 4 h to afford the title compound (0.082 mol, yield 82%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Structure description top

For background to Schiff bases, see: Cimerman et al. (1997).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.

Ethyl 3-(3-ethoxy-2-hydroxybenzylidene)carbazate top

Crystal data top

C₁₂H₁₆N₂O₄	F(000) = 536
M_r = 252.27	D_x = 1.321 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1982 reflections
a = 7.1140 (14) Å	θ = 3.5–27.3°
b = 9.6010 (19) Å	µ = 0.10 mm⁻¹
c = 18.570 (4) Å	T = 293 K
V = 1268.4 (4) Å³	Block, colourless
Z = 4	0.22 × 0.20 × 0.19 mm

Data collection top

Bruker SMART CCD diffractometer	2680 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −8→9
11976 measured reflections	k = −12→12
2917 independent reflections	l = −23→24

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0474P)² + 0.0849P] where P = (F_o² + 2F_c²)/3
2917 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₂H₁₆N₂O₄	V = 1268.4 (4) Å³
M_r = 252.27	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.1140 (14) Å	µ = 0.10 mm⁻¹
b = 9.6010 (19) Å	T = 293 K
c = 18.570 (4) Å	0.22 × 0.20 × 0.19 mm

Data collection top

Bruker SMART CCD diffractometer	2680 reflections with I > 2σ(I)
11976 measured reflections	R_int = 0.043
2917 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	Δρ_max = 0.14 e Å⁻³
2917 reflections	Δρ_min = −0.18 e Å⁻³
163 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	0.32636 (13)	0.00340 (9)	0.17092 (5)	0.0507 (3)
N2	0.73581 (14)	−0.03948 (10)	0.26990 (6)	0.0400 (2)
O4	0.90478 (14)	−0.23476 (9)	0.34513 (6)	0.0514 (3)
H4A	0.8193	−0.2008	0.3212	0.077*
N1	0.59340 (15)	0.01343 (11)	0.22830 (6)	0.0447 (3)
H1A	0.5964	0.0986	0.2140	0.054*
O2	0.43343 (15)	−0.19175 (9)	0.22560 (6)	0.0530 (3)
C3	0.44812 (18)	−0.07057 (13)	0.21020 (7)	0.0398 (3)
O3	1.19430 (15)	−0.31435 (11)	0.41917 (6)	0.0563 (3)
C10	1.04046 (17)	−0.13798 (13)	0.35560 (7)	0.0379 (3)
C4	0.87138 (19)	0.04316 (13)	0.28510 (7)	0.0418 (3)
H4B	0.8679	0.1344	0.2684	0.050*
C5	1.03034 (18)	−0.00269 (13)	0.32791 (7)	0.0396 (3)
C8	1.3410 (2)	−0.08581 (17)	0.40856 (8)	0.0522 (3)
H8A	1.4449	−0.1125	0.4356	0.063*
C9	1.1983 (2)	−0.17984 (14)	0.39607 (7)	0.0433 (3)
C11	1.3491 (2)	−0.36144 (18)	0.46182 (8)	0.0569 (4)
H11A	1.3584	−0.3070	0.5057	0.068*
H11B	1.4657	−0.3519	0.4352	0.068*
C6	1.1784 (2)	0.08977 (15)	0.34131 (8)	0.0500 (3)
H6A	1.1732	0.1799	0.3231	0.060*
C2	0.1594 (2)	−0.06859 (15)	0.14570 (9)	0.0503 (3)
H2B	0.0623	−0.0007	0.1351	0.060*
H2C	0.1131	−0.1291	0.1836	0.060*
C7	1.3308 (2)	0.04877 (18)	0.38097 (9)	0.0583 (4)
H7A	1.4282	0.1112	0.3895	0.070*
C12	1.3135 (3)	−0.51120 (19)	0.47940 (11)	0.0702 (5)
H12A	1.4159	−0.5468	0.5076	0.105*
H12B	1.3032	−0.5638	0.4356	0.105*
H12C	1.1987	−0.5191	0.5063	0.105*
C1	0.1972 (3)	−0.1532 (2)	0.08008 (10)	0.0710 (5)
H1B	0.0839	−0.1994	0.0654	0.106*
H1C	0.2922	−0.2212	0.0905	0.106*
H1D	0.2399	−0.0933	0.0420	0.106*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0523 (5)	0.0346 (5)	0.0654 (6)	0.0008 (4)	−0.0193 (5)	0.0033 (4)
N2	0.0422 (5)	0.0344 (5)	0.0433 (5)	0.0040 (4)	−0.0032 (4)	0.0007 (4)
O4	0.0488 (5)	0.0345 (5)	0.0708 (6)	−0.0054 (4)	−0.0190 (5)	0.0043 (4)
N1	0.0486 (6)	0.0311 (5)	0.0545 (6)	0.0019 (4)	−0.0116 (5)	0.0051 (4)
O2	0.0618 (6)	0.0288 (4)	0.0683 (6)	0.0011 (4)	−0.0139 (5)	0.0029 (4)
C3	0.0454 (6)	0.0310 (5)	0.0429 (6)	0.0050 (5)	−0.0035 (6)	−0.0037 (5)
O3	0.0554 (6)	0.0443 (5)	0.0693 (6)	0.0021 (4)	−0.0214 (5)	0.0068 (4)
C10	0.0393 (6)	0.0355 (6)	0.0387 (6)	−0.0011 (5)	−0.0014 (5)	−0.0041 (5)
C4	0.0484 (6)	0.0325 (6)	0.0445 (6)	0.0012 (5)	0.0015 (6)	0.0015 (5)
C5	0.0413 (6)	0.0398 (6)	0.0376 (6)	−0.0017 (5)	0.0014 (5)	−0.0025 (5)
C8	0.0446 (7)	0.0583 (9)	0.0535 (8)	−0.0041 (6)	−0.0122 (7)	−0.0008 (6)
C9	0.0457 (7)	0.0416 (7)	0.0426 (6)	0.0011 (5)	−0.0049 (6)	−0.0016 (5)
C11	0.0536 (8)	0.0620 (9)	0.0550 (8)	0.0109 (7)	−0.0132 (7)	0.0057 (7)
C6	0.0533 (8)	0.0414 (7)	0.0554 (8)	−0.0104 (6)	−0.0007 (7)	0.0036 (6)
C2	0.0455 (7)	0.0405 (7)	0.0647 (8)	0.0012 (6)	−0.0117 (7)	−0.0035 (6)
C7	0.0506 (8)	0.0592 (9)	0.0650 (9)	−0.0189 (7)	−0.0082 (7)	−0.0003 (7)
C12	0.0665 (10)	0.0650 (10)	0.0791 (11)	0.0153 (9)	−0.0034 (9)	0.0201 (9)
C1	0.0691 (10)	0.0819 (12)	0.0618 (9)	0.0041 (10)	−0.0130 (9)	−0.0153 (9)

Geometric parameters (Å, º) top

O1—C3	1.3367 (15)	C8—C7	1.392 (2)
O1—C2	1.4516 (17)	C8—H8A	0.9300
N2—C4	1.2803 (17)	C11—C12	1.496 (3)
N2—N1	1.3715 (14)	C11—H11A	0.9700
O4—C10	1.3539 (15)	C11—H11B	0.9700
O4—H4A	0.8200	C6—C7	1.368 (2)
N1—C3	1.3533 (16)	C6—H6A	0.9300
N1—H1A	0.8600	C2—C1	1.489 (2)
O2—C3	1.2026 (15)	C2—H2B	0.9700
O3—C9	1.3611 (17)	C2—H2C	0.9700
O3—C11	1.4299 (17)	C7—H7A	0.9300
C10—C5	1.3988 (18)	C12—H12A	0.9600
C10—C9	1.4095 (18)	C12—H12B	0.9600
C4—C5	1.4508 (18)	C12—H12C	0.9600
C4—H4B	0.9300	C1—H1B	0.9600
C5—C6	1.3998 (18)	C1—H1C	0.9600
C8—C9	1.3783 (19)	C1—H1D	0.9600

C3—O1—C2	116.95 (10)	O3—C11—H11B	110.3
C4—N2—N1	116.81 (10)	C12—C11—H11B	110.3
C10—O4—H4A	109.5	H11A—C11—H11B	108.5
C3—N1—N2	118.90 (10)	C7—C6—C5	120.62 (13)
C3—N1—H1A	120.5	C7—C6—H6A	119.7
N2—N1—H1A	120.5	C5—C6—H6A	119.7
O2—C3—O1	125.97 (12)	O1—C2—C1	112.09 (13)
O2—C3—N1	125.72 (12)	O1—C2—H2B	109.2
O1—C3—N1	108.29 (10)	C1—C2—H2B	109.2
C9—O3—C11	117.30 (12)	O1—C2—H2C	109.2
O4—C10—C5	123.22 (11)	C1—C2—H2C	109.2
O4—C10—C9	116.66 (11)	H2B—C2—H2C	107.9
C5—C10—C9	120.12 (11)	C6—C7—C8	120.42 (13)
N2—C4—C5	121.33 (11)	C6—C7—H7A	119.8
N2—C4—H4B	119.3	C8—C7—H7A	119.8
C5—C4—H4B	119.3	C11—C12—H12A	109.5
C10—C5—C6	119.00 (12)	C11—C12—H12B	109.5
C10—C5—C4	121.56 (11)	H12A—C12—H12B	109.5
C6—C5—C4	119.44 (12)	C11—C12—H12C	109.5
C9—C8—C7	120.52 (13)	H12A—C12—H12C	109.5
C9—C8—H8A	119.7	H12B—C12—H12C	109.5
C7—C8—H8A	119.7	C2—C1—H1B	109.5
O3—C9—C8	125.71 (12)	C2—C1—H1C	109.5
O3—C9—C10	114.97 (12)	H1B—C1—H1C	109.5
C8—C9—C10	119.32 (12)	C2—C1—H1D	109.5
O3—C11—C12	107.13 (14)	H1B—C1—H1D	109.5
O3—C11—H11A	110.3	H1C—C1—H1D	109.5
C12—C11—H11A	110.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N2	0.82	1.91	2.6290 (15)	145
N1—H1A···O2ⁱ	0.86	2.31	2.9633 (15)	132

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₄
M_r	252.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.1140 (14), 9.6010 (19), 18.570 (4)
V (Å³)	1268.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.22 × 0.20 × 0.19

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11976, 2917, 2680
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.07
No. of reflections	2917
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), 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
O4—H4A···N2	0.82	1.91	2.6290 (15)	145
N1—H1A···O2ⁱ	0.86	2.31	2.9633 (15)	132

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

Acknowledgements

The authors would like to thank the Science Foundation of Weifang University (No. 2009Z24).

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cimerman, Z., Galic, N. & Bosner, B. (1997). Anal. Chim. Acta, 343, 145–153. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar