Crystal structure of 4-(2,2-di­methyl­propanamido)­pyridin-3-yl N,N-diiso­propyl­dithio­carbamate

Gamal A El-Hiti; Keith Smith; Amany S Hegazy; Mohammed Baashen; Benson M Kariuki

doi:10.1107/S1600536814019321

. 2014 Aug 30;70(Pt 9):o1069–o1070. doi: 10.1107/S1600536814019321

Crystal structure of 4-(2,2-dimethylpropanamido)pyridin-3-yl N,N-diisopropyldithiocarbamate

Gamal A El-Hiti ^a,^*, Keith Smith ^b, Amany S Hegazy ^b, Mohammed Baashen ^c, Benson M Kariuki ^b,^*

PMCID: PMC4186077 PMID: 25309230

Abstract

In the title compound, C₁₇H₂₇N₃OS₂, the amide group is approximately coplanar with the pyridine ring [dihedral angle = 1.6 (1)°], whereas the dithiocarbamate group is nearly perpendicular to the pyridine ring [dihedral angle = 76.7 (1)°]. In the crystal, pairs of weak C—H⋯O hydrogen bonds link the molecules into inversion dimers.

Keywords: crystal structure, dithiocarbamate, pyridine derivatives, hydrogen bonding

Related literature

For background to pyridine derivatives, see: Joule & Mills (2000 ▶); Smith et al. (1999 ▶). For the synthesis of the title compound, see: Smith et al. (1988 ▶). For spectroscopic data for this compound, see: Smith et al. (1994 ▶). For routes to modify the pyridine ring, see: El-Hiti (2003 ▶); Turner (1983 ▶). For crystal structures of related compounds, see: El-Hiti et al. (2014 ▶); Koch et al. (2008 ▶); Mazik & Sicking (2004 ▶).

Experimental

Crystal data

C₁₇H₂₇N₃OS₂
M _r = 353.53
Triclinic,
a = 7.9776 (7) Å
b = 9.5412 (9) Å
c = 13.0541 (14) Å
α = 83.099 (8)°
β = 83.227 (8)°
γ = 84.608 (7)°
V = 976.33 (17) Å³
Z = 2
Cu Kα radiation
μ = 2.52 mm⁻¹
T = 293 K
0.36 × 0.24 × 0.19 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014 ▶) T _min = 0.662, T _max = 1.000
6616 measured reflections
3779 independent reflections
3391 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.211
S = 1.16
3779 reflections
215 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2014 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019321/xu5816sup1.cif

e-70-o1069-sup1.cif^{(238.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019321/xu5816Isup2.hkl

e-70-o1069-Isup2.hkl^{(207.4KB, hkl)}

Click here for additional data file.^{(6.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814019321/xu5816Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S1600536814019321/xu5816fig1.tif

The symmetric unit of the title compound with atom labels and 50% probability displacement ellipsoids.

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S1600536814019321/xu5816fig2.tif

Packing in the crystal structure showing C—H⋯O contacts as dotted lines with hydrogen atoms omitted for clarity.

CCDC reference: 1021242

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.54	3.447 (5)	164

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to extend their appreciation to the Cornea Research Chair, Department of Optometry, College of Applied Medical Sciences, King Saud University, for funding this research.

supplementary crystallographic information

S1. Chemical context

Pyridine derivatives are important compounds (Joule & Mills, 2000) and various substituted derivatives can be synthesized via lithiation and subsequent reaction with electrophiles (Turner, 1983). During research focused on synthesis of novel substituted pyridines (El-Hiti, 2003; Smith et al., 1999) we have synthesized the title compound in high yield. For the X-ray structures for related compounds, see: El-Hiti et al., 2014; Koch et al., 2008; Mazik & Sicking, 2004.

S2. Structural commentary

In the molecule of the title compound, C₁₇H₂₇N₃OS₂, (Fig. 1), the pyridine group is almost co-planar (1.6 (1)^o) to the amide group whereas the angle to the carbamodithioate is 76.7 (1)^o. No strong hydrogen bonding interactions occur, with pairs of molecules being linked by pairs of C—H..O contacts (Fig. 2). The molecular pairs are stacked along [010] leading to a structure in which the t-butyl groups form bilayers parallel to the ab plane.

S3. Synthesis and crystallization

4-Pivalamidopyridin-3-yl diisopropylcarbamodithioate was obtained in 93% yield from double lithiation of 4-(pivaloylamino)pyridin-3-yl with n-butyllithium at –78 to 0°C in anhydrous THF under nitrogen followed by reaction with tetraisopropylthiuram disulfide (Smith et al., 1988, 1994). Crystallization from ethyl acetate gave colorless crystals of the title compound. The spectroscopic data of the title compound, including NMR and low and high resolution mass spectra, were consistent with those reported (Smith et al., 1994).

S4. Refinement details

H atoms were positioned geometrically and refined using a riding model, with U_iso(H) constrained to be 1.2 times U_eq for the bonded atom except for methyl groups where it was 1.5 times with free rotation about the C—C bond.