(4-Meth­oxy­phen­yl)methanaminium chloride

Kefi, R.; Matthias, Z.; Ben Nasr, C.

doi:10.1107/S1600536811004363

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o634

doi:10.1107/S1600536811004363

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(4-Methoxyphenyl)methanaminium chloride

Riadh Kefi,^a Zeller Matthias ^b and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia, and ^bYoungstown State University, Department of Chemistry, One University Plaza, Youngstown, Ohio 44555-3663, USA
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 21 January 2011; accepted 5 February 2011; online 16 February 2011)

In the crystal structure of the title salt, C₈H₁₂NO⁺·Cl⁻, the methoxy group of the cation is co-planar with the phenylene moiety with an r.m.s. deviation from the mean plane of only 0.005 Å. The ammonium N atom deviates from this plane by 1.403 (1) Å. In the crystal, the (4-methoxyphenyl)methanaminium cations and chloride anions are linked by N—H⋯Cl and C—H⋯O hydrogen bonds, resulting in an open framework architecture with hydrogen-bonded ammonium groups and chloride anions located in layers parallel to (011), separated by more hydrophobic layers with interdigitating anisole groups.

Related literature

For related compounds, see: Oueslati et al. (2005a ); Ben Gharbia et al. (2008 ). For hydrogen-bond networks, see: Oueslati et al. (2005b ); Zaouali et al. (2009 ). For graph-set theory, see: Bernstein et al. (1995 ). For mesomeric effects in related structures, see: Kefi et al. (2006 ); El Glaoui et al. (2009 ).

Experimental

Crystal data

C₈H₁₂NO⁺·Cl⁻
M_r = 173.64
Monoclinic, P 2₁ /c
a = 11.4234 (11) Å
b = 8.9384 (9) Å
c = 8.9490 (9) Å
β = 105.904 (1)°
V = 878.78 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 100 K
0.55 × 0.42 × 0.38 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.675, T_max = 0.746
7028 measured reflections
2593 independent reflections
2411 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.072
S = 1.07
2593 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.91	2.24	3.1475 (9)	176
N1—H1B⋯Cl1ⁱⁱ	0.91	2.25	3.1502 (8)	170
N1—H1C⋯Cl1	0.91	2.27	3.1680 (8)	170
C6—H6⋯O1ⁱⁱⁱ	0.95	2.58	3.4090 (11)	147
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004363/rz2550sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004363/rz2550Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations in molecular salts of amine hydrochloride compounds (Oueslati et al., 2005a; Ben Gharbia et al., 2008), we report here the crystal structure of one such compound, (4-methoxyphenyl)methanaminium chloride, C₈H₁₂ClNO (Fig. 1).

The crystal structure consists of a network of the constituent ammonium and chloride ions connected by N—H···Cl hydrogen bonds (Fig. 2), with a chloride anion acting as a threefold acceptor as similarly observed in related compounds (Oueslati et al., 2005b). The N···Cl distances vary between 3.1475 (9) and 3.1680 (8) Å, indicating strong interactions between the ammonium and halogenide ions (Zaouali et al., 2009). Multiple hydrogen bonds connect the different entities of the compound to form inorganic layers, built from the chloride anions and the ammonium groups, parallel to the bc plane (Fig. 2). Within the layers, various graph-set motifs (Bernstein et al., 1995) are apparent, including R₂⁴(8) and R₂⁸(16) motifs. The organic fragments are located between successive inorganic layers (Fig. 3). No π-π stacking interactions between the phenylene rings or C—H···π interactions towards them are observed. A weak intermolecular C—H···O hydrogen interaction involving an aromatic hydrogen atom is present (Table 1). The organic molecule exhibits a regular spatial configuration with usual distances and angles. The distance C1—O1 [1.3637 (11) Å] is slightly shorter than that of C8—O1 [1.4362 (12) Å], which can be attributed to the donor mesomeric effect of the methoxy group. All the geometrical features of the title compound agree with those found in related compounds (e.g. Kefi et al., 2006; El Glaoui et al., 2009).

Related literature top

For related compounds, see: Oueslati et al. (2005a); Ben Gharbia et al. (2008). For hydrogen-bond networks, see: Oueslati et al. (2005b); Zaouali et al. (2009). For graph-set theory, see: Bernstein et al. (1995). For mesomeric effects in related structures, see: Kefi et al. (2006); El Glaoui et al. (2009).

Experimental top

4-Methoxybenzylamine (2 mmol, 0.274 g) was dissolved in aqueous HCl (10 ml, 1M). Colourless crystals suitable for single-crystal X-ray analysis were grown by slow evaporation at room temperature over a period of three weeks (yield 63%).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound, showing 60% probability displacement ellipsoids and arbitrary spheres for the H atoms.
	Fig. 2. Projection along the a axis of the inorganic layer in the structure of the title compound, showing the N—H···Cl hydrogen bonding interactions (dashed lines). Only the ammonium and chloride sections are shown for clarity.
	Fig. 3. Projection of the structure of the title compound along the b axis. Hydrogen bonds are shown as thin black lines.

(4-Methoxyphenyl)methanaminium chloride top

Crystal data top

C₈H₁₂NO⁺·Cl⁻	F(000) = 368
M_r = 173.64	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4317 reflections
a = 11.4234 (11) Å	θ = 2.3–30.9°
b = 8.9384 (9) Å	µ = 0.38 mm⁻¹
c = 8.9490 (9) Å	T = 100 K
β = 105.904 (1)°	Block, colourless
V = 878.78 (15) Å³	0.55 × 0.42 × 0.38 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2593 independent reflections
Radiation source: fine-focus sealed tube	2411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 31.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→16
T_min = 0.675, T_max = 0.746	k = −12→12
7028 measured reflections	l = −12→12

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0349P)² + 0.3154P] where P = (F_o² + 2F_c²)/3
2593 reflections	(Δ/σ)_max = 0.001
102 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₈H₁₂NO⁺·Cl⁻	V = 878.78 (15) Å³
M_r = 173.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4234 (11) Å	µ = 0.38 mm⁻¹
b = 8.9384 (9) Å	T = 100 K
c = 8.9490 (9) Å	0.55 × 0.42 × 0.38 mm
β = 105.904 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2593 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2411 reflections with I > 2σ(I)
T_min = 0.675, T_max = 0.746	R_int = 0.015
7028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.07	Δρ_max = 0.44 e Å⁻³
2593 reflections	Δρ_min = −0.23 e Å⁻³
102 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	0.874270 (19)	0.40670 (2)	0.15865 (3)	0.01574 (7)
O1	0.54020 (6)	1.00932 (8)	0.27742 (9)	0.01962 (15)
N1	0.97373 (7)	0.71225 (9)	0.06200 (9)	0.01532 (15)
H1A	1.0144	0.7700	0.1435	0.023*
H1B	1.0261	0.6811	0.0080	0.023*
H1C	0.9417	0.6312	0.0982	0.023*
C2	0.71566 (8)	1.04328 (10)	0.19393 (11)	0.01744 (18)
H2	0.7270	1.1373	0.2454	0.021*
C5	0.68479 (8)	0.76756 (10)	0.04614 (11)	0.01565 (17)
H5	0.6743	0.6728	−0.0039	0.019*
C1	0.61611 (8)	0.95355 (10)	0.19710 (11)	0.01482 (17)
C6	0.60029 (8)	0.81501 (10)	0.12293 (11)	0.01576 (17)
H6	0.5328	0.7536	0.1246	0.019*
C3	0.79770 (8)	0.99464 (10)	0.11556 (11)	0.01656 (18)
H3	0.8644	1.0568	0.1124	0.020*
C7	0.87306 (9)	0.80189 (11)	−0.04294 (11)	0.01650 (17)
H7A	0.9082	0.8891	−0.0835	0.020*
H7B	0.8300	0.7394	−0.1325	0.020*
C4	0.78390 (8)	0.85561 (10)	0.04109 (10)	0.01412 (16)
C8	0.43276 (9)	0.92405 (12)	0.27309 (13)	0.0218 (2)
H8A	0.3835	0.9135	0.1652	0.033*
H8B	0.3852	0.9757	0.3334	0.033*
H8C	0.4562	0.8247	0.3177	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01692 (12)	0.01417 (11)	0.01804 (12)	0.00094 (7)	0.00799 (8)	0.00074 (7)
O1	0.0163 (3)	0.0169 (3)	0.0289 (4)	0.0001 (2)	0.0116 (3)	−0.0034 (3)
N1	0.0178 (4)	0.0137 (3)	0.0164 (3)	0.0002 (3)	0.0080 (3)	−0.0007 (3)
C2	0.0162 (4)	0.0132 (4)	0.0233 (5)	−0.0005 (3)	0.0062 (3)	−0.0019 (3)
C5	0.0175 (4)	0.0148 (4)	0.0148 (4)	−0.0011 (3)	0.0048 (3)	−0.0012 (3)
C1	0.0138 (4)	0.0143 (4)	0.0169 (4)	0.0020 (3)	0.0051 (3)	0.0008 (3)
C6	0.0149 (4)	0.0151 (4)	0.0177 (4)	−0.0019 (3)	0.0051 (3)	−0.0003 (3)
C3	0.0144 (4)	0.0149 (4)	0.0208 (4)	−0.0013 (3)	0.0055 (3)	0.0010 (3)
C7	0.0182 (4)	0.0191 (4)	0.0135 (4)	0.0010 (3)	0.0065 (3)	0.0014 (3)
C4	0.0144 (4)	0.0155 (4)	0.0127 (4)	0.0010 (3)	0.0042 (3)	0.0017 (3)
C8	0.0145 (4)	0.0227 (4)	0.0304 (5)	−0.0001 (3)	0.0096 (4)	−0.0008 (4)

Geometric parameters (Å, º) top

O1—C1	1.3634 (11)	C5—H5	0.9500
O1—C8	1.4362 (12)	C1—C6	1.3932 (13)
N1—C7	1.5015 (12)	C6—H6	0.9500
N1—H1A	0.9100	C3—C4	1.3984 (13)
N1—H1B	0.9100	C3—H3	0.9500
N1—H1C	0.9100	C7—C4	1.5011 (13)
C2—C3	1.3854 (13)	C7—H7A	0.9900
C2—C1	1.3982 (13)	C7—H7B	0.9900
C2—H2	0.9500	C8—H8A	0.9800
C5—C4	1.3897 (13)	C8—H8B	0.9800
C5—C6	1.3954 (13)	C8—H8C	0.9800

C1—O1—C8	117.00 (8)	C2—C3—C4	121.10 (8)
C7—N1—H1A	109.5	C2—C3—H3	119.4
C7—N1—H1B	109.5	C4—C3—H3	119.4
H1A—N1—H1B	109.5	C4—C7—N1	111.46 (7)
C7—N1—H1C	109.5	C4—C7—H7A	109.3
H1A—N1—H1C	109.5	N1—C7—H7A	109.3
H1B—N1—H1C	109.5	C4—C7—H7B	109.3
C3—C2—C1	119.80 (8)	N1—C7—H7B	109.3
C3—C2—H2	120.1	H7A—C7—H7B	108.0
C1—C2—H2	120.1	C5—C4—C3	118.31 (8)
C4—C5—C6	121.57 (8)	C5—C4—C7	120.38 (8)
C4—C5—H5	119.2	C3—C4—C7	121.31 (8)
C6—C5—H5	119.2	O1—C8—H8A	109.5
O1—C1—C6	123.91 (8)	O1—C8—H8B	109.5
O1—C1—C2	116.06 (8)	H8A—C8—H8B	109.5
C6—C1—C2	120.02 (8)	O1—C8—H8C	109.5
C1—C6—C5	119.20 (8)	H8A—C8—H8C	109.5
C1—C6—H6	120.4	H8B—C8—H8C	109.5
C5—C6—H6	120.4

C8—O1—C1—C6	−5.30 (13)	C1—C2—C3—C4	−1.01 (14)
C8—O1—C1—C2	175.73 (8)	C6—C5—C4—C3	0.05 (14)
C3—C2—C1—O1	179.65 (8)	C6—C5—C4—C7	−179.76 (8)
C3—C2—C1—C6	0.64 (14)	C2—C3—C4—C5	0.66 (14)
O1—C1—C6—C5	−178.88 (9)	C2—C3—C4—C7	−179.53 (9)
C2—C1—C6—C5	0.05 (14)	N1—C7—C4—C5	−88.82 (10)
C4—C5—C6—C1	−0.40 (14)	N1—C7—C4—C3	91.37 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.91	2.24	3.1475 (9)	176
N1—H1B···Cl1ⁱⁱ	0.91	2.25	3.1502 (8)	170
N1—H1C···Cl1	0.91	2.27	3.1680 (8)	170
C6—H6···O1ⁱⁱⁱ	0.95	2.58	3.4090 (11)	147

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂NO⁺·Cl⁻
M_r	173.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.4234 (11), 8.9384 (9), 8.9490 (9)
β (°)	105.904 (1)
V (Å³)	878.78 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.55 × 0.42 × 0.38

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.675, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	7028, 2593, 2411
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.725

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 1.07
No. of reflections	2593
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.23

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.91	2.24	3.1475 (9)	176
N1—H1B···Cl1ⁱⁱ	0.91	2.25	3.1502 (8)	170
N1—H1C···Cl1	0.91	2.27	3.1680 (8)	170
C6—H6···O1ⁱⁱⁱ	0.95	2.58	3.4090 (11)	147

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

Acknowledgements

We would like to acknowledge support by the Secretary of State for Scientific Research and Technology of Tunisia. The diffractometer was funded by the NSF (grant 0087210), the Ohio Board of Regents (grant CAP-491) and YSU.

References

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