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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2064.
Published online 2008 October 4. doi:  10.1107/S1600536808031474
PMCID: PMC2959714

(Methoxy­carbon­yl)hydrazinium chloride monohydrate

Abstract

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 [triangle]); Hadjoudis et al. (1987 [triangle]). For the crystal structure of a nickel methyl­carbazate complex, see: Song et al. (2003 [triangle]).

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Object name is e-64-o2064-scheme1.jpg

Experimental

Crystal data

  • C2H7N2O2 +·Cl·H2O
  • M r = 144.56
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2064-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.080
  • S = 1.04
  • 1445 reflections
  • 97 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031474/ci2680sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031474/ci2680Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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).

Refinement

O- and N-bound H atoms were located in a difference map and were refined with O-H and N2-H2 distances restrained to 0.85 (2) Å and 0.87 (1) Å, respectively. The methyl H atoms were disordered over two orientations and their occupancies were initially refined and later fixed at 0.75 and 0.25, with C-H = 0.96 å and Uiso(H) = 1.5Ueq(C).

Figures

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.

Crystal data

C2H7N2O2+·Cl·H2OF(000) = 304
Mr = 144.56Dx = 1.494 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1122 reflections
a = 12.6621 (13) Åθ = 1.6–25.0°
b = 7.6444 (7) ŵ = 0.53 mm1
c = 6.6948 (7) ÅT = 123 K
β = 97.199 (4)°Block, colourless
V = 642.91 (11) Å30.28 × 0.24 × 0.23 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer1445 independent reflections
Radiation source: fine-focus sealed tube1360 reflections with I > 2σ(I)
graphiteRint = 0.021
[var phi] and ω scansθmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)h = −14→15
Tmin = 0.861, Tmax = 0.881k = −9→9
7105 measured reflectionsl = −8→8

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0389P)2 + 0.2916P] where P = (Fo2 + 2Fc2)/3
1445 reflections(Δ/σ)max = 0.001
97 parametersΔρmax = 0.59 e Å3
3 restraintsΔρmin = −0.30 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
O10.83051 (8)0.17986 (13)0.89504 (15)0.0351 (2)
O20.88232 (9)−0.10131 (13)0.86201 (17)0.0380 (3)
N10.69905 (11)0.07910 (18)1.1544 (2)0.0343 (3)
H1A0.6428 (16)0.110 (3)1.061 (3)0.047 (6)*
H1B0.6731 (14)0.031 (3)1.267 (3)0.042 (5)*
H1C0.7342 (16)0.174 (3)1.203 (3)0.047 (5)*
N20.77164 (10)−0.04049 (16)1.08177 (18)0.0337 (3)
H20.7430 (14)−0.1422 (16)1.064 (3)0.045 (5)*
C10.82736 (11)0.02547 (18)0.93676 (19)0.0287 (3)
C20.93930 (14)−0.0505 (2)0.6966 (3)0.0441 (4)
H2A0.9769−0.14980.65300.066*0.75
H2B0.98920.04050.74020.066*0.75
H2C0.8896−0.00860.58690.066*0.75
H2D0.92690.07120.66700.066*0.25
H2E0.9146−0.11910.57990.066*0.25
H2F1.0141−0.07000.73320.066*0.25
O1W0.55461 (12)0.1831 (2)0.8367 (2)0.0561 (4)
H1W0.4948 (17)0.216 (4)0.867 (4)0.095 (10)*
H2W0.537 (3)0.109 (4)0.751 (4)0.115 (12)*
Cl10.64630 (3)−0.09761 (5)0.54932 (5)0.03710 (14)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0401 (6)0.0279 (5)0.0388 (5)−0.0011 (4)0.0106 (4)0.0032 (4)
O20.0416 (6)0.0320 (5)0.0426 (6)0.0058 (4)0.0136 (5)0.0020 (4)
N10.0351 (7)0.0369 (7)0.0323 (6)−0.0037 (5)0.0101 (5)−0.0023 (5)
N20.0381 (7)0.0275 (6)0.0371 (6)−0.0032 (5)0.0113 (5)0.0010 (5)
C10.0276 (6)0.0293 (6)0.0285 (6)−0.0009 (5)0.0013 (5)0.0005 (5)
C20.0430 (9)0.0471 (9)0.0455 (8)0.0020 (7)0.0182 (7)−0.0039 (7)
O1W0.0544 (8)0.0635 (9)0.0482 (7)0.0110 (7)−0.0022 (6)−0.0172 (6)
Cl10.0391 (2)0.0390 (2)0.0344 (2)0.00628 (14)0.00935 (14)0.00276 (13)

Geometric parameters (Å, °)

O1—C11.2146 (17)C2—H2A0.96
O2—C11.3272 (17)C2—H2B0.96
O2—C21.4486 (19)C2—H2C0.96
N1—N21.4243 (17)C2—H2D0.96
N1—H1A0.92 (2)C2—H2E0.96
N1—H1B0.93 (2)C2—H2F0.96
N1—H1C0.89 (2)O1W—H1W0.847 (17)
N2—C11.3661 (17)O1W—H2W0.819 (18)
N2—H20.860 (9)
C1—O2—C2115.31 (12)H2B—C2—H2C109.5
N2—N1—H1A114.1 (12)O2—C2—H2D109.5
N2—N1—H1B109.4 (12)H2A—C2—H2D141.1
H1A—N1—H1B109.2 (16)H2B—C2—H2D56.3
N2—N1—H1C109.5 (13)H2C—C2—H2D56.3
H1A—N1—H1C110.5 (18)O2—C2—H2E109.5
H1B—N1—H1C103.5 (17)H2A—C2—H2E56.3
C1—N2—N1114.74 (12)H2B—C2—H2E141.1
C1—N2—H2118.7 (13)H2C—C2—H2E56.3
N1—N2—H2110.5 (13)H2D—C2—H2E109.5
O1—C1—O2126.08 (13)O2—C2—H2F109.5
O1—C1—N2123.84 (13)H2A—C2—H2F56.3
O2—C1—N2109.90 (12)H2B—C2—H2F56.3
O2—C2—H2A109.5H2C—C2—H2F141.1
O2—C2—H2B109.5H2D—C2—H2F109.5
H2A—C2—H2B109.5H2E—C2—H2F109.5
O2—C2—H2C109.5H1W—O1W—H2W102 (3)
H2A—C2—H2C109.5
C2—O2—C1—O1−8.8 (2)N1—N2—C1—O112.3 (2)
C2—O2—C1—N2175.92 (13)N1—N2—C1—O2−172.27 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1W0.92 (2)1.84 (2)2.743 (2)167 (2)
N1—H1B···Cl1i0.93 (2)2.20 (2)3.1152 (14)168 (2)
N1—H1C···O1ii0.89 (2)2.00 (2)2.8443 (17)158 (2)
O1W—H1W···Cl1iii0.85 (2)2.41 (3)3.2172 (16)161 (3)
N2—H2···Cl1iv0.86 (1)2.33 (1)3.1833 (13)171 (2)
O1W—H2W···Cl10.82 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2680).

References

  • Bruker (2002). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.
  • Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Song, J. C., Zhang, T. L., Zhang, J. G., Ma, G. X., Li, Y. F. & Yu, K. B. (2003). Huaxue Xuebao, 61, 1444–1448.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography