(E)-Ethyl N′-(3,4-dimethoxy­benzyl­idene)hydrazinecarboxyl­ate monohydrate

Lv, L.-P.; Zhang, Y.-Z.; Ding, X.-M.; Li, W.-W.; Hu, X.-C.

doi:10.1107/S1600536808034417

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2196

doi:10.1107/S1600536808034417

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(E)-Ethyl N′-(3,4-dimethoxybenzylidene)hydrazinecarboxylate monohydrate

Lu-Ping Lv,^a Yong-Zhao Zhang,^a Xiao-Min Ding,^a Wei-Wei Li ^a and Xian-Chao Hu ^b ^*

^aDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, and ^bResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 12 October 2008; accepted 21 October 2008; online 25 October 2008)

In the title compound, C₁₂H₁₆N₂O₄·H₂O, the molecular skeleton of the hydrazinecarboxylate is nearly planar [within 0.053 (3) Å]. In the crystal, chains propagating along the c axis arise, composed of alternating hydrazinecarboxylate molecules and crystalline water, which interact via N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For general background, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For a related structure, see Shang et al. (2007 ).

Experimental

Crystal data

C₁₂H₁₆N₂O₄·H₂O
M_r = 270.28
Orthorhombic, P n a 2₁
a = 7.211 (2) Å
b = 17.688 (5) Å
c = 11.026 (3) Å
V = 1406.3 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 193 (2) K
0.27 × 0.25 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.969, T_max = 0.976
7281 measured reflections
1312 independent reflections
1181 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.085
S = 1.07
1312 reflections
180 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1F⋯O3	0.833 (19)	2.14 (2)	2.899 (3)	151 (3)
N2—H2⋯O1Wⁱ	0.88	2.12	2.899 (3)	148
Symmetry code: (i) $[-x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 I, global. DOI: 10.1107/S1600536808034417/cv2464sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034417/cv2464Isup2.hkl

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attention for a long time due to their pharmacological activity (Parashar et al., 1988) and photochromic properties (Hadjoudis et al., 1987). Meanwhile, it is an important intermediate of 1,3,4-oxadiazoles, which have been reported to be compounds with versatile useful properties (Borg et al., 1999). As a further investigation of this type of derivatives, we report herein the crystal structure of the title compound.

In the title compound, C₁₂H₁₆N₂O₄ (I) .H₂O, the molecular skeleton of (I) is nearly planar. The main molecule, (I), adopts a trans configuration with respect to the C═N bond. The hydrazine carboxylic acid methyl ester group is slightly twisted away from the attached ring. The bond lengths and angles of the main molecule agree with those observed in (E)-methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate (Shang et al., 2007).

The crystal packing exhibits hydrogen-bonded chains extended along c axis and composed from alternating molecules of (I) and crystalline water, which interact via N-H···O [N···O 2.899 (3) Å] and O-H···O [O···O 2.899 (3) Å] hydrogen bonds (Table 1).

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see Shang et al. (2007).

Experimental top

3,4-Dimethoxybenzaldehyde (1.66g, 0.01mol) and ethyl hydrazinecarboxylate(1.04g, 0.01mol) were dissolved in stirred methanol (20ml) and left for 3h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Crystals suitable for X-ray analysis were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 458-460 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. Molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.

(E)-Ethyl N'-(3,4-dimethoxybenzylidene)hydrazinecarboxylate monohydrate top

Crystal data top

C₁₂H₁₆N₂O₄·H₂O	F(000) = 576
M_r = 270.28	D_x = 1.277 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1312 reflections
a = 7.211 (2) Å	θ = 2.2–25.5°
b = 17.688 (5) Å	µ = 0.10 mm⁻¹
c = 11.026 (3) Å	T = 193 K
V = 1406.3 (7) Å³	Block, colourless
Z = 4	0.27 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1312 independent reflections
Radiation source: fine-focus sealed tube	1181 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.969, T_max = 0.976	k = −20→20
7281 measured reflections	l = −13→12

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0551P)² + 0.0753P] where P = (F_o² + 2F_c²)/3
1312 reflections	(Δ/σ)_max < 0.001
180 parameters	Δρ_max = 0.16 e Å⁻³
3 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₂H₁₆N₂O₄·H₂O	V = 1406.3 (7) Å³
M_r = 270.28	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 7.211 (2) Å	µ = 0.10 mm⁻¹
b = 17.688 (5) Å	T = 193 K
c = 11.026 (3) Å	0.27 × 0.25 × 0.23 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1312 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1181 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.976	R_int = 0.026
7281 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	3 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.16 e Å⁻³
1312 reflections	Δρ_min = −0.15 e Å⁻³
180 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	1.0427 (4)	0.67958 (16)	0.2893 (3)	0.0656 (7)
H1A	1.1372	0.7154	0.3172	0.098*
H1B	0.9915	0.6969	0.2117	0.098*
H1C	1.0989	0.6296	0.2786	0.098*
C2	0.4765 (4)	0.69467 (15)	0.6084 (3)	0.0610 (6)
H2A	0.5117	0.7319	0.6701	0.091*
H2B	0.4388	0.6476	0.6482	0.091*
H2C	0.3730	0.7144	0.5603	0.091*
C3	0.6065 (3)	0.62962 (12)	0.4381 (2)	0.0458 (5)
C4	0.7529 (3)	0.62623 (13)	0.3535 (2)	0.0458 (6)
C5	0.4527 (3)	0.58339 (12)	0.4241 (2)	0.0462 (5)
H5	0.3536	0.5859	0.4806	0.055*
C6	0.7444 (3)	0.57723 (14)	0.2568 (2)	0.0514 (6)
H6	0.8428	0.5753	0.1995	0.062*
C7	0.5889 (3)	0.53002 (14)	0.2433 (2)	0.0519 (6)
H7	0.5833	0.4959	0.1769	0.062*
C8	0.4438 (3)	0.53255 (13)	0.3255 (2)	0.0469 (5)
C9	0.2842 (3)	0.48227 (14)	0.3094 (3)	0.0513 (6)
H9	0.2729	0.4534	0.2371	0.062*
C10	−0.1176 (4)	0.42102 (13)	0.4535 (2)	0.0511 (6)
C11	−0.4016 (4)	0.36234 (19)	0.5028 (3)	0.0719 (8)
H11A	−0.4699	0.4105	0.5130	0.086*
H11B	−0.3517	0.3471	0.5828	0.086*
C12	−0.5286 (5)	0.3030 (2)	0.4560 (4)	0.0882 (11)
H12A	−0.6307	0.2956	0.5134	0.132*
H12B	−0.4602	0.2555	0.4463	0.132*
H12C	−0.5786	0.3188	0.3773	0.132*
N1	0.1595 (3)	0.47690 (10)	0.3921 (2)	0.0520 (5)
N2	0.0153 (3)	0.42736 (11)	0.3681 (2)	0.0525 (5)
H2	0.0107	0.4012	0.3002	0.063*
O1	0.8976 (2)	0.67502 (9)	0.37704 (18)	0.0578 (5)
O2	0.6305 (2)	0.68036 (11)	0.53107 (17)	0.0620 (5)
O3	−0.1179 (3)	0.45274 (11)	0.55163 (18)	0.0689 (5)
O4	−0.2508 (2)	0.37243 (9)	0.41722 (18)	0.0582 (5)
O1W	0.0397 (3)	0.59890 (12)	0.6111 (2)	0.0667 (5)
H1E	0.003 (5)	0.6288 (18)	0.561 (3)	0.090 (12)*
H1F	0.030 (5)	0.5563 (13)	0.579 (3)	0.088 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0528 (15)	0.0662 (16)	0.0777 (18)	−0.0115 (12)	0.0121 (14)	−0.0002 (15)
C2	0.0693 (16)	0.0566 (14)	0.0570 (15)	−0.0026 (12)	0.0121 (15)	−0.0057 (13)
C3	0.0457 (12)	0.0442 (11)	0.0474 (12)	0.0005 (8)	−0.0055 (11)	−0.0020 (10)
C4	0.0389 (12)	0.0447 (10)	0.0537 (15)	0.0004 (9)	−0.0033 (10)	0.0030 (11)
C5	0.0414 (11)	0.0506 (12)	0.0466 (13)	−0.0001 (9)	−0.0005 (10)	0.0029 (10)
C6	0.0456 (12)	0.0538 (12)	0.0548 (15)	0.0026 (10)	0.0029 (11)	0.0000 (12)
C7	0.0536 (13)	0.0510 (12)	0.0513 (13)	0.0004 (10)	−0.0048 (12)	−0.0061 (11)
C8	0.0430 (12)	0.0462 (11)	0.0515 (13)	0.0010 (9)	−0.0065 (11)	0.0051 (10)
C9	0.0512 (12)	0.0483 (12)	0.0543 (14)	−0.0020 (10)	−0.0075 (12)	−0.0013 (11)
C10	0.0553 (14)	0.0453 (11)	0.0526 (14)	−0.0034 (10)	−0.0067 (12)	0.0022 (11)
C11	0.0618 (17)	0.082 (2)	0.0724 (19)	−0.0143 (14)	0.0081 (15)	0.0022 (15)
C12	0.0713 (19)	0.097 (2)	0.096 (3)	−0.0260 (18)	0.004 (2)	0.003 (2)
N1	0.0493 (11)	0.0485 (10)	0.0582 (13)	−0.0066 (8)	−0.0074 (11)	0.0029 (9)
N2	0.0500 (11)	0.0521 (11)	0.0554 (13)	−0.0116 (8)	−0.0024 (10)	−0.0037 (9)
O1	0.0451 (9)	0.0621 (10)	0.0661 (11)	−0.0105 (7)	0.0053 (9)	−0.0080 (9)
O2	0.0529 (10)	0.0723 (10)	0.0607 (12)	−0.0111 (8)	0.0041 (9)	−0.0181 (10)
O3	0.0744 (12)	0.0770 (11)	0.0553 (11)	−0.0204 (10)	0.0011 (10)	−0.0043 (10)
O4	0.0546 (10)	0.0570 (9)	0.0628 (12)	−0.0138 (7)	0.0022 (8)	−0.0010 (9)
O1W	0.0778 (13)	0.0662 (12)	0.0561 (12)	−0.0123 (10)	−0.0078 (11)	0.0050 (11)

Geometric parameters (Å, º) top

C1—O1	1.427 (3)	C7—H7	0.9500
C1—H1A	0.9800	C8—C9	1.465 (3)
C1—H1B	0.9800	C9—N1	1.284 (3)
C1—H1C	0.9800	C9—H9	0.9500
C2—O2	1.423 (3)	C10—O3	1.219 (3)
C2—H2A	0.9800	C10—N2	1.348 (3)
C2—H2B	0.9800	C10—O4	1.350 (3)
C2—H2C	0.9800	C11—O4	1.451 (4)
C3—O2	1.374 (3)	C11—C12	1.485 (5)
C3—C5	1.387 (3)	C11—H11A	0.9900
C3—C4	1.410 (3)	C11—H11B	0.9900
C4—C6	1.376 (4)	C12—H12A	0.9800
C4—O1	1.379 (3)	C12—H12B	0.9800
C5—C8	1.412 (4)	C12—H12C	0.9800
C5—H5	0.9500	N1—N2	1.385 (3)
C6—C7	1.406 (4)	N2—H2	0.8800
C6—H6	0.9500	O1W—H1E	0.812 (19)
C7—C8	1.385 (3)	O1W—H1F	0.833 (19)

O1—C1—H1A	109.5	C7—C8—C9	119.6 (2)
O1—C1—H1B	109.5	C5—C8—C9	121.0 (2)
H1A—C1—H1B	109.5	N1—C9—C8	120.6 (2)
O1—C1—H1C	109.5	N1—C9—H9	119.7
H1A—C1—H1C	109.5	C8—C9—H9	119.7
H1B—C1—H1C	109.5	O3—C10—N2	125.7 (2)
O2—C2—H2A	109.5	O3—C10—O4	123.7 (2)
O2—C2—H2B	109.5	N2—C10—O4	110.6 (2)
H2A—C2—H2B	109.5	O4—C11—C12	108.8 (3)
O2—C2—H2C	109.5	O4—C11—H11A	109.9
H2A—C2—H2C	109.5	C12—C11—H11A	109.9
H2B—C2—H2C	109.5	O4—C11—H11B	109.9
O2—C3—C5	124.7 (2)	C12—C11—H11B	109.9
O2—C3—C4	115.30 (19)	H11A—C11—H11B	108.3
C5—C3—C4	120.0 (2)	C11—C12—H12A	109.5
C6—C4—O1	125.0 (2)	C11—C12—H12B	109.5
C6—C4—C3	120.4 (2)	H12A—C12—H12B	109.5
O1—C4—C3	114.5 (2)	C11—C12—H12C	109.5
C3—C5—C8	119.8 (2)	H12A—C12—H12C	109.5
C3—C5—H5	120.1	H12B—C12—H12C	109.5
C8—C5—H5	120.1	C9—N1—N2	115.9 (2)
C4—C6—C7	119.5 (2)	C10—N2—N1	116.9 (2)
C4—C6—H6	120.3	C10—N2—H2	121.5
C7—C6—H6	120.3	N1—N2—H2	121.5
C8—C7—C6	120.9 (2)	C4—O1—C1	117.5 (2)
C8—C7—H7	119.5	C3—O2—C2	117.7 (2)
C6—C7—H7	119.5	C10—O4—C11	114.8 (2)
C7—C8—C5	119.3 (2)	H1E—O1W—H1F	106 (4)

O2—C3—C4—C6	179.8 (2)	C7—C8—C9—N1	171.3 (2)
C5—C3—C4—C6	0.0 (3)	C5—C8—C9—N1	−8.3 (3)
O2—C3—C4—O1	−0.4 (3)	C8—C9—N1—N2	−179.5 (2)
C5—C3—C4—O1	179.8 (2)	O3—C10—N2—N1	−3.1 (4)
O2—C3—C5—C8	−179.2 (2)	O4—C10—N2—N1	178.61 (19)
C4—C3—C5—C8	0.5 (3)	C9—N1—N2—C10	−179.8 (2)
O1—C4—C6—C7	179.7 (2)	C6—C4—O1—C1	5.4 (3)
C3—C4—C6—C7	−0.5 (3)	C3—C4—O1—C1	−174.4 (2)
C4—C6—C7—C8	0.5 (4)	C5—C3—O2—C2	−9.6 (3)
C6—C7—C8—C5	0.0 (4)	C4—C3—O2—C2	170.6 (2)
C6—C7—C8—C9	−179.6 (2)	O3—C10—O4—C11	2.3 (3)
C3—C5—C8—C7	−0.5 (3)	N2—C10—O4—C11	−179.4 (2)
C3—C5—C8—C9	179.1 (2)	C12—C11—O4—C10	−175.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1F···O3	0.83 (2)	2.14 (2)	2.899 (3)	151 (3)
O1W—H1E···O1ⁱ	0.81 (2)	2.31 (2)	3.086 (3)	160 (4)
N2—H2···O1Wⁱⁱ	0.88	2.12	2.899 (3)	148

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂O₄·H₂O
M_r	270.28
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	193
a, b, c (Å)	7.211 (2), 17.688 (5), 11.026 (3)
V (Å³)	1406.3 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.27 × 0.25 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.969, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	7281, 1312, 1181
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.085, 1.07
No. of reflections	1312
No. of parameters	180
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.15

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
O1W—H1F···O3	0.833 (19)	2.14 (2)	2.899 (3)	151 (3)
N2—H2···O1Wⁱ	0.88	2.12	2.899 (3)	147.6

Symmetry code: (i) −x, −y+1, z−1/2.

Acknowledgements

The authors thank Hangzhou Vocational and Technical College, China, for financial support.

References

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360. CrossRef CAS Web of Science Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar