4-Chloro-anilinium (4-chloro-phen-yl)guanidinium dichloride hemihydrate.

In the title hydrated molecular salt, C(6)H(7)ClN(+)·C(7)H(9)ClN(3) (+)·2Cl(-)·0.5H(2)O, the water O atom lies on a crystallographic twofold axis. In the crystal, inter-molecular N-H⋯Cl and O-H⋯Cl hydrogen bonds form layers perpendicular to the ac plane in which both the water mol-ecule and the chloride anion are involved in connecting the layers into a three-dimensional structure.

Related literature

For applications of guanidine-containing compounds, see: Yonehara & Otake (1966 ▶); Berlinck (1995 ▶); Gobbi & Frenking (1993 ▶). For related structures, see: Ploug-Sørenson & Andersen 1985 ▶; Kolev et al. (1997 ▶); Glidewell et al. (2005 ▶); Smith et al. (2005 ▶).

Experimental

Crystal data

C6H7ClN+·C7H9ClN3 +·2Cl−·0.5H2O

M = 379.11

Monoclinic,

a = 41.297 (8) Å

b = 4.2089 (8) Å

c = 23.695 (5) Å

β = 120.164 (2)°

V = 3560.8 (12) Å3

Z = 8

Mo Kα radiation

μ = 0.67 mm−1

T = 298 K

0.51 × 0.50 × 0.34 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.727, T max = 0.805

8167 measured reflections

3078 independent reflections

2495 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.122

S = 1.03

3078 reflections

211 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007774/hg2652sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007774/hg2652Isup2.hkl

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

C6H7ClN+·C7H9ClN3+·2Cl−·0.5H2O	F(000) = 1560
Mr = 379.11	Dx = 1.414 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2794 reflections
a = 41.297 (8) Å	θ = 2.6–24.3°
b = 4.2089 (8) Å	µ = 0.67 mm−1
c = 23.695 (5) Å	T = 298 K
β = 120.164 (2)°	Block, colorless
V = 3560.8 (12) Å3	0.51 × 0.50 × 0.34 mm
Z = 8

Bruker SMART CCD area-detector diffractometer	3078 independent reflections
Radiation source: fine-focus sealed tube	2495 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −45→48
Tmin = 0.727, Tmax = 0.805	k = −5→4
8167 measured reflections	l = −27→28

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0657P)2 + 0.9195P] where P = (Fo2 + 2Fc2)/3
3078 reflections	(Δ/σ)max = 0.001
211 parameters	Δρmax = 0.33 e Å−3
1 restraint	Δρmin = −0.22 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	0.073762 (19)	0.49131 (14)	0.32708 (3)	0.0542 (2)
Cl2	0.062005 (17)	−0.51049 (14)	0.49527 (3)	0.0496 (2)
Cl3	0.20900 (2)	0.7771 (2)	0.72411 (4)	0.0787 (3)
Cl4	0.26245 (2)	0.1128 (3)	0.59514 (5)	0.0943 (3)
O1	0.0000	0.9261 (7)	0.7500	0.0535 (6)
H14A	−0.0188 (6)	0.815 (7)	0.7317 (14)	0.074 (10)*
N1	0.06411 (5)	1.1656 (6)	0.69506 (9)	0.0560 (6)
H1A	0.0648	1.1745	0.7319	0.067*
N2	0.02658 (6)	1.2676 (6)	0.58408 (9)	0.0583 (6)
H2A	0.0051	1.3206	0.5519	0.070*
H2B	0.0450	1.2324	0.5777	0.070*
N3	0.00277 (6)	1.2948 (6)	0.65192 (10)	0.0614 (6)
H3A	−0.0186	1.3477	0.6193	0.074*
H3B	0.0055	1.2777	0.6902	0.074*
N4	0.09760 (8)	−0.0049 (7)	0.43996 (17)	0.0644 (7)
C1	0.19749 (9)	−0.0652 (8)	0.48977 (15)	0.0711 (8)
H1B	0.2122	−0.1407	0.4731	0.085*
C2	0.15937 (8)	−0.0937 (7)	0.45442 (14)	0.0649 (7)
H2C	0.1480	−0.1909	0.4137	0.078*
C3	0.13796 (7)	0.0206 (5)	0.47893 (13)	0.0473 (6)
C4	0.15458 (8)	0.1594 (7)	0.53908 (13)	0.0604 (7)
H4C	0.1399	0.2353	0.5557	0.073*
C5	0.19272 (8)	0.1877 (7)	0.57510 (13)	0.0649 (7)
H5A	0.2040	0.2820	0.6161	0.078*
C6	0.21393 (8)	0.0766 (6)	0.55030 (13)	0.0569 (7)
C7	0.16604 (7)	0.8951 (6)	0.71382 (12)	0.0500 (6)
C8	0.16519 (8)	1.0740 (6)	0.76169 (13)	0.0572 (7)
H8A	0.1873	1.1340	0.7988	0.069*
C9	0.13103 (7)	1.1630 (7)	0.75378 (12)	0.0567 (7)
H9A	0.1301	1.2838	0.7858	0.068*
C10	0.09795 (6)	1.0742 (6)	0.69845 (11)	0.0429 (5)
C11	0.09949 (7)	0.8967 (6)	0.65113 (11)	0.0482 (6)
H11A	0.0775	0.8364	0.6137	0.058*
C12	0.13380 (7)	0.8084 (6)	0.65932 (13)	0.0522 (6)
H12A	0.1348	0.6886	0.6273	0.063*
C13	0.03129 (7)	1.2401 (6)	0.64323 (11)	0.0455 (6)
H4D	0.0856 (16)	0.130 (14)	0.446 (3)	0.17 (2)*
H4B	0.0890 (13)	−0.130 (12)	0.457 (2)	0.14 (2)*
H4A	0.0872 (15)	−0.110 (14)	0.400 (3)	0.18 (2)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0552 (4)	0.0610 (4)	0.0393 (4)	−0.0094 (3)	0.0185 (3)	0.0031 (3)
Cl2	0.0461 (4)	0.0655 (4)	0.0406 (3)	0.0053 (3)	0.0243 (3)	0.0064 (3)
Cl3	0.0503 (4)	0.1045 (6)	0.0858 (6)	0.0173 (4)	0.0377 (4)	0.0099 (5)
Cl4	0.0518 (5)	0.1166 (7)	0.0872 (6)	−0.0050 (5)	0.0146 (4)	−0.0111 (5)
O1	0.0472 (16)	0.0582 (16)	0.0483 (15)	0.000	0.0191 (13)	0.000
N1	0.0399 (12)	0.0949 (17)	0.0320 (10)	0.0124 (12)	0.0172 (9)	0.0028 (11)
N2	0.0430 (12)	0.0954 (17)	0.0388 (11)	0.0095 (11)	0.0223 (10)	0.0160 (11)
N3	0.0434 (12)	0.1009 (18)	0.0432 (11)	0.0155 (12)	0.0241 (10)	0.0109 (12)
N4	0.0506 (15)	0.0518 (14)	0.081 (2)	−0.0028 (12)	0.0254 (15)	0.0001 (14)
C1	0.0595 (19)	0.093 (2)	0.0647 (18)	−0.0002 (17)	0.0344 (16)	−0.0173 (17)
C2	0.0610 (18)	0.0809 (19)	0.0507 (16)	−0.0073 (16)	0.0266 (14)	−0.0191 (15)
C3	0.0495 (15)	0.0382 (12)	0.0510 (14)	−0.0007 (10)	0.0230 (12)	0.0069 (11)
C4	0.0640 (18)	0.0716 (18)	0.0497 (15)	0.0065 (15)	0.0315 (14)	−0.0041 (14)
C5	0.0687 (19)	0.0749 (19)	0.0416 (14)	0.0009 (16)	0.0207 (14)	−0.0103 (13)
C6	0.0506 (15)	0.0593 (16)	0.0502 (15)	−0.0015 (13)	0.0174 (13)	0.0017 (13)
C7	0.0422 (14)	0.0550 (14)	0.0540 (15)	0.0063 (12)	0.0251 (12)	0.0086 (13)
C8	0.0439 (15)	0.0668 (17)	0.0461 (15)	0.0004 (13)	0.0116 (12)	−0.0033 (13)
C9	0.0479 (15)	0.0759 (18)	0.0364 (13)	0.0103 (14)	0.0137 (12)	−0.0065 (13)
C10	0.0394 (13)	0.0513 (13)	0.0351 (12)	0.0064 (11)	0.0167 (11)	0.0063 (10)
C11	0.0423 (14)	0.0536 (13)	0.0414 (13)	−0.0010 (12)	0.0155 (11)	−0.0049 (11)
C12	0.0545 (16)	0.0547 (15)	0.0514 (15)	0.0049 (12)	0.0295 (13)	−0.0057 (12)
C13	0.0404 (13)	0.0579 (14)	0.0382 (12)	0.0012 (11)	0.0197 (11)	0.0034 (11)

Cl3—C7	1.738 (2)	C1—H1B	0.9300
Cl4—C6	1.740 (3)	C2—C3	1.366 (4)
O1—H14A	0.820 (17)	C2—H2C	0.9300
N1—C13	1.331 (3)	C3—C4	1.364 (4)
N1—C10	1.412 (3)	C4—C5	1.369 (4)
N1—H1A	0.8600	C4—H4C	0.9300
N2—C13	1.320 (3)	C5—C6	1.359 (4)
N2—H2A	0.8600	C5—H5A	0.9300
N2—H2B	0.8600	C7—C12	1.359 (4)
N3—C13	1.314 (3)	C7—C8	1.377 (4)
N3—H3A	0.8600	C8—C9	1.379 (4)
N3—H3B	0.8600	C8—H8A	0.9300
N4—C3	1.448 (4)	C9—C10	1.387 (3)
N4—H4D	0.82 (6)	C9—H9A	0.9300
N4—H4B	0.84 (5)	C10—C11	1.375 (3)
N4—H4A	0.93 (6)	C11—C12	1.381 (3)
C1—C2	1.367 (4)	C11—H11A	0.9300
C1—C6	1.377 (4)	C12—H12A	0.9300
C13—N1—C10	129.5 (2)	C6—C5—C4	119.4 (3)
C13—N1—H1A	115.2	C6—C5—H5A	120.3
C10—N1—H1A	115.2	C4—C5—H5A	120.3
C13—N2—H2A	120.0	C5—C6—C1	120.8 (3)
C13—N2—H2B	120.0	C5—C6—Cl4	120.0 (2)
H2A—N2—H2B	120.0	C1—C6—Cl4	119.2 (2)
C13—N3—H3A	120.0	C12—C7—C8	120.8 (2)
C13—N3—H3B	120.0	C12—C7—Cl3	120.0 (2)
H3A—N3—H3B	120.0	C8—C7—Cl3	119.2 (2)
C3—N4—H4D	116 (4)	C7—C8—C9	119.0 (2)
C3—N4—H4B	112 (3)	C7—C8—H8A	120.5
H4D—N4—H4B	85 (5)	C9—C8—H8A	120.5
C3—N4—H4A	119 (3)	C8—C9—C10	120.6 (2)
H4D—N4—H4A	120 (5)	C8—C9—H9A	119.7
H4B—N4—H4A	95 (4)	C10—C9—H9A	119.7
C2—C1—C6	119.3 (3)	C11—C10—C9	119.3 (2)
C2—C1—H1B	120.3	C11—C10—N1	123.5 (2)
C6—C1—H1B	120.3	C9—C10—N1	117.2 (2)
C3—C2—C1	120.0 (3)	C10—C11—C12	119.8 (2)
C3—C2—H2C	120.0	C10—C11—H11A	120.1
C1—C2—H2C	120.0	C12—C11—H11A	120.1
C4—C3—C2	120.1 (3)	C7—C12—C11	120.5 (2)
C4—C3—N4	120.8 (3)	C7—C12—H12A	119.7
C2—C3—N4	119.1 (3)	C11—C12—H12A	119.7
C3—C4—C5	120.4 (2)	N3—C13—N2	119.1 (2)
C3—C4—H4C	119.8	N3—C13—N1	118.3 (2)
C5—C4—H4C	119.8	N2—C13—N1	122.6 (2)
C6—C1—C2—C3	0.6 (5)	C7—C8—C9—C10	−0.1 (4)
C1—C2—C3—C4	−0.9 (4)	C8—C9—C10—C11	−0.3 (4)
C1—C2—C3—N4	178.4 (3)	C8—C9—C10—N1	177.9 (2)
C2—C3—C4—C5	0.5 (4)	C13—N1—C10—C11	−34.1 (4)
N4—C3—C4—C5	−178.8 (3)	C13—N1—C10—C9	147.8 (3)
C3—C4—C5—C6	0.1 (4)	C9—C10—C11—C12	0.2 (4)
C4—C5—C6—C1	−0.4 (4)	N1—C10—C11—C12	−177.8 (2)
C4—C5—C6—Cl4	179.6 (2)	C8—C7—C12—C11	−0.4 (4)
C2—C1—C6—C5	0.0 (5)	Cl3—C7—C12—C11	179.0 (2)
C2—C1—C6—Cl4	−180.0 (2)	C10—C11—C12—C7	0.1 (4)
C12—C7—C8—C9	0.4 (4)	C10—N1—C13—N3	174.8 (3)
Cl3—C7—C8—C9	−179.0 (2)	C10—N1—C13—N2	−6.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H14A···Cl1i	0.82 (2)	2.36 (2)	3.1797 (17)	177 (3)
N2—H2A···Cl2i	0.86	2.54	3.324 (2)	152
N3—H3A···Cl2i	0.86	2.48	3.281 (2)	155
N4—H4D···Cl2ii	0.82 (6)	2.39 (5)	3.185 (3)	164 (5)
N2—H2B···Cl2iii	0.86	2.62	3.2457 (19)	131
N4—H4A···Cl1iv	0.93 (6)	2.27 (6)	3.158 (3)	160 (5)
N1—H1A···Cl1v	0.86	2.52	3.283 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H14A⋯Cl1i	0.82 (2)	2.36 (2)	3.1797 (17)	177 (3)
N2—H2A⋯Cl2i	0.86	2.54	3.324 (2)	152
N3—H3A⋯Cl2i	0.86	2.48	3.281 (2)	155
N4—H4D⋯Cl2ii	0.82 (6)	2.39 (5)	3.185 (3)	164 (5)
N2—H2B⋯Cl2iii	0.86	2.62	3.2457 (19)	131
N4—H4A⋯Cl1iv	0.93 (6)	2.27 (6)	3.158 (3)	160 (5)
N1—H1A⋯Cl1v	0.86	2.52	3.283 (2)	148

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