Bis(2-amino-4,5-dimethyl­anilinium chloride) 4,5-dimethyl­benz­ene-1,2-diamine monohydrate

Ng, S.W.

doi:10.1107/S1600536809013816

organic compounds

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Volume 65| Part 5| May 2009| Page o1069

doi:10.1107/S1600536809013816

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Bis(2-amino-4,5-dimethylanilinium chloride) 4,5-dimethylbenzene-1,2-diamine monohydrate

Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 1 April 2009; accepted 13 April 2009; online 18 April 2009)

The title compound, 2C₈H₁₃N₂⁺·2Cl⁻·C₈H₁₂N₂·H₂O, is a hydrated 2:1 cocrystal of the 2-amino-4,5-dimethylanilinium chloride salt and the 4,5-dimethylbenzene-1,2-diamine free base. An intramolecular N—H⋯N hydrogen bond occurs in one of the organic molecules. In the crystal structure, the components are linked by N—H⋯Cl, N—H⋯N, N—H⋯O and O—H⋯Cl hydrogen bonds into a layered motif.

Related literature

4,5-Dimethylphenylene-1,2-diamine is used in the synthesis of benzimidazoles; see: El Ashry et al. (1986 ). The crystal structures of several metal complexes of 4,5-dimethylphenylene-1,2-diamine have been reported; see: Pérez-Cabré et al. (2004 ); Eremenko et al. (2005 ); Kiskin et al. (2006 ); Malkov et al. (2003 ); Mikhailova et al. (2002 ); Redshaw et al. (1992 ).

Experimental

Crystal data

2C₈H₁₃N₂⁺·2Cl⁻·C₈H₁₂N₂·H₂O
M_r = 499.52
Monoclinic, P 2₁ /n
a = 11.7102 (5) Å
b = 6.0938 (3) Å
c = 35.948 (1) Å
β = 91.257 (2)°
V = 2564.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 123 K
0.40 × 0.12 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.896, T_max = 0.994
16985 measured reflections
5877 independent reflections
3608 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.166
S = 1.06
5877 reflections
368 parameters
27 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl1	0.85 (2)	2.37 (2)	3.212 (3)	172 (4)
O1—H2⋯Cl1ⁱ	0.85 (4)	2.82 (3)	3.402 (3)	128 (4)
O1—H2⋯Cl1ⁱⁱ	0.85 (4)	2.73 (4)	3.331 (2)	129 (3)
N1—H12⋯Cl1ⁱ	0.88 (3)	2.81 (3)	3.661 (3)	164 (3)
N2—H21⋯Cl1	0.87 (2)	2.61 (3)	3.361 (3)	145 (3)
N2—H22⋯N1	0.87 (4)	2.49 (4)	2.810 (4)	102 (3)
N2—H22⋯Cl1ⁱⁱ	0.87 (4)	2.79 (4)	3.599 (3)	155 (3)
N3—H31⋯N2	0.89 (2)	2.08 (2)	2.927 (4)	160 (2)
N3—H32⋯Cl1ⁱ	0.89 (3)	2.22 (3)	3.092 (3)	168 (2)
N3—H33⋯Cl2	0.89 (2)	2.347 (19)	3.216 (3)	167 (2)
N4—H41⋯Cl2ⁱ	0.87 (2)	2.38 (3)	3.233 (3)	165 (3)
N4—H42⋯Cl1ⁱ	0.87 (3)	2.63 (3)	3.434 (3)	155 (3)
N5—H51⋯O1	0.88 (2)	1.88 (2)	2.758 (3)	172 (3)
N5—H52⋯Cl2ⁱⁱⁱ	0.89 (2)	2.354 (19)	3.242 (3)	176 (2)
N5—H53⋯Cl2	0.89 (2)	2.75 (3)	3.176 (3)	111 (2)
N5—H53⋯Cl2^iv	0.89 (2)	2.730 (19)	3.540 (3)	153 (2)
N6—H61⋯Cl2^iv	0.88 (3)	2.71 (3)	3.408 (3)	138 (2)
N6—H62⋯N1ⁱⁱ	0.88 (2)	2.45 (3)	3.277 (5)	156 (3)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013816/hb2941sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013816/hb2941Isup2.hkl

checkCIF report

Related literature top

4,5-Dimethylbenzene-1,2-diamine is used in the synthesis of benzimidazoles; see: El Ashry et al. (1986). The crystal structures of several metal complexes with 4,5-dimethylbenzene-1,2-diamine have been reported; see: Pérez-Cabré et al. (2004); Eremenko et al. (2005); Kiskin et al. (2006); Malkov et al. (2003); Mikhailova et al. (2002); Redshaw et al. (1992).

Experimental top

Colourless plates of (I) were unexpectedly isolated from the reaction of dibenzyltin dichloride (1 mmol) and 4,5-dimethylphenene-1,2-diamine in ethanol, in an attempt at synthesizing a tin complex. Atmospheric water was presumably incorporated into the crystal.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. The molecular structure of (I) showing 70% displacement ellipsoids Hydrogen atoms are drawn as spheres of arbitrary radius.

Bis(2-amino-4,5-dimethylanilinium chloride) 4,5-dimethylbenzene-1,2-diamine monohydrate top

Crystal data top

2C₈H₁₃N₂⁺·2Cl⁻·C₈H₁₂N₂·H₂O	F(000) = 1072
M_r = 499.52	D_x = 1.294 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1367 reflections
a = 11.7102 (5) Å	θ = 2.3–21.3°
b = 6.0938 (3) Å	µ = 0.28 mm⁻¹
c = 35.948 (1) Å	T = 123 K
β = 91.257 (2)°	Plate, colourless
V = 2564.7 (2) Å³	0.40 × 0.12 × 0.02 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	5877 independent reflections
Radiation source: fine-focus sealed tube	3608 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ω scans	θ_max = 27.5°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.896, T_max = 0.994	k = −7→7
16985 measured reflections	l = −46→46

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0711P)²] where P = (F_o² + 2F_c²)/3
5877 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 0.47 e Å⁻³
27 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

2C₈H₁₃N₂⁺·2Cl⁻·C₈H₁₂N₂·H₂O	V = 2564.7 (2) Å³
M_r = 499.52	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.7102 (5) Å	µ = 0.28 mm⁻¹
b = 6.0938 (3) Å	T = 123 K
c = 35.948 (1) Å	0.40 × 0.12 × 0.02 mm
β = 91.257 (2)°

Data collection top

Bruker SMART APEX diffractometer	5877 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3608 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.994	R_int = 0.087
16985 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	27 restraints
wR(F²) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.47 e Å⁻³
5877 reflections	Δρ_min = −0.45 e Å⁻³
368 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.34435 (7)	−0.08992 (14)	0.23602 (2)	0.0211 (2)
Cl2	0.73644 (7)	0.46400 (14)	0.21359 (2)	0.0195 (2)
O1	0.4381 (2)	0.3932 (4)	0.25526 (7)	0.0223 (5)
H1	0.407 (3)	0.269 (3)	0.2515 (12)	0.056 (16)*
H2	0.386 (3)	0.480 (5)	0.2618 (15)	0.09 (2)*
N1	0.1622 (3)	0.7021 (5)	0.15983 (8)	0.0221 (7)
H11	0.134 (3)	0.828 (3)	0.1521 (10)	0.045 (13)*
H12	0.206 (3)	0.723 (6)	0.1798 (8)	0.063 (16)*
N2	0.2902 (2)	0.3227 (5)	0.17615 (8)	0.0187 (6)
H21	0.309 (3)	0.188 (3)	0.1818 (10)	0.044 (13)*
H22	0.247 (4)	0.380 (6)	0.1931 (10)	0.077 (18)*
N3	0.4870 (2)	0.6160 (5)	0.18456 (8)	0.0182 (6)
H31	0.439 (2)	0.508 (4)	0.1786 (9)	0.047 (13)*
H32	0.454 (2)	0.696 (5)	0.2021 (7)	0.055 (15)*
H33	0.5496 (15)	0.557 (4)	0.1946 (8)	0.020 (9)*
N4	0.5951 (3)	1.0243 (5)	0.19219 (8)	0.0226 (7)
H41	0.623 (3)	1.156 (3)	0.1953 (9)	0.033 (11)*
H42	0.547 (3)	0.991 (5)	0.2094 (7)	0.034 (11)*
N5	0.6403 (2)	0.4368 (5)	0.29539 (7)	0.0192 (6)
H51	0.5748 (14)	0.436 (5)	0.2828 (8)	0.039 (12)*
H52	0.675 (2)	0.309 (3)	0.2918 (8)	0.017 (9)*
H53	0.684 (2)	0.543 (3)	0.2867 (10)	0.049 (14)*
N6	0.5083 (3)	0.7947 (5)	0.31996 (8)	0.0225 (7)
H61	0.549 (3)	0.828 (5)	0.3006 (7)	0.039 (12)*
H62	0.480 (3)	0.914 (3)	0.3300 (9)	0.037 (12)*
C1	0.1979 (3)	0.5659 (5)	0.13072 (8)	0.0163 (7)
C2	0.2533 (3)	0.3666 (5)	0.13923 (8)	0.0164 (7)
C3	0.2794 (3)	0.2259 (6)	0.11040 (9)	0.0176 (7)
H3	0.3158	0.0903	0.1161	0.021*
C4	0.2541 (3)	0.2765 (6)	0.07322 (9)	0.0181 (7)
C5	0.2002 (3)	0.4753 (6)	0.06478 (9)	0.0184 (7)
C6	0.1728 (3)	0.6154 (6)	0.09380 (9)	0.0182 (7)
H6	0.1356	0.7501	0.0881	0.022*
C7	0.2850 (3)	0.1172 (6)	0.04304 (9)	0.0240 (8)
H7A	0.3161	−0.0171	0.0543	0.036*
H7B	0.3423	0.1837	0.0271	0.036*
H7C	0.2166	0.0814	0.0281	0.036*
C8	0.1731 (3)	0.5393 (6)	0.02498 (9)	0.0238 (8)
H8A	0.1289	0.6758	0.0246	0.036*
H8B	0.1285	0.4225	0.0128	0.036*
H8C	0.2444	0.5610	0.0117	0.036*
C9	0.5147 (3)	0.7433 (5)	0.15144 (9)	0.0165 (7)
C10	0.4943 (3)	0.6604 (6)	0.11619 (9)	0.0178 (7)
H10	0.4577	0.5221	0.1135	0.021*
C11	0.5260 (3)	0.7745 (6)	0.08461 (9)	0.0189 (7)
C12	0.5794 (3)	0.9785 (6)	0.08938 (9)	0.0197 (7)
C13	0.5985 (3)	1.0614 (6)	0.12482 (9)	0.0207 (7)
H13	0.6342	1.2006	0.1275	0.025*
C14	0.5672 (3)	0.9480 (6)	0.15672 (9)	0.0185 (7)
C15	0.5057 (3)	0.6771 (6)	0.04653 (9)	0.0214 (8)
H15A	0.4568	0.5473	0.0485	0.032*
H15B	0.5789	0.6349	0.0360	0.032*
H15C	0.4681	0.7859	0.0303	0.032*
C16	0.6182 (3)	1.1097 (6)	0.05619 (10)	0.0284 (9)
H16A	0.6576	1.2428	0.0649	0.043*
H16B	0.5517	1.1506	0.0407	0.043*
H16C	0.6705	1.0208	0.0415	0.043*
C17	0.6155 (3)	0.4633 (6)	0.33487 (8)	0.0166 (7)
C18	0.6513 (3)	0.3053 (6)	0.35998 (9)	0.0164 (7)
H18	0.6924	0.1814	0.3514	0.020*
C19	0.6281 (3)	0.3241 (6)	0.39766 (9)	0.0176 (7)
C20	0.5686 (3)	0.5114 (6)	0.40946 (8)	0.0169 (7)
C21	0.5321 (3)	0.6663 (6)	0.38371 (9)	0.0183 (7)
H21A	0.4912	0.7907	0.3922	0.022*
C22	0.5531 (3)	0.6466 (5)	0.34573 (9)	0.0170 (7)
C23	0.6664 (3)	0.1477 (6)	0.42444 (9)	0.0226 (8)
H23A	0.7183	0.2110	0.4433	0.034*
H23B	0.7060	0.0321	0.4109	0.034*
H23C	0.5997	0.0853	0.4366	0.034*
C24	0.5461 (3)	0.5479 (6)	0.45022 (9)	0.0231 (8)
H24A	0.4901	0.6661	0.4529	0.035*
H24B	0.6175	0.5886	0.4632	0.035*
H24C	0.5161	0.4126	0.4611	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0203 (4)	0.0185 (4)	0.0246 (4)	0.0007 (3)	0.0029 (3)	0.0014 (3)
Cl2	0.0167 (4)	0.0210 (4)	0.0209 (4)	−0.0039 (3)	0.0022 (3)	0.0002 (3)
O1	0.0174 (12)	0.0246 (14)	0.0250 (13)	−0.0005 (12)	0.0000 (10)	0.0010 (11)
N1	0.0231 (16)	0.0224 (17)	0.0207 (16)	0.0022 (14)	−0.0007 (13)	−0.0035 (13)
N2	0.0186 (15)	0.0185 (16)	0.0189 (15)	−0.0029 (13)	−0.0023 (12)	0.0046 (12)
N3	0.0171 (14)	0.0151 (15)	0.0223 (15)	−0.0023 (13)	−0.0008 (12)	0.0013 (12)
N4	0.0234 (16)	0.0199 (17)	0.0244 (16)	−0.0070 (13)	0.0001 (13)	−0.0029 (13)
N5	0.0158 (14)	0.0259 (18)	0.0160 (14)	0.0036 (13)	−0.0005 (12)	−0.0020 (12)
N6	0.0245 (16)	0.0235 (17)	0.0196 (16)	0.0050 (14)	0.0012 (13)	0.0049 (13)
C1	0.0139 (15)	0.0179 (18)	0.0172 (16)	−0.0006 (14)	0.0002 (12)	0.0009 (14)
C2	0.0139 (16)	0.0182 (18)	0.0169 (16)	−0.0025 (13)	−0.0012 (12)	0.0040 (13)
C3	0.0126 (16)	0.0172 (18)	0.0229 (17)	0.0018 (13)	−0.0003 (13)	0.0033 (14)
C4	0.0165 (16)	0.0181 (18)	0.0197 (17)	−0.0043 (14)	0.0017 (13)	−0.0037 (14)
C5	0.0156 (16)	0.0206 (18)	0.0188 (16)	−0.0032 (14)	−0.0012 (13)	0.0009 (14)
C6	0.0148 (16)	0.0159 (18)	0.0236 (17)	−0.0010 (14)	−0.0034 (13)	0.0019 (14)
C7	0.0222 (18)	0.024 (2)	0.0257 (18)	0.0004 (16)	0.0005 (15)	−0.0042 (15)
C8	0.0251 (18)	0.026 (2)	0.0203 (17)	0.0016 (16)	0.0028 (14)	0.0003 (15)
C9	0.0132 (16)	0.0161 (17)	0.0203 (17)	0.0007 (13)	0.0010 (13)	0.0025 (13)
C10	0.0101 (15)	0.0176 (18)	0.0257 (18)	0.0018 (13)	0.0007 (13)	−0.0021 (14)
C11	0.0137 (16)	0.0206 (19)	0.0222 (17)	0.0020 (14)	−0.0004 (13)	0.0008 (14)
C12	0.0138 (16)	0.0219 (19)	0.0233 (17)	0.0058 (14)	0.0007 (13)	0.0066 (14)
C13	0.0148 (16)	0.0168 (18)	0.0305 (19)	0.0019 (14)	−0.0011 (14)	0.0033 (15)
C14	0.0120 (15)	0.0168 (18)	0.0267 (17)	0.0019 (14)	−0.0008 (13)	−0.0025 (14)
C15	0.0212 (18)	0.0211 (19)	0.0219 (18)	0.0018 (15)	0.0012 (14)	−0.0011 (14)
C16	0.028 (2)	0.028 (2)	0.030 (2)	−0.0002 (17)	0.0019 (16)	0.0093 (16)
C17	0.0121 (15)	0.0220 (18)	0.0156 (15)	0.0002 (14)	−0.0005 (12)	−0.0016 (14)
C18	0.0126 (16)	0.0174 (18)	0.0193 (16)	−0.0002 (13)	0.0004 (13)	−0.0028 (14)
C19	0.0133 (16)	0.0175 (17)	0.0219 (17)	−0.0045 (14)	−0.0023 (13)	0.0019 (14)
C20	0.0125 (15)	0.0212 (18)	0.0171 (16)	−0.0028 (14)	0.0000 (12)	−0.0022 (14)
C21	0.0095 (15)	0.0218 (19)	0.0236 (17)	−0.0007 (14)	0.0005 (13)	−0.0037 (14)
C22	0.0115 (15)	0.0197 (18)	0.0198 (17)	−0.0034 (14)	0.0004 (13)	0.0004 (14)
C23	0.0237 (18)	0.022 (2)	0.0220 (18)	−0.0005 (15)	−0.0026 (14)	0.0032 (14)
C24	0.0235 (18)	0.028 (2)	0.0178 (17)	0.0007 (16)	0.0019 (14)	−0.0021 (15)

Geometric parameters (Å, º) top

O1—H1	0.85 (1)	C8—H8A	0.9800
O1—H2	0.85 (4)	C8—H8B	0.9800
N1—C1	1.406 (4)	C8—H8C	0.9800
N1—H11	0.88 (1)	C9—C10	1.380 (4)
N1—H12	0.87 (4)	C9—C14	1.401 (5)
N2—C2	1.412 (4)	C10—C11	1.389 (4)
N2—H21	0.87 (1)	C10—H10	0.9500
N2—H22	0.87 (4)	C11—C12	1.400 (5)
N3—C9	1.463 (4)	C11—C15	1.506 (4)
N3—H31	0.89 (3)	C12—C13	1.384 (5)
N3—H32	0.89 (3)	C12—C16	1.514 (5)
N3—H33	0.89 (1)	C13—C14	1.395 (5)
N4—C14	1.390 (4)	C13—H13	0.9500
N4—H41	0.88 (1)	C15—H15A	0.9800
N4—H42	0.87 (3)	C15—H15B	0.9800
N5—C17	1.464 (4)	C15—H15C	0.9800
N5—H51	0.88 (1)	C16—H16A	0.9800
N5—H52	0.89 (1)	C16—H16B	0.9800
N5—H53	0.89 (1)	C16—H16C	0.9800
N6—C22	1.388 (4)	C17—C18	1.379 (5)
N6—H61	0.88 (3)	C17—C22	1.395 (5)
N6—H62	0.88 (1)	C18—C19	1.392 (4)
C1—C6	1.387 (4)	C18—H18	0.9500
C1—C2	1.407 (5)	C19—C20	1.407 (5)
C2—C3	1.384 (4)	C19—C23	1.505 (5)
C3—C4	1.397 (4)	C20—C21	1.383 (5)
C3—H3	0.9500	C20—C24	1.511 (4)
C4—C5	1.396 (5)	C21—C22	1.398 (4)
C4—C7	1.505 (4)	C21—H21A	0.9500
C5—C6	1.391 (4)	C23—H23A	0.9800
C5—C8	1.510 (4)	C23—H23B	0.9800
C6—H6	0.9500	C23—H23C	0.9800
C7—H7A	0.9800	C24—H24A	0.9800
C7—H7B	0.9800	C24—H24B	0.9800
C7—H7C	0.9800	C24—H24C	0.9800

H1—O1—H2	107.4 (17)	C9—C10—C11	121.5 (3)
C1—N1—H11	113 (3)	C9—C10—H10	119.2
C1—N1—H12	121 (3)	C11—C10—H10	119.2
H11—N1—H12	110.0 (17)	C10—C11—C12	118.1 (3)
C2—N2—H21	118 (3)	C10—C11—C15	120.4 (3)
C2—N2—H22	114 (3)	C12—C11—C15	121.5 (3)
H21—N2—H22	111.0 (17)	C13—C12—C11	120.0 (3)
C9—N3—H31	110 (2)	C13—C12—C16	119.2 (3)
C9—N3—H32	113 (2)	C11—C12—C16	120.9 (3)
H31—N3—H32	107.1 (15)	C12—C13—C14	122.4 (3)
C9—N3—H33	111 (2)	C12—C13—H13	118.8
H31—N3—H33	108.4 (15)	C14—C13—H13	118.8
H32—N3—H33	107.4 (14)	N4—C14—C13	121.9 (3)
C14—N4—H41	120 (2)	N4—C14—C9	121.0 (3)
C14—N4—H42	115 (2)	C13—C14—C9	116.9 (3)
H41—N4—H42	111.9 (16)	C11—C15—H15A	109.5
C17—N5—H51	108 (2)	C11—C15—H15B	109.5
C17—N5—H52	110 (2)	H15A—C15—H15B	109.5
H51—N5—H52	108.5 (15)	C11—C15—H15C	109.5
C17—N5—H53	113 (2)	H15A—C15—H15C	109.5
H51—N5—H53	109.2 (15)	H15B—C15—H15C	109.5
H52—N5—H53	108.2 (14)	C12—C16—H16A	109.5
C22—N6—H61	119 (2)	C12—C16—H16B	109.5
C22—N6—H62	114 (2)	H16A—C16—H16B	109.5
H61—N6—H62	110.3 (16)	C12—C16—H16C	109.5
C6—C1—N1	121.6 (3)	H16A—C16—H16C	109.5
C6—C1—C2	118.9 (3)	H16B—C16—H16C	109.5
N1—C1—C2	119.4 (3)	C18—C17—C22	122.0 (3)
C3—C2—C1	118.7 (3)	C18—C17—N5	119.6 (3)
C3—C2—N2	121.2 (3)	C22—C17—N5	118.4 (3)
C1—C2—N2	119.8 (3)	C17—C18—C19	121.1 (3)
C2—C3—C4	122.3 (3)	C17—C18—H18	119.5
C2—C3—H3	118.9	C19—C18—H18	119.5
C4—C3—H3	118.9	C18—C19—C20	117.9 (3)
C3—C4—C5	119.0 (3)	C18—C19—C23	120.1 (3)
C3—C4—C7	119.9 (3)	C20—C19—C23	121.9 (3)
C5—C4—C7	121.2 (3)	C21—C20—C19	120.0 (3)
C6—C5—C4	118.7 (3)	C21—C20—C24	119.4 (3)
C6—C5—C8	120.3 (3)	C19—C20—C24	120.6 (3)
C4—C5—C8	120.9 (3)	C20—C21—C22	122.5 (3)
C1—C6—C5	122.5 (3)	C20—C21—H21A	118.8
C1—C6—H6	118.8	C22—C21—H21A	118.8
C5—C6—H6	118.8	N6—C22—C17	121.8 (3)
C4—C7—H7A	109.5	N6—C22—C21	121.6 (3)
C4—C7—H7B	109.5	C17—C22—C21	116.5 (3)
H7A—C7—H7B	109.5	C19—C23—H23A	109.5
C4—C7—H7C	109.5	C19—C23—H23B	109.5
H7A—C7—H7C	109.5	H23A—C23—H23B	109.5
H7B—C7—H7C	109.5	C19—C23—H23C	109.5
C5—C8—H8A	109.5	H23A—C23—H23C	109.5
C5—C8—H8B	109.5	H23B—C23—H23C	109.5
H8A—C8—H8B	109.5	C20—C24—H24A	109.5
C5—C8—H8C	109.5	C20—C24—H24B	109.5
H8A—C8—H8C	109.5	H24A—C24—H24B	109.5
H8B—C8—H8C	109.5	C20—C24—H24C	109.5
C10—C9—C14	121.1 (3)	H24A—C24—H24C	109.5
C10—C9—N3	121.1 (3)	H24B—C24—H24C	109.5
C14—C9—N3	117.8 (3)

C6—C1—C2—C3	−0.9 (5)	C11—C12—C13—C14	0.5 (5)
N1—C1—C2—C3	174.7 (3)	C16—C12—C13—C14	−178.7 (3)
C6—C1—C2—N2	173.5 (3)	C12—C13—C14—N4	174.6 (3)
N1—C1—C2—N2	−10.9 (5)	C12—C13—C14—C9	0.0 (5)
C1—C2—C3—C4	1.0 (5)	C10—C9—C14—N4	−175.3 (3)
N2—C2—C3—C4	−173.4 (3)	N3—C9—C14—N4	1.9 (5)
C2—C3—C4—C5	−0.3 (5)	C10—C9—C14—C13	−0.6 (5)
C2—C3—C4—C7	179.7 (3)	N3—C9—C14—C13	176.6 (3)
C3—C4—C5—C6	−0.5 (5)	C22—C17—C18—C19	−1.1 (5)
C7—C4—C5—C6	179.5 (3)	N5—C17—C18—C19	−179.3 (3)
C3—C4—C5—C8	178.8 (3)	C17—C18—C19—C20	−1.0 (5)
C7—C4—C5—C8	−1.2 (5)	C17—C18—C19—C23	179.0 (3)
N1—C1—C6—C5	−175.3 (3)	C18—C19—C20—C21	2.0 (5)
C2—C1—C6—C5	0.1 (5)	C23—C19—C20—C21	−178.1 (3)
C4—C5—C6—C1	0.6 (5)	C18—C19—C20—C24	−176.8 (3)
C8—C5—C6—C1	−178.8 (3)	C23—C19—C20—C24	3.2 (5)
C14—C9—C10—C11	0.8 (5)	C19—C20—C21—C22	−0.8 (5)
N3—C9—C10—C11	−176.3 (3)	C24—C20—C21—C22	177.9 (3)
C9—C10—C11—C12	−0.3 (5)	C18—C17—C22—N6	−173.9 (3)
C9—C10—C11—C15	178.3 (3)	N5—C17—C22—N6	4.2 (5)
C10—C11—C12—C13	−0.3 (5)	C18—C17—C22—C21	2.3 (5)
C15—C11—C12—C13	−178.9 (3)	N5—C17—C22—C21	−179.6 (3)
C10—C11—C12—C16	178.8 (3)	C20—C21—C22—N6	174.9 (3)
C15—C11—C12—C16	0.3 (5)	C20—C21—C22—C17	−1.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.85 (2)	2.37 (2)	3.212 (3)	172 (4)
O1—H2···Cl1ⁱ	0.85 (4)	2.82 (3)	3.402 (3)	128 (4)
O1—H2···Cl1ⁱⁱ	0.85 (4)	2.73 (4)	3.331 (2)	129 (3)
N1—H12···Cl1ⁱ	0.88 (3)	2.81 (3)	3.661 (3)	164 (3)
N2—H21···Cl1	0.87 (2)	2.61 (3)	3.361 (3)	145 (3)
N2—H22···N1	0.87 (4)	2.49 (4)	2.810 (4)	102 (3)
N2—H22···Cl1ⁱⁱ	0.87 (4)	2.79 (4)	3.599 (3)	155 (3)
N3—H31···N2	0.89 (2)	2.08 (2)	2.927 (4)	160 (2)
N3—H32···Cl1ⁱ	0.89 (3)	2.22 (3)	3.092 (3)	168 (2)
N3—H33···Cl2	0.89 (2)	2.35 (2)	3.216 (3)	167 (2)
N4—H41···Cl2ⁱ	0.87 (2)	2.38 (3)	3.233 (3)	165 (3)
N4—H42···Cl1ⁱ	0.87 (3)	2.63 (3)	3.434 (3)	155 (3)
N5—H51···O1	0.88 (2)	1.88 (2)	2.758 (3)	172 (3)
N5—H52···Cl2ⁱⁱⁱ	0.89 (2)	2.35 (2)	3.242 (3)	176 (2)
N5—H53···Cl2	0.89 (2)	2.75 (3)	3.176 (3)	111 (2)
N5—H53···Cl2^iv	0.89 (2)	2.73 (2)	3.540 (3)	153 (2)
N6—H61···Cl2^iv	0.88 (3)	2.71 (3)	3.408 (3)	138 (2)
N6—H62···N1ⁱⁱ	0.88 (2)	2.45 (3)	3.277 (5)	156 (3)

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

Experimental details

Crystal data
Chemical formula	2C₈H₁₃N₂⁺·2Cl⁻·C₈H₁₂N₂·H₂O
M_r	499.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	11.7102 (5), 6.0938 (3), 35.948 (1)
β (°)	91.257 (2)
V (Å³)	2564.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.40 × 0.12 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.896, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	16985, 5877, 3608
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.166, 1.06
No. of reflections	5877
No. of parameters	368
No. of restraints	27
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.45

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.85 (2)	2.37 (2)	3.212 (3)	172 (4)
O1—H2···Cl1ⁱ	0.85 (4)	2.82 (3)	3.402 (3)	128 (4)
O1—H2···Cl1ⁱⁱ	0.85 (4)	2.73 (4)	3.331 (2)	129 (3)
N1—H12···Cl1ⁱ	0.88 (3)	2.81 (3)	3.661 (3)	164 (3)
N2—H21···Cl1	0.87 (2)	2.61 (3)	3.361 (3)	145 (3)
N2—H22···N1	0.87 (4)	2.49 (4)	2.810 (4)	102 (3)
N2—H22···Cl1ⁱⁱ	0.87 (4)	2.79 (4)	3.599 (3)	155 (3)
N3—H31···N2	0.89 (2)	2.08 (2)	2.927 (4)	160 (2)
N3—H32···Cl1ⁱ	0.89 (3)	2.22 (3)	3.092 (3)	168 (2)
N3—H33···Cl2	0.89 (2)	2.347 (19)	3.216 (3)	167 (2)
N4—H41···Cl2ⁱ	0.87 (2)	2.38 (3)	3.233 (3)	165 (3)
N4—H42···Cl1ⁱ	0.87 (3)	2.63 (3)	3.434 (3)	155 (3)
N5—H51···O1	0.88 (2)	1.88 (2)	2.758 (3)	172 (3)
N5—H52···Cl2ⁱⁱⁱ	0.89 (2)	2.354 (19)	3.242 (3)	176 (2)
N5—H53···Cl2	0.89 (2)	2.75 (3)	3.176 (3)	111 (2)
N5—H53···Cl2^iv	0.89 (2)	2.730 (19)	3.540 (3)	153 (2)
N6—H61···Cl2^iv	0.88 (3)	2.71 (3)	3.408 (3)	138 (2)
N6—H62···N1ⁱⁱ	0.88 (2)	2.45 (3)	3.277 (5)	156 (3)

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

Acknowledgements

We thank the University of Malaya for supporting this study.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2-amino-4,5-di­methyl­anilinium chloride) 4,5-di­methyl­benz­ene-1,2-di­amine monohydrate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Bis(2-amino-4,5-dimethylanilinium chloride) 4,5-dimethylbenzene-1,2-diamine monohydrate