organic compounds
of 3-[({[bis(2-cyanoethyl)carbamothioyl]disulfanyl}methanethioyl)(2-cyanoethyl) amino]propanenitrile
aDepartment of Chemistry, Annamalai University, Annamalainagar, Chidambaram 608 002, India, and bPG & Research Department of Physics, Government Arts College, Melur 625 106, India
*Correspondence e-mail: rbaskaran54@gmail.com
In the title compound, C14H16N6S4, the molecule resides on a twofold rotation axis, which runs through the central S—S bond. In the crystal, molecules are linked via weak C—H⋯N hydrogen bonds, forming C(5) chains propagating in a helical arrangement along [010].
Keywords: crystal structure; cyano derivatives; weak C—H⋯N hydrogen bonds; short intramolecular contacts; twofold rotation symmetry.
CCDC reference: 1504588
Structure description
In a continuation of the work in our laboratory on the
analysis of cyano derivatives, we have undertaken the single-crystal X-ray diffraction study of the title compound, and the results are presented herein.The molecular structure of the title compound is illustrated in Fig. 1. The molecule resides on a crystallographic twofold rotation axis, which runs through the central S—S bond. The molecular structure maybe influenced by a series of very weak intramolecular C—H⋯S hydrogen bonds (Table 1).
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In the crystal, weak C—H⋯N hydrogen bonds link the molecules, forming C(5) chains propagating in a helical arrangement along [010]; see Fig. 2. The structure also forms a cavity consisting of 24 atoms between two molecules in an R22(24) graph-set motif.
Synthesis and crystallization
All chemicals were commercially available and analytical grade materials were used directly without further purification. A stoichiometric amount (0.1732 g, 2 mmol) of carbon disulfide, CS2, was added dropwise to a methanol solution containing (0.2463 g, 2 mmol) 3,3′-azanediyldipropanenitrile and 0.24 g potassium hydroxide. The mixture was stirred for about 25 minutes until a white precipitate appeared. The clear filtrate was then left at temperature of 278 K for crystallization. After few days, crystals suitable for X-ray analysis were collected (yield = 83%, m.p. 431 K). The presence of the C≡N groups was confirmed by FT–IR analysis.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1504588
https://doi.org/10.1107/S2414314617003467/lh4017sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617003467/lh4017Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617003467/lh4017Isup3.cml
Data collection: APEX2 (Bruker, 2004); cell
APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).C14H16N6S4 | F(000) = 824 |
Mr = 396.57 | Dx = 1.404 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 15.4313 (7) Å | Cell parameters from 8307 reflections |
b = 5.6117 (2) Å | θ = 2.3–31.7° |
c = 22.8702 (12) Å | µ = 0.52 mm−1 |
β = 108.713 (2)° | T = 293 K |
V = 1875.77 (15) Å3 | Block, brown |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Bruker Kappa APEXII CCD diffractometer | 2569 reflections with I > 2σ(I) |
Radiation source: Sealed tube | Rint = 0.024 |
ω and φ scan | θmax = 33.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −23→19 |
Tmin = 0.81, Tmax = 0.89 | k = −8→8 |
19984 measured reflections | l = −34→34 |
3347 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0427P)2 + 1.4682P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
3347 reflections | Δρmax = 0.34 e Å−3 |
109 parameters | Δρmin = −0.27 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | −0.00264 (3) | 0.57876 (7) | 0.20581 (2) | 0.03874 (11) | |
S2 | 0.13996 (3) | 0.20336 (9) | 0.26542 (2) | 0.05086 (14) | |
N1 | 0.06850 (8) | 0.2800 (2) | 0.14508 (5) | 0.0328 (2) | |
N2 | −0.09703 (13) | −0.1278 (3) | 0.02598 (9) | 0.0644 (5) | |
N3 | 0.21226 (12) | 0.6016 (3) | 0.08156 (8) | 0.0610 (4) | |
C1 | 0.07351 (10) | 0.3344 (3) | 0.20300 (6) | 0.0325 (3) | |
C2 | 0.00524 (10) | 0.3986 (3) | 0.09077 (6) | 0.0351 (3) | |
H2A | 0.0289 | 0.3838 | 0.0565 | 0.042* | |
H2B | 0.0027 | 0.5669 | 0.0997 | 0.042* | |
C3 | −0.09148 (10) | 0.2961 (3) | 0.07169 (7) | 0.0388 (3) | |
H3A | −0.1125 | 0.2922 | 0.1074 | 0.047* | |
H3B | −0.1322 | 0.3997 | 0.0411 | 0.047* | |
C4 | −0.09592 (11) | 0.0566 (3) | 0.04630 (8) | 0.0429 (3) | |
C5 | 0.12945 (11) | 0.0991 (3) | 0.13344 (8) | 0.0389 (3) | |
H5A | 0.1026 | 0.0367 | 0.0920 | 0.047* | |
H5B | 0.1356 | −0.0318 | 0.1622 | 0.047* | |
C6 | 0.22415 (11) | 0.2006 (3) | 0.14036 (9) | 0.0487 (4) | |
H6A | 0.2567 | 0.2279 | 0.1838 | 0.058* | |
H6B | 0.2586 | 0.0851 | 0.1252 | 0.058* | |
C7 | 0.21877 (11) | 0.4242 (4) | 0.10651 (8) | 0.0455 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0506 (2) | 0.03350 (19) | 0.03374 (19) | 0.00673 (15) | 0.01572 (16) | 0.00523 (14) |
S2 | 0.0572 (3) | 0.0543 (3) | 0.0332 (2) | 0.0171 (2) | 0.00349 (17) | 0.00587 (17) |
N1 | 0.0318 (5) | 0.0356 (6) | 0.0300 (5) | 0.0003 (5) | 0.0086 (4) | 0.0007 (5) |
N2 | 0.0730 (12) | 0.0457 (9) | 0.0650 (11) | −0.0021 (8) | 0.0088 (9) | −0.0066 (8) |
N3 | 0.0552 (9) | 0.0645 (11) | 0.0605 (10) | −0.0191 (8) | 0.0146 (8) | 0.0024 (9) |
C1 | 0.0335 (6) | 0.0312 (6) | 0.0306 (6) | −0.0009 (5) | 0.0071 (5) | 0.0013 (5) |
C2 | 0.0367 (7) | 0.0390 (7) | 0.0283 (6) | −0.0023 (6) | 0.0084 (5) | 0.0035 (5) |
C3 | 0.0332 (7) | 0.0430 (8) | 0.0360 (7) | −0.0003 (6) | 0.0054 (5) | −0.0027 (6) |
C4 | 0.0407 (8) | 0.0437 (8) | 0.0386 (8) | −0.0027 (7) | 0.0047 (6) | 0.0008 (7) |
C5 | 0.0408 (7) | 0.0349 (7) | 0.0422 (8) | 0.0006 (6) | 0.0150 (6) | −0.0045 (6) |
C6 | 0.0360 (7) | 0.0490 (9) | 0.0610 (11) | 0.0050 (7) | 0.0155 (7) | −0.0001 (8) |
C7 | 0.0346 (7) | 0.0570 (10) | 0.0456 (9) | −0.0093 (7) | 0.0140 (6) | −0.0090 (8) |
S1—C1 | 1.8201 (15) | C2—H2B | 0.9700 |
S1—S1i | 1.9968 (7) | C3—C4 | 1.457 (2) |
S2—C1 | 1.6405 (14) | C3—H3A | 0.9700 |
N1—C1 | 1.3375 (18) | C3—H3B | 0.9700 |
N1—C5 | 1.4651 (19) | C5—C6 | 1.529 (2) |
N1—C2 | 1.4699 (18) | C5—H5A | 0.9700 |
N2—C4 | 1.132 (2) | C5—H5B | 0.9700 |
N3—C7 | 1.136 (3) | C6—C7 | 1.462 (3) |
C2—C3 | 1.527 (2) | C6—H6A | 0.9700 |
C2—H2A | 0.9700 | C6—H6B | 0.9700 |
C1—S1—S1i | 102.62 (5) | C2—C3—H3B | 109.2 |
C1—N1—C5 | 120.13 (12) | H3A—C3—H3B | 107.9 |
C1—N1—C2 | 123.03 (12) | N2—C4—C3 | 177.8 (2) |
C5—N1—C2 | 116.82 (12) | N1—C5—C6 | 111.78 (13) |
N1—C1—S2 | 125.50 (11) | N1—C5—H5A | 109.3 |
N1—C1—S1 | 111.98 (10) | C6—C5—H5A | 109.3 |
S2—C1—S1 | 122.52 (8) | N1—C5—H5B | 109.3 |
N1—C2—C3 | 113.23 (12) | C6—C5—H5B | 109.3 |
N1—C2—H2A | 108.9 | H5A—C5—H5B | 107.9 |
C3—C2—H2A | 108.9 | C7—C6—C5 | 112.02 (14) |
N1—C2—H2B | 108.9 | C7—C6—H6A | 109.2 |
C3—C2—H2B | 108.9 | C5—C6—H6A | 109.2 |
H2A—C2—H2B | 107.7 | C7—C6—H6B | 109.2 |
C4—C3—C2 | 112.20 (14) | C5—C6—H6B | 109.2 |
C4—C3—H3A | 109.2 | H6A—C6—H6B | 107.9 |
C2—C3—H3A | 109.2 | N3—C7—C6 | 177.1 (2) |
C4—C3—H3B | 109.2 | ||
C5—N1—C1—S2 | −3.8 (2) | C1—N1—C2—C3 | −82.14 (17) |
C2—N1—C1—S2 | 177.86 (11) | C5—N1—C2—C3 | 99.48 (15) |
C5—N1—C1—S1 | 175.66 (10) | N1—C2—C3—C4 | −69.60 (17) |
C2—N1—C1—S1 | −2.67 (17) | C1—N1—C5—C6 | −81.15 (18) |
S1i—S1—C1—N1 | 170.16 (9) | C2—N1—C5—C6 | 97.28 (16) |
S1i—S1—C1—S2 | −10.36 (10) | N1—C5—C6—C7 | −48.7 (2) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···S1 | 0.97 | 2.46 | 2.857 (2) | 105 |
C3—H3A···S1 | 0.97 | 2.84 | 3.332 (2) | 112 |
C5—H5B···S2 | 0.97 | 2.69 | 3.028 (2) | 101 |
C2—H2B···N2ii | 0.97 | 2.55 | 3.202 (2) | 125 |
Symmetry code: (ii) x, y+1, z. |
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