(4-Methyl­phen­yl)methanaminium bromide hemi­hydrate

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

doi:10.1107/S2414314618002705

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 2| February 2018| x180270

https://doi.org/10.1107/S2414314618002705

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(4-Methylphenyl)methanaminium bromide 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 Naacchiyaar Government Arts College for Women (Autonomous), Thanjavur 613 007, Tamilnadu, India
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 February 2018; accepted 15 February 2018; online 20 February 2018)

In the title hydrated salt, C₈H₁₂N⁺·Br⁻·0.5H₂O, which is isostructural with its chloride congener, the water O atom lies on a crystallographic twofold axis. In the crystal, the components are linked via C—H⋯Br, O—H⋯Br, N—H⋯Br and N—H⋯O hydrogen bonds to generate (100) sheets. The sheets are linked by two weak C—H⋯π interactions, generating a three-dimensional network.

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

CCDC reference: 1824161

Structure description

Some noncentrosymmetric organic crystals exhibit high nonlinear efficiency and can be functionalized very easily but it is difficult to grow bulk crystals and their physical and mechanical properties are poor (Dolbecq et al., 2010 ). As part of our ongoing studies in this area (Aarthi et al., 2017 ), we now describe the synthesis and structure of (4-methylphenyl)methanaminium bromide hemihydrate, (I) (Fig. 1), which crystallized in a centrosymmetric space group.

Figure 1
A view 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.]

The water O atom lies on a crystallographic twofold axis. In the crystal, the components are linked via C8—H8B⋯Br1ⁱ, O1—H1⋯Br1ⁱ, N1—H1D⋯Br1, N1—H1E⋯O1ⁱⁱ, N1—H1F⋯Br1ⁱ and N1—H1F⋯Br1ⁱⁱ hydrogen bonds (see Fig. 2 and Table 1), generating layers lying parallel to the bc plane. Furthermore, the crystal structure features weak C1—H1A⋯πⁱⁱⁱ and C8—H8A⋯πⁱ interactions, forming a three-dimensional network (see Fig. 3 and 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
O1—H1⋯Br1ⁱ	0.85 (2)	2.45 (2)	3.2870 (17)	169 (3)
N1—H1D⋯Br1	0.92 (2)	2.40 (2)	3.314 (2)	178 (2)
N1—H1E⋯O1ⁱⁱ	0.90 (2)	2.05 (2)	2.883 (3)	155 (2)
N1—H1F⋯Br1ⁱ	0.91 (2)	2.89 (2)	3.554 (2)	131 (2)
N1—H1F⋯Br1ⁱⁱ	0.91 (2)	2.74 (3)	3.4383 (17)	134 (2)
C8—H8B⋯Br1ⁱ	0.97	3.05	3.670 (2)	123
C1—H1A⋯Cg1ⁱⁱⁱ	0.96	2.73	3.634 (2)	157
C8—H8A⋯Cg1ⁱ	0.97	2.90	3.530 (2)	123
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z+1; (iii) x, y+1, 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.

Figure 3
A partial packing diagram of (I), viewed down the b axis, showing the C—H⋯π interactions.

Souissi et al. (2010 ) have reported the related crystal structure of (4-chlorophenyl)methanaminium chloride hemihydrate.

Synthesis and crystallization

An aqueous solution containing 2 mmol of HBr in 20 ml of water was added to 2 mmol of 4-methylbenzylamine in 20 ml of water. The resultant solution was well stirred using a magnetic stirrer for 3 h and left to stand at room temperature. After 15 d, colourless blocks of (I) were harvested.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The O– and N-bonded H atoms were refined with restraints and the C-bound H atoms were positioned geometrically and refined as riding 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⁺·Br⁻·0.5H₂O
M_r	211.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	30.7456 (18), 5.0266 (3), 12.0636 (7)
β (°)	98.430 (2)
V (Å³)	1844.24 (19)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	4.40
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Bruker KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.534, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11261, 2479, 2129
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.06
No. of reflections	2479
No. of parameters	113
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)	0.35, −0.51
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT2014 (Sheldrick, 2015a ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ), SHELXL2018 (Sheldrick, 2015b ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1824161

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002705/hb4211sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002705/hb4211Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002705/hb4211Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002705/hb4211Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(4-Methylphenyl)methanaminium bromide hemihydrate top

Crystal data top

C₈H₁₂N⁺·Br⁻·0.5(H₂O)	F(000) = 856
M_r = 211.10	D_x = 1.521 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 30.7456 (18) Å	Cell parameters from 7215 reflections
b = 5.0266 (3) Å	θ = 3.4–29.2°
c = 12.0636 (7) Å	µ = 4.40 mm⁻¹
β = 98.430 (2)°	T = 293 K
V = 1844.24 (19) Å³	Block, colourless
Z = 8	0.10 × 0.10 × 0.05 mm

Data collection top

Bruker KappaCCD diffractometer	2479 independent reflections
Radiation source: fine-focus sealed tube	2129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and φ scan	θ_max = 29.2°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −40→42
T_min = 0.534, T_max = 0.746	k = −6→6
11261 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0267P)² + 2.3541P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2479 reflections	Δρ_max = 0.35 e Å⁻³
113 parameters	Δρ_min = −0.51 e Å⁻³
7 restraints

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	0.27703 (8)	1.1301 (4)	0.6636 (2)	0.0494 (6)
H1A	0.286021	1.299079	0.637653	0.074*
H1B	0.275755	1.140043	0.742564	0.074*
H1C	0.248504	1.085224	0.624468	0.074*
C2	0.30965 (6)	0.9198 (4)	0.64201 (18)	0.0340 (4)
C3	0.31078 (7)	0.8211 (4)	0.53533 (18)	0.0406 (4)
H3	0.291045	0.886455	0.475733	0.049*
C4	0.34066 (7)	0.6273 (4)	0.51557 (17)	0.0399 (4)
H4	0.340822	0.565059	0.443038	0.048*
C5	0.37039 (6)	0.5248 (4)	0.60273 (17)	0.0321 (4)
C6	0.36998 (7)	0.6264 (4)	0.70908 (17)	0.0385 (4)
H6	0.390104	0.563229	0.768332	0.046*
C7	0.34002 (7)	0.8212 (4)	0.72890 (18)	0.0402 (4)
H7	0.340289	0.886252	0.801160	0.048*
C8	0.40117 (7)	0.3025 (4)	0.5831 (2)	0.0427 (5)
H8A	0.400833	0.169245	0.641177	0.051*
H8B	0.390675	0.219026	0.511705	0.051*
N1	0.44665 (6)	0.3933 (4)	0.58300 (18)	0.0420 (4)
Br1	0.44849 (2)	0.86079 (4)	0.38999 (2)	0.04217 (8)
O1	0.500000	0.2903 (5)	0.250000	0.0548 (6)
H1	0.4840 (11)	0.196 (6)	0.286 (3)	0.096 (13)*
H1D	0.4466 (9)	0.520 (4)	0.5282 (17)	0.065 (8)*
H1E	0.4585 (9)	0.465 (5)	0.6483 (14)	0.063 (8)*
H1F	0.4636 (9)	0.255 (4)	0.566 (2)	0.072 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0401 (11)	0.0394 (11)	0.0728 (16)	0.0092 (9)	0.0221 (11)	0.0048 (11)
C2	0.0284 (9)	0.0293 (8)	0.0465 (11)	0.0002 (7)	0.0126 (8)	0.0030 (8)
C3	0.0335 (10)	0.0479 (11)	0.0391 (10)	0.0058 (9)	0.0005 (8)	0.0056 (9)
C4	0.0382 (10)	0.0492 (11)	0.0330 (9)	0.0004 (9)	0.0073 (8)	−0.0061 (9)
C5	0.0274 (9)	0.0287 (8)	0.0416 (10)	−0.0015 (7)	0.0096 (7)	−0.0021 (7)
C6	0.0379 (10)	0.0410 (10)	0.0359 (9)	0.0089 (9)	0.0027 (8)	0.0029 (8)
C7	0.0459 (11)	0.0410 (10)	0.0348 (10)	0.0063 (9)	0.0096 (8)	−0.0016 (8)
C8	0.0373 (11)	0.0319 (9)	0.0615 (14)	0.0011 (8)	0.0165 (10)	−0.0053 (9)
N1	0.0315 (8)	0.0403 (9)	0.0550 (11)	0.0086 (8)	0.0094 (8)	0.0002 (9)
Br1	0.03836 (12)	0.03826 (12)	0.05064 (14)	0.00097 (9)	0.00907 (8)	−0.00115 (9)
O1	0.0631 (16)	0.0452 (13)	0.0609 (16)	0.000	0.0250 (13)	0.000

Geometric parameters (Å, º) top

C1—C2	1.506 (3)	C6—C7	1.389 (3)
C1—H1A	0.9600	C6—H6	0.9300
C1—H1B	0.9600	C7—H7	0.9300
C1—H1C	0.9600	C8—N1	1.471 (3)
C2—C3	1.384 (3)	C8—H8A	0.9700
C2—C7	1.389 (3)	C8—H8B	0.9700
C3—C4	1.384 (3)	N1—H1D	0.919 (15)
C3—H3	0.9300	N1—H1E	0.895 (15)
C4—C5	1.387 (3)	N1—H1F	0.909 (15)
C4—H4	0.9300	O1—H1	0.848 (17)
C5—C6	1.383 (3)	O1—H1ⁱ	0.848 (17)
C5—C8	1.505 (3)

C2—C1—H1A	109.5	C5—C6—H6	119.4
C2—C1—H1B	109.5	C7—C6—H6	119.4
H1A—C1—H1B	109.5	C6—C7—C2	120.74 (19)
C2—C1—H1C	109.5	C6—C7—H7	119.6
H1A—C1—H1C	109.5	C2—C7—H7	119.6
H1B—C1—H1C	109.5	N1—C8—C5	112.91 (17)
C3—C2—C7	117.90 (18)	N1—C8—H8A	109.0
C3—C2—C1	121.4 (2)	C5—C8—H8A	109.0
C7—C2—C1	120.7 (2)	N1—C8—H8B	109.0
C4—C3—C2	121.34 (19)	C5—C8—H8B	109.0
C4—C3—H3	119.3	H8A—C8—H8B	107.8
C2—C3—H3	119.3	C8—N1—H1D	108.4 (18)
C3—C4—C5	120.75 (18)	C8—N1—H1E	113.0 (18)
C3—C4—H4	119.6	H1D—N1—H1E	108.0 (19)
C5—C4—H4	119.6	C8—N1—H1F	109.8 (19)
C6—C5—C4	118.12 (18)	H1D—N1—H1F	107.9 (19)
C6—C5—C8	120.76 (19)	H1E—N1—H1F	110 (2)
C4—C5—C8	121.08 (19)	H1—O1—H1ⁱ	112 (5)
C5—C6—C7	121.11 (19)

C7—C2—C3—C4	1.0 (3)	C8—C5—C6—C7	−176.38 (19)
C1—C2—C3—C4	−179.8 (2)	C5—C6—C7—C2	−0.2 (3)
C2—C3—C4—C5	0.3 (3)	C3—C2—C7—C6	−1.1 (3)
C3—C4—C5—C6	−1.6 (3)	C1—C2—C7—C6	179.71 (19)
C3—C4—C5—C8	176.30 (19)	C6—C5—C8—N1	−77.2 (3)
C4—C5—C6—C7	1.5 (3)	C4—C5—C8—N1	105.0 (2)

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
O1—H1···Br1ⁱⁱ	0.85 (2)	2.45 (2)	3.2870 (17)	169 (3)
N1—H1D···Br1	0.92 (2)	2.40 (2)	3.314 (2)	178 (2)
N1—H1E···O1ⁱⁱⁱ	0.90 (2)	2.05 (2)	2.883 (3)	155 (2)
N1—H1F···Br1ⁱⁱ	0.91 (2)	2.89 (2)	3.554 (2)	131 (2)
N1—H1F···Br1ⁱⁱⁱ	0.91 (2)	2.74 (3)	3.4383 (17)	134 (2)
C8—H8B···Br1ⁱⁱ	0.97	3.05	3.670 (2)	123
C1—H1A···Cg1^iv	0.96	2.73	3.634 (2)	157
C8—H8A···Cg1ⁱⁱ	0.97	2.90	3.530 (2)	123

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

Acknowledgements

The authors thank 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 CRR).

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