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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o909.
Published online 2010 March 24. doi:  10.1107/S1600536810010019
PMCID: PMC2983812

5′-Amino-1,3-dioxo-2′,3′-di­hydro-7′H-spiro­[indane-2,7′-thieno[3,2-b]pyran]-6′-carbonitrile 1′,1′-dioxide

Abstract

The title compound, C16H10N2O5S, was synthesized via the condesation of dihydro­thio­phen-3(2H)-one 1,1-dioxide, 1H-indene-1,2,3-trione and malononitrile in ethanol. The 2,3-dihydro­thio­phene 1,1-dioxide and pyran rings adopt envelope conformations. The mean planes through the planar part of the pyran ring and the benzene ring are nearly perpendicular, forming a dihedral angle of 88.40 (7)°. The crystal packing is stabilized by inter­molecular N—H(...)O and N—H(...)N hydrogen bonds with the sulfone O atom and the cyano N atom acting as acceptors.

Related literature

For the uses of thienopyranyl compounds such as thieno[3,2-b]pyran derivatives as anti­viral agents and α-2C adreno­receptor agonists, see: Chao et al. (2009 [triangle]); Friary et al. (1991 [triangle]). For puckering parameters, see: Cremer & Pople (1975 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o909-scheme1.jpg

Experimental

Crystal data

  • C16H10N2O5S
  • M r = 342.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o909-efi1.jpg
  • a = 9.436 (3) Å
  • b = 10.602 (3) Å
  • c = 14.777 (4) Å
  • β = 99.137 (4)°
  • V = 1459.6 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.25 mm−1
  • T = 116 K
  • 0.28 × 0.20 × 0.18 mm

Data collection

  • Rigaku Saturn CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 [triangle]) T min = 0.933, T max = 0.956
  • 9619 measured reflections
  • 2549 independent reflections
  • 1985 reflections with I > 2σ(I)
  • R int = 0.068

Refinement

  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.127
  • S = 1.00
  • 2549 reflections
  • 226 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.64 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2002 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010019/hg2656sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010019/hg2656Isup2.hkl

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

Acknowledgments

The authors acknowledge the financial support of the Natural Science Foundation of Gansu Province (No. 0916RJZA0500).

supplementary crystallographic information

Comment

Thienopyranyl compounds, such as thieno [3,2-b]pyran derivatives, can be used as antiviral agents (Friary et al., 1991) and α-2 C adrenoreceptor agonists ( Chao et al., 2009). This led us to pay attention to the synthesis and bioactivity of these compounds. During the synthesis of thieno[3,2-b]pyran derivatives, the title compound, (I) was isolated and its structure was determined by X-ray diffraction. Here we report its crystal structure.

The molecular structure of (I) is shown in Fig. 1. In the molecular structure, the thiophene ring is in envelope conformation, for the deviation of C1 from the C2/C3/C4/S1 plane is 0.364 (3)Å with r.m.s. of 0.0056.

The pyran ring adopts an envelope conformation with atome C5 deviating from the C3/C4/C6/C7/O5 plane 0.228 (3) Å. According to Cremer & Pople analysis (Cremer & Pople, 1975), the puckering amplitude (Q) is 0.168 (2) Å. Its θ and [var phi] are 103.2 (7) and 349.6 (7)°, respectively. The weighted planes of the pyran and phenyl rings are nearly perpendicular, with the dihedral angle between them 88.40 (7)°. The five membered ring of 1H-indene-1,3(2H)-dione fragment adopts an envelope conformation, for the deviation of C5 from the C9/C10/C15/C16 plane is 0.149 (3)Å with r.m.s. of 0.0033. The crystal packing is stabilized by intermolecular hydrogen bonds: N1—H1C···N2, N1—H1D···O2(Fig.2 & Table 1).

Experimental

The title compound was synthesized by the reaction of dihydrothiophen-3(2H)-one-1,1-dioxide (1 mmol), 1H-indene-1,2,3-trione (1 mmol) and malononitrile (1 mmol) in 10 ml ethanol under reluxing until completion (monitored by TLC). Cooling the reaction mixture slowly gave single crystals suitable for X-ray diffraction.

Refinement

The hydrogen atoms bonded to the nitrogen atom were positioned from a Fourier difference map. The N—H bond lengths were restrained to 0.90Å with an estimated standard deviation 0.01. The distance between H1C and H1D was restrained to 1.50Å with an estimated standard deviation 0.01. Other H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(parent atom).

Figures

Fig. 1.
The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The packing diagram of (I). Intermolecular hydrogen bonds are shown as dashed lines.

Crystal data

C16H10N2O5SF(000) = 704
Mr = 342.32Dx = 1.558 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5046 reflections
a = 9.436 (3) Åθ = 1.4–27.9°
b = 10.602 (3) ŵ = 0.25 mm1
c = 14.777 (4) ÅT = 116 K
β = 99.137 (4)°Prism, colorless
V = 1459.6 (6) Å30.28 × 0.20 × 0.18 mm
Z = 4

Data collection

Rigaku Saturn CCD area-detector diffractometer2549 independent reflections
Radiation source: rotating anode1985 reflections with I > 2σ(I)
multilayerRint = 0.068
Detector resolution: 14.63 pixels mm-1θmax = 25.0°, θmin = 2.2°
ω and [var phi] scansh = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)k = −12→12
Tmin = 0.933, Tmax = 0.956l = −17→11
9619 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.127w = 1/[σ2(Fo2) + (0.0872P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
2549 reflectionsΔρmax = 0.58 e Å3
226 parametersΔρmin = −0.64 e Å3
3 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.287 (14)

Special details

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)

xyzUiso*/Ueq
S10.97876 (6)0.43469 (5)0.18224 (4)0.0160 (2)
O10.95541 (18)0.55710 (13)0.14090 (11)0.0236 (4)
O20.95173 (17)0.32826 (14)0.12109 (11)0.0253 (4)
O30.68230 (16)0.65052 (13)0.24233 (10)0.0205 (4)
O40.68085 (16)0.20574 (13)0.21541 (10)0.0216 (4)
O50.93203 (15)0.34731 (13)0.42896 (10)0.0183 (4)
N10.7756 (2)0.36526 (18)0.52595 (13)0.0224 (5)
N20.4414 (2)0.46284 (18)0.40031 (13)0.0242 (5)
C11.1509 (2)0.42085 (19)0.25136 (15)0.0170 (5)
H1A1.21450.37050.22040.020*
H1B1.19360.50340.26440.020*
C21.1251 (2)0.35644 (19)0.33972 (15)0.0172 (5)
H2A1.14710.26720.33790.021*
H2B1.18540.39370.39220.021*
C30.9718 (2)0.37524 (18)0.34620 (14)0.0151 (5)
C40.8818 (2)0.41635 (18)0.27348 (14)0.0148 (5)
C50.7227 (2)0.42359 (18)0.26815 (15)0.0149 (5)
C60.6933 (2)0.41396 (18)0.36651 (15)0.0150 (5)
C70.7939 (2)0.37715 (18)0.43869 (14)0.0160 (5)
C80.5539 (2)0.43993 (18)0.38449 (15)0.0160 (5)
C90.6480 (2)0.54337 (19)0.22236 (15)0.0158 (5)
C100.5243 (2)0.50111 (19)0.15446 (14)0.0151 (5)
C110.4185 (2)0.5739 (2)0.10321 (15)0.0201 (5)
H110.42070.66150.10740.024*
C120.3101 (2)0.5133 (2)0.04602 (15)0.0233 (6)
H120.23750.56040.01180.028*
C130.3079 (3)0.3814 (2)0.03878 (15)0.0226 (5)
H130.23400.3425−0.00050.027*
C140.4129 (2)0.3084 (2)0.08852 (14)0.0197 (5)
H140.41170.22100.08310.024*
C150.5215 (2)0.36997 (18)0.14740 (14)0.0152 (5)
C160.6443 (2)0.31490 (19)0.20917 (14)0.0156 (5)
H1C0.6992 (18)0.394 (2)0.5484 (15)0.036 (7)*
H1D0.841 (2)0.325 (2)0.5651 (14)0.047 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0134 (4)0.0201 (4)0.0148 (3)−0.0004 (2)0.0034 (2)−0.0006 (2)
O10.0225 (10)0.0262 (9)0.0231 (9)0.0053 (6)0.0064 (7)0.0088 (7)
O20.0227 (10)0.0316 (9)0.0226 (9)−0.0070 (7)0.0062 (7)−0.0101 (7)
O30.0213 (10)0.0148 (8)0.0257 (9)−0.0017 (6)0.0046 (7)−0.0003 (7)
O40.0219 (9)0.0154 (8)0.0268 (9)0.0029 (6)0.0016 (7)0.0006 (7)
O50.0147 (9)0.0241 (8)0.0167 (8)0.0048 (6)0.0043 (6)0.0037 (6)
N10.0222 (12)0.0287 (11)0.0171 (10)0.0084 (9)0.0056 (9)0.0052 (9)
N20.0179 (12)0.0353 (11)0.0196 (11)0.0024 (8)0.0039 (9)−0.0013 (8)
C10.0133 (12)0.0185 (11)0.0191 (12)−0.0018 (9)0.0029 (9)−0.0009 (9)
C20.0152 (12)0.0183 (10)0.0181 (11)0.0014 (9)0.0025 (9)0.0007 (9)
C30.0175 (12)0.0131 (10)0.0157 (11)0.0008 (8)0.0051 (9)−0.0015 (9)
C40.0135 (12)0.0162 (10)0.0156 (11)−0.0006 (8)0.0053 (9)−0.0018 (9)
C50.0124 (12)0.0157 (10)0.0167 (11)−0.0001 (8)0.0027 (9)0.0002 (9)
C60.0141 (12)0.0150 (10)0.0167 (11)0.0009 (8)0.0047 (9)0.0005 (9)
C70.0168 (12)0.0127 (10)0.0196 (12)0.0011 (8)0.0065 (9)−0.0003 (9)
C80.0185 (13)0.0163 (11)0.0125 (11)−0.0024 (9)0.0005 (9)0.0002 (8)
C90.0140 (12)0.0193 (11)0.0158 (11)0.0014 (8)0.0074 (9)0.0002 (9)
C100.0139 (12)0.0187 (11)0.0136 (11)0.0013 (9)0.0050 (9)0.0010 (9)
C110.0217 (13)0.0201 (11)0.0192 (12)0.0054 (9)0.0052 (10)0.0012 (9)
C120.0215 (14)0.0305 (12)0.0168 (12)0.0077 (10)−0.0007 (10)0.0042 (10)
C130.0189 (13)0.0309 (12)0.0169 (12)−0.0023 (10)−0.0008 (10)−0.0034 (10)
C140.0214 (13)0.0205 (11)0.0175 (12)−0.0008 (9)0.0040 (10)−0.0001 (9)
C150.0138 (12)0.0187 (10)0.0135 (11)−0.0001 (8)0.0038 (9)−0.0001 (9)
C160.0143 (12)0.0179 (11)0.0158 (11)−0.0012 (9)0.0064 (9)0.0017 (9)

Geometric parameters (Å, °)

S1—O11.4364 (15)C4—C51.493 (3)
S1—O21.4428 (16)C5—C61.526 (3)
S1—C41.756 (2)C5—C91.554 (3)
S1—C11.782 (2)C5—C161.559 (3)
O3—C91.205 (2)C6—C71.368 (3)
O4—C161.207 (2)C6—C81.409 (3)
O5—C31.367 (2)C9—C101.482 (3)
O5—C71.371 (3)C10—C111.388 (3)
N1—C71.334 (3)C10—C151.394 (3)
N1—H1C0.893 (9)C11—C121.378 (3)
N1—H1D0.889 (9)C11—H110.9300
N2—C81.149 (3)C12—C131.403 (3)
C1—C21.527 (3)C12—H120.9300
C1—H1A0.9700C13—C141.374 (3)
C1—H1B0.9700C13—H130.9300
C2—C31.478 (3)C14—C151.396 (3)
C2—H2A0.9700C14—H140.9300
C2—H2B0.9700C15—C161.477 (3)
C3—C41.333 (3)
O1—S1—O2116.12 (10)C9—C5—C16102.61 (17)
O1—S1—C4111.29 (10)C7—C6—C8117.51 (19)
O2—S1—C4109.41 (9)C7—C6—C5123.58 (19)
O1—S1—C1112.48 (10)C8—C6—C5118.87 (19)
O2—S1—C1110.42 (10)N1—C7—C6126.9 (2)
C4—S1—C195.13 (10)N1—C7—O5110.57 (19)
C3—O5—C7116.39 (16)C6—C7—O5122.56 (18)
C7—N1—H1C124.3 (15)N2—C8—C6178.7 (2)
C7—N1—H1D119.4 (16)O3—C9—C10127.1 (2)
H1C—N1—H1D116.3 (15)O3—C9—C5125.3 (2)
C2—C1—S1105.81 (14)C10—C9—C5107.55 (16)
C2—C1—H1A110.6C11—C10—C15120.68 (19)
S1—C1—H1A110.6C11—C10—C9128.46 (19)
C2—C1—H1B110.6C15—C10—C9110.84 (17)
S1—C1—H1B110.6C12—C11—C10118.3 (2)
H1A—C1—H1B108.7C12—C11—H11120.8
C3—C2—C1106.59 (17)C10—C11—H11120.8
C3—C2—H2A110.4C11—C12—C13120.8 (2)
C1—C2—H2A110.4C11—C12—H12119.6
C3—C2—H2B110.4C13—C12—H12119.6
C1—C2—H2B110.4C14—C13—C12121.3 (2)
H2A—C2—H2B108.6C14—C13—H13119.3
C4—C3—O5124.2 (2)C12—C13—H13119.3
C4—C3—C2119.78 (19)C13—C14—C15117.7 (2)
O5—C3—C2116.05 (18)C13—C14—H14121.1
C3—C4—C5124.48 (19)C15—C14—H14121.1
C3—C4—S1108.20 (16)C10—C15—C14121.09 (19)
C5—C4—S1126.58 (16)C10—C15—C16110.13 (17)
C4—C5—C6106.25 (17)C14—C15—C16128.78 (19)
C4—C5—C9116.60 (17)O4—C16—C15127.8 (2)
C6—C5—C9109.32 (16)O4—C16—C5124.15 (19)
C4—C5—C16112.07 (16)C15—C16—C5108.03 (16)
C6—C5—C16109.94 (16)
O1—S1—C1—C2135.04 (14)C3—O5—C7—C610.1 (3)
O2—S1—C1—C2−93.46 (15)C7—C6—C8—N259 (11)
C4—S1—C1—C219.47 (15)C5—C6—C8—N2−123 (11)
S1—C1—C2—C3−20.47 (19)C4—C5—C9—O3−51.7 (3)
C7—O5—C3—C4−7.2 (3)C6—C5—C9—O368.8 (3)
C7—O5—C3—C2173.23 (16)C16—C5—C9—O3−174.58 (19)
C1—C2—C3—C413.2 (3)C4—C5—C9—C10131.25 (19)
C1—C2—C3—O5−167.28 (16)C6—C5—C9—C10−108.26 (18)
O5—C3—C4—C5−7.5 (3)C16—C5—C9—C108.4 (2)
C2—C3—C4—C5172.05 (18)O3—C9—C10—C11−3.5 (4)
O5—C3—C4—S1−178.14 (15)C5—C9—C10—C11173.4 (2)
C2—C3—C4—S11.4 (2)O3—C9—C10—C15177.91 (19)
O1—S1—C4—C3−129.26 (15)C5—C9—C10—C15−5.1 (2)
O2—S1—C4—C3101.07 (16)C15—C10—C11—C120.6 (3)
C1—S1—C4—C3−12.70 (16)C9—C10—C11—C12−177.8 (2)
O1—S1—C4—C560.3 (2)C10—C11—C12—C13−0.9 (3)
O2—S1—C4—C5−69.34 (19)C11—C12—C13—C140.3 (3)
C1—S1—C4—C5176.89 (18)C12—C13—C14—C150.6 (3)
C3—C4—C5—C616.4 (3)C11—C10—C15—C140.3 (3)
S1—C4—C5—C6−174.71 (14)C9—C10—C15—C14178.97 (19)
C3—C4—C5—C9138.5 (2)C11—C10—C15—C16−179.47 (19)
S1—C4—C5—C9−52.6 (2)C9—C10—C15—C16−0.8 (2)
C3—C4—C5—C16−103.7 (2)C13—C14—C15—C10−0.9 (3)
S1—C4—C5—C1665.2 (2)C13—C14—C15—C16178.8 (2)
C4—C5—C6—C7−13.2 (3)C10—C15—C16—O4−173.9 (2)
C9—C5—C6—C7−139.8 (2)C14—C15—C16—O46.3 (4)
C16—C5—C6—C7108.3 (2)C10—C15—C16—C56.4 (2)
C4—C5—C6—C8169.09 (17)C14—C15—C16—C5−173.4 (2)
C9—C5—C6—C842.5 (2)C4—C5—C16—O445.5 (3)
C16—C5—C6—C8−69.4 (2)C6—C5—C16—O4−72.4 (2)
C8—C6—C7—N1−1.5 (3)C9—C5—C16—O4171.39 (18)
C5—C6—C7—N1−179.2 (2)C4—C5—C16—C15−134.76 (18)
C8—C6—C7—O5178.80 (17)C6—C5—C16—C15107.32 (18)
C5—C6—C7—O51.0 (3)C9—C5—C16—C15−8.9 (2)
C3—O5—C7—N1−169.63 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···N2i0.89 (1)2.23 (1)3.067 (3)157 (2)
N1—H1D···O2ii0.89 (1)2.03 (1)2.865 (2)156 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2656).

References

  • Chao, J. H., Zheng, J. Y. & Aslanian, R. G. (2009). WO Patent No. 2009020578.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Friary, R. J., Schwerdt, J. H. & Ganguly, A. K. (1991). US Patent No. 5 034 531.
  • Rigaku/MSC (2002). CrystalClear Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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