(4-Chloro­phen­yl)methanaminium chloride hemihydrate

Souissi, S.; Smirani Sta, W.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536810021100

organic compounds

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Volume 66| Part 7| July 2010| Page o1627

doi:10.1107/S1600536810021100

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(4-Chlorophenyl)methanaminium chloride hemihydrate

Sofiane Souissi,^a Wajda Smirani Sta,^a Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bPetrochemical Research Chair, College of Science, King Saud University, Riyadh, Saudi Arabia
^*Correspondence e-mail: wajda_sta@yahoo.fr

(Received 1 June 2010; accepted 2 June 2010; online 16 June 2010)

In the title hydrated salt, C₇H₉ClN⁺·Cl⁻·0.5H₂O, the water O atom lies on a crystallographic twofold axis. In the crystal, the monoprotonated 4-chlorobenzylammonium cation forms N—H⋯Cl and N—H⋯O hydrogen bonds and the water molecule forms O—H⋯Cl hydrogen bonds, generating layers lying parallel to the bc plane.

Related literature

For the properties of benzylamines, see: Markwardt et al. (2005 ). For a related structure, see: Dhaouadi et al. (2008 ).

Experimental

Crystal data

C₇H₉ClN⁺·Cl⁻·0.5H₂O
M_r = 187.06
Monoclinic, C 2/c
a = 30.462 (2) Å
b = 4.890 (3) Å
c = 11.738 (2) Å
β = 99.97 (3)°
V = 1722.1 (11) Å³
Z = 8
Ag Kα radiation
λ = 0.56085 Å
μ = 0.35 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
5908 measured reflections
4207 independent reflections
2217 reflections with I > 2σ(I)
R_int = 0.031
2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.130
S = 1.00
4207 reflections
101 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯Cl1ⁱ	0.89	2.60	3.2930 (19)	136
N—H0A⋯Cl1ⁱⁱ	0.89	2.78	3.417 (2)	130
N—H0B⋯O	0.89	2.04	2.866 (2)	155
N—H0C⋯Cl1ⁱⁱⁱ	0.89	2.26	3.144 (2)	175
O—H1⋯Cl1	0.85 (3)	2.28 (3)	3.1230 (18)	171 (3)
Symmetry codes: (i) $[-x, y-1, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+1, z+{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021100/hb5481sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810021100/hb5481Isup2.hkl

checkCIF report

Comment top

Derivatives of benzylamine were found to be competitive inhibitors of the proteolytic enzymes trypsin, plasmin, and thrombin. So, the 4-chlorobenzylamine is a strong thrombin inhibitor but only of low effectiveness against trypsin and plasmin for the hydrolysis of N-α-benzoyl catalyzed by these three enzymes. Relations between the chemical structure and the activity against trypsin, plasmin and thrombin were deduced by comparing the inhibitor constants (Markwardt, F. et al., 2005). In this work, we report the crystal structure of the title compound (I). As shown in (Fig.1), the asymmetric unit of (I) is built up from one 4-chlorobenzylammonium cation, one chloride anion and one water molecule. The Cl^- anions, water molecules and R—NH₃⁺ groups are lineked via O—H···Cl, N—H···O and N—H···Cl hydrogen bonds and ionic interactions, so as to built inorganic layers spreading around the (b,c) planes. The 4-chlorobenzylammonium cations are anchored onto the successive inorganic layers via hydrogen bonds and electrostatic interactions, to composite their negative charges.

The examination of the organic cation shows that the values of N—C, C—C, C—Cl distances and N—C—C, C—C—C, C—C—Cl angles range from 1.376 (3) to 1.736 (3) Å and 115.72 (19) to 122.80 (19)°, respectively. These values show no significant difference from those obtained in other organic materials associated with the same organic groups (Dhaouadi, H. et al., 2008).

In this structure, the water molecules play a very important role in the cohesion of the various groups. It participates with the organic cations and chloride anions in the H-bonding scheme of N—H···O and O—H···Cl interactions in the crystal structure. The four hydrogen bonds are relatively weak, and their donor acceptor distances vary from 2.866 (2) to 3.417 (3) Å. Thus, these different interactions (hydrogen bonds, Van der Waals, and electrostatic) form a stable three-dimensional network.

Related literature top

For the properties of benzylamines, see: Markwardt et al. (2005). For a related structure, see: Dhaouadi et al. (2008).

Experimental top

An ethanolic solution of 4-chlorobenzylamine (10 mmol, in 10 ml) was added, with stirring, to 20 ml of an aqueous HCl solution (0.5M) at room temperature. Colourless blocks of (I) were obtained on slow evaporation of the solvent.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. A view of the packing of (I) along the b axis.

(4-Chlorophenyl)methanaminium chloride hemihydrate top

Crystal data top

C₇H₉ClN⁺·Cl⁻·0.5H₂O	F(000) = 776
M_r = 187.06	D_x = 1.443 Mg m⁻³
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 30.462 (2) Å	θ = 9–11°
b = 4.890 (3) Å	µ = 0.35 mm⁻¹
c = 11.738 (2) Å	T = 293 K
β = 99.97 (3)°	Block, colourless
V = 1722.1 (11) Å³	0.30 × 0.25 × 0.20 mm
Z = 8

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.031
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.3°
Graphite monochromator	h = −50→50
non–profiled ω scans	k = 0→8
5908 measured reflections	l = −5→19
4207 independent reflections	2 standard reflections every 120 min
2217 reflections with I > 2σ(I)	intensity decay: 5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.130	w = 1/[σ²(F_o²) + (0.0585P)² + 0.2911P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
4207 reflections	Δρ_max = 0.34 e Å⁻³
101 parameters	Δρ_min = −0.32 e Å⁻³
0 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: 0.0080 (12)

Crystal data top

C₇H₉ClN⁺·Cl⁻·0.5H₂O	V = 1722.1 (11) Å³
M_r = 187.06	Z = 8
Monoclinic, C2/c	Ag Kα radiation, λ = 0.56085 Å
a = 30.462 (2) Å	µ = 0.35 mm⁻¹
b = 4.890 (3) Å	T = 293 K
c = 11.738 (2) Å	0.30 × 0.25 × 0.20 mm
β = 99.97 (3)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.031
5908 measured reflections	2 standard reflections every 120 min
4207 independent reflections	intensity decay: 5%
2217 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.34 e Å⁻³
4207 reflections	Δρ_min = −0.32 e Å⁻³
101 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	0.049348 (13)	0.63727 (9)	0.11132 (4)	0.04257 (13)
O	0.0000	0.2285 (4)	0.2500	0.0494 (5)
H1	0.0151 (8)	0.323 (5)	0.210 (2)	0.089 (9)*
C1	0.12851 (4)	0.0280 (3)	0.40289 (14)	0.0313 (3)
C2	0.12629 (5)	0.1317 (3)	0.29253 (14)	0.0364 (3)
H2	0.1048	0.0661	0.2328	0.044*
C3	0.15582 (5)	0.3328 (3)	0.26977 (14)	0.0371 (3)
H3	0.1538	0.4046	0.1957	0.045*
C4	0.18814 (4)	0.4244 (3)	0.35851 (14)	0.0329 (3)
C5	0.19059 (5)	0.3278 (4)	0.46938 (15)	0.0386 (4)
H5	0.2121	0.3947	0.5289	0.046*
C6	0.16065 (5)	0.1293 (4)	0.49129 (14)	0.0380 (3)
H6	0.1621	0.0631	0.5661	0.046*
C7	0.09748 (5)	−0.1977 (3)	0.42512 (18)	0.0399 (4)
H7A	0.0966	−0.3362	0.3656	0.048*
H7B	0.1090	−0.2824	0.4990	0.048*
Cl2	0.225682 (14)	0.66901 (9)	0.32754 (5)	0.04948 (15)
N	0.05166 (4)	−0.0999 (3)	0.42641 (13)	0.0404 (3)
H0A	0.0347	−0.2400	0.4401	0.061*
H0B	0.0406	−0.0261	0.3582	0.061*
H0C	0.0521	0.0251	0.4817	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0390 (2)	0.0365 (2)	0.0527 (3)	0.00140 (16)	0.00925 (17)	0.00195 (19)
O	0.0523 (11)	0.0428 (10)	0.0574 (12)	0.000	0.0215 (9)	0.000
C1	0.0289 (6)	0.0260 (6)	0.0403 (8)	0.0011 (5)	0.0097 (6)	−0.0002 (6)
C2	0.0372 (7)	0.0376 (8)	0.0333 (8)	−0.0070 (6)	0.0033 (6)	−0.0044 (7)
C3	0.0441 (8)	0.0367 (8)	0.0314 (8)	−0.0060 (7)	0.0086 (6)	0.0008 (7)
C4	0.0281 (6)	0.0281 (6)	0.0444 (9)	−0.0017 (5)	0.0117 (6)	−0.0042 (6)
C5	0.0318 (7)	0.0436 (9)	0.0388 (9)	−0.0035 (6)	0.0011 (6)	−0.0064 (7)
C6	0.0388 (7)	0.0407 (8)	0.0342 (8)	0.0015 (7)	0.0057 (6)	0.0049 (7)
C7	0.0384 (7)	0.0263 (7)	0.0577 (11)	0.0010 (6)	0.0153 (7)	0.0043 (7)
Cl2	0.0432 (2)	0.0391 (2)	0.0709 (3)	−0.01276 (17)	0.0229 (2)	−0.0055 (2)
N	0.0339 (6)	0.0355 (7)	0.0529 (9)	−0.0069 (5)	0.0101 (6)	0.0005 (6)

Geometric parameters (Å, º) top

O—H1	0.84 (2)	C5—C6	1.386 (2)
C1—C2	1.382 (2)	C5—H5	0.9300
C1—C6	1.389 (2)	C6—H6	0.9300
C1—C7	1.505 (2)	C7—N	1.4779 (19)
C2—C3	1.389 (2)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C4	1.379 (2)	N—H0A	0.8900
C3—H3	0.9300	N—H0B	0.8900
C4—C5	1.374 (2)	N—H0C	0.8900
C4—Cl2	1.7361 (15)

C2—C1—C6	118.89 (14)	C5—C6—C1	120.84 (15)
C2—C1—C7	120.10 (15)	C5—C6—H6	119.6
C6—C1—C7	120.98 (15)	C1—C6—H6	119.6
C1—C2—C3	120.78 (15)	N—C7—C1	112.77 (13)
C1—C2—H2	119.6	N—C7—H7A	109.0
C3—C2—H2	119.6	C1—C7—H7A	109.0
C4—C3—C2	119.10 (15)	N—C7—H7B	109.0
C4—C3—H3	120.5	C1—C7—H7B	109.0
C2—C3—H3	120.5	H7A—C7—H7B	107.8
C5—C4—C3	121.21 (14)	C7—N—H0A	109.5
C5—C4—Cl2	120.36 (12)	C7—N—H0B	109.5
C3—C4—Cl2	118.42 (13)	H0A—N—H0B	109.5
C4—C5—C6	119.14 (14)	C7—N—H0C	109.5
C4—C5—H5	120.4	H0A—N—H0C	109.5
C6—C5—H5	120.4	H0B—N—H0C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Cl1ⁱ	0.89	2.60	3.2930 (19)	136
N—H0A···Cl1ⁱⁱ	0.89	2.78	3.417 (2)	130
N—H0B···O	0.89	2.04	2.866 (2)	155
N—H0C···Cl1ⁱⁱⁱ	0.89	2.26	3.144 (2)	175
O—H1···Cl1	0.85 (3)	2.28 (3)	3.1230 (18)	171 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₉ClN⁺·Cl⁻·0.5H₂O
M_r	187.06
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	30.462 (2), 4.890 (3), 11.738 (2)
β (°)	99.97 (3)
V (Å³)	1722.1 (11)
Z	8
Radiation type	Ag Kα, λ = 0.56085 Å
µ (mm⁻¹)	0.35
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5908, 4207, 2217
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.836

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.00
No. of reflections	4207
No. of parameters	101
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.32

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···Cl1ⁱ	0.89	2.60	3.2930 (19)	136
N—H0A···Cl1ⁱⁱ	0.89	2.78	3.417 (2)	130
N—H0B···O	0.89	2.04	2.866 (2)	155
N—H0C···Cl1ⁱⁱⁱ	0.89	2.26	3.144 (2)	175
O—H1···Cl1	0.85 (3)	2.28 (3)	3.1230 (18)	171 (3)

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

References

Dhaouadi, H., Marouani, H., Rzaigui, M. & Madani, A. (2008). Mater. Res. Bull. 43, 3234–3244. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Markwardt, F., Landmann, H. & Walsmann, P. (2005). Eur. J. Biochem. 6, 502–506. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1627

doi:10.1107/S1600536810021100

Open

access