(Methoxy­carbon­yl)hydrazinium chloride monohydrate

Xie, J.-W.; Lv, L.-P.; Yu, W.-B.; Li, W.-W.; Hu, X.-C.

doi:10.1107/S1600536808031474

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2064

doi:10.1107/S1600536808031474

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(Methoxycarbonyl)hydrazinium chloride monohydrate

Jian-Wu Xie,^a Lu-Ping Lv,^a Wen-Bo Yu,^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 21 September 2008; accepted 29 September 2008; online 4 October 2008)

In the title compound, C₂H₇N₂O₂⁺·Cl⁻·H₂O, the non-H atoms of the cation are approximately coplanar. The organic cations, chloride ions and water molecules are linked into a two-dimensional network parallel to the bc plane by N—H⋯O, N—H⋯Cl and O—H⋯Cl hydrogen bonds.

Related literature

For applications of benzaldehydehydrazone derivatives, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ). For the crystal structure of a nickel methylcarbazate complex, see: Song et al. (2003 ).

Experimental

Crystal data

C₂H₇N₂O₂⁺·Cl⁻·H₂O
M_r = 144.56
Monoclinic, P 2₁ /c
a = 12.6621 (13) Å
b = 7.6444 (7) Å
c = 6.6948 (7) Å
β = 97.199 (4)°
V = 642.91 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 123 (2) K
0.28 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.861, T_max = 0.881
7105 measured reflections
1445 independent reflections
1360 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.04
1445 reflections
97 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1W	0.92 (2)	1.84 (2)	2.743 (2)	167 (2)
N1—H1B⋯Cl1ⁱ	0.93 (2)	2.20 (2)	3.1152 (14)	168 (2)
N1—H1C⋯O1ⁱⁱ	0.89 (2)	2.00 (2)	2.8443 (17)	158 (2)
O1W—H1W⋯Cl1ⁱⁱⁱ	0.85 (2)	2.41 (3)	3.2172 (16)	161 (3)
N2—H2⋯Cl1^iv	0.86 (1)	2.33 (1)	3.1833 (13)	171 (2)
O1W—H2W⋯Cl1	0.82 (2)	2.58 (3)	3.1959 (14)	133 (3)
Symmetry codes: (i) x, y, z+1; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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/S1600536808031474/ci2680sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031474/ci2680Isup2.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 their photochromic properties (Hadjoudis et al., 1987). The title compound is an important intermediate in the synthesis of benzaldehydehydrazone derivatives. We report here the crystal structure of the title compound (Fig. 1).

In the cation, atoms O1, O2, N2, C1 and C2 are coplanar (r.m.s. deviation 0.029 Å) and atom N1 deviates by 0.260 (2) Å from the C1/C2/O1/O2/N2 plane. The bond lengths and angles in the organic cation are comparable to those in a related structure (Song et al., 2003).

The molecules are linked into a two-dimensional network parallel to the bc plane by N–H···O, N—H···Cl and O—H···Cl hydrogen bonds involving the water molecule and chloride ions (Table 1 and Fig.2).

Related literature top

For applications of benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987). For the crystal structure of a nickel methylcarbazate complex, see: Song et al. (2003).

Experimental top

Methyl hydrazinecarboxylate (0.90 g, 0.01 mol) was dissolved in ethanol- dilute HCl and single crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature (m.p. 463–465 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. The molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atomic numbering. Hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the c axis. Hydrogen bonds are shown as dashed lines.

(Methoxycarbonyl)hydrazinium chloride monohydrate top

Crystal data top

C₂H₇N₂O₂⁺·Cl⁻·H₂O	F(000) = 304
M_r = 144.56	D_x = 1.494 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1122 reflections
a = 12.6621 (13) Å	θ = 1.6–25.0°
b = 7.6444 (7) Å	µ = 0.53 mm⁻¹
c = 6.6948 (7) Å	T = 123 K
β = 97.199 (4)°	Block, colourless
V = 642.91 (11) Å³	0.28 × 0.24 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1445 independent reflections
Radiation source: fine-focus sealed tube	1360 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→15
T_min = 0.861, T_max = 0.881	k = −9→9
7105 measured reflections	l = −8→8

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0389P)² + 0.2916P] where P = (F_o² + 2F_c²)/3
1445 reflections	(Δ/σ)_max = 0.001
97 parameters	Δρ_max = 0.59 e Å⁻³
3 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₂H₇N₂O₂⁺·Cl⁻·H₂O	V = 642.91 (11) Å³
M_r = 144.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.6621 (13) Å	µ = 0.53 mm⁻¹
b = 7.6444 (7) Å	T = 123 K
c = 6.6948 (7) Å	0.28 × 0.24 × 0.23 mm
β = 97.199 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1445 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1360 reflections with I > 2σ(I)
T_min = 0.861, T_max = 0.881	R_int = 0.021
7105 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	3 restraints
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.59 e Å⁻³
1445 reflections	Δρ_min = −0.30 e Å⁻³
97 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	Occ. (<1)
O1	0.83051 (8)	0.17986 (13)	0.89504 (15)	0.0351 (2)
O2	0.88232 (9)	−0.10131 (13)	0.86201 (17)	0.0380 (3)
N1	0.69905 (11)	0.07910 (18)	1.1544 (2)	0.0343 (3)
H1A	0.6428 (16)	0.110 (3)	1.061 (3)	0.047 (6)*
H1B	0.6731 (14)	0.031 (3)	1.267 (3)	0.042 (5)*
H1C	0.7342 (16)	0.174 (3)	1.203 (3)	0.047 (5)*
N2	0.77164 (10)	−0.04049 (16)	1.08177 (18)	0.0337 (3)
H2	0.7430 (14)	−0.1422 (16)	1.064 (3)	0.045 (5)*
C1	0.82736 (11)	0.02547 (18)	0.93676 (19)	0.0287 (3)
C2	0.93930 (14)	−0.0505 (2)	0.6966 (3)	0.0441 (4)
H2A	0.9769	−0.1498	0.6530	0.066*	0.75
H2B	0.9892	0.0405	0.7402	0.066*	0.75
H2C	0.8896	−0.0086	0.5869	0.066*	0.75
H2D	0.9269	0.0712	0.6670	0.066*	0.25
H2E	0.9146	−0.1191	0.5799	0.066*	0.25
H2F	1.0141	−0.0700	0.7332	0.066*	0.25
O1W	0.55461 (12)	0.1831 (2)	0.8367 (2)	0.0561 (4)
H1W	0.4948 (17)	0.216 (4)	0.867 (4)	0.095 (10)*
H2W	0.537 (3)	0.109 (4)	0.751 (4)	0.115 (12)*
Cl1	0.64630 (3)	−0.09761 (5)	0.54932 (5)	0.03710 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0401 (6)	0.0279 (5)	0.0388 (5)	−0.0011 (4)	0.0106 (4)	0.0032 (4)
O2	0.0416 (6)	0.0320 (5)	0.0426 (6)	0.0058 (4)	0.0136 (5)	0.0020 (4)
N1	0.0351 (7)	0.0369 (7)	0.0323 (6)	−0.0037 (5)	0.0101 (5)	−0.0023 (5)
N2	0.0381 (7)	0.0275 (6)	0.0371 (6)	−0.0032 (5)	0.0113 (5)	0.0010 (5)
C1	0.0276 (6)	0.0293 (6)	0.0285 (6)	−0.0009 (5)	0.0013 (5)	0.0005 (5)
C2	0.0430 (9)	0.0471 (9)	0.0455 (8)	0.0020 (7)	0.0182 (7)	−0.0039 (7)
O1W	0.0544 (8)	0.0635 (9)	0.0482 (7)	0.0110 (7)	−0.0022 (6)	−0.0172 (6)
Cl1	0.0391 (2)	0.0390 (2)	0.0344 (2)	0.00628 (14)	0.00935 (14)	0.00276 (13)

Geometric parameters (Å, º) top

O1—C1	1.2146 (17)	C2—H2A	0.96
O2—C1	1.3272 (17)	C2—H2B	0.96
O2—C2	1.4486 (19)	C2—H2C	0.96
N1—N2	1.4243 (17)	C2—H2D	0.96
N1—H1A	0.92 (2)	C2—H2E	0.96
N1—H1B	0.93 (2)	C2—H2F	0.96
N1—H1C	0.89 (2)	O1W—H1W	0.847 (17)
N2—C1	1.3661 (17)	O1W—H2W	0.819 (18)
N2—H2	0.860 (9)

C1—O2—C2	115.31 (12)	H2B—C2—H2C	109.5
N2—N1—H1A	114.1 (12)	O2—C2—H2D	109.5
N2—N1—H1B	109.4 (12)	H2A—C2—H2D	141.1
H1A—N1—H1B	109.2 (16)	H2B—C2—H2D	56.3
N2—N1—H1C	109.5 (13)	H2C—C2—H2D	56.3
H1A—N1—H1C	110.5 (18)	O2—C2—H2E	109.5
H1B—N1—H1C	103.5 (17)	H2A—C2—H2E	56.3
C1—N2—N1	114.74 (12)	H2B—C2—H2E	141.1
C1—N2—H2	118.7 (13)	H2C—C2—H2E	56.3
N1—N2—H2	110.5 (13)	H2D—C2—H2E	109.5
O1—C1—O2	126.08 (13)	O2—C2—H2F	109.5
O1—C1—N2	123.84 (13)	H2A—C2—H2F	56.3
O2—C1—N2	109.90 (12)	H2B—C2—H2F	56.3
O2—C2—H2A	109.5	H2C—C2—H2F	141.1
O2—C2—H2B	109.5	H2D—C2—H2F	109.5
H2A—C2—H2B	109.5	H2E—C2—H2F	109.5
O2—C2—H2C	109.5	H1W—O1W—H2W	102 (3)
H2A—C2—H2C	109.5

C2—O2—C1—O1	−8.8 (2)	N1—N2—C1—O1	12.3 (2)
C2—O2—C1—N2	175.92 (13)	N1—N2—C1—O2	−172.27 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1W	0.92 (2)	1.84 (2)	2.743 (2)	167 (2)
N1—H1B···Cl1ⁱ	0.93 (2)	2.20 (2)	3.1152 (14)	168 (2)
N1—H1C···O1ⁱⁱ	0.89 (2)	2.00 (2)	2.8443 (17)	158 (2)
O1W—H1W···Cl1ⁱⁱⁱ	0.85 (2)	2.41 (3)	3.2172 (16)	161 (3)
N2—H2···Cl1^iv	0.86 (1)	2.33 (1)	3.1833 (13)	171 (2)
O1W—H2W···Cl1	0.82 (2)	2.58 (3)	3.1959 (14)	133 (3)

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂H₇N₂O₂⁺·Cl⁻·H₂O
M_r	144.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	12.6621 (13), 7.6444 (7), 6.6948 (7)
β (°)	97.199 (4)
V (Å³)	642.91 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.28 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.861, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	7105, 1445, 1360
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.05
No. of reflections	1445
No. of parameters	97
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)	0.59, −0.30

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
N1—H1A···O1W	0.92 (2)	1.84 (2)	2.743 (2)	167 (2)
N1—H1B···Cl1ⁱ	0.93 (2)	2.20 (2)	3.1152 (14)	168 (2)
N1—H1C···O1ⁱⁱ	0.89 (2)	2.00 (2)	2.8443 (17)	158 (2)
O1W—H1W···Cl1ⁱⁱⁱ	0.85 (2)	2.41 (3)	3.2172 (16)	161 (3)
N2—H2···Cl1^iv	0.86 (1)	2.33 (1)	3.1833 (13)	171 (2)
O1W—H2W···Cl1	0.82 (2)	2.58 (3)	3.1959 (14)	133 (3)

Symmetry codes: (i) x, y, z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y−1/2, z+1/2.

Acknowledgements

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

References

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Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
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