3-Chloro-2-methyl­anilinium dihydrogenphosphate

Khemiri, H.; Akriche, S.; Rzaigui, M.

doi:10.1107/S1600536808001700

organic compounds

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Volume 64| Part 2| February 2008| Page o526

doi:10.1107/S1600536808001700

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3-Chloro-2-methylanilinium dihydrogenphosphate

Hamed Khemiri,^a Samah Akriche ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: samah.akriche@fsb.rnu.tn

(Received 14 January 2008; accepted 16 January 2008; online 30 January 2008)

The structure of the title compound, C₇H₉ClN⁺·H₂PO₄⁻, contains inorganic layers built by (H₂PO₄)⁻ anions and which are parallel to the ab planes around z = $[{1 \over 2}]$ . 3-Chloro-2-methylanilinium cations are anchored between the inorganic layers through N—H⋯O hydrogen bonds. Electrostatic and van der Waals interactions, as well as hydrogen bonds, maintain the structural cohesion.

Related literature

For related literature, see: Adams (1977 ); Blessing (1986 ); Chtioui & Jouini (2004 ); Desiraju (1989 , 1995 ); Hebert (1978 ); Oueslati & Ben Nasr (2006 ).

Experimental

Crystal data

C₇H₉ClN⁺·H₂PO₄⁻
M_r = 239.59
Monoclinic, P 2₁ /c
a = 16.942 (6) Å
b = 8.272 (2) Å
c = 7.979 (7) Å
β = 100.11 (5)°
V = 1100.8 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 292 K
0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction: none
3304 measured reflections
1932 independent reflections
1736 reflections with I > 2σ(I)
R_int = 0.027
2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.122
S = 1.08
1932 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.82	1.83	2.634 (3)	166
O2—H2⋯O3ⁱⁱ	0.82	1.83	2.596 (2)	154
N1—H1A⋯O3	0.89	2.04	2.886 (3)	158
N1—H1B⋯O4ⁱⁱⁱ	0.89	1.84	2.722 (3)	172
N1—H1C⋯O4ⁱⁱ	0.89	1.84	2.708 (3)	166
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z.

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 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001700/dn2313sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808001700/dn2313Isup2.hkl

checkCIF report

Comment top

Inorganic-organic hybrid materials have been studied extensively because the blending of organic and inorganic components allows to the development of materials with novel properties. In particular the family of material which combine monophosphate anions with organic molecules such as aliphatic and aromatic amines has been studied intensively due to their numerous uses in various fields such as biomolecular science, liquid crystals, catalysts and fuel cells (Adams, 1977; Blessing, 1986; Desiraju, 1989, 1995). As a contribution to the study of this compound family, we report in this work the synthesis and the crystal structure of a new organic cation monophosphate [3-Cl-2-CH₃C₆H₃NH₃]H₂PO₄ (I).

The asymmetric unit in the structure of I consists of one phosphate anion (H₂PO₄)^- and one organic cation (3-Cl-2-CH₃C₆H₃NH₃)⁺(Fig. 1). A projection of the structure in the [001] direction shows that the (H₂PO₄) groups are interconnected by O—H···.O hydrogen bonds to form inorganic layers parallel to the (a, b) planes (Fig. 2). On both sides of each inorganic layer (Fig. 3), are grafted the organic cations compensating their negatives charges. Each (H₂PO₄) group is connected to three neighbours by strong hydrogen bonds, with O···O separations ranging from 2.596 (2) Å to 2.634 (3) Å (Table 1). Among the P—O distances in the PO₄ tetrahedron, we can distinguish two different types: the shortest ones (1.498 (2) Å and 1.509 (2) Å) correspond to the phosphorus atom double bonded to oxygen atom (P=O); the largest ones (1.563 (2) Å and 1.564 (2) Å) can be attributed to P—OH distances. The average P—O distances and O—P—O bond angles are 1.534 Å and 109.42°, respectively, which fall in the range of the values observed in many phosphate materials (Hebert, 1978)). The strength of O—H···O hydrogen bond and the values of P···P distances (with a minimum value of 4.383 (4) Å) between two successive inorganic layers could allow us to consider the (H₂PO₄)_n^- subnetwork as a polymeric species. Similar arrangement have been observed in other crystal structures (Chtioui & Jouini, 2004). The C—C bond lengths spreading between are 1.361 (6) and 1.500 (5) Å, which are between single and double bond and agree with that in 4-chloroanilinium dihydrogenmonophosphate (Oueslati & Ben Nasr, 2006).

Related literature top

For related literature, see: Adams (1977); Blessing (1986); Chtioui & Jouini (2004); Desiraju (1989, 1995); Hebert (1978); Oueslati & Ben Nasr (2006).

Experimental top

Single crystals of the title compound (I) were prepared by adding drop by drop under stirring, an aqueous solution (10 ml) of orthophosphoric acid (0.25 mmol) (85 weight from Fluka %) to an alcoholic solution (10 ml) of 3-Cloro-2-methylaniline (0.15 mmol)(Across 98). The obtained solution was then slowly evaporated at room temperature until the formation of single crystals which were stable under normal condition of temperature and humidity.

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 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. H bond is shown as dashed line.
	Fig. 2. Projection of (H₂PO₄)_n^- subnetwork along c axis.
	Fig. 3. Projection of (I) along b axis.

3-Chloro-2-methylanilinium dihydrogenphosphate top

Crystal data top

C₇H₉ClN⁺·H₂PO₄⁻	F(000) = 496
M_r = 239.59	D_x = 1.446 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 16.942 (6) Å	θ = 8–11°
b = 8.272 (2) Å	µ = 0.48 mm⁻¹
c = 7.979 (7) Å	T = 292 K
β = 100.11 (5)°	Prism, colorless
V = 1100.8 (11) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Enraf–Nonius TurboCAD4 diffractometer	R_int = 0.027
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.4°
Graphite monochromator	h = −10→20
non–profiled ω scans	k = −9→0
3304 measured reflections	l = −9→9
1932 independent reflections	2 standard reflections every 120 min
1736 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.044	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0675P)² + 0.6257P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.011
1932 reflections	Δρ_max = 0.36 e Å⁻³
132 parameters	Δρ_min = −0.38 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: 0.015 (3)

Crystal data top

C₇H₉ClN⁺·H₂PO₄⁻	V = 1100.8 (11) Å³
M_r = 239.59	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.942 (6) Å	µ = 0.48 mm⁻¹
b = 8.272 (2) Å	T = 292 K
c = 7.979 (7) Å	0.40 × 0.30 × 0.20 mm
β = 100.11 (5)°

Data collection top

Enraf–Nonius TurboCAD4 diffractometer	R_int = 0.027
3304 measured reflections	2 standard reflections every 120 min
1932 independent reflections	intensity decay: 1%
1736 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.08	Δρ_max = 0.36 e Å⁻³
1932 reflections	Δρ_min = −0.38 e Å⁻³
132 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
P1	0.43820 (3)	0.46630 (6)	0.23711 (6)	0.0298 (2)
O1	0.39492 (10)	0.5342 (2)	0.3800 (2)	0.0503 (5)
H1	0.4278	0.5477	0.4674	0.075*
O2	0.44438 (12)	0.60754 (19)	0.11002 (19)	0.0462 (5)
H2	0.4562	0.6914	0.1634	0.069*
O3	0.52069 (9)	0.40766 (18)	0.31601 (17)	0.0346 (4)
O4	0.38537 (10)	0.34256 (19)	0.13619 (18)	0.0408 (4)
Cl1	0.95781 (6)	0.6138 (3)	0.2672 (2)	0.1564 (8)
N1	0.65051 (11)	0.5738 (2)	0.1985 (2)	0.0342 (4)
H1A	0.6130	0.5026	0.2138	0.051*
H1B	0.6435	0.6023	0.0893	0.051*
H1C	0.6468	0.6609	0.2621	0.051*
C1	0.72967 (14)	0.5010 (3)	0.2480 (3)	0.0392 (5)
C2	0.79647 (15)	0.5918 (4)	0.2317 (3)	0.0524 (7)
C3	0.86992 (18)	0.5110 (6)	0.2839 (5)	0.0784 (10)
C4	0.8752 (2)	0.3579 (6)	0.3475 (6)	0.0954 (13)
H4	0.9252	0.3102	0.3805	0.114*
C5	0.8074 (2)	0.2742 (5)	0.3631 (6)	0.0875 (12)
H5	0.8110	0.1701	0.4078	0.105*
C6	0.73348 (18)	0.3460 (3)	0.3116 (4)	0.0617 (8)
H6	0.6867	0.2900	0.3199	0.074*
C7	0.7899 (2)	0.7623 (5)	0.1667 (5)	0.0807 (11)
H7A	0.7432	0.8123	0.1966	0.121*
H7B	0.7856	0.7619	0.0451	0.121*
H7C	0.8368	0.8219	0.2168	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0413 (4)	0.0243 (3)	0.0221 (3)	−0.0007 (2)	0.0007 (2)	−0.00082 (18)
O1	0.0444 (9)	0.0731 (13)	0.0312 (9)	0.0113 (9)	0.0005 (7)	−0.0125 (8)
O2	0.0800 (12)	0.0248 (8)	0.0297 (8)	−0.0045 (8)	−0.0020 (8)	0.0030 (6)
O3	0.0448 (9)	0.0301 (8)	0.0276 (7)	0.0037 (6)	0.0023 (6)	−0.0020 (6)
O4	0.0548 (9)	0.0355 (9)	0.0285 (7)	−0.0119 (7)	−0.0026 (7)	0.0004 (6)
Cl1	0.0485 (6)	0.2330 (19)	0.1867 (15)	−0.0312 (8)	0.0178 (7)	0.0464 (14)
N1	0.0391 (10)	0.0352 (9)	0.0272 (8)	−0.0005 (8)	0.0029 (7)	−0.0024 (7)
C1	0.0416 (12)	0.0449 (12)	0.0305 (11)	0.0019 (10)	0.0048 (9)	−0.0055 (9)
C2	0.0451 (14)	0.0698 (18)	0.0419 (13)	−0.0073 (13)	0.0061 (11)	−0.0006 (13)
C3	0.0414 (15)	0.118 (3)	0.075 (2)	−0.0034 (18)	0.0094 (15)	0.001 (2)
C4	0.060 (2)	0.113 (3)	0.109 (3)	0.035 (2)	0.005 (2)	0.011 (3)
C5	0.072 (2)	0.066 (2)	0.120 (3)	0.0236 (18)	0.005 (2)	0.017 (2)
C6	0.0540 (15)	0.0458 (15)	0.083 (2)	0.0069 (13)	0.0066 (14)	0.0043 (14)
C7	0.075 (2)	0.085 (2)	0.079 (2)	−0.0277 (19)	0.0063 (18)	0.0238 (19)

Geometric parameters (Å, º) top

P1—O4	1.4980 (16)	C1—C2	1.383 (4)
P1—O3	1.5087 (17)	C2—C3	1.409 (4)
P1—O2	1.5626 (17)	C2—C7	1.500 (5)
P1—O1	1.5641 (19)	C3—C4	1.361 (6)
O1—H1	0.8200	C4—C5	1.365 (6)
O2—H2	0.8200	C4—H4	0.9300
Cl1—C3	1.740 (4)	C5—C6	1.382 (4)
N1—C1	1.460 (3)	C5—H5	0.9300
N1—H1A	0.8900	C6—H6	0.9300
N1—H1B	0.8900	C7—H7A	0.9600
N1—H1C	0.8900	C7—H7B	0.9600
C1—C6	1.377 (4)	C7—H7C	0.9600

O4—P1—O3	115.27 (9)	C3—C2—C7	123.8 (3)
O4—P1—O2	105.31 (10)	C4—C3—C2	123.3 (3)
O3—P1—O2	110.39 (10)	C4—C3—Cl1	118.8 (3)
O4—P1—O1	108.96 (11)	C2—C3—Cl1	117.9 (3)
O3—P1—O1	109.25 (10)	C3—C4—C5	120.3 (3)
O2—P1—O1	107.34 (11)	C3—C4—H4	119.9
P1—O1—H1	109.5	C5—C4—H4	119.9
P1—O2—H2	109.5	C4—C5—C6	119.2 (4)
C1—N1—H1A	109.5	C4—C5—H5	120.4
C1—N1—H1B	109.5	C6—C5—H5	120.4
H1A—N1—H1B	109.5	C1—C6—C5	119.4 (3)
C1—N1—H1C	109.5	C1—C6—H6	120.3
H1A—N1—H1C	109.5	C5—C6—H6	120.3
H1B—N1—H1C	109.5	C2—C7—H7A	109.5
C6—C1—C2	123.7 (3)	C2—C7—H7B	109.5
C6—C1—N1	117.7 (2)	H7A—C7—H7B	109.5
C2—C1—N1	118.6 (2)	C2—C7—H7C	109.5
C1—C2—C3	114.2 (3)	H7A—C7—H7C	109.5
C1—C2—C7	122.1 (3)	H7B—C7—H7C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.83	2.634 (3)	166
O2—H2···O3ⁱⁱ	0.82	1.83	2.596 (2)	154
N1—H1A···O3	0.89	2.04	2.886 (3)	158
N1—H1B···O4ⁱⁱⁱ	0.89	1.84	2.722 (3)	172
N1—H1C···O4ⁱⁱ	0.89	1.84	2.708 (3)	166

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

Experimental details

Crystal data
Chemical formula	C₇H₉ClN⁺·H₂PO₄⁻
M_r	239.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	16.942 (6), 8.272 (2), 7.979 (7)
β (°)	100.11 (5)
V (Å³)	1100.8 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.48
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius TurboCAD4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3304, 1932, 1736
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.122, 1.08
No. of reflections	1932
No. of parameters	132
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.82	1.83	2.634 (3)	165.8
O2—H2···O3ⁱⁱ	0.82	1.83	2.596 (2)	154.3
N1—H1A···O3	0.89	2.04	2.886 (3)	157.5
N1—H1B···O4ⁱⁱⁱ	0.89	1.84	2.722 (3)	172.4
N1—H1C···O4ⁱⁱ	0.89	1.84	2.708 (3)	166.3

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

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o526

doi:10.1107/S1600536808001700

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