2,5-Dichloro­anilinium chloride monohydrate

Gowda, B.T.; Foro, S.; Saraswathi, B.S.; Terao, H.; Fuess, H.

doi:10.1107/S1600536809004395

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o516

doi:10.1107/S1600536809004395

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2,5-Dichloroanilinium chloride monohydrate

B. Thimme Gowda,^a ^* Sabine Foro,^b B. S. Saraswathi,^a Hiromitsu Terao ^c and Hartmut Fuess ^b

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany, and ^cFaculty of Integrated Arts and Sciences, Tokushima University, Minamijosanjima-cho, Tokushima 770-8502, Japan
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 4 February 2009; accepted 6 February 2009; online 13 February 2009)

The title compound, C₆H₆Cl₂N⁺·Cl⁻·H₂O, is composed of discrete cations, choride anions and water molecules, which are connected through N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonding. Two H atoms of the positively charged –NH₃⁺ group have two chloride acceptors and the other one has the O atom of the water molecule as acceptor. The chloride anions form hydrogen bonds with two H atoms from two different water molecules and two H atoms from two positively charged –NH₃⁺ groups.

Related literature

For water-free 2,5-dichloroanilinium chloride see: Gray & Jones (2002 ).

Experimental

Crystal data

C₆H₆Cl₂N⁺·Cl⁻·H₂O
M_r = 216.48
Monoclinic, P 2₁ /n
a = 7.679 (1) Å
b = 6.476 (1) Å
c = 19.060 (5) Å
β = 96.95 (3)°
V = 940.9 (3) Å³
Z = 4
Cu Kα radiation
μ = 8.39 mm⁻¹
T = 299 (2) K
0.35 × 0.30 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.109, T_max = 0.432
3331 measured reflections
1669 independent reflections
1421 reflections with I > 2σ(I)
R_int = 0.068
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.143
S = 1.10
1669 reflections
125 parameters
3 restraints
Only H-atom coordinates refined
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯Cl3ⁱ	0.92 (4)	2.24 (4)	3.123 (3)	162 (3)
N1—H12⋯Cl3	0.94 (4)	2.16 (4)	3.099 (3)	172 (3)
N1—H13⋯O1ⁱⁱ	0.88 (4)	1.82 (4)	2.699 (4)	175 (4)
O1—H1A⋯Cl3	0.85 (3)	2.37 (3)	3.212 (3)	172 (4)
O1—H1B⋯Cl3ⁱⁱⁱ	0.83 (3)	2.34 (3)	3.158 (3)	169 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4-PC (Enraf–Nonius, 1996 ); cell refinement: CAD-4-PC; data reduction: REDU4 (Stoe & Cie, 1987 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004395/bt2865sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004395/bt2865Isup2.hkl

checkCIF report

Comment top

The crystal structure of water free 2,5-dichloroanilinium chloride has been reported (Gray & Jones, 2002). We report herein the crystal structure of 2,5-dichloroanilinium chloride monohydrate. The title compound showed interesting H-bonding in its crystal structure (Fig. 1). Two H-atoms of the positively charged NH₃ group have two chloride acceptors and the other H has O atom acceptor of the water molecule, while chloride anions are linked by four-center hydrogen bonds, with each chloride forming H-bonding with two H-atoms, one each from two different water molecules and two H-atoms, one each from two positively charged NH₃ groups. This is in comparison with the usual set of hydrogen bonds from NH₃ to chloride leading to layer structure observed with water free 2,5-dichloroanilinium chloride (Gray & Jones, 2002), with a short Cl1..Cl3 contact. Further, the water free structure involved four weak interactions, namely the three hydrogen bonds H4···Cl3, H6···Cl2 and H3···Cl1 and the chlorine-chlorine interaction Cl2···Cl3. The crystal packing of (I) through N—H···Cl, O—H···Cl and N—H···O hydrogen bonding (Table 1) is shown in Fig.2

Related literature top

For water-free 2,5-dichloroanilinium chloride see: Gray & Jones (2002).

Experimental top

The solution of pure 2,5-dichloroaniline (0.02 mole) in ethanol (20 cc) was treated dropwise with dilute hydrochloric acid (>0.025 mole) with constant stirring. The resulting mixture was slowly evaporated at room temperature to obtain 2,5-dichloroanilinium hydrochloride monohydrate. The resultant solid was recrystallized to constant melting point from ethanol. The single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.

Computing details top

Data collection: CAD-4-PC (Enraf–Nonius, 1996); cell refinement: CAD-4-PC (Enraf–Nonius, 1996); data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom labeling scheme. The displacement ellipsoids are drawn at the 50% probability level. The H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Molecular packing of the title compound with hydrogen bonding shown as dashed lines.

2,5-Dichloroanilinium chloride monohydrate top

Crystal data top

C₆H₆Cl₂N⁺·Cl⁻·H₂O	F(000) = 440
M_r = 216.48	D_x = 1.528 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.679 (1) Å	θ = 6.0–20.3°
b = 6.476 (1) Å	µ = 8.39 mm⁻¹
c = 19.060 (5) Å	T = 299 K
β = 96.95 (3)°	Plate, colourless
V = 940.9 (3) Å³	0.35 × 0.30 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1421 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.068
Graphite monochromator	θ_max = 67.2°, θ_min = 4.7°
ω/2θ scans	h = −9→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.109, T_max = 0.432	l = −22→22
3331 measured reflections	3 standard reflections every 120 min
1669 independent reflections	intensity decay: 1.0%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Only H-atom coordinates refined
wR(F²) = 0.143	w = 1/[σ²(F_o²) + (0.0831P)² + 0.169P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.012
1669 reflections	Δρ_max = 0.39 e Å⁻³
125 parameters	Δρ_min = −0.49 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0126 (16)

Crystal data top

C₆H₆Cl₂N⁺·Cl⁻·H₂O	V = 940.9 (3) Å³
M_r = 216.48	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 7.679 (1) Å	µ = 8.39 mm⁻¹
b = 6.476 (1) Å	T = 299 K
c = 19.060 (5) Å	0.35 × 0.30 × 0.10 mm
β = 96.95 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1421 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.068
T_min = 0.109, T_max = 0.432	3 standard reflections every 120 min
3331 measured reflections	intensity decay: 1.0%
1669 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.143	Only H-atom coordinates refined
S = 1.10	Δρ_max = 0.39 e Å⁻³
1669 reflections	Δρ_min = −0.49 e Å⁻³
125 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
Cl1	0.64647 (11)	−0.35617 (13)	0.11963 (6)	0.0720 (4)
Cl2	0.84843 (12)	0.33419 (16)	−0.08256 (4)	0.0716 (4)
N1	0.8342 (3)	0.0359 (4)	0.16645 (11)	0.0476 (6)
H11	0.872 (4)	−0.079 (6)	0.1920 (19)	0.057*
H12	0.736 (5)	0.083 (5)	0.1868 (18)	0.057*
H13	0.917 (5)	0.128 (6)	0.179 (2)	0.057*
C1	0.7922 (3)	0.0096 (5)	0.09016 (13)	0.0441 (6)
C2	0.7056 (4)	−0.1657 (5)	0.06338 (18)	0.0529 (7)
C3	0.6664 (4)	−0.1873 (6)	−0.0093 (2)	0.0635 (9)
H3	0.604 (5)	−0.303 (7)	−0.024 (2)	0.076*
C4	0.7107 (4)	−0.0333 (6)	−0.05366 (16)	0.0626 (9)
H4	0.681 (5)	−0.046 (6)	−0.100 (2)	0.075*
C5	0.7943 (4)	0.1398 (5)	−0.02646 (15)	0.0534 (7)
C6	0.8371 (4)	0.1651 (5)	0.04598 (15)	0.0474 (6)
H6	0.905 (4)	0.288 (5)	0.065 (2)	0.057*
O1	0.0902 (3)	0.3197 (4)	0.19565 (15)	0.0697 (7)
H1A	0.200 (4)	0.301 (6)	0.206 (3)	0.084*
H1B	0.067 (5)	0.413 (6)	0.223 (2)	0.084*
Cl3	0.50259 (9)	0.21839 (12)	0.22100 (4)	0.0565 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0655 (6)	0.0603 (5)	0.0883 (6)	−0.0101 (3)	0.0009 (5)	0.0022 (4)
Cl2	0.0671 (6)	0.0981 (7)	0.0499 (4)	0.0101 (4)	0.0085 (4)	0.0145 (4)
N1	0.0485 (13)	0.0551 (13)	0.0379 (10)	0.0017 (11)	−0.0002 (9)	−0.0007 (10)
C1	0.0377 (13)	0.0528 (14)	0.0402 (11)	0.0065 (11)	−0.0015 (10)	−0.0062 (11)
C2	0.0400 (13)	0.0555 (16)	0.0615 (17)	0.0031 (12)	−0.0004 (13)	−0.0084 (13)
C3	0.0500 (17)	0.0694 (19)	0.0677 (19)	0.0019 (15)	−0.0065 (15)	−0.0270 (17)
C4	0.0522 (16)	0.086 (2)	0.0470 (14)	0.0111 (16)	−0.0034 (13)	−0.0205 (15)
C5	0.0436 (14)	0.076 (2)	0.0405 (13)	0.0130 (13)	0.0032 (12)	−0.0027 (13)
C6	0.0415 (13)	0.0578 (15)	0.0419 (13)	0.0044 (12)	0.0009 (11)	−0.0054 (12)
O1	0.0571 (14)	0.0722 (16)	0.0776 (15)	−0.0017 (11)	−0.0004 (12)	−0.0175 (12)
Cl3	0.0529 (5)	0.0671 (5)	0.0484 (4)	−0.0018 (3)	0.0015 (3)	−0.0101 (3)

Geometric parameters (Å, º) top

Cl1—C2	1.731 (3)	C3—C4	1.377 (6)
Cl2—C5	1.735 (3)	C3—H3	0.92 (4)
N1—C1	1.461 (3)	C4—C5	1.362 (5)
N1—H11	0.92 (4)	C4—H4	0.88 (4)
N1—H12	0.94 (4)	C5—C6	1.390 (4)
N1—H13	0.88 (4)	C6—H6	1.00 (4)
C1—C2	1.382 (4)	O1—H1A	0.85 (3)
C1—C6	1.383 (4)	O1—H1B	0.83 (3)
C2—C3	1.388 (5)

C1—N1—H11	117 (2)	C4—C3—H3	124 (3)
C1—N1—H12	111 (2)	C2—C3—H3	116 (3)
H11—N1—H12	105 (3)	C5—C4—C3	120.1 (3)
C1—N1—H13	114 (2)	C5—C4—H4	121 (3)
H11—N1—H13	104 (3)	C3—C4—H4	119 (3)
H12—N1—H13	105 (3)	C4—C5—C6	121.3 (3)
C2—C1—C6	121.2 (3)	C4—C5—Cl2	120.0 (2)
C2—C1—N1	120.1 (3)	C6—C5—Cl2	118.8 (3)
C6—C1—N1	118.7 (3)	C1—C6—C5	118.2 (3)
C1—C2—C3	119.2 (3)	C1—C6—H6	121 (2)
C1—C2—Cl1	120.5 (2)	C5—C6—H6	121 (2)
C3—C2—Cl1	120.3 (3)	H1A—O1—H1B	104 (4)
C4—C3—C2	120.0 (3)

C6—C1—C2—C3	1.3 (4)	C3—C4—C5—C6	0.2 (5)
N1—C1—C2—C3	179.8 (3)	C3—C4—C5—Cl2	−179.5 (3)
C6—C1—C2—Cl1	−178.6 (2)	C2—C1—C6—C5	−0.6 (4)
N1—C1—C2—Cl1	−0.2 (4)	N1—C1—C6—C5	−179.1 (3)
C1—C2—C3—C4	−1.3 (5)	C4—C5—C6—C1	−0.2 (4)
Cl1—C2—C3—C4	178.7 (3)	Cl2—C5—C6—C1	179.6 (2)
C2—C3—C4—C5	0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Cl3ⁱ	0.92 (4)	2.24 (4)	3.123 (3)	162 (3)
N1—H12···Cl3	0.94 (4)	2.16 (4)	3.099 (3)	172 (3)
N1—H13···O1ⁱⁱ	0.88 (4)	1.82 (4)	2.699 (4)	175 (4)
O1—H1A···Cl3	0.85 (3)	2.37 (3)	3.212 (3)	172 (4)
O1—H1B···Cl3ⁱⁱⁱ	0.83 (3)	2.34 (3)	3.158 (3)	169 (4)

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

Experimental details

Crystal data
Chemical formula	C₆H₆Cl₂N⁺·Cl⁻·H₂O
M_r	216.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	299
a, b, c (Å)	7.679 (1), 6.476 (1), 19.060 (5)
β (°)	96.95 (3)
V (Å³)	940.9 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	8.39
Crystal size (mm)	0.35 × 0.30 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.109, 0.432
No. of measured, independent and observed [I > 2σ(I)] reflections	3331, 1669, 1421
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.143, 1.10
No. of reflections	1669
No. of parameters	125
No. of restraints	3
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.49

Computer programs: CAD-4-PC (Enraf–Nonius, 1996), REDU4 (Stoe & Cie, 1987), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···Cl3ⁱ	0.92 (4)	2.24 (4)	3.123 (3)	162 (3)
N1—H12···Cl3	0.94 (4)	2.16 (4)	3.099 (3)	172 (3)
N1—H13···O1ⁱⁱ	0.88 (4)	1.82 (4)	2.699 (4)	175 (4)
O1—H1A···Cl3	0.85 (3)	2.37 (3)	3.212 (3)	172 (4)
O1—H1B···Cl3ⁱⁱⁱ	0.83 (3)	2.34 (3)	3.158 (3)	169 (4)

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

Acknowledgements

BTG thanks the Alexander von Humboldt Foundation, Bonn, Germany, for extensions of his research fellowship.

References

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Gray, L. & Jones, P. G. (2002). Z. Naturforsch. Teil B, 57, 73–82. CAS Google Scholar
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