3,9-Diisopropyl-2,4,8,10-tetra­thia­spiro­[5.5]undeca­ne

Gâz, Ş.A.; Dobra, I.; Woiczechowski-Pop, A.; Varga, R.A.; Grosu, I.

doi:10.1107/S1600536810037281

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2618

doi:10.1107/S1600536810037281

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3,9-Diisopropyl-2,4,8,10-tetrathiaspiro[5.5]undecane

Şerban Andrei Gâz,^a Ioana Dobra,^a Adrian Woiczechowski-Pop,^a Richard A. Varga ^b and Ion Grosu ^a ^*

^aOrganic Chemistry Department, CCSOOM, Faculty of Chemistry and Chemical Engineering, `Babes-Bolyai' University, Arany Janos Street 11, RO-400028 Cluj Napoca, Romania, and ^bFaculty of Chemistry and Chemical Engineering, `Babes-Bolyai' University, Arany Janos Street 11, RO-400028 Cluj Napoca, Romania
^*Correspondence e-mail: igrosu@chem.ubbcluj.ro

(Received 27 August 2010; accepted 17 September 2010; online 25 September 2010)

The molecule of the title compound, C₁₃H₂₄S₄, has C2 symmetry and it crystallizes as a racemate. The structure displays two six-membered rings exhibiting chair conformations, with the isopropyl substituents in equatorial positions. In the crystal structure, weak intermolecular C—H⋯S interactions are observed, leading to a channel-like arrangement along the c axis.

Related literature

For background to the chemistry of spirans, see: Cismaş et al. (2005 ); Eliel & Wilen (1994 ); Grosu et al. (1995 , 1997 ); Terec et al. (2001 , 2004 ). For other studies regarding the synthesis and stereochemistry of spiranes bearing 1,3-dithiane units, see: Backer & Evenhuis (1937 ); Gâz et al. (2008 ); Mitkin et al. (2001 ). For the crystal structure of a spiran beaing 1,3-dithiane unit atoms, see: Zhou et al. (2001 ).

Experimental

Crystal data

C₁₃H₂₄S₄
M_r = 308.56
Monoclinic, C 2/c
a = 16.701 (5) Å
b = 10.241 (3) Å
c = 12.063 (3) Å
β = 128.418 (4)°
V = 1616.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 297 K
0.32 × 0.31 × 0.28 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.839, T_max = 0.857
7606 measured reflections
1432 independent reflections
1311 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.153
S = 1.27
1432 reflections
80 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7C⋯S1ⁱ	0.96	2.93	3.827 (6)	156 (1)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg & Putz, 2004 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037281/jh2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037281/jh2201Isup2.hkl

checkCIF report

Comment top

Despite the rich literature dealing with spiro compounds (Cismaş et al., 2005; Eliel & Wilen, 1994; Grosu et al., 1995, 1997; Terec et al., 2001, 2004) new papers were written recently especially including spiro derivatives having sulfur or selenium heteroatoms. Only few spirans bearing 1,3 dithiane units were reported (Backer & Evenhuis, 1937; Gâz et al., 2008; Mitkin et al., 2001) and only 2 crystals were obtained so far (Zhou et al., 2001). The title compound (Fig. 1) exhibits a C2 symmetry unit with chair conformation for both six-membered rings.

Due to the space arrangement there are differences between positions 2, 4 and 2', 4'. Due to these differencies positions 4 and 4' which are oriented towards the other 1,3-dithiane ring are named methylene inside, while the other two CH₂ groups (positions 2 and 2') are oriented in opposite direction and they are named methylene outside groups.

In the crystal packing (Fig. 2 and Fig. 3) the sulfur atom from a neighbour molecule is hydrogen-bonded (weak interactions) via a intermolecular C7—H7c ···S1 connection (Table 1).

These weak interactions stabilize the lattice and form a three-dimensional network as a channel-like arrangement along the c axis.

Related literature top

For background to the chemistry of spirans, see: Cismaş et al. (2005); Eliel & Wilen (1994); Grosu et al. (1995, 1997); Terec et al. (2001, 2004). For other studies regarding the synthesis and stereochemistry of spiranes bearing 1,3-dithiane units, see: Backer & Evenhuis (1937); Gâz et al. (2008); Mitkin et al. (2001). For the crystal structure of a spiran beaing 1,3-dithiane unit atoms, see: Zhou et al. (2001).

Experimental top

The synthesis of I has been described elsewhere (Gâz et al., 2008). Crystal were obtained from dichloromethane, by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2004); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP digram of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the molecular structure exhibiting the hydrogen bonding interactions.
	Fig. 3. The crystal packing viewed along c axis, exhibiting channel-like arrangement formed most probably by weak interaction between the methyl group H atoms and the sulfur atom from a neighbour molecule.

3,9-Diisopropyl-2,4,8,10-tetrathiaspiro[5.5]undecane top

Crystal data top

C₁₃H₂₄S₄	F(000) = 664
M_r = 308.56	D_x = 1.268 Mg m⁻³
Monoclinic, C2/c	Melting point = 416–418 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 16.701 (5) Å	Cell parameters from 3441 reflections
b = 10.241 (3) Å	θ = 2.5–28.1°
c = 12.063 (3) Å	µ = 0.57 mm⁻¹
β = 128.418 (4)°	T = 297 K
V = 1616.5 (8) Å³	Block, colourless
Z = 4	0.32 × 0.31 × 0.28 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1432 independent reflections
Radiation source: fine-focus sealed tube	1311 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −19→19
T_min = 0.839, T_max = 0.857	k = −12→12
7606 measured reflections	l = −14→14

Refinement top

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.27	w = 1/[σ²(F_o²) + (0.0592P)² + 2.605P] where P = (F_o² + 2F_c²)/3
1432 reflections	(Δ/σ)_max < 0.001
80 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₃H₂₄S₄	V = 1616.5 (8) Å³
M_r = 308.56	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.701 (5) Å	µ = 0.57 mm⁻¹
b = 10.241 (3) Å	T = 297 K
c = 12.063 (3) Å	0.32 × 0.31 × 0.28 mm
β = 128.418 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1432 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1311 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.857	R_int = 0.035
7606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.27	Δρ_max = 0.36 e Å⁻³
1432 reflections	Δρ_min = −0.28 e Å⁻³
80 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

	x	y	z	U_iso*/U_eq
C1	0.5000	0.7036 (5)	1.2500	0.0439 (11)
C2	0.4969 (3)	0.6137 (4)	1.1462 (4)	0.0596 (11)
H2A	0.4357	0.5606	1.0981	0.071*
H2B	0.5551	0.5551	1.2001	0.071*
C3	0.3816 (3)	0.7866 (4)	0.9229 (4)	0.0486 (9)
H3	0.3245	0.7260	0.8842	0.058*
C4	0.4026 (3)	0.7860 (4)	1.1697 (4)	0.0484 (9)
H4A	0.4024	0.8353	1.2382	0.058*
H4B	0.3444	0.7273	1.1218	0.058*
C5	0.3655 (3)	0.8601 (4)	0.7999 (4)	0.0585 (11)
H5	0.4243	0.9179	0.8388	0.070*
C6	0.3597 (5)	0.7656 (6)	0.6974 (5)	0.103 (2)
H6A	0.2997	0.7123	0.6529	0.154*
H6B	0.4193	0.7110	0.7483	0.154*
H6C	0.3564	0.8140	0.6266	0.154*
C7	0.2696 (4)	0.9437 (6)	0.7207 (5)	0.0846 (16)
H7A	0.2571	0.9797	0.6377	0.127*
H7B	0.2786	1.0132	0.7809	0.127*
H7C	0.2124	0.8908	0.6934	0.127*
S1	0.49848 (9)	0.69295 (11)	1.01407 (11)	0.0627 (4)
S2	0.38431 (7)	0.89852 (9)	1.04130 (10)	0.0529 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.050 (3)	0.036 (3)	0.041 (3)	0.000	0.026 (2)	0.000
C2	0.076 (3)	0.050 (2)	0.049 (2)	0.016 (2)	0.037 (2)	0.0054 (18)
C3	0.047 (2)	0.048 (2)	0.044 (2)	−0.0022 (16)	0.0251 (18)	0.0052 (16)
C4	0.040 (2)	0.055 (2)	0.046 (2)	−0.0010 (16)	0.0251 (17)	−0.0052 (17)
C5	0.055 (2)	0.061 (2)	0.050 (2)	−0.0053 (19)	0.028 (2)	0.0109 (19)
C6	0.139 (5)	0.112 (5)	0.061 (3)	0.014 (4)	0.064 (4)	0.018 (3)
C7	0.062 (3)	0.102 (4)	0.068 (3)	0.014 (3)	0.029 (2)	0.039 (3)
S1	0.0744 (8)	0.0695 (7)	0.0527 (6)	0.0285 (6)	0.0437 (6)	0.0142 (5)
S2	0.0497 (6)	0.0444 (6)	0.0520 (6)	0.0097 (4)	0.0254 (5)	0.0033 (4)

Geometric parameters (Å, º) top

C1—C4ⁱ	1.529 (4)	C4—H4A	0.9700
C1—C4	1.529 (4)	C4—H4B	0.9700
C1—C2	1.529 (5)	C5—C7	1.520 (6)
C1—C2ⁱ	1.529 (5)	C5—C6	1.524 (7)
C2—S1	1.803 (4)	C5—H5	0.9800
C2—H2A	0.9700	C6—H6A	0.9600
C2—H2B	0.9700	C6—H6B	0.9600
C3—C5	1.531 (5)	C6—H6C	0.9600
C3—S1	1.809 (4)	C7—H7A	0.9600
C3—S2	1.810 (4)	C7—H7B	0.9600
C3—H3	0.9800	C7—H7C	0.9600
C4—S2	1.798 (4)

C4ⁱ—C1—C4	113.0 (4)	S2—C4—H4B	108.2
C4ⁱ—C1—C2	109.4 (2)	H4A—C4—H4B	107.4
C4—C1—C2	109.4 (2)	C7—C5—C6	109.7 (4)
C4ⁱ—C1—C2ⁱ	109.4 (2)	C7—C5—C3	111.6 (4)
C4—C1—C2ⁱ	109.4 (2)	C6—C5—C3	111.0 (4)
C2—C1—C2ⁱ	106.0 (4)	C7—C5—H5	108.2
C1—C2—S1	116.2 (3)	C6—C5—H5	108.2
C1—C2—H2A	108.2	C3—C5—H5	108.2
S1—C2—H2A	108.2	C5—C6—H6A	109.5
C1—C2—H2B	108.2	C5—C6—H6B	109.5
S1—C2—H2B	108.2	H6A—C6—H6B	109.5
H2A—C2—H2B	107.4	C5—C6—H6C	109.5
C5—C3—S1	108.9 (3)	H6A—C6—H6C	109.5
C5—C3—S2	110.9 (3)	H6B—C6—H6C	109.5
S1—C3—S2	111.59 (19)	C5—C7—H7A	109.5
C5—C3—H3	108.5	C5—C7—H7B	109.5
S1—C3—H3	108.5	H7A—C7—H7B	109.5
S2—C3—H3	108.5	C5—C7—H7C	109.5
C1—C4—S2	116.3 (2)	H7A—C7—H7C	109.5
C1—C4—H4A	108.2	H7B—C7—H7C	109.5
S2—C4—H4A	108.2	C2—S1—C3	99.99 (18)
C1—C4—H4B	108.2	C4—S2—C3	100.49 (17)

C4ⁱ—C1—C2—S1	−59.6 (4)	S1—C3—C5—C6	58.7 (4)
C4—C1—C2—S1	64.8 (4)	S2—C3—C5—C6	−178.1 (3)
C2ⁱ—C1—C2—S1	−177.4 (4)	C1—C2—S1—C3	−61.4 (3)
C4ⁱ—C1—C4—S2	58.00 (19)	C5—C3—S1—C2	−178.1 (3)
C2—C1—C4—S2	−64.2 (4)	S2—C3—S1—C2	59.1 (2)
C2ⁱ—C1—C4—S2	−179.8 (2)	C1—C4—S2—C3	60.4 (3)
S1—C3—C5—C7	−178.6 (3)	C5—C3—S2—C4	179.5 (3)
S2—C3—C5—C7	−55.5 (4)	S1—C3—S2—C4	−58.9 (2)

Symmetry code: (i) −x+1, y, −z+5/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···S1ⁱⁱ	0.96	2.93	3.827 (6)	156 (1)

Symmetry code: (ii) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₂₄S₄
M_r	308.56
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	297
a, b, c (Å)	16.701 (5), 10.241 (3), 12.063 (3)
β (°)	128.418 (4)
V (Å³)	1616.5 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.32 × 0.31 × 0.28

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.839, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	7606, 1432, 1311
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.153, 1.27
No. of reflections	1432
No. of parameters	80
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28

Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2004), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7C···S1ⁱ	0.961	2.928	3.827 (6)	156.20 (4)

Symmetry code: (i) x−1/2, −y+3/2, z−1/2.

Acknowledgements

This work was supported by CNCSIS–UEFISCSU, project number PNII–IDEI515/2007. We also thank the National Centre for X-Ray Diffraction, Cluj-Napoca, for support with the solid-state structure determination.

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