Crystal structure of N,N′-bis­(4-methyl­phen­yl)di­thio­oxamide

Antonino Giannetto; Santo Lanza; Giuseppe Bruno; Francesco Nicoló; Hadi Amiri Rudbari

doi:10.1107/S2056989014027911

. 2015 Jan 3;71(Pt 2):o67. doi: 10.1107/S2056989014027911

Crystal structure of N,N′-bis(4-methylphenyl)dithiooxamide

Antonino Giannetto ^a,^*, Santo Lanza ^a, Giuseppe Bruno ^a, Francesco Nicoló ^a, Hadi Amiri Rudbari ^b

PMCID: PMC4384591 PMID: 25878874

Abstract

Two half molecules of the title compound, C₁₆H₁₆N₂S₂, are present in the asymmetric unit and both molecules are completed by crystallographic inversion centers at the mid-points of the central C—C bonds: the lengths of these bonds [1.538 (5) and 1.533 (5) Å] indicate negligible electronic delocalization. The trans-dithiooxamide fragment in each molecule is characterized by a pair of intramolecular N—H⋯S hydrogen bonds. In the crystal, molecules are linked by weak C—H..π interactions, generating a three-dimensional network.

Keywords: crystal structure, dithiooxamide, ethanedithioamide, intramolecular N—H⋯S hydrogen bonds, C—H..π interactions

Related literature

For the mesogenic properties of related compounds, see: Aversa et al. (1997 ▸, 2000 ▸). For the general procedure for the preparation of secondary and tertiary dithiooxamides, see: Lanza et al. (1993 ▸, 2000 ▸, 2003 ▸); Rosace et al. (1993 ▸). For similar crystal structures, see: Shimanouchi & Sasada (1979 ▸). graphic file with name e-71-00o67-scheme1.jpg

Experimental

Crystal data

C₁₆H₁₆N₂S₂
M _r = 300.43
Monoclinic,
a = 33.9423 (7) Å
b = 11.3880 (2) Å
c = 7.8049 (2) Å
β = 99.439 (1)°
V = 2976.02 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: integration (SADABS; Bruker, 2012 ▸) T _min = 0.657, T _max = 0.745
45528 measured reflections
2621 independent reflections
1626 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.152
S = 1.11
2621 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014027911/hb7339sup1.cif

e-71-00o67-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014027911/hb7339Isup2.hkl

e-71-00o67-Isup2.hkl^{(144.1KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014027911/hb7339Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989014027911/hb7339fig1.tif

Perspective view of the title molecule with displacement ellipsoids plotted at the 50% probability level, while H atoms are shown as small spheres of arbitrary radius.

Click here for additional data file.^{(2MB, tif)}

c . DOI: 10.1107/S2056989014027911/hb7339fig2.tif

Packing diagram of the title compound viewed along the c axis.

Click here for additional data file.^{(2.1MB, tif)}

b . DOI: 10.1107/S2056989014027911/hb7339fig3.tif

Packing diagram of the title compound viewed normal the b axis and showing molecular arrangement on the (40 Inline graphic ) plane.

CCDC reference: 1040609

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the C2C7 and C10C15 rings, respectively.

DHA	DH	HA	D A	DHA
N1H1S1ⁱ	0.86	2.35	2.904(3)	122
N2H2S2ⁱⁱ	0.86	2.35	2.901(3)	122
C7H7Cg1ⁱⁱⁱ	0.93	2.90	3.587(3)	132
C11H11Cg1^iv	0.93	2.77	3.524(3)	139
C14H14Cg2^v	0.93	2.88	3.654(3)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

S1. Comment

Aryl-substituted secondary dithiooxamides H₂N₂C₂S₂R₂ (R=-C₆H₄X, C₆H₃X₂, X =-O-(CH₂)_n-CH₃, 7 <n > 11) have been exploited to prepare platinum(II) complexes which exhibit mesogenic properties (Aversa, et al. 1997; Aversa, et al. 2000). The title compound has been synthesized for a better understanding of the reactivity of the said mesogenic complexes, in the aim to avoid contingent steric hindrance of long chain substituents and the influence on the acid base equilibria of ether moieties. In fact, both the oxygen lone pairs in ether moieties and the exceedingly long alkyl chains of X substituents prevents the formation of ion pairs in the first step of the reaction of secondary dithioxamides with cis-Pt(Me₂SO)₂Cl₂ (Lanza et al., 1993). A detailed analysis of the bond distances reveals a strong double-bond character for both C—S and C—N [1.662 (3) Å and 1.318 (4) Å, respectively], confirming that the important electronic π-delocalization of the N—C—S system does not affect the central C—C bond. In the title compound the central C—C bond distances are 1.538 (5) Å and 1.533 (5) Å respectively for C1—C1' and C9—C9'. Going from a secondary dithiooxamide to a tertiary one we observe a large changing in structural parameters:essentially in the planarity loss of the central fragment and to the significant shortening of central C—C bond. The p-tolyl groups are rotated by -36.4° (5) and -35.4° (5) with respect to the central DTO fragments.

S2. Experimental

The title compound was obtained from para-toluidine according to a described two-step strategy based on primary amine reaction with oxalyl chloride followed by P₂S₅ treatment. ¹H NMR: δ 12.33 (bs, NH), 7.92 (d, J_ortho 8.4 Hz, H_2,6), 7.28 (d, H_3,5), 2.40 (s, Me). ¹³CNMR: δ 180.56 (CS), 137,75 (C₄), 135.80 (C₁), 129.64 (C_3,5), 122.17 (C_2,6), 21.27 (Me)