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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o526.
Published online 2008 January 30. doi:  10.1107/S1600536808001700
PMCID: PMC2960226

3-Chloro-2-methyl­anilinium dihydrogenphosphate

Abstract

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 = An external file that holds a picture, illustration, etc.
Object name is e-64-0o526-efi1.jpg. 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 [triangle]); Blessing (1986 [triangle]); Chtioui & Jouini (2004 [triangle]); Desiraju (1989 [triangle], 1995 [triangle]); Hebert (1978 [triangle]); Oueslati & Ben Nasr (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o526-scheme1.jpg

Experimental

Crystal data

  • C7H9ClN+·H2PO4
  • M r = 239.59
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o526-efi2.jpg
  • 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[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.122
  • S = 1.08
  • 1932 reflections
  • 132 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.38 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

All H atoms attached to C, N and O atoms were fixed geometrically and treated as riding with C—H = 0.93 Å (Caromatic) or 0.96 Å (Cmethyl), N—H= 0.89 Å and O—H = 0.82 Å and with Uiso=1.2Ueq(Caromatic,O) or Uiso=1.5Ueq(Cmethyl,N).

Figures

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.

Crystal data

C7H9ClN+·H2PO4F000 = 496
Mr = 239.59Dx = 1.446 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 16.942 (6) Åθ = 8–11º
b = 8.272 (2) ŵ = 0.48 mm1
c = 7.979 (7) ÅT = 292 K
β = 100.11 (5)ºPrism, colorless
V = 1100.8 (11) Å30.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius TurboCAD4 diffractometerRint = 0.027
Radiation source: fine-focus sealed tubeθmax = 25.0º
Monochromator: graphiteθmin = 2.4º
T = 292 Kh = −10→20
non–profiled ω scansk = −9→0
Absorption correction: nonel = −9→9
3304 measured reflections2 standard reflections
1932 independent reflections every 120 min
1736 reflections with I > 2σ(I) intensity decay: 1%

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044  w = 1/[σ2(Fo2) + (0.0675P)2 + 0.6257P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.122(Δ/σ)max = 0.011
S = 1.08Δρmax = 0.36 e Å3
1932 reflectionsΔρmin = −0.38 e Å3
132 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.015 (3)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
P10.43820 (3)0.46630 (6)0.23711 (6)0.0298 (2)
O10.39492 (10)0.5342 (2)0.3800 (2)0.0503 (5)
H10.42780.54770.46740.075*
O20.44438 (12)0.60754 (19)0.11002 (19)0.0462 (5)
H20.45620.69140.16340.069*
O30.52069 (9)0.40766 (18)0.31601 (17)0.0346 (4)
O40.38537 (10)0.34256 (19)0.13619 (18)0.0408 (4)
Cl10.95781 (6)0.6138 (3)0.2672 (2)0.1564 (8)
N10.65051 (11)0.5738 (2)0.1985 (2)0.0342 (4)
H1A0.61300.50260.21380.051*
H1B0.64350.60230.08930.051*
H1C0.64680.66090.26210.051*
C10.72967 (14)0.5010 (3)0.2480 (3)0.0392 (5)
C20.79647 (15)0.5918 (4)0.2317 (3)0.0524 (7)
C30.86992 (18)0.5110 (6)0.2839 (5)0.0784 (10)
C40.8752 (2)0.3579 (6)0.3475 (6)0.0954 (13)
H40.92520.31020.38050.114*
C50.8074 (2)0.2742 (5)0.3631 (6)0.0875 (12)
H50.81100.17010.40780.105*
C60.73348 (18)0.3460 (3)0.3116 (4)0.0617 (8)
H60.68670.29000.31990.074*
C70.7899 (2)0.7623 (5)0.1667 (5)0.0807 (11)
H7A0.74320.81230.19660.121*
H7B0.78560.76190.04510.121*
H7C0.83680.82190.21680.121*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0413 (4)0.0243 (3)0.0221 (3)−0.0007 (2)0.0007 (2)−0.00082 (18)
O10.0444 (9)0.0731 (13)0.0312 (9)0.0113 (9)0.0005 (7)−0.0125 (8)
O20.0800 (12)0.0248 (8)0.0297 (8)−0.0045 (8)−0.0020 (8)0.0030 (6)
O30.0448 (9)0.0301 (8)0.0276 (7)0.0037 (6)0.0023 (6)−0.0020 (6)
O40.0548 (9)0.0355 (9)0.0285 (7)−0.0119 (7)−0.0026 (7)0.0004 (6)
Cl10.0485 (6)0.2330 (19)0.1867 (15)−0.0312 (8)0.0178 (7)0.0464 (14)
N10.0391 (10)0.0352 (9)0.0272 (8)−0.0005 (8)0.0029 (7)−0.0024 (7)
C10.0416 (12)0.0449 (12)0.0305 (11)0.0019 (10)0.0048 (9)−0.0055 (9)
C20.0451 (14)0.0698 (18)0.0419 (13)−0.0073 (13)0.0061 (11)−0.0006 (13)
C30.0414 (15)0.118 (3)0.075 (2)−0.0034 (18)0.0094 (15)0.001 (2)
C40.060 (2)0.113 (3)0.109 (3)0.035 (2)0.005 (2)0.011 (3)
C50.072 (2)0.066 (2)0.120 (3)0.0236 (18)0.005 (2)0.017 (2)
C60.0540 (15)0.0458 (15)0.083 (2)0.0069 (13)0.0066 (14)0.0043 (14)
C70.075 (2)0.085 (2)0.079 (2)−0.0277 (19)0.0063 (18)0.0238 (19)

Geometric parameters (Å, °)

P1—O41.4980 (16)C1—C21.383 (4)
P1—O31.5087 (17)C2—C31.409 (4)
P1—O21.5626 (17)C2—C71.500 (5)
P1—O11.5641 (19)C3—C41.361 (6)
O1—H10.8200C4—C51.365 (6)
O2—H20.8200C4—H40.9300
Cl1—C31.740 (4)C5—C61.382 (4)
N1—C11.460 (3)C5—H50.9300
N1—H1A0.8900C6—H60.9300
N1—H1B0.8900C7—H7A0.9600
N1—H1C0.8900C7—H7B0.9600
C1—C61.377 (4)C7—H7C0.9600
O4—P1—O3115.27 (9)C3—C2—C7123.8 (3)
O4—P1—O2105.31 (10)C4—C3—C2123.3 (3)
O3—P1—O2110.39 (10)C4—C3—Cl1118.8 (3)
O4—P1—O1108.96 (11)C2—C3—Cl1117.9 (3)
O3—P1—O1109.25 (10)C3—C4—C5120.3 (3)
O2—P1—O1107.34 (11)C3—C4—H4119.9
P1—O1—H1109.5C5—C4—H4119.9
P1—O2—H2109.5C4—C5—C6119.2 (4)
C1—N1—H1A109.5C4—C5—H5120.4
C1—N1—H1B109.5C6—C5—H5120.4
H1A—N1—H1B109.5C1—C6—C5119.4 (3)
C1—N1—H1C109.5C1—C6—H6120.3
H1A—N1—H1C109.5C5—C6—H6120.3
H1B—N1—H1C109.5C2—C7—H7A109.5
C6—C1—C2123.7 (3)C2—C7—H7B109.5
C6—C1—N1117.7 (2)H7A—C7—H7B109.5
C2—C1—N1118.6 (2)C2—C7—H7C109.5
C1—C2—C3114.2 (3)H7A—C7—H7C109.5
C1—C2—C7122.1 (3)H7B—C7—H7C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.821.832.634 (3)166
O2—H2···O3ii0.821.832.596 (2)154
N1—H1A···O30.892.042.886 (3)158
N1—H1B···O4iii0.891.842.722 (3)172
N1—H1C···O4ii0.891.842.708 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2313).

References

  • Adams, J. M. (1977). Acta Cryst. B33, 1513–1515.
  • Blessing, R. H. (1986). Acta Cryst. B42, 613–621.
  • Brandenburg, K. & Putz, H. (2005). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Chtioui, A. & Jouini, A. (2004). J. Chem. Crystallogr.34, 43–49.
  • Desiraju, G. R. (1989). Crystal Engineering: the Design of Organic Solids , Vol. 54. New York: Elsevier.
  • Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl.34, 2311–2321.
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Hebert, H. (1978). Acta Cryst. B34, 611–615.
  • Oueslati, A. & Ben Nasr, C. (2006). Anal. Sci. X-ray Struct. Anal. Online, 22, x177–x178.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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