Tris{2-[(3-thien-yl)methyl-idene-amino]-eth-yl}amine.

The title compound, C(21)H(24)N(4)S(3), is a tripodal Schiff base that was obtained from the reaction of tris-(2-amino-eth-yl)amine (tren) and thio-phene-3-carbaldehyde. The compound forms a cavity with approximate C3 symmetry. One of the thio-phene units is disordered in a 0.764 (2):0.236 (2) ratio. In the crystal, the three thio-phene ligands are involved in intra-molecular C-H⋯π inter-actions and the mol-ecules are connected by C-H⋯N inter-actions, 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 = 428.62

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.092

S = 1.04

3884 reflections

261 parameters

28 restraints

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.44 e Å−3

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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810039206/zq2062Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H24N4S3	F(000) = 1808
Mr = 428.62	Dx = 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

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

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(Fo2) + (0.0403P)2 + 7.6616P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3884 reflections	Δρmax = 0.41 e Å−3
261 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

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) .