7-Chloro-4-[(E)-N′-(4-fluoro­benzyl­idene)hydrazin­yl]quinoline monohydrate

Souza, M.V.N. de; Howie, R.A.; Tiekink, E.R.T.; Wardell, J.L.; Wardell, S.M.S.V.

doi:10.1107/S1600536809053367

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Pages o152-o153

doi:10.1107/S1600536809053367

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7-Chloro-4-[(E)-N′-(4-fluorobenzylidene)hydrazinyl]quinoline monohydrate

Marcus V. N. de Souza,^a R. Alan Howie,^b Edward R. T. Tiekink,^c ^* James L. Wardell ^d ‡ and Solange M. S. V. Wardell ^e

^aInstituto de Tecnologia em Farmacos, Fundação Oswaldo Cruz (FIOCRUZ), FarManguinhos, Rua Sizenando Nabuco, 100, Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Old Aberdeen AB15 5NY, Scotland, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, ^dCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Av. Brasil 4365, 21040-900 Rio de Janeiro, RJ, Brazil, and ^eCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 9 December 2009; accepted 11 December 2009; online 16 December 2009)

The molecule of the title hydrate, C₁₆H₁₁ClFN₃·H₂O, is slightly twisted, as indicated by the dihedral angle of 9.55 (10)° formed between the quinoline ring system and the benzene ring. The conformation about the C=N double bond is E, and the amine-H atom is oriented towards the quinoline residue. In the crystal structure, the water molecule accepts an N—H⋯O and makes two O—H⋯N_quinoline hydrogen bonds, generating a two-dimensional array in the ab plane, which is further stabilized by C—H⋯O interactions. The most significant contacts between layers are of the type C—H⋯F.

Related literature

For background information on the pharmacological activity of quinoline derivatives, see: Elslager et al. (1969 ); Font et al. (1997 ); Kaminsky & Meltzer (1968 ); Musiol et al. (2006 ); Nakamura et al. (1999 ); Palmer et al. (1993 ); Ridley (2002 ); Sloboda et al. (1991 ); Tanenbaum & Tuffanelli (1980 ); Warshakoon et al. (2006 ). For recent studies into quinoline-based anti-malarials, see: Andrade et al. (2007 ); Cunico et al. (2006 ); da Silva et al. (2003 ); de Souza et al. (2005 ). For crystallographic studies on molecules related to the title compound, see: Kaiser et al. (2009 ); de Souza et al. (2009 ); de Ferreira et al. (2009 ). For the synthesis, see: Pellerano et al. (1976 ).

Experimental

Crystal data

C₁₆H₁₁ClFN₃·H₂O
M_r = 317.74
Monoclinic, P 2₁ /c
a = 3.7795 (2) Å
b = 15.4188 (11) Å
c = 24.8576 (16) Å
β = 90.286 (4)°
V = 1448.57 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 120 K
0.90 × 0.04 × 0.04 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.614, T_max = 0.746
19494 measured reflections
3291 independent reflections
2009 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.131
S = 1.04
3291 reflections
205 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w⋯N1ⁱ	0.84 (2)	2.28 (2)	2.999 (3)	144 (2)
O1w—H2w⋯N1ⁱⁱ	0.85 (2)	1.93 (2)	2.761 (3)	166 (3)
N2—H2n⋯O1wⁱⁱⁱ	0.88	2.01	2.865 (3)	165
C5—H5⋯O1wⁱⁱⁱ	0.95	2.45	3.379 (3)	164
C10—H10⋯O1wⁱⁱⁱ	0.95	2.50	3.302 (3)	142
C1—H1⋯F1^iv	0.95	2.56	3.399 (3)	147
C6—H6⋯F1^v	0.95	2.56	3.477 (3)	161
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) -x, -y, -z; (v) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053367/lh2970sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809053367/lh2970Isup2.hkl

checkCIF report

Comment top

The title compound, crystallized as a hydrate, (I), was prepared as part of continuing studies designed to develop antimalarial compounds based on the quinoline nucleus (Andrade et al., 2007; Cunico et al., 2006; da Silva et al., 2003; de Souza et al., 2005). The systematic examination of quinoline derivatives comes about owing to the fact that the majority of antimalarial agents, including chloroquine (Tanenbaum & Tuffanelli, 1980), mefloquine (Palmer et al., 1993), primaquine (Elslager et al., 1969) and amodiaquine (Ridley, 2002), have a quinoline ring substructure, the mainstay of malaria chemotherapy for much of the past 40 years (Font et al., 1997; Kaminsky & Meltzer, 1968; Musiol et al., 2006; Nakamura et al., 1999; Sloboda et al., 1991; Warshakoon et al., 2006). Allied with these investigations are structural studies aimed at elucidating systematic structural trends in these molecules (Kaiser et al. 2009; de Souza et al. 2009; de Ferreira et al. 2009).

The molecule in (I), Fig. 1, features an effectively planar quinoline residue (maximum deviations of 0.018 (2) Å for atom C4 and -0.025 (2) Å for atom C2) which forms a dihedral angle of 9.55 (10) ° with the C11–C16 benzene ring. Twists in the molecule are evident about the N2–C3 and C10–C11 bonds as seen in the values of the N3–N2–C3–C2 and N3–C10–C11—C12 torsion angles of 6.9 (4) and -6.6 (4) °, respectively. As observed in related systems, the amine-H is orientated over the quinoline residue (Kaiser et al. 2009; de Souza et al. 2009; de Ferreira et al., 2009). The conformation about the N3═C10 double bond is E. The molecule crystallizes as a hydrate and the latter species is pivotal in stabilizing the crystal structure. Thus, the water-H atoms form donor O–H···N hydrogen bonds to quinoline-N atoms derived from two molecules. At the same time, the water-O atom accepts a N–H···O hydrogen bond from the amine-N2 of another molecule. Thus, the water molecule provides links between three molecules, leading to the formation of a 2-D array, Fig. 2 and Table 1. The resultant layer in the ab plane is further stabilized by C–H···O interactions, Table 1, and weak π···π contacts [ring centroid(N1,C1—C4,C9)···ring centroid(C4–C9)ⁱ = 3.7070 (14) Å, dihedral angle = 1.45 (11) ° for i: -1 + x, y, z]. Layers stack along the c direction with the most significant contacts between layers being of the type C–H···F whereby the fluoride is bifurcated, Table 1 and Fig. 3.

Related literature top

For background information on the pharmacological activity of quinoline derivatives, see: Elslager et al. (1969); Font et al. (1997); Kaminsky & Meltzer (1968); Musiol et al. (2006); Nakamura et al. (1999); Palmer et al. (1993); Ridley (2002); Sloboda et al. (1991); Tanenbaum & Tuffanelli (1980); Warshakoon et al. (2006). For recent studies into quinoline-based anti-malarials, see: Andrade et al. (2007); Cunico et al. (2006); da Silva et al. (2003); de Souza et al. (2005). For crystallographic studies on molecules related to the title compound, see: Kaiser et al. (2009); de Souza et al. (2009); de Ferreira et al. (2009). For the synthesis, see: Pellerano et al. (1976).

Experimental top

A solution of 7-chloro-4-hydrazinoquinoline (0.20 g, 1.0 mmol) and 4-fluorobenzaldehyde (0.15 g, 1.2 mmol) in EtOH (5 ml) was maintained at room temperature overnight and rotary evaporated. The solid residue, was washed with cold Et₂O (3 x 10 ml) and recrystallized from EtOH m.pt. 518–519 K, lit. value 518 K (Pellerano et al., 1976), yield 74%. The sample for the X-ray study was slowly grown from moist EtOH and was found to be the monohydrate. ¹H NMR (400 MHz, DMSO-d₆) δ: 7.28–7.32 (3H, m), 7.54 (1H, d, J = 8.4 Hz), 7.84–7.88 (3H, m), 8.34–8.40 (3H, m), 11.3 (1H, br.s, NH). MS/ESI: [M^+. - H]: 298. IR ν_max (cm^-1; KBr disc): 3232 (N–H), 1585 (C═N), 817 (C–F).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. The molecular structure of both components comprising the asymmetric unit of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the 2-D supramolecular array in (I) showing the O–H···N and N–H···O hydrogen bonds as orange and blue dashed lines, respectively. Colour code: Cl, cyan; F, pink; O, red; N, blue; C, grey; and H, green.
	Fig. 3. A view in projection along the a axis of the unit-cell contents in (I) showing the stacking of layers along the c direction. The O–H···N and N–H···O hydrogen bonds are shown as orange and blue dashed lines, respectively, and the C–H···F contacts are represented by pink dashed lines. One of the 2-D arrays, as shown in Fig. 2, has been highlighted in space-filling mode. Colour code: Cl, cyan; F, pink; O, red; N, blue; C, grey; and H, green.

7-Chloro-4-[(E)-N'-(4-fluorobenzylidene)hydrazinyl]quinoline monohydrate top

Crystal data top

C₁₆H₁₁ClFN₃·H₂O	F(000) = 656
M_r = 317.74	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13530 reflections
a = 3.7795 (2) Å	θ = 2.9–27.5°
b = 15.4188 (11) Å	µ = 0.28 mm⁻¹
c = 24.8576 (16) Å	T = 120 K
β = 90.286 (4)°	Needle, colourless
V = 1448.57 (16) Å³	0.90 × 0.04 × 0.04 mm
Z = 4

Data collection top

Enraf–Nonius KappaCCD area-detector diffractometer	3291 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	2009 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.098
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −20→19
T_min = 0.614, T_max = 0.746	l = −32→32
19494 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0463P)² + 0.5902P] where P = (F_o² + 2F_c²)/3
3291 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.33 e Å⁻³
3 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₆H₁₁ClFN₃·H₂O	V = 1448.57 (16) Å³
M_r = 317.74	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.7795 (2) Å	µ = 0.28 mm⁻¹
b = 15.4188 (11) Å	T = 120 K
c = 24.8576 (16) Å	0.90 × 0.04 × 0.04 mm
β = 90.286 (4)°

Data collection top

Enraf–Nonius KappaCCD area-detector diffractometer	3291 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	2009 reflections with I > 2σ(I)
T_min = 0.614, T_max = 0.746	R_int = 0.098
19494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	3 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.33 e Å⁻³
3291 reflections	Δρ_min = −0.37 e Å⁻³
205 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.85154 (18)	−0.01273 (5)	0.43677 (3)	0.0319 (2)
F1	0.1997 (4)	0.22958 (11)	−0.11624 (6)	0.0367 (5)
N1	0.3942 (5)	−0.13713 (14)	0.26095 (9)	0.0214 (5)
N2	0.6585 (5)	0.08516 (14)	0.17189 (8)	0.0221 (5)
H2N	0.7847	0.1268	0.1867	0.027*
N3	0.5476 (5)	0.09163 (15)	0.11914 (8)	0.0212 (5)
C1	0.3270 (7)	−0.12969 (18)	0.20855 (11)	0.0225 (6)
H1	0.2176	−0.1776	0.1911	0.027*
C2	0.4043 (6)	−0.05737 (18)	0.17733 (10)	0.0210 (6)
H2	0.3436	−0.0566	0.1402	0.025*
C3	0.5701 (6)	0.01357 (17)	0.20052 (10)	0.0178 (6)
C4	0.6457 (6)	0.01003 (16)	0.25750 (10)	0.0176 (6)
C5	0.8024 (6)	0.07868 (18)	0.28696 (11)	0.0210 (6)
H5	0.8680	0.1303	0.2687	0.025*
C6	0.8613 (6)	0.07213 (18)	0.34118 (10)	0.0220 (6)
H6	0.9655	0.1189	0.3605	0.026*
C7	0.7663 (7)	−0.00432 (18)	0.36790 (11)	0.0218 (6)
C8	0.6151 (6)	−0.07217 (18)	0.34132 (10)	0.0214 (6)
H8	0.5531	−0.1233	0.3604	0.026*
C9	0.5501 (6)	−0.06654 (16)	0.28533 (10)	0.0179 (6)
C10	0.6205 (7)	0.16293 (18)	0.09495 (11)	0.0219 (6)
H10	0.7507	0.2064	0.1136	0.026*
C11	0.5085 (7)	0.17884 (18)	0.03962 (11)	0.0216 (6)
C12	0.3483 (7)	0.11448 (18)	0.00825 (11)	0.0231 (6)
H12	0.3087	0.0586	0.0232	0.028*
C13	0.2471 (7)	0.13101 (18)	−0.04411 (11)	0.0237 (6)
H13	0.1409	0.0871	−0.0656	0.028*
C14	0.3041 (7)	0.21294 (19)	−0.06453 (11)	0.0256 (7)
C15	0.4572 (7)	0.27824 (19)	−0.03525 (11)	0.0269 (7)
H15	0.4911	0.3342	−0.0504	0.032*
C16	0.5614 (7)	0.26028 (18)	0.01715 (11)	0.0232 (6)
H16	0.6708	0.3044	0.0380	0.028*
O1W	0.0566 (5)	0.23633 (12)	0.20098 (8)	0.0287 (5)
H1W	0.262 (3)	0.2503 (17)	0.2111 (12)	0.043*
H2W	−0.086 (5)	0.2775 (13)	0.2069 (12)	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0381 (4)	0.0386 (5)	0.0191 (4)	−0.0007 (3)	−0.0065 (3)	−0.0001 (3)
F1	0.0475 (10)	0.0422 (11)	0.0205 (9)	0.0086 (8)	−0.0082 (8)	0.0037 (8)
N1	0.0218 (12)	0.0225 (13)	0.0200 (13)	0.0000 (10)	−0.0006 (9)	−0.0006 (10)
N2	0.0269 (12)	0.0218 (13)	0.0177 (12)	−0.0046 (10)	−0.0046 (9)	0.0001 (10)
N3	0.0219 (12)	0.0265 (14)	0.0153 (12)	0.0018 (10)	−0.0022 (9)	0.0005 (10)
C1	0.0185 (14)	0.0204 (16)	0.0286 (17)	0.0005 (11)	−0.0024 (12)	−0.0026 (13)
C2	0.0204 (14)	0.0270 (16)	0.0156 (14)	0.0007 (12)	−0.0052 (11)	−0.0005 (12)
C3	0.0150 (13)	0.0189 (15)	0.0195 (14)	0.0014 (11)	−0.0008 (10)	−0.0011 (12)
C4	0.0151 (13)	0.0168 (14)	0.0209 (14)	0.0033 (11)	−0.0002 (10)	−0.0018 (12)
C5	0.0204 (14)	0.0189 (15)	0.0237 (15)	0.0012 (11)	0.0001 (11)	−0.0018 (12)
C6	0.0242 (15)	0.0210 (16)	0.0208 (15)	−0.0003 (12)	−0.0035 (11)	−0.0059 (12)
C7	0.0204 (14)	0.0276 (17)	0.0175 (14)	0.0030 (12)	−0.0016 (11)	−0.0034 (12)
C8	0.0198 (14)	0.0223 (16)	0.0220 (15)	0.0050 (12)	−0.0007 (11)	0.0046 (12)
C9	0.0154 (13)	0.0149 (14)	0.0233 (15)	0.0003 (11)	−0.0026 (10)	−0.0030 (12)
C10	0.0222 (15)	0.0215 (16)	0.0221 (16)	0.0019 (12)	0.0000 (11)	−0.0046 (13)
C11	0.0185 (14)	0.0253 (16)	0.0209 (15)	0.0030 (12)	0.0004 (11)	0.0010 (12)
C12	0.0261 (15)	0.0194 (15)	0.0238 (16)	−0.0004 (12)	0.0010 (12)	−0.0001 (12)
C13	0.0240 (15)	0.0241 (16)	0.0229 (16)	0.0009 (12)	−0.0018 (12)	−0.0045 (13)
C14	0.0273 (15)	0.0350 (18)	0.0145 (14)	0.0051 (13)	−0.0025 (11)	0.0012 (13)
C15	0.0265 (15)	0.0256 (17)	0.0287 (17)	0.0025 (13)	−0.0004 (12)	0.0043 (13)
C16	0.0244 (15)	0.0240 (16)	0.0213 (15)	−0.0016 (12)	−0.0012 (11)	−0.0037 (13)
O1W	0.0255 (11)	0.0227 (11)	0.0377 (13)	−0.0003 (9)	−0.0020 (9)	−0.0045 (9)

Geometric parameters (Å, º) top

Cl1—C7	1.745 (3)	C6—H6	0.9500
F1—C14	1.367 (3)	C7—C8	1.362 (4)
N1—C1	1.331 (3)	C8—C9	1.414 (3)
N1—C9	1.377 (3)	C8—H8	0.9500
N2—C3	1.356 (3)	C10—C11	1.458 (4)
N2—N3	1.378 (3)	C10—H10	0.9500
N2—H2N	0.8800	C11—C16	1.389 (4)
N3—C10	1.284 (3)	C11—C12	1.398 (4)
C1—C2	1.390 (4)	C12—C13	1.379 (4)
C1—H1	0.9500	C12—H12	0.9500
C2—C3	1.385 (4)	C13—C14	1.379 (4)
C2—H2	0.9500	C13—H13	0.9500
C3—C4	1.445 (3)	C14—C15	1.369 (4)
C4—C5	1.415 (4)	C15—C16	1.387 (4)
C4—C9	1.416 (4)	C15—H15	0.9500
C5—C6	1.369 (3)	C16—H16	0.9500
C5—H5	0.9500	O1W—H1W	0.841 (10)
C6—C7	1.401 (4)	O1W—H2W	0.845 (10)

C1—N1—C9	116.2 (2)	C7—C8—H8	120.0
C3—N2—N3	118.9 (2)	C9—C8—H8	120.0
C3—N2—H2N	120.5	N1—C9—C8	117.2 (2)
N3—N2—H2N	120.5	N1—C9—C4	123.6 (2)
C10—N3—N2	116.3 (2)	C8—C9—C4	119.2 (2)
N1—C1—C2	125.2 (3)	N3—C10—C11	121.6 (2)
N1—C1—H1	117.4	N3—C10—H10	119.2
C2—C1—H1	117.4	C11—C10—H10	119.2
C3—C2—C1	119.8 (2)	C16—C11—C12	118.7 (2)
C3—C2—H2	120.1	C16—C11—C10	119.3 (2)
C1—C2—H2	120.1	C12—C11—C10	122.0 (3)
N2—C3—C2	122.4 (2)	C13—C12—C11	120.8 (3)
N2—C3—C4	119.8 (2)	C13—C12—H12	119.6
C2—C3—C4	117.7 (2)	C11—C12—H12	119.6
C5—C4—C9	118.5 (2)	C12—C13—C14	118.3 (3)
C5—C4—C3	124.0 (2)	C12—C13—H13	120.9
C9—C4—C3	117.4 (2)	C14—C13—H13	120.9
C6—C5—C4	121.3 (3)	F1—C14—C15	118.8 (3)
C6—C5—H5	119.3	F1—C14—C13	118.3 (2)
C4—C5—H5	119.3	C15—C14—C13	123.0 (3)
C5—C6—C7	119.2 (2)	C14—C15—C16	118.0 (3)
C5—C6—H6	120.4	C14—C15—H15	121.0
C7—C6—H6	120.4	C16—C15—H15	121.0
C8—C7—C6	121.6 (2)	C15—C16—C11	121.2 (3)
C8—C7—Cl1	119.6 (2)	C15—C16—H16	119.4
C6—C7—Cl1	118.8 (2)	C11—C16—H16	119.4
C7—C8—C9	120.0 (2)	H1W—O1W—H2W	110.0 (16)

C3—N2—N3—C10	176.0 (2)	C7—C8—C9—N1	−179.5 (2)
C9—N1—C1—C2	0.5 (4)	C7—C8—C9—C4	0.3 (4)
N1—C1—C2—C3	1.3 (4)	C5—C4—C9—N1	179.6 (2)
N3—N2—C3—C2	6.9 (4)	C3—C4—C9—N1	0.7 (4)
N3—N2—C3—C4	−172.4 (2)	C5—C4—C9—C8	−0.2 (3)
C1—C2—C3—N2	178.6 (2)	C3—C4—C9—C8	−179.1 (2)
C1—C2—C3—C4	−2.0 (4)	N2—N3—C10—C11	−178.2 (2)
N2—C3—C4—C5	1.6 (4)	N3—C10—C11—C16	173.3 (2)
C2—C3—C4—C5	−177.7 (2)	N3—C10—C11—C12	−6.6 (4)
N2—C3—C4—C9	−179.5 (2)	C16—C11—C12—C13	0.5 (4)
C2—C3—C4—C9	1.1 (3)	C10—C11—C12—C13	−179.5 (2)
C9—C4—C5—C6	−0.1 (4)	C11—C12—C13—C14	−0.8 (4)
C3—C4—C5—C6	178.7 (2)	C12—C13—C14—F1	−179.2 (2)
C4—C5—C6—C7	0.4 (4)	C12—C13—C14—C15	0.2 (4)
C5—C6—C7—C8	−0.3 (4)	F1—C14—C15—C16	180.0 (2)
C5—C6—C7—Cl1	178.65 (19)	C13—C14—C15—C16	0.5 (4)
C6—C7—C8—C9	0.0 (4)	C14—C15—C16—C11	−0.8 (4)
Cl1—C7—C8—C9	−178.98 (18)	C12—C11—C16—C15	0.2 (4)
C1—N1—C9—C8	178.3 (2)	C10—C11—C16—C15	−179.7 (2)
C1—N1—C9—C4	−1.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w···N1ⁱ	0.84 (2)	2.28 (2)	2.999 (3)	144 (2)
O1w—H2w···N1ⁱⁱ	0.85 (2)	1.93 (2)	2.761 (3)	166 (3)
N2—H2n···O1wⁱⁱⁱ	0.88	2.01	2.865 (3)	165
C5—H5···O1wⁱⁱⁱ	0.95	2.45	3.379 (3)	164
C10—H10···O1wⁱⁱⁱ	0.95	2.50	3.302 (3)	142
C1—H1···F1^iv	0.95	2.56	3.399 (3)	147
C6—H6···F1^v	0.95	2.56	3.477 (3)	161

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁ClFN₃·H₂O
M_r	317.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	3.7795 (2), 15.4188 (11), 24.8576 (16)
β (°)	90.286 (4)
V (Å³)	1448.57 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.90 × 0.04 × 0.04

Data collection
Diffractometer	Enraf–Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.614, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	19494, 3291, 2009
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.131, 1.04
No. of reflections	3291
No. of parameters	205
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w···N1ⁱ	0.843 (16)	2.28 (2)	2.999 (3)	144 (2)
O1w—H2w···N1ⁱⁱ	0.85 (2)	1.93 (2)	2.761 (3)	166 (3)
N2—H2n···O1wⁱⁱⁱ	0.88	2.01	2.865 (3)	165
C5—H5···O1wⁱⁱⁱ	0.95	2.45	3.379 (3)	164
C10—H10···O1wⁱⁱⁱ	0.95	2.50	3.302 (3)	142
C1—H1···F1^iv	0.95	2.56	3.399 (3)	147
C6—H6···F1^v	0.95	2.56	3.477 (3)	161

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

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

References

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