Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052233/wn2211sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052233/wn2211Isup2.hkl |
CCDC reference: 667442
To a solution of 2H-indene-1,3-dione (1 mmol) in dry toluene (20 ml), 2-[N-(3-methylbut-2-enyl)-N-tosylamino]acetaldehyde (1 mmol) and a catalytic amount of the base ethylenediamine-N,N'-diacetate (EDDA) were added and the reaction mixture was refluxed for 12 h. After completion of the reaction, the solvent was evaporated under reduced pressure and the crude product was chromatographed using a hexane–ethyl acetate (8:2 v/v) mixture to obtain the title compound. The compound was recrystallized from ethyl acetate solution by slow evaporation.
H atoms were positioned geometrically (C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(Cmethyl) or 1.2Ueq(C). A rotating group model was used for the methyl group attached to the aromatic ring.
As part of our ongoing studies on pyrrolo[3,4-c]pyran derivatives (Chinnakali et al., 2007a,b), we report here the crystal structure of the title compound (Fig. 1).
Bond lengths and angles show normal values (Allen et al., 1987), and are comparable with those in related structures (Chinnakali et al., 2007a,b). As a result of the repulsive interaction between the short S═O bonds, atom S1 has a distorted tetrahedral configuration, with the O2—S1—O1 [120.17 (4)°] angle deviating significantly from the ideal tetrahedral value.
The pyrrolidine ring (N1/C1–C4) has an envelope conformation with atom C2 deviating by 0.586 (1) Å from the least-squares plane formed by the remaining four ring atoms. The puckering parameters (q2, φ2; Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Duax et al., 1976) for the pyrrolidine ring are q2 = 0.3821 (8) Å, φ2 = 260.23 (11)° and ΔCs[C2] = 6.18 (7)°. The tosyl group is equatorially attached to the pyrrolidine ring. The dihydropyran ring adopts a half-chair conformation with a local twofold rotation axis passing through the C2—C5 and C6—C7 bonds; the puckering (Q, θ, φ) and asymmetry (ΔC2[C2–C5]) parameters are 0.4439 (8) Å, 129.98 (10)°, 276.03 (12)° and 3.45 (9)°, respectively. The pyrrolidine and dihydropyran rings are cis-fused.
The indenone ring system is essentially planar, with atom O4 deviating from the indene plane by 0.088 (1) Å. The dihedral angle between the indene ring system and the C8–C13 benzene ring is 25.12 (3)°. The molecule adopts a folded conformation, with the cyclopentadienone and C8–C13 benzene rings arranged in an almost face-to-face fashion. However, no significant π–π interactions are observed between these rings as their centroids are separated by 3.9135 (5) Å.
In the crystal structure, molecules translated by one unit cell along the a-axis direction are linked by C3—H3···O1i and C16—H16C···O1i [symmetry code: (i) 1 + x, y, z] hydrogen-bonding interactions to form a chain. These interactions together constitute a pair of bifurcated acceptor bonds, generating an R12(7) motif (Bernstein et al., 1995). The inversion-related molecules of adjacent chains are alternately linked along the c axis by pairs of C16—H16A···O3ii and C21—H21···O4iii [symmetry codes: (ii) 2 - x, 2 - y, -z; (iii) 2 - x, 2 - y, 1 - z] hydrogen bonds (Table 1) into a sheet-like structure parallel to the ac plane (Fig. 2). The pairs of C16—H16A···O3ii and C21—H21···O4iii interactions generate rings of graph-set motif R22(10) and R22(8), respectively.
For bond-length data, see: Allen et al. (1987). For related pyrrolo[3,4-c]pyran structures, see: Chinnakali et al. (2007a,b). For ring-puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976). For notation of hydrogen-bonding motifs, see: Bernstein et al. (1995).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
C23H23NO4S | Z = 2 |
Mr = 409.48 | F(000) = 432 |
Triclinic, P1 | Dx = 1.377 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0219 (2) Å | Cell parameters from 8302 reflections |
b = 8.6106 (2) Å | θ = 2.5–40.2° |
c = 15.0432 (4) Å | µ = 0.19 mm−1 |
α = 104.557 (1)° | T = 100 K |
β = 99.182 (1)° | Block, light yellow |
γ = 93.192 (1)° | 0.60 × 0.56 × 0.37 mm |
V = 987.84 (4) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 8635 independent reflections |
Radiation source: fine-focus sealed tube | 7903 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 8.33 pixels mm-1 | θmax = 35.0°, θmin = 1.4° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −13→13 |
Tmin = 0.862, Tmax = 0.932 | l = −24→24 |
42977 measured reflections |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0596P)2 + 0.2351P] where P = (Fo2 + 2Fc2)/3 |
8635 reflections | (Δ/σ)max = 0.001 |
263 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C23H23NO4S | γ = 93.192 (1)° |
Mr = 409.48 | V = 987.84 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.0219 (2) Å | Mo Kα radiation |
b = 8.6106 (2) Å | µ = 0.19 mm−1 |
c = 15.0432 (4) Å | T = 100 K |
α = 104.557 (1)° | 0.60 × 0.56 × 0.37 mm |
β = 99.182 (1)° |
Bruker SMART APEXII CCD area-detector diffractometer | 8635 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 7903 reflections with I > 2σ(I) |
Tmin = 0.862, Tmax = 0.932 | Rint = 0.024 |
42977 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.58 e Å−3 |
8635 reflections | Δρmin = −0.36 e Å−3 |
263 parameters |
Experimental. The low-temparture data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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 > 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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.39580 (2) | 0.63360 (2) | 0.220153 (13) | 0.01541 (5) | |
O1 | 0.23678 (8) | 0.62916 (8) | 0.15941 (5) | 0.02275 (12) | |
O2 | 0.41576 (9) | 0.52386 (7) | 0.27782 (5) | 0.02174 (12) | |
O3 | 0.83313 (8) | 0.95635 (6) | 0.09401 (4) | 0.01588 (10) | |
O4 | 0.99483 (9) | 0.77446 (7) | 0.36449 (4) | 0.02030 (11) | |
N1 | 0.53669 (8) | 0.59825 (7) | 0.15218 (4) | 0.01406 (10) | |
C1 | 0.55116 (9) | 0.69996 (9) | 0.08746 (5) | 0.01553 (12) | |
H1A | 0.5482 | 0.8129 | 0.1182 | 0.019* | |
H1B | 0.4608 | 0.6678 | 0.0334 | 0.019* | |
C2 | 0.72446 (9) | 0.66848 (8) | 0.05984 (5) | 0.01418 (11) | |
H2 | 0.7114 | 0.5658 | 0.0118 | 0.017* | |
C3 | 0.83158 (9) | 0.64700 (8) | 0.15018 (5) | 0.01296 (11) | |
H3 | 0.9272 | 0.5848 | 0.1361 | 0.016* | |
C4 | 0.70506 (9) | 0.55341 (8) | 0.18884 (5) | 0.01496 (11) | |
H4A | 0.7108 | 0.4381 | 0.1671 | 0.018* | |
H4B | 0.7277 | 0.5847 | 0.2566 | 0.018* | |
C5 | 0.80278 (10) | 0.79956 (8) | 0.02205 (5) | 0.01600 (12) | |
C6 | 0.88902 (9) | 0.94690 (8) | 0.18073 (5) | 0.01282 (11) | |
C7 | 0.89279 (9) | 0.81174 (8) | 0.21169 (5) | 0.01246 (11) | |
C8 | 0.44908 (9) | 0.83213 (9) | 0.29019 (5) | 0.01570 (12) | |
C9 | 0.56938 (10) | 0.86295 (10) | 0.37214 (5) | 0.01873 (13) | |
H9 | 0.6141 | 0.7784 | 0.3930 | 0.022* | |
C10 | 0.62124 (11) | 1.02188 (10) | 0.42204 (6) | 0.02109 (14) | |
H10 | 0.7008 | 1.0433 | 0.4769 | 0.025* | |
C11 | 0.55587 (11) | 1.15034 (10) | 0.39124 (6) | 0.02036 (14) | |
C12 | 0.43419 (11) | 1.11695 (10) | 0.30990 (6) | 0.02146 (14) | |
H12 | 0.3886 | 1.2014 | 0.2893 | 0.026* | |
C13 | 0.38025 (10) | 0.95850 (10) | 0.25916 (6) | 0.01916 (13) | |
H13 | 0.2989 | 0.9370 | 0.2050 | 0.023* | |
C14 | 0.61644 (14) | 1.32121 (11) | 0.44569 (8) | 0.0315 (2) | |
H14A | 0.5504 | 1.3937 | 0.4193 | 0.047* | |
H14B | 0.7338 | 1.3436 | 0.4430 | 0.047* | |
H14C | 0.6038 | 1.3354 | 0.5095 | 0.047* | |
C15 | 0.68402 (13) | 0.83273 (10) | −0.05901 (6) | 0.02343 (16) | |
H15A | 0.7383 | 0.9153 | −0.0803 | 0.035* | |
H15B | 0.5815 | 0.8679 | −0.0388 | 0.035* | |
H15C | 0.6573 | 0.7359 | −0.1091 | 0.035* | |
C16 | 0.97315 (11) | 0.75615 (10) | −0.00403 (6) | 0.02156 (15) | |
H16A | 1.0209 | 0.8391 | −0.0276 | 0.032* | |
H16B | 0.9573 | 0.6554 | −0.0512 | 0.032* | |
H16C | 1.0488 | 0.7466 | 0.0502 | 0.032* | |
C17 | 0.95601 (9) | 1.09335 (8) | 0.25648 (5) | 0.01349 (11) | |
C18 | 0.97941 (10) | 1.25424 (9) | 0.25762 (5) | 0.01705 (12) | |
H18 | 0.9517 | 1.2876 | 0.2034 | 0.020* | |
C19 | 1.04670 (11) | 1.36602 (9) | 0.34373 (6) | 0.02031 (14) | |
H19 | 1.0648 | 1.4749 | 0.3465 | 0.024* | |
C20 | 1.08615 (11) | 1.31523 (10) | 0.42432 (6) | 0.02093 (14) | |
H20 | 1.1278 | 1.3910 | 0.4808 | 0.025* | |
C21 | 1.06429 (10) | 1.15118 (9) | 0.42228 (5) | 0.01811 (13) | |
H21 | 1.0919 | 1.1172 | 0.4763 | 0.022* | |
C22 | 1.00078 (9) | 1.04233 (8) | 0.33774 (5) | 0.01415 (11) | |
C23 | 0.96614 (9) | 0.86138 (8) | 0.31201 (5) | 0.01398 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01277 (8) | 0.01370 (8) | 0.01945 (8) | −0.00091 (5) | 0.00437 (6) | 0.00339 (6) |
O1 | 0.0122 (2) | 0.0237 (3) | 0.0283 (3) | −0.0010 (2) | 0.0010 (2) | 0.0016 (2) |
O2 | 0.0258 (3) | 0.0168 (2) | 0.0261 (3) | 0.0000 (2) | 0.0109 (2) | 0.0087 (2) |
O3 | 0.0234 (3) | 0.0116 (2) | 0.0113 (2) | −0.00181 (18) | 0.00137 (17) | 0.00251 (16) |
O4 | 0.0277 (3) | 0.0166 (2) | 0.0169 (2) | 0.0031 (2) | 0.0006 (2) | 0.00693 (19) |
N1 | 0.0124 (2) | 0.0139 (2) | 0.0163 (2) | 0.00059 (18) | 0.00296 (18) | 0.00469 (19) |
C1 | 0.0147 (3) | 0.0155 (3) | 0.0161 (3) | −0.0007 (2) | 0.0002 (2) | 0.0056 (2) |
C2 | 0.0165 (3) | 0.0118 (3) | 0.0131 (3) | −0.0018 (2) | 0.0026 (2) | 0.0020 (2) |
C3 | 0.0131 (3) | 0.0104 (2) | 0.0150 (3) | 0.00002 (19) | 0.0033 (2) | 0.00229 (19) |
C4 | 0.0133 (3) | 0.0129 (3) | 0.0198 (3) | 0.0007 (2) | 0.0031 (2) | 0.0065 (2) |
C5 | 0.0226 (3) | 0.0125 (3) | 0.0115 (3) | −0.0027 (2) | 0.0032 (2) | 0.0013 (2) |
C6 | 0.0145 (3) | 0.0111 (2) | 0.0121 (2) | −0.0003 (2) | 0.0023 (2) | 0.00204 (19) |
C7 | 0.0133 (3) | 0.0106 (2) | 0.0129 (3) | 0.00010 (19) | 0.0021 (2) | 0.00233 (19) |
C8 | 0.0144 (3) | 0.0150 (3) | 0.0176 (3) | 0.0017 (2) | 0.0040 (2) | 0.0034 (2) |
C9 | 0.0201 (3) | 0.0172 (3) | 0.0182 (3) | 0.0039 (2) | 0.0030 (2) | 0.0033 (2) |
C10 | 0.0208 (3) | 0.0194 (3) | 0.0199 (3) | 0.0032 (3) | 0.0021 (3) | 0.0000 (2) |
C11 | 0.0198 (3) | 0.0160 (3) | 0.0237 (3) | 0.0021 (2) | 0.0071 (3) | 0.0001 (2) |
C12 | 0.0225 (3) | 0.0159 (3) | 0.0265 (4) | 0.0051 (3) | 0.0059 (3) | 0.0050 (3) |
C13 | 0.0177 (3) | 0.0171 (3) | 0.0221 (3) | 0.0040 (2) | 0.0023 (2) | 0.0045 (2) |
C14 | 0.0332 (5) | 0.0175 (4) | 0.0372 (5) | 0.0005 (3) | 0.0063 (4) | −0.0044 (3) |
C15 | 0.0344 (4) | 0.0192 (3) | 0.0143 (3) | −0.0040 (3) | −0.0016 (3) | 0.0051 (2) |
C16 | 0.0268 (4) | 0.0185 (3) | 0.0202 (3) | −0.0023 (3) | 0.0116 (3) | 0.0030 (2) |
C17 | 0.0154 (3) | 0.0106 (2) | 0.0135 (3) | 0.0005 (2) | 0.0023 (2) | 0.00183 (19) |
C18 | 0.0216 (3) | 0.0115 (3) | 0.0172 (3) | 0.0007 (2) | 0.0032 (2) | 0.0028 (2) |
C19 | 0.0257 (4) | 0.0115 (3) | 0.0210 (3) | −0.0008 (2) | 0.0032 (3) | 0.0006 (2) |
C20 | 0.0256 (4) | 0.0147 (3) | 0.0178 (3) | −0.0013 (3) | 0.0010 (3) | −0.0018 (2) |
C21 | 0.0212 (3) | 0.0162 (3) | 0.0139 (3) | −0.0002 (2) | 0.0001 (2) | 0.0008 (2) |
C22 | 0.0155 (3) | 0.0123 (3) | 0.0134 (3) | 0.0005 (2) | 0.0015 (2) | 0.0019 (2) |
C23 | 0.0148 (3) | 0.0126 (3) | 0.0139 (3) | 0.0011 (2) | 0.0019 (2) | 0.0029 (2) |
S1—O2 | 1.4337 (6) | C9—H9 | 0.93 |
S1—O1 | 1.4383 (7) | C10—C11 | 1.3992 (12) |
S1—N1 | 1.6329 (6) | C10—H10 | 0.93 |
S1—C8 | 1.7563 (8) | C11—C12 | 1.3942 (13) |
O3—C6 | 1.3343 (8) | C11—C14 | 1.5031 (12) |
O3—C5 | 1.4827 (9) | C12—C13 | 1.3916 (12) |
O4—C23 | 1.2226 (9) | C12—H12 | 0.93 |
N1—C1 | 1.4770 (9) | C13—H13 | 0.93 |
N1—C4 | 1.4849 (9) | C14—H14A | 0.96 |
C1—C2 | 1.5325 (10) | C14—H14B | 0.96 |
C1—H1A | 0.97 | C14—H14C | 0.96 |
C1—H1B | 0.97 | C15—H15A | 0.96 |
C2—C5 | 1.5328 (10) | C15—H15B | 0.96 |
C2—C3 | 1.5462 (10) | C15—H15C | 0.96 |
C2—H2 | 0.98 | C16—H16A | 0.96 |
C3—C7 | 1.4923 (9) | C16—H16B | 0.96 |
C3—C4 | 1.5332 (10) | C16—H16C | 0.96 |
C3—H3 | 0.98 | C17—C18 | 1.3831 (10) |
C4—H4A | 0.97 | C17—C22 | 1.4012 (10) |
C4—H4B | 0.97 | C18—C19 | 1.4099 (11) |
C5—C15 | 1.5202 (11) | C18—H18 | 0.93 |
C5—C16 | 1.5217 (12) | C19—C20 | 1.3859 (12) |
C6—C7 | 1.3581 (9) | C19—H19 | 0.93 |
C6—C17 | 1.4779 (9) | C20—C21 | 1.4057 (11) |
C7—C23 | 1.4734 (10) | C20—H20 | 0.93 |
C8—C13 | 1.3953 (11) | C21—C22 | 1.3770 (10) |
C8—C9 | 1.3960 (11) | C21—H21 | 0.93 |
C9—C10 | 1.3892 (11) | C22—C23 | 1.5063 (10) |
O2—S1—O1 | 120.17 (4) | C9—C10—C11 | 121.18 (8) |
O2—S1—N1 | 106.46 (4) | C9—C10—H10 | 119.4 |
O1—S1—N1 | 105.76 (4) | C11—C10—H10 | 119.4 |
O2—S1—C8 | 109.35 (4) | C12—C11—C10 | 118.97 (7) |
O1—S1—C8 | 107.78 (4) | C12—C11—C14 | 120.94 (8) |
N1—S1—C8 | 106.52 (3) | C10—C11—C14 | 120.09 (8) |
C6—O3—C5 | 114.81 (6) | C13—C12—C11 | 120.66 (8) |
C1—N1—C4 | 111.34 (6) | C13—C12—H12 | 119.7 |
C1—N1—S1 | 118.53 (5) | C11—C12—H12 | 119.7 |
C4—N1—S1 | 119.42 (5) | C12—C13—C8 | 119.49 (7) |
N1—C1—C2 | 103.05 (6) | C12—C13—H13 | 120.3 |
N1—C1—H1A | 111.2 | C8—C13—H13 | 120.3 |
C2—C1—H1A | 111.2 | C11—C14—H14A | 109.5 |
N1—C1—H1B | 111.2 | C11—C14—H14B | 109.5 |
C2—C1—H1B | 111.2 | H14A—C14—H14B | 109.5 |
H1A—C1—H1B | 109.1 | C11—C14—H14C | 109.5 |
C1—C2—C5 | 114.46 (6) | H14A—C14—H14C | 109.5 |
C1—C2—C3 | 103.08 (5) | H14B—C14—H14C | 109.5 |
C5—C2—C3 | 113.88 (6) | C5—C15—H15A | 109.5 |
C1—C2—H2 | 108.4 | C5—C15—H15B | 109.5 |
C5—C2—H2 | 108.4 | H15A—C15—H15B | 109.5 |
C3—C2—H2 | 108.4 | C5—C15—H15C | 109.5 |
C7—C3—C4 | 113.62 (6) | H15A—C15—H15C | 109.5 |
C7—C3—C2 | 107.12 (5) | H15B—C15—H15C | 109.5 |
C4—C3—C2 | 103.12 (6) | C5—C16—H16A | 109.5 |
C7—C3—H3 | 110.9 | C5—C16—H16B | 109.5 |
C4—C3—H3 | 110.9 | H16A—C16—H16B | 109.5 |
C2—C3—H3 | 110.9 | C5—C16—H16C | 109.5 |
N1—C4—C3 | 104.45 (6) | H16A—C16—H16C | 109.5 |
N1—C4—H4A | 110.9 | H16B—C16—H16C | 109.5 |
C3—C4—H4A | 110.9 | C18—C17—C22 | 121.23 (6) |
N1—C4—H4B | 110.9 | C18—C17—C6 | 132.27 (7) |
C3—C4—H4B | 110.9 | C22—C17—C6 | 106.50 (6) |
H4A—C4—H4B | 108.9 | C17—C18—C19 | 117.81 (7) |
O3—C5—C15 | 104.14 (6) | C17—C18—H18 | 121.1 |
O3—C5—C16 | 107.55 (6) | C19—C18—H18 | 121.1 |
C15—C5—C16 | 111.62 (7) | C20—C19—C18 | 120.64 (7) |
O3—C5—C2 | 110.56 (5) | C20—C19—H19 | 119.7 |
C15—C5—C2 | 112.44 (6) | C18—C19—H19 | 119.7 |
C16—C5—C2 | 110.27 (6) | C19—C20—C21 | 121.16 (7) |
O3—C6—C7 | 127.24 (6) | C19—C20—H20 | 119.4 |
O3—C6—C17 | 120.89 (6) | C21—C20—H20 | 119.4 |
C7—C6—C17 | 111.87 (6) | C22—C21—C20 | 117.92 (7) |
C6—C7—C23 | 107.48 (6) | C22—C21—H21 | 121.0 |
C6—C7—C3 | 123.28 (6) | C20—C21—H21 | 121.0 |
C23—C7—C3 | 129.24 (6) | C21—C22—C17 | 121.20 (7) |
C13—C8—C9 | 120.73 (7) | C21—C22—C23 | 130.91 (7) |
C13—C8—S1 | 119.21 (6) | C17—C22—C23 | 107.89 (6) |
C9—C8—S1 | 119.85 (6) | O4—C23—C7 | 127.46 (6) |
C10—C9—C8 | 118.95 (7) | O4—C23—C22 | 126.32 (7) |
C10—C9—H9 | 120.5 | C7—C23—C22 | 106.23 (6) |
C8—C9—H9 | 120.5 | ||
O2—S1—N1—C1 | −177.15 (5) | O1—S1—C8—C13 | −23.07 (7) |
O1—S1—N1—C1 | 53.96 (6) | N1—S1—C8—C13 | 90.05 (7) |
C8—S1—N1—C1 | −60.54 (6) | O2—S1—C8—C9 | 29.79 (7) |
O2—S1—N1—C4 | −35.69 (6) | O1—S1—C8—C9 | 162.01 (6) |
O1—S1—N1—C4 | −164.58 (5) | N1—S1—C8—C9 | −84.87 (7) |
C8—S1—N1—C4 | 80.92 (6) | C13—C8—C9—C10 | −0.70 (12) |
C4—N1—C1—C2 | 18.78 (7) | S1—C8—C9—C10 | 174.14 (6) |
S1—N1—C1—C2 | 163.14 (5) | C8—C9—C10—C11 | −0.40 (12) |
N1—C1—C2—C5 | −159.04 (6) | C9—C10—C11—C12 | 1.24 (13) |
N1—C1—C2—C3 | −34.83 (6) | C9—C10—C11—C14 | −178.93 (8) |
C1—C2—C3—C7 | −81.83 (6) | C10—C11—C12—C13 | −0.99 (13) |
C5—C2—C3—C7 | 42.77 (8) | C14—C11—C12—C13 | 179.17 (8) |
C1—C2—C3—C4 | 38.33 (6) | C11—C12—C13—C8 | −0.07 (13) |
C5—C2—C3—C4 | 162.92 (6) | C9—C8—C13—C12 | 0.93 (12) |
C1—N1—C4—C3 | 5.19 (7) | S1—C8—C13—C12 | −173.94 (6) |
S1—N1—C4—C3 | −138.82 (5) | O3—C6—C17—C18 | −1.65 (12) |
C7—C3—C4—N1 | 88.79 (7) | C7—C6—C17—C18 | 178.60 (8) |
C2—C3—C4—N1 | −26.79 (7) | O3—C6—C17—C22 | 179.12 (6) |
C6—O3—C5—C15 | 160.01 (6) | C7—C6—C17—C22 | −0.63 (8) |
C6—O3—C5—C16 | −81.43 (7) | C22—C17—C18—C19 | −1.27 (11) |
C6—O3—C5—C2 | 39.02 (9) | C6—C17—C18—C19 | 179.59 (8) |
C1—C2—C5—O3 | 61.71 (8) | C17—C18—C19—C20 | −0.60 (12) |
C3—C2—C5—O3 | −56.54 (8) | C18—C19—C20—C21 | 1.57 (13) |
C1—C2—C5—C15 | −54.22 (8) | C19—C20—C21—C22 | −0.63 (13) |
C3—C2—C5—C15 | −172.46 (6) | C20—C21—C22—C17 | −1.25 (12) |
C1—C2—C5—C16 | −179.49 (6) | C20—C21—C22—C23 | 178.69 (8) |
C3—C2—C5—C16 | 62.27 (8) | C18—C17—C22—C21 | 2.25 (11) |
C5—O3—C6—C7 | −12.17 (10) | C6—C17—C22—C21 | −178.42 (7) |
C5—O3—C6—C17 | 168.12 (6) | C18—C17—C22—C23 | −177.71 (7) |
O3—C6—C7—C23 | 179.60 (7) | C6—C17—C22—C23 | 1.63 (8) |
C17—C6—C7—C23 | −0.67 (8) | C6—C7—C23—O4 | −177.94 (8) |
O3—C6—C7—C3 | −0.19 (11) | C3—C7—C23—O4 | 1.83 (12) |
C17—C6—C7—C3 | 179.54 (6) | C6—C7—C23—C22 | 1.63 (8) |
C4—C3—C7—C6 | −128.50 (7) | C3—C7—C23—C22 | −178.61 (7) |
C2—C3—C7—C6 | −15.31 (9) | C21—C22—C23—O4 | −2.41 (13) |
C4—C3—C7—C23 | 51.76 (10) | C17—C22—C23—O4 | 177.54 (7) |
C2—C3—C7—C23 | 164.96 (7) | C21—C22—C23—C7 | 178.01 (8) |
O2—S1—C8—C13 | −155.29 (6) | C17—C22—C23—C7 | −2.03 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.98 | 2.45 | 3.2451 (10) | 138 |
C16—H16A···O3ii | 0.96 | 2.55 | 3.5075 (11) | 175 |
C16—H16C···O1i | 0.96 | 2.49 | 3.4151 (11) | 161 |
C21—H21···O4iii | 0.93 | 2.56 | 3.2266 (9) | 129 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z; (iii) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H23NO4S |
Mr | 409.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.0219 (2), 8.6106 (2), 15.0432 (4) |
α, β, γ (°) | 104.557 (1), 99.182 (1), 93.192 (1) |
V (Å3) | 987.84 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.60 × 0.56 × 0.37 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.862, 0.932 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42977, 8635, 7903 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.807 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.106, 1.07 |
No. of reflections | 8635 |
No. of parameters | 263 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.36 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 1998) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.98 | 2.45 | 3.2451 (10) | 138 |
C16—H16A···O3ii | 0.96 | 2.55 | 3.5075 (11) | 175 |
C16—H16C···O1i | 0.96 | 2.49 | 3.4151 (11) | 161 |
C21—H21···O4iii | 0.93 | 2.56 | 3.2266 (9) | 129 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z; (iii) −x+2, −y+2, −z+1. |
As part of our ongoing studies on pyrrolo[3,4-c]pyran derivatives (Chinnakali et al., 2007a,b), we report here the crystal structure of the title compound (Fig. 1).
Bond lengths and angles show normal values (Allen et al., 1987), and are comparable with those in related structures (Chinnakali et al., 2007a,b). As a result of the repulsive interaction between the short S═O bonds, atom S1 has a distorted tetrahedral configuration, with the O2—S1—O1 [120.17 (4)°] angle deviating significantly from the ideal tetrahedral value.
The pyrrolidine ring (N1/C1–C4) has an envelope conformation with atom C2 deviating by 0.586 (1) Å from the least-squares plane formed by the remaining four ring atoms. The puckering parameters (q2, φ2; Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Duax et al., 1976) for the pyrrolidine ring are q2 = 0.3821 (8) Å, φ2 = 260.23 (11)° and ΔCs[C2] = 6.18 (7)°. The tosyl group is equatorially attached to the pyrrolidine ring. The dihydropyran ring adopts a half-chair conformation with a local twofold rotation axis passing through the C2—C5 and C6—C7 bonds; the puckering (Q, θ, φ) and asymmetry (ΔC2[C2–C5]) parameters are 0.4439 (8) Å, 129.98 (10)°, 276.03 (12)° and 3.45 (9)°, respectively. The pyrrolidine and dihydropyran rings are cis-fused.
The indenone ring system is essentially planar, with atom O4 deviating from the indene plane by 0.088 (1) Å. The dihedral angle between the indene ring system and the C8–C13 benzene ring is 25.12 (3)°. The molecule adopts a folded conformation, with the cyclopentadienone and C8–C13 benzene rings arranged in an almost face-to-face fashion. However, no significant π–π interactions are observed between these rings as their centroids are separated by 3.9135 (5) Å.
In the crystal structure, molecules translated by one unit cell along the a-axis direction are linked by C3—H3···O1i and C16—H16C···O1i [symmetry code: (i) 1 + x, y, z] hydrogen-bonding interactions to form a chain. These interactions together constitute a pair of bifurcated acceptor bonds, generating an R12(7) motif (Bernstein et al., 1995). The inversion-related molecules of adjacent chains are alternately linked along the c axis by pairs of C16—H16A···O3ii and C21—H21···O4iii [symmetry codes: (ii) 2 - x, 2 - y, -z; (iii) 2 - x, 2 - y, 1 - z] hydrogen bonds (Table 1) into a sheet-like structure parallel to the ac plane (Fig. 2). The pairs of C16—H16A···O3ii and C21—H21···O4iii interactions generate rings of graph-set motif R22(10) and R22(8), respectively.