supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

bi2231 scheme

Acta Cryst. (2007). E63, o3976    [ doi:10.1107/S1600536807041931 ]

2-Bromo-3-ethoxy-3-[4-(methylsulfanyl)phenyl]-1-[3-(p-tolyl)-4-sydnonyl]propan-1-one

S. J. Prathap, S. R. Nooji, B. Kalluraya and T. N. G. Row

Abstract top

In the title compound, C21H21BrN2O4S, the carbonyl group of the central propan-1-one unit is twisted by 14.7 (4)° from the plane of the cyclic sydnone group (C2N2O2) to which it is attached, and an intramolecular C-H...O contact is formed to the exocyclic O atom of the sydnone group. Intermolecular C-H...O, C-H...S and C-H...[pi] contacts are observed.

Comment top

Sydnones are products of dehydration of N-nitroso-alpha-amino acids (Earl & Mackney, 1935). Although less toxic (Pillai et al., 1993) than the latter, they remain potent porphyrinogenic (Sutherland et al., 1986) and anti-inflammatory (Satyanarayana & Rao, 1995) compounds. They are also known to scavenge free radicals (Narla & Rao, 1995).

The molecular conformation of the title compound is influenced by π conjugation through the C2—C3 bond and an intramolecular C—H···O hydogen bond, resulting in near coplanarity of the atoms H4, C4, C3, C2, C1 and O2 (torsion angle C4/C3/C2/C1 = −14.7 (4)°) (Fig. 1). The crystal structure exhibits C—H···O intermolecular contacts which define dimeric units (Fig. 2 and Table 1). C—H···S contacts exist between adjacent dimers along the b-axis (Fig. 2 and Table 1). Intermolecular C—H···π contacts are also observed.

Related literature top

For related structures see: Abdul Ajees et al. (2002); Balamurugan et al. (2006); Thamotharan et al. (2003). For general literature related to sydnones, see: Earl & Mackney (1935); Narla & Rao (1995); Pillai et al. (1993); Satyanarayana & Rao (1995); Sutherland et al. (1986).

Experimental top

2,3-Dibromo-1-(3-p-tolylsydnon-4-yl)-3-p-thiomethylphenyl-propan-1-one (0.01 mol) was dissolved in ethanol by heating and triethylamine (0.05 mol) in ethanol was added. The clear solution was stirred for 24 h then filtered. The filtrate was left to stand for a few days, then the solid was collected by filtration and recrystallized from ethanol to yield the title compound.

Refinement top

H atoms were placed geometrically and refined using a riding model with C—H = 0.93–0.98 Å and with Uiso(H) = 1.2 or 1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1999) and CAMERON (Pearce & Watkin, 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound showing displacement ellipsoids at 50% probability for non-H atoms. The dashed line indicates an intramolecular C—H···O contact.
[Figure 2] Fig. 2. Packing diagram viewed down the b axis. The dotted lines indicate intermolecular contacts.
2-Bromo-3-ethoxy-3-[4-(methylsulfanyl)phenyl]-1-[3-(p-tolyl)-4-\ sydnonyl]propan-1-one top
Crystal data top
C21H21BrN2O4SF000 = 1952
Mr = 477.37Dx = 1.444 Mg m−3
Monoclinic, C2/cMelting point: 398-400 K
Hall symbol: -C 2ycMo Kα radiation
λ = 0.71073 Å
a = 24.420 (3) ÅCell parameters from 1152 reflections
b = 12.3883 (13) Åθ = 2.1–25.5º
c = 18.3113 (19) ŵ = 2.00 mm−1
β = 127.564 (1)ºT = 292 (2) K
V = 4391.1 (8) Å3Block, yellow
Z = 80.37 × 0.19 × 0.14 mm
Data collection top
Bruker SMART CCD
diffractometer		4028 independent reflections
Radiation source: fine-focus sealed tube2844 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 292(2) Kθmax = 25.5º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −29→29
Tmin = 0.526, Tmax = 0.760k = −14→14
21297 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.110  w = 1/[σ2(Fo2) + (0.0686P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
4028 reflectionsΔρmax = 0.61 e Å−3
265 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C21H21BrN2O4SV = 4391.1 (8) Å3
Mr = 477.37Z = 8
Monoclinic, C2/cMo Kα
a = 24.420 (3) ŵ = 2.00 mm−1
b = 12.3883 (13) ÅT = 292 (2) K
c = 18.3113 (19) Å0.37 × 0.19 × 0.14 mm
β = 127.564 (1)º
Data collection top
Bruker SMART CCD
diffractometer		4028 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2844 reflections with I > 2σ(I)
Tmin = 0.526, Tmax = 0.760Rint = 0.030
21297 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040265 parameters
wR(F2) = 0.110H-atom parameters constrained
S = 1.00Δρmax = 0.61 e Å−3
4028 reflectionsΔρmin = −0.20 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
Br10.129744 (17)0.37658 (3)0.35683 (2)0.08060 (16)
S10.40477 (5)0.71008 (7)0.60362 (7)0.0927 (3)
O1−0.08313 (11)0.4536 (2)0.36798 (17)0.0953 (7)
O20.01082 (12)0.55252 (19)0.41210 (17)0.0961 (7)
O30.09233 (9)0.22010 (15)0.46713 (14)0.0724 (5)
O40.18750 (9)0.39308 (14)0.61802 (13)0.0624 (5)
N1−0.10169 (14)0.3481 (3)0.3577 (2)0.0883 (8)
N2−0.04712 (11)0.2940 (2)0.38361 (14)0.0647 (6)
C1−0.01380 (16)0.4642 (3)0.4000 (2)0.0758 (8)
C20.00835 (13)0.3559 (2)0.40954 (18)0.0578 (6)
C30.07635 (13)0.3141 (2)0.44795 (17)0.0563 (6)
C40.12791 (13)0.39690 (19)0.46110 (18)0.0559 (6)
H40.11120.46970.45860.067*
C50.19940 (13)0.38213 (19)0.55155 (18)0.0548 (6)
H50.21620.30920.55460.066*
C60.24287 (16)0.3559 (3)0.7073 (2)0.0831 (9)
H6A0.28610.38600.72510.100*
H6B0.24590.27790.70700.100*
C70.23095 (19)0.3895 (3)0.7747 (2)0.1050 (13)
H7A0.26430.35510.83290.158*
H7B0.18530.36860.75230.158*
H7C0.23560.46640.78240.158*
C80.25044 (12)0.46434 (19)0.56521 (16)0.0515 (6)
C90.24604 (13)0.5709 (2)0.58355 (18)0.0573 (6)
H90.21190.59090.58880.069*
C100.29095 (13)0.6482 (2)0.59430 (18)0.0586 (7)
H100.28620.71970.60510.070*
C110.34295 (14)0.6192 (2)0.58894 (18)0.0586 (7)
C120.34768 (14)0.5135 (2)0.57035 (19)0.0658 (7)
H120.38210.49330.56560.079*
C130.30206 (13)0.4374 (2)0.55881 (18)0.0620 (7)
H130.30610.36620.54640.074*
C140.39791 (19)0.8274 (3)0.6521 (2)0.0859 (9)
H14A0.43050.88030.66180.129*
H14B0.40760.80970.71000.129*
H14C0.35190.85600.61100.129*
C15−0.05548 (12)0.1771 (2)0.37652 (17)0.0617 (7)
C16−0.07699 (15)0.1260 (3)0.4219 (2)0.0737 (9)
H16−0.08480.16490.45820.088*
C17−0.08666 (15)0.0150 (3)0.4120 (2)0.0773 (8)
H17−0.1015−0.02030.44190.093*
C18−0.07508 (14)−0.0435 (3)0.35973 (18)0.0717 (8)
C19−0.05431 (16)0.0108 (3)0.31505 (19)0.0750 (8)
H19−0.0466−0.02810.27860.090*
C20−0.04448 (16)0.1203 (2)0.3223 (2)0.0725 (8)
H20−0.03060.15540.29110.087*
C21−0.0857 (2)−0.1642 (3)0.3507 (2)0.0961 (11)
H21A−0.0941−0.18890.39280.144*
H21B−0.1246−0.18180.28880.144*
H21C−0.0451−0.19890.36480.144*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0936 (3)0.0849 (3)0.0608 (2)−0.01660 (16)0.04580 (19)−0.00885 (15)
S10.1017 (6)0.0901 (6)0.1243 (7)−0.0290 (5)0.0884 (6)−0.0232 (5)
O10.0724 (14)0.0963 (18)0.1152 (18)0.0283 (13)0.0562 (14)0.0039 (14)
O20.0999 (16)0.0629 (15)0.129 (2)0.0177 (13)0.0712 (16)0.0076 (13)
O30.0580 (11)0.0553 (12)0.0945 (14)0.0018 (9)0.0417 (11)0.0058 (10)
O40.0515 (10)0.0764 (13)0.0553 (11)0.0026 (8)0.0304 (9)0.0046 (9)
N10.0588 (15)0.101 (2)0.099 (2)0.0147 (15)0.0451 (15)−0.0009 (17)
N20.0478 (13)0.0880 (18)0.0532 (13)0.0064 (12)0.0281 (11)−0.0032 (12)
C10.070 (2)0.078 (2)0.078 (2)0.0163 (17)0.0443 (17)0.0027 (17)
C20.0508 (15)0.0632 (17)0.0536 (15)0.0035 (12)0.0289 (13)−0.0003 (12)
C30.0546 (15)0.0545 (17)0.0545 (15)0.0007 (12)0.0306 (13)−0.0016 (12)
C40.0561 (15)0.0491 (15)0.0582 (15)0.0006 (11)0.0327 (13)−0.0013 (11)
C50.0538 (15)0.0507 (15)0.0573 (15)0.0045 (11)0.0325 (13)−0.0017 (11)
C60.0639 (18)0.108 (3)0.0596 (18)0.0037 (16)0.0282 (16)0.0175 (17)
C70.087 (2)0.159 (4)0.065 (2)−0.014 (2)0.044 (2)0.009 (2)
C80.0480 (13)0.0513 (15)0.0514 (14)0.0019 (11)0.0284 (12)−0.0024 (11)
C90.0535 (14)0.0597 (16)0.0645 (16)0.0020 (13)0.0389 (13)−0.0087 (13)
C100.0617 (16)0.0524 (15)0.0620 (16)−0.0011 (12)0.0378 (14)−0.0082 (12)
C110.0612 (16)0.0628 (17)0.0561 (16)−0.0041 (13)0.0380 (14)−0.0048 (13)
C120.0649 (17)0.0696 (19)0.0795 (19)0.0005 (14)0.0525 (16)−0.0103 (15)
C130.0637 (16)0.0539 (16)0.0721 (18)0.0046 (13)0.0434 (15)−0.0078 (13)
C140.100 (2)0.0644 (19)0.093 (2)−0.0192 (18)0.058 (2)−0.0040 (17)
C150.0443 (14)0.081 (2)0.0505 (15)−0.0072 (13)0.0240 (13)−0.0074 (14)
C160.0562 (16)0.115 (3)0.0531 (16)0.0031 (16)0.0348 (14)0.0014 (16)
C170.0709 (18)0.097 (3)0.0656 (18)−0.0126 (17)0.0423 (16)0.0062 (17)
C180.0614 (16)0.095 (2)0.0432 (15)−0.0177 (15)0.0239 (13)−0.0043 (15)
C190.085 (2)0.083 (2)0.0588 (17)−0.0221 (17)0.0447 (16)−0.0167 (15)
C200.0765 (19)0.090 (2)0.0631 (18)−0.0193 (16)0.0487 (16)−0.0108 (15)
C210.104 (3)0.092 (2)0.073 (2)−0.032 (2)0.044 (2)−0.0061 (19)
Geometric parameters (Å, °) top
Br1—C41.953 (3)C9—C101.377 (4)
S1—C141.764 (3)C9—H90.930
S1—C111.767 (3)C10—C111.380 (4)
O1—N11.359 (4)C10—H100.930
O1—C11.420 (4)C11—C121.376 (3)
O2—C11.202 (4)C12—C131.374 (4)
O3—C31.210 (3)C12—H120.930
O4—C51.420 (3)C13—H130.930
O4—C61.421 (3)C14—H14A0.960
N1—N21.296 (3)C14—H14B0.960
C1—C21.417 (4)C14—H14C0.960
C2—N21.366 (3)C15—C201.370 (4)
C2—C31.448 (4)C15—C161.377 (4)
C3—C41.525 (3)C15—N21.457 (4)
C4—C51.516 (4)C16—C171.388 (4)
C4—H40.980C16—H160.930
C5—C81.508 (3)C17—C181.360 (4)
C5—H50.980C17—H170.930
C6—C71.489 (5)C18—C191.373 (4)
C6—H6A0.970C18—C211.510 (5)
C6—H6B0.970C19—C201.371 (4)
C7—H7A0.960C19—H190.930
C7—H7B0.960C20—H200.930
C7—H7C0.960C21—H21A0.960
C8—C131.376 (3)C21—H21B0.960
C8—C91.382 (3)C21—H21C0.960
C14—S1—C11105.46 (14)C10—C9—H9119.1
N1—O1—C1111.0 (2)C8—C9—H9119.1
C5—O4—C6114.0 (2)C9—C10—C11119.8 (2)
N2—N1—O1105.4 (2)C9—C10—H10120.1
N1—N2—C2114.6 (3)C11—C10—H10120.1
N1—N2—C15115.1 (2)C12—C11—C10119.0 (2)
C2—N2—C15130.2 (2)C12—C11—S1116.8 (2)
O2—C1—C2136.8 (3)C10—C11—S1124.2 (2)
O2—C1—O1119.8 (3)C13—C12—C11120.6 (2)
C2—C1—O1103.5 (3)C13—C12—H12119.7
N2—C2—C1105.4 (2)C11—C12—H12119.7
N2—C2—C3124.6 (2)C12—C13—C8121.3 (2)
C1—C2—C3129.6 (3)C12—C13—H13119.4
O3—C3—C2123.8 (2)C8—C13—H13119.4
O3—C3—C4120.8 (2)S1—C14—H14A109.5
C2—C3—C4115.3 (2)S1—C14—H14B109.5
C5—C4—C3112.4 (2)S1—C14—H14C109.5
C5—C4—Br1110.79 (17)H14A—C14—H14B109.5
C3—C4—Br1105.53 (17)H14A—C14—H14C109.5
C5—C4—H4109.3H14B—C14—H14C109.5
C3—C4—H4109.3C20—C15—C16121.1 (3)
Br1—C4—H4109.3C20—C15—N2119.8 (3)
O4—C5—C8112.0 (2)C16—C15—N2119.1 (3)
O4—C5—C4102.9 (2)C15—C16—C17118.2 (3)
C8—C5—C4112.6 (2)C15—C16—H16120.9
O4—C5—H5109.7C17—C16—H16120.9
C8—C5—H5109.7C18—C17—C16121.9 (3)
C4—C5—H5109.7C18—C17—H17119.1
O4—C6—C7109.5 (3)C16—C17—H17119.1
O4—C6—H6A109.8C17—C18—C19118.0 (3)
C7—C6—H6A109.8C17—C18—C21120.6 (3)
O4—C6—H6B109.8C19—C18—C21121.4 (3)
C7—C6—H6B109.8C20—C19—C18122.2 (3)
H6A—C6—H6B108.2C20—C19—H19118.9
C6—C7—H7A109.5C18—C19—H19118.9
C6—C7—H7B109.5C15—C20—C19118.6 (3)
H7A—C7—H7B109.5C15—C20—H20120.7
C6—C7—H7C109.5C19—C20—H20120.7
H7A—C7—H7C109.5C18—C21—H21A109.5
H7B—C7—H7C109.5C18—C21—H21C109.5
C13—C8—C9117.6 (2)H21A—C21—H21C109.5
C13—C8—C5122.0 (2)C18—C21—H21B109.5
C9—C8—C5120.4 (2)H21A—C21—H21B109.5
C10—C9—C8121.7 (2)H21C—C21—H21B109.5
C1—O1—N1—N21.5 (3)C9—C10—C11—C121.8 (4)
N1—O1—C1—O2179.3 (3)C9—C10—C11—S1−178.8 (2)
N1—O1—C1—C2−0.9 (3)C14—S1—C11—C12−166.6 (2)
O2—C1—C2—N2179.7 (4)C14—S1—C11—C1013.9 (3)
O1—C1—C2—N20.0 (3)C10—C11—C12—C13−1.1 (4)
O2—C1—C2—C36.3 (6)S1—C11—C12—C13179.4 (2)
O1—C1—C2—C3−173.5 (3)C11—C12—C13—C80.2 (4)
N2—C2—C3—O3−5.5 (4)C9—C8—C13—C120.1 (4)
C1—C2—C3—O3166.9 (3)C5—C8—C13—C12179.2 (2)
N2—C2—C3—C4173.0 (2)C20—C15—C16—C170.6 (4)
C1—C2—C3—C4−14.7 (4)N2—C15—C16—C17178.1 (2)
O3—C3—C4—C5−42.9 (3)C15—C16—C17—C180.4 (4)
C2—C3—C4—C5138.6 (2)C16—C17—C18—C19−1.0 (5)
O3—C3—C4—Br177.9 (3)C16—C17—C18—C21179.6 (3)
C2—C3—C4—Br1−100.6 (2)C17—C18—C19—C200.6 (5)
C6—O4—C5—C8−73.9 (3)C21—C18—C19—C20180.0 (3)
C6—O4—C5—C4164.9 (2)C16—C15—C20—C19−1.0 (4)
C3—C4—C5—O4−58.8 (2)N2—C15—C20—C19−178.4 (3)
Br1—C4—C5—O4−176.61 (14)C18—C19—C20—C150.4 (5)
C3—C4—C5—C8−179.6 (2)O1—N1—N2—C2−1.5 (3)
Br1—C4—C5—C862.6 (2)O1—N1—N2—C15−178.8 (2)
C5—O4—C6—C7169.5 (2)C1—C2—N2—N11.0 (3)
O4—C5—C8—C13136.9 (2)C3—C2—N2—N1174.8 (3)
C4—C5—C8—C13−107.6 (3)C1—C2—N2—C15177.7 (3)
O4—C5—C8—C9−43.9 (3)C3—C2—N2—C15−8.4 (4)
C4—C5—C8—C971.5 (3)C20—C15—N2—N1120.7 (3)
C13—C8—C9—C100.6 (4)C16—C15—N2—N1−56.8 (3)
C5—C8—C9—C10−178.5 (2)C20—C15—N2—C2−56.1 (4)
C8—C9—C10—C11−1.6 (4)C16—C15—N2—C2126.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O20.982.293.093 (4)139
C6—H6A···Cgi0.972.963.830150
C16—H16···S1ii0.932.883.763 (4)159
C21—H21A···O3iii0.962.573.506 (4)165
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, y−1/2, z; (iii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O20.982.293.093 (4)139
C6—H6A···Cgi0.972.963.830150
C16—H16···S1ii0.932.883.763 (4)159
C21—H21A···O3iii0.962.573.506 (4)165
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x−1/2, y−1/2, z; (iii) −x, −y, −z+1.
Acknowledgements top

We thank the Department of Science and Technology, India, for use of the CCD facility under the IRHPA-DST program at IISc.

references
References top

Abdul Ajees, A., Karthikeyan, S., Yelamaggad, C. V. & Badami, B. V. (2002). Acta Cryst. E58, o784–o786.

Balamurugan, S., Thiruvalluvar, A. & Kalluraya, B. (2006). Acta Cryst. E62, o1126–o1128.

Bruker (2004). SMART (Version 5.628) and SAINT (Version 6.45a). Bruker AXS Inc., Madison, Wisconsin, USA.

Earl, J. C. & Mackney, A. W. (1935). J. Chem. Soc. pp. 899–903.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Narla, R. S. & Rao, M. N. (1995). J. Pharm. Pharmacol. 47, 623–625.

Pearce, L. J. & Watkin, D. J. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Pillai, H. G., Safak, C. & Abbasoglu, U. (1993). Arch. Pharm. (Weinheim), 326, 559–561.

Satyanarayana, K. & Rao, M. N. (1995). J. Pharm. Sci. 84, 263–266.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Sutherland, E. P., Marks, G. S., Grab, L. A. & Ortiz de Montellano, P. R. (1986). FEBS Lett. 197, 17–20.

Thamotharan, S., Parthasarathi, V., Sanyal, R., Badami, B. & Linden, A. (2003). Acta Cryst. E59, o894–o896.