Home Physical Sciences Crystal structure of di(pyrrolidin-1-yl)methane-thione, C9H16N2S
Article Open Access

Crystal structure of di(pyrrolidin-1-yl)methane-thione, C9H16N2S

  • and EMAIL logo
Published/Copyright: September 26, 2015
Download Article (PDF)
Become an author with De Gruyter Brill
Submit Manuscript Author Information
Zeitschrift für Kristallographie - New Crystal Structures
From the journal Zeitschrift für Kristallographie - New Crystal Structures Volume 230 Issue 4

Abstract

C9H16N2S, orthorhombic, Pbca (no. 61), a = 9.1580(4) Å, b = 11.8157(4) Å, c = 18.0202(8) Å, V = 1949.9 Å3, Z = 8, Rgt(F) = 0.0293, wRref(F2) = 0.0838, T = 200 K.

CCDC no.:: 1267/4327

Source of material

The compound was obtained commercially as “ammonium pyrrolidine dithiocarbamate” (APDC) from Hopkin & Williams Ltd. Crystals suitable for the diffraction study were obtained directly from the crystalline reaction product. An explanation for the presence of the title compound in the provided product is not at hand.

Experimental details

Carbon-bound H atoms were placed in calculated positions (C–H 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).

Table 1

Data collection and handling.

Crystal:Colourless platelets,
size 0.173×0.211×0.262 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:2.81 cm–1
Diffractometer, scan mode:Bruker APEX-II CCD, φ and ω
2θmax:56.6°
N(hkl)measured, N(hkl)unique:17721, 2420
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2038
N(param)refined:109
Programs:SHELX, WinGX, MERCURY,
PLATON [12–15]
Table 2

Atomic coordinates and displacement parameters (in Å2).

AtomSitexyzUiso
H(11A)8c0.40760.51320.03900.043
H(11B)8c0.23480.51500.05600.043
H(12A)8c0.20450.33070.01780.050
H(12B)8c0.33220.3699−0.03830.050
H(13A)8c0.51370.29510.03760.050
H(13B)8c0.38810.19970.04230.050
H(14A)8c0.30840.26180.15610.041
H(14B)8c0.47930.29260.16380.041
H(21A)8c0.40330.60130.32530.046
H(21B)8c0.56200.54440.31440.046
H(22A)8c0.42180.49710.43340.052
H(22B)8c0.50670.39510.39230.052
H(23A)8c0.20100.45090.37590.051
H(23B)8c0.26660.32830.39690.051
H(24A)8c0.34460.29510.27800.040
H(24B)8c0.20530.37350.25920.040

Discussion

Carboxylic acids have been used as ligands in coordination chemistry for many decades. Especially for acetic acid, interesting bonding patterns have been realized for transition metals due to its ability to act as bridging ligand, e.g. for chromium(II)acetate where the presence of a metal-metal quadruple bond has been established on grounds of diffraction studies conducted on single crystals [1–3]. Considerably less work has been conducted for dithiocarboxylic acids in general as well as dithioacetic acid in particular. For the latter, only few compounds whose molecular structure has been elucidated on grounds of diffraction studies based in single crystals have been reported, among others, for platinum [4] and gold [5]. At the beginning of a study about the coordination behaviour of dithiocarboxylic acids bearing heterocyclic substituents, ammonium pyrrolidine dithiocarbamate was chosen as a starting point. As the spectral and analytical properties of the commercially-obtained compound deviated significantly from the expected ones, a structural analysis of the crystalline material was conducted. The results showed the presence of an unexpected compound. The title compound is the C2 symmetric dithioamide derived from pyrrolidine and thiophosgene. The two heterocycles connect to the central C=S unit via their nitrogen atoms. The C–S bond is measured at 1.6928(11) Å while the two C–N bonds towards the central carbon atom are found at 1.3467(14) Å and 1.3575(14) Å. The latter values are in good agreement with the most common ones reported for other dithioamide compounds whose metrical parameters have been deposited with the Cambridge Structural Database [6] and are indicative of amide-type resonance. A puckering analysis of the five-membered rings according to Cremer & Pople [7] shows the adoption of 4T3 conformations in both cases (C13TC12 and C23TC22, respectively) [8]. The least-squares planes as defined by the non-hydrogen atoms of both rings enclose an angle of 62.87(4)°. In the crystal, C–H⋯S contacts whose range falls below the sum of van-der-Waals radii can be observed [9]. These are established by one hydrogen atom on one of the methylene groups directly bonded to the nitrogen atom each in both cycles. In terms of graph-set analysis [10, 11], the descriptor for these contacts is C11(5)C11(5) on the unary level. In total, the molecules are connected to planes perpendicular to the crystallographic c axis.

Table 3

Atomic coordinates and displacement parameters (in Å2).

AtomSitexyzU11U22U33U12U13U23
S(1)8c0.44663(4)0.63687(2)0.16880(2)0.0456(2)0.0230(2)0.0514(2)−0.0050(1)0.0053(1)0.0014(1)
N(11)8c0.3526(1)0.42941(7)0.13436(5)0.0289(4)0.0242(4)0.0329(5)−0.0001(3)0.0006(4)0.0010(3)
N(21)8c0.3995(1)0.46129(7)0.25795(5)0.0287(4)0.0266(4)0.0339(5)−0.0023(4)−0.0021(4)−0.0013(4)
C(1)8c0.3970(1)0.50208(9)0.18818(6)0.0215(4)0.0234(5)0.0378(5)0.0015(4)0.0021(4)−0.0002(4)
C(11)8c0.3245(1)0.4684(1)0.05824(6)0.0380(6)0.0380(6)0.0317(6)0.0018(5)0.0020(4)0.0031(5)
C(12)8c0.3059(1)0.3592(1)0.01455(7)0.0397(6)0.0493(7)0.0350(6)−0.0052(5)0.0015(5)−0.0060(5)
C(13)8c0.4119(1)0.2798(1)0.05299(7)0.0417(6)0.0354(6)0.0480(7)−0.0021(5)0.0041(5)−0.0127(5)
C(14)8c0.3893(1)0.30707(9)0.13491(7)0.0362(6)0.0230(5)0.0435(6)−0.0006(4)−0.0013(5)−0.0027(4)
C(21)8c0.4565(1)0.5287(1)0.32046(7)0.0352(6)0.0390(6)0.0398(6)−0.0026(5)−0.0043(5)−0.0084(5)
C(22)8c0.4288(1)0.4526(1)0.38694(7)0.0394(7)0.0557(8)0.0357(6)0.0030(6)−0.0066(5)−0.0033(6)
C(23)8c0.2831(1)0.3979(1)0.36744(7)0.0382(6)0.0530(7)0.0352(6)0.0001(5)0.0004(5)0.0056(5)
C(24)8c0.3006(1)0.37081(9)0.28515(6)0.0308(5)0.0321(5)0.0367(6)−0.0030(4)−0.0017(4)0.0059(4)
Corresponding author: Richard Betz, Nelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa, e-mail:

Acknowledgments:

The authors thank Mr. Musiegh Madatt for helpful discussions.

References

1. Cotton, F. A.; DeBoer, B. G.; LaPrade, M. D.; Pipal, J. R.; Ucko, D. A.: The Crystal and Molecular Structures of Dichromium Tetra-Acetate Dihydrate and Dirhodium Tetra-Acetate Dihydrate. Acta Crystallogr. B27 (1971) 1664–1671.Search in Google Scholar

2. Benard, M.; Coppens, P.; DeLucia, M. L.; Stevens, E. D.: Experimental and Theoretical Electron Density Analysis of Metal-Metal Bonding in Dichromium Tetraacetate. Inorg. Chem. 19 (1980) 1924–1930.Search in Google Scholar

3. Cotton, F. A.; Rice, G. W.: Further Studies of Cr-Cr Bond Lengths in Quadruply Bonded Dinuclear Compounds. Inorg. Chem. 17 (1978) 2004–2009.Search in Google Scholar

4. Bellito, C.; Flamini, A.; Gastaldi, L.; Scaramuzza, L.: Halogen Oxidation of Tetrakis(dithioacetato)diplatinum(II) Complexes, Pt2(CH3CS2)4. Synthesis and Characterization of Pt2(CH3CS2)4X2 (X = Cl, Br, I) and Structural, Electrical, and Optical Properties of Linear-Chain (Μ-Iodo)tetrakis(dithioacetato)diplatinum, Pt2(CH3S2)4I. Inorg. Chem. 22 (1983) 444–449.Search in Google Scholar

5. Chiari, B.; Piovesana, O.; Tarantelli, T.; Zanazzi, P. F.: Gold dithiocarboxylates. Inorg. Chem. 24 (1985) 366–371.10.1021/ic00197a024Search in Google Scholar

6. Allen, F. H.: The Cambridge Structural Database: a quarter of a million crystal structures and rising. Acta Crystallogr. B58 (2002) 380–388.Search in Google Scholar

7. Cremer, D.; Pople, J. A.: General definition of ring puckering coordinates. J. Am. Chem. Soc. 97 (1975) 1354–1358.Search in Google Scholar

8. Siri, D.; Gaudel-Siri, A.; Tordo, P.: Conformational analysis of five-membered rings by molecular mechanics: application to nitroxides. J. Molec. Struct. (Theochem) 582 (2002) 171–185.Search in Google Scholar

9. Bondi, A.: van der Waals Volumes and Radii. J. Phys. Chem. 68 (1964) 441–451.Search in Google Scholar

10. Bernstein, J.; Davis, R. E.; Shimoni, L.; Chang, N.-L.: Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals. Angew. Chem. Int. Ed. Engl. 34 (1995) 1555–1573.Search in Google Scholar

11. Etter, M. C.; MacDonald, J. C.; Bernstein, J.: Graph-set analysis of hydrogen-bond patterns in organic crystals. Acta Crystallogr. B46 (1990) 256–262.Search in Google Scholar

12. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122.10.1107/S0108767307043930Search in Google Scholar PubMed

13. Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Crystallogr. 45 (2012) 849–854.Search in Google Scholar

14. Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood, P.A.: Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures. J. Appl. Crystallogr. 41 (2008) 466–470.Search in Google Scholar

15. Spek, A. L.: Structure validation in chemical crystallography. Acta Crystallogr. D65 (2009) 148–155.10.1107/S090744490804362XSearch in Google Scholar PubMed PubMed Central

Received: 2015-1-15
Accepted: 2015-6-3
Published Online: 2015-9-26
Published in Print: 2015-12-1

©2015 April Lulama et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Articles in the same Issue

  1. Frontmatter
  2. Crystal structure of bis(ethyltriphenylphos-phonium) tetrabromidozincate(II), C40H40Br4P2Zn
  3. Crystal structure of chlorido-(2-ethoxy-6-(((quinolin-8-yl)methyl)-phenolato-κ3N,N′,O)-copper(II), C18H15ClCuN2O2
  4. Crystal structure of bis(ethyltriphenylphos-phonium) tetrabromidocobaltate(II), C40H40Br4CoP2
  5. Crystal structure of di(pyrrolidin-1-yl)methane-thione, C9H16N2S
  6. Crystal structure of ammonium phenylglyoxylate, C8H9NO3
  7. Crystal structure of 2-hydroxy-2-methyl-2-phenyl acetic acid hemihydrate, C9H11O3.50
  8. Crystal structure of 2-((E)-2-(1H-benzo[d]imidazol-2-yl)vinyl)-1H-benzo[d]imidazolium dichloride dihydrate, C16H18Cl2N4O2
  9. Crystal structure of 1,2-dimethylimidazolium iodide, C5H9IN2
  10. Crystal structure of catena-poly[(μ2-4,4′-bipyridine-κ2N:N′)-tetraqua-cobalt(II)] – (3-(carboxylatomethyl)benzoic acid) – water (1/2/2), C28H34CoN2O14
  11. Crystal structure of bis(2,2′-bipyridine-κ2N,N′)-bis(thiophene-3,4-dicarboxylato-κ2O,O′)-cadmium(II), C32H22CdN4O8S2
  12. Crystal structure of tetraaqua-(4,4′-diamino-1,1′-biphenyl-2,2′-disulfonato-κN)(4,4′-bipyridyl-κN)zinc(II) trihydrate, C22H32N4O13S2Zn
  13. Crystal structure of poly[[[(1,3-dimethyl-2-imidazolidinone-κ1O11) zinc(II)]-μ-1,4-benzenedi-carboxylato-κ4O1,O2:O3,O4]—1,3-dimethyl-2-imidazolidinone (1:1)], [Zn(C5H10N2O)(C8H4O4)]· C5H10N2O, C18H24N4O6Zn
  14. Crystal structure of poly[[(1,3-dimethyl-2-imidazolidinone-κ1O) zinc(II)]-μ-furan-2,5-dicarboxylato-κ4O,O′:O′′,O′′′], [Zn(C5H10N2O)(C6H2O5)], C22H24N4O12Zn2
  15. Crystal structure of catena-poly[(μ2-4,4′-bipyridine-κ2N:N′)-tetraquamanganese(II)] – (3-(carboxylatomethyl)benzoic acid) – water (1/2/2), C28H34MnN2O14
  16. Crystal structure of chlorido-tricarbonyl-bis(2-pyridylmethanone-N,N′)-rhenium(I), C14H8ClN2O4Re
  17. Crystal structure of (2-(benzoyl)phenolato-κ2O,O′)-trans-dichlorido -cis- bis(methoxido) niobium(V), C15H15Cl2NbO4
  18. Crystal structure of potassium diaqua dihydroxy(methylenediphosphonato-κ2-O,O′)cobaltate(III), CH10CoKO10P2
  19. Crystal structure of hexakis(4-(dimethylamino)pyridin-1-ium) decavanadate-water (1:16), C42H98N12O44V10
  20. Crystal structure of 4-diethylaminobenzaldehyde isonicotinoylhydrazone monohydrate, C17H20N4O·H2O, C17H22N4O2
  21. Crystal structure of bis[μ-1-[(2-ethyl-1H-imidazol-1-yl)methyl]-1H-benzotriazole-κ2N:N′]bis[dibromido]dimercury(II), C24H26Br4Hg2N10
  22. Crystal structure of poly{bis-[(4,4′-biphenyl-dicarboxylate-κ2O:O′)-μ-1,1′-oxy-bis-(ethane-2,1-diyl)-bis-(1H-imidazole)-κ2N:N′] zinc(II)}dihydrate, C48H48N8O12Zn2
  23. Crystal structure of sodium poly[(μ4-2,2′,2′′-nitrilotriacetato-κ4O,O′,O′′,N)magnesium(II)] monohydrate
  24. The crystal structure of 1-(2-(2-chloroethoxy)phenyl)ethanone
  25. The crystal structure of tris(μ2-1,3-bis(4,4,4-Trifluoro-3-oxido-1-(oxo)but-2-en-1-yl)phenyl-/κ4O,O′:O′′,O′′′)-bis(1,2-dimethoxyethane-O,O′)-diterbium(III)
  26. Crystal structure of (S)-2-(2,2′-diethoxy-[1,1′-binaphthalen]-6-yl)-4,4,5,5-tetra-methyl-2-imidazoline-1-oxyle, C31H33N2O3
  27. Crystal structure of cis-tetrachloridobis-(pyridine-κN)platinum(IV), C10H10Cl4N2Pt
  28. Crystal structure of catena-poly[aqua-(μ2-5-norbornene-2,3-dicarboxylato-κ3O,O′:O′′)-(1,10-phenanthroline-κ2N,N′)zinc(II)], [Zn(C9H8O4)(C12H8N2)(H2O)]n
https://doi.org/10.1515/ncrs-2014-9017
Creative Commons
BY-NC-ND 3.0

Articles in the same Issue

  1. Frontmatter
  2. Crystal structure of bis(ethyltriphenylphos-phonium) tetrabromidozincate(II), C40H40Br4P2Zn
  3. Crystal structure of chlorido-(2-ethoxy-6-(((quinolin-8-yl)methyl)-phenolato-κ3N,N′,O)-copper(II), C18H15ClCuN2O2
  4. Crystal structure of bis(ethyltriphenylphos-phonium) tetrabromidocobaltate(II), C40H40Br4CoP2
  5. Crystal structure of di(pyrrolidin-1-yl)methane-thione, C9H16N2S
  6. Crystal structure of ammonium phenylglyoxylate, C8H9NO3
  7. Crystal structure of 2-hydroxy-2-methyl-2-phenyl acetic acid hemihydrate, C9H11O3.50
  8. Crystal structure of 2-((E)-2-(1H-benzo[d]imidazol-2-yl)vinyl)-1H-benzo[d]imidazolium dichloride dihydrate, C16H18Cl2N4O2
  9. Crystal structure of 1,2-dimethylimidazolium iodide, C5H9IN2
  10. Crystal structure of catena-poly[(μ2-4,4′-bipyridine-κ2N:N′)-tetraqua-cobalt(II)] – (3-(carboxylatomethyl)benzoic acid) – water (1/2/2), C28H34CoN2O14
  11. Crystal structure of bis(2,2′-bipyridine-κ2N,N′)-bis(thiophene-3,4-dicarboxylato-κ2O,O′)-cadmium(II), C32H22CdN4O8S2
  12. Crystal structure of tetraaqua-(4,4′-diamino-1,1′-biphenyl-2,2′-disulfonato-κN)(4,4′-bipyridyl-κN)zinc(II) trihydrate, C22H32N4O13S2Zn
  13. Crystal structure of poly[[[(1,3-dimethyl-2-imidazolidinone-κ1O11) zinc(II)]-μ-1,4-benzenedi-carboxylato-κ4O1,O2:O3,O4]—1,3-dimethyl-2-imidazolidinone (1:1)], [Zn(C5H10N2O)(C8H4O4)]· C5H10N2O, C18H24N4O6Zn
  14. Crystal structure of poly[[(1,3-dimethyl-2-imidazolidinone-κ1O) zinc(II)]-μ-furan-2,5-dicarboxylato-κ4O,O′:O′′,O′′′], [Zn(C5H10N2O)(C6H2O5)], C22H24N4O12Zn2
  15. Crystal structure of catena-poly[(μ2-4,4′-bipyridine-κ2N:N′)-tetraquamanganese(II)] – (3-(carboxylatomethyl)benzoic acid) – water (1/2/2), C28H34MnN2O14
  16. Crystal structure of chlorido-tricarbonyl-bis(2-pyridylmethanone-N,N′)-rhenium(I), C14H8ClN2O4Re
  17. Crystal structure of (2-(benzoyl)phenolato-κ2O,O′)-trans-dichlorido -cis- bis(methoxido) niobium(V), C15H15Cl2NbO4
  18. Crystal structure of potassium diaqua dihydroxy(methylenediphosphonato-κ2-O,O′)cobaltate(III), CH10CoKO10P2
  19. Crystal structure of hexakis(4-(dimethylamino)pyridin-1-ium) decavanadate-water (1:16), C42H98N12O44V10
  20. Crystal structure of 4-diethylaminobenzaldehyde isonicotinoylhydrazone monohydrate, C17H20N4O·H2O, C17H22N4O2
  21. Crystal structure of bis[μ-1-[(2-ethyl-1H-imidazol-1-yl)methyl]-1H-benzotriazole-κ2N:N′]bis[dibromido]dimercury(II), C24H26Br4Hg2N10
  22. Crystal structure of poly{bis-[(4,4′-biphenyl-dicarboxylate-κ2O:O′)-μ-1,1′-oxy-bis-(ethane-2,1-diyl)-bis-(1H-imidazole)-κ2N:N′] zinc(II)}dihydrate, C48H48N8O12Zn2
  23. Crystal structure of sodium poly[(μ4-2,2′,2′′-nitrilotriacetato-κ4O,O′,O′′,N)magnesium(II)] monohydrate
  24. The crystal structure of 1-(2-(2-chloroethoxy)phenyl)ethanone
  25. The crystal structure of tris(μ2-1,3-bis(4,4,4-Trifluoro-3-oxido-1-(oxo)but-2-en-1-yl)phenyl-/κ4O,O′:O′′,O′′′)-bis(1,2-dimethoxyethane-O,O′)-diterbium(III)
  26. Crystal structure of (S)-2-(2,2′-diethoxy-[1,1′-binaphthalen]-6-yl)-4,4,5,5-tetra-methyl-2-imidazoline-1-oxyle, C31H33N2O3
  27. Crystal structure of cis-tetrachloridobis-(pyridine-κN)platinum(IV), C10H10Cl4N2Pt
  28. Crystal structure of catena-poly[aqua-(μ2-5-norbornene-2,3-dicarboxylato-κ3O,O′:O′′)-(1,10-phenanthroline-κ2N,N′)zinc(II)], [Zn(C9H8O4)(C12H8N2)(H2O)]n
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Winner of the OpenAthens UX Award 2026
Winner of the OpenAthens UX Award 2026
Have an idea on how to improve our website?
Please write us.
© 2026 De Gruyter Brill
Downloaded on 27.3.2026 from https://www.degruyterbrill.com/document/doi/10.1515/ncrs-2014-9017/html
Scroll to top button