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The title compound, C21H23IN2O2S, was synthesized by the intermolecular [3 + 2]-cyclo­addition of azomethine yl­ide and 5-benzyl­idene-3-benzyl­thia­zolidine-2,4-dione, followed by alkyl­ation with methyl iodide. The spiro ring involves thia­zolidine and pyrrolidine rings, the former planar and the latter in an envelope conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008298/cv6184sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008298/cv6184Isup2.hkl
Contains datablock I

CCDC reference: 214624

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.009 Å
  • R factor = 0.039
  • wR factor = 0.104
  • Data-to-parameter ratio = 17.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C21 H23 I1 N2 O2 S1 Atom count from _chemical_formula_moiety:C21 H23 I2 N2 O2 S1

Comment top

Spiro compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are important processes for the construction of spiro compounds (Caramella & Grunanger, 1984). In this paper, the structure of the title compound, (I), is reported. The molecular structure of (I) is illustrated in Fig. 1. A l l bond lengths and angles of (I) are within normal ranges (Table 1).

There is a spiro ring in (I), consisting of pyrrolidine and thiazolidine rings. The pyrrolidine ring C6—C3—C4—N2—C5 is not planar and has an envelope conformation. C6—C3—C4—N2 is nearly planar with the mean deviation from this plane of 0.0304 (3) Å. Atom C5 is 0.6221 (2) Å out from this plane, forming the flap of the envelopes. The dihedral angle between the C6—C5—N2 and C6—C3—C4—N2 planes is 138.4 (4)°, The dihedral angle between the C6—C3—C4—N2 plane and phenyl plane C16—C17—C18—C19—C20—C21 is 111.7 (4) Å. The thiazolidine ring S1—C2—N1—C1—C3 is planar, the mean deviation from this plane is 0.0330 (3) Å. Atoms O1 and O2 deviate by 0.0624 (3) and 0.1308 (3) Å, respectively, from this plane. The dihedral angle between C6—C3—C4—N2 plane of pyrrolidine ring and thiazolidine ring is 94.7 (4)°.

Experimental top

A 100 ml round-bottomed flask equipped with a condenser and an air moisture-impermeable seal, was charged with sarcosine (4 mmol), paraformaldehyde (8 mmol) and 5-benzylidene-3-benzyl-thiazolidine-2,4-dione (2 mmol). The reaction mixture was refluxed in dry toluene (60 ml) until the starting 5-benzylidene-3-benzylthiazolidine-2,4-dione was consumed. After evaporation of the solvent, the residue was separated by column chromatography (silica gel, petroleum ether/ethyl acetate = 2:1), the product got from column chromatography then stirred with methyl iodide in acetone at room temperature for 1 h, the title compound, (I), was achieved by filtration. M.p. 535–536 K; IR (KBr): 2920 (CH2CH3), 1753, 1676 (CO) cm−1; 1H NMR (CD3CN, p.p.m.): 3.52 (6H, s), 4.04–4.11 (1H, m), 4.34–4.42 (2H, m), 4.50–4.59 (2H, m), 4.68–4.79 (2H, m), 6.94–7.44 (10H, m); 20 mg of (I) was dissolved in 15 ml CH3CN, the solution was kept at room temperature for 20 d by natural evaporation to give colorless single crystals of (I), suitable for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
3-Benzyl-7,7-dimethyl-9-phenyl-1-thia-3-aza-7-azoniaspiro[4.4]nonane-2,4-dione iodide top
Crystal data top
C21H23IN2O2S+·IF(000) = 992
Mr = 494.37Dx = 1.540 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 20.791 (7) ÅCell parameters from 953 reflections
b = 7.606 (3) Åθ = 2.9–25.6°
c = 13.484 (5) ŵ = 1.62 mm1
β = 90.685 (5)°T = 293 K
V = 2132.1 (12) Å3Plate, colorless
Z = 40.30 × 0.14 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
4347 independent reflections
Radiation source: fine-focus sealed tube2790 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ϕ and ω scansθmax = 26.4°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 2525
Tmin = 0.675, Tmax = 0.851k = 95
11395 measured reflectionsl = 1616
Refinement top
Refinement on F2H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.084P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.039(Δ/σ)max = 0.001
wR(F2) = 0.104Δρmax = 0.74 e Å3
S = 1.02Δρmin = 0.47 e Å3
4347 reflectionsExtinction correction: SHELXL97
247 parametersExtinction coefficient: 0.0077 (4)
0 restraints
Crystal data top
C21H23IN2O2S+·IV = 2132.1 (12) Å3
Mr = 494.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 20.791 (7) ŵ = 1.62 mm1
b = 7.606 (3) ÅT = 293 K
c = 13.484 (5) Å0.30 × 0.14 × 0.10 mm
β = 90.685 (5)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
4347 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2790 reflections with I > 2σ(I)
Tmin = 0.675, Tmax = 0.851Rint = 0.040
11395 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.74 e Å3
4347 reflectionsΔρmin = 0.47 e Å3
247 parameters
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 > 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
xyzUiso*/Ueq
I10.077786 (15)0.76597 (4)0.30466 (2)0.05754 (15)
S10.19206 (6)0.67442 (15)0.02632 (8)0.0498 (3)
N10.23735 (17)0.6319 (5)0.2053 (2)0.0429 (8)
N20.09920 (15)0.2477 (4)0.0182 (2)0.0367 (7)
O10.19851 (17)0.3631 (4)0.2508 (2)0.0604 (9)
O20.25474 (18)0.9042 (4)0.1376 (3)0.0794 (12)
C10.2041 (2)0.4794 (5)0.1898 (3)0.0387 (10)
C20.2329 (2)0.7566 (6)0.1314 (4)0.0514 (11)
C30.17776 (19)0.4612 (5)0.0846 (3)0.0336 (9)
C40.1053 (2)0.4141 (6)0.0797 (4)0.0507 (12)
H4A0.08900.39470.14590.061*
H4B0.08100.50900.04910.061*
C50.16060 (19)0.2397 (5)0.0403 (3)0.0438 (10)
H5A0.15840.31690.09750.053*
H5B0.16920.12080.06260.053*
C60.21191 (19)0.3012 (5)0.0332 (3)0.0384 (10)
H60.21630.20880.08340.046*
C70.2652 (2)0.6746 (8)0.3041 (4)0.0660 (15)
H7A0.24400.60310.35360.079*
H7B0.25600.79680.31900.079*
C80.3375 (3)0.6451 (7)0.3125 (4)0.0639 (14)
C90.3788 (3)0.6811 (11)0.2369 (6)0.108 (3)
H90.36210.71540.17560.130*
C100.4447 (4)0.6680 (13)0.2493 (8)0.127 (3)
H100.47210.69610.19770.152*
C110.4687 (4)0.6138 (13)0.3373 (10)0.145 (5)
H110.51280.60010.34590.174*
C120.4283 (5)0.5788 (13)0.4141 (9)0.147 (4)
H120.44540.54310.47490.176*
C130.3616 (3)0.5959 (8)0.4025 (6)0.096 (2)
H130.33430.57410.45530.115*
C140.0422 (2)0.2554 (6)0.0515 (4)0.0577 (12)
H14A0.04160.15230.09250.086*
H14B0.04540.35810.09250.086*
H14C0.00340.26070.01390.086*
C150.0924 (2)0.0890 (6)0.0835 (4)0.0597 (13)
H15A0.09230.01530.04340.089*
H15B0.05280.09650.11910.089*
H15C0.12780.08450.12980.089*
C160.2790 (2)0.3374 (5)0.0058 (4)0.0466 (11)
C170.2904 (3)0.3710 (6)0.1053 (4)0.0622 (14)
H170.25630.36950.15070.075*
C180.3523 (3)0.4068 (7)0.1378 (5)0.0820 (19)
H180.35970.42770.20470.098*
C190.4027 (3)0.4112 (9)0.0707 (6)0.094 (2)
H190.44390.43740.09210.112*
C200.3922 (3)0.3773 (9)0.0271 (6)0.093 (2)
H200.42640.38040.07220.112*
C210.3302 (2)0.3378 (8)0.0599 (5)0.0720 (15)
H210.32350.31180.12640.086*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0515 (2)0.0679 (2)0.0534 (2)0.00499 (17)0.00931 (14)0.00278 (17)
S10.0705 (8)0.0409 (6)0.0382 (6)0.0115 (6)0.0036 (6)0.0102 (5)
N10.043 (2)0.049 (2)0.0362 (19)0.0022 (17)0.0004 (16)0.0101 (17)
N20.0386 (17)0.0338 (18)0.0379 (17)0.0002 (15)0.0067 (14)0.0014 (16)
O10.083 (2)0.062 (2)0.0358 (17)0.0117 (19)0.0116 (16)0.0174 (16)
O20.084 (3)0.0392 (19)0.115 (3)0.0095 (18)0.003 (2)0.010 (2)
C10.042 (2)0.043 (2)0.032 (2)0.0121 (19)0.0072 (19)0.0017 (19)
C20.050 (3)0.040 (3)0.065 (3)0.007 (2)0.010 (2)0.009 (2)
C30.040 (2)0.031 (2)0.030 (2)0.0045 (17)0.0053 (17)0.0007 (16)
C40.045 (3)0.050 (3)0.057 (3)0.003 (2)0.007 (2)0.020 (2)
C50.046 (2)0.042 (2)0.043 (2)0.003 (2)0.0163 (19)0.010 (2)
C60.043 (2)0.032 (2)0.041 (2)0.0036 (17)0.0103 (19)0.0039 (17)
C70.057 (3)0.095 (4)0.046 (3)0.003 (3)0.007 (2)0.026 (3)
C80.056 (3)0.064 (3)0.071 (4)0.003 (3)0.016 (3)0.024 (3)
C90.059 (4)0.175 (7)0.091 (5)0.024 (4)0.001 (4)0.036 (5)
C100.059 (5)0.171 (8)0.150 (8)0.021 (5)0.000 (5)0.050 (7)
C110.058 (5)0.123 (8)0.252 (15)0.008 (5)0.035 (7)0.033 (9)
C120.106 (7)0.123 (7)0.210 (12)0.008 (6)0.093 (8)0.029 (7)
C130.095 (5)0.079 (4)0.113 (6)0.008 (4)0.036 (5)0.014 (4)
C140.044 (3)0.070 (3)0.058 (3)0.001 (3)0.006 (2)0.001 (3)
C150.053 (3)0.051 (3)0.076 (3)0.007 (2)0.016 (3)0.023 (3)
C160.042 (3)0.038 (2)0.061 (3)0.0032 (19)0.013 (2)0.007 (2)
C170.064 (3)0.059 (3)0.064 (3)0.011 (3)0.023 (3)0.013 (3)
C180.082 (4)0.075 (4)0.090 (4)0.019 (3)0.043 (4)0.018 (3)
C190.061 (4)0.085 (5)0.137 (7)0.007 (3)0.040 (4)0.019 (5)
C200.047 (3)0.106 (5)0.126 (6)0.012 (3)0.003 (4)0.017 (5)
C210.046 (3)0.084 (4)0.087 (4)0.016 (3)0.005 (3)0.007 (3)
Geometric parameters (Å, º) top
S1—C21.759 (5)C9—C101.382 (10)
S1—C31.828 (4)C9—H90.9300
N1—C11.366 (5)C10—C111.345 (13)
N1—C21.377 (6)C10—H100.9300
N1—C71.482 (5)C11—C121.366 (13)
N2—C151.501 (5)C11—H110.9300
N2—C141.504 (6)C12—C131.401 (10)
N2—C51.510 (5)C12—H120.9300
N2—C41.518 (5)C13—H130.9300
O1—C11.215 (5)C14—H14A0.9600
O2—C21.214 (5)C14—H14B0.9600
C1—C31.520 (5)C14—H14C0.9600
C3—C41.549 (6)C15—H15A0.9600
C3—C61.574 (5)C15—H15B0.9600
C4—H4A0.9700C15—H15C0.9600
C4—H4B0.9700C16—C211.376 (7)
C5—C61.521 (6)C16—C171.389 (7)
C5—H5A0.9700C17—C181.392 (7)
C5—H5B0.9700C17—H170.9300
C6—C161.522 (6)C18—C191.375 (9)
C6—H60.9800C18—H180.9300
C7—C81.524 (7)C19—C201.363 (9)
C7—H7A0.9700C19—H190.9300
C7—H7B0.9700C20—C211.401 (8)
C8—C131.360 (8)C20—H200.9300
C8—C91.368 (9)C21—H210.9300
C2—S1—C392.8 (2)C13—C8—C7117.3 (6)
C1—N1—C2116.4 (4)C9—C8—C7122.9 (6)
C1—N1—C7121.0 (4)C8—C9—C10121.7 (8)
C2—N1—C7121.4 (4)C8—C9—H9119.1
C15—N2—C14108.6 (3)C10—C9—H9119.1
C15—N2—C5111.1 (3)C11—C10—C9119.0 (9)
C14—N2—C5109.9 (3)C11—C10—H10120.5
C15—N2—C4110.9 (4)C9—C10—H10120.5
C14—N2—C4111.6 (3)C10—C11—C12120.3 (9)
C5—N2—C4104.7 (3)C10—C11—H11119.9
O1—C1—N1124.5 (4)C12—C11—H11119.9
O1—C1—C3122.0 (4)C11—C12—C13120.9 (9)
N1—C1—C3113.4 (3)C11—C12—H12119.5
O2—C2—N1124.5 (5)C13—C12—H12119.5
O2—C2—S1124.1 (4)C8—C13—C12118.6 (8)
N1—C2—S1111.5 (3)C8—C13—H13120.7
C1—C3—C4113.5 (3)C12—C13—H13120.7
C1—C3—C6108.8 (3)N2—C14—H14A109.5
C4—C3—C6104.3 (3)N2—C14—H14B109.5
C1—C3—S1105.2 (3)H14A—C14—H14B109.5
C4—C3—S1110.5 (3)N2—C14—H14C109.5
C6—C3—S1114.8 (3)H14A—C14—H14C109.5
N2—C4—C3106.9 (3)H14B—C14—H14C109.5
N2—C4—H4A110.3N2—C15—H15A109.5
C3—C4—H4A110.3N2—C15—H15B109.5
N2—C4—H4B110.3H15A—C15—H15B109.5
C3—C4—H4B110.3N2—C15—H15C109.5
H4A—C4—H4B108.6H15A—C15—H15C109.5
N2—C5—C6103.8 (3)H15B—C15—H15C109.5
N2—C5—H5A111.0C21—C16—C17118.9 (5)
C6—C5—H5A111.0C21—C16—C6118.8 (4)
N2—C5—H5B111.0C17—C16—C6122.3 (4)
C6—C5—H5B111.0C16—C17—C18120.6 (6)
H5A—C5—H5B109.0C16—C17—H17119.7
C5—C6—C16118.0 (3)C18—C17—H17119.7
C5—C6—C3102.0 (3)C19—C18—C17119.8 (6)
C16—C6—C3115.7 (3)C19—C18—H18120.1
C5—C6—H6106.8C17—C18—H18120.1
C16—C6—H6106.8C20—C19—C18120.2 (6)
C3—C6—H6106.8C20—C19—H19119.9
N1—C7—C8114.1 (4)C18—C19—H19119.9
N1—C7—H7A108.7C19—C20—C21120.3 (6)
C8—C7—H7A108.7C19—C20—H20119.9
N1—C7—H7B108.7C21—C20—H20119.9
C8—C7—H7B108.7C16—C21—C20120.3 (6)
H7A—C7—H7B107.6C16—C21—H21119.9
C13—C8—C9119.5 (6)C20—C21—H21119.9
C2—N1—C1—O1173.5 (4)C1—C3—C6—C5151.1 (3)
C7—N1—C1—O15.6 (6)C4—C3—C6—C529.6 (4)
C2—N1—C1—C310.6 (5)S1—C3—C6—C591.4 (3)
C7—N1—C1—C3178.5 (3)C1—C3—C6—C1679.6 (4)
C1—N1—C2—O2173.1 (4)C4—C3—C6—C16159.0 (4)
C7—N1—C2—O25.3 (7)S1—C3—C6—C1638.0 (5)
C1—N1—C2—S17.2 (5)C1—N1—C7—C8102.8 (5)
C7—N1—C2—S1175.0 (3)C2—N1—C7—C889.9 (6)
C3—S1—C2—O2179.0 (4)N1—C7—C8—C13148.3 (5)
C3—S1—C2—N11.4 (3)N1—C7—C8—C937.7 (8)
O1—C1—C3—C454.5 (5)C13—C8—C9—C100.4 (11)
N1—C1—C3—C4129.5 (4)C7—C8—C9—C10174.2 (7)
O1—C1—C3—C661.1 (5)C8—C9—C10—C111.8 (14)
N1—C1—C3—C6114.9 (4)C9—C10—C11—C122.4 (16)
O1—C1—C3—S1175.4 (3)C10—C11—C12—C131.0 (17)
N1—C1—C3—S18.6 (4)C9—C8—C13—C121.8 (10)
C2—S1—C3—C13.9 (3)C7—C8—C13—C12176.0 (6)
C2—S1—C3—C4126.7 (3)C11—C12—C13—C81.2 (13)
C2—S1—C3—C6115.7 (3)C5—C6—C16—C21159.5 (4)
C15—N2—C4—C3100.0 (4)C3—C6—C16—C2179.4 (5)
C14—N2—C4—C3138.7 (4)C5—C6—C16—C1720.9 (6)
C5—N2—C4—C319.9 (4)C3—C6—C16—C17100.2 (5)
C1—C3—C4—N2124.5 (4)C21—C16—C17—C180.8 (7)
C6—C3—C4—N26.2 (4)C6—C16—C17—C18178.7 (4)
S1—C3—C4—N2117.7 (3)C16—C17—C18—C190.8 (8)
C15—N2—C5—C680.4 (4)C17—C18—C19—C201.3 (10)
C14—N2—C5—C6159.4 (3)C18—C19—C20—C210.0 (11)
C4—N2—C5—C639.4 (4)C17—C16—C21—C202.1 (8)
N2—C5—C6—C16170.5 (3)C6—C16—C21—C20177.5 (5)
N2—C5—C6—C342.6 (4)C19—C20—C21—C161.7 (10)

Experimental details

Crystal data
Chemical formulaC21H23IN2O2S+·I
Mr494.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)20.791 (7), 7.606 (3), 13.484 (5)
β (°) 90.685 (5)
V3)2132.1 (12)
Z4
Radiation typeMo Kα
µ (mm1)1.62
Crystal size (mm)0.30 × 0.14 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.675, 0.851
No. of measured, independent and
observed [I > 2σ(I)] reflections
11395, 4347, 2790
Rint0.040
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.104, 1.02
No. of reflections4347
No. of parameters247
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.74, 0.47

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C21.759 (5)O1—C11.215 (5)
S1—C31.828 (4)O2—C21.214 (5)
C2—S1—C392.8 (2)O2—C2—S1124.1 (4)
C1—N1—C2116.4 (4)N1—C2—S1111.5 (3)
C5—N2—C4104.7 (3)
C6—C3—C4—N26.2 (4)C1—C3—C6—C5151.1 (3)
 

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