4-Methyl­benzyl­ammonium chloride hemihydrate

Aarthi, R.; Thiruvalluvar, A.; Ramachandra Raja, C.

doi:10.1107/S2414314617012135

organic compounds

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ISSN: 2414-3146

Volume 2| Part 8| August 2017| x171213

https://doi.org/10.1107/S2414314617012135

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4-Methylbenzylammonium chloride hemihydrate

R. Aarthi,^a A. Thiruvalluvar ^b ^* and C. Ramachandra Raja ^a

^aDepartment of Physics, Government Arts College (Autonomous), Kumbakonam 612 002, Tamilnadu, India, and ^bKunthavai Naacchiyar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by R. J. Butcher, Howard University, USA (Received 10 August 2017; accepted 22 August 2017; online 25 August 2017)

In the title hydrated salt, C₈H₁₂N⁺·Cl⁻·0.5H₂O, the water O atom lies on a crystallographic twofold axis. In the crystal, the cation, anion and water molecule are linked to one another via C—H⋯Cl, O—H⋯Cl, N—H⋯O and N—H⋯Cl hydrogen bonds. The crystal structure is further stabilized by two weak C—H⋯π interactions involving the benzene ring to form a three-dimensional network.

Keywords: crystal structure; hydrated salt; hydrogen bonds; C—H⋯π interactions.

CCDC reference: 1570202

Structure description

We report here the growth and single-crystal X-ray structure of 4-methylbenzylammonium chloride hemihydrate, prepared by the slow evaporation method. Derivatives of benzylamine act as good inhibitors for proteolytic enzymes, such as trypsin, plasmin and thrombin (Markwardt et al., 2005 ). These derivatives are also used in the field of microelectronics (Sahbani et al., 2017 ).

In the title hydrated salt (Fig. 1), the water O atom lies on a crystallographic twofold axis. In the crystal, the cation, anion and water molecule are linked to one another via C8—H8B⋯Cl1ⁱ, O1—H1⋯Cl1ⁱ, N1—H1D⋯O1ⁱⁱ, N1—H1E⋯Cl1, N1—H1F⋯Cl1ⁱ and N1—H1F⋯Cl1ⁱⁱ hydrogen bonds (see Fig. 2 and Table 1), generating layers lying parallel to the bc plane. Furthermore, the crystal structure is stabilized by C1—H1B⋯πⁱⁱⁱ and C8—H8A⋯πⁱ weak interactions involving the C2–C7 benzene ring, to form a three-dimensional network (see Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C2–C7 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯Cl1ⁱ	0.97	2.96	3.5656 (16)	122
O1—H1⋯Cl1ⁱ	0.86 (1)	2.27 (1)	3.1231 (13)	177 (2)
N1—H1D⋯O1ⁱⁱ	0.92 (1)	1.98 (2)	2.8707 (18)	163 (2)
N1—H1E⋯Cl1	0.93 (1)	2.22 (1)	3.1531 (15)	177 (2)
N1—H1F⋯Cl1ⁱ	0.91 (1)	2.85 (2)	3.4430 (15)	124 (2)
N1—H1F⋯Cl1ⁱⁱ	0.91 (1)	2.52 (2)	3.2733 (13)	141 (2)
C1—H1B⋯Cg1ⁱⁱⁱ	0.96	2.64	3.5656 (16)	162
C8—H8A⋯Cg1ⁱ	0.97	2.91	3.4693 (16)	118
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, z.

Figure 1
A view of the components of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dotted lines. [Symmetry code: (i) 1 − x, y, $[{1\over 2}]$ − z.]

Figure 2
The crystal structure of (I), viewed down the b axis, showing the formation of hydrogen bonding. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

Souissi et al. (2010 ) have reported the crystal structure of (4-chlorophenyl)methanaminium chloride hemihydrate, in which the water O atom lies on a crystallographic twofold axis.

Synthesis and crystallization

A solution of 4-methylbenzylamine (2 mmol, 0.242 g) was dissolved in dilute HCl (10 ml, 1 mol) and CaCl₂ (1 mmol, 0.147 g) was added. The resulting clear solution was stirred for 3 h and left to stand at room temperature. Colourless single crystals of the title compound were obtained after 15 d.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. `DFIX 0.85 0.02 O1 H1' was used to fix the water O—H distance. `DFIX 0.90 0.02 N1 H1D N1 H1E N1 H1F' was used to fix the N—H distances in the –NH₃ group. `DFIX 1.48 0.02 H1D H1E H1E H1F H1F H1D' was used to fix the three H⋯H distances in the –NH₃ group. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 (aromatic), 0.97 (–CH₂–) and 0.96 Å (–CH₃), and with U_iso(H) = 1.2–1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₁₂N⁺·Cl⁻·0.5H₂O
M_r	166.65
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	30.5325 (14), 4.8966 (2), 11.8973 (5)
β (°)	99.067 (2)
V (Å³)	1756.49 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.37
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.703, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	14479, 2985, 2030
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.761

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.04
No. of reflections	2985
No. of parameters	112
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.25
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993 ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2015 ), SHELXL2017 (Sheldrick, 2015 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1570202

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012135/bv4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012135/bv4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617012135/bv4010Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314617012135/bv4010Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2/SAINT (Bruker, 2004); data reduction: SAINT/XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2015); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015), PLATON (Spek, 2015) and publCIF (Westrip, 2010).

4-Methylbenzylammonium chloride hemihydrate top

Crystal data top

C₈H₁₂N⁺·Cl⁻·0.5H₂O	D_x = 1.260 Mg m⁻³
M_r = 166.65	Melting point: 533(3) K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 30.5325 (14) Å	Cell parameters from 3525 reflections
b = 4.8966 (2) Å	θ = 2.7–27.2°
c = 11.8973 (5) Å	µ = 0.37 mm⁻¹
β = 99.067 (2)°	T = 296 K
V = 1756.49 (13) Å³	Block, colourless
Z = 4	0.20 × 0.20 × 0.15 mm
F(000) = 712

Data collection top

Bruker Kappa APEXII CCD diffractometer	2985 independent reflections
Radiation source: fine-focus sealed tube	2030 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scan	θ_max = 32.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −43→44
T_min = 0.703, T_max = 0.747	k = −7→7
14479 measured reflections	l = −17→17

Refinement top

Refinement on F²	7 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.118	w = 1/[σ²(F_o²) + (0.0474P)² + 1.1506P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2985 reflections	Δρ_max = 0.26 e Å⁻³
112 parameters	Δρ_min = −0.25 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.27846 (5)	1.1363 (3)	0.66526 (16)	0.0457 (4)
H1A	0.250753	1.104215	0.616561	0.069*
H1B	0.289350	1.314261	0.650098	0.069*
H1C	0.274153	1.126064	0.743349	0.069*
C2	0.31162 (5)	0.9233 (3)	0.64291 (13)	0.0329 (3)
C3	0.34309 (5)	0.8260 (3)	0.73017 (13)	0.0381 (3)
H3	0.343895	0.894951	0.803292	0.046*
C4	0.37344 (5)	0.6277 (3)	0.71083 (13)	0.0370 (3)
H4	0.394078	0.564484	0.771108	0.044*
C5	0.37334 (4)	0.5229 (3)	0.60280 (12)	0.0317 (3)
C6	0.34264 (5)	0.6250 (3)	0.51457 (13)	0.0380 (3)
H6	0.342469	0.560761	0.440939	0.046*
C7	0.31220 (5)	0.8218 (3)	0.53477 (13)	0.0385 (3)
H7	0.291774	0.886742	0.474401	0.046*
C8	0.40494 (5)	0.2992 (3)	0.58295 (16)	0.0409 (4)
H8A	0.406778	0.167653	0.644475	0.049*
H8B	0.393489	0.205408	0.512626	0.049*
N1	0.44988 (4)	0.4038 (3)	0.57608 (13)	0.0409 (3)
O1	0.500000	0.2659 (4)	0.250000	0.0520 (4)
Cl1	0.45068 (2)	0.86388 (8)	0.39101 (4)	0.04364 (13)
H1	0.4865 (6)	0.151 (3)	0.2865 (16)	0.052*
H1D	0.4625 (7)	0.492 (4)	0.6416 (12)	0.066 (6)*
H1E	0.4504 (7)	0.535 (4)	0.5197 (14)	0.073 (7)*
H1F	0.4686 (6)	0.265 (3)	0.5654 (16)	0.071 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0397 (8)	0.0368 (8)	0.0643 (11)	0.0070 (7)	0.0201 (8)	0.0028 (7)
C2	0.0297 (6)	0.0284 (6)	0.0425 (8)	−0.0003 (5)	0.0118 (6)	0.0024 (6)
C3	0.0424 (8)	0.0394 (8)	0.0335 (7)	0.0055 (6)	0.0094 (6)	−0.0025 (6)
C4	0.0359 (7)	0.0396 (8)	0.0348 (7)	0.0062 (6)	0.0033 (6)	0.0029 (6)
C5	0.0282 (6)	0.0269 (6)	0.0413 (7)	−0.0016 (5)	0.0102 (5)	−0.0008 (6)
C6	0.0388 (8)	0.0425 (8)	0.0334 (7)	0.0013 (6)	0.0079 (6)	−0.0050 (6)
C7	0.0339 (7)	0.0425 (8)	0.0379 (8)	0.0057 (6)	0.0022 (6)	0.0041 (6)
C8	0.0372 (8)	0.0296 (7)	0.0590 (10)	0.0006 (6)	0.0173 (7)	−0.0025 (7)
N1	0.0312 (6)	0.0389 (7)	0.0543 (8)	0.0075 (6)	0.0117 (6)	0.0026 (6)
O1	0.0542 (11)	0.0444 (10)	0.0619 (11)	0.000	0.0227 (9)	0.000
Cl1	0.0389 (2)	0.0404 (2)	0.0523 (2)	0.00223 (16)	0.00932 (16)	0.00296 (17)

Geometric parameters (Å, º) top

C1—C2	1.506 (2)	C6—C7	1.386 (2)
C1—H1A	0.9600	C6—H6	0.9300
C1—H1B	0.9600	C7—H7	0.9300
C1—H1C	0.9600	C8—N1	1.479 (2)
C2—C7	1.382 (2)	C8—H8A	0.9700
C2—C3	1.383 (2)	C8—H8B	0.9700
C3—C4	1.386 (2)	N1—H1D	0.921 (13)
C3—H3	0.9300	N1—H1E	0.931 (14)
C4—C5	1.384 (2)	N1—H1F	0.911 (14)
C4—H4	0.9300	O1—H1	0.855 (14)
C5—C6	1.386 (2)	O1—H1ⁱ	0.855 (14)
C5—C8	1.503 (2)

C2—C1—H1A	109.5	C7—C6—H6	119.6
C2—C1—H1B	109.5	C5—C6—H6	119.6
H1A—C1—H1B	109.5	C2—C7—C6	121.25 (14)
C2—C1—H1C	109.5	C2—C7—H7	119.4
H1A—C1—H1C	109.5	C6—C7—H7	119.4
H1B—C1—H1C	109.5	N1—C8—C5	112.37 (12)
C7—C2—C3	117.75 (13)	N1—C8—H8A	109.1
C7—C2—C1	121.40 (14)	C5—C8—H8A	109.1
C3—C2—C1	120.85 (14)	N1—C8—H8B	109.1
C2—C3—C4	121.34 (14)	C5—C8—H8B	109.1
C2—C3—H3	119.3	H8A—C8—H8B	107.9
C4—C3—H3	119.3	C8—N1—H1D	112.5 (13)
C5—C4—C3	120.70 (14)	C8—N1—H1E	113.5 (14)
C5—C4—H4	119.7	H1D—N1—H1E	103.5 (16)
C3—C4—H4	119.7	C8—N1—H1F	110.9 (13)
C4—C5—C6	118.15 (13)	H1D—N1—H1F	106.4 (15)
C4—C5—C8	120.61 (14)	H1E—N1—H1F	109.6 (16)
C6—C5—C8	121.22 (14)	H1—O1—H1ⁱ	98 (3)
C7—C6—C5	120.77 (14)

C7—C2—C3—C4	−1.8 (2)	C8—C5—C6—C7	176.79 (14)
C1—C2—C3—C4	179.25 (14)	C3—C2—C7—C6	1.3 (2)
C2—C3—C4—C5	0.6 (2)	C1—C2—C7—C6	−179.75 (15)
C3—C4—C5—C6	1.1 (2)	C5—C6—C7—C2	0.4 (2)
C3—C4—C5—C8	−177.28 (14)	C4—C5—C8—N1	−80.09 (18)
C4—C5—C6—C7	−1.6 (2)	C6—C5—C8—N1	101.57 (17)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C2-C7) benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···Cl1ⁱⁱ	0.97	2.96	3.5656 (16)	122
O1—H1···Cl1ⁱⁱ	0.86 (1)	2.27 (1)	3.1231 (13)	177 (2)
N1—H1D···O1ⁱⁱⁱ	0.92 (1)	1.98 (2)	2.8707 (18)	163 (2)
N1—H1E···Cl1	0.93 (1)	2.22 (1)	3.1531 (15)	177 (2)
N1—H1F···Cl1ⁱⁱ	0.91 (1)	2.85 (2)	3.4430 (15)	124 (2)
N1—H1F···Cl1ⁱⁱⁱ	0.91 (1)	2.52 (2)	3.2733 (13)	141 (2)
C1—H1B···Cg1^iv	0.96	2.64	3.5656 (16)	162
C8—H8A···Cg1ⁱⁱ	0.97	2.91	3.4693 (16)	118

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

Acknowledgements

The authors are thankful to the Sophisticated Analytical Instrument Facility (SAIF), IITM, Chennai, Tamilnadu, India, for the single-crystal X-ray diffraction data.

Funding information

Funding for this research was provided by: Council of Scientific and Industrial Research (CSIR), New Delhi, India (grant No. 03(1301)13/EMR II to CR).

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