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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1627.
Published online 2010 June 16. doi:  10.1107/S1600536810021100
PMCID: PMC3006684

(4-Chloro­phen­yl)methanaminium chloride hemihydrate

Abstract

In the title hydrated salt, C7H9ClN+·Cl·0.5H2O, the water O atom lies on a crystallographic twofold axis. In the crystal, the monoprotonated 4-chloro­benzyl­ammonium cation forms N—H(...)Cl and N—H(...)O hydrogen bonds and the water mol­ecule forms O—H(...)Cl hydrogen bonds, generating layers lying parallel to the bc plane.

Related literature

For the properties of benzyl­amines, see: Markwardt et al. (2005 [triangle]). For a related structure, see: Dhaouadi et al. (2008 [triangle]).

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Object name is e-66-o1627-scheme1.jpg

Experimental

Crystal data

  • C7H9ClN+·Cl·0.5H2O
  • M r = 187.06
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1627-efi1.jpg
  • a = 30.462 (2) Å
  • b = 4.890 (3) Å
  • c = 11.738 (2) Å
  • β = 99.97 (3)°
  • V = 1722.1 (11) Å3
  • Z = 8
  • Ag Kα radiation
  • λ = 0.56085 Å
  • μ = 0.35 mm−1
  • T = 293 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Enraf–Nonius TurboCAD-4 diffractometer
  • 5908 measured reflections
  • 4207 independent reflections
  • 2217 reflections with I > 2σ(I)
  • R int = 0.031
  • 2 standard reflections every 120 min intensity decay: 5%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.130
  • S = 1.00
  • 4207 reflections
  • 101 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.32 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 (Farrugia, 1997 [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/S1600536810021100/hb5481sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021100/hb5481Isup2.hkl

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

supplementary crystallographic information

Comment

Derivatives of benzylamine were found to be competitive inhibitors of the proteolytic enzymes trypsin, plasmin, and thrombin. So, the 4-chlorobenzylamine is a strong thrombin inhibitor but only of low effectiveness against trypsin and plasmin for the hydrolysis of N-α-benzoyl catalyzed by these three enzymes. Relations between the chemical structure and the activity against trypsin, plasmin and thrombin were deduced by comparing the inhibitor constants (Markwardt, F. et al., 2005). In this work, we report the crystal structure of the title compound (I). As shown in (Fig.1), the asymmetric unit of (I) is built up from one 4-chlorobenzylammonium cation, one chloride anion and one water molecule. The Cl- anions, water molecules and R—NH3+ groups are lineked via O—H···Cl, N—H···O and N—H···Cl hydrogen bonds and ionic interactions, so as to built inorganic layers spreading around the (b,c) planes. The 4-chlorobenzylammonium cations are anchored onto the successive inorganic layers via hydrogen bonds and electrostatic interactions, to composite their negative charges.

The examination of the organic cation shows that the values of N—C, C—C, C—Cl distances and N—C—C, C—C—C, C—C—Cl angles range from 1.376 (3) to 1.736 (3) Å and 115.72 (19) to 122.80 (19)°, respectively. These values show no significant difference from those obtained in other organic materials associated with the same organic groups (Dhaouadi, H. et al., 2008).

In this structure, the water molecules play a very important role in the cohesion of the various groups. It participates with the organic cations and chloride anions in the H-bonding scheme of N—H···O and O—H···Cl interactions in the crystal structure. The four hydrogen bonds are relatively weak, and their donor acceptor distances vary from 2.866 (2) to 3.417 (3) Å. Thus, these different interactions (hydrogen bonds, Van der Waals, and electrostatic) form a stable three-dimensional network.

Experimental

An ethanolic solution of 4-chlorobenzylamine (10 mmol, in 10 ml) was added, with stirring, to 20 ml of an aqueous HCl solution (0.5M) at room temperature. Colourless blocks of (I) were obtained on slow evaporation of the solvent.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms, [N–H = 0.89, C–H =0.96 Å (CH3 ) with with Uiso(H) = 1.5Ueq and C–H =0.96 Å (Ar–H), with Uiso(H) = 1.5Ueq], but those attached to oxygen atom are located in a difference map

Figures

Fig. 1.
View of (I) with displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
Fig. 2.
A view of the packing of (I) along the b axis.

Crystal data

C7H9ClN+·Cl·0.5H2OF(000) = 776
Mr = 187.06Dx = 1.443 Mg m3
Monoclinic, C2/cAg Kα radiation, λ = 0.56085 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 30.462 (2) Åθ = 9–11°
b = 4.890 (3) ŵ = 0.35 mm1
c = 11.738 (2) ÅT = 293 K
β = 99.97 (3)°Block, colourless
V = 1722.1 (11) Å30.30 × 0.25 × 0.20 mm
Z = 8

Data collection

Enraf–Nonius TurboCAD-4 diffractometerRint = 0.031
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.3°
graphiteh = −50→50
non–profiled ω scansk = 0→8
5908 measured reflectionsl = −5→19
4207 independent reflections2 standard reflections every 120 min
2217 reflections with I > 2σ(I) intensity decay: 5%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.130w = 1/[σ2(Fo2) + (0.0585P)2 + 0.2911P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
4207 reflectionsΔρmax = 0.34 e Å3
101 parametersΔρmin = −0.32 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0080 (12)

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
Cl10.049348 (13)0.63727 (9)0.11132 (4)0.04257 (13)
O0.00000.2285 (4)0.25000.0494 (5)
H10.0151 (8)0.323 (5)0.210 (2)0.089 (9)*
C10.12851 (4)0.0280 (3)0.40289 (14)0.0313 (3)
C20.12629 (5)0.1317 (3)0.29253 (14)0.0364 (3)
H20.10480.06610.23280.044*
C30.15582 (5)0.3328 (3)0.26977 (14)0.0371 (3)
H30.15380.40460.19570.045*
C40.18814 (4)0.4244 (3)0.35851 (14)0.0329 (3)
C50.19059 (5)0.3278 (4)0.46938 (15)0.0386 (4)
H50.21210.39470.52890.046*
C60.16065 (5)0.1293 (4)0.49129 (14)0.0380 (3)
H60.16210.06310.56610.046*
C70.09748 (5)−0.1977 (3)0.42512 (18)0.0399 (4)
H7A0.0966−0.33620.36560.048*
H7B0.1090−0.28240.49900.048*
Cl20.225682 (14)0.66901 (9)0.32754 (5)0.04948 (15)
N0.05166 (4)−0.0999 (3)0.42641 (13)0.0404 (3)
H0A0.0347−0.24000.44010.061*
H0B0.0406−0.02610.35820.061*
H0C0.05210.02510.48170.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0390 (2)0.0365 (2)0.0527 (3)0.00140 (16)0.00925 (17)0.00195 (19)
O0.0523 (11)0.0428 (10)0.0574 (12)0.0000.0215 (9)0.000
C10.0289 (6)0.0260 (6)0.0403 (8)0.0011 (5)0.0097 (6)−0.0002 (6)
C20.0372 (7)0.0376 (8)0.0333 (8)−0.0070 (6)0.0033 (6)−0.0044 (7)
C30.0441 (8)0.0367 (8)0.0314 (8)−0.0060 (7)0.0086 (6)0.0008 (7)
C40.0281 (6)0.0281 (6)0.0444 (9)−0.0017 (5)0.0117 (6)−0.0042 (6)
C50.0318 (7)0.0436 (9)0.0388 (9)−0.0035 (6)0.0011 (6)−0.0064 (7)
C60.0388 (7)0.0407 (8)0.0342 (8)0.0015 (7)0.0057 (6)0.0049 (7)
C70.0384 (7)0.0263 (7)0.0577 (11)0.0010 (6)0.0153 (7)0.0043 (7)
Cl20.0432 (2)0.0391 (2)0.0709 (3)−0.01276 (17)0.0229 (2)−0.0055 (2)
N0.0339 (6)0.0355 (7)0.0529 (9)−0.0069 (5)0.0101 (6)0.0005 (6)

Geometric parameters (Å, °)

O—H10.84 (2)C5—C61.386 (2)
C1—C21.382 (2)C5—H50.9300
C1—C61.389 (2)C6—H60.9300
C1—C71.505 (2)C7—N1.4779 (19)
C2—C31.389 (2)C7—H7A0.9700
C2—H20.9300C7—H7B0.9700
C3—C41.379 (2)N—H0A0.8900
C3—H30.9300N—H0B0.8900
C4—C51.374 (2)N—H0C0.8900
C4—Cl21.7361 (15)
C2—C1—C6118.89 (14)C5—C6—C1120.84 (15)
C2—C1—C7120.10 (15)C5—C6—H6119.6
C6—C1—C7120.98 (15)C1—C6—H6119.6
C1—C2—C3120.78 (15)N—C7—C1112.77 (13)
C1—C2—H2119.6N—C7—H7A109.0
C3—C2—H2119.6C1—C7—H7A109.0
C4—C3—C2119.10 (15)N—C7—H7B109.0
C4—C3—H3120.5C1—C7—H7B109.0
C2—C3—H3120.5H7A—C7—H7B107.8
C5—C4—C3121.21 (14)C7—N—H0A109.5
C5—C4—Cl2120.36 (12)C7—N—H0B109.5
C3—C4—Cl2118.42 (13)H0A—N—H0B109.5
C4—C5—C6119.14 (14)C7—N—H0C109.5
C4—C5—H5120.4H0A—N—H0C109.5
C6—C5—H5120.4H0B—N—H0C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N—H0A···Cl1i0.892.603.2930 (19)136
N—H0A···Cl1ii0.892.783.417 (2)130
N—H0B···O0.892.042.866 (2)155
N—H0C···Cl1iii0.892.263.144 (2)175
O—H1···Cl10.85 (3)2.28 (3)3.1230 (18)171 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5481).

References

  • Dhaouadi, H., Marouani, H., Rzaigui, M. & Madani, A. (2008). Mater. Res. Bull.43, 3234–3244.
  • 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.
  • Markwardt, F., Landmann, H. & Walsmann, P. (2005). Eur. J. Biochem.6, 502–506. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography