2-[2-Chloro-5-(trifluoro­methyl)­phen­yl]hexa­hydro­pyrimidine monohydrate

Fun, H.-K.; Kia, R.

doi:10.1107/S1600536808027232

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages o1840-o1841

doi:10.1107/S1600536808027232

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2-[2-Chloro-5-(trifluoromethyl)phenyl]hexahydropyrimidine monohydrate

Hoong-Kun Fun ^a ^* and Reza Kia ^a ‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 19 August 2008; accepted 23 August 2008; online 30 August 2008)

The molecule of the title compound, C₁₁H₁₂ClF₃N₂·H₂O, is a substituted hexahydropyrimidine. There are two crystallographically independent molecules (A and B) and two water molecules in the asymmetric unit of the title compound. Intermolecular C—H⋯Cl (× 2), C—H⋯F, and C—H⋯N (× 2) hydrogen bonds generate S(5) ring motifs. The dihedral angle between the two benzene rings is 8.17 (11)°. The F atoms in molecule B are disordered over four positions with refined site-occupancies of ca 0.35/0.19/0.29/0.17 for the four components. In the crystal structure, molecules are arranged into one-dimensional extended chains along the c axis and are further stacked along the a axis by directed four-membered O—H⋯O—H interactions, forming two-dimensional networks parallel to the ac plane. The short distances between the centroids of the benzene rings (3.8002–3.8327 Å) indicate the existence of π–π interactions. In addition, the crystal structure is further stabilized by N—H⋯O, O—H⋯N (× 4), N—H⋯Cl and C—H⋯O (× 2) hydrogen-bonding interactions.

Related literature

For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformations, see: Cremer & Pople (1975 ). For related literature and properties, see, for example: Riebsomer & Morey (1950 ); Finch et al. (1952 ); Drandarov et al. (1999 ); Siddiqui et al. (1999 ); Horvath (1997 ); Katritzky et al. (2002 ).

Experimental

Crystal data

C₁₁H₁₂ClF₃N₂·H₂O
M_r = 282.69
Monoclinic, P 2₁ /c
a = 7.0745 (2) Å
b = 18.6119 (5) Å
c = 19.0631 (5) Å
β = 91.010 (2)°
V = 2509.65 (12) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100.0 (1) K
0.24 × 0.05 × 0.02 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.924, T_max = 0.992
30107 measured reflections
7308 independent reflections
4995 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.145
S = 1.08
7308 reflections
379 parameters
41 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1Wⁱ	0.90 (3)	2.07 (4)	2.885 (3)	151 (3)
N1B—H1NB⋯Cl1Aⁱⁱ	0.89 (3)	2.76 (3)	3.595 (2)	156 (2)
N2B—H2NB⋯O2W	0.84 (3)	2.18 (4)	2.969 (3)	156 (3)
O1W—H1W1⋯N2Bⁱⁱⁱ	0.86 (4)	1.95 (4)	2.815 (3)	174 (4)
O1W—H2W1⋯N2A^iv	0.87 (4)	2.02 (3)	2.867 (3)	165 (3)
O2W—H1W2⋯N1B^v	0.83 (3)	2.09 (3)	2.891 (3)	161 (3)
O2W—H2W2⋯N1A^vi	0.87 (4)	1.98 (4)	2.844 (3)	176 (4)
C2A—H2AA⋯O2W	0.93	2.35	3.249 (3)	164
C5A—H5AA⋯F1A	0.93	2.42	2.747 (3)	100
C5A—H5AA⋯N1A	0.93	2.52	2.835 (3)	100
C7A—H7AA⋯Cl1A	0.98	2.67	3.076 (3)	105
C2B—H2BA⋯O1W^iv	0.93	2.52	3.414 (3)	162
C5B—H5BA⋯N2B	0.93	2.53	2.838 (3)	100
C7B—H7BA⋯Cl1B	0.98	2.68	3.070 (3)	104
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) x-1, y, z; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808027232/at2619sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808027232/at2619Isup2.hkl

checkCIF report

Comment top

Hexahydropyrimidines are prepared classically by condensations of substituted propane-1,3-diamines with aldehydes and ketones. Hexahydropyrimidines are biologically important. N,N'-Bisalkylhexahydro pyrimidines are effective against Ehrlich carcinoma, LK lymphoma, and Staphylococcus aureus. The hexahydropyrimidine skeleton occurs in alkaloids such as verbamethine and verbametrine. N-Substituted hexahydropyrimidines are synthetic intermediates for recently discovered spermidine-nitroimidazole drugs for the treatment of A549 lung carcinoma and structural units in new trypanothione reductase inhibiting ligands for the regulation of oxidative stress in parasitic cells. Benzo-fused hexahydropyrimidines or 1,2,3,4-tetrahydroquinazolines are potential R-adrenergic blockers and possess antiplatelet activity.

In the title compound (I) (Fig. 1), intramolecular C—H···Cl (x 2), C—H···F, and C—H···N (x 2) hydrogen bonds generate S(5) ring motifs (Bernstein et al., 1995). The bond lengths and angles are within normal ranges (Allen et al., 1987). There are two crystallographically independent molecules (A, and B) and two water molecules in the asymmetric unit of the title compound. The dihedral angle between the two benzene rings is 8.17 (11)°. The pyrimidine rings in molecules A and B adopt chair conformation with the puckering parameter (Cremer & Pople, 1975) Q=0.603 (3)°; θ=1.2 (3)°; ϕ=31 (9)° for ring A and Q=0.601 (3)°; θ=2.5 (3)°; ϕ=48 (6)° for ring B. The CF₃ fragment in molecule B, was disordered over four positions with the refined site-occupancies of 0.351 (7)/0.189 (5)/0.289 (9)/0.168 (6) for these four components, respectively. In the crystal structure, molecules are arranged into 1-D extended chains along the c-axis and are further stacked along the a-axis by directed four-membered O—H···O—H interactions to form 2-D networks which is parralell to ac-plane. The short distances between the centroids of the benzene rings prove an existence of π-π interactions with distances of 3.8002–3.8327 Å. In addition, the crystal structure is further stabilized by N—H···O, O—H···N (x 4), N—H···Cl, and C—H···O (x 2) hydrogen bonding interactions.

Related literature top

For bond-lengts data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations, see: Cremer & Pople (1975). For related literature and properties, see, for example: Riebsomer & Morey (1950); Finch et al. (1952); Drandarov et al. (1999); Siddiqui et al. (1999); Horvath (1997); Katritzky et al. (2002).

Experimental top

The title compound was synthesized based on the previous method (Finch et al., 1952). Single crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids. For clarity, only hydrogen atoms of the water molecules and those H atoms involved in intramolecular and intermolecular interactions (shown as dashed lines) were drawn. Open bonds indicate the minor disordered component.
	Fig. 2. The crystal packing of the major component of (I), viewed down the a-axis, showing 1-D extended chains along the c-axis and stacking of these chains along the a-axis. Intra and intermolecular interactions are shown as dashed lines.
	Fig. 3. The crystal structure of the major component of (I), showing 1-D extended chains along the a-axis.

2-[2-Chloro-5-(trifluoromethyl)phenyl]hexahydropyrimidine monohydrate top

Crystal data top

C₁₁H₁₂ClF₃N₂·H₂O	F(000) = 1168
M_r = 282.69	D_x = 1.496 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6400 reflections
a = 7.0745 (2) Å	θ = 2.4–23.0°
b = 18.6119 (5) Å	µ = 0.33 mm⁻¹
c = 19.0631 (5) Å	T = 100 K
β = 91.010 (2)°	Block, colourless
V = 2509.65 (12) Å³	0.24 × 0.05 × 0.02 mm
Z = 8

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7308 independent reflections
Radiation source: fine-focus sealed tube	4995 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 30.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→9
T_min = 0.924, T_max = 0.992	k = −26→20
30107 measured reflections	l = −16→26

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0411P)² + 3.5237P] where P = (F_o² + 2F_c²)/3
7308 reflections	(Δ/σ)_max < 0.001
379 parameters	Δρ_max = 0.61 e Å⁻³
41 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₁₁H₁₂ClF₃N₂·H₂O	V = 2509.65 (12) Å³
M_r = 282.69	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.0745 (2) Å	µ = 0.33 mm⁻¹
b = 18.6119 (5) Å	T = 100 K
c = 19.0631 (5) Å	0.24 × 0.05 × 0.02 mm
β = 91.010 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7308 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4995 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.992	R_int = 0.053
30107 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	41 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.61 e Å⁻³
7308 reflections	Δρ_min = −0.60 e Å⁻³
379 parameters

Special details top

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

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	Occ. (<1)
Cl1A	0.20441 (9)	0.10260 (4)	0.33890 (4)	0.02426 (16)
F1A	0.1451 (3)	0.40379 (9)	0.52585 (9)	0.0364 (4)
F2A	0.0671 (3)	0.44306 (10)	0.42408 (11)	0.0431 (5)
F3A	0.3579 (2)	0.43149 (10)	0.45284 (10)	0.0382 (5)
N1A	0.0590 (3)	0.15070 (12)	0.56007 (12)	0.0182 (5)
N2A	0.3521 (3)	0.10898 (12)	0.51715 (12)	0.0182 (5)
C1A	0.1928 (3)	0.18840 (15)	0.37603 (14)	0.0195 (5)
C2A	0.2034 (3)	0.24683 (16)	0.33062 (14)	0.0226 (6)
H2AA	0.2129	0.2397	0.2825	0.027*
C3A	0.1998 (3)	0.31528 (16)	0.35780 (14)	0.0227 (6)
H3AA	0.2056	0.3548	0.3280	0.027*
C4A	0.1874 (3)	0.32524 (14)	0.42968 (14)	0.0193 (5)
C5A	0.1752 (3)	0.26648 (14)	0.47436 (14)	0.0169 (5)
H5AA	0.1667	0.2739	0.5224	0.020*
C6A	0.1758 (3)	0.19653 (14)	0.44817 (13)	0.0163 (5)
C7A	0.1603 (3)	0.13238 (14)	0.49649 (13)	0.0176 (5)
H7AA	0.0946	0.0932	0.4719	0.021*
C8A	0.0401 (4)	0.08749 (15)	0.60549 (14)	0.0234 (6)
H8AA	−0.0277	0.0498	0.5805	0.028*
H8AB	−0.0309	0.1000	0.6468	0.028*
C9A	0.2355 (4)	0.06120 (16)	0.62705 (15)	0.0246 (6)
H9AA	0.2249	0.0184	0.6558	0.030*
H9AB	0.3003	0.0979	0.6545	0.030*
C10A	0.3474 (4)	0.04425 (15)	0.56176 (15)	0.0240 (6)
H10A	0.4751	0.0300	0.5749	0.029*
H10B	0.2883	0.0049	0.5362	0.029*
C11A	0.1886 (4)	0.40020 (15)	0.45793 (15)	0.0224 (6)
Cl1B	0.70385 (9)	0.13065 (3)	0.38275 (3)	0.02102 (15)
C11B	0.6923 (5)	0.43786 (17)	0.29294 (17)	0.0364 (8)
F4	0.5910 (12)	0.4539 (3)	0.2403 (5)	0.0226 (12)*	0.351 (7)
F5	0.6856 (18)	0.4849 (5)	0.3431 (5)	0.0241 (10)*	0.351 (7)
F6	0.8935 (10)	0.4523 (3)	0.2682 (4)	0.0163 (15)*	0.351 (7)
F4B	0.7521 (16)	0.4863 (4)	0.3361 (5)	0.0226 (12)*	0.189 (5)
F5B	0.716 (2)	0.4505 (6)	0.2289 (7)	0.041 (4)*	0.189 (5)
F6B	0.4747 (12)	0.4605 (4)	0.2919 (6)	0.021 (2)*	0.189 (5)
F4C	0.8220 (14)	0.4554 (3)	0.2541 (5)	0.025 (2)*	0.288 (9)
F5C	0.6978 (15)	0.4818 (5)	0.3569 (5)	0.0241 (10)*	0.288 (9)
F6C	0.5245 (14)	0.4566 (3)	0.2635 (5)	0.027 (2)*	0.288 (9)
F4D	0.639 (2)	0.4462 (6)	0.2155 (8)	0.0226 (12)*	0.167 (6)
F5D	0.619 (2)	0.4824 (6)	0.3297 (7)	0.0241 (10)*	0.167 (6)
F6D	0.866 (2)	0.4612 (8)	0.2826 (8)	0.029 (4)*	0.167 (6)
N1B	0.8534 (3)	0.15394 (12)	0.20979 (12)	0.0178 (5)
N2B	0.5654 (3)	0.20191 (12)	0.16508 (12)	0.0189 (5)
C1B	0.6915 (3)	0.21978 (14)	0.35477 (14)	0.0183 (5)
C2B	0.6998 (3)	0.27234 (15)	0.40623 (14)	0.0200 (5)
H2BA	0.7062	0.2599	0.4535	0.024*
C3B	0.6985 (4)	0.34360 (15)	0.38604 (15)	0.0230 (6)
H3BA	0.7045	0.3797	0.4197	0.028*
C4B	0.6883 (4)	0.36098 (15)	0.31531 (15)	0.0226 (6)
C5B	0.6763 (3)	0.30779 (14)	0.26472 (14)	0.0204 (5)
H5BA	0.6687	0.3205	0.2176	0.024*
C6B	0.6756 (3)	0.23534 (14)	0.28350 (13)	0.0167 (5)
C7B	0.6615 (3)	0.17660 (14)	0.22863 (14)	0.0181 (5)
H7BA	0.5927	0.1355	0.2477	0.022*
C8B	0.8473 (4)	0.09305 (15)	0.16030 (15)	0.0241 (6)
H8BA	0.7840	0.0524	0.1814	0.029*
H8BB	0.9748	0.0785	0.1488	0.029*
C9B	0.7411 (4)	0.11657 (15)	0.09448 (15)	0.0243 (6)
H9BA	0.8109	0.1544	0.0714	0.029*
H9BB	0.7294	0.0764	0.0623	0.029*
C10B	0.5465 (4)	0.14364 (15)	0.11302 (16)	0.0251 (6)
H10C	0.4817	0.1613	0.0712	0.030*
H10D	0.4723	0.1047	0.1322	0.030*
O1W	0.3328 (3)	0.80736 (12)	0.43314 (11)	0.0258 (5)
O2W	0.1595 (3)	0.24257 (12)	0.16075 (11)	0.0240 (4)
H1NA	−0.054 (5)	0.1675 (17)	0.5461 (17)	0.034 (9)*
H2NA	0.410 (5)	0.0988 (19)	0.478 (2)	0.046 (11)*
H1NB	0.908 (4)	0.1397 (17)	0.2501 (17)	0.029 (9)*
H2NB	0.457 (5)	0.2150 (17)	0.1772 (16)	0.028 (8)*
H1W1	0.370 (5)	0.777 (2)	0.402 (2)	0.053 (12)*
H2W1	0.440 (5)	0.8277 (19)	0.4430 (18)	0.037 (10)*
H1W2	0.056 (5)	0.2231 (18)	0.1680 (18)	0.035 (9)*
H2W2	0.131 (5)	0.277 (2)	0.1315 (19)	0.043 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.0223 (3)	0.0306 (4)	0.0199 (3)	0.0021 (3)	−0.0001 (2)	−0.0072 (3)
F1A	0.0535 (11)	0.0211 (9)	0.0352 (11)	0.0018 (8)	0.0155 (9)	−0.0009 (8)
F2A	0.0460 (11)	0.0220 (10)	0.0606 (14)	0.0058 (8)	−0.0230 (10)	0.0078 (9)
F3A	0.0254 (9)	0.0295 (10)	0.0599 (13)	−0.0107 (7)	0.0116 (8)	−0.0090 (9)
N1A	0.0174 (10)	0.0182 (12)	0.0192 (11)	0.0007 (8)	0.0042 (8)	0.0018 (9)
N2A	0.0168 (10)	0.0200 (12)	0.0180 (12)	0.0028 (8)	0.0025 (8)	0.0027 (9)
C1A	0.0153 (11)	0.0243 (14)	0.0188 (13)	−0.0012 (10)	−0.0013 (9)	−0.0022 (11)
C2A	0.0179 (12)	0.0352 (17)	0.0146 (13)	−0.0008 (11)	0.0013 (10)	0.0029 (12)
C3A	0.0185 (12)	0.0286 (16)	0.0209 (14)	−0.0020 (10)	−0.0018 (10)	0.0100 (12)
C4A	0.0142 (11)	0.0205 (14)	0.0232 (14)	−0.0007 (9)	−0.0007 (10)	0.0047 (11)
C5A	0.0152 (11)	0.0205 (14)	0.0150 (12)	−0.0008 (9)	0.0007 (9)	0.0005 (10)
C6A	0.0141 (11)	0.0192 (13)	0.0155 (12)	−0.0020 (9)	−0.0013 (9)	0.0005 (10)
C7A	0.0169 (11)	0.0180 (13)	0.0179 (13)	−0.0004 (9)	0.0000 (9)	−0.0033 (11)
C8A	0.0277 (13)	0.0231 (15)	0.0197 (14)	−0.0025 (11)	0.0076 (11)	0.0024 (11)
C9A	0.0332 (14)	0.0208 (14)	0.0199 (14)	0.0039 (11)	0.0027 (11)	0.0056 (11)
C10A	0.0282 (14)	0.0174 (14)	0.0264 (15)	0.0069 (11)	0.0008 (11)	0.0043 (11)
C11A	0.0185 (12)	0.0246 (15)	0.0242 (15)	−0.0010 (10)	−0.0002 (10)	0.0064 (12)
Cl1B	0.0223 (3)	0.0196 (3)	0.0212 (3)	0.0010 (2)	0.0028 (2)	0.0060 (3)
C11B	0.057 (2)	0.0221 (16)	0.0300 (18)	0.0024 (14)	−0.0009 (15)	−0.0044 (14)
N1B	0.0179 (10)	0.0163 (11)	0.0191 (12)	0.0035 (8)	0.0014 (9)	0.0031 (9)
N2B	0.0137 (10)	0.0225 (12)	0.0204 (12)	0.0015 (8)	0.0005 (8)	0.0015 (9)
C1B	0.0144 (11)	0.0186 (13)	0.0221 (14)	0.0010 (9)	0.0028 (10)	0.0033 (11)
C2B	0.0157 (11)	0.0246 (15)	0.0197 (14)	0.0009 (10)	0.0025 (10)	−0.0001 (11)
C3B	0.0201 (12)	0.0236 (15)	0.0253 (15)	0.0010 (10)	0.0020 (10)	−0.0045 (12)
C4B	0.0202 (12)	0.0185 (14)	0.0293 (15)	0.0012 (10)	0.0018 (11)	0.0016 (12)
C5B	0.0204 (12)	0.0203 (14)	0.0204 (14)	0.0002 (10)	0.0026 (10)	0.0035 (11)
C6B	0.0132 (11)	0.0175 (13)	0.0196 (13)	0.0000 (9)	0.0034 (9)	0.0007 (10)
C7B	0.0165 (11)	0.0182 (13)	0.0199 (13)	−0.0008 (9)	0.0034 (10)	0.0031 (11)
C8B	0.0299 (14)	0.0160 (14)	0.0263 (15)	0.0040 (11)	−0.0001 (11)	−0.0012 (11)
C9B	0.0321 (14)	0.0205 (15)	0.0203 (14)	0.0019 (11)	−0.0006 (11)	−0.0025 (11)
C10B	0.0264 (14)	0.0219 (15)	0.0270 (15)	−0.0039 (11)	−0.0040 (11)	−0.0010 (12)
O1W	0.0178 (9)	0.0318 (12)	0.0279 (11)	0.0006 (8)	0.0029 (8)	−0.0099 (10)
O2W	0.0183 (9)	0.0300 (12)	0.0236 (11)	−0.0010 (8)	0.0003 (8)	0.0074 (9)

Geometric parameters (Å, º) top

Cl1A—C1A	1.749 (3)	C11B—F5	1.298 (10)
F1A—C11A	1.338 (3)	C11B—F6D	1.323 (16)
F2A—C11A	1.331 (3)	C11B—F6C	1.350 (8)
F3A—C11A	1.337 (3)	C11B—F5C	1.467 (10)
N1A—C7A	1.459 (3)	C11B—C4B	1.493 (4)
N1A—C8A	1.468 (3)	C11B—F4D	1.525 (14)
N1A—H1NA	0.90 (3)	C11B—F6	1.532 (7)
N2A—C7A	1.472 (3)	N1B—C7B	1.472 (3)
N2A—C10A	1.475 (3)	N1B—C8B	1.475 (3)
N2A—H2NA	0.88 (4)	N1B—H1NB	0.89 (3)
C1A—C6A	1.391 (4)	N2B—C7B	1.457 (3)
C1A—C2A	1.393 (4)	N2B—C10B	1.475 (4)
C2A—C3A	1.376 (4)	N2B—H2NB	0.84 (3)
C2A—H2AA	0.9300	C1B—C2B	1.386 (4)
C3A—C4A	1.387 (4)	C1B—C6B	1.392 (4)
C3A—H3AA	0.9300	C2B—C3B	1.381 (4)
C4A—C5A	1.390 (4)	C2B—H2BA	0.9300
C4A—C11A	1.495 (4)	C3B—C4B	1.387 (4)
C5A—C6A	1.394 (4)	C3B—H3BA	0.9300
C5A—H5AA	0.9300	C4B—C5B	1.384 (4)
C6A—C7A	1.513 (4)	C5B—C6B	1.395 (4)
C7A—H7AA	0.9800	C5B—H5BA	0.9300
C8A—C9A	1.516 (4)	C6B—C7B	1.515 (4)
C8A—H8AA	0.9700	C7B—H7BA	0.9800
C8A—H8AB	0.9700	C8B—C9B	1.516 (4)
C9A—C10A	1.520 (4)	C8B—H8BA	0.9700
C9A—H9AA	0.9700	C8B—H8BB	0.9700
C9A—H9AB	0.9700	C9B—C10B	1.514 (4)
C10A—H10A	0.9700	C9B—H9BA	0.9700
C10A—H10B	0.9700	C9B—H9BB	0.9700
Cl1B—C1B	1.744 (3)	C10B—H10C	0.9700
C11B—F5D	1.209 (11)	C10B—H10D	0.9700
C11B—F4C	1.233 (8)	O1W—H1W1	0.86 (4)
C11B—F5B	1.257 (13)	O1W—H2W1	0.87 (4)
C11B—F4	1.258 (6)	O2W—H1W2	0.83 (4)
C11B—F4B	1.287 (5)	O2W—H2W2	0.87 (4)

C7A—N1A—C8A	110.7 (2)	F4—C11B—F5C	122.5 (6)
C7A—N1A—H1NA	107 (2)	F4B—C11B—F5C	22.3 (6)
C8A—N1A—H1NA	111 (2)	F5—C11B—F5C	9.3 (7)
C7A—N2A—C10A	111.5 (2)	F6D—C11B—F5C	86.0 (9)
C7A—N2A—H2NA	106 (2)	F6C—C11B—F5C	102.2 (6)
C10A—N2A—H2NA	109 (2)	F5D—C11B—C4B	118.8 (6)
C6A—C1A—C2A	122.4 (2)	F4C—C11B—C4B	116.3 (4)
C6A—C1A—Cl1A	120.3 (2)	F5B—C11B—C4B	117.4 (6)
C2A—C1A—Cl1A	117.2 (2)	F4—C11B—C4B	116.2 (3)
C3A—C2A—C1A	119.2 (2)	F4B—C11B—C4B	119.7 (5)
C3A—C2A—H2AA	120.4	F5—C11B—C4B	115.7 (5)
C1A—C2A—H2AA	120.4	F6D—C11B—C4B	112.3 (7)
C2A—C3A—C4A	119.8 (3)	F6C—C11B—C4B	110.3 (4)
C2A—C3A—H3AA	120.1	F5C—C11B—C4B	107.3 (5)
C4A—C3A—H3AA	120.1	F5D—C11B—F4D	113.0 (8)
C3A—C4A—C5A	120.4 (3)	F4C—C11B—F4D	64.3 (7)
C3A—C4A—C11A	118.7 (2)	F5B—C11B—F4D	22.4 (7)
C5A—C4A—C11A	120.9 (2)	F4—C11B—F4D	22.6 (5)
C4A—C5A—C6A	121.0 (2)	F4B—C11B—F4D	128.4 (7)
C4A—C5A—H5AA	119.5	F5—C11B—F4D	129.3 (6)
C6A—C5A—H5AA	119.5	F6D—C11B—F4D	92.1 (8)
C1A—C6A—C5A	117.2 (2)	F6C—C11B—F4D	51.0 (7)
C1A—C6A—C7A	121.6 (2)	F5C—C11B—F4D	138.6 (6)
C5A—C6A—C7A	121.2 (2)	C4B—C11B—F4D	111.6 (5)
N1A—C7A—N2A	108.1 (2)	F5D—C11B—F6	118.0 (7)
N1A—C7A—C6A	111.3 (2)	F4C—C11B—F6	20.4 (5)
N2A—C7A—C6A	108.7 (2)	F5B—C11B—F6	61.9 (8)
N1A—C7A—H7AA	109.6	F4—C11B—F6	103.4 (5)
N2A—C7A—H7AA	109.6	F4B—C11B—F6	77.1 (6)
C6A—C7A—H7AA	109.6	F5—C11B—F6	98.9 (6)
N1A—C8A—C9A	109.0 (2)	F6D—C11B—F6	12.7 (7)
N1A—C8A—H8AA	109.9	F6C—C11B—F6	129.9 (6)
C9A—C8A—H8AA	109.9	F5C—C11B—F6	98.4 (6)
N1A—C8A—H8AB	109.9	C4B—C11B—F6	106.2 (3)
C9A—C8A—H8AB	109.9	F4D—C11B—F6	84.2 (6)
H8AA—C8A—H8AB	108.3	C7B—N1B—C8B	111.1 (2)
C8A—C9A—C10A	109.3 (2)	C7B—N1B—H1NB	105 (2)
C8A—C9A—H9AA	109.8	C8B—N1B—H1NB	109 (2)
C10A—C9A—H9AA	109.8	C7B—N2B—C10B	110.9 (2)
C8A—C9A—H9AB	109.8	C7B—N2B—H2NB	106 (2)
C10A—C9A—H9AB	109.8	C10B—N2B—H2NB	109 (2)
H9AA—C9A—H9AB	108.3	C2B—C1B—C6B	123.1 (2)
N2A—C10A—C9A	108.6 (2)	C2B—C1B—Cl1B	117.0 (2)
N2A—C10A—H10A	110.0	C6B—C1B—Cl1B	119.9 (2)
C9A—C10A—H10A	110.0	C3B—C2B—C1B	118.7 (3)
N2A—C10A—H10B	110.0	C3B—C2B—H2BA	120.6
C9A—C10A—H10B	110.0	C1B—C2B—H2BA	120.6
H10A—C10A—H10B	108.3	C2B—C3B—C4B	119.7 (3)
F2A—C11A—F3A	106.0 (2)	C2B—C3B—H3BA	120.2
F2A—C11A—F1A	106.4 (2)	C4B—C3B—H3BA	120.2
F3A—C11A—F1A	105.7 (2)	C5B—C4B—C3B	120.8 (3)
F2A—C11A—C4A	112.6 (2)	C5B—C4B—C11B	119.2 (3)
F3A—C11A—C4A	112.3 (2)	C3B—C4B—C11B	120.0 (3)
F1A—C11A—C4A	113.3 (2)	C4B—C5B—C6B	120.9 (3)
F5D—C11B—F4C	119.8 (7)	C4B—C5B—H5BA	119.6
F5D—C11B—F5B	120.0 (8)	C6B—C5B—H5BA	119.6
F4C—C11B—F5B	41.9 (7)	C1B—C6B—C5B	116.8 (2)
F5D—C11B—F4	93.2 (7)	C1B—C6B—C7B	121.8 (2)
F4C—C11B—F4	83.0 (5)	C5B—C6B—C7B	121.4 (2)
F5B—C11B—F4	42.6 (8)	N2B—C7B—N1B	108.0 (2)
F5D—C11B—F4B	44.6 (8)	N2B—C7B—C6B	111.4 (2)
F4C—C11B—F4B	87.6 (7)	N1B—C7B—C6B	109.0 (2)
F5B—C11B—F4B	116.3 (8)	N2B—C7B—H7BA	109.5
F4—C11B—F4B	121.4 (6)	N1B—C7B—H7BA	109.5
F5D—C11B—F5	24.3 (6)	C6B—C7B—H7BA	109.5
F4C—C11B—F5	107.5 (6)	N1B—C8B—C9B	108.4 (2)
F5B—C11B—F5	126.7 (7)	N1B—C8B—H8BA	110.0
F4—C11B—F5	113.6 (5)	C9B—C8B—H8BA	110.0
F4B—C11B—F5	21.9 (6)	N1B—C8B—H8BB	110.0
F5D—C11B—F6D	105.7 (9)	C9B—C8B—H8BB	110.0
F4C—C11B—F6D	28.3 (7)	H8BA—C8B—H8BB	108.4
F5B—C11B—F6D	69.8 (10)	C10B—C9B—C8B	110.0 (2)
F4—C11B—F6D	108.7 (8)	C10B—C9B—H9BA	109.7
F4B—C11B—F6D	64.5 (8)	C8B—C9B—H9BA	109.7
F5—C11B—F6D	86.2 (8)	C10B—C9B—H9BB	109.7
F5D—C11B—F6C	71.4 (8)	C8B—C9B—H9BB	109.7
F4C—C11B—F6C	109.8 (6)	H9BA—C9B—H9BB	108.2
F5B—C11B—F6C	71.2 (8)	N2B—C10B—C9B	109.2 (2)
F4—C11B—F6C	28.7 (4)	N2B—C10B—H10C	109.8
F4B—C11B—F6C	111.2 (6)	C9B—C10B—H10C	109.8
F5—C11B—F6C	95.1 (6)	N2B—C10B—H10D	109.8
F6D—C11B—F6C	131.7 (8)	C9B—C10B—H10D	109.8
F5D—C11B—F5C	30.9 (8)	H10C—C10B—H10D	108.3
F4C—C11B—F5C	110.0 (7)	H1W1—O1W—H2W1	99 (3)
F5B—C11B—F5C	134.4 (7)	H1W2—O2W—H2W2	104 (3)

C6A—C1A—C2A—C3A	0.9 (4)	F4—C11B—C4B—C5B	36.6 (7)
Cl1A—C1A—C2A—C3A	−178.32 (19)	F4B—C11B—C4B—C5B	−161.8 (7)
C1A—C2A—C3A—C4A	0.6 (4)	F5—C11B—C4B—C5B	173.8 (7)
C2A—C3A—C4A—C5A	−1.1 (4)	F6D—C11B—C4B—C5B	−89.4 (8)
C2A—C3A—C4A—C11A	178.5 (2)	F6C—C11B—C4B—C5B	67.3 (6)
C3A—C4A—C5A—C6A	0.2 (4)	F5C—C11B—C4B—C5B	177.8 (5)
C11A—C4A—C5A—C6A	−179.4 (2)	F4D—C11B—C4B—C5B	12.4 (7)
C2A—C1A—C6A—C5A	−1.9 (4)	F6—C11B—C4B—C5B	−77.7 (4)
Cl1A—C1A—C6A—C5A	177.39 (18)	F5D—C11B—C4B—C3B	−34.1 (9)
C2A—C1A—C6A—C7A	178.7 (2)	F4C—C11B—C4B—C3B	120.7 (6)
Cl1A—C1A—C6A—C7A	−2.0 (3)	F5B—C11B—C4B—C3B	168.0 (8)
C4A—C5A—C6A—C1A	1.3 (3)	F4—C11B—C4B—C3B	−144.0 (6)
C4A—C5A—C6A—C7A	−179.3 (2)	F4B—C11B—C4B—C3B	17.5 (7)
C8A—N1A—C7A—N2A	−62.4 (3)	F5—C11B—C4B—C3B	−6.9 (8)
C8A—N1A—C7A—C6A	178.3 (2)	F6D—C11B—C4B—C3B	89.9 (8)
C10A—N2A—C7A—N1A	61.8 (3)	F6C—C11B—C4B—C3B	−113.4 (6)
C10A—N2A—C7A—C6A	−177.3 (2)	F5C—C11B—C4B—C3B	−2.8 (6)
C1A—C6A—C7A—N1A	−153.3 (2)	F4D—C11B—C4B—C3B	−168.2 (7)
C5A—C6A—C7A—N1A	27.3 (3)	F6—C11B—C4B—C3B	101.7 (4)
C1A—C6A—C7A—N2A	87.8 (3)	C3B—C4B—C5B—C6B	−0.5 (4)
C5A—C6A—C7A—N2A	−91.6 (3)	C11B—C4B—C5B—C6B	178.9 (3)
C7A—N1A—C8A—C9A	61.3 (3)	C2B—C1B—C6B—C5B	2.7 (4)
N1A—C8A—C9A—C10A	−57.6 (3)	Cl1B—C1B—C6B—C5B	−176.75 (18)
C7A—N2A—C10A—C9A	−59.3 (3)	C2B—C1B—C6B—C7B	−178.4 (2)
C8A—C9A—C10A—N2A	56.3 (3)	Cl1B—C1B—C6B—C7B	2.2 (3)
C3A—C4A—C11A—F2A	48.9 (3)	C4B—C5B—C6B—C1B	−1.3 (4)
C5A—C4A—C11A—F2A	−131.5 (3)	C4B—C5B—C6B—C7B	179.7 (2)
C3A—C4A—C11A—F3A	−70.7 (3)	C10B—N2B—C7B—N1B	62.4 (3)
C5A—C4A—C11A—F3A	108.9 (3)	C10B—N2B—C7B—C6B	−178.0 (2)
C3A—C4A—C11A—F1A	169.7 (2)	C8B—N1B—C7B—N2B	−63.0 (3)
C5A—C4A—C11A—F1A	−10.7 (3)	C8B—N1B—C7B—C6B	175.8 (2)
C6B—C1B—C2B—C3B	−2.1 (4)	C1B—C6B—C7B—N2B	154.7 (2)
Cl1B—C1B—C2B—C3B	177.29 (19)	C5B—C6B—C7B—N2B	−26.4 (3)
C1B—C2B—C3B—C4B	0.2 (4)	C1B—C6B—C7B—N1B	−86.3 (3)
C2B—C3B—C4B—C5B	1.0 (4)	C5B—C6B—C7B—N1B	92.6 (3)
C2B—C3B—C4B—C11B	−178.3 (3)	C7B—N1B—C8B—C9B	60.2 (3)
F5D—C11B—C4B—C5B	146.6 (9)	N1B—C8B—C9B—C10B	−56.1 (3)
F4C—C11B—C4B—C5B	−58.6 (7)	C7B—N2B—C10B—C9B	−59.7 (3)
F5B—C11B—C4B—C5B	−11.4 (9)	C8B—C9B—C10B—N2B	56.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1Wⁱ	0.90 (3)	2.07 (4)	2.885 (3)	151 (3)
N1B—H1NB···Cl1Aⁱⁱ	0.89 (3)	2.76 (3)	3.595 (2)	156 (2)
N2B—H2NB···O2W	0.84 (3)	2.18 (4)	2.969 (3)	156 (3)
O1W—H1W1···N2Bⁱⁱⁱ	0.86 (4)	1.95 (4)	2.815 (3)	174 (4)
O1W—H2W1···N2A^iv	0.87 (4)	2.02 (3)	2.867 (3)	165 (3)
O2W—H1W2···N1B^v	0.83 (3)	2.09 (3)	2.891 (3)	161 (3)
O2W—H2W2···N1A^vi	0.87 (4)	1.98 (4)	2.844 (3)	176 (4)
C2A—H2AA···O2W	0.93	2.35	3.249 (3)	164
C5A—H5AA···F1A	0.93	2.42	2.747 (3)	100
C5A—H5AA···N1A	0.93	2.52	2.835 (3)	100
C7A—H7AA···Cl1A	0.98	2.67	3.076 (3)	105
C2B—H2BA···O1W^iv	0.93	2.52	3.414 (3)	162
C5B—H5BA···N2B	0.93	2.53	2.838 (3)	100
C7B—H7BA···Cl1B	0.98	2.68	3.070 (3)	104

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClF₃N₂·H₂O
M_r	282.69
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	7.0745 (2), 18.6119 (5), 19.0631 (5)
β (°)	91.010 (2)
V (Å³)	2509.65 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.24 × 0.05 × 0.02

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.924, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	30107, 7308, 4995
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.145, 1.08
No. of reflections	7308
No. of parameters	379
No. of restraints	41
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.60

Computer programs: APEX2 (Bruker, 2005), APEX2, SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···O1Wⁱ	0.90 (3)	2.07 (4)	2.885 (3)	151 (3)
N1B—H1NB···Cl1Aⁱⁱ	0.89 (3)	2.76 (3)	3.595 (2)	156 (2)
N2B—H2NB···O2W	0.84 (3)	2.18 (4)	2.969 (3)	156 (3)
O1W—H1W1···N2Bⁱⁱⁱ	0.86 (4)	1.95 (4)	2.815 (3)	174 (4)
O1W—H2W1···N2A^iv	0.87 (4)	2.02 (3)	2.867 (3)	165 (3)
O2W—H1W2···N1B^v	0.83 (3)	2.09 (3)	2.891 (3)	161 (3)
O2W—H2W2···N1A^vi	0.87 (4)	1.98 (4)	2.844 (3)	176 (4)
C2A—H2AA···O2W	0.93	2.35	3.249 (3)	164
C5A—H5AA···F1A	0.93	2.42	2.747 (3)	100
C5A—H5AA···N1A	0.93	2.52	2.835 (3)	100
C7A—H7AA···Cl1A	0.98	2.67	3.076 (3)	105
C2B—H2BA···O1W^iv	0.93	2.52	3.414 (3)	162
C5B—H5BA···N2B	0.93	2.53	2.838 (3)	100
C7B—H7BA···Cl1B	0.98	2.68	3.070 (3)	104

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

Footnotes

‡Additional correspondance author, e-mail: zsrkk@yahoo.com.

Acknowledgements

HKF and RK thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for the award of a post-doctoral research fellowship.

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