4-(Diphenyl­amino)­benzaldehyde 4-phenyl­thio­semicarbazone

Mendoza-Meroño, R.; Menéndez-Taboada, L.; García-Granda, S.

doi:10.1107/S160053681203053X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2402-o2403

https://doi.org/10.1107/S160053681203053X

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4-(Diphenylamino)benzaldehyde 4-phenylthiosemicarbazone

Rafael Mendoza-Meroño,^a Laura Menéndez-Taboada ^a and Santiago García-Granda ^a ^*

^aDepartamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo – CINN, C/ Julián Clavería, 8, 33006 Oviedo, Spain
^*Correspondence e-mail: sgg@uniovi.es

(Received 13 June 2012; accepted 4 July 2012; online 10 July 2012)

The title molecule, C₂₆H₂₂N₄S, is composed of three main parts, viz. a triphenylamine group is connected to a phenyl ring by a thiosemicarbazone moiety. The C= N double bond has an E conformation. The crystal packing is dominated by strong hydrogen bonds through the thiosemicarbazone moiety, with pairs of N—H⋯S hydrogen bonds linking the molecules to form inversion dimers with an R₂²(8) ring motif. An intramolecular N—H⋯N hydrogen bond is also present, generating an S(5) ring motif. Although the structure contains four phenyl rings, π–π stacking interactions are not formed between them, probably due to the conformation adopted by the triphenylamine group. However, a weak π–π stacking interaction is observed between the phenyl ring and the delocalized thiosemicarbazone moiety.

Related literature

For related compounds and their biological activity, see: Gupta et al. (2007 ); Lee et al. (2010 ); Odenike et al. (2008 ). For hydrogen-bond motifs, see Bernstein et al. (1995 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₂₆H₂₂N₄S
M_r = 422.55
Monoclinic, P 2₁ /c
a = 13.6069 (3) Å
b = 15.2763 (3) Å
c = 11.2778 (2) Å
β = 104.094 (2)°
V = 2273.67 (8) Å³
Z = 4
Cu Kα radiation
μ = 1.41 mm⁻¹
T = 285 K
0.17 × 0.09 × 0.05 mm

Data collection

Oxford Xcalibur diffractometer with Onyx Nova detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.726, T_max = 1.000
26370 measured reflections
4623 independent reflections
3535 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.149
S = 1.07
4623 reflections
369 parameters
All H-atom parameters refined
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H28⋯N2	0.88 (3)	2.19 (3)	2.629 (2)	110 (2)
N3—H27⋯S1ⁱ	0.98 (2)	2.36 (3)	3.318 (2)	169 (2)
Symmetry code: (i) -x+2, -y, -z.

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO, CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SIR08 (Burla et al., 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), PLATON (Spek, 2009 ), PARST95 (Nardelli, 1995 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681203053X/lr2069sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681203053X/lr2069Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681203053X/lr2069Isup3.cml

checkCIF report

Comment top

Thiosemicarbazones are a broad class of biologically active organic compounds with antibacterial (Gupta et al.,2007) and antitumoral (Odenike et al., 2008) properties. According to recent studies, apolar groups in thiosemicarbazone compounds enhanced in some cases the biological activity (Lee et al., 2010). Following this work line, we have synthesized and crystallized a new thiosemicarbazone (Fig. 1), which is composed of three main parts: triphenylamine group (R1R2R3 lipophylic domain) conected to phenyl ring (R4 -liphophilic group) by thiosemicarbazone moiety (H-bonding domain an and electron-donor group) (Fig. 2).

Molecule is the trans isomer with respect to the C═N double bond. The values of distances N(2)–N(3) length (1.372 (2) Å) and the dihedral angle C(8)═N(2)—N(3)—C(7) (175.71 (2)°) are similar to those found in CSD (Allen, 2002) for thiosemicarbazone systems [selected 371 hits, distance mean N—N is 1.374 Å and dihedral angle mean is 178.21°]. The N atom in the triaphenylamine is sp2 and the three benzene rings [(R1(C21–C26), R2(C15–C20 ), R3(C9–C14)] are twisted with respect to one another, with followed dihedral angle between rings [R1R2 = 66.82 (7)° R2R3 = 61.05 (7)° R1R3 = 71.07 (7) °].

Molecular crystals are dominated by strong hydrogen bonds interactions through thiosemicarbazone moiety, forming a centrosymmetry synthon through N(3)—H(27)···S(1) hydrogen bond, this interactions form a R²₂(8) graph set (Bernstein et al., 1995). Additional intramolecular hydrogen N(4)—H(28)···N(2) helps to stabilize the molecular conformation (Fig. 3a and 3b).

Taking into account geometrical values calculated with Platon program is not feasible the existence π–π interactions involved triaphenylamine group. However, we observed a weak π–π stacking interaction between phenyl ring (R4) and the thiosemicarbazone deslocalized system (C═N—NH—C═S—NH) with distance to N3 (3.834 (3) Å) and dihedral angle (4.68 (2)°) shown in Fig. 4.

Related literature top

For related compounds and their biological activity, see: Gupta et al. (2007); Lee et al. (2010); Odenike et al. (2008). For hydrogen-bond motifs, see Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

A solution of 4-(diphenylamino)benzaldehyde (2.7333 g, 0.01 mol) and 4-phenylthiosemicarbazide (1.6723 g, 0.01 mol) in absolute ethanol (70 ml) was refluxed for 4 h in the presence of p-toluenesulfonic acid as catalyst, with continuous stirring. On cooling to room temperature the precipitate was filtered off, washed with copious cold ethanol and dried in air. Yellow single crystals of compound (I) were obtained after recrystallization from a solution in ethanol after 2 d.

Structure description top

For related compounds and their biological activity, see: Gupta et al. (2007); Lee et al. (2010); Odenike et al. (2008). For hydrogen-bond motifs, see Bernstein et al. (1995). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell refinement: CrysAlis RED (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SIR08 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2009), PARST95 (Nardelli, 1995) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the molecular structure of the title molecule. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The three main parts of the molecular structure, divided into apolar groups (R1, R2, R3, R4) and H-bonding domain.
	Fig. 3. (a) Intermolecular and intramolecular hydrogen bonds, atoms not involved in hydrogen bonding have been omitted for clarity. (b) Packing diagram viewed down the c axis.
	Fig. 4. Representation of the weak π–π stacking interaction between phenyl ring (R4) and the thiosemicarbazone deslocalized system.

4-(Diphenylamino)benzaldehyde 4-phenylthiosemicarbazone top

Crystal data top

C₂₆H₂₂N₄S	F(000) = 888
M_r = 422.55	D_x = 1.234 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 8693 reflections
a = 13.6069 (3) Å	θ = 2.9–75.3°
b = 15.2763 (3) Å	µ = 1.41 mm⁻¹
c = 11.2778 (2) Å	T = 285 K
β = 104.094 (2)°	Plate, dark yellow
V = 2273.67 (8) Å³	0.17 × 0.09 × 0.05 mm
Z = 4

Data collection top

Oxford Xcalibur diffractometer with Onyx Nova detector	4623 independent reflections
Radiation source: Nova (Cu) X-ray Source	3535 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.067
Detector resolution: 8.2640 pixels mm^-1	θ_max = 75.5°, θ_min = 3.4°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −17→18
T_min = 0.726, T_max = 1.000	l = −11→14
26370 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	All H-atom parameters refined
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0766P)² + 0.2813P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
4623 reflections	Δρ_max = 0.20 e Å⁻³
369 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0012 (3)

Crystal data top

C₂₆H₂₂N₄S	V = 2273.67 (8) Å³
M_r = 422.55	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.6069 (3) Å	µ = 1.41 mm⁻¹
b = 15.2763 (3) Å	T = 285 K
c = 11.2778 (2) Å	0.17 × 0.09 × 0.05 mm
β = 104.094 (2)°

Data collection top

Oxford Xcalibur diffractometer with Onyx Nova detector	4623 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3535 reflections with I > 2σ(I)
T_min = 0.726, T_max = 1.000	R_int = 0.067
26370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.149	All H-atom parameters refined
S = 1.07	Δρ_max = 0.20 e Å⁻³
4623 reflections	Δρ_min = −0.29 e Å⁻³
369 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.36 (release 02-08-2010 CrysAlis171 .NET) (compiled Aug 2 2010,13:00:58) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.94600 (4)	0.03619 (4)	0.15627 (5)	0.0689 (2)
N2	1.16947 (11)	0.16240 (10)	0.07520 (14)	0.0504 (4)
N3	1.08689 (11)	0.10941 (11)	0.06823 (15)	0.0522 (4)
N4	1.08031 (14)	0.15773 (11)	0.25732 (15)	0.0591 (4)
N1	1.56053 (12)	0.35772 (12)	−0.02307 (15)	0.0597 (4)
C8	1.21068 (14)	0.15830 (13)	−0.01584 (17)	0.0520 (4)
C14	1.33120 (14)	0.27924 (13)	0.06329 (17)	0.0527 (4)
C9	1.29891 (13)	0.21151 (12)	−0.01924 (16)	0.0490 (4)
C7	1.04293 (14)	0.10515 (12)	0.16271 (16)	0.0510 (4)
C12	1.47208 (13)	0.30889 (12)	−0.02447 (17)	0.0508 (4)
C13	1.41611 (15)	0.32736 (13)	0.06068 (18)	0.0534 (4)
C15	1.58656 (15)	0.38294 (13)	−0.13237 (19)	0.0554 (5)
C11	1.43998 (16)	0.24198 (14)	−0.10803 (19)	0.0611 (5)
C10	1.35392 (16)	0.19418 (14)	−0.10567 (18)	0.0585 (5)
C6	1.04960 (16)	0.15504 (13)	0.37043 (18)	0.0573 (5)
C21	1.62500 (14)	0.38028 (13)	0.09250 (18)	0.0559 (5)
C20	1.68751 (18)	0.39145 (16)	−0.1348 (3)	0.0717 (6)
C5	0.97506 (19)	0.20986 (19)	0.3890 (2)	0.0749 (6)
C16	1.5132 (2)	0.40044 (16)	−0.2379 (2)	0.0706 (6)
C22	1.66006 (18)	0.46481 (15)	0.1163 (2)	0.0680 (6)
C3	0.9924 (3)	0.1471 (2)	0.5872 (3)	0.0880 (8)
C1	1.0965 (2)	0.09751 (18)	0.4592 (2)	0.0832 (7)
C19	1.7123 (3)	0.4176 (2)	−0.2411 (4)	0.0966 (10)
C23	1.7227 (2)	0.4862 (2)	0.2285 (3)	0.0841 (7)
C17	1.5399 (3)	0.4254 (2)	−0.3436 (3)	0.0895 (8)
C18	1.6401 (3)	0.4340 (2)	−0.3447 (4)	0.1005 (10)
C26	1.6521 (2)	0.31817 (18)	0.1832 (2)	0.0818 (7)
C2	1.0684 (3)	0.0947 (2)	0.5689 (3)	0.1006 (10)
C4	0.9469 (2)	0.2052 (2)	0.5001 (3)	0.0877 (8)
C24	1.7493 (2)	0.4241 (2)	0.3180 (3)	0.0984 (9)
C25	1.7131 (3)	0.3415 (2)	0.2959 (3)	0.1070 (11)
H8	1.1832 (15)	0.1157 (13)	−0.0856 (18)	0.052 (5)*
H13	1.4370 (18)	0.3751 (16)	0.116 (2)	0.069 (6)*
H10	1.3326 (17)	0.1481 (15)	−0.163 (2)	0.064 (6)*
H27	1.0675 (17)	0.0693 (16)	−0.001 (2)	0.069 (6)*
H14	1.2919 (17)	0.2952 (15)	0.123 (2)	0.067 (6)*
H28	1.131 (2)	0.1912 (18)	0.249 (2)	0.076 (7)*
H11	1.4793 (19)	0.2228 (16)	−0.164 (2)	0.076 (7)*
H22	1.639 (2)	0.509 (2)	0.055 (3)	0.088 (8)*
H5	0.945 (2)	0.249 (2)	0.327 (3)	0.094 (9)*
H20	1.737 (2)	0.3775 (17)	−0.064 (2)	0.076 (7)*
H16	1.446 (2)	0.3934 (18)	−0.237 (2)	0.085 (8)*
H1	1.157 (3)	0.057 (2)	0.454 (3)	0.116 (10)*
H26	1.631 (2)	0.259 (2)	0.162 (3)	0.099 (9)*
H23	1.743 (2)	0.545 (2)	0.249 (3)	0.100 (9)*
H4	0.893 (3)	0.242 (3)	0.507 (3)	0.127 (12)*
H3	0.970 (3)	0.139 (2)	0.657 (3)	0.110 (10)*
H17	1.486 (2)	0.4377 (19)	−0.416 (3)	0.095 (9)*
H25	1.729 (2)	0.295 (2)	0.356 (3)	0.114 (10)*
H18	1.650 (3)	0.453 (2)	−0.425 (3)	0.123 (11)*
H24	1.793 (3)	0.435 (2)	0.402 (3)	0.117 (10)*
H2	1.094 (3)	0.047 (3)	0.627 (4)	0.156 (15)*
H19	1.776 (3)	0.418 (2)	−0.242 (3)	0.115 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0620 (3)	0.0902 (4)	0.0645 (3)	−0.0305 (3)	0.0346 (3)	−0.0166 (2)
N2	0.0435 (8)	0.0544 (9)	0.0571 (9)	−0.0051 (6)	0.0197 (7)	0.0061 (6)
N3	0.0470 (8)	0.0611 (9)	0.0538 (9)	−0.0103 (6)	0.0227 (7)	0.0001 (7)
N4	0.0621 (10)	0.0633 (10)	0.0595 (10)	−0.0172 (8)	0.0291 (8)	−0.0071 (7)
N1	0.0513 (9)	0.0729 (11)	0.0580 (10)	−0.0204 (7)	0.0194 (7)	0.0007 (7)
C8	0.0469 (10)	0.0628 (11)	0.0496 (10)	−0.0083 (8)	0.0181 (8)	0.0027 (8)
C14	0.0495 (10)	0.0655 (11)	0.0478 (10)	−0.0069 (8)	0.0208 (8)	−0.0009 (8)
C9	0.0435 (9)	0.0603 (10)	0.0457 (9)	−0.0073 (7)	0.0158 (7)	0.0046 (7)
C7	0.0456 (10)	0.0591 (11)	0.0518 (10)	−0.0002 (7)	0.0187 (8)	0.0028 (7)
C12	0.0446 (9)	0.0591 (10)	0.0511 (10)	−0.0118 (7)	0.0164 (8)	0.0016 (7)
C13	0.0527 (11)	0.0601 (11)	0.0504 (10)	−0.0097 (8)	0.0180 (8)	−0.0041 (8)
C15	0.0517 (10)	0.0556 (10)	0.0659 (12)	−0.0092 (8)	0.0274 (9)	0.0009 (8)
C11	0.0612 (12)	0.0715 (13)	0.0593 (12)	−0.0200 (9)	0.0315 (10)	−0.0112 (9)
C10	0.0605 (12)	0.0674 (12)	0.0533 (11)	−0.0206 (9)	0.0244 (9)	−0.0099 (9)
C6	0.0601 (11)	0.0618 (11)	0.0555 (11)	−0.0156 (8)	0.0248 (9)	−0.0101 (8)
C21	0.0446 (10)	0.0610 (11)	0.0626 (11)	−0.0097 (8)	0.0141 (8)	0.0007 (8)
C20	0.0556 (13)	0.0799 (15)	0.0902 (17)	−0.0125 (10)	0.0380 (13)	−0.0069 (12)
C5	0.0682 (14)	0.0901 (17)	0.0703 (15)	0.0024 (12)	0.0241 (12)	−0.0077 (12)
C16	0.0648 (14)	0.0816 (15)	0.0711 (14)	−0.0047 (11)	0.0274 (11)	0.0119 (11)
C22	0.0681 (14)	0.0619 (13)	0.0732 (14)	−0.0122 (10)	0.0160 (11)	−0.0012 (10)
C3	0.109 (2)	0.100 (2)	0.0674 (16)	−0.0263 (16)	0.0463 (16)	−0.0164 (14)
C1	0.109 (2)	0.0796 (16)	0.0722 (15)	0.0111 (14)	0.0446 (14)	0.0038 (11)
C19	0.088 (2)	0.100 (2)	0.125 (3)	−0.0330 (16)	0.071 (2)	−0.0205 (18)
C23	0.0795 (17)	0.0834 (18)	0.0887 (18)	−0.0274 (13)	0.0189 (13)	−0.0199 (14)
C17	0.111 (2)	0.0909 (19)	0.0725 (17)	−0.0087 (15)	0.0344 (16)	0.0171 (13)
C18	0.133 (3)	0.097 (2)	0.094 (2)	−0.0332 (18)	0.070 (2)	0.0010 (16)
C26	0.0736 (15)	0.0710 (15)	0.0876 (17)	−0.0168 (12)	−0.0056 (12)	0.0146 (12)
C2	0.144 (3)	0.097 (2)	0.0718 (17)	0.0073 (19)	0.0487 (18)	0.0130 (14)
C4	0.0747 (17)	0.111 (2)	0.0872 (19)	−0.0094 (15)	0.0392 (15)	−0.0299 (16)
C24	0.0808 (18)	0.124 (3)	0.0789 (18)	−0.0342 (17)	−0.0022 (14)	−0.0033 (16)
C25	0.097 (2)	0.111 (2)	0.091 (2)	−0.0268 (17)	−0.0221 (16)	0.0267 (17)

Geometric parameters (Å, º) top

S1—C7	1.6757 (19)	C21—C26	1.378 (3)
N2—C8	1.286 (2)	C21—C22	1.380 (3)
N2—N3	1.372 (2)	C20—C19	1.380 (4)
N3—C7	1.345 (2)	C20—H20	0.94 (3)
N3—N2	1.372 (2)	C5—C4	1.399 (4)
N3—H27	0.98 (2)	C5—H5	0.94 (3)
N4—C7	1.333 (2)	C16—C17	1.382 (3)
N4—C6	1.436 (2)	C16—H16	0.92 (3)
N4—H28	0.88 (3)	C22—C23	1.381 (4)
N1—C12	1.413 (2)	C22—H22	0.96 (3)
N1—C15	1.416 (2)	C3—C4	1.357 (5)
N1—C21	1.425 (3)	C3—C2	1.362 (5)
C8—N2	1.286 (2)	C3—H3	0.92 (4)
C8—C9	1.458 (2)	C1—C2	1.381 (4)
C8—H8	1.02 (2)	C1—H1	1.04 (4)
C14—C13	1.376 (3)	C19—C18	1.354 (5)
C14—C9	1.390 (3)	C19—H19	0.87 (4)
C14—H14	0.98 (2)	C23—C24	1.368 (4)
C9—C10	1.391 (3)	C23—H23	0.95 (3)
C12—C11	1.387 (3)	C17—C18	1.373 (5)
C12—C13	1.392 (3)	C17—H17	0.98 (3)
C13—H13	0.96 (2)	C18—H18	0.99 (4)
C15—C16	1.381 (3)	C26—C25	1.385 (4)
C15—C20	1.387 (3)	C26—H26	0.97 (3)
C11—C10	1.386 (3)	C2—H2	0.99 (5)
C11—H11	0.97 (3)	C4—H4	0.94 (4)
C10—H10	0.95 (2)	C24—C25	1.356 (5)
C6—C1	1.368 (4)	C24—H24	1.01 (3)
C6—C5	1.370 (3)	C25—H25	0.97 (4)

C8—N2—N3	115.86 (16)	C19—C20—H20	121.7 (17)
C7—N3—N2	119.97 (16)	C15—C20—H20	118.5 (17)
C7—N3—H27	121.1 (14)	C6—C5—C4	118.7 (3)
N2—N3—H27	118.4 (14)	C6—C5—H5	118.7 (18)
C7—N4—C6	123.82 (16)	C4—C5—H5	122.6 (18)
C7—N4—H28	114.7 (17)	C15—C16—C17	120.7 (3)
C6—N4—H28	121.1 (17)	C15—C16—H16	118.7 (17)
C12—N1—C15	121.79 (16)	C17—C16—H16	120.6 (17)
C12—N1—C21	118.09 (15)	C21—C22—C23	120.4 (2)
C15—N1—C21	120.11 (15)	C21—C22—H22	118.8 (17)
N2—C8—C9	121.06 (17)	C23—C22—H22	120.8 (17)
N2—C8—H8	119.9 (11)	C4—C3—C2	120.3 (3)
C9—C8—H8	119.0 (11)	C4—C3—H3	121 (2)
C13—C14—C9	120.91 (18)	C2—C3—H3	118 (2)
C13—C14—H14	118.7 (13)	C6—C1—C2	119.6 (3)
C9—C14—H14	120.3 (13)	C6—C1—H1	125.0 (19)
C14—C9—C10	118.33 (16)	C2—C1—H1	115.3 (19)
C14—C9—C8	121.71 (17)	C18—C19—C20	121.6 (3)
C10—C9—C8	119.95 (17)	C18—C19—H19	120 (2)
N4—C7—N3	116.64 (16)	C20—C19—H19	118 (2)
N4—C7—S1	123.79 (14)	C24—C23—C22	120.4 (3)
N3—C7—S1	119.57 (14)	C24—C23—H23	118.0 (18)
C11—C12—C13	118.91 (16)	C22—C23—H23	121.4 (18)
C11—C12—N1	121.55 (17)	C18—C17—C16	120.3 (3)
C13—C12—N1	119.53 (17)	C18—C17—H17	121.6 (18)
C14—C13—C12	120.66 (18)	C16—C17—H17	118.1 (18)
C14—C13—H13	120.6 (14)	C19—C18—C17	119.2 (3)
C12—C13—H13	118.7 (14)	C19—C18—H18	128 (2)
C16—C15—C20	118.5 (2)	C17—C18—H18	113 (2)
C16—C15—N1	121.41 (18)	C21—C26—C25	119.8 (3)
C20—C15—N1	120.1 (2)	C21—C26—H26	117.1 (18)
C10—C11—C12	120.20 (19)	C25—C26—H26	122.9 (18)
C10—C11—H11	117.2 (14)	C3—C2—C1	120.2 (3)
C12—C11—H11	122.3 (14)	C3—C2—H2	120 (3)
C11—C10—C9	120.97 (18)	C1—C2—H2	119 (3)
C11—C10—H10	119.6 (14)	C3—C4—C5	120.4 (3)
C9—C10—H10	119.4 (14)	C3—C4—H4	124 (2)
C1—C6—C5	120.8 (2)	C5—C4—H4	116 (2)
C1—C6—N4	118.9 (2)	C25—C24—C23	119.4 (3)
C5—C6—N4	120.3 (2)	C25—C24—H24	116 (2)
C26—C21—C22	118.8 (2)	C23—C24—H24	125 (2)
C26—C21—N1	120.42 (19)	C24—C25—C26	121.2 (3)
C22—C21—N1	120.73 (19)	C24—C25—H25	123 (2)
C19—C20—C15	119.8 (3)	C26—C25—H25	116 (2)

C8—N2—N3—C7	175.71 (17)	C7—N4—C6—C1	85.9 (3)
N3—N2—C8—C9	179.95 (16)	C7—N4—C6—C5	−94.6 (3)
C13—C14—C9—C10	−0.8 (3)	C12—N1—C21—C26	46.8 (3)
C13—C14—C9—C8	178.35 (18)	C15—N1—C21—C26	−132.2 (2)
N2—C8—C9—C14	−11.5 (3)	C12—N1—C21—C22	−132.1 (2)
N2—C8—C9—C14	−11.5 (3)	C15—N1—C21—C22	48.9 (3)
N2—C8—C9—C10	167.58 (19)	C16—C15—C20—C19	0.5 (4)
N2—C8—C9—C10	167.58 (19)	N1—C15—C20—C19	−178.8 (2)
C6—N4—C7—N3	−173.22 (18)	C1—C6—C5—C4	−0.7 (4)
C6—N4—C7—S1	7.0 (3)	N4—C6—C5—C4	179.8 (2)
N2—N3—C7—N4	3.5 (3)	C20—C15—C16—C17	0.3 (4)
N2—N3—C7—N4	3.5 (3)	N1—C15—C16—C17	179.7 (2)
N2—N3—C7—S1	−176.74 (13)	C26—C21—C22—C23	1.1 (4)
N2—N3—C7—S1	−176.74 (13)	N1—C21—C22—C23	−179.9 (2)
C15—N1—C12—C11	39.0 (3)	C5—C6—C1—C2	−0.1 (4)
C21—N1—C12—C11	−139.9 (2)	N4—C6—C1—C2	179.4 (3)
C15—N1—C12—C13	−141.7 (2)	C15—C20—C19—C18	−1.1 (4)
C21—N1—C12—C13	39.3 (3)	C21—C22—C23—C24	−1.0 (4)
C9—C14—C13—C12	−0.4 (3)	C15—C16—C17—C18	−0.7 (4)
C11—C12—C13—C14	1.0 (3)	C20—C19—C18—C17	0.8 (5)
N1—C12—C13—C14	−178.29 (18)	C16—C17—C18—C19	0.1 (5)
C12—N1—C15—C16	31.7 (3)	C22—C21—C26—C25	0.3 (4)
C21—N1—C15—C16	−149.4 (2)	N1—C21—C26—C25	−178.6 (3)
C12—N1—C15—C20	−149.0 (2)	C4—C3—C2—C1	−3.0 (5)
C21—N1—C15—C20	30.0 (3)	C6—C1—C2—C3	1.9 (5)
C13—C12—C11—C10	−0.4 (3)	C2—C3—C4—C5	2.2 (5)
N1—C12—C11—C10	178.82 (19)	C6—C5—C4—C3	−0.3 (4)
C12—C11—C10—C9	−0.7 (3)	C22—C23—C24—C25	−0.5 (5)
C14—C9—C10—C11	1.3 (3)	C23—C24—C25—C26	2.0 (6)
C8—C9—C10—C11	−177.8 (2)	C21—C26—C25—C24	−2.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H28···N2	0.88 (3)	2.19 (3)	2.629 (2)	110 (2)
N3—H27···S1ⁱ	0.98 (2)	2.36 (3)	3.318 (2)	169 (2)

Symmetry code: (i) −x+2, −y, −z.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₂N₄S
M_r	422.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	285
a, b, c (Å)	13.6069 (3), 15.2763 (3), 11.2778 (2)
β (°)	104.094 (2)
V (Å³)	2273.67 (8)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.41
Crystal size (mm)	0.17 × 0.09 × 0.05

Data collection
Diffractometer	Oxford Xcalibur diffractometer with Onyx Nova detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.726, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	26370, 4623, 3535
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.149, 1.07
No. of reflections	4623
No. of parameters	369
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.29

Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SIR08 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), WinGX (Farrugia, 1999), PLATON (Spek, 2009), PARST95 (Nardelli, 1995) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H28···N2	0.88 (3)	2.19 (3)	2.629 (2)	110 (2)
N3—H27···S1ⁱ	0.98 (2)	2.36 (3)	3.318 (2)	169 (2)

Symmetry code: (i) −x+2, −y, −z.

Acknowledgements

Financial support of this work was given by the Agencia Española de Cooperación Internacional y Desarrollo (AECID). The authors also acknowledge FEDER funding and funds from the Spanish MINECO (grant Nos. MAT2006-01997, MAT2010-15094) and Factoría de Cristalización Consolider Ingenio-2010.

References

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