2-(4-Chloro-benzo-yl)-1-(diamino-methyl-ene)hydrazinium chloride monohydrate.

In the cation of the title compound, C(8)H(10)ClN(4)O(+)·Cl(-)·H(2)O, the guanidinium group is planar (maximum deviation = 0.0001 Å) and nearly perpendicular to carboxamide group, making a dihedral angle of 87.0 (3)°. The N atoms of the guanidine fragment have a planar trigonal configuration and the N atom of the carboxamide group adopts a pyramidal configuration. In the crystal structure, inter-molecular N-H⋯O, N-H⋯Cl and O-H⋯Cl hydrogen bonds link the cations, anions and water mol-ecules into layers parallel to the bc plane.

Related literature

For a related structure, see: Kolev & Petrova (2003 ▶). For amino­guanidine structures, see: Bharatam et al. (2004 ▶); Koskinen et al. (1997 ▶); Hammerl et al. (2005 ▶); Macháčková et al. (2007 ▶); Murugavel et al. (2009a ▶,b ▶). For the preparation of guanyl hydrazides, see: Grinstein & Chipen (1961 ▶). For the application of guanyl hydrazides in the synthesis of 3-substituted 5-amino-1,2,4-triazoles, see: Dolzhenko et al. (2009 ▶).

Experimental

Crystal data

C8H10ClN4O+·Cl−·H2O

M = 267.12

Monoclinic,

a = 19.349 (4) Å

b = 4.3563 (9) Å

c = 14.516 (3) Å

β = 102.360 (3)°

V = 1195.2 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.54 mm−1

T = 100 K

0.40 × 0.30 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.814, T max = 0.924

9756 measured reflections

2330 independent reflections

2099 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.142

S = 1.17

2330 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810014108/cv2710sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014108/cv2710Isup2.hkl

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

C8H10ClN4O+·Cl−·H2O	F(000) = 552
Mr = 267.12	Dx = 1.484 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 195 reflections
a = 19.349 (4) Å	θ = 3–25°
b = 4.3563 (9) Å	µ = 0.54 mm−1
c = 14.516 (3) Å	T = 100 K
β = 102.360 (3)°	Plate, colourless
V = 1195.2 (4) Å3	0.40 × 0.30 × 0.15 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	2330 independent reflections
Radiation source: fine-focus sealed tube	2099 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −23→23
Tmin = 0.814, Tmax = 0.924	k = −5→5
9756 measured reflections	l = −17→17

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: difference Fourier map
wR(F2) = 0.142	H-atom parameters constrained
S = 1.17	w = 1/[σ2(Fo2) + (0.P)2 + 7.6548P] where P = (Fo2 + 2Fc2)/3
2330 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

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 > 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.

	x	y	z	Uiso*/Ueq
Cl1	0.04674 (6)	0.7630 (4)	0.43499 (8)	0.0378 (3)
Cl2	0.61291 (5)	0.8080 (2)	0.16436 (7)	0.0176 (2)
O1	0.23490 (15)	0.4393 (7)	0.1141 (2)	0.0206 (6)
N1	0.30500 (17)	0.8203 (8)	0.1875 (2)	0.0167 (7)
H1	0.3168	0.9410	0.2387	0.020*
N2	0.36010 (18)	0.7335 (8)	0.1466 (2)	0.0168 (7)
H2	0.3904	0.5813	0.1693	0.020*
N3	0.32072 (18)	1.0675 (8)	0.0221 (2)	0.0170 (7)
H3B	0.2901	1.1579	0.0524	0.020*
H3A	0.3270	1.1318	−0.0344	0.020*
N4	0.41145 (18)	0.7296 (8)	0.0186 (2)	0.0191 (8)
H4B	0.4390	0.5690	0.0416	0.023*
H4A	0.4156	0.8225	−0.0354	0.023*
C1	0.3636 (2)	0.8462 (9)	0.0616 (3)	0.0151 (8)
C2	0.2468 (2)	0.6400 (10)	0.1752 (3)	0.0167 (8)
C3	0.1974 (2)	0.6938 (10)	0.2392 (3)	0.0189 (9)
C4	0.1303 (2)	0.5694 (12)	0.2146 (3)	0.0255 (10)
H4	0.1166	0.4678	0.1573	0.031*
C5	0.0832 (2)	0.5933 (12)	0.2738 (3)	0.0288 (11)
H5	0.0379	0.5112	0.2564	0.035*
C6	0.1048 (2)	0.7415 (12)	0.3591 (3)	0.0248 (10)
C7	0.1710 (2)	0.8685 (12)	0.3853 (3)	0.0294 (11)
H7	0.1843	0.9706	0.4426	0.035*
C8	0.2176 (2)	0.8438 (12)	0.3260 (3)	0.0253 (10)
H8	0.2627	0.9273	0.3437	0.030*
O1W	0.48997 (16)	0.3347 (7)	0.1577 (2)	0.0256 (7)
H1W	0.5036	0.1484	0.1625	0.038*
H2W	0.5283	0.4382	0.1677	0.038*

	U11	U22	U33	U12	U13	U23
Cl1	0.0308 (6)	0.0615 (9)	0.0261 (6)	0.0026 (6)	0.0171 (5)	−0.0009 (6)
Cl2	0.0268 (5)	0.0130 (4)	0.0146 (5)	0.0001 (4)	0.0079 (4)	0.0004 (4)
O1	0.0231 (15)	0.0225 (16)	0.0159 (14)	0.0020 (13)	0.0038 (11)	−0.0030 (13)
N1	0.0226 (17)	0.0160 (17)	0.0134 (16)	0.0018 (15)	0.0078 (13)	−0.0013 (14)
N2	0.0253 (18)	0.0142 (17)	0.0126 (16)	0.0030 (14)	0.0079 (13)	0.0017 (13)
N3	0.0267 (18)	0.0169 (17)	0.0094 (15)	0.0041 (15)	0.0083 (13)	0.0026 (14)
N4	0.0297 (19)	0.0139 (17)	0.0172 (17)	0.0031 (15)	0.0125 (14)	0.0020 (14)
C1	0.022 (2)	0.0111 (19)	0.0118 (18)	−0.0043 (16)	0.0037 (15)	−0.0046 (15)
C2	0.023 (2)	0.017 (2)	0.0103 (18)	0.0039 (17)	0.0025 (15)	0.0039 (16)
C3	0.023 (2)	0.022 (2)	0.0126 (19)	0.0048 (18)	0.0052 (16)	0.0013 (17)
C4	0.024 (2)	0.035 (3)	0.017 (2)	0.000 (2)	0.0056 (17)	−0.011 (2)
C5	0.022 (2)	0.038 (3)	0.029 (2)	−0.002 (2)	0.0102 (18)	−0.002 (2)
C6	0.024 (2)	0.037 (3)	0.016 (2)	0.007 (2)	0.0109 (17)	0.0046 (19)
C7	0.032 (2)	0.042 (3)	0.016 (2)	0.001 (2)	0.0092 (18)	−0.006 (2)
C8	0.024 (2)	0.037 (3)	0.016 (2)	−0.004 (2)	0.0059 (17)	−0.0025 (19)
O1W	0.0256 (16)	0.0157 (15)	0.0359 (18)	0.0004 (13)	0.0076 (13)	0.0033 (14)

Cl1—C6	1.736 (4)	C2—C3	1.488 (5)
O1—C2	1.232 (5)	C3—C4	1.381 (6)
N1—C2	1.352 (5)	C3—C8	1.398 (6)
N1—N2	1.379 (4)	C4—C5	1.384 (6)
N1—H1	0.8999	C4—H4	0.9300
N2—C1	1.343 (5)	C5—C6	1.380 (7)
N2—H2	0.9001	C5—H5	0.9300
N3—C1	1.321 (5)	C6—C7	1.373 (7)
N3—H3B	0.9002	C7—C8	1.377 (6)
N3—H3A	0.9000	C7—H7	0.9300
N4—C1	1.324 (5)	C8—H8	0.9300
N4—H4B	0.8999	O1W—H1W	0.8517
N4—H4A	0.9002	O1W—H2W	0.8542
C2—N1—N2	118.8 (3)	C4—C3—C2	118.1 (4)
C2—N1—H1	120.3	C8—C3—C2	122.8 (4)
N2—N1—H1	115.6	C3—C4—C5	121.2 (4)
C1—N2—N1	119.4 (3)	C3—C4—H4	119.4
C1—N2—H2	116.6	C5—C4—H4	119.4
N1—N2—H2	123.2	C6—C5—C4	118.6 (4)
C1—N3—H3B	121.8	C6—C5—H5	120.7
C1—N3—H3A	115.4	C4—C5—H5	120.7
H3B—N3—H3A	122.7	C7—C6—C5	121.5 (4)
C1—N4—H4B	122.8	C7—C6—Cl1	119.7 (3)
C1—N4—H4A	116.1	C5—C6—Cl1	118.8 (4)
H4B—N4—H4A	121.1	C6—C7—C8	119.5 (4)
N3—C1—N4	120.9 (4)	C6—C7—H7	120.2
N3—C1—N2	121.0 (4)	C8—C7—H7	120.2
N4—C1—N2	118.2 (4)	C7—C8—C3	120.3 (4)
O1—C2—N1	122.0 (4)	C7—C8—H8	119.8
O1—C2—C3	121.0 (4)	C3—C8—H8	119.8
N1—C2—C3	117.1 (4)	H1W—O1W—H2W	104.3
C4—C3—C8	118.9 (4)
C2—N1—N2—C1	94.5 (4)	C2—C3—C4—C5	175.8 (4)
N1—N2—C1—N3	8.8 (6)	C3—C4—C5—C6	−0.8 (8)
N1—N2—C1—N4	−171.3 (3)	C4—C5—C6—C7	1.1 (8)
N2—N1—C2—O1	−15.4 (6)	C4—C5—C6—Cl1	−178.3 (4)
N2—N1—C2—C3	164.5 (3)	C5—C6—C7—C8	−1.1 (8)
O1—C2—C3—C4	−15.6 (6)	Cl1—C6—C7—C8	178.3 (4)
N1—C2—C3—C4	164.5 (4)	C6—C7—C8—C3	0.8 (8)
O1—C2—C3—C8	159.5 (4)	C4—C3—C8—C7	−0.5 (7)
N1—C2—C3—C8	−20.5 (6)	C2—C3—C8—C7	−175.5 (4)
C8—C3—C4—C5	0.5 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2i	0.90	2.36	3.194 (4)	154
N2—H2···O1W	0.90	2.24	3.031 (4)	146
N2—H2···Cl2ii	0.90	2.71	3.260 (4)	121
N3—H3B···O1iii	0.90	1.96	2.848 (3)	167
N3—H3A···Cl2iv	0.90	2.43	3.280 (4)	157
N4—H4B···O1W	0.90	2.04	2.834 (4)	147
N4—H4A···Cl2iv	0.90	2.44	3.286 (4)	156
O1W—H1W···Cl2v	0.85	2.58	3.292 (4)	142
O1W—H2W···Cl2	0.85	2.30	3.134 (4)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2i	0.90	2.36	3.194 (4)	154
N2—H2⋯O1W	0.90	2.24	3.031 (4)	146
N2—H2⋯Cl2ii	0.90	2.71	3.260 (4)	121
N3—H3B⋯O1iii	0.90	1.96	2.848 (3)	167
N3—H3A⋯Cl2iv	0.90	2.43	3.280 (4)	157
N4—H4B⋯O1W	0.90	2.04	2.834 (4)	147
N4—H4A⋯Cl2iv	0.90	2.44	3.286 (4)	156
O1W—H1W⋯Cl2v	0.85	2.58	3.292 (4)	142
O1W—H2W⋯Cl2	0.85	2.30	3.134 (4)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .