Single crystal X-ray structure of 2-[({[(4-methylphenyl)sulfonyl]methyl} amino)carbonyl]-1,3-dioxo-2,3-dihydro-1hinden- 2-yl 2-thiophenecarboxylate

Article abstract of DOI:10.1134/S0022476611060072

The title compound 2-[({[(4-methylphenyl)sulfonyl]methyl}amino)carbonyl]-1, 3-dioxo-2,3-dihydro-1Hinden- 2-yl 2-thiophenecarboxylate is synthesized and studied by the single crystal X-ray diffraction method. The structure of the product is confirmed by IR, ¹H and ¹³C NMR spectroscopy, and mass spectrometry. The structure is solved in the C2/c monoclinic space group with a = 16.739(3) ?, b = 11.087(3) ?, c = 23.194(4) ?, β = 93.32(3)°, V = 4297.2(16) ?3, Z = 8, R1 = 0.033 and wR2 = 0.088. Original Russian Text Copyright

Full text of DOI:10.1134/S0022476611060072

Journal of Structural Chemistry. Vol. 52, No. 6, pp. 1085-1090, 2011
Original Russian Text Copyright © 2011 by A. Ramazani, A. R. Kazemizadeh, K. Ślepokura, and T. Lis
SINGLE CRYSTAL X-RAY STRUCTURE OF
2-[({[(4-METHYLPHENYL)SULFONYL]METHYL}
AMINO)CARBONYL]-1,3-DIOXO-2,3-DIHYDRO-1H-
INDEN-2-YL 2-THIOPHENECARBOXYLATE
1
A. Ramazani, A. R. Kazemizadeh, K. Ślepokura,
1
2
UDC 548.73:548.737
©
2
and T. Lis
The title compound 2-[({[(4-methylphenyl)sulfonyl]methyl}amino)carbonyl]-1,3-dioxo-2,3-dihydro-1H-
inden-2-yl 2-thiophenecarboxylate is synthesized and studied by the single crystal X-ray diffraction
1 13
method. The structure of the product is confirmed by IR, H and C NMR spectroscopy, and mass
spectrometry. The structure is solved in the C2/c monoclinic space group with a = 16.739(3) Å, b =
3
11.087(3) Å, c = 23.194(4) Å, β = 93.32(3)°, V = 4297.2(16) Å , Z = 8, R1 = 0.033 and wR2 = 0.088.
Keywords: Single crystal X-ray structure, α-acyloxycarboxamide, multi-component reaction, Passerini
reaction, indane-1,2,3-trione, tosylmethyl isocyanide, 2-thiophenecarboxylic acid.
INTRODUCTION
Among the known multi-component reactions, the most valuable reactions are those based on isocyanides.
Isocyanide-based multi-component reactions (abbreviated to IMCRs by Ugi and Dömling) by virtue of their synthetic
potential, inherent atom efficiency, convergent nature, ease of implementation, and the generation of molecular diversity have
attracted much attention because of the advantages they offer to the field of combinatorial chemistry [1, 2]. Today, IMCR
chemistry is mostly related to the classical reactions of Passerini and Ugi [3-6]. The Passerini reactions involve an oxo
component, an isocyanide, and a nucleophile. In connection with our recent interest to isocyanide chemistry [7-12], we report
the synthesis and structure of α-acyloxycarboxamide derived from the Passerini multi-component reaction between indane-
1,2,3-trione, tosylmethyl isocyanide, and 2-thiophenecarboxylic acid.
EXPERIMENTAL
Melting points were measured on an Electrothermal 9100 apparatus and were uncorrected. IR spectra were measured
1
13
on a Jasco FT-IR 6300 spectrometer. H and C NMR spectra were measured (CDCl3 solution) with a BRUKER DRX-250
AVANCE spectrometer at 250.0 MHz and 62.5 MHz respectively. Mass spectra were recorded on a FINNIGAN-MAT 8430
mass spectrometer operating at an ionization potential of 70 eV. Elemental analyses were performed using a Heraeus CHN-
O-Rapid analyzer. The results agreed favorably with the calculated values.
1
Research Laboratory of MCRs, Department of Chemistry, Zanjan Branch, Islamic Azad University, P O Box
2
49195-467, Zanjan, Iran; aliramazani@yahoo.com. Faculty of Chemistry, University of Wrocław, 14 Joliot-Curie St., 50-
383 Wrocław, Poland. The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 52, No. 6,
pp. 1123-1128, November-December, 2011. Original article submitted December 14, 2010.
0022-4766/11/5206-1085
1085

TABLE 1. Crystal Data and Structure Refinement Details for 4
Crystalized from
Empirical formula
Mr
n-heptane/CH2Cl2
C23H17NO7S2
483.50
F(000), e
Scan type
2000
ω and ϕ
Radiation type, λ, Å
Index ranges
MoKα, 0.71073
Crystal color, habit
Crystal dimensions, mm
Temperature, K
Crystal system
Space group
colorless, block
0.39×0.18×0.11
80(2)
–23 ≤ h ≤ 23, –15 ≤ k ≤ 11,
–32 ≤ l ≤ 32
6250
Independent reflections
Reflections with I > 2σ(I)
Rint
Monoclinic
C2/c
5039
0.035
Z
8
1.00
Completeness to θ = 30.0°
Refinement on
4.14-30.00
F 2
θ range, deg
Unit cell parameters:
Data, restraints, parameters
R (F02 > 2σ(F02))
6250, 10, 375
16.739(3), 11.087(3),
R1 = 0.033, wR2 = 0.088
a, b, c, Å; β, deg
23.194(4); 93.32(3)
4297.2(16)
1.495
R (all data)
R1 = 0.044, wR2 = 0.091
1.047
3
V, Å
Goodness-of-fit = S
–3
Weighting parameter a/b
–3
Δρ (max; min), e⋅Å
0.0546/0.3920
0.42; –0.36
Dx (calc), g⋅cm
–1
μ, mm
0.30
2
2
2
0
[w(F2 − F2 )2 ] / [w(F ) ]. Weighting scheme: w = 1/[σ2(F ) + (aP) + bP],
2
R1 = ∑||F0| – |Fc||/∑|F0|, wR2 =
∑
∑
0 c 0
where P = (F02 + 2Fc2)/3.
General procedure. To a magnetically stirred solution of indane-1,2,3-trione (1) (0.2 mmol) and 2-thiophene-
carboxylic acids (3) (0.2 mmol) in dry CH2Cl2 (5 ml) tosylmethyl isocyanide (2) (0.2 mmol) was added over 10 min at room
temperature. The mixture was stirred at room temperature for 72 h. After completion of the reaction, the solvent was removed
under reduced pressure and pure products (4) were obtained. The characterization data of the compound are given below.
2-[({[(4-Methylphenyl)sulfonyl]methyl}amino)carbonyl]-1,3-dioxo-2,3-dihydro-1H-inden-2-yl
–1
2-thiophene-
–1 –1
carboxylate (4): Light yellow powder, yield 90%, M.p. 207-209°C. IR (KBr): v = 3433 cm , 3106 cm , 3020 cm ,
–1
2952 cm , 1730 cm , 1689 cm , 1598 cm , 1517 cm , 1280 cm . HNMR (CDCl3, 250 MHz): δ = 2.40 (s, 3H, CH3); 4.69
–1
–1
–1
–1
–1 1
3
13
(d, 2H, J = 6.75 Hz, NCH2); 6.64 (br, 1H, NH); 7.12–8.08 (m, 11H, arom CH). CNMR (CDCl3, 62.5 MHz): δ = 21.74
(CH3); 59.76 (NCH2); 83.62 (C–O); 124.20, 128.62, 128.91, 129.19, 130.26, 132.80, 135.27, 136.18, 136.28, 141.07, 145.64
(aromatic carbons); 158.93 (CO of ester); 162.03 (CO of amide); 189.74 (CO of ketone). MS (70 eV) m/z (%): 299 ([M–
+
NHR] , 43), 111 ([C4H3SCO] , 100), 91 ([C6H4CH3] , 9), 76 (7). — C23H17NO7S2 (483.52): C 57.13, H 3.54, N 2.90; found C
+
+
57.02, H 3.59, N 2.95.
Crystals of 4 for the X-ray analysis were obtained by very slow evaporation of a 5:2 CH2Cl2/n — heptane solution
(20-25°C) in 48 h. Light yellow single crystals were filtered off, washed with the cold solvent mixture, and dried at room
temperature.
X-Ray Crystal Structure Determination of 4 (Table 1 and Fig. 1)*. The crystallographic measurement was
performed on a κ-geometry Xcalibur PX automated four-circle diffractometer with graphite-monochromatized MoKα
radiation (λ = 0.71073 Å). The crystal data were collected at 80(2) K using the Oxford-Cryosystems cooler. The data were
corrected for Lorentz and polarization effects. Data collection, cell refinement, and data reduction and analysis were carried
out with the Xcalibur PX software (Oxford Diffraction, Poland): CrysAlis CCD and CrysAlis RED respectively [13].
*CCDC-732237 contains the supplementary crystallographic data for 4. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/data_request/cif.
1086

Fig. 1. Molecular structure of compound 4, showing the
X-ray atom numbering scheme and intramolecular N–
H⋯O close contact forming S(5) motif (dashed line).
Displacement ellipsoids represent the 40% probability
level. For clarity only one orientation, with high s.o.f.
[0.712(2)] of the disordered thiophene ring is shown.
The structure was solved by direct methods with the SHELXS-97 program [14], and refined by a fullmatrix least-squares
technique with SHELXL-97 [14] and anisotropic thermal parameters for all ordered or fully occupied non-H-atoms. The
thiophene ring is slightly disordered over two positions with two different orientations of the S(2) atom relative to the
carbonyl O(7) atom: syn with a site-occupation-factor (s.o.f.) of 0.712(2) and anti with s.o.f. = 0.288(2). Two positions of the
C(20) atom were refined with the same fractional coordinates and anisotropic displacement parameters (constrains were
applied with EXYZ and EADP instructions). The remaining low-occupied positions of thiophene carbon atoms (C(210)–
2
C(230)) were refined isotropically with Uiso for the C(210) atom fixed at 0.05 Å . In the refinement procedure, some
geometrical parameters of the two positions of the disordered thiophene ring (equivalent bond distances and angles) were
restrained to be equal with the use of SAME instruction. All fully-occupied H atoms were found in difference Fourier maps
and refined isotropically. Those from the thiophene ring were included from geometry and refined as rigid atoms with C–H
distances of 0.95 Å and Uiso(H) values of 1.2Ueq(C). All figures were made with the XP program [15].
RESULTS AND DISCUSSION
Indane-1,2,3-trione (1), tosylmethyl isocyanide (2), and 2-thiophenecarboxylic acid (3) in dichloromethane react
together in a 1:1:1 ratio at room temperature to produce an α-acyloxycarboxamide derivative (4) (Scheme 1). The structure of
1 13
the product was deduced from its IR, H NMR, C NMR, mass spectrometry, and elemental analysis.
Scheme 1
1087

TABLE 2. Selected Interatomic Distances (Å), Bond Angles (deg) and Torsion Angles (deg) of 4
Bond lengths
S(1)–O(5)
S(1)–O(6)
S(1)–C(11)
S(1)–C(12)
1.4438(10)
1.4447(10)
1.806(2)
S(2)–C(20)
S(2)–C(23)
N(1)–C(10)
N(1)–C(11)
1.682(2)
1.711(3)
1.346(2)
1.435(2)
1.754(2)
Bond angles
O(5)–S(1)–O(6)
O(5)–S(1)–C(11)
O(6)–S(1)–C(11)
O(5)–S(1)–C(12)
119.45(6)
106.73(6)
106.95(6)
110.51(6)
O(6)–S(1)–C(12)
C(12)–S(1)–C(11)
C(20)–S(2)–C(23)
C(10)–N(1)–C(11)
108.67(6)
103.23(6)
91.96(9)
121.60(10)
Torsion angles
C(11)–N(1)–C(10)–C(2)
O(5)–S(1)–C(11)–N(1)
O(6)–S(1)–C(11)–N(1)
C(12)–S(1)–C(11)–N(1)
O(5)–S(1)–C(12)–C(18)
O(6)–S(1)–C(12)–C(18)
C(11)–S(1)–C(12)–C(18)
C(19)–O(2)–C(2)–C(1)
C(19)–O(2)–C(2)–C(10)
C(2)–O(2)–C(19)–O(7)
C(2)–O(2)–C(19)–C(20)
170.43(8)
41.50(10)
–73.05(9)
33.6(1)
–175.4(1)
100.9(1)
37.7(2)
–83.4(2)
–17.6(1)
13.3(2)
172.9(1)
47.8(2)
2.2(2)
C(10)–N(1)–C(11)–S(1)
O(1)–C(1)–C(2)–O(2)
O(1)–C(1)–C(2)–C(10)
C(9)–C(1)–C(2)–C(3)
C(2)–C(1)–C(9)–C(4)
O(2)–C(2)–C(10)–(4)
C(3)–C(2)–C(10)–O(4)
S(2)–C(20)–C(19)–O(7)
166.47(9)
–80.2(1)
56.9(2)
176.65(9)
–0.9(2)
179.05(9)
Crystal structure of 4. A summary of the conditions for the data collection and the structure refinement parameters
are given in Table 1. The values of bond lengths and valence angles (Table 2) correspond well with those typical of the
respective types of chemical connections [16]. The molecular structure of the compound reveals three planar regions (Fig. 1).
These are: plane 1 extending from the thiophene ring to the methylene C(11) atom (with a r.m.s. of fitted atoms = 0.112 Å),
plane 2 defined by the 1,3-dioxo-2,3-dihydro-1H-indenyl moiety (r.m.s. = 0.112 Å), and plane 3 formed by the S(1) atom and
the toluene part from the (4-methylphenyl)sulfonyl group (r.m.s. = 0.069 Å). The thiophene ring is slightly disordered over
two positions with two different orientations of the S(2) atom relative to the carbonyl O(7) atom. Site occupation factors
determined for the two orientations reveal that over 70% of the molecules in the crystal of compound 4 exist in syn
conformation (with the S(2)–C(20)–C(19)–O(7) torsion angle of 2.2(2)°), which is shown in Fig. 1. The analogous S(20)–
C(200)–C(19)–O(7) torsion angle is –176.8(3)°.
The planar amide moiety [N(1)–C(10) bond of 1.346(2) Å] is in trans conformation, which is reflected in the value
of the C(11)–N(1)–C(10)–C(2) torsion angle of –175.4(1)°. It is possible that the mutual orientation of these two planar
regions of the molecule, i.e. 2-thiophenecarboxylate and the amide moieties, is stabilized by the intramolecular N(1)–
H(1)⋯O(2) hydrogen bond (Fig. 1, Table 3) forming the S(5) motif and resulting in the planarity of this part of the molecule.
The discussed plane 1 is almost perpendicular to plane 2 (1,3-dioxo-2,3-dihydro-1H-indenyl group), with the dihedral angle
between planes 1 and 2 amounting to 88.3(1)°. At the same time, plane 1 is twisted at 25.9(1)° relative to plane 3.
The only hydrogen contact formed by the N(1) atom is the intramolecular N(1)–H(1)⋯O(2) hydrogen bond
stabilizing the overall structure of compound 4 (Fig. 1). Apart from that, there are no more donors of classic hydrogen bonds
present in the molecule of the compound, and thus, no such intermolecular interactions are possible. Instead, the crystal
structure of 4 is stabilized by a three-dimensional network of weak intermolecular C–H⋯O contacts, in which most of the
oxygen atoms act as acceptors (only the O(5) atom is not involved; Table 3). Among them two centrosymmetric hydrogen
ii
bonds formed by the methylene C(11) group may be of importance for the crystal structure of 4. Both C(11)–H(11A)⋯O(3)
1088

Fig. 2. Arrangement of 4 within the three-dimensional network of weak
C–H⋯O/π interactions. Intra- and intermolecular contacts are shown
with dashed lines. Symmetry codes are given in Table 3.
Fig. 3. Two molecules of 4 related by a centre of inversion, linked by
the C–H⋯O interactions (dashed lines) forming the R22 (14) ring
motif. Symmetry codes are given in Table 3.
iii
and C(11)–H(11B)⋯O(6) interactions, involving two adjacent molecules related by a centre of inversion, give rise to ring
motifs: R22 (8) (shown in Fig. 2) and R22 (14) (Fig. 3) respectively. As shown in Fig. 2, the adjacent molecules related by the
action of 21 screw axes and a direct translation are joined to each other by the extensive network of weaker C–H⋯O as well
as C–H⋯π contacts (Table 3). In this way, the respective dimers are linked into a three-dimensional network, the fragment of
which is shown in Fig. 2. Additionally, some close O⋯π (ring) contacts are observed in the crystal of 4. The engaged oxygen
atoms are O(4), O(5), and O(7); the O⋯Cg (π-thiophene/toluene ring) distances range from 3.504(2) Å to 3.716(2) Å;
C/S⋯Cg (π-ring) distances range from 3.910(2) Å to 4.288(2) Å, and C/S=O⋯Cg (π-ring) angles are in the 98.7(1)-
120.3(1)° range.
1089

TABLE 3. Geometry of Proposed N/C–H⋯O/π Close Contacts for 4
D–H⋯A
D–H, Å
H⋯A, Å
D⋯A, Å
D–H⋯A, deg
Offset, Å
N(1)–H(1)⋯O(2)
0.87(2)
0.94(2)
0.97(2)
0.93(2)
0.97(2)
0.98(2)
0.95
2.16(2)
2.43(2)
2.51(2)
2.32(2)
2.67(2)
2.56(2)
2.47
2.576(2)
3.214(2)
3.437(2)
3.169(2)
3.459(2)
3.096(2)
3.210(3)
3.276(4)
3.704(3)
109(2)
140(2)
160(2)
151(2)
139(2)
114(1)
135
—
—
i
C(7)–H(7)⋯O(1)
ii
C(11)–H(11A)⋯O(3)
—
iii
i
C(11)–H(11B)⋯O(6)
—
C(16)–H(16C)⋯O(7)
—
iv
C(18)–H(18)⋯O(3)
—
v
C(23)–H(23)⋯O(4)
—
v
C(230)–H(230)⋯O(4)
0.95
2.61
128
—
v
C(23)–H(23)⋯Cg(1)
0.95
2.96
136
0.34
Symmetry codes: (i) –x+1/2, y+1/2, –z+3/2; (ii) –x+1/2, –y+3/2, –z+1; (iii) –x+1, –y+1, –z+1; (iv) x+1/2, y+1/2, z;
(v) x, y–1, z. Cg(1) is the centroid of the C(4)–C(9) phenylene ring.
The authors are thankful to the Zanjan Branch, Islamic Azad University for the partial support of this work.
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1090