Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802000211/ya6081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802000211/ya6081Isup2.hkl |
CCDC reference: 182624
Carbon disulfide (25.2 g, 0.33 mol) was added dropwise to a solution of ethylenediamine (12.0 g, 0.33 mol) in 95% ethanol at a temperature below 273 K. Mixing was carried out under constant stirring with a magnetic stirrer. The white percipitate which formed was filtered off and washed first with cold ethanol and then with petroleum ether. The dried percipitate was dissolved in hot water, poured into a crystal dish and covered with aluminium foil to allow evaporation of the solvent. After one day, white single crystals were obtained and washed with ethanol.
After checking their presence in a difference map, all H atoms were fixed geometrically and allowed to ride on their parent C or N atoms, with C—H = 0.97 Å and N—H = 0.89 Å. Their Uiso values were constrained to be 1.5Ueq of the carrier atom for the NH3 group H atoms and 1.2Ueq for the remaining H atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
C3H8N2S2 | F(000) = 288 |
Mr = 136.23 | Dx = 1.449 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0173 (3) Å | Cell parameters from 3039 reflections |
b = 10.2294 (4) Å | θ = 3.1–28.3° |
c = 8.7064 (4) Å | µ = 0.73 mm−1 |
β = 92.561 (2)° | T = 293 K |
V = 624.35 (5) Å3 | Block, colorless |
Z = 4 | 0.30 × 0.20 × 0.20 mm |
Siemens SMART CCD area-detector diffractometer | 1513 independent reflections |
Radiation source: fine-focus sealed tube | 1235 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.2°, θmin = 3.1° |
ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −13→13 |
Tmin = 0.810, Tmax = 0.867 | l = −8→11 |
3678 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0848P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
1513 reflections | Δρmax = 0.97 e Å−3 |
65 parameters | Δρmin = −1.03 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.21 (2) |
C3H8N2S2 | V = 624.35 (5) Å3 |
Mr = 136.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.0173 (3) Å | µ = 0.73 mm−1 |
b = 10.2294 (4) Å | T = 293 K |
c = 8.7064 (4) Å | 0.30 × 0.20 × 0.20 mm |
β = 92.561 (2)° |
Siemens SMART CCD area-detector diffractometer | 1513 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1235 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 0.867 | Rint = 0.079 |
3678 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.97 e Å−3 |
1513 reflections | Δρmin = −1.03 e Å−3 |
65 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.69363 (9) | 0.53355 (6) | 0.32874 (8) | 0.0325 (3) | |
S2 | 0.79847 (9) | 0.26177 (6) | 0.43143 (7) | 0.0279 (3) | |
N1 | 0.5013 (3) | 0.3179 (2) | 0.2507 (2) | 0.0243 (5) | |
H1A | 0.4735 | 0.2380 | 0.2704 | 0.029* | |
N2 | 0.1553 (3) | 0.4989 (2) | 0.3016 (3) | 0.0297 (5) | |
H2C | 0.0338 | 0.5046 | 0.3263 | 0.045* | |
H2D | 0.1936 | 0.5756 | 0.2660 | 0.045* | |
H2E | 0.2269 | 0.4773 | 0.3847 | 0.045* | |
C1 | 0.6525 (3) | 0.3678 (2) | 0.3297 (2) | 0.0193 (5) | |
C2 | 0.3784 (3) | 0.3834 (2) | 0.1351 (3) | 0.0262 (5) | |
H2A | 0.3800 | 0.3344 | 0.0398 | 0.031* | |
H2B | 0.4296 | 0.4696 | 0.1160 | 0.031* | |
C3 | 0.1743 (3) | 0.3972 (2) | 0.1814 (3) | 0.0281 (6) | |
H3A | 0.0942 | 0.4202 | 0.0917 | 0.034* | |
H3B | 0.1303 | 0.3141 | 0.2199 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0281 (4) | 0.0153 (4) | 0.0528 (5) | −0.0007 (2) | −0.0102 (3) | 0.0023 (2) |
S2 | 0.0292 (5) | 0.0200 (4) | 0.0340 (4) | 0.0039 (2) | −0.0051 (3) | 0.0023 (2) |
N1 | 0.0232 (10) | 0.0179 (10) | 0.0312 (11) | −0.0015 (7) | −0.0031 (8) | 0.0004 (8) |
N2 | 0.0272 (11) | 0.0287 (11) | 0.0333 (12) | 0.0016 (9) | 0.0024 (9) | −0.0030 (9) |
C1 | 0.0180 (10) | 0.0178 (10) | 0.0224 (11) | 0.0013 (8) | 0.0043 (8) | −0.0005 (8) |
C2 | 0.0257 (13) | 0.0307 (13) | 0.0220 (11) | 0.0006 (10) | −0.0021 (9) | −0.0012 (9) |
C3 | 0.0233 (13) | 0.0281 (13) | 0.0323 (13) | −0.0023 (9) | −0.0038 (10) | −0.0047 (10) |
S1—C1 | 1.720 (2) | N2—H2D | 0.8900 |
S2—C1 | 1.712 (2) | N2—H2E | 0.8900 |
N1—C1 | 1.339 (3) | C2—C3 | 1.511 (3) |
N1—C2 | 1.458 (3) | C2—H2A | 0.9700 |
N1—H1A | 0.8600 | C2—H2B | 0.9700 |
N2—C3 | 1.486 (3) | C3—H3A | 0.9700 |
N2—H2C | 0.8900 | C3—H3B | 0.9700 |
C1—N1—C2 | 127.6 (2) | N1—C2—C3 | 113.4 (2) |
C1—N1—H1A | 116.2 | N1—C2—H2A | 108.9 |
C2—N1—H1A | 116.2 | C3—C2—H2A | 108.9 |
C3—N2—H2C | 109.5 | N1—C2—H2B | 108.9 |
C3—N2—H2D | 109.5 | C3—C2—H2B | 108.9 |
H2C—N2—H2D | 109.5 | H2A—C2—H2B | 107.7 |
C3—N2—H2E | 109.5 | N2—C3—C2 | 111.7 (2) |
H2C—N2—H2E | 109.5 | N2—C3—H3A | 109.3 |
H2D—N2—H2E | 109.5 | C2—C3—H3A | 109.3 |
N1—C1—S2 | 117.81 (17) | N2—C3—H3B | 109.3 |
N1—C1—S1 | 120.16 (17) | C2—C3—H3B | 109.3 |
S2—C1—S1 | 122.03 (13) | H3A—C3—H3B | 107.9 |
C2—N1—C1—S2 | −167.90 (18) | C1—N1—C2—C3 | −116.4 (3) |
C2—N1—C1—S1 | 12.9 (3) | N1—C2—C3—N2 | 73.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S1i | 0.86 | 2.53 | 3.275 (2) | 145 |
N2—H2C···S1ii | 0.89 | 2.41 | 3.278 (2) | 166 |
N2—H2D···S2iii | 0.89 | 2.57 | 3.393 (2) | 155 |
N2—H2E···S1iv | 0.89 | 2.53 | 3.360 (3) | 154 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C3H8N2S2 |
Mr | 136.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.0173 (3), 10.2294 (4), 8.7064 (4) |
β (°) | 92.561 (2) |
V (Å3) | 624.35 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.73 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.810, 0.867 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3678, 1513, 1235 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.159, 1.09 |
No. of reflections | 1513 |
No. of parameters | 65 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.97, −1.03 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
S1—C1 | 1.720 (2) | N1—C2 | 1.458 (3) |
S2—C1 | 1.712 (2) | N2—C3 | 1.486 (3) |
N1—C1 | 1.339 (3) | ||
C1—N1—C2 | 127.6 (2) | S2—C1—S1 | 122.03 (13) |
N1—C1—S2 | 117.81 (17) | N1—C2—C3 | 113.4 (2) |
N1—C1—S1 | 120.16 (17) | N2—C3—C2 | 111.7 (2) |
C2—N1—C1—S2 | −167.90 (18) | C1—N1—C2—C3 | −116.4 (3) |
C2—N1—C1—S1 | 12.9 (3) | N1—C2—C3—N2 | 73.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S1i | 0.86 | 2.53 | 3.275 (2) | 145 |
N2—H2C···S1ii | 0.89 | 2.41 | 3.278 (2) | 166 |
N2—H2D···S2iii | 0.89 | 2.57 | 3.393 (2) | 155 |
N2—H2E···S1iv | 0.89 | 2.53 | 3.360 (3) | 154 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1, −y+1, −z+1. |
Studies on dithiocarbamic acids of the NH3(CH2)nNHCS2 type are relatively scarce compared with their hydrazine analogues RNHNHCS2H or [RNHNH3]+[RNHNHCS2]- (Battistoni et al., 1971; Iskander & El-Syed, 1971). This is rather surprising, taking into account that pyrolysis of N-(2-aminoethyl)dithiocarbamic acid provides a convenient method for the preparation of ethylenethiourea. Alkyl-substituted N-(2-aminoethyl)dithiocarbamic acid, namely zwitterionic alkylaminoalkyldithiocarbamates, have also been of interest in an attempt to delineate the effect of the alkyl substituent on the structure of the thiocarbamate ligands (Kokkou et al., 1988; Stergioudis et al., 1989). This interest prompted us to study the structure of the title compound, (I).
The molecule exists as a zwitterion, H3N+(CH2)2NHCS2-. The NCS2 dithiocarbamate group is planar with a maximum deviation of 0.004 (2) Å for the C1 atom. The N1—C1 bond length of 1.339 (3) Å (Table 1) is that of a typical Csp2—Nsp2 bond (Allen et al., 1987), and is close to the analogous bond lengths in the reported thiocarbamates with alkyl substituents [C—N = 1.345 (5) and 1.340 (6) Å; Kokkou et al., 1988; Stergioudis et al., 1989] and to the corresponding distance of 1.339 (4) Å in sodium dimethylaminodithiocarbamate hydrate (Oskarsson & Ymén, 1983). The C1—S1 and C1—S2 bond lengths of 1.720 (2) and 1.712 (2) Å are typical of the CS2- anion (Allen et al., 1987). The Δ(C—S) = 0.008 (4) Å is negligible compared with that in the dimethylaminoethyldithiocarbamate [0.048 (6) Å; Stergioudis et al., 1989] or diethylaminoethyldithiocarbamate [0.032 (7) Å; Kokkou et al., 1988]. This implies that the two C—S bonds in the title compound have almost equal partial double-bond character. The bond length N2—C3 of 1.486 (3) Å is within the normal range for the C—N+ distance. The conformation about the N2—C3 bond is staggered.
All active H atoms (one H atom at N1 and three H atoms at N2) participate in N—H.·S ydrogen bonding (Table 2). The N1—H1A···S1i, N2—H2C···S1ii and N2—H2D···S2iii bonds link the molecules into layers parallel to the ab crystal plane [symmetry codes: (i) 1 - x, y - 1/2, 1/2 - z; (ii) x - 1, y, z; (iii) 1 - x, y + 1/2, 1/2 - z]. A fourth N2—H2E···S1iv bond interconnects the layers into the three-dimensional infinite network [symmetry code: (iv) 1 - x, 1 - y, 1 - z].