N,N′-Bis(2-amino­phen­yl)-3,4-diphenyl­thio­phene-2,5-dicarboxamide acetonitrile solvate

Askerov, R.K.; Roznyatovsky, V.V.; Katayev, E.A.; Maharramov, A.M.; Khrustalev, V.N.

doi:10.1107/S1600536810008780

organic compounds

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Volume 66| Part 4| April 2010| Page o793

doi:10.1107/S1600536810008780

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N,N′-Bis(2-aminophenyl)-3,4-diphenylthiophene-2,5-dicarboxamide acetonitrile solvate

Rizvan K. Askerov,^a ^* Vladimir V. Roznyatovsky,^b Evgeny A. Katayev,^c Abel M. Maharramov ^a and Victor N. Khrustalev ^c

^aBaku State University, Z. Khalilov St 23, Baku AZ-1148, Azerbaijan, ^bChemistry Department, M. V. Lomonosov Moscow State University, Leninskie gory 1/3, Moscow 119991, Russian Federation, and ^cA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov St 28, B-334, Moscow 119991, Russian Federation
^*Correspondence e-mail: vkh@xray.ineos.ac.ru

(Received 24 February 2010; accepted 8 March 2010; online 13 March 2010)

In the title solvate, C₃₀H₂₄N₄O₂S·CH₃CN, the substituted thiophene possesses approximate C_s(m) intrinsic symmetry, with the mirror plane passing through the S atom and the mid-point of the (Ph)C—C(Ph) bond. Despite the main backbone of the molecule being a long chain of conjugated bonds, it adopts a non-planar conformation due to the presence of various intra- and intermolecular hydrogen bonds. The hydrogen bonds result in twist configurations for both the amido and aminophenyl fragments relative to the central thiophene ring. There are two intramolecular N_amine—H⋯O hydrogen bonds within the thiophene-2,5-dicarboxamide molecule that form seven-membered rings. In the crystal, the thiophene-2,5-dicarboxamide molecules form inversion dimers by four amide–amine N—H⋯N hydrogen bonds. The dimers are further linked into layers propagating in (100) both directly (via N_amine—H⋯O hydrogen bonds) and through the acetonitrile solvate molecules (via amine–cyano N—H⋯N and C_Me—H⋯O interactions).

Related literature

For general background to aromatic diamide diamines, see: Picard et al. (2001 ); Schneider & Yatsimirsky (2008 ). For related compounds, see: Sessler et al. (2005a ,b ), Katayev et al. (2007 ); Askerov et al. (2010 ).

Experimental

Crystal data

C₃₀H₂₄N₄O₂S·C₂H₃N
M_r = 545.65
Triclinic, $[P \overline 1]$
a = 9.0314 (9) Å
b = 11.5470 (11) Å
c = 13.0140 (12) Å
α = 93.206 (2)°
β = 92.504 (2)°
γ = 90.017 (2)°
V = 1353.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 120 K
0.24 × 0.21 × 0.18 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.965, T_max = 0.972
13964 measured reflections
6491 independent reflections
5153 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.122
S = 1.01
6491 reflections
362 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.91	2.43	3.124 (2)	134
N2—H2A⋯O1	0.91	2.12	2.841 (2)	135
N2—H2B⋯N5ⁱⁱ	0.91	2.43	3.322 (2)	165
N3—H3⋯N2ⁱ	0.90	2.50	3.125 (2)	127
N4—H4A⋯O2	0.91	2.08	2.860 (2)	143
N4—H4B⋯O2ⁱⁱⁱ	0.91	2.35	3.108 (2)	142
C32—H32A⋯O1	0.98	2.55	3.245 (2)	128
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) -x+1, -y+2, -z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL ; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008780/fl2294sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008780/fl2294Isup2.hkl

checkCIF report

Comment top

Aromatic diamide diamines are useful precursors for the construction of larger molecules which are used in host-guest chemistry (Schneider &Yatsimirsky, 2008). Such diamines can bind neutral or anionic species using hydrogen bonds. We and others have reported several approaches for the synthesis of such type of diamines (Picard et al., 2001; Sessler et al., 2005a, 2005b; Katayev et al., 2007). In this work we present the synthesis and crystal structure of a diamine used by us recently to prepare anion selective receptors (Sessler et al., 2005a; Askerov et al., 2010).

The synthesis consists of the conversion of dicarboxylic acid into the corresponding chloride followed by coupling with 2-mercaptothiazoline (Fig. 1). The activated acid was transformed into (I) by the reaction with 1,2-phenylenediamine.

(I) crystallizes as a solvate with an acetonitrile molecule. The molecule possesses approximate C_s(m) intrinsic symmetry, with the mirror plane passing through the sulfur atom and the middle of the (Ph)C—C(Ph) bond (Fig. 2). Despite the main backbone of (I) being a long chain of conjugated bonds (C_Ar—N(H)—C(O)—C═C—C(O)—N(H)—C_Ar), it adopts a non-planar conformation due to the presence of various intra- and intermolecular hydrogen bonding interactions (Table 1). These hydrogen bonds result in twist configurations for both the amido and aminophenyl fragments relative to the central thiophene ring. The dihedral angles between the O1═C5—N1—H1 and O2═ C24—N3—H3 amido planes and the S1—C1—C2—C3—C4 thiophene ring plane are 16.08 (8) and 19.30 (11)°, respectively, while that between the N2—C7—C8—C9—C10—C11—C6 and N4—C26—C27—C28—C29—C30—C25 aminophenyl planes and the S1—C1—C2—C3—C4 thiophene ring plane are 39.16 (5) and 33.43 (6)°, respectively. The dihedral angles between the planes of the C12—C13—C14—C15—C16—C17 and C18—C19—C20—C21—C22—C23 phenyl substituents and the S1—C1—C2—C3—C4 thiophene ring plane are 62.55 (6) and 74.62 (5)°, respectively.

There are two intramolecular N_amine—H···O hydrogen bonds in (I) closing the O1—C5—N1—C6—C7—N2—H2A and O2—C24—N3—C25—C26—N4—H4A seven-membered rings (Table 1, Fig. 2). In the crystal, the molecules form centrosymmetrical dimers through four N1—H1···N4ⁱ and N3—H3···N2ⁱ hydrogen bonds (Table 1, Fig. 3). The dimers are further linked into layers parallel to (100) both directly (via N4—H4B···O2ⁱⁱⁱ hydrogen bonds, Table 1) and through the solvate acetonitrile molecules (via N2—H2B···N5ⁱⁱ and C32—H32A···O1 hydrogen bonds, Table 1) (Fig. 4).

Related literature top

For general background to aromatic diamide diamines, see: Picard et al. (2001); Schneider & Yatsimirsky (2008). For related compounds, see: Sessler et al. (2005a,b), Katayev et al. (2007); Askerov et al. (2010).

Experimental top

2,5-Bis((2-thio-1,3-thiazolidine-3-yl)carbonyl)-3,4-diphenylthiophene (II). 3,4-Diphenylthiophene-2,5-dicarboxylic acid (9 g, 27.7 mmol) was suspended in 35 ml freshly distilled SOCl₂ in the presence of several drops of DMF. The resulting mixture was heated at reflux for 1 hour. The excess SOCl₂ was removed under reduced pressure and the residue was further dried at 373 K under high vacuum. The thiophene diacid chloride obtained in this way was dissolved in 130 ml dry THF and added drop-wise during a 2 hour period to a solution containing 1,3-thiazolidine-2-thione (6.6 g, 55.4 mmol) and triethylamine (20 ml) in 330 ml dry THF. During this process carried out under continuous stirring the reaction temperature was kept at 323 K. After the addition was complete the reaction mixture was maintained under the same conditions for an additional 2 hours and then for a further 16 h at room temperature with stirring. The reaction mixture was then filtered, and the resulting solid was washed with cold THF. The filtrate was reduced in volume to a dark paste using a rotary evaporator. This paste-like material was then taken up into 30 ml of ethyl acetate. After this mixing procedure, crude product was filtered off as a dark-yellow powder. Recrystallization from dichloroethane yielded 10.8 g (74%) of yellow crystals. M.p. = 527-529 K. Found: C, 54.73; H, 3.44; N, 5.32. Calcd for C₂₄H₁₈N₂O₂S₅: C, 54.98; H, 3.23; N, 5.36. ¹H NMR (400 MHz, CDCl₃): \d = 2.72 (t, 4H), 4.21 (t, 4H), 7.05 (m, 4H), 7.22 (m. 6H). ¹³C NMR (100 MHz, CDCl₃): \d = 29.61, 55.80, 127.90, 127.99, 129.60, 134.21, 136.08, 144.34, 164.16, 200.37. Mass spectrometry (ESI+): 548.9 [M+Na]⁺, 1074.3 [2M+Na]⁺, 1601.8 [3M+Na]⁺.

(II) (5.0 g, 9.45 mmol) was added to a solution of 1,2-diaminobenzene (3.1 g, 28.4 mmol) in 125 ml of dry methylene chloride. The resulting mixture was stirred at room temperature for 2 days. At this juncture, the desired product, compound I, was obtained via filtration in a yield of 78% (3.7 g). M.p. = 501-503 K. Found: C, 71.40; H, 4.77; N, 11.45. Calcd for C₃₀H₂₄N₄O₂S: C, 71.41; H, 4.79; N, 11.10. ¹H NMR (400 MHz, DMSO-d₆): δ = 4.50 (s, 4H), 6.53 (t, 2H), 6.68 (d, 2H), 6.90 (t, 2H), 7.02 (d, 2H), 7.17 (m, 4H), 7.25 (m, 6H), 8.76 (s, 2H). ¹³C NMR (100 MHz, DMSO-d₆): δ = 127.48, 127.90, 133.71, 136.90, 138.13, 139.58, 139.37, 141.32, 145.59, 147.12, 153.39, 153.48, 171.99. Mass spectrometry (ESI+): 527.1 [M+Na]⁺, 1030.9 [2M+Na]⁺, 1535.8 [3M+Na]⁺. Crystals suitable for X-ray diffraction were obtained by slow evaporation from an acetonitrile solution.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Synthesis of the ligand I.
	Fig. 2. Molecular structure of I.CH₃CN. Displacement ellipsoids are shown at the 50% probability level. Dashed lines indicate the hydrogen bonds.
	Fig. 3. Centrosymmetrical dimers of I. Displacement ellipsoids are shown at the 50% probability level. Only H-atoms participating in the formation of the hydrogen bonds are presented. Dashed lines indicate the hydrogen bonds.
	Fig. 4. Crystal packing of dimers of I. Dashed lines indicate the hydrogen bonds.

N,N'-Bis(2-aminophenyl)-3,4-diphenylthiophene-2,5-dicarboxamide acetonitrile solvate top

Crystal data top

C₃₀H₂₄N₄O₂S·C₂H₃N	Z = 2
M_r = 545.65	F(000) = 572
Triclinic, P1	D_x = 1.339 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0314 (9) Å	Cell parameters from 7103 reflections
b = 11.5470 (11) Å	θ = 2.3–28.0°
c = 13.0140 (12) Å	µ = 0.16 mm⁻¹
α = 93.206 (2)°	T = 120 K
β = 92.504 (2)°	Prism, yellow
γ = 90.017 (2)°	0.24 × 0.21 × 0.18 mm
V = 1353.7 (2) Å³

Data collection top

Bruker SMART 1K CCD diffractometer	6491 independent reflections
Radiation source: normal-focus sealed tube	5153 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ϕ and ω scans	θ_max = 28.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −11→11
T_min = 0.965, T_max = 0.972	k = −15→15
13964 measured reflections	l = −16→17

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)] = 0.048	Hydrogen site location: difference Fourier map
wR(F²) = 0.122	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.06P)² + 0.82P] where P = (F_o² + 2F_c²)/3
6491 reflections	(Δ/σ)_max = 0.001
362 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₃₀H₂₄N₄O₂S·C₂H₃N	γ = 90.017 (2)°
M_r = 545.65	V = 1353.7 (2) Å³
Triclinic, P1	Z = 2
a = 9.0314 (9) Å	Mo Kα radiation
b = 11.5470 (11) Å	µ = 0.16 mm⁻¹
c = 13.0140 (12) Å	T = 120 K
α = 93.206 (2)°	0.24 × 0.21 × 0.18 mm
β = 92.504 (2)°

Data collection top

Bruker SMART 1K CCD diffractometer	6491 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	5153 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.972	R_int = 0.018
13964 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.01	Δρ_max = 0.40 e Å⁻³
6491 reflections	Δρ_min = −0.26 e Å⁻³
362 parameters

Special details top

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 > 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
S1	0.32334 (4)	0.62254 (3)	0.58968 (3)	0.02296 (11)
O1	0.24008 (14)	0.49411 (10)	0.75610 (9)	0.0285 (3)
O2	0.35642 (14)	0.83180 (10)	0.48613 (9)	0.0309 (3)
N1	0.23655 (15)	0.31177 (11)	0.68036 (10)	0.0241 (3)
H1	0.2481	0.2662	0.6220	0.029*
N2	0.42197 (16)	0.33682 (12)	0.86449 (11)	0.0276 (3)
H2A	0.4023	0.4114	0.8488	0.033*
H2B	0.4786	0.3342	0.9242	0.033*
N3	0.40740 (15)	0.75501 (11)	0.32722 (10)	0.0239 (3)
H3	0.4154	0.6902	0.2858	0.029*
N4	0.62869 (16)	0.91705 (12)	0.41468 (11)	0.0281 (3)
H4A	0.5702	0.8894	0.4633	0.034*
H4B	0.6792	0.9802	0.4416	0.034*
C1	0.26943 (17)	0.47972 (13)	0.57739 (12)	0.0225 (3)
C2	0.25071 (17)	0.43918 (13)	0.47550 (12)	0.0216 (3)
C3	0.28338 (17)	0.52709 (13)	0.40610 (12)	0.0217 (3)
C4	0.32623 (17)	0.63027 (14)	0.45839 (12)	0.0225 (3)
C5	0.24737 (17)	0.42824 (14)	0.67855 (12)	0.0229 (3)
C6	0.20591 (18)	0.25151 (13)	0.77046 (12)	0.0238 (3)
C7	0.29838 (18)	0.26348 (14)	0.86012 (12)	0.0250 (3)
C8	0.2672 (2)	0.19380 (15)	0.94138 (13)	0.0308 (4)
H8	0.3280	0.1996	1.0029	0.037*
C9	0.1493 (2)	0.11687 (16)	0.93351 (14)	0.0346 (4)
H9	0.1306	0.0703	0.9895	0.042*
C10	0.0585 (2)	0.10680 (16)	0.84531 (15)	0.0336 (4)
H10	−0.0227	0.0541	0.8404	0.040*
C11	0.08769 (19)	0.17493 (14)	0.76388 (13)	0.0283 (3)
H11	0.0257	0.1688	0.7029	0.034*
C12	0.19053 (17)	0.32216 (13)	0.44120 (12)	0.0221 (3)
C13	0.04857 (18)	0.29170 (14)	0.46735 (13)	0.0263 (3)
H13	−0.0102	0.3464	0.5045	0.032*
C14	−0.0081 (2)	0.18195 (15)	0.43950 (14)	0.0314 (4)
H14	−0.1044	0.1614	0.4589	0.038*
C15	0.0755 (2)	0.10268 (15)	0.38373 (14)	0.0323 (4)
H15	0.0366	0.0276	0.3651	0.039*
C16	0.2158 (2)	0.13241 (15)	0.35487 (14)	0.0306 (4)
H16	0.2724	0.0784	0.3154	0.037*
C17	0.27350 (19)	0.24181 (14)	0.38395 (13)	0.0269 (3)
H17	0.3701	0.2619	0.3647	0.032*
C18	0.25880 (17)	0.51370 (13)	0.29169 (12)	0.0225 (3)
C19	0.3573 (2)	0.45298 (15)	0.22964 (13)	0.0282 (3)
H19	0.4423	0.4177	0.2600	0.034*
C20	0.3317 (2)	0.44371 (16)	0.12320 (14)	0.0343 (4)
H20	0.3991	0.4015	0.0814	0.041*
C21	0.2092 (2)	0.49542 (17)	0.07780 (14)	0.0360 (4)
H21	0.1922	0.4888	0.0051	0.043*
C22	0.1116 (2)	0.55669 (18)	0.13886 (15)	0.0383 (4)
H22	0.0277	0.5928	0.1080	0.046*
C23	0.1357 (2)	0.56590 (16)	0.24561 (13)	0.0307 (4)
H23	0.0679	0.6080	0.2871	0.037*
C24	0.36380 (17)	0.74725 (13)	0.42408 (12)	0.0229 (3)
C25	0.43963 (18)	0.86137 (13)	0.28064 (12)	0.0240 (3)
C26	0.54734 (18)	0.93901 (14)	0.32371 (13)	0.0249 (3)
C27	0.5790 (2)	1.03668 (15)	0.26837 (14)	0.0319 (4)
H27	0.6484	1.0927	0.2970	0.038*
C28	0.5105 (2)	1.05222 (16)	0.17287 (15)	0.0363 (4)
H28	0.5352	1.1178	0.1360	0.044*
C29	0.4066 (2)	0.97321 (16)	0.13054 (14)	0.0346 (4)
H29	0.3604	0.9839	0.0647	0.041*
C30	0.37053 (19)	0.87819 (15)	0.18545 (13)	0.0282 (3)
H30	0.2979	0.8243	0.1576	0.034*
N5	0.3348 (2)	0.71107 (17)	0.94378 (15)	0.0518 (5)
C31	0.2246 (3)	0.71979 (17)	0.89885 (16)	0.0402 (5)
C32	0.0842 (3)	0.7313 (2)	0.8419 (2)	0.0555 (6)
H32A	0.0772	0.6723	0.7847	0.083*
H32B	0.0027	0.7209	0.8878	0.083*
H32C	0.0778	0.8087	0.8146	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0254 (2)	0.02091 (19)	0.02226 (19)	−0.00233 (14)	0.00057 (14)	−0.00059 (14)
O1	0.0368 (7)	0.0234 (6)	0.0250 (6)	0.0031 (5)	0.0028 (5)	−0.0015 (4)
O2	0.0380 (7)	0.0236 (6)	0.0313 (6)	−0.0048 (5)	0.0103 (5)	−0.0040 (5)
N1	0.0285 (7)	0.0221 (6)	0.0218 (6)	0.0015 (5)	0.0010 (5)	0.0006 (5)
N2	0.0301 (7)	0.0267 (7)	0.0255 (7)	−0.0006 (6)	−0.0023 (6)	0.0002 (5)
N3	0.0270 (7)	0.0192 (6)	0.0254 (7)	−0.0022 (5)	0.0024 (5)	−0.0008 (5)
N4	0.0283 (7)	0.0262 (7)	0.0294 (7)	−0.0042 (6)	−0.0005 (6)	−0.0009 (6)
C1	0.0207 (7)	0.0202 (7)	0.0264 (8)	0.0001 (6)	0.0002 (6)	0.0016 (6)
C2	0.0192 (7)	0.0215 (7)	0.0239 (7)	0.0014 (6)	0.0006 (6)	−0.0001 (6)
C3	0.0202 (7)	0.0217 (7)	0.0232 (7)	0.0011 (6)	0.0008 (6)	0.0006 (6)
C4	0.0206 (7)	0.0237 (7)	0.0233 (7)	−0.0002 (6)	0.0017 (6)	0.0009 (6)
C5	0.0216 (7)	0.0231 (7)	0.0240 (7)	0.0019 (6)	0.0010 (6)	0.0017 (6)
C6	0.0282 (8)	0.0202 (7)	0.0235 (7)	0.0029 (6)	0.0038 (6)	0.0018 (6)
C7	0.0260 (8)	0.0238 (8)	0.0253 (8)	0.0036 (6)	0.0025 (6)	0.0000 (6)
C8	0.0378 (10)	0.0308 (9)	0.0241 (8)	0.0021 (7)	−0.0007 (7)	0.0043 (7)
C9	0.0394 (10)	0.0331 (9)	0.0328 (9)	0.0003 (8)	0.0064 (8)	0.0106 (7)
C10	0.0309 (9)	0.0301 (9)	0.0405 (10)	−0.0044 (7)	0.0023 (8)	0.0075 (7)
C11	0.0283 (8)	0.0245 (8)	0.0319 (9)	−0.0006 (6)	−0.0026 (7)	0.0032 (6)
C12	0.0241 (8)	0.0215 (7)	0.0205 (7)	−0.0014 (6)	−0.0019 (6)	0.0018 (6)
C13	0.0240 (8)	0.0267 (8)	0.0277 (8)	0.0007 (6)	0.0006 (6)	−0.0023 (6)
C14	0.0258 (8)	0.0319 (9)	0.0361 (9)	−0.0082 (7)	0.0003 (7)	0.0006 (7)
C15	0.0370 (10)	0.0220 (8)	0.0371 (9)	−0.0073 (7)	−0.0031 (7)	−0.0020 (7)
C16	0.0327 (9)	0.0247 (8)	0.0336 (9)	0.0025 (7)	0.0013 (7)	−0.0043 (7)
C17	0.0255 (8)	0.0245 (8)	0.0308 (8)	−0.0005 (6)	0.0040 (6)	0.0009 (6)
C18	0.0242 (8)	0.0205 (7)	0.0226 (7)	−0.0051 (6)	−0.0007 (6)	0.0008 (6)
C19	0.0294 (9)	0.0286 (8)	0.0266 (8)	0.0008 (7)	0.0016 (6)	−0.0002 (6)
C20	0.0403 (10)	0.0357 (9)	0.0264 (9)	−0.0049 (8)	0.0054 (7)	−0.0052 (7)
C21	0.0464 (11)	0.0377 (10)	0.0232 (8)	−0.0113 (8)	−0.0027 (7)	−0.0005 (7)
C22	0.0375 (10)	0.0440 (11)	0.0325 (9)	−0.0004 (8)	−0.0099 (8)	0.0044 (8)
C23	0.0298 (9)	0.0330 (9)	0.0287 (9)	0.0030 (7)	−0.0011 (7)	−0.0006 (7)
C24	0.0222 (7)	0.0208 (7)	0.0258 (8)	−0.0011 (6)	0.0024 (6)	0.0000 (6)
C25	0.0248 (8)	0.0206 (7)	0.0272 (8)	0.0007 (6)	0.0056 (6)	0.0020 (6)
C26	0.0248 (8)	0.0217 (7)	0.0282 (8)	0.0016 (6)	0.0049 (6)	−0.0002 (6)
C27	0.0309 (9)	0.0256 (8)	0.0397 (10)	−0.0046 (7)	0.0071 (7)	0.0029 (7)
C28	0.0400 (10)	0.0297 (9)	0.0408 (10)	−0.0012 (8)	0.0075 (8)	0.0121 (8)
C29	0.0366 (10)	0.0361 (10)	0.0319 (9)	0.0040 (8)	0.0021 (7)	0.0097 (7)
C30	0.0275 (8)	0.0273 (8)	0.0297 (8)	0.0010 (7)	0.0019 (7)	0.0014 (7)
N5	0.0561 (12)	0.0509 (11)	0.0484 (11)	−0.0142 (9)	−0.0086 (9)	0.0104 (9)
C31	0.0526 (13)	0.0312 (10)	0.0372 (10)	−0.0072 (9)	0.0043 (9)	0.0038 (8)
C32	0.0540 (14)	0.0523 (14)	0.0587 (15)	0.0085 (11)	−0.0028 (11)	−0.0056 (11)

Geometric parameters (Å, º) top

S1—C1	1.7162 (16)	C13—C14	1.390 (2)
S1—C4	1.7171 (16)	C13—H13	0.9500
O1—C5	1.2334 (19)	C14—C15	1.381 (3)
O2—C24	1.2354 (19)	C14—H14	0.9500
N1—C5	1.350 (2)	C15—C16	1.386 (3)
N1—C6	1.434 (2)	C15—H15	0.9500
N1—H1	0.9092	C16—C17	1.393 (2)
N2—C7	1.398 (2)	C16—H16	0.9500
N2—H2A	0.9120	C17—H17	0.9500
N2—H2B	0.9136	C18—C19	1.391 (2)
N3—C24	1.345 (2)	C18—C23	1.393 (2)
N3—C25	1.435 (2)	C19—C20	1.392 (2)
N3—H3	0.9029	C19—H19	0.9500
N4—C26	1.401 (2)	C20—C21	1.383 (3)
N4—H4A	0.9125	C20—H20	0.9500
N4—H4B	0.9060	C21—C22	1.381 (3)
C1—C2	1.384 (2)	C21—H21	0.9500
C1—C5	1.495 (2)	C22—C23	1.395 (2)
C2—C3	1.435 (2)	C22—H22	0.9500
C2—C12	1.494 (2)	C23—H23	0.9500
C3—C4	1.385 (2)	C25—C30	1.386 (2)
C3—C18	1.495 (2)	C25—C26	1.400 (2)
C4—C24	1.490 (2)	C26—C27	1.407 (2)
C6—C11	1.383 (2)	C27—C28	1.385 (3)
C6—C7	1.405 (2)	C27—H27	0.9500
C7—C8	1.402 (2)	C28—C29	1.384 (3)
C8—C9	1.383 (3)	C28—H28	0.9500
C8—H8	0.9500	C29—C30	1.389 (2)
C9—C10	1.381 (3)	C29—H29	0.9500
C9—H9	0.9500	C30—H30	0.9500
C10—C11	1.389 (2)	N5—C31	1.139 (3)
C10—H10	0.9500	C31—C32	1.451 (3)
C11—H11	0.9500	C32—H32A	0.9800
C12—C13	1.391 (2)	C32—H32B	0.9800
C12—C17	1.396 (2)	C32—H32C	0.9800

C1—S1—C4	91.55 (8)	C14—C15—C16	120.17 (16)
C5—N1—C6	124.09 (13)	C14—C15—H15	119.9
C5—N1—H1	120.3	C16—C15—H15	119.9
C6—N1—H1	115.6	C15—C16—C17	119.79 (16)
C7—N2—H2A	114.9	C15—C16—H16	120.1
C7—N2—H2B	113.7	C17—C16—H16	120.1
H2A—N2—H2B	111.3	C16—C17—C12	120.48 (16)
C24—N3—C25	124.93 (13)	C16—C17—H17	119.8
C24—N3—H3	119.9	C12—C17—H17	119.8
C25—N3—H3	115.2	C19—C18—C23	119.01 (15)
C26—N4—H4A	112.0	C19—C18—C3	121.86 (15)
C26—N4—H4B	112.6	C23—C18—C3	119.11 (14)
H4A—N4—H4B	109.5	C18—C19—C20	120.21 (16)
C2—C1—C5	134.26 (14)	C18—C19—H19	119.9
C2—C1—S1	112.53 (12)	C20—C19—H19	119.9
C5—C1—S1	113.16 (11)	C21—C20—C19	120.58 (17)
C1—C2—C3	111.71 (14)	C21—C20—H20	119.7
C1—C2—C12	124.44 (14)	C19—C20—H20	119.7
C3—C2—C12	123.63 (14)	C22—C21—C20	119.51 (17)
C4—C3—C2	111.76 (14)	C22—C21—H21	120.2
C4—C3—C18	123.61 (14)	C20—C21—H21	120.2
C2—C3—C18	124.32 (14)	C21—C22—C23	120.36 (18)
C3—C4—C24	133.19 (14)	C21—C22—H22	119.8
C3—C4—S1	112.44 (12)	C23—C22—H22	119.8
C24—C4—S1	114.22 (11)	C18—C23—C22	120.32 (17)
O1—C5—N1	123.27 (15)	C18—C23—H23	119.8
O1—C5—C1	118.49 (14)	C22—C23—H23	119.8
N1—C5—C1	118.25 (14)	O2—C24—N3	123.20 (15)
C11—C6—C7	120.89 (15)	O2—C24—C4	118.76 (14)
C11—C6—N1	117.59 (15)	N3—C24—C4	118.02 (14)
C7—C6—N1	121.37 (15)	C30—C25—C26	121.14 (15)
N2—C7—C8	121.83 (15)	C30—C25—N3	116.87 (14)
N2—C7—C6	120.62 (15)	C26—C25—N3	121.66 (15)
C8—C7—C6	117.42 (15)	C25—C26—N4	121.71 (15)
C9—C8—C7	121.12 (16)	C25—C26—C27	117.49 (16)
C9—C8—H8	119.4	N4—C26—C27	120.64 (15)
C7—C8—H8	119.4	C28—C27—C26	120.95 (16)
C10—C9—C8	120.84 (17)	C28—C27—H27	119.5
C10—C9—H9	119.6	C26—C27—H27	119.5
C8—C9—H9	119.6	C29—C28—C27	120.68 (17)
C9—C10—C11	118.92 (17)	C29—C28—H28	119.7
C9—C10—H10	120.5	C27—C28—H28	119.7
C11—C10—H10	120.5	C28—C29—C30	119.16 (17)
C6—C11—C10	120.80 (16)	C28—C29—H29	120.4
C6—C11—H11	119.6	C30—C29—H29	120.4
C10—C11—H11	119.6	C25—C30—C29	120.52 (16)
C13—C12—C17	118.89 (15)	C25—C30—H30	119.7
C13—C12—C2	119.39 (14)	C29—C30—H30	119.7
C17—C12—C2	121.72 (14)	N5—C31—C32	179.8 (3)
C14—C13—C12	120.54 (16)	C31—C32—H32A	109.5
C14—C13—H13	119.7	C31—C32—H32B	109.5
C12—C13—H13	119.7	H32A—C32—H32B	109.5
C15—C14—C13	120.11 (16)	C31—C32—H32C	109.5
C15—C14—H14	119.9	H32A—C32—H32C	109.5
C13—C14—H14	119.9	H32B—C32—H32C	109.5

C4—S1—C1—C2	−1.32 (13)	C17—C12—C13—C14	1.8 (2)
C4—S1—C1—C5	−179.05 (12)	C2—C12—C13—C14	−177.74 (15)
C5—C1—C2—C3	177.89 (16)	C12—C13—C14—C15	−1.2 (3)
S1—C1—C2—C3	0.80 (17)	C13—C14—C15—C16	−0.3 (3)
C5—C1—C2—C12	3.2 (3)	C14—C15—C16—C17	1.2 (3)
S1—C1—C2—C12	−173.88 (12)	C15—C16—C17—C12	−0.6 (3)
C1—C2—C3—C4	0.33 (19)	C13—C12—C17—C16	−0.9 (2)
C12—C2—C3—C4	175.06 (14)	C2—C12—C17—C16	178.63 (15)
C1—C2—C3—C18	−173.50 (14)	C4—C3—C18—C19	107.51 (19)
C12—C2—C3—C18	1.2 (2)	C2—C3—C18—C19	−79.4 (2)
C2—C3—C4—C24	−176.42 (16)	C4—C3—C18—C23	−70.9 (2)
C18—C3—C4—C24	−2.5 (3)	C2—C3—C18—C23	102.24 (19)
C2—C3—C4—S1	−1.32 (17)	C23—C18—C19—C20	−0.7 (3)
C18—C3—C4—S1	172.56 (12)	C3—C18—C19—C20	−179.11 (15)
C1—S1—C4—C3	1.51 (13)	C18—C19—C20—C21	0.6 (3)
C1—S1—C4—C24	177.59 (12)	C19—C20—C21—C22	0.0 (3)
C6—N1—C5—O1	4.2 (3)	C20—C21—C22—C23	−0.4 (3)
C6—N1—C5—C1	−175.83 (14)	C19—C18—C23—C22	0.3 (3)
C2—C1—C5—O1	−163.05 (17)	C3—C18—C23—C22	178.76 (16)
S1—C1—C5—O1	14.02 (19)	C21—C22—C23—C18	0.2 (3)
C2—C1—C5—N1	17.0 (3)	C25—N3—C24—O2	−5.1 (3)
S1—C1—C5—N1	−165.92 (12)	C25—N3—C24—C4	176.44 (14)
C5—N1—C6—C11	125.82 (17)	C3—C4—C24—O2	158.95 (17)
C5—N1—C6—C7	−58.5 (2)	S1—C4—C24—O2	−16.1 (2)
C11—C6—C7—N2	176.85 (15)	C3—C4—C24—N3	−22.5 (3)
N1—C6—C7—N2	1.3 (2)	S1—C4—C24—N3	162.48 (12)
C11—C6—C7—C8	0.9 (2)	C24—N3—C25—C30	−128.99 (17)
N1—C6—C7—C8	−174.68 (14)	C24—N3—C25—C26	57.6 (2)
N2—C7—C8—C9	−176.27 (16)	C30—C25—C26—N4	−173.44 (15)
C6—C7—C8—C9	−0.4 (3)	N3—C25—C26—N4	−0.3 (2)
C7—C8—C9—C10	−0.3 (3)	C30—C25—C26—C27	2.1 (2)
C8—C9—C10—C11	0.4 (3)	N3—C25—C26—C27	175.29 (15)
C7—C6—C11—C10	−0.8 (3)	C25—C26—C27—C28	−2.8 (3)
N1—C6—C11—C10	174.92 (15)	N4—C26—C27—C28	172.85 (16)
C9—C10—C11—C6	0.2 (3)	C26—C27—C28—C29	1.5 (3)
C1—C2—C12—C13	59.9 (2)	C27—C28—C29—C30	0.5 (3)
C3—C2—C12—C13	−114.13 (18)	C26—C25—C30—C29	−0.2 (3)
C1—C2—C12—C17	−119.63 (18)	N3—C25—C30—C29	−173.68 (15)
C3—C2—C12—C17	66.3 (2)	C28—C29—C30—C25	−1.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.91	2.43	3.124 (2)	134
N2—H2A···O1	0.91	2.12	2.841 (2)	135
N2—H2B···N5ⁱⁱ	0.91	2.43	3.322 (2)	165
N3—H3···N2ⁱ	0.90	2.50	3.125 (2)	127
N4—H4A···O2	0.91	2.08	2.860 (2)	143
N4—H4B···O2ⁱⁱⁱ	0.91	2.35	3.108 (2)	142
C32—H32A···O1	0.98	2.55	3.245 (2)	128

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

Experimental details

Crystal data
Chemical formula	C₃₀H₂₄N₄O₂S·C₂H₃N
M_r	545.65
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	9.0314 (9), 11.5470 (11), 13.0140 (12)
α, β, γ (°)	93.206 (2), 92.504 (2), 90.017 (2)
V (Å³)	1353.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.24 × 0.21 × 0.18

Data collection
Diffractometer	Bruker SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.965, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	13964, 6491, 5153
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.122, 1.01
No. of reflections	6491
No. of parameters	362
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.26

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.91	2.43	3.124 (2)	134
N2—H2A···O1	0.91	2.12	2.841 (2)	135
N2—H2B···N5ⁱⁱ	0.91	2.43	3.322 (2)	165
N3—H3···N2ⁱ	0.90	2.50	3.125 (2)	127
N4—H4A···O2	0.91	2.08	2.860 (2)	143
N4—H4B···O2ⁱⁱⁱ	0.91	2.35	3.108 (2)	142
C32—H32A···O1	0.98	2.55	3.245 (2)	128

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

References

Askerov, R. K., Roznyatovsky, V. V., Katayev, E. A., Maharramov, A. M. & Khrustalev, V. N. (2010). Acta Cryst. E66, o660–o661. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (1998). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Katayev, E. A., Sessler, J. L., Khrustalev, V. N. & Ustynyuk, Y. A. (2007). J. Org. Chem. 72, 7244–7252. Web of Science CSD CrossRef PubMed CAS Google Scholar
Picard, C., Arnaud, N. & Tisnes, P. (2001). Synthesis, pp. 1471–1478. CrossRef Google Scholar
Schneider, H. J. & Yatsimirsky, A. K. (2008). Chem. Soc. Rev. 37, 263–277. Web of Science CrossRef PubMed CAS Google Scholar
Sessler, J. L., Katayev, E., Pantos, G. D., Scherbakov, P., Reshetova, M. D., Khrustalev, V. N., Lynch, V. M. & Ustynyuk, Y. A. (2005a). J. Am. Chem. Soc. 127, 11442–11446. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sessler, J. L., Roznyatovskiy, V., Pantos, G. D., Borisova, N. E., Reshetova, M. D., Lynch, V. M., Khrustalev, V. N. & Ustynyuk, Y. A. (2005b). Org. Lett. 7, 5277–5280. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1998). 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

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N,N′-Bis(2-amino­phen­yl)-3,4-di­phenyl­thio­phene-2,5-dicarboxamide aceto­nitrile solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

N,N′-Bis(2-aminophenyl)-3,4-diphenylthiophene-2,5-dicarboxamide acetonitrile solvate