2-({4-[(1H-Imidazol-2-ylsulfanyl)methyl]-2,5-dimethylbenzyl}sulfanyl)-1H-imidazole

Applewhite, M.J.; Potts, S.V.

doi:10.1107/S1600536810039607

organic compounds

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2-({4-[(1H-Imidazol-2-ylsulfanyl)methyl]-2,5-dimethylbenzyl}sulfanyl)-1H-imidazole

Malcolm J. Applewhite ^a ^* and Storm V. Potts ^a

^aDepartment of Chemistry and Polymer Science, Stellenbosch University, Private Bag X1, Matieland, 7602, South Africa
^*Correspondence e-mail: malcolma@sun.ac.za

(Received 8 September 2010; accepted 4 October 2010; online 9 October 2010)

The title compound, C₁₆H₁₈N₄S₂, was prepared by the substitution reaction of two equivalents of 2-mercaptoimidazole for every bromine substituent of 1,4-bis(bromomethyl)-2,5-dimethylbenzene. The molecule is located on a crystallographic centre of inversion and therefore adopts a trans configuration with regards to the orientation of the two sulfur atoms. An intermolecular N—H⋯N hydrogen bond forms layers of molecules parallel to ( $[\overline{1}]$ 03). The dihedral angle between the central and terminal rings is 174.8 (2)°.

Related literature

For related structures, see: Fan et al. (2003 ); Voo et al. (2003 ).

Experimental

Crystal data

C₁₆H₁₈N₄S₂
M_r = 330.46
Monoclinic, P 2₁ /n
a = 6.169 (3) Å
b = 9.491 (5) Å
c = 13.722 (8) Å
β = 95.392 (8)°
V = 799.8 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.2 × 0.14 × 0.07 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.945, T_max = 0.977
4896 measured reflections
1875 independent reflections
1154 reflections with I > 2sσ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.149
S = 1.01
1875 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.88	1.93	2.791 (4)	165
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: X-SEED.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536810039607/bt5352sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039607/bt5352Isup2.hkl

checkCIF report

Comment top

The molecule adopts a trans configuration with regards to the orientation of the two sulfur atoms.

Related literature top

For related structures, see: Fan et al. (2003); Voo et al. (2003).

Experimental top

2-Mercaptoimidazole (1.60 g, 16 mmol) was added to 1,4-bis(bromomethyl)-2,5-dimethylbenzene (1.30 g, 4 mmol) in 200 mL of MeOH. The resulting solution was refluxed for 24 h.

The solvent was then removed in vacuo and K₂CO₃ (6.91 g, 50 mmol) in 100 mL of H₂O was added. The solution was stirred until the product precipitated. The white solid was then filtered, washed with 100 mL of H₂O and left to air dry.

Structure description top

The molecule adopts a trans configuration with regards to the orientation of the two sulfur atoms.

For related structures, see: Fan et al. (2003); Voo et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

Figures top

	Fig. 1. The molecular structure of the title compound which has 50% probability ellipsoids. The trans relationship between the sulfur atoms can clearly be seen.
	Fig. 2. The crystal packing viewed down the c axis shows N—H···N hydrogen bonding occurring to form chains throughout a layer of the crystal structure.

2-({4-[(1H-Imidazol-2-ylsulfanyl)methyl]-2,5- dimethylbenzyl}sulfanyl)-1H-imidazole top

Crystal data top

C₁₆H₁₈N₄S₂	F(000) = 348
M_r = 330.46	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 394 reflections
a = 6.169 (3) Å	θ = 2.6–28.2°
b = 9.491 (5) Å	µ = 0.33 mm⁻¹
c = 13.722 (8) Å	T = 100 K
β = 95.392 (8)°	Shard, colourless
V = 799.8 (8) Å³	0.2 × 0.14 × 0.07 mm
Z = 2

Data collection top

Bruker APEX CCD area-detector diffractometer	1875 independent reflections
Radiation source: fine-focus sealed tube	1154 reflections with I > 2sσ(I)
Graphite monochromator	R_int = 0.075
ω scans	θ_max = 28.2°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→7
T_min = 0.945, T_max = 0.977	k = −12→6
4896 measured reflections	l = −17→18

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0617P)²] where P = (F_o² + 2F_c²)/3
1875 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₆H₁₈N₄S₂	V = 799.8 (8) Å³
M_r = 330.46	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.169 (3) Å	µ = 0.33 mm⁻¹
b = 9.491 (5) Å	T = 100 K
c = 13.722 (8) Å	0.2 × 0.14 × 0.07 mm
β = 95.392 (8)°

Data collection top

Bruker APEX CCD area-detector diffractometer	1875 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1154 reflections with I > 2sσ(I)
T_min = 0.945, T_max = 0.977	R_int = 0.075
4896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	Δρ_max = 0.67 e Å⁻³
1875 reflections	Δρ_min = −0.39 e Å⁻³
101 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
N1	0.7634 (4)	0.7794 (3)	0.28821 (19)	0.0230 (7)
H1	0.7160	0.6949	0.2705	0.028*
C2	0.8959 (5)	0.8119 (4)	0.3693 (2)	0.0249 (8)
H2	0.9548	0.7482	0.4182	0.030*
C3	0.9285 (5)	0.9529 (4)	0.3674 (2)	0.0257 (8)
H3	1.0158	1.0050	0.4154	0.031*
N4	0.8168 (4)	1.0086 (3)	0.28587 (18)	0.0250 (7)
C5	0.7181 (5)	0.8997 (4)	0.2400 (2)	0.0205 (7)
S6	0.55288 (13)	0.91254 (10)	0.12971 (6)	0.0241 (3)
C7	0.2861 (5)	0.9423 (4)	0.1750 (2)	0.0275 (8)
H7A	0.2403	0.8586	0.2109	0.033*
H7B	0.2914	1.0246	0.2195	0.033*
C8	0.1309 (5)	0.9690 (4)	0.0855 (2)	0.0233 (8)
C9	0.0933 (5)	1.1077 (4)	0.0551 (2)	0.0243 (8)
H9	0.1587	1.1819	0.0939	0.029*
C10	0.0364 (5)	0.8586 (4)	0.0300 (2)	0.0242 (8)
C11	0.0624 (6)	0.7085 (4)	0.0609 (3)	0.0320 (9)
H11A	−0.0269	0.6900	0.1149	0.048*
H11B	0.2156	0.6898	0.0825	0.048*
H11C	0.0154	0.6469	0.0055	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0274 (15)	0.0207 (16)	0.0199 (14)	−0.0032 (13)	−0.0031 (11)	−0.0010 (12)
C2	0.0244 (19)	0.030 (2)	0.0189 (17)	0.0024 (15)	−0.0067 (14)	0.0045 (15)
C3	0.0272 (19)	0.032 (2)	0.0163 (16)	−0.0024 (16)	−0.0055 (13)	0.0015 (15)
N4	0.0290 (16)	0.0248 (16)	0.0201 (14)	−0.0021 (13)	−0.0035 (12)	−0.0009 (13)
C5	0.0209 (17)	0.0212 (18)	0.0190 (16)	0.0042 (15)	−0.0002 (13)	−0.0013 (14)
S6	0.0221 (5)	0.0314 (5)	0.0177 (4)	0.0031 (4)	−0.0038 (3)	−0.0002 (4)
C7	0.0235 (18)	0.039 (2)	0.0194 (16)	0.0085 (16)	−0.0035 (13)	0.0023 (16)
C8	0.0189 (17)	0.032 (2)	0.0185 (16)	0.0028 (15)	0.0004 (13)	0.0008 (15)
C9	0.0182 (17)	0.029 (2)	0.0249 (17)	0.0009 (15)	0.0002 (13)	−0.0051 (15)
C10	0.0229 (18)	0.0268 (19)	0.0230 (17)	0.0031 (15)	0.0017 (14)	0.0031 (15)
C11	0.034 (2)	0.027 (2)	0.036 (2)	0.0035 (17)	0.0045 (16)	0.0035 (17)

Geometric parameters (Å, º) top

N1—C5	1.336 (4)	C7—H7A	0.9900
N1—C2	1.354 (4)	C7—H7B	0.9900
N1—H1	0.8800	C8—C10	1.391 (5)
C2—C3	1.353 (5)	C8—C9	1.394 (5)
C2—H2	0.9500	C9—C10ⁱ	1.389 (4)
C3—N4	1.364 (4)	C9—H9	0.9500
C3—H3	0.9500	C10—C9ⁱ	1.389 (4)
N4—C5	1.327 (4)	C10—C11	1.491 (5)
C5—S6	1.748 (3)	C11—H11A	0.9800
S6—C7	1.835 (3)	C11—H11B	0.9800
C7—C8	1.506 (4)	C11—H11C	0.9800

C5—N1—C2	107.1 (3)	S6—C7—H7B	110.6
C5—N1—H1	126.5	H7A—C7—H7B	108.7
C2—N1—H1	126.5	C10—C8—C9	119.8 (3)
C3—C2—N1	106.8 (3)	C10—C8—C7	121.4 (3)
C3—C2—H2	126.6	C9—C8—C7	118.6 (3)
N1—C2—H2	126.6	C10ⁱ—C9—C8	122.4 (3)
C2—C3—N4	109.6 (3)	C10ⁱ—C9—H9	118.8
C2—C3—H3	125.2	C8—C9—H9	118.8
N4—C3—H3	125.2	C9ⁱ—C10—C8	117.8 (3)
C5—N4—C3	105.1 (3)	C9ⁱ—C10—C11	119.8 (3)
N4—C5—N1	111.5 (3)	C8—C10—C11	122.4 (3)
N4—C5—S6	124.1 (3)	C10—C11—H11A	109.5
N1—C5—S6	124.5 (3)	C10—C11—H11B	109.5
C5—S6—C7	100.70 (15)	H11A—C11—H11B	109.5
C8—C7—S6	105.7 (2)	C10—C11—H11C	109.5
C8—C7—H7A	110.6	H11A—C11—H11C	109.5
S6—C7—H7A	110.6	H11B—C11—H11C	109.5
C8—C7—H7B	110.6

C5—N1—C2—C3	−0.4 (4)	C5—S6—C7—C8	174.8 (2)
N1—C2—C3—N4	0.2 (4)	S6—C7—C8—C10	83.0 (3)
C2—C3—N4—C5	0.1 (4)	S6—C7—C8—C9	−93.0 (3)
C3—N4—C5—N1	−0.4 (4)	C10—C8—C9—C10ⁱ	−0.2 (5)
C3—N4—C5—S6	−179.6 (2)	C7—C8—C9—C10ⁱ	175.9 (3)
C2—N1—C5—N4	0.5 (4)	C9—C8—C10—C9ⁱ	0.2 (5)
C2—N1—C5—S6	179.7 (2)	C7—C8—C10—C9ⁱ	−175.8 (3)
N4—C5—S6—C7	−90.1 (3)	C9—C8—C10—C11	−177.2 (3)
N1—C5—S6—C7	90.8 (3)	C7—C8—C10—C11	6.9 (5)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱⁱ	0.88	1.93	2.791 (4)	165

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈N₄S₂
M_r	330.46
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	6.169 (3), 9.491 (5), 13.722 (8)
β (°)	95.392 (8)
V (Å³)	799.8 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.2 × 0.14 × 0.07

Data collection
Diffractometer	Bruker APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.945, 0.977
No. of measured, independent and observed [I > 2sσ(I)] reflections	4896, 1875, 1154
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.149, 1.01
No. of reflections	1875
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.39

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.88	1.93	2.791 (4)	164.5

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

Acknowledgements

The authors would like to thank the Central Analytical Facility (CAF) at the University of Stellenbosch (US) for the use of their diffractometer as well as the US and NRF for funding.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fan, C., Ma, C., Chen, C., Chen, F. & Liu, Q. (2003). Inorg. Chem. Commun. 6, 491–494 Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Voo, J. K., Lam, K. C., Rheingold, A. L. & Riordan, C. G. (2003). J. Chem. Soc. Dalton Trans. pp. 1803–1805. Google Scholar

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CRYSTALLOGRAPHIC
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https://doi.org/10.1107/S1600536810039607

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-({4-[(1H-Imidazol-2-ylsulfanyl)methyl]-2,5-di­methylbenzyl}sulfanyl)-1H-imidazole

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-({4-[(1H-Imidazol-2-ylsulfanyl)methyl]-2,5-dimethylbenzyl}sulfanyl)-1H-imidazole