Crystal structure of chlorido­(2-{[2-(phenyl­car­bamo­thioyl)hydrazin-1-ylidene](pyridin-2-yl)methyl}pyridin-1-ium)gold(I) chloride sesqui­hydrate

Gatto, C.C.; Lima, I.J.

doi:10.1107/S2056989015015480

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Volume 71| Part 9| September 2015| Pages 1070-1072

https://doi.org/10.1107/S2056989015015480

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Crystal structure of chlorido(2-{[2-(phenylcarbamothioyl)hydrazin-1-ylidene](pyridin-2-yl)methyl}pyridin-1-ium)gold(I) chloride sesquihydrate

Claudia C. Gatto ^a ^* and Iariane J. Lima ^a

^aLaboratory of Inorganic Synthesis and Crystallography, University of Brasília, IQ, Campus Universitário Darcy Ribeiro, CEP 70904970, PO Box 4478, Brasília - DF, Brazil
^*Correspondence e-mail: ccgatto@gmail.com

Edited by M. Zeller, Youngstown State University, USA (Received 5 August 2015; accepted 18 August 2015; online 26 August 2015)

The title complex, [AuCl(C₁₈H₁₆N₅S)]Cl·1.5H₂O, may be considered as a gold(I) compound with the corresponding metal site coordinated by a thiosemicarbazone ligand through the S atom. The ligand adopts an E conformation and the gold(I) atom displays the expected linear geometry with a Cl atom also bonded to the metal ion [Cl—Au—S = 174.23 (5)°]. One of the pyridyl rings is protonated, giving the gold complex an overall positive charge. Two solvent water molecules, one of which is located on a twofold rotation axis, and a non-coordinating chloride ion complete the structural assembly. The molecular structure is stabilized by intramolecular and intermolecular N—H⋯Cl, N—H⋯N, O—H⋯Cl and O—H⋯O hydrogen bonding.

Keywords: crystal structure; gold(I) complex; thiosemicarbazone; hydrogen bonding.

CCDC reference: 1419509

1. Chemical context

Thiosemicarbazones are generated from reactions of thiosemicarbazides with either an aldehyde or a ketone. They are compounds that can coordinate to transition metals and exhibit keto–enol tautomerism (Duan et al., 1996 ). Thiosemicarbazones are known to have diverse biological activity, including anti-malarial properties and antibacterial, antitubercular, antiviral and antitumor activity (Beraldo & Gambino, 2004 , Casini et al., 2008 , Khanye et al., 2010 ). The study of gold compounds with thiosemicarbazones has great importance: the literature reports that some compounds of this type have been shown to exhibit biological activity and have potential applications (Casini et al., 2008, Lessa et al., 2011 ).

2. Structural commentary

In the title complex (Fig. 1), the di-2-pyridyl ketone phenylthiosemicarbazone ligand is protonated at the pyridine (py) nitrogen and only the sulfur donor atom is used to bond to the central metal ion. The thiosemicarbazone adopts the E conformation in relation to the C6=N3 and N4—C12 bonds.

Figure 1
Perspective view of [AuCl(C₁₈H₁₆N₅S)]Cl·1.5H₂O with 30% probability ellipsoids and atom labeling.

The crystal structure data confirm reduction of gold(III) of the starting material [HPy][AuCl₄] during the synthesis. Two solvent water molecules and an non-coordinating chloride ion complete the structural assembly and are hydrogen bonded to the cationic complex.

The gold(I) atom displays the expected linear geometry, with a Cl—Au—S coordination angle of 174.23 (5)°, close to the ideal angle of 180° expected for sp hybridization of the metal.

The C12—S1 bond length reported for di-2-pyridyl ketone phenylthiosemicarbazone is 1.676 (2) Å and it is lengthened to 1.713 (4) Å on coordination to gold; this is typical of the ketone form with a concomitant shortening of the N3—N4 bond (Suni et al., 2006 ).

An intramolecular N4—H4A⋯N2 hydrogen bond (Table 1) is observed.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯Cl2	0.86	2.46	3.246 (4)	153
N4—H4A⋯N2	0.86	1.97	2.629 (5)	133
N1—H1A⋯Cl2	0.80 (4)	2.26 (4)	2.989 (4)	150 (4)
O1—H1W1⋯Cl1ⁱ	0.80 (2)	2.70 (5)	3.353 (4)	140 (6)
O1—H1W2⋯Cl2ⁱⁱ	0.81 (2)	2.39 (2)	3.206 (4)	177 (6)
O2—H2W2⋯O1	0.82 (2)	2.06 (3)	2.855 (5)	163 (7)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ .

3. Supramolecular features

In the crystal, the chloride ion is linked to the complex molecule by N—H⋯Cl hydrogen bonds. The molecular structure is also stabilized by intermolecular O—H⋯Cl and O—H⋯O hydrogen bonding involving the water molecules. Therefore, upon protonation of the ligand, hydrogen-bond formation with the chloride ion results in a stabilization of the conformation of the cationic gold complex, and hydrogen bonding plays an important role in the crystallization of the compound (Table 1 and Fig. 2).

Figure 2
Perspective view of the compound showing the components connected by N—H⋯Cl and N—H⋯N hydrogen bonds (dashed lines), viewed along the c axis. Solvent water molecules have been omitted for clarity.

4. Related studies

For the preparation of coordination compounds of thiomemicarbazones with gold, see: Castiñeiras et al. (2012 ); Khanye et al. (2010); Lessa et al. (2011); Sreekanth et al. (2004 ). For the spectroscopic (FT–IR) properties of thiosemicarbazones and the crystal structure of thiosemicarbazones, see: Beraldo & Gambino (2004); Duan et al. (1996); Pereiras-Gabián et al. (2004 ); Suni et al. (2006). For the crystal structures of di-2-pyridyl ketone phenylthiosemicarbazone and coordination compounds with this thiosemicarbazone, see: Bernhardt et al. (2009 ); Philip et al. (2005 ); Suni et al. (2006, 2007 ). For structure–activity studies of thiosemicarbazones, see: Bernhardt et al. (2009); Casini et al. (2008); Duan et al. (1996).

5. Synthesis and crystallization

Di-2-pyridyl ketone phenylthiosemicarbazone (1 mmol) was dissolved in about 5 ml of CH₃CN and added to a solution of [HPy][AuCl₄] (1 mmol) in 5 ml of CH₃CN. A clear yellow solution was formed after heating the mixture to reflux for three h. Orange crystals deposited upon slow cooling of the solvent. Yield: 69%, m.p. 491 K. Elemental analysis, found: C, 33.71; H, 3.15; N, 10.04%; calculated for C₃₆H₃₈Au₂Cl₄N₁₀O₃S₂: C, 33.87; H, 3.16; N, 10.97%. IR (ν_max cm⁻¹): 3421 (O—H), 3281 (N—H), 2927 (N—H⁺), 1694 (C=N), 1150 (N—N), 765 (C=S).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms potentially involved in hydrogen-bonding interactions were located in difference electron-density maps and their positional and isotropic displacement parameters were refined. Hydrogen atoms of water molecules were refined with distance restraints, with an H⋯H separation of 1.38 (2) Å, the H—O distance restrained to 0.82 (2) Å and with U_iso = 1.5U_eq(O). Other H atoms were included in the refinement at calculated positions and treated as riding with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[AuCl(C₁₈H₁₆N₅S)]Cl·1.5H₂O
M_r	629.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	31.0939 (7), 12.2704 (3), 11.8851 (3)
β (°)	110.174 (1)
V (Å³)	4256.38 (18)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	7.28
Crystal size (mm)	0.24 × 0.22 × 0.14

Data collection
Diffractometer	Bruker CCD SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.274, 0.429
No. of measured, independent and observed [I > 2σ(I)] reflections	15424, 4345, 3220
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.072, 0.97
No. of reflections	4345
No. of parameters	271
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)	0.97, −0.78
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), DIAMOND (Crystal Impact, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1419509

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015480/zl2637sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015480/zl2637Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Crystal Impact, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

Chlorido(2-{[2-(phenylcarbamothioyl)hydrazin-1-ylidene](pyridin-2-yl)methyl}pyridin-1-ium)gold(I) chloride sesquihydrate top

Crystal data top

[AuCl(C₁₈H₁₆N₅S)]Cl·1.5H₂O	D_x = 1.964 Mg m⁻³
M_r = 629.31	Melting point: 491 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 31.0939 (7) Å	Cell parameters from 4811 reflections
b = 12.2704 (3) Å	θ = 2.7–25.2°
c = 11.8851 (3) Å	µ = 7.28 mm⁻¹
β = 110.174 (1)°	T = 296 K
V = 4256.38 (18) Å³	Block, red
Z = 8	0.24 × 0.22 × 0.14 mm
F(000) = 2424

Data collection top

Bruker CCD SMART APEXII diffractometer	3220 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
phi & ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −37→38
T_min = 0.274, T_max = 0.429	k = −14→15
15424 measured reflections	l = −14→14
4345 independent 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)] = 0.031	Hydrogen site location: mixed
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0364P)²] where P = (F_o² + 2F_c²)/3
4345 reflections	(Δ/σ)_max = 0.001
271 parameters	Δρ_max = 0.97 e Å⁻³
3 restraints	Δρ_min = −0.78 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Au1	0.25092 (2)	0.60284 (2)	0.04569 (2)	0.04892 (9)
S1	0.32514 (5)	0.61867 (10)	0.16165 (13)	0.0581 (4)
Cl1	0.17486 (5)	0.57863 (11)	−0.05533 (12)	0.0610 (4)
C12	0.34886 (15)	0.4928 (3)	0.1607 (4)	0.0388 (10)
N3	0.35315 (13)	0.3345 (3)	0.0578 (3)	0.0370 (9)
N5	0.38617 (12)	0.4607 (3)	0.2458 (3)	0.0424 (9)
H5A	0.3953	0.3954	0.2403	0.051*
N4	0.32925 (13)	0.4234 (3)	0.0690 (3)	0.0401 (9)
H4A	0.3022	0.4355	0.0190	0.048*
C13	0.41343 (15)	0.5235 (4)	0.3473 (4)	0.0410 (11)
C5	0.36773 (15)	0.1810 (3)	−0.0344 (4)	0.0355 (10)
C6	0.33459 (15)	0.2653 (3)	−0.0268 (3)	0.0342 (10)
C7	0.28703 (16)	0.2612 (3)	−0.1109 (3)	0.0376 (10)
C4	0.36887 (17)	0.1356 (3)	−0.1392 (4)	0.0431 (11)
H4	0.3469	0.1549	−0.2121	0.052*
C1	0.43375 (18)	0.0813 (3)	0.0737 (5)	0.0479 (12)
H1	0.4560	0.0642	0.1470	0.057*
C18	0.43406 (17)	0.6200 (4)	0.3336 (5)	0.0472 (12)
H18	0.4292	0.6490	0.2579	0.057*
C15	0.45009 (18)	0.5339 (4)	0.5600 (4)	0.0560 (14)
H15	0.4557	0.5049	0.6360	0.067*
C16	0.47070 (18)	0.6300 (4)	0.5471 (5)	0.0585 (14)
H16	0.4903	0.6657	0.6142	0.070*
C14	0.42124 (16)	0.4803 (4)	0.4608 (4)	0.0481 (12)
H14	0.4071	0.4158	0.4697	0.058*
C17	0.46232 (17)	0.6725 (4)	0.4362 (5)	0.0553 (13)
H17	0.4758	0.7384	0.4286	0.066*
C3	0.40278 (18)	0.0613 (4)	−0.1356 (4)	0.0492 (12)
H3	0.4037	0.0304	−0.2062	0.059*
C2	0.43484 (18)	0.0335 (4)	−0.0286 (5)	0.0536 (13)
H2	0.4573	−0.0177	−0.0254	0.064*
N2	0.26250 (14)	0.3552 (3)	−0.1220 (3)	0.0471 (10)
N1	0.40084 (13)	0.1526 (3)	0.0690 (3)	0.0393 (9)
C9	0.22292 (19)	0.1715 (5)	−0.2508 (5)	0.0588 (14)
H9	0.2095	0.1095	−0.2936	0.071*
C8	0.26759 (17)	0.1682 (4)	−0.1724 (4)	0.0486 (12)
H8	0.2844	0.1038	−0.1612	0.058*
C11	0.21949 (19)	0.3548 (5)	−0.1966 (4)	0.0586 (14)
H11	0.2024	0.4181	−0.2030	0.070*
C10	0.19855 (19)	0.2663 (5)	−0.2653 (4)	0.0592 (14)
H10	0.1688	0.2710	−0.3197	0.071*
Cl2	0.42609 (4)	0.21756 (9)	0.32609 (9)	0.0506 (3)
O1	0.42303 (14)	0.7870 (4)	0.0930 (3)	0.0663 (10)
H1W1	0.3956 (7)	0.787 (6)	0.069 (6)	0.099*
H1W2	0.424 (2)	0.783 (5)	0.025 (3)	0.099*
O2	0.5000	0.9028 (5)	0.2500	0.087 (2)
H2W2	0.4803 (19)	0.859 (4)	0.213 (6)	0.130*
H1A	0.3997 (14)	0.186 (3)	0.126 (4)	0.033 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Au1	0.04494 (14)	0.05060 (13)	0.04726 (13)	0.01206 (9)	0.01084 (10)	−0.00251 (9)
S1	0.0458 (8)	0.0439 (7)	0.0735 (9)	0.0109 (6)	0.0064 (7)	−0.0198 (6)
Cl1	0.0451 (8)	0.0752 (9)	0.0550 (8)	0.0134 (6)	0.0075 (7)	0.0022 (6)
C12	0.042 (3)	0.032 (2)	0.043 (2)	0.001 (2)	0.014 (2)	−0.005 (2)
N3	0.041 (2)	0.033 (2)	0.0358 (19)	0.0044 (16)	0.0122 (18)	−0.0029 (16)
N5	0.043 (3)	0.0311 (19)	0.047 (2)	0.0033 (16)	0.008 (2)	−0.0065 (17)
N4	0.033 (2)	0.037 (2)	0.046 (2)	0.0049 (16)	0.0089 (19)	−0.0062 (17)
C13	0.036 (3)	0.038 (2)	0.047 (3)	0.004 (2)	0.012 (2)	−0.004 (2)
C5	0.040 (3)	0.030 (2)	0.036 (2)	−0.0010 (19)	0.012 (2)	0.0018 (19)
C6	0.038 (3)	0.033 (2)	0.033 (2)	0.0017 (18)	0.013 (2)	0.0008 (19)
C7	0.041 (3)	0.042 (2)	0.032 (2)	0.000 (2)	0.016 (2)	0.002 (2)
C4	0.052 (3)	0.040 (2)	0.037 (2)	0.005 (2)	0.015 (2)	−0.002 (2)
C1	0.050 (3)	0.040 (3)	0.047 (3)	0.008 (2)	0.007 (3)	0.003 (2)
C18	0.046 (3)	0.043 (3)	0.050 (3)	0.004 (2)	0.014 (3)	0.003 (2)
C15	0.056 (4)	0.066 (3)	0.044 (3)	0.002 (3)	0.015 (3)	−0.008 (3)
C16	0.040 (3)	0.066 (3)	0.060 (3)	0.000 (3)	0.006 (3)	−0.023 (3)
C14	0.045 (3)	0.050 (3)	0.052 (3)	0.000 (2)	0.019 (3)	0.001 (2)
C17	0.046 (3)	0.041 (3)	0.075 (4)	−0.005 (2)	0.016 (3)	−0.012 (3)
C3	0.056 (3)	0.043 (3)	0.050 (3)	0.003 (2)	0.020 (3)	−0.012 (2)
C2	0.053 (3)	0.044 (3)	0.069 (4)	0.011 (2)	0.027 (3)	−0.003 (3)
N2	0.043 (3)	0.054 (2)	0.040 (2)	0.0091 (19)	0.008 (2)	0.0055 (18)
N1	0.044 (3)	0.033 (2)	0.037 (2)	0.0027 (17)	0.010 (2)	−0.0038 (18)
C9	0.045 (3)	0.073 (4)	0.054 (3)	−0.024 (3)	0.012 (3)	−0.006 (3)
C8	0.045 (3)	0.050 (3)	0.051 (3)	−0.006 (2)	0.016 (3)	−0.001 (2)
C11	0.048 (4)	0.076 (4)	0.047 (3)	0.013 (3)	0.009 (3)	0.008 (3)
C10	0.041 (3)	0.088 (4)	0.044 (3)	−0.006 (3)	0.009 (3)	−0.001 (3)
Cl2	0.0610 (9)	0.0450 (6)	0.0386 (6)	−0.0022 (6)	0.0080 (6)	0.0000 (5)
O1	0.065 (3)	0.079 (2)	0.051 (2)	0.002 (2)	0.015 (2)	0.003 (2)
O2	0.077 (5)	0.064 (4)	0.092 (5)	0.000	−0.004 (4)	0.000

Geometric parameters (Å, º) top

Au1—S1	2.2515 (14)	C18—H18	0.9300
Au1—Cl1	2.2725 (14)	C15—C16	1.376 (7)
S1—C12	1.713 (4)	C15—C14	1.377 (6)
C12—N5	1.309 (5)	C15—H15	0.9300
C12—N4	1.351 (5)	C16—C17	1.357 (7)
N3—C6	1.290 (5)	C16—H16	0.9300
N3—N4	1.353 (5)	C14—H14	0.9300
N5—C13	1.436 (5)	C17—H17	0.9300
N5—H5A	0.8600	C3—C2	1.362 (7)
N4—H4A	0.8600	C3—H3	0.9300
C13—C18	1.383 (6)	C2—H2	0.9300
C13—C14	1.391 (6)	N2—C11	1.325 (6)
C5—N1	1.349 (5)	N1—H1A	0.80 (4)
C5—C4	1.375 (6)	C9—C10	1.366 (7)
C5—C6	1.485 (6)	C9—C8	1.381 (7)
C6—C7	1.473 (6)	C9—H9	0.9300
C7—N2	1.364 (5)	C8—H8	0.9300
C7—C8	1.378 (6)	C11—C10	1.380 (7)
C4—C3	1.384 (6)	C11—H11	0.9300
C4—H4	0.9300	C10—H10	0.9300
C1—N1	1.332 (6)	O1—H1W1	0.80 (2)
C1—C2	1.361 (7)	O1—H1W2	0.813 (19)
C1—H1	0.9300	O2—H2W2	0.82 (2)
C18—C17	1.390 (6)

S1—Au1—Cl1	174.23 (5)	C16—C15—H15	119.9
C12—S1—Au1	105.72 (16)	C14—C15—H15	119.9
N5—C12—N4	117.8 (4)	C17—C16—C15	119.8 (5)
N5—C12—S1	122.3 (3)	C17—C16—H16	120.1
N4—C12—S1	119.8 (3)	C15—C16—H16	120.1
C6—N3—N4	119.6 (4)	C15—C14—C13	119.5 (5)
C12—N5—C13	126.6 (4)	C15—C14—H14	120.2
C12—N5—H5A	116.7	C13—C14—H14	120.2
C13—N5—H5A	116.7	C16—C17—C18	121.7 (5)
C12—N4—N3	118.5 (4)	C16—C17—H17	119.2
C12—N4—H4A	120.7	C18—C17—H17	119.2
N3—N4—H4A	120.7	C2—C3—C4	119.9 (5)
C18—C13—C14	120.5 (4)	C2—C3—H3	120.1
C18—C13—N5	121.6 (4)	C4—C3—H3	120.1
C14—C13—N5	117.7 (4)	C1—C2—C3	119.4 (5)
N1—C5—C4	118.1 (4)	C1—C2—H2	120.3
N1—C5—C6	116.9 (4)	C3—C2—H2	120.3
C4—C5—C6	124.9 (4)	C11—N2—C7	117.6 (4)
N3—C6—C7	128.7 (4)	C1—N1—C5	122.8 (4)
N3—C6—C5	111.9 (4)	C1—N1—H1A	124 (3)
C7—C6—C5	119.4 (4)	C5—N1—H1A	113 (3)
N2—C7—C8	121.4 (4)	C10—C9—C8	119.7 (5)
N2—C7—C6	115.7 (4)	C10—C9—H9	120.2
C8—C7—C6	122.8 (4)	C8—C9—H9	120.2
C5—C4—C3	119.7 (4)	C7—C8—C9	119.2 (5)
C5—C4—H4	120.1	C7—C8—H8	120.4
C3—C4—H4	120.1	C9—C8—H8	120.4
N1—C1—C2	120.0 (5)	N2—C11—C10	124.1 (5)
N1—C1—H1	120.0	N2—C11—H11	118.0
C2—C1—H1	120.0	C10—C11—H11	118.0
C13—C18—C17	118.2 (5)	C9—C10—C11	117.9 (5)
C13—C18—H18	120.9	C9—C10—H10	121.1
C17—C18—H18	120.9	C11—C10—H10	121.1
C16—C15—C14	120.3 (5)	H1W1—O1—H1W2	92 (6)

Au1—S1—C12—N5	−157.3 (4)	N5—C13—C18—C17	−175.9 (4)
Au1—S1—C12—N4	23.6 (4)	C14—C15—C16—C17	0.4 (8)
N4—C12—N5—C13	176.7 (4)	C16—C15—C14—C13	0.7 (8)
S1—C12—N5—C13	−2.5 (7)	C18—C13—C14—C15	−0.6 (7)
N5—C12—N4—N3	−12.1 (6)	N5—C13—C14—C15	175.0 (4)
S1—C12—N4—N3	167.0 (3)	C15—C16—C17—C18	−1.6 (8)
C6—N3—N4—C12	177.8 (4)	C13—C18—C17—C16	1.6 (8)
C12—N5—C13—C18	−60.4 (7)	C5—C4—C3—C2	−0.1 (8)
C12—N5—C13—C14	124.1 (5)	N1—C1—C2—C3	1.7 (8)
N4—N3—C6—C7	−7.3 (6)	C4—C3—C2—C1	−1.5 (8)
N4—N3—C6—C5	173.0 (3)	C8—C7—N2—C11	−1.7 (6)
N1—C5—C6—N3	31.7 (5)	C6—C7—N2—C11	−179.8 (4)
C4—C5—C6—N3	−143.8 (4)	C2—C1—N1—C5	−0.2 (7)
N1—C5—C6—C7	−148.1 (4)	C4—C5—N1—C1	−1.4 (7)
C4—C5—C6—C7	36.4 (6)	C6—C5—N1—C1	−177.2 (4)
N3—C6—C7—N2	18.1 (6)	N2—C7—C8—C9	2.8 (7)
C5—C6—C7—N2	−162.1 (4)	C6—C7—C8—C9	−179.2 (4)
N3—C6—C7—C8	−160.0 (4)	C10—C9—C8—C7	−0.7 (7)
C5—C6—C7—C8	19.7 (6)	C7—N2—C11—C10	−1.6 (7)
N1—C5—C4—C3	1.5 (7)	C8—C9—C10—C11	−2.3 (8)
C6—C5—C4—C3	176.9 (4)	N2—C11—C10—C9	3.6 (8)
C14—C13—C18—C17	−0.5 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···Cl2	0.86	2.46	3.246 (4)	153
N4—H4A···N2	0.86	1.97	2.629 (5)	133
N1—H1A···Cl2	0.80 (4)	2.26 (4)	2.989 (4)	150 (4)
O1—H1W1···Cl1ⁱ	0.80 (2)	2.70 (5)	3.353 (4)	140 (6)
O1—H1W2···Cl2ⁱⁱ	0.81 (2)	2.39 (2)	3.206 (4)	177 (6)
O2—H2W2···O1	0.82 (2)	2.06 (3)	2.855 (5)	163 (7)

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) x, −y+1, z−1/2.

Acknowledgements

This work was supported by CNPq, FAPDF, Finatec and, DDP-UnB.

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