Tris{2-[(3-thien­yl)methyl­idene­amino]­eth­yl}amine

Işıklan, M.; Pramanik, A.; Fronczek, F.R.; Hossain, M.A.

doi:10.1107/S1600536810039206

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2739-o2740

https://doi.org/10.1107/S1600536810039206

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Tris{2-[(3-thienyl)methylideneamino]ethyl}amine

Muhammet Işıklan,^a Avijit Pramanik,^a Frank R. Fronczek ^b and Md. Alamgir Hossain ^a ^*

^aDepartment of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: alamgir@chem.jsums.edu

(Received 21 September 2010; accepted 30 September 2010; online 9 October 2010)

The title compound, C₂₁H₂₄N₄S₃, is a tripodal Schiff base that was obtained from the reaction of tris(2-aminoethyl)amine (tren) and thiophene-3-carbaldehyde. The compound forms a cavity with approximate C3 symmetry. One of the thiophene units is disordered in a 0.764 (2):0.236 (2) ratio. In the crystal, the three thiophene ligands are involved in intramolecular C—H⋯π interactions and the molecules are connected by C—H⋯N interactions, forming hydrogen-bonded chains.

Related literature

For general background to tren-based imines, see: Ballester et al. (1999 ); Bianchi et al. (1997 ); Fan et al. (2002 ); Kang et al. (2005 ); McLachlan et al. (1996 ); Kaur et al. (2009 ); Salehzadeh et al. (2006 ). For related structures, see: Alyea et al. (1989 ); Bazzicalupi et al. (2009 ); Burgess et al. (1991 ); Hossain et al. (2004 ); Mazik et al. (2001 ).

Experimental

Crystal data

C₂₁H₂₄N₄S₃
M_r = 428.62
Monoclinic, C 2/c
a = 28.694 (3) Å
b = 9.2529 (10) Å
c = 16.427 (2) Å
β = 96.150 (5)°
V = 4336.3 (8) Å³
Z = 8
Cu Kα radiation
μ = 3.23 mm⁻¹
T = 90 K
0.30 × 0.28 × 0.22 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.444, T_max = 0.537
13414 measured reflections
3884 independent reflections
3571 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.04
3884 reflections
261 parameters
28 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg3 are the centroids of the S1,C4–C7, S2,C11–C14 and S3,C18–C21 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20⋯N2ⁱ	0.95	2.55	3.354 (7)	143
C21—H21⋯Cg1	0.95	2.61	3.437 (2)	146
C5—H5⋯Cg2	0.95	2.65	3.452 (2)	142
C12—H12⋯Cg3	0.95	2.61	3.432 (3)	145
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810039206/zq2062sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039206/zq2062Isup2.hkl

checkCIF report

Comment top

Tren-based imines synthesized from the reaction of tris(2-aminoethyl)amine (tren) and an aldehyde are versatile ligands for transitional metals (Salehzadeh et al., 2006; McLachlan et al., 1996). Because of the simplicity, such imines are often converted directly into the corresponding amines, which are potential to bind a wide range of cations and anions (Bianchi et al., 1997; Kang et al., 2005). The connecting arms play an important role in achieving shape and size selectivity of a particular guest. Compared with a monopodal or dipodal receptor, a tripodal receptor often binds a guest species strongly due to the enhanced chelating effect and controlled cavity (Ballester et al., 1999; Fan et al., 2002). Therefore, an increasing attention is being paid to the development of new tripodal receptors (Kaur et al., 2009). During the course of our study, we synthesized a new Schiff base from the reaction of tris(2-aminoethyl)amine (tren) and 3-thiophene aldehyde, and obtained crystals. Herein, we report the structure of tris[(4–2-thienyl)-3-aza-3-butenyl]amine (I), which was prepared by condensation of 3-thiophene aldehyde with tris(2-aminoethyl)amine. A related Schiff base, tris[4-(2-thienyl)-3-aza-3-butenyl]amine was synthesized and analyzed previously by crystallography (Alyea et al., 1989). Although our compound is isomerically different, it shows almost similar cell parameters observed in the tris[(4–2-thienyl)-3-aza-3-butenyl]amine.

The structural analysis of the title compound shows that it forms a cavity with three arms (Figure 1). The compound contains an approximate C₃ symmetry axis passing through the tertiary N atom. One of the thiophene moieties is disordered by twofold rotation about C17—C18. All three aromatic units are involved in CH···π interactions with C···centroid distances of 3.452 (2), 3.432 (2) and 3.437 (3) Å (Table 1 and Figure 2). A related tren based receptor with three phenyl groups was reported earlier, showing a relatively flat structure where no CH···π interaction was observed (Hossain et al., 2004). The presence of sulfur in the aromatic rings perhaps facilitates CH···π interactions by increasing the electron density to aromatic rings. In the crystal structure, neighboring units are connected by intermolecular C20—H20···N2 interactions (C···N = 3.354 (7) Å), forming hydrogen-bonded chains (Figure 3). Such distances are comparable with those observed in the crystal structure of an α,β-unsaturated ketone (CH···N interactions with C···N = 3.41 to 3.71 Å) with a terminal pyridine subunit (Mazik et al., 2001).

Related literature top

For general background to tren-based imines, see: Ballester et al. (1999); Bianchi et al. (1997); Fan et al. (2002); Kang et al. (2005); McLachlan et al. (1996); Kaur et al. (2009); Salehzadeh et al. (2006). For related structures, see: Alyea et al. (1989); Bazzicalupi et al. (2009); Burgess et al. (1991); Hossain et al. (2004); Mazik et al. (2001).

Experimental top

To a solution of 3-thiophene aldehyde (2.30 g, 20.5 mmol) in diethylether (50 ml) was added tris(2-aminoethyl)amine (1.00 g, 6.84 mmol) in ethanol (50 ml). The mixture was stirred overnight at room temperature, and the solvent was evaporated. The product was suspended in water (50 ml) and an extraction was made with CH₂Cl₂(3 x 50 ml). The organic layers were combined and dried by anhydrous MgSO₄ (1.5 g). The yellowish solution was collected by filtration, and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography on a neutral-alumina column (2% CH₃OH in CH₂Cl₂) to give the imine as a white powder. Yield = 3.98 g (67%). M.P. 80 °C. ¹H NMR (500 MHz, CDCl₃, TMS): δ 2.85 (t, 6H, NCH₂),3.59 ((t, 6H, NCH₂CH₂), δ 8.011 (s, 3H, NCH), 7.11 (m, 3H, ArH), 7.28 (m, 3H, ArH), 7.45 (m, 3H, ArH). The compound was redissolved in ethanol (1 ml) and crystals suitable for X-ray analysis were grown from slow evaporation of the solvent at room temperature.

Structure description top

For general background to tren-based imines, see: Ballester et al. (1999); Bianchi et al. (1997); Fan et al. (2002); Kang et al. (2005); McLachlan et al. (1996); Kaur et al. (2009); Salehzadeh et al. (2006). For related structures, see: Alyea et al. (1989); Bazzicalupi et al. (2009); Burgess et al. (1991); Hossain et al. (2004); Mazik et al. (2001).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with displacement ellipsoids drawn at the 50% probability level and H atoms with arbitrary radius.
	Fig. 2. CH···π interactions (dotted lines) in the crystal structure of the title compound.
	Fig. 3. Hydrogen bonded chain in the lattice of the title compound viewed down a axis.

Tris{2-[(3-thienyl)methylideneamino]ethyl}amine top

Crystal data top

C₂₁H₂₄N₄S₃	F(000) = 1808
M_r = 428.62	D_x = 1.313 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 7541 reflections
a = 28.694 (3) Å	θ = 5.0–68.3°
b = 9.2529 (10) Å	µ = 3.23 mm⁻¹
c = 16.427 (2) Å	T = 90 K
β = 96.150 (5)°	Fragment, colourless
V = 4336.3 (8) Å³	0.30 × 0.28 × 0.22 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	3884 independent reflections
Radiation source: fine-focus sealed tube	3571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 68.3°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −34→33
T_min = 0.444, T_max = 0.537	k = −11→10
13414 measured reflections	l = −19→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0403P)² + 7.6616P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3884 reflections	Δρ_max = 0.41 e Å⁻³
261 parameters	Δρ_min = −0.44 e Å⁻³
28 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: 0.00060 (5)

Crystal data top

C₂₁H₂₄N₄S₃	V = 4336.3 (8) Å³
M_r = 428.62	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 28.694 (3) Å	µ = 3.23 mm⁻¹
b = 9.2529 (10) Å	T = 90 K
c = 16.427 (2) Å	0.30 × 0.28 × 0.22 mm
β = 96.150 (5)°

Data collection top

Bruker APEXII CCD diffractometer	3884 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3571 reflections with I > 2σ(I)
T_min = 0.444, T_max = 0.537	R_int = 0.031
13414 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	28 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
3884 reflections	Δρ_min = −0.44 e Å⁻³
261 parameters

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.

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)
S2	0.292078 (17)	0.23863 (5)	0.25479 (3)	0.02483 (15)
N1	0.42630 (5)	0.04730 (16)	0.62236 (9)	0.0153 (3)
N2	0.34778 (5)	0.26041 (17)	0.65167 (9)	0.0174 (3)
N3	0.37162 (5)	−0.07966 (17)	0.46740 (9)	0.0188 (3)
N4	0.47792 (5)	0.26700 (17)	0.52115 (9)	0.0179 (3)
C1	0.40953 (6)	0.0885 (2)	0.70049 (11)	0.0180 (4)
H1A	0.4269	0.1750	0.7224	0.022*
H1B	0.4162	0.0090	0.7404	0.022*
C2	0.35725 (6)	0.1209 (2)	0.69159 (11)	0.0198 (4)
H2A	0.3402	0.0440	0.6588	0.024*
H2B	0.3458	0.1222	0.7463	0.024*
C3	0.32751 (6)	0.2597 (2)	0.57929 (11)	0.0155 (4)
H3	0.3206	0.1700	0.5525	0.019*
S1	0.276626 (16)	0.57210 (5)	0.42956 (3)	0.02137 (14)
C4	0.31449 (6)	0.3943 (2)	0.53614 (11)	0.0148 (4)
C5	0.28869 (6)	0.3986 (2)	0.46128 (11)	0.0175 (4)
H5	0.2786	0.3153	0.4305	0.021*
C6	0.30664 (6)	0.6422 (2)	0.51705 (11)	0.0194 (4)
H6	0.3100	0.7425	0.5283	0.023*
C7	0.32484 (6)	0.5360 (2)	0.56788 (11)	0.0166 (4)
H7	0.3426	0.5539	0.6191	0.020*
C8	0.41542 (6)	−0.1043 (2)	0.60370 (12)	0.0191 (4)
H8A	0.3847	−0.1282	0.6224	0.023*
H8B	0.4394	−0.1662	0.6343	0.023*
C9	0.41392 (6)	−0.1375 (2)	0.51287 (12)	0.0212 (4)
H9A	0.4418	−0.0951	0.4913	0.025*
H9B	0.4150	−0.2435	0.5049	0.025*
C10	0.37694 (6)	0.0228 (2)	0.41808 (11)	0.0171 (4)
H10	0.4075	0.0603	0.4150	0.021*
C11	0.33762 (6)	0.0855 (2)	0.36569 (11)	0.0165 (4)
C12	0.34322 (6)	0.1941 (2)	0.31106 (11)	0.0195 (4)
H12	0.3724	0.2395	0.3052	0.023*
C13	0.26031 (6)	0.11281 (19)	0.30122 (11)	0.0156 (4)
H13	0.2277	0.0957	0.2886	0.019*
C14	0.29004 (6)	0.0380 (2)	0.36131 (11)	0.0174 (4)
H14	0.2795	−0.0358	0.3951	0.021*
C15	0.47680 (6)	0.0740 (2)	0.62364 (11)	0.0172 (4)
H15A	0.4893	0.0128	0.5816	0.021*
H15B	0.4926	0.0450	0.6777	0.021*
C16	0.48832 (6)	0.2312 (2)	0.60779 (11)	0.0194 (4)
H16A	0.4698	0.2945	0.6407	0.023*
H16B	0.5220	0.2490	0.6251	0.023*
C17	0.44833 (6)	0.3661 (2)	0.50276 (11)	0.0179 (4)
H17	0.4334	0.4100	0.5453	0.021*
S3	0.43695 (3)	0.45750 (11)	0.26243 (4)	0.0223 (3)	0.764 (2)
C20	0.3950 (3)	0.5473 (10)	0.3129 (5)	0.0236 (13)	0.764 (2)
H20	0.3724	0.6120	0.2871	0.028*	0.764 (2)
S3A	0.3904 (3)	0.5578 (10)	0.3071 (4)	0.0223 (3)	0.236 (2)
C20A	0.4402 (5)	0.4535 (15)	0.2850 (7)	0.0236 (13)	0.236 (2)
H20A	0.4517	0.4506	0.2329	0.028*	0.236 (2)
C18	0.43616 (6)	0.4160 (2)	0.41825 (11)	0.0178 (4)
C19	0.45957 (6)	0.3789 (2)	0.35179 (11)	0.0215 (4)
H19	0.4858	0.3156	0.3557	0.026*	0.764 (2)
H19A	0.4849	0.3126	0.3526	0.026*	0.236 (2)
C21	0.39888 (6)	0.5126 (2)	0.39551 (13)	0.0230 (4)
H21	0.3787	0.5496	0.4327	0.028*	0.764 (2)
H21A	0.3797	0.5479	0.4348	0.028*	0.236 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2	0.0283 (3)	0.0242 (3)	0.0219 (3)	−0.00055 (19)	0.00263 (19)	0.00012 (19)
N1	0.0126 (7)	0.0167 (8)	0.0168 (7)	0.0004 (6)	0.0022 (6)	0.0013 (6)
N2	0.0138 (7)	0.0177 (8)	0.0212 (8)	0.0023 (6)	0.0038 (6)	0.0021 (6)
N3	0.0157 (8)	0.0177 (8)	0.0229 (8)	−0.0007 (6)	0.0014 (6)	−0.0038 (7)
N4	0.0161 (7)	0.0199 (8)	0.0182 (8)	−0.0030 (6)	0.0036 (6)	0.0007 (6)
C1	0.0186 (9)	0.0199 (9)	0.0157 (8)	0.0021 (7)	0.0029 (7)	0.0037 (7)
C2	0.0183 (9)	0.0195 (10)	0.0225 (9)	0.0025 (7)	0.0061 (7)	0.0052 (8)
C3	0.0115 (8)	0.0150 (9)	0.0211 (9)	0.0000 (7)	0.0067 (7)	−0.0020 (7)
S1	0.0178 (2)	0.0234 (3)	0.0225 (2)	0.00528 (18)	0.00034 (17)	0.00436 (18)
C4	0.0096 (8)	0.0174 (9)	0.0181 (8)	0.0010 (7)	0.0054 (6)	−0.0002 (7)
C5	0.0142 (8)	0.0198 (9)	0.0190 (9)	0.0008 (7)	0.0038 (7)	−0.0018 (7)
C6	0.0167 (9)	0.0144 (9)	0.0277 (10)	0.0004 (7)	0.0057 (7)	−0.0012 (8)
C7	0.0131 (8)	0.0175 (9)	0.0194 (9)	0.0006 (7)	0.0032 (7)	−0.0019 (7)
C8	0.0161 (9)	0.0159 (9)	0.0252 (9)	0.0014 (7)	0.0011 (7)	0.0035 (8)
C9	0.0162 (9)	0.0176 (10)	0.0293 (10)	0.0020 (7)	0.0004 (7)	−0.0048 (8)
C10	0.0129 (8)	0.0188 (10)	0.0205 (9)	−0.0033 (7)	0.0057 (7)	−0.0082 (8)
C11	0.0161 (9)	0.0166 (9)	0.0174 (9)	−0.0016 (7)	0.0050 (7)	−0.0070 (7)
C12	0.0190 (9)	0.0182 (9)	0.0223 (9)	−0.0039 (7)	0.0067 (7)	−0.0048 (8)
C13	0.0141 (8)	0.0148 (9)	0.0198 (9)	−0.0054 (7)	0.0109 (7)	−0.0080 (7)
C14	0.0166 (9)	0.0184 (9)	0.0179 (9)	−0.0018 (7)	0.0045 (7)	−0.0038 (7)
C15	0.0124 (9)	0.0228 (10)	0.0160 (8)	0.0011 (7)	−0.0001 (7)	0.0014 (7)
C16	0.0170 (9)	0.0250 (10)	0.0163 (8)	−0.0042 (7)	0.0018 (7)	−0.0009 (7)
C17	0.0143 (8)	0.0188 (9)	0.0212 (9)	−0.0045 (7)	0.0051 (7)	−0.0053 (7)
S3	0.0200 (4)	0.0282 (4)	0.0190 (4)	−0.0019 (3)	0.0040 (3)	0.0048 (3)
C20	0.023 (3)	0.017 (2)	0.028 (2)	−0.0090 (16)	−0.0093 (16)	0.0049 (15)
S3A	0.0200 (4)	0.0282 (4)	0.0190 (4)	−0.0019 (3)	0.0040 (3)	0.0048 (3)
C20A	0.023 (3)	0.017 (2)	0.028 (2)	−0.0090 (16)	−0.0093 (16)	0.0049 (15)
C18	0.0131 (8)	0.0159 (9)	0.0246 (9)	−0.0044 (7)	0.0026 (7)	−0.0002 (7)
C19	0.0172 (9)	0.0246 (10)	0.0232 (9)	−0.0010 (8)	0.0052 (7)	0.0027 (8)
C21	0.0149 (9)	0.0166 (10)	0.0374 (11)	−0.0029 (7)	0.0028 (8)	−0.0044 (8)

Geometric parameters (Å, º) top

S2—C12	1.6990 (19)	C9—H9B	0.9900
S2—C13	1.7079 (18)	C10—C11	1.464 (3)
N1—C8	1.462 (2)	C10—H10	0.9500
N1—C15	1.468 (2)	C11—C12	1.368 (3)
N1—C1	1.468 (2)	C11—C14	1.429 (3)
N2—C3	1.266 (2)	C12—H12	0.9500
N2—C2	1.460 (2)	C13—C14	1.414 (3)
N3—C10	1.267 (2)	C13—H13	0.9500
N3—C9	1.457 (2)	C14—H14	0.9500
N4—C17	1.264 (2)	C15—C16	1.521 (3)
N4—C16	1.461 (2)	C15—H15A	0.9900
C1—C2	1.522 (2)	C15—H15B	0.9900
C1—H1A	0.9900	C16—H16A	0.9900
C1—H1B	0.9900	C16—H16B	0.9900
C2—H2A	0.9900	C17—C18	1.469 (3)
C2—H2B	0.9900	C17—H17	0.9500
C3—C4	1.461 (2)	S3—C19	1.703 (2)
C3—H3	0.9500	S3—C20	1.743 (7)
S1—C5	1.7113 (19)	C20—C21	1.387 (8)
S1—C6	1.7211 (19)	C20—H20	0.9500
C4—C5	1.367 (3)	S3A—C21	1.506 (7)
C4—C7	1.431 (3)	S3A—C20A	1.793 (13)
C5—H5	0.9500	C20A—C19	1.363 (11)
C6—C7	1.357 (3)	C20A—H20A	0.9500
C6—H6	0.9500	C18—C19	1.385 (3)
C7—H7	0.9500	C18—C21	1.413 (3)
C8—C9	1.520 (3)	C19—H19	0.9500
C8—H8A	0.9900	C19—H19A	0.9500
C8—H8B	0.9900	C21—H21	0.9500
C9—H9A	0.9900	C21—H21A	0.9500

C12—S2—C13	93.62 (9)	C14—C11—C10	125.46 (17)
C8—N1—C15	110.65 (14)	C11—C12—S2	112.30 (14)
C8—N1—C1	110.47 (14)	C11—C12—H12	123.9
C15—N1—C1	111.05 (14)	S2—C12—H12	123.9
C3—N2—C2	117.52 (16)	C14—C13—S2	109.53 (13)
C10—N3—C9	116.86 (16)	C14—C13—H13	125.2
C17—N4—C16	117.33 (16)	S2—C13—H13	125.2
N1—C1—C2	112.29 (14)	C13—C14—C11	112.72 (16)
N1—C1—H1A	109.1	C13—C14—H14	123.6
C2—C1—H1A	109.1	C11—C14—H14	123.6
N1—C1—H1B	109.1	N1—C15—C16	113.01 (15)
C2—C1—H1B	109.1	N1—C15—H15A	109.0
H1A—C1—H1B	107.9	C16—C15—H15A	109.0
N2—C2—C1	110.59 (15)	N1—C15—H15B	109.0
N2—C2—H2A	109.5	C16—C15—H15B	109.0
C1—C2—H2A	109.5	H15A—C15—H15B	107.8
N2—C2—H2B	109.5	N4—C16—C15	110.99 (15)
C1—C2—H2B	109.5	N4—C16—H16A	109.4
H2A—C2—H2B	108.1	C15—C16—H16A	109.4
N2—C3—C4	121.28 (17)	N4—C16—H16B	109.4
N2—C3—H3	119.4	C15—C16—H16B	109.4
C4—C3—H3	119.4	H16A—C16—H16B	108.0
C5—S1—C6	91.85 (9)	N4—C17—C18	122.64 (17)
C5—C4—C7	111.84 (16)	N4—C17—H17	118.7
C5—C4—C3	123.20 (17)	C18—C17—H17	118.7
C7—C4—C3	124.89 (15)	C19—S3—C20	90.7 (2)
C4—C5—S1	111.98 (14)	C21—C20—S3	111.6 (4)
C4—C5—H5	124.0	C21—C20—H20	124.2
S1—C5—H5	124.0	S3—C20—H20	124.2
C7—C6—S1	111.50 (14)	C21—S3A—C20A	89.8 (5)
C7—C6—H6	124.3	C19—C20A—S3A	112.0 (8)
S1—C6—H6	124.3	C19—C20A—H20A	124.0
C6—C7—C4	112.84 (16)	S3A—C20A—H20A	124.0
C6—C7—H7	123.6	C19—C18—C21	111.44 (17)
C4—C7—H7	123.6	C19—C18—C17	125.50 (17)
N1—C8—C9	112.52 (15)	C21—C18—C17	123.04 (17)
N1—C8—H8A	109.1	C20A—C19—C18	108.6 (5)
C9—C8—H8A	109.1	C18—C19—S3	113.67 (15)
N1—C8—H8B	109.1	C20A—C19—H19	128.1
C9—C8—H8B	109.1	C18—C19—H19	123.2
H8A—C8—H8B	107.8	S3—C19—H19	123.2
N3—C9—C8	111.31 (15)	C20A—C19—H19A	125.7
N3—C9—H9A	109.4	C18—C19—H19A	125.7
C8—C9—H9A	109.4	S3—C19—H19A	120.6
N3—C9—H9B	109.4	C20—C21—C18	112.6 (3)
C8—C9—H9B	109.4	C18—C21—S3A	118.0 (3)
H9A—C9—H9B	108.0	C20—C21—H21	123.7
N3—C10—C11	122.30 (16)	C18—C21—H21	123.7
N3—C10—H10	118.9	S3A—C21—H21	118.3
C11—C10—H10	118.9	C20—C21—H21A	126.4
C12—C11—C14	111.82 (17)	C18—C21—H21A	121.0
C12—C11—C10	122.64 (16)	S3A—C21—H21A	121.0

C8—N1—C1—C2	−80.05 (18)	C10—C11—C14—C13	−175.99 (16)
C15—N1—C1—C2	156.79 (15)	C8—N1—C15—C16	156.43 (15)
C3—N2—C2—C1	109.39 (18)	C1—N1—C15—C16	−80.51 (18)
N1—C1—C2—N2	−74.34 (19)	C17—N4—C16—C15	120.22 (18)
C2—N2—C3—C4	176.83 (15)	N1—C15—C16—N4	−75.56 (19)
N2—C3—C4—C5	−173.54 (17)	C16—N4—C17—C18	177.60 (16)
N2—C3—C4—C7	3.2 (3)	C19—S3—C20—C21	−1.2 (6)
C7—C4—C5—S1	−0.38 (19)	C21—S3A—C20A—C19	3.9 (11)
C3—C4—C5—S1	176.71 (13)	N4—C17—C18—C19	−10.2 (3)
C6—S1—C5—C4	0.30 (15)	N4—C17—C18—C21	171.36 (18)
C5—S1—C6—C7	−0.13 (15)	S3A—C20A—C19—C18	−4.2 (11)
S1—C6—C7—C4	−0.1 (2)	S3A—C20A—C19—S3	146 (7)
C5—C4—C7—C6	0.3 (2)	C21—C18—C19—C20A	2.7 (7)
C3—C4—C7—C6	−176.75 (16)	C17—C18—C19—C20A	−175.9 (7)
C15—N1—C8—C9	−79.14 (17)	C21—C18—C19—S3	−0.5 (2)
C1—N1—C8—C9	157.46 (15)	C17—C18—C19—S3	−179.13 (15)
C10—N3—C9—C8	112.60 (19)	C20—S3—C19—C20A	−30 (6)
N1—C8—C9—N3	−74.04 (19)	C20—S3—C19—C18	1.0 (4)
C9—N3—C10—C11	176.80 (15)	S3—C20—C21—C18	1.2 (8)
N3—C10—C11—C12	−178.59 (18)	S3—C20—C21—S3A	−172 (9)
N3—C10—C11—C14	−2.2 (3)	C19—C18—C21—C20	−0.4 (5)
C14—C11—C12—S2	−0.2 (2)	C17—C18—C21—C20	178.2 (5)
C10—C11—C12—S2	176.66 (13)	C19—C18—C21—S3A	0.3 (5)
C13—S2—C12—C11	−0.32 (15)	C17—C18—C21—S3A	178.9 (5)
C12—S2—C13—C14	0.73 (14)	C20A—S3A—C21—C20	5 (8)
S2—C13—C14—C11	−0.95 (19)	C20A—S3A—C21—C18	−2.3 (8)
C12—C11—C14—C13	0.7 (2)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the S1,C4–C7, S2,C11–C14 and S3,C18–C21 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···N2ⁱ	0.95	2.55	3.354 (7)	143
C21—H21···Cg1	0.95	2.61	3.437 (2)	146
C5—H5···Cg2	0.95	2.65	3.452 (2)	142
C12—H12···Cg3	0.95	2.61	3.432 (3)	145

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₄N₄S₃
M_r	428.62
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	90
a, b, c (Å)	28.694 (3), 9.2529 (10), 16.427 (2)
β (°)	96.150 (5)
V (Å³)	4336.3 (8)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	3.23
Crystal size (mm)	0.30 × 0.28 × 0.22

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.444, 0.537
No. of measured, independent and observed [I > 2σ(I)] reflections	13414, 3884, 3571
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.04
No. of reflections	3884
No. of parameters	261
No. of restraints	28
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.44

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg3 are the centroids of the S1,C4–C7, S2,C11–C14 and S3,C18–C21 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20···N2ⁱ	0.95	2.55	3.354 (7)	142.5
C21—H21···Cg1	0.95	2.61	3.437 (2)	146.0
C5—H5···Cg2	0.95	2.65	3.452 (2)	142.1
C12—H12···Cg3	0.95	2.61	3.432 (3)	144.5

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

This work was supported by the National Institutes of Health, Division of National Center for Research Resources, under grant No. G12RR013459. This material is based upon work supported by the National Science Foundation under CHE-0821357.

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