7-Chloro-4-[(E)-(3-chloro­benzyl­idene)hydrazinyl]-1λ4-quinolinium 3-chloro­benzoate

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

doi:10.1107/S1600536809049794

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3204-o3205

doi:10.1107/S1600536809049794

Open

access

7-Chloro-4-[(E)-(3-chlorobenzylidene)hydrazinyl]-1λ⁴-quinolinium 3-chlorobenzoate

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 19 November 2009; accepted 20 November 2009; online 25 November 2009)

The title salt, C₁₆H₁₂Cl₂N₃⁺·C₇H₄ClO₂⁻, features a non-planar cation, the dihedral angle between the quinolinium and benzene residues being 18.98 (10)°. The cation adopts an E conformation about the C—N bond, and the amine group is oriented towards the quinolinium residue. In the crystal, N—H⋯O hydrogen bonds link two cations with two anions, forming a 20-membered {⋯OCO⋯HNC₃NH}₂ synthon. The dimeric units are connected into a linear supramolecular chain along [100] via π–π interactions [centroid–centroid distance = 3.5625 (13) Å].

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 (2005 ). For a related crystallographic study on neutral species related to the title compound, see: Kaiser et al. (2009 ).

Experimental

Crystal data

C₁₆H₁₂Cl₂N₃⁺·C₇H₄ClO₂⁻
M_r = 472.74
Triclinic, $[P \overline 1]$
a = 8.8777 (2) Å
b = 10.7064 (3) Å
c = 11.9807 (3) Å
α = 112.5318 (12)°
β = 91.6382 (15)°
γ = 97.4362 (15)°
V = 1039.17 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 120 K
0.06 × 0.04 × 0.03 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.922, T_max = 1.000
16836 measured reflections
4746 independent reflections
3949 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.104
S = 1.07
4746 reflections
283 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯O2ⁱ	0.89 (3)	1.76 (3)	2.641 (3)	175 (3)
N2—H2n⋯O1ⁱⁱ	0.88	2.00	2.809 (3)	152
Symmetry codes: (i) x-1, y-1, z; (ii) -x+1, -y+1, -z+1.

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/S1600536809049794/hg2605sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049794/hg2605Isup2.hkl

checkCIF report

Comment top

The majority of anti-malarial drugs, such as chloroquine (Tanenbaum & Tuffanelli, 1980), mefloquine (Palmer et al., 1993), primaquine (Elslager et al., 1969) and amodiaquine (Ridley, 2002), possess a quinoline ring, 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). The above motivates our studies aimed towards the development anti-malarial 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 title salt, (I), was prepared as a part of these investigations.

The cation in (I) is twisted about the N2–N3 bond, Fig. 1, as seen in the C3–N2–N3–C10 torsion angle of -168.3 (2) °. This is also reflected in the dihedral angle formed between the quinolinium (maximum deviation = 0.043 (2) for the C2 atom) and benzene planes of 18.98 (10) °. The conformation about the C10═N3 bond is E, and the amine-H is oriented towards the quinolinium residue as seen in related structures (Kaiser et al., 2009). The benzoate anion, Fig. 2, is planar with the O1–C17–C18–C19 torsion angle being -10.0 (3) °. The C17–O1, O2 distances in the carboxylate residue are 1.250 (3) and 1.269 (3) Å, respectively, consistent with deprotonation.

The crystal packing is dominated by N–H···O hydrogen bonding, Table 1. A pair of centrosymmetrically related benzoate anions each bridge the quinolinium-H and amine-H atoms of a cation to form a centrosymmetric 20-membered {···OCO···HNC₃NH}₂ synthon, Fig. 3. The dimeric units face each other to allow the formation of π–π interactions between the quinolinium residues with the Cg(N1, C1—C4, C9)···Cg(C4—C9)ⁱ distance = 3.5625 (13) Å for i: -x, -y, 1 - z. The net result is the formation of linear supramolecular chains aligned along [1 0 0], Fig. 4.

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 a related crystallographic study on neutral species related to the title compound, see: Kaiser et al. (2009).

Experimental top

A solution of 7-chloro-4-hydrazinylquinoline (0.20 g, 1.0 mmol) and 3-chorobenzaldehyde (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. 463–465 K, yield 0.24 g The sample for the X-ray study was slowly grown from moist EtOH and the compound isolated was found to be the salt with 3-chlorobenzoic acid. MS/ESI: 315 [C₁₆H₁₀Cl₂N₃], based on ³⁵Cl. IR [KBr, cm^-1] ν 3197 (NH), 1611 and 1552 (CN), 1362 (C—O). The 3-chlorobenzoic acid was subsequently found to be an impurity in the 3-chlorobenzaldehyde reagent.

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 the cation in (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 2. The molecular structure of the anion in (I) showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.
	Fig. 3. View of the centrosymmetric 20-membered {···OCO···HNC₃NH}₂ synthon in (I) showing the N–H···O hydrogen bonding as orange dashed lines. Colour code: Cl, cyan; O, red; N, blue; C, grey; and H, green.
	Fig. 4. A view of the linear supramolecular chain aligned along [1 0 0] in (I) where the dimeric aggregates illustrated in Fig. 3 are linked by π–π interactions (pink dashed lines).

7-Chloro-4-[(E)-(3-chlorobenzylidene)hydrazinyl]-1λ⁴-quinolinium 3-chlorobenzoate top

Crystal data top

C₁₆H₁₂Cl₂N₃⁺·C₇H₄ClO₂⁻	Z = 2
M_r = 472.74	F(000) = 484
Triclinic, P1	D_x = 1.511 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8777 (2) Å	Cell parameters from 16230 reflections
b = 10.7064 (3) Å	θ = 2.9–27.5°
c = 11.9807 (3) Å	µ = 0.47 mm⁻¹
α = 112.5318 (12)°	T = 120 K
β = 91.6382 (15)°	Block, yellow
γ = 97.4362 (15)°	0.06 × 0.04 × 0.03 mm
V = 1039.17 (5) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	4746 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	3949 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.044
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −13→13
T_min = 0.922, T_max = 1.000	l = −15→15
16836 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0078P)² + 1.9095P] where P = (F_o² + 2F_c²)/3
4746 reflections	(Δ/σ)_max = 0.001
283 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₆H₁₂Cl₂N₃⁺·C₇H₄ClO₂⁻	γ = 97.4362 (15)°
M_r = 472.74	V = 1039.17 (5) Å³
Triclinic, P1	Z = 2
a = 8.8777 (2) Å	Mo Kα radiation
b = 10.7064 (3) Å	µ = 0.47 mm⁻¹
c = 11.9807 (3) Å	T = 120 K
α = 112.5318 (12)°	0.06 × 0.04 × 0.03 mm
β = 91.6382 (15)°

Data collection top

Nonius KappaCCD area-detector diffractometer	4746 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3949 reflections with I > 2σ(I)
T_min = 0.922, T_max = 1.000	R_int = 0.044
16836 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.40 e Å⁻³
4746 reflections	Δρ_min = −0.45 e Å⁻³
283 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	−0.20629 (7)	−0.15682 (6)	0.12224 (5)	0.02306 (14)
Cl2	0.85051 (7)	0.10932 (6)	1.02577 (5)	0.02465 (15)
N1	0.0669 (2)	−0.2783 (2)	0.43607 (18)	0.0167 (4)
H1N	−0.007 (3)	−0.349 (3)	0.417 (2)	0.020*
N2	0.3644 (2)	0.08652 (19)	0.57378 (17)	0.0161 (4)
H2N	0.3580	0.1499	0.5448	0.019*
N3	0.4690 (2)	0.1101 (2)	0.67007 (17)	0.0165 (4)
C1	0.1764 (3)	−0.2566 (2)	0.5229 (2)	0.0176 (5)
H1	0.1815	−0.3246	0.5550	0.021*
C2	0.2826 (3)	−0.1393 (2)	0.5677 (2)	0.0169 (5)
H2	0.3619	−0.1290	0.6269	0.020*
C3	0.2724 (2)	−0.0350 (2)	0.5250 (2)	0.0150 (4)
C4	0.1584 (2)	−0.0590 (2)	0.4281 (2)	0.0152 (4)
C5	0.1406 (3)	0.0354 (2)	0.3736 (2)	0.0160 (4)
H5	0.2070	0.1203	0.4012	0.019*
C6	0.0291 (3)	0.0063 (2)	0.2819 (2)	0.0178 (5)
H6	0.0173	0.0709	0.2469	0.021*
C7	−0.0678 (3)	−0.1204 (2)	0.2400 (2)	0.0174 (5)
C8	−0.0558 (3)	−0.2149 (2)	0.2900 (2)	0.0163 (4)
H8	−0.1226	−0.2996	0.2607	0.020*
C9	0.0570 (2)	−0.1842 (2)	0.3852 (2)	0.0148 (4)
C10	0.5321 (3)	0.2345 (2)	0.7240 (2)	0.0183 (5)
H10	0.5072	0.3008	0.6948	0.022*
C11	0.6420 (3)	0.2766 (2)	0.8300 (2)	0.0190 (5)
C12	0.6897 (3)	0.1816 (2)	0.8718 (2)	0.0178 (5)
H12	0.6519	0.0869	0.8313	0.021*
C13	0.7928 (3)	0.2280 (2)	0.9730 (2)	0.0197 (5)
C14	0.8501 (3)	0.3651 (3)	1.0350 (2)	0.0262 (6)
H14	0.9208	0.3945	1.1043	0.031*
C15	0.8015 (3)	0.4585 (3)	0.9931 (2)	0.0316 (6)
H15	0.8388	0.5532	1.0346	0.038*
C16	0.6988 (3)	0.4153 (3)	0.8908 (2)	0.0274 (6)
H16	0.6673	0.4803	0.8625	0.033*
Cl3	0.12274 (6)	0.37851 (6)	0.30843 (6)	0.02426 (14)
O1	0.67939 (19)	0.66372 (16)	0.43847 (15)	0.0212 (4)
O2	0.84256 (18)	0.51324 (17)	0.36860 (16)	0.0216 (4)
C17	0.7100 (3)	0.5460 (2)	0.3827 (2)	0.0165 (5)
C18	0.5784 (3)	0.4312 (2)	0.3217 (2)	0.0164 (4)
C19	0.4291 (3)	0.4533 (2)	0.3442 (2)	0.0173 (5)
H19	0.4091	0.5382	0.4019	0.021*
C20	0.3100 (3)	0.3500 (2)	0.2816 (2)	0.0182 (5)
C21	0.3357 (3)	0.2254 (2)	0.1967 (2)	0.0218 (5)
H21	0.2526	0.1564	0.1535	0.026*
C22	0.4848 (3)	0.2028 (3)	0.1756 (2)	0.0243 (5)
H22	0.5041	0.1175	0.1183	0.029*
C23	0.6058 (3)	0.3051 (2)	0.2385 (2)	0.0206 (5)
H23	0.7077	0.2889	0.2245	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0229 (3)	0.0245 (3)	0.0229 (3)	−0.0014 (2)	−0.0066 (2)	0.0127 (2)
Cl2	0.0323 (3)	0.0204 (3)	0.0219 (3)	0.0074 (2)	−0.0037 (2)	0.0082 (2)
N1	0.0171 (10)	0.0126 (9)	0.0215 (10)	0.0015 (7)	0.0001 (8)	0.0081 (8)
N2	0.0163 (9)	0.0142 (9)	0.0183 (10)	0.0005 (7)	−0.0038 (7)	0.0080 (8)
N3	0.0153 (9)	0.0180 (10)	0.0158 (9)	0.0014 (7)	−0.0011 (7)	0.0067 (8)
C1	0.0199 (11)	0.0147 (11)	0.0211 (12)	0.0062 (9)	0.0018 (9)	0.0092 (9)
C2	0.0163 (11)	0.0156 (11)	0.0181 (11)	0.0020 (9)	−0.0011 (9)	0.0061 (9)
C3	0.0127 (10)	0.0143 (11)	0.0177 (11)	0.0041 (8)	0.0035 (8)	0.0051 (9)
C4	0.0141 (10)	0.0159 (11)	0.0165 (11)	0.0047 (8)	0.0028 (8)	0.0065 (9)
C5	0.0173 (11)	0.0125 (10)	0.0178 (11)	0.0025 (8)	0.0033 (9)	0.0052 (9)
C6	0.0210 (12)	0.0159 (11)	0.0188 (11)	0.0043 (9)	0.0030 (9)	0.0087 (9)
C7	0.0162 (11)	0.0200 (12)	0.0156 (11)	0.0033 (9)	0.0003 (9)	0.0067 (9)
C8	0.0161 (11)	0.0132 (10)	0.0177 (11)	−0.0001 (8)	0.0014 (9)	0.0048 (9)
C9	0.0159 (11)	0.0128 (10)	0.0162 (11)	0.0025 (8)	0.0019 (8)	0.0060 (9)
C10	0.0195 (11)	0.0164 (11)	0.0195 (12)	0.0004 (9)	−0.0005 (9)	0.0085 (9)
C11	0.0211 (12)	0.0179 (11)	0.0179 (11)	0.0009 (9)	−0.0007 (9)	0.0075 (9)
C12	0.0183 (11)	0.0150 (11)	0.0177 (11)	−0.0006 (9)	−0.0001 (9)	0.0050 (9)
C13	0.0231 (12)	0.0198 (12)	0.0190 (12)	0.0044 (9)	0.0018 (9)	0.0103 (10)
C14	0.0321 (14)	0.0227 (13)	0.0207 (12)	−0.0044 (11)	−0.0088 (10)	0.0083 (10)
C15	0.0453 (17)	0.0165 (12)	0.0277 (14)	−0.0068 (11)	−0.0131 (12)	0.0077 (11)
C16	0.0376 (15)	0.0193 (12)	0.0257 (13)	−0.0007 (11)	−0.0082 (11)	0.0115 (11)
Cl3	0.0161 (3)	0.0240 (3)	0.0307 (3)	0.0009 (2)	−0.0005 (2)	0.0094 (3)
O1	0.0227 (9)	0.0133 (8)	0.0253 (9)	0.0007 (6)	−0.0033 (7)	0.0061 (7)
O2	0.0170 (8)	0.0168 (8)	0.0296 (10)	0.0006 (6)	−0.0019 (7)	0.0085 (7)
C17	0.0195 (11)	0.0154 (11)	0.0166 (11)	0.0018 (9)	−0.0025 (9)	0.0092 (9)
C18	0.0180 (11)	0.0145 (11)	0.0175 (11)	−0.0012 (8)	−0.0011 (9)	0.0085 (9)
C19	0.0208 (11)	0.0145 (11)	0.0165 (11)	0.0020 (9)	−0.0003 (9)	0.0065 (9)
C20	0.0168 (11)	0.0195 (12)	0.0205 (11)	0.0012 (9)	0.0002 (9)	0.0108 (9)
C21	0.0222 (12)	0.0180 (12)	0.0208 (12)	−0.0049 (9)	−0.0012 (10)	0.0054 (10)
C22	0.0279 (13)	0.0158 (11)	0.0233 (13)	−0.0006 (10)	0.0033 (10)	0.0024 (10)
C23	0.0208 (12)	0.0195 (12)	0.0211 (12)	0.0019 (9)	0.0029 (9)	0.0077 (10)

Geometric parameters (Å, º) top

Cl1—C7	1.735 (2)	C11—C16	1.395 (3)
Cl2—C13	1.744 (2)	C11—C12	1.398 (3)
N1—C1	1.334 (3)	C12—C13	1.383 (3)
N1—C9	1.373 (3)	C12—H12	0.9500
N1—H1N	0.89 (3)	C13—C14	1.384 (3)
N2—C3	1.348 (3)	C14—C15	1.386 (4)
N2—N3	1.383 (3)	C14—H14	0.9500
N2—H2N	0.8800	C15—C16	1.392 (4)
N3—C10	1.277 (3)	C15—H15	0.9500
C1—C2	1.379 (3)	C16—H16	0.9500
C1—H1	0.9500	Cl3—C20	1.745 (2)
C2—C3	1.407 (3)	O1—C17	1.250 (3)
C2—H2	0.9500	O2—C17	1.269 (3)
C3—C4	1.440 (3)	C17—C18	1.517 (3)
C4—C9	1.416 (3)	C18—C19	1.392 (3)
C4—C5	1.420 (3)	C18—C23	1.394 (3)
C5—C6	1.371 (3)	C19—C20	1.385 (3)
C5—H5	0.9500	C19—H19	0.9500
C6—C7	1.408 (3)	C20—C21	1.385 (3)
C6—H6	0.9500	C21—C22	1.389 (4)
C7—C8	1.372 (3)	C21—H21	0.9500
C8—C9	1.405 (3)	C22—C23	1.392 (3)
C8—H8	0.9500	C22—H22	0.9500
C10—C11	1.465 (3)	C23—H23	0.9500
C10—H10	0.9500

C1—N1—C9	120.8 (2)	C16—C11—C10	118.8 (2)
C1—N1—H1N	119.7 (17)	C12—C11—C10	121.6 (2)
C9—N1—H1N	119.0 (17)	C13—C12—C11	118.9 (2)
C3—N2—N3	119.06 (18)	C13—C12—H12	120.6
C3—N2—H2N	120.5	C11—C12—H12	120.6
N3—N2—H2N	120.5	C12—C13—C14	122.4 (2)
C10—N3—N2	114.66 (19)	C12—C13—Cl2	118.72 (18)
N1—C1—C2	122.5 (2)	C14—C13—Cl2	118.83 (19)
N1—C1—H1	118.8	C13—C14—C15	118.2 (2)
C2—C1—H1	118.8	C13—C14—H14	120.9
C1—C2—C3	119.4 (2)	C15—C14—H14	120.9
C1—C2—H2	120.3	C14—C15—C16	120.9 (2)
C3—C2—H2	120.3	C14—C15—H15	119.6
N2—C3—C2	121.7 (2)	C16—C15—H15	119.6
N2—C3—C4	119.7 (2)	C15—C16—C11	120.0 (2)
C2—C3—C4	118.6 (2)	C15—C16—H16	120.0
C9—C4—C5	117.9 (2)	C11—C16—H16	120.0
C9—C4—C3	118.0 (2)	O1—C17—O2	125.9 (2)
C5—C4—C3	124.1 (2)	O1—C17—C18	118.0 (2)
C6—C5—C4	121.1 (2)	O2—C17—C18	116.1 (2)
C6—C5—H5	119.4	C19—C18—C23	119.6 (2)
C4—C5—H5	119.4	C19—C18—C17	120.1 (2)
C5—C6—C7	119.3 (2)	C23—C18—C17	120.1 (2)
C5—C6—H6	120.4	C20—C19—C18	119.3 (2)
C7—C6—H6	120.4	C20—C19—H19	120.4
C8—C7—C6	121.8 (2)	C18—C19—H19	120.4
C8—C7—Cl1	119.40 (18)	C19—C20—C21	121.6 (2)
C6—C7—Cl1	118.75 (17)	C19—C20—Cl3	119.25 (18)
C7—C8—C9	118.8 (2)	C21—C20—Cl3	119.13 (18)
C7—C8—H8	120.6	C20—C21—C22	119.1 (2)
C9—C8—H8	120.6	C20—C21—H21	120.5
N1—C9—C8	118.6 (2)	C22—C21—H21	120.5
N1—C9—C4	120.5 (2)	C21—C22—C23	120.0 (2)
C8—C9—C4	120.9 (2)	C21—C22—H22	120.0
N3—C10—C11	121.2 (2)	C23—C22—H22	120.0
N3—C10—H10	119.4	C22—C23—C18	120.4 (2)
C11—C10—H10	119.4	C22—C23—H23	119.8
C16—C11—C12	119.6 (2)	C18—C23—H23	119.8

C3—N2—N3—C10	−168.3 (2)	C11—C12—C13—C14	0.3 (4)
C9—N1—C1—C2	1.3 (3)	C11—C12—C13—Cl2	179.37 (18)
N1—C1—C2—C3	2.9 (3)	C12—C13—C14—C15	0.0 (4)
N3—N2—C3—C2	−1.5 (3)	Cl2—C13—C14—C15	−179.1 (2)
N3—N2—C3—C4	177.33 (19)	C13—C14—C15—C16	−0.5 (4)
C1—C2—C3—N2	173.8 (2)	C14—C15—C16—C11	0.7 (4)
C1—C2—C3—C4	−5.1 (3)	C12—C11—C16—C15	−0.4 (4)
N2—C3—C4—C9	−175.6 (2)	C10—C11—C16—C15	178.9 (2)
C2—C3—C4—C9	3.3 (3)	O1—C17—C18—C19	−10.0 (3)
N2—C3—C4—C5	3.8 (3)	O2—C17—C18—C19	172.1 (2)
C2—C3—C4—C5	−177.3 (2)	O1—C17—C18—C23	166.8 (2)
C9—C4—C5—C6	−0.3 (3)	O2—C17—C18—C23	−11.1 (3)
C3—C4—C5—C6	−179.7 (2)	C23—C18—C19—C20	−1.1 (3)
C4—C5—C6—C7	−0.9 (3)	C17—C18—C19—C20	175.7 (2)
C5—C6—C7—C8	1.2 (3)	C18—C19—C20—C21	−0.3 (3)
C5—C6—C7—Cl1	−178.96 (18)	C18—C19—C20—Cl3	−179.20 (17)
C6—C7—C8—C9	−0.3 (3)	C19—C20—C21—C22	1.2 (4)
Cl1—C7—C8—C9	179.89 (17)	Cl3—C20—C21—C22	−179.88 (19)
C1—N1—C9—C8	176.9 (2)	C20—C21—C22—C23	−0.7 (4)
C1—N1—C9—C4	−3.2 (3)	C21—C22—C23—C18	−0.7 (4)
C7—C8—C9—N1	179.0 (2)	C19—C18—C23—C22	1.7 (4)
C7—C8—C9—C4	−1.0 (3)	C17—C18—C23—C22	−175.2 (2)
C5—C4—C9—N1	−178.7 (2)	C2—C3—N2—N3	−1.5 (3)
C3—C4—C9—N1	0.8 (3)	C4—C3—N2—N3	177.33 (19)
C5—C4—C9—C8	1.3 (3)	N3—C10—C11—C12	4.1 (4)
C3—C4—C9—C8	−179.3 (2)	N3—C10—C11—C16	−175.2 (2)
N2—N3—C10—C11	178.2 (2)	C19—C18—C17—O1	−10.0 (3)
N3—C10—C11—C16	−175.2 (2)	C19—C18—C17—O2	172.1 (2)
N3—C10—C11—C12	4.1 (4)	C23—C18—C17—O1	166.8 (2)
C16—C11—C12—C13	−0.1 (4)	C23—C18—C17—O2	−11.1 (3)
C10—C11—C12—C13	−179.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2ⁱ	0.89 (3)	1.76 (3)	2.641 (3)	175 (3)
N2—H2n···O1ⁱⁱ	0.88	2.00	2.809 (3)	152

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₂N₃⁺·C₇H₄ClO₂⁻
M_r	472.74
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	8.8777 (2), 10.7064 (3), 11.9807 (3)
α, β, γ (°)	112.5318 (12), 91.6382 (15), 97.4362 (15)
V (Å³)	1039.17 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.06 × 0.04 × 0.03

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2007)
T_min, T_max	0.922, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	16836, 4746, 3949
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.104, 1.07
No. of reflections	4746
No. of parameters	283
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.45

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
N1—H1n···O2ⁱ	0.89 (3)	1.76 (3)	2.641 (3)	175 (3)
N2—H2n···O1ⁱⁱ	0.88	2.00	2.809 (3)	152

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

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

Andrade, A. A., Varotti, F. D., de Freitas, I. Q., de Souza, M. V. N., Vasconcelos, T. R. A., Boechat, N. & Krettli, A. U. (2007). Eur. J. Pharm. 558, 194–198. CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Cunico, W., Cechinel, C. A., Bonacorso, H. G., Martins, G. M. A. P., Zanetta, N., de Souza, M. V. N., Freitas, I. Q., Soares, R. P. P. & Krettli, A. U. (2006). Bioorg. Med. Chem. Lett. 16, 649–653. Web of Science CrossRef PubMed CAS Google Scholar
Elslager, E. F., Tendick, F. H. & Werbel, L. M. (1969). J. Med. Chem. 12, 600–607. CrossRef CAS PubMed Web of Science Google Scholar
Font, M., Monge, A., Ruiz, I. & Heras, B. (1997). Drug. Des. Disc. 14, 259–272. CAS Google Scholar
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Kaiser, C. R., Pais, K. C., de Souza, M. V. N., Wardell, J. L., Wardell, S. M. S. V. & Tiekink, E. R. T. (2009). CrystEngComm, 11, 1133–1140. Web of Science CSD CrossRef CAS Google Scholar
Kaminsky, D. & Meltzer, R. I. (1968). J. Med. Chem. 11, 160–163. CrossRef CAS PubMed Web of Science Google Scholar
Musiol, R., Jampilek, J., Buchta, V., Silva, L., Halina, H., Podeszwa, B., Palka, A., Majerz-Maniecka, K., Oleksyn, B. & Polanski, J. (2006). Bioorg. Med. Chem. 14, 3592–3598. Web of Science CrossRef PubMed CAS Google Scholar
Nakamura, T., Oka, M., Aizawa, K., Soda, H., Fukuda, M., Terashi, K., Ikeda, K., Mizuta, Y., Noguchi, Y., Kimura, Y., Tsuruo, T. & Kohno, S. (1999). Biochem. Biophys. Res. Commun. 255, 618–624. Web of Science CrossRef PubMed CAS Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Palmer, K. J., Holliday, S. M. & and Brogden, R. N. (1993). Drugs, 45, 430–475. CrossRef CAS PubMed Web of Science Google Scholar
Ridley, R. G. (2002). Nature (London), 415, 686–693. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2007). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Silva, A. D. da, de Almeida, M. V., de Souza, M. V. N. & Couri, M. R. C. (2003). Curr. Med. Chem. 10, 21–39. Web of Science PubMed Google Scholar
Sloboda, A. E., Powell, D., Poletto, J. F., Pickett, W. C., Gibbons, J. J., Bell, D. H., Oronsky, A. L. & Kerwar, S. S. (1991). J. Rheumatol. 18, 855–860. PubMed CAS Web of Science Google Scholar
Souza, M. V. N. de (2005). Mini Rev. Med. Chem. 5, 1009–1017. Web of Science PubMed Google Scholar
Tanenbaum, L. & Tuffanelli, D. L. (1980). Arch. Dermatol. 116, 587–591. CrossRef CAS PubMed Web of Science Google Scholar
Warshakoon, N. C., Sheville, J., Bhatt, R. T., Ji, W., Mendez-Andino, J. L., Meyers, K. M., Kim, N., Wos, J. A., Mitchell, C., Paris, J. L., Pinney, B. B. O., Reizes, O. & Hu, X. E. (2006). Bioorg. Med. Chem. Lett. 16, 5207–5211. Web of Science CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.