2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24-tetra­aza­penta­cyclo­[24.2.1.112,15.04,9.018,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodeca­ene chloro­form disolvate

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

doi:10.1107/S1600536810006173

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages o660-o661

doi:10.1107/S1600536810006173

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2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24-tetraazapentacyclo[24.2.1.1^12,15.0^4,9.0^18,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodecaene chloroform disolvate

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 11 February 2010; accepted 16 February 2010; online 20 February 2010)

The macrocycle of the title compound, C₃₆H₂₄N₄O₃S·2CHCl₃, contains a rigid framework with the nitrogen and oxygen heteroatoms pointing in towards the center of the macrocyclic cavity. The macrocycle is essentially planar (r.m.s. deviation = 0.027 Å) except for the thiophene ring. The dihedral angle between the thiophene ring plane and the mean plane of the central macrocyclic core including all atoms except sulfur is 21.6 (1)°. Four intramolecular hydrogen bonds occur: two are between the amide hydrogen atoms and the Schiff base nitrogen atoms, while the others are between the amide hydrogen atoms and the sulfur atom of the thiophene. The two solvate chloroform molecules are bound to the carbonyl oxygen atoms of the ligand by weak C—H⋯O hydrogen bonding. In addition, the structure reveals intermolecular Cl⋯Cl close contacts [3.308 (2), 3.404 (2) and 3.280 (2) Å] between the chloroform solvate molecules. In the crystal, the macrocycles form layers parallel to (101), with an interlayer distance of 3.362 (3) Å. This short distance is determined by the stacking interactions between the amide carbonyl and imine fragments of neighboring ligands.

Related literature

For general background to biological anion–receptor interactions, see: Caltagirone & Gale (2009 ). For the synthesis of synthetic anion receptors, see: Aydogan et al. (2008 ). For related compounds, see: Sessler et al. (2005a ,b ).

Experimental

Crystal data

C₃₆H₂₄N₄O₃S·2CHCl₃
M_r = 831.40
Monoclinic, P 2₁ /c
a = 13.0957 (15) Å
b = 31.854 (3) Å
c = 8.7368 (9) Å
β = 98.857 (3)°
V = 3601.1 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 120 K
0.30 × 0.24 × 0.21 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ) T_min = 0.845, T_max = 0.888
29858 measured reflections
7802 independent reflections
4582 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.108
S = 1.01
7802 reflections
469 parameters
H-atom parameters constrained
Δρ_max = 0.42 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
N1—H1N⋯N2	0.90	2.13	2.622 (3)	114
N1—H1N⋯S1	0.90	2.48	2.970 (3)	115
N4—H4N⋯N3	0.90	2.13	2.620 (3)	114
N4—H4N⋯S1	0.90	2.53	2.986 (3)	112
C32—H32⋯Cl6ⁱ	0.95	2.69	3.461 (3)	139
C37—H37⋯O1	1.00	2.34	3.149 (3)	137
C38—H38⋯O3	1.00	2.46	3.205 (3)	131
Symmetry code: (i) x, y, z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006173/rk2192sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006173/rk2192Isup2.hkl

checkCIF report

Comment top

The ubiquity of anions in nature makes an understanding of biological anion–receptor interactions a topic of considerable current interest (Caltagirone & Gale, 2009). It is also inspiring the synthesis of synthetic anion receptors, systems whose potential utility could span the full spectrum of applications from separations and waste remediation to biomedical analysis and therapy (Aydogan et al., 2008). We are particularly interested in the design of rigid macrocyclic hosts for anions and use for this purpose aromatics linked by amide or imine bonds. These bonds and pyrrole rings serve as efficient coordination site for anions functioning by means of hydrogen bonds. In our previous works, it has been shown that rigid scaffold of a receptor results in a higher selectivity that the one with flexible skeleton (Sessler et al., 2005a,b). In this work, we present the new receptor bearing furan and thiophen-2,5-dicarboxamide units in one macrocycle.

The target receptor was synthesized according to the method of template synthesis using chloride anion as a template. The dialdehyde (2,5–diformylfuran) and diamine (N,N'-bis(2-aminophenyl)-3,4-diphenylthiophen-2,5-dicarboxamide) were condensed in the presence of hydrochloric acid affording hydrochloric acid salt of the macrocyclic receptor I. The HCl that was subsequently neutralized by triethylamine to give free base ligand I (Fig. 1). The single crystals of I suitable for X–ray diffraction analysis were obtained by slow crystallization from chloroform–methanol mixture.

The title compound I crystallizes as a solvate with two chloroform molecules, i. e., C₃₆H₂₄N₄O₃S^.2CHCl₃. The macrocycle I contains a rigid framework with the N1, N2, O2, N3 and N4 heteroatoms pointing in toward the center of the macrocyclic cavity (Fig. 2). It is practically planar excepting for the thiophene ring. By the intermolecular C—H···O hydrogen bond (Table 1), the phenyl group at the C3 carbon atom of the thiophene forces this ring to deviate from the plane of the central macrocyclic core passed through the C1/C4/C5/N1/C6/C7/N2/C12/C13/O2/C16/C17/N3/C18/C19/N4/C24 atoms (the dihedral angle is 21.6 (1)°. There are four internal hydrogen bonds in I. Two are between the amide NH protons and the Schiff base nitrogen atoms, while the other are between the amide NH protons and the sulfur atom of the thiophene (Table 1). The two solvate chloroform molecules are bound to the carbonyl oxygen atoms of the ligand by weak C—H···O hydrogen bonding (Table 1). In addition to these effects, the structure reveals the intermolecular Cl···Cl attractive interactions between the chloroform solvate molecules (Cl1···Cl3ⁱⁱ, Cl1···Cl4ⁱⁱⁱ and Cl2···Cl5^iv distances are 3.308 (2)Å, 3.404 (2)Å and 3.280 (2)Å, respectively). In the crystal, the macrocycles I form the layers parallel to (101), with the interlayer distance of 3.362 (3)Å (Fig. 3). This short distance is determined by the stacking interactions between amide carbonyl and imine fragments of neighboring ligands. Symmetry codes: (ii) x, -y+1/2, z-1/2; (iii) x-1, y, z; (iv) x-1, y, z+1.

Related literature top

For general background to biological anion–receptor interactions, see: Caltagirone & Gale (2009). For the synthesis of synthetic anion receptors, see: Aydogan et al. (2008). For related compounds, see: Sessler et al. (2005a,b).

Experimental top

Concentrated hydrochloric acid (21.5 µl, 0.18 mmol) was added to a mixture of 2,5-diformylfuran (13 mg, 0.1 mmol) and N,N'-bis(2-aminophenyl)-3,4-diphenylthiophen-2,5-dicarboxamide (51 mg, 0.1 mmol) in 20 ml dry MeOH. The colourless clear solution was stirred for overnight at 296 K. The precipitate formed was filtrated off and suspended in 1.5 ml dry dichloromethane. Then triethylamine (25.3 µl, 0.18 mmol) was added to the suspension affording yellow clear solution, which was passed through a plug of silica gel. Evaporation of the solvent yielded 44 mg (73%) of product I. M.p. > 623 K (decomp.). Found (%): C, 72.87; H, 4.08; N, 9.43. Calcd. for C₃₆H₂₄N₄O₃S (%): C, 72.96; H, 4.08; N, 9.45. ¹H NMR (CDCl₃, 293 K): \d = 7.05–7.24 (m, 16H), 7.36 (d, 2H), 8.50 (d, 2H), 8.52 (s, 2H), 10.38 (s, 2H). ¹³C NMR (CDCl₃, 293 K): \d = 114.67, 119.41, 120.56, 123.68, 127.37, 127.54, 129.43, 130.12, 132.25, 134.41, 135.43, 135.82, 142.66, 148.52, 154.21, 157.99. Mass spectrum (MALDI–TOF), m/z (I_r, %): 593.10 [M+H]⁺.

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Synthesis of the macrocyclic ligand I.
	Fig. 2. Molecular structure of I with the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Dashed lines indicate the hydrogen bonds.
	Fig. 3. Crystal packing of I. Dashed lines indicate the hydrogen bonding and Cl···Cl interactions.

2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24- tetraazapentacyclo[24.2.1.1^12,15.0^4,9.0^18,23]triaconta- 5,7,9(4),10,12,14,16,18,20,22,26,28-dodecaene chloroform disolvate top

Crystal data top

C₃₆H₂₄N₄O₃S·2CHCl₃	F(000) = 1696
M_r = 831.40	D_x = 1.533 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5725 reflections
a = 13.0957 (15) Å	θ = 2.5–26.6°
b = 31.854 (3) Å	µ = 0.58 mm⁻¹
c = 8.7368 (9) Å	T = 120 K
β = 98.857 (3)°	Prism, dark–orange
V = 3601.1 (7) Å³	0.30 × 0.24 × 0.21 mm
Z = 4

Data collection top

Bruker SMART 1K CCD diffractometer	7802 independent reflections
Radiation source: fine–focus sealed tube	4582 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ϕ– and ω–scans	θ_max = 27.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	h = −16→16
T_min = 0.845, T_max = 0.888	k = −40→40
29858 measured reflections	l = −11→11

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.045P)²] where P = (F_o² + 2F_c²)/3
7802 reflections	(Δ/σ)_max = 0.001
469 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₃₆H₂₄N₄O₃S·2CHCl₃	V = 3601.1 (7) Å³
M_r = 831.40	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.0957 (15) Å	µ = 0.58 mm⁻¹
b = 31.854 (3) Å	T = 120 K
c = 8.7368 (9) Å	0.30 × 0.24 × 0.21 mm
β = 98.857 (3)°

Data collection top

Bruker SMART 1K CCD diffractometer	7802 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	4582 reflections with I > 2σ(I)
T_min = 0.845, T_max = 0.888	R_int = 0.061
29858 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.108	H-atom parameters constrained
S = 1.01	Δρ_max = 0.42 e Å⁻³
7802 reflections	Δρ_min = −0.29 e Å⁻³
469 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
S1	0.57191 (5)	0.45496 (2)	0.59993 (9)	0.02602 (18)
O1	0.38015 (15)	0.39570 (6)	0.8264 (2)	0.0325 (5)
O2	0.58881 (14)	0.58584 (5)	0.6945 (2)	0.0255 (4)
O3	0.80044 (15)	0.41512 (6)	0.4006 (2)	0.0338 (5)
N1	0.42143 (17)	0.46535 (7)	0.8191 (3)	0.0241 (5)
H1N	0.4641	0.4840	0.7846	0.029*
N2	0.43040 (17)	0.54752 (7)	0.8331 (3)	0.0255 (5)
N3	0.74814 (18)	0.56185 (7)	0.5267 (3)	0.0265 (6)
N4	0.76316 (17)	0.48108 (7)	0.4781 (3)	0.0258 (6)
H4N	0.7254	0.4959	0.5370	0.031*
C1	0.6697 (2)	0.42298 (8)	0.5574 (3)	0.0248 (7)
C2	0.6625 (2)	0.38325 (8)	0.6169 (3)	0.0238 (6)
C3	0.5764 (2)	0.37870 (8)	0.6978 (3)	0.0229 (6)
C4	0.5207 (2)	0.41545 (8)	0.6990 (3)	0.0228 (6)
C5	0.4332 (2)	0.42398 (8)	0.7865 (3)	0.0253 (7)
C6	0.3511 (2)	0.48458 (9)	0.9041 (3)	0.0260 (7)
C7	0.3535 (2)	0.52889 (8)	0.9089 (3)	0.0245 (6)
C8	0.2852 (2)	0.54974 (9)	0.9897 (3)	0.0286 (7)
H8	0.2848	0.5796	0.9918	0.034*
C9	0.2181 (2)	0.52777 (9)	1.0667 (3)	0.0326 (7)
H9A	0.1718	0.5424	1.1214	0.039*
C10	0.2181 (2)	0.48450 (9)	1.0643 (4)	0.0341 (8)
H10	0.1732	0.4695	1.1203	0.041*
C11	0.2827 (2)	0.46250 (9)	0.9815 (3)	0.0284 (7)
H11	0.2803	0.4327	0.9775	0.034*
C12	0.4479 (2)	0.58709 (9)	0.8440 (3)	0.0279 (7)
H12	0.4060	0.6035	0.9006	0.033*
C13	0.5266 (2)	0.60808 (8)	0.7761 (3)	0.0268 (7)
C14	0.5540 (2)	0.64955 (9)	0.7810 (3)	0.0314 (7)
H14	0.5227	0.6715	0.8308	0.038*
C15	0.6373 (2)	0.65331 (9)	0.6985 (3)	0.0300 (7)
H15	0.6730	0.6784	0.6810	0.036*
C16	0.6570 (2)	0.61423 (8)	0.6485 (3)	0.0255 (7)
C17	0.7350 (2)	0.60029 (9)	0.5601 (3)	0.0271 (7)
H17	0.7788	0.6207	0.5250	0.033*
C18	0.8263 (2)	0.54995 (9)	0.4407 (3)	0.0253 (7)
C19	0.8333 (2)	0.50648 (9)	0.4126 (3)	0.0269 (7)
C20	0.9060 (2)	0.49109 (9)	0.3278 (3)	0.0293 (7)
H20	0.9100	0.4618	0.3091	0.035*
C21	0.9727 (2)	0.51832 (9)	0.2706 (4)	0.0348 (8)
H21	1.0225	0.5077	0.2122	0.042*
C22	0.9675 (2)	0.56104 (9)	0.2977 (4)	0.0339 (8)
H22	1.0141	0.5795	0.2583	0.041*
C23	0.8952 (2)	0.57689 (9)	0.3816 (4)	0.0320 (7)
H23	0.8921	0.6063	0.3993	0.038*
C24	0.7509 (2)	0.43888 (9)	0.4706 (3)	0.0260 (7)
C25	0.7390 (2)	0.34909 (8)	0.6047 (3)	0.0258 (7)
C26	0.7238 (2)	0.31965 (9)	0.4887 (4)	0.0356 (8)
H26	0.6637	0.3210	0.4125	0.043*
C27	0.7960 (3)	0.28761 (9)	0.4816 (4)	0.0438 (9)
H27	0.7851	0.2674	0.4007	0.053*
C28	0.8824 (3)	0.28547 (10)	0.5916 (4)	0.0451 (9)
H28	0.9313	0.2636	0.5880	0.054*
C29	0.8980 (3)	0.31500 (11)	0.7067 (4)	0.0463 (9)
H29	0.9583	0.3136	0.7825	0.056*
C30	0.8277 (2)	0.34644 (9)	0.7135 (4)	0.0353 (8)
H30	0.8397	0.3667	0.7940	0.042*
C31	0.5545 (2)	0.33855 (8)	0.7748 (3)	0.0232 (6)
C32	0.6213 (2)	0.32491 (8)	0.9032 (3)	0.0274 (7)
H32	0.6791	0.3417	0.9442	0.033*
C33	0.6045 (2)	0.28673 (9)	0.9726 (4)	0.0330 (7)
H33	0.6496	0.2780	1.0628	0.040*
C34	0.5235 (2)	0.26168 (9)	0.9119 (4)	0.0330 (8)
H34	0.5131	0.2354	0.9584	0.040*
C35	0.4571 (2)	0.27476 (9)	0.7830 (4)	0.0311 (7)
H35	0.4010	0.2573	0.7404	0.037*
C36	0.4715 (2)	0.31338 (8)	0.7147 (3)	0.0250 (6)
H36	0.4246	0.3225	0.6271	0.030*
Cl1	0.18557 (6)	0.31001 (2)	0.69064 (9)	0.0365 (2)
Cl2	0.15795 (6)	0.35523 (2)	0.96738 (9)	0.0391 (2)
Cl3	0.24483 (7)	0.27221 (2)	0.99017 (10)	0.0428 (2)
C37	0.2369 (2)	0.31996 (9)	0.8865 (3)	0.0328 (7)
H37	0.3077	0.3322	0.8923	0.039*
Cl4	1.05290 (6)	0.31392 (3)	0.32391 (10)	0.0456 (2)
Cl5	1.01463 (7)	0.39768 (3)	0.20247 (12)	0.0556 (3)
Cl6	0.86232 (7)	0.33276 (3)	0.12830 (11)	0.0590 (3)
C38	0.9583 (2)	0.35249 (10)	0.2702 (4)	0.0385 (8)
H38	0.9263	0.3602	0.3632	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0279 (4)	0.0193 (3)	0.0321 (4)	0.0014 (3)	0.0086 (3)	0.0029 (3)
O1	0.0336 (12)	0.0225 (10)	0.0444 (14)	0.0006 (9)	0.0154 (10)	0.0023 (10)
O2	0.0273 (11)	0.0208 (10)	0.0294 (11)	−0.0001 (8)	0.0077 (9)	−0.0004 (9)
O3	0.0362 (12)	0.0253 (11)	0.0439 (13)	0.0022 (9)	0.0185 (11)	0.0012 (10)
N1	0.0263 (13)	0.0197 (12)	0.0277 (14)	−0.0027 (10)	0.0080 (11)	0.0030 (10)
N2	0.0251 (13)	0.0217 (12)	0.0302 (14)	−0.0007 (10)	0.0061 (11)	0.0017 (11)
N3	0.0296 (13)	0.0216 (12)	0.0289 (14)	−0.0014 (10)	0.0063 (11)	0.0000 (11)
N4	0.0273 (13)	0.0202 (12)	0.0323 (14)	0.0012 (10)	0.0119 (11)	0.0009 (11)
C1	0.0267 (16)	0.0230 (15)	0.0258 (17)	−0.0009 (12)	0.0072 (13)	−0.0029 (13)
C2	0.0248 (15)	0.0216 (14)	0.0244 (16)	0.0005 (12)	0.0018 (13)	−0.0023 (12)
C3	0.0285 (15)	0.0196 (14)	0.0206 (16)	−0.0015 (12)	0.0035 (13)	−0.0002 (12)
C4	0.0254 (15)	0.0198 (14)	0.0232 (16)	−0.0017 (12)	0.0032 (13)	−0.0005 (12)
C5	0.0242 (15)	0.0218 (15)	0.0299 (17)	0.0012 (13)	0.0047 (13)	0.0042 (13)
C6	0.0230 (15)	0.0290 (16)	0.0264 (17)	0.0030 (13)	0.0050 (13)	−0.0007 (13)
C7	0.0236 (15)	0.0247 (15)	0.0246 (16)	−0.0029 (12)	0.0019 (13)	0.0002 (13)
C8	0.0282 (16)	0.0231 (15)	0.0351 (18)	−0.0020 (13)	0.0070 (14)	−0.0052 (14)
C9	0.0304 (17)	0.0334 (17)	0.0363 (19)	0.0006 (14)	0.0130 (15)	−0.0042 (15)
C10	0.0318 (17)	0.0328 (17)	0.040 (2)	−0.0058 (14)	0.0138 (15)	0.0029 (15)
C11	0.0292 (16)	0.0262 (16)	0.0316 (17)	0.0009 (13)	0.0100 (14)	0.0039 (14)
C12	0.0304 (17)	0.0242 (16)	0.0306 (17)	0.0021 (13)	0.0096 (14)	−0.0007 (13)
C13	0.0314 (16)	0.0232 (15)	0.0266 (17)	0.0017 (13)	0.0068 (14)	−0.0022 (13)
C14	0.0396 (18)	0.0210 (15)	0.0353 (18)	−0.0008 (13)	0.0107 (15)	−0.0047 (14)
C15	0.0354 (17)	0.0223 (15)	0.0334 (18)	−0.0041 (13)	0.0090 (15)	0.0008 (14)
C16	0.0292 (16)	0.0215 (15)	0.0253 (16)	−0.0055 (13)	0.0031 (13)	0.0016 (13)
C17	0.0267 (16)	0.0255 (16)	0.0292 (17)	−0.0023 (13)	0.0046 (14)	0.0022 (13)
C18	0.0241 (15)	0.0258 (16)	0.0259 (16)	−0.0011 (12)	0.0030 (13)	0.0016 (13)
C19	0.0266 (16)	0.0251 (15)	0.0289 (17)	−0.0030 (13)	0.0038 (14)	0.0007 (13)
C20	0.0292 (16)	0.0251 (15)	0.0351 (18)	0.0008 (13)	0.0095 (14)	0.0008 (14)
C21	0.0356 (18)	0.0314 (17)	0.041 (2)	0.0021 (14)	0.0182 (16)	0.0017 (15)
C22	0.0310 (17)	0.0286 (16)	0.045 (2)	−0.0043 (14)	0.0158 (16)	0.0068 (15)
C23	0.0343 (17)	0.0231 (15)	0.0396 (19)	−0.0022 (13)	0.0088 (15)	0.0018 (14)
C24	0.0305 (16)	0.0213 (14)	0.0264 (17)	−0.0014 (13)	0.0048 (14)	0.0014 (13)
C25	0.0253 (16)	0.0192 (15)	0.0355 (18)	−0.0024 (12)	0.0132 (14)	0.0044 (13)
C26	0.0327 (18)	0.0286 (17)	0.047 (2)	0.0010 (14)	0.0113 (16)	−0.0046 (15)
C27	0.046 (2)	0.0222 (16)	0.068 (3)	0.0012 (15)	0.025 (2)	−0.0064 (17)
C28	0.042 (2)	0.0302 (18)	0.069 (3)	0.0100 (16)	0.027 (2)	0.0088 (19)
C29	0.0312 (18)	0.049 (2)	0.060 (3)	0.0069 (16)	0.0106 (18)	0.010 (2)
C30	0.0305 (17)	0.0358 (18)	0.040 (2)	−0.0005 (14)	0.0053 (15)	0.0002 (15)
C31	0.0262 (15)	0.0176 (14)	0.0276 (17)	0.0026 (12)	0.0103 (13)	−0.0005 (13)
C32	0.0274 (16)	0.0243 (15)	0.0310 (18)	0.0001 (13)	0.0064 (14)	−0.0031 (14)
C33	0.0365 (18)	0.0275 (16)	0.0358 (19)	0.0063 (14)	0.0080 (15)	0.0059 (14)
C34	0.0403 (19)	0.0204 (15)	0.041 (2)	0.0021 (14)	0.0141 (17)	0.0074 (14)
C35	0.0352 (17)	0.0224 (15)	0.0375 (19)	−0.0069 (13)	0.0111 (15)	−0.0031 (14)
C36	0.0270 (15)	0.0221 (15)	0.0256 (16)	−0.0016 (13)	0.0028 (13)	0.0013 (13)
Cl1	0.0452 (5)	0.0326 (4)	0.0310 (4)	0.0049 (4)	0.0039 (4)	−0.0022 (4)
Cl2	0.0468 (5)	0.0352 (4)	0.0373 (5)	0.0007 (4)	0.0129 (4)	−0.0049 (4)
Cl3	0.0531 (5)	0.0313 (4)	0.0430 (5)	−0.0014 (4)	0.0043 (4)	0.0102 (4)
C37	0.0353 (17)	0.0287 (17)	0.0343 (19)	−0.0015 (14)	0.0049 (15)	0.0005 (14)
Cl4	0.0384 (5)	0.0557 (5)	0.0414 (5)	0.0030 (4)	0.0017 (4)	0.0052 (4)
Cl5	0.0587 (6)	0.0352 (5)	0.0798 (7)	0.0018 (4)	0.0321 (5)	−0.0095 (5)
Cl6	0.0527 (6)	0.0570 (6)	0.0582 (6)	−0.0022 (5)	−0.0200 (5)	−0.0019 (5)
C38	0.0342 (18)	0.045 (2)	0.037 (2)	−0.0028 (15)	0.0050 (15)	−0.0029 (16)

Geometric parameters (Å, º) top

S1—C4	1.721 (3)	C17—H17	0.9500
S1—C1	1.721 (3)	C18—C23	1.401 (4)
O1—C5	1.221 (3)	C18—C19	1.412 (4)
O2—C13	1.361 (3)	C19—C20	1.384 (4)
O2—C16	1.374 (3)	C20—C21	1.378 (4)
O3—C24	1.221 (3)	C20—H20	0.9500
N1—C5	1.362 (3)	C21—C22	1.385 (4)
N1—C6	1.409 (3)	C21—H21	0.9500
N1—H1N	0.8999	C22—C23	1.379 (4)
N2—C12	1.282 (3)	C22—H22	0.9500
N2—C7	1.418 (3)	C23—H23	0.9500
N3—C17	1.276 (3)	C25—C26	1.373 (4)
N3—C18	1.411 (3)	C25—C30	1.385 (4)
N4—C24	1.354 (3)	C26—C27	1.399 (4)
N4—C19	1.410 (3)	C26—H26	0.9500
N4—H4N	0.8999	C27—C28	1.369 (5)
C1—C2	1.377 (4)	C27—H27	0.9500
C1—C24	1.486 (4)	C28—C29	1.369 (5)
C2—C3	1.427 (4)	C28—H28	0.9500
C2—C25	1.495 (4)	C29—C30	1.369 (4)
C3—C4	1.380 (4)	C29—H29	0.9500
C3—C31	1.493 (4)	C30—H30	0.9500
C4—C5	1.497 (4)	C31—C32	1.383 (4)
C6—C11	1.393 (4)	C31—C36	1.387 (4)
C6—C7	1.412 (4)	C32—C33	1.392 (4)
C7—C8	1.391 (4)	C32—H32	0.9500
C8—C9	1.377 (4)	C33—C34	1.368 (4)
C8—H8	0.9500	C33—H33	0.9500
C9—C10	1.378 (4)	C34—C35	1.377 (4)
C9—H9A	0.9500	C34—H34	0.9500
C10—C11	1.385 (4)	C35—C36	1.393 (4)
C10—H10	0.9500	C35—H35	0.9500
C11—H11	0.9500	C36—H36	0.9500
C12—C13	1.431 (4)	Cl1—C37	1.768 (3)
C12—H12	0.9500	Cl2—C37	1.748 (3)
C13—C14	1.368 (4)	Cl3—C37	1.765 (3)
C14—C15	1.402 (4)	C37—H37	1.0000
C14—H14	0.9500	Cl4—C38	1.757 (3)
C15—C16	1.357 (4)	Cl5—C38	1.761 (3)
C15—H15	0.9500	Cl6—C38	1.741 (3)
C16—C17	1.442 (4)	C38—H38	1.0000

C4—S1—C1	92.08 (13)	C20—C19—C18	120.6 (3)
C13—O2—C16	106.2 (2)	N4—C19—C18	115.4 (2)
C5—N1—C6	129.4 (2)	C21—C20—C19	119.9 (3)
C5—N1—H1N	118.3	C21—C20—H20	120.1
C6—N1—H1N	112.3	C19—C20—H20	120.1
C12—N2—C7	120.6 (2)	C20—C21—C22	120.4 (3)
C17—N3—C18	120.9 (2)	C20—C21—H21	119.8
C24—N4—C19	129.0 (2)	C22—C21—H21	119.8
C24—N4—H4N	118.4	C23—C22—C21	120.4 (3)
C19—N4—H4N	112.4	C23—C22—H22	119.8
C2—C1—C24	127.0 (2)	C21—C22—H22	119.8
C2—C1—S1	111.4 (2)	C22—C23—C18	120.4 (3)
C24—C1—S1	121.5 (2)	C22—C23—H23	119.8
C1—C2—C3	112.7 (2)	C18—C23—H23	119.8
C1—C2—C25	123.8 (2)	O3—C24—N4	124.9 (3)
C3—C2—C25	123.5 (2)	O3—C24—C1	121.4 (2)
C4—C3—C2	112.1 (2)	N4—C24—C1	113.7 (2)
C4—C3—C31	125.8 (2)	C26—C25—C30	118.5 (3)
C2—C3—C31	122.1 (2)	C26—C25—C2	121.8 (3)
C3—C4—C5	127.2 (2)	C30—C25—C2	119.7 (3)
C3—C4—S1	111.7 (2)	C25—C26—C27	120.6 (3)
C5—C4—S1	120.81 (19)	C25—C26—H26	119.7
O1—C5—N1	124.5 (3)	C27—C26—H26	119.7
O1—C5—C4	121.7 (2)	C28—C27—C26	119.8 (3)
N1—C5—C4	113.7 (2)	C28—C27—H27	120.1
C11—C6—N1	123.9 (2)	C26—C27—H27	120.1
C11—C6—C7	120.2 (3)	C29—C28—C27	119.7 (3)
N1—C6—C7	115.9 (2)	C29—C28—H28	120.1
C8—C7—C6	118.6 (3)	C27—C28—H28	120.1
C8—C7—N2	126.6 (2)	C30—C29—C28	120.6 (3)
C6—C7—N2	114.8 (2)	C30—C29—H29	119.7
C9—C8—C7	120.9 (3)	C28—C29—H29	119.7
C9—C8—H8	119.5	C29—C30—C25	120.9 (3)
C7—C8—H8	119.5	C29—C30—H30	119.6
C8—C9—C10	119.9 (3)	C25—C30—H30	119.6
C8—C9—H9A	120.0	C32—C31—C36	119.1 (2)
C10—C9—H9A	120.0	C32—C31—C3	119.5 (2)
C9—C10—C11	121.1 (3)	C36—C31—C3	121.2 (3)
C9—C10—H10	119.5	C31—C32—C33	120.3 (3)
C11—C10—H10	119.5	C31—C32—H32	119.8
C10—C11—C6	119.2 (3)	C33—C32—H32	119.8
C10—C11—H11	120.4	C34—C33—C32	120.4 (3)
C6—C11—H11	120.4	C34—C33—H33	119.8
N2—C12—C13	124.1 (3)	C32—C33—H33	119.8
N2—C12—H12	118.0	C33—C34—C35	119.7 (3)
C13—C12—H12	118.0	C33—C34—H34	120.2
O2—C13—C14	110.1 (2)	C35—C34—H34	120.2
O2—C13—C12	120.1 (2)	C34—C35—C36	120.5 (3)
C14—C13—C12	129.8 (3)	C34—C35—H35	119.8
C13—C14—C15	106.7 (2)	C36—C35—H35	119.8
C13—C14—H14	126.6	C31—C36—C35	119.9 (3)
C15—C14—H14	126.6	C31—C36—H36	120.0
C16—C15—C14	106.8 (2)	C35—C36—H36	120.0
C16—C15—H15	126.6	Cl2—C37—Cl3	109.78 (16)
C14—C15—H15	126.6	Cl2—C37—Cl1	110.25 (16)
C15—C16—O2	110.1 (2)	Cl3—C37—Cl1	109.00 (16)
C15—C16—C17	129.9 (3)	Cl2—C37—H37	109.3
O2—C16—C17	120.0 (2)	Cl3—C37—H37	109.3
N3—C17—C16	123.3 (3)	Cl1—C37—H37	109.3
N3—C17—H17	118.3	Cl6—C38—Cl4	109.85 (17)
C16—C17—H17	118.3	Cl6—C38—Cl5	110.45 (18)
C23—C18—N3	126.4 (3)	Cl4—C38—Cl5	110.26 (17)
C23—C18—C19	118.3 (3)	Cl6—C38—H38	108.7
N3—C18—C19	115.3 (2)	Cl4—C38—H38	108.7
C20—C19—N4	124.0 (3)	Cl5—C38—H38	108.7

C4—S1—C1—C2	0.3 (2)	C18—N3—C17—C16	−179.5 (3)
C4—S1—C1—C24	−178.1 (2)	C15—C16—C17—N3	176.6 (3)
C24—C1—C2—C3	178.4 (3)	O2—C16—C17—N3	−3.3 (4)
S1—C1—C2—C3	0.1 (3)	C17—N3—C18—C23	−0.9 (4)
C24—C1—C2—C25	1.0 (5)	C17—N3—C18—C19	179.5 (3)
S1—C1—C2—C25	−177.3 (2)	C24—N4—C19—C20	−1.4 (5)
C1—C2—C3—C4	−0.6 (3)	C24—N4—C19—C18	179.5 (3)
C25—C2—C3—C4	176.8 (3)	C23—C18—C19—C20	−0.4 (4)
C1—C2—C3—C31	−178.7 (3)	N3—C18—C19—C20	179.2 (3)
C25—C2—C3—C31	−1.4 (4)	C23—C18—C19—N4	178.7 (3)
C2—C3—C4—C5	−172.8 (3)	N3—C18—C19—N4	−1.7 (4)
C31—C3—C4—C5	5.3 (5)	N4—C19—C20—C21	−178.8 (3)
C2—C3—C4—S1	0.8 (3)	C18—C19—C20—C21	0.2 (4)
C31—C3—C4—S1	178.9 (2)	C19—C20—C21—C22	0.2 (5)
C1—S1—C4—C3	−0.7 (2)	C20—C21—C22—C23	−0.4 (5)
C1—S1—C4—C5	173.4 (2)	C21—C22—C23—C18	0.2 (5)
C6—N1—C5—O1	1.3 (5)	N3—C18—C23—C22	−179.3 (3)
C6—N1—C5—C4	−177.0 (3)	C19—C18—C23—C22	0.2 (4)
C3—C4—C5—O1	−24.3 (4)	C19—N4—C24—O3	−0.9 (5)
S1—C4—C5—O1	162.6 (2)	C19—N4—C24—C1	178.9 (3)
C3—C4—C5—N1	154.1 (3)	C2—C1—C24—O3	24.1 (5)
S1—C4—C5—N1	−19.0 (3)	S1—C1—C24—O3	−157.8 (2)
C5—N1—C6—C11	4.6 (5)	C2—C1—C24—N4	−155.7 (3)
C5—N1—C6—C7	−175.9 (3)	S1—C1—C24—N4	22.5 (3)
C11—C6—C7—C8	−1.2 (4)	C1—C2—C25—C26	−95.4 (4)
N1—C6—C7—C8	179.3 (2)	C3—C2—C25—C26	87.5 (4)
C11—C6—C7—N2	176.6 (2)	C1—C2—C25—C30	85.3 (4)
N1—C6—C7—N2	−2.9 (4)	C3—C2—C25—C30	−91.8 (3)
C12—N2—C7—C8	5.3 (4)	C30—C25—C26—C27	0.4 (4)
C12—N2—C7—C6	−172.3 (3)	C2—C25—C26—C27	−178.9 (3)
C6—C7—C8—C9	1.5 (4)	C25—C26—C27—C28	0.3 (5)
N2—C7—C8—C9	−175.9 (3)	C26—C27—C28—C29	−0.7 (5)
C7—C8—C9—C10	0.0 (5)	C27—C28—C29—C30	0.5 (5)
C8—C9—C10—C11	−2.0 (5)	C28—C29—C30—C25	0.1 (5)
C9—C10—C11—C6	2.3 (5)	C26—C25—C30—C29	−0.6 (4)
N1—C6—C11—C10	178.7 (3)	C2—C25—C30—C29	178.8 (3)
C7—C6—C11—C10	−0.7 (4)	C4—C3—C31—C32	−110.0 (3)
C7—N2—C12—C13	177.5 (3)	C2—C3—C31—C32	67.9 (4)
C16—O2—C13—C14	0.3 (3)	C4—C3—C31—C36	73.7 (4)
C16—O2—C13—C12	−178.4 (3)	C2—C3—C31—C36	−108.4 (3)
N2—C12—C13—O2	−0.4 (5)	C36—C31—C32—C33	−1.0 (4)
N2—C12—C13—C14	−178.9 (3)	C3—C31—C32—C33	−177.4 (3)
O2—C13—C14—C15	0.1 (3)	C31—C32—C33—C34	2.0 (4)
C12—C13—C14—C15	178.7 (3)	C32—C33—C34—C35	−1.3 (4)
C13—C14—C15—C16	−0.4 (3)	C33—C34—C35—C36	−0.4 (4)
C14—C15—C16—O2	0.7 (3)	C32—C31—C36—C35	−0.6 (4)
C14—C15—C16—C17	−179.2 (3)	C3—C31—C36—C35	175.7 (3)
C13—O2—C16—C15	−0.6 (3)	C34—C35—C36—C31	1.3 (4)
C13—O2—C16—C17	179.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.90	2.13	2.622 (3)	114
N1—H1N···S1	0.90	2.48	2.970 (3)	115
N4—H4N···N3	0.90	2.13	2.620 (3)	114
N4—H4N···S1	0.90	2.53	2.986 (3)	112
C32—H32···Cl6ⁱ	0.95	2.69	3.461 (3)	139
C37—H37···O1	1.00	2.34	3.149 (3)	137
C38—H38···O3	1.00	2.46	3.205 (3)	131

Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₃₆H₂₄N₄O₃S·2CHCl₃
M_r	831.40
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	13.0957 (15), 31.854 (3), 8.7368 (9)
β (°)	98.857 (3)
V (Å³)	3601.1 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.30 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1998)
T_min, T_max	0.845, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	29858, 7802, 4582
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.108, 1.01
No. of reflections	7802
No. of parameters	469
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.29

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.90	2.13	2.622 (3)	114
N1—H1N···S1	0.90	2.48	2.970 (3)	115
N4—H4N···N3	0.90	2.13	2.620 (3)	114
N4—H4N···S1	0.90	2.53	2.986 (3)	112
C32—H32···Cl6ⁱ	0.95	2.69	3.461 (3)	139
C37—H37···O1	1.00	2.34	3.149 (3)	137
C38—H38···O3	1.00	2.46	3.205 (3)	131

Symmetry code: (i) x, y, z+1.

References

Aydogan, A., Coady, D. J., Kim, S. K., Akar, A., Bielawski, C. W., Marquez, M. & Sessler, J. L. (2008). Angew. Chem. Int. Ed. 47, 9648–9652. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1998). SMART and SAINT-Plus . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Caltagirone, C. & Gale, P. A. (2009). Chem. Soc. Rev. 38, 520–563. 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, Yu. 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, Yu. A. (2005b). Org. Lett. 7, 5277–5280. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1998). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 3| March 2010| Pages o660-o661

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

2,25-Dioxo-27,28-di­phenyl-30-oxa-29-thia-3,10,17,24-tetra­aza­penta­cyclo­[24.2.1.112,15.04,9.018,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodeca­ene chloro­form disolvate

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organic compounds

2,25-Dioxo-27,28-diphenyl-30-oxa-29-thia-3,10,17,24-tetraazapentacyclo[24.2.1.1^12,15.0^4,9.0^18,23]triaconta-5,7,9(4),10,12,14,16,18,20,22,26,28-dodecaene chloroform disolvate