Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013756/ta1383sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013756/ta1383Isup2.hkl |
CCDC reference: 195621
The title compound was synthesized according to the previously reported method of Nakayama & Akiyama (1992). Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution in acetonitrile at room temperature.
All H atoms were located from a difference Fourier map and refined isotropically [C—H 0.89 (2)–0.99 (2) Å].
Data collection: SMART (Bruker, 1995); cell refinement: SMART (Bruker, 1995); data reduction: SHELXTL (Sheldrick, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound, shown with 50% probability displacement ellipsoids and the atom-numbering scheme. |
C10H16N2O2S2 | ? # Insert any comments here. |
Mr = 260.37 | Dx = 1.441 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4110 reflections |
a = 14.991 (1) Å | θ = 2.7–31.0° |
b = 10.633 (1) Å | µ = 0.43 mm−1 |
c = 15.064 (1) Å | T = 100 K |
V = 2401.2 (3) Å3 | Plate, red |
Z = 8 | 0.30 × 0.27 × 0.14 mm |
F(000) = 1104 |
Bruker CCD area-detector diffractometer | 3638 independent reflections |
Radiation source: fine-focus sealed tube | 3021 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 83.66 pixels mm-1 | θmax = 31.0°, θmin = 2.7° |
η and ω scans | h = −20→20 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→15 |
Tmin = 0.882, Tmax = 0.942 | l = −20→21 |
18623 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.103 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0372P)2 + 1.4616P] where P = (Fo2 + 2Fc2)/3 |
3638 reflections | (Δ/σ)max = 0.001 |
209 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C10H16N2O2S2 | V = 2401.2 (3) Å3 |
Mr = 260.37 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.991 (1) Å | µ = 0.43 mm−1 |
b = 10.633 (1) Å | T = 100 K |
c = 15.064 (1) Å | 0.30 × 0.27 × 0.14 mm |
Bruker CCD area-detector diffractometer | 3638 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3021 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.942 | Rint = 0.055 |
18623 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.103 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.37 e Å−3 |
3638 reflections | Δρmin = −0.28 e Å−3 |
209 parameters |
Experimental. ? #Insert any special details here. |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.226 (0.006) x + 6.396 (0.003) y + 8.179 (0.015) z = 8.176 (0.006) * 0.009 (0.000) S4 * -0.024 (0.001) C3 * 0.025 (0.001) N2 * -0.011 (0.000) O1 0.510 (0.003) C5 - 0.367 (0.003) C6 Rms deviation of fitted atoms = 0.019 3.053 (0.003) x + 6.740 (0.003) y + 7.254 (0.009) z = 7.952 (0.002) Angle to previous plane (with approximate e.s.d.) = 4.1 (1) * -0.011 (0.001) S11 * -0.023 (0.001) C12 * 0.006 (0.001) C13 * 0.018 (0.002) C13A * 0.007 (0.002) C14 * -0.019 (0.002) C15 * -0.017 (0.002) C16 * 0.014 (0.002) C17 * 0.025 (0.002) C17A Rms deviation of fitted atoms = 0.017 2.936 (0.004) x + 6.763 (0.003) y + 7.425 (0.012) z = 7.960 (0.002) Angle to previous plane (with approximate e.s.d.) = 1.1 (1) * 0.000 (0.001) S11 * -0.003 (0.001) C12 * 0.006 (0.001) C13 * -0.006 (0.001) C13A * 0.003 (0.001) C17A -0.041 (0.003) C14 - 0.087 (0.004) C15 - 0.082 (0.004) C16 - 0.027 (0.003) C17 Rms deviation of fitted atoms = 0.004 3.160 (0.006) x + 6.714 (0.004) y + 7.110 (0.014) z = 7.988 (0.003) Angle to previous plane (with approximate e.s.d.) = 2.0 (1) * -0.005 (0.001) C13A * 0.007 (0.001) C14 * -0.002 (0.002) C15 * -0.004 (0.002) C16 * 0.006 (0.001) C17 * -0.002 (0.001) C17A -0.065 (0.003) S11 - 0.084 (0.003) C12 - 0.037 (0.003) C13 Rms deviation of fitted atoms = 0.005 |
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 | ||
C1 | 0.28498 (11) | 0.25376 (18) | 0.60986 (12) | 0.0159 (3) | |
C2 | 0.34088 (12) | 0.37232 (18) | 0.61439 (12) | 0.0184 (3) | |
C3 | 0.27008 (12) | 0.43506 (18) | 0.74512 (12) | 0.0182 (3) | |
C4 | 0.21124 (11) | 0.31897 (18) | 0.74779 (11) | 0.0155 (3) | |
C5 | 0.03496 (11) | 0.18953 (17) | 0.74419 (11) | 0.0150 (3) | |
C6 | −0.02966 (11) | 0.07980 (17) | 0.73417 (12) | 0.0173 (3) | |
C7 | −0.10195 (12) | 0.17133 (18) | 0.61357 (12) | 0.0180 (3) | |
C8 | −0.04234 (11) | 0.28616 (17) | 0.61723 (11) | 0.0152 (3) | |
C9 | 0.12116 (10) | 0.26882 (15) | 0.61460 (11) | 0.0123 (3) | |
C10 | 0.11938 (11) | 0.28218 (17) | 0.51480 (11) | 0.0143 (3) | |
H1 | 0.2742 (14) | 0.227 (2) | 0.5522 (14) | 0.021 (5)* | |
H2 | 0.3135 (14) | 0.185 (2) | 0.6370 (14) | 0.020 (5)* | |
H3 | 0.3134 (13) | 0.436 (2) | 0.5805 (14) | 0.014 (5)* | |
H4 | 0.4001 (15) | 0.355 (2) | 0.5881 (15) | 0.026 (6)* | |
H5 | 0.2389 (14) | 0.502 (2) | 0.7132 (13) | 0.019 (5)* | |
H6 | 0.2835 (15) | 0.462 (2) | 0.8058 (15) | 0.025 (6)* | |
H7 | 0.1528 (14) | 0.344 (2) | 0.7705 (13) | 0.016 (5)* | |
H8 | 0.2365 (14) | 0.259 (2) | 0.7810 (14) | 0.020 (5)* | |
H9 | 0.0137 (13) | 0.2501 (19) | 0.7867 (13) | 0.013 (5)* | |
H10 | 0.0908 (14) | 0.1548 (19) | 0.7617 (13) | 0.012 (5)* | |
H11 | −0.0422 (14) | 0.041 (2) | 0.7942 (15) | 0.024 (6)* | |
H12 | −0.0059 (14) | 0.020 (2) | 0.6965 (13) | 0.017 (5)* | |
H13 | −0.1599 (16) | 0.196 (2) | 0.5918 (15) | 0.030 (6)* | |
H14 | −0.0772 (13) | 0.112 (2) | 0.5741 (14) | 0.016 (5)* | |
H15 | −0.0677 (13) | 0.3493 (19) | 0.6544 (13) | 0.010 (5)* | |
H16 | −0.0333 (14) | 0.322 (2) | 0.5580 (14) | 0.019 (5)* | |
N1 | 0.19925 (9) | 0.27269 (14) | 0.65624 (9) | 0.0133 (3) | |
N2 | 0.04439 (9) | 0.25281 (14) | 0.65719 (9) | 0.0127 (3) | |
O1 | 0.35417 (8) | 0.41056 (13) | 0.70414 (8) | 0.0192 (3) | |
O2 | −0.11381 (8) | 0.11813 (12) | 0.69987 (8) | 0.0173 (3) | |
S1 | 0.10528 (3) | 0.14676 (4) | 0.46107 (3) | 0.02035 (12) | |
S2 | 0.13231 (3) | 0.42912 (5) | 0.47783 (3) | 0.02289 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0123 (7) | 0.0191 (9) | 0.0164 (8) | 0.0007 (6) | 0.0033 (6) | 0.0008 (6) |
C2 | 0.0152 (8) | 0.0235 (9) | 0.0166 (8) | −0.0028 (7) | 0.0024 (6) | 0.0047 (7) |
C3 | 0.0155 (8) | 0.0188 (9) | 0.0202 (8) | −0.0013 (7) | −0.0003 (6) | −0.0027 (7) |
C4 | 0.0147 (8) | 0.0216 (9) | 0.0102 (7) | −0.0008 (7) | −0.0015 (6) | −0.0016 (6) |
C5 | 0.0150 (8) | 0.0186 (8) | 0.0113 (7) | 0.0001 (6) | 0.0000 (6) | 0.0036 (6) |
C6 | 0.0139 (8) | 0.0163 (8) | 0.0218 (8) | 0.0003 (6) | 0.0004 (6) | 0.0033 (7) |
C7 | 0.0145 (8) | 0.0241 (9) | 0.0154 (8) | −0.0008 (7) | −0.0018 (6) | −0.0002 (7) |
C8 | 0.0123 (7) | 0.0180 (8) | 0.0154 (8) | 0.0034 (6) | −0.0013 (6) | 0.0012 (6) |
C9 | 0.0137 (7) | 0.0103 (7) | 0.0128 (7) | 0.0011 (6) | 0.0007 (6) | 0.0005 (6) |
C10 | 0.0141 (7) | 0.0175 (8) | 0.0112 (7) | 0.0010 (6) | 0.0009 (6) | 0.0028 (6) |
N1 | 0.0122 (6) | 0.0161 (7) | 0.0115 (6) | −0.0010 (5) | 0.0018 (5) | −0.0008 (5) |
N2 | 0.0126 (6) | 0.0154 (7) | 0.0103 (6) | 0.0001 (5) | 0.0001 (5) | 0.0016 (5) |
O1 | 0.0129 (6) | 0.0242 (7) | 0.0204 (6) | −0.0032 (5) | 0.0000 (5) | −0.0005 (5) |
O2 | 0.0120 (5) | 0.0211 (6) | 0.0188 (6) | −0.0012 (5) | 0.0014 (5) | 0.0019 (5) |
S1 | 0.0297 (2) | 0.0196 (2) | 0.01174 (19) | 0.00058 (18) | −0.00091 (16) | −0.00211 (15) |
S2 | 0.0296 (2) | 0.0186 (2) | 0.0205 (2) | −0.00104 (18) | 0.00022 (18) | 0.00820 (17) |
C1—N1 | 1.476 (2) | C5—H10 | 0.95 (2) |
C1—C2 | 1.515 (3) | C6—O2 | 1.423 (2) |
C1—H1 | 0.93 (2) | C6—H11 | 1.01 (2) |
C1—H2 | 0.94 (2) | C6—H12 | 0.92 (2) |
C2—O1 | 1.426 (2) | C7—O2 | 1.429 (2) |
C2—H3 | 0.94 (2) | C7—C8 | 1.514 (3) |
C2—H4 | 0.99 (2) | C7—H13 | 0.96 (2) |
C3—O1 | 1.428 (2) | C7—H14 | 0.94 (2) |
C3—C4 | 1.518 (3) | C8—N2 | 1.476 (2) |
C3—H5 | 0.98 (2) | C8—H15 | 0.95 (2) |
C3—H6 | 0.98 (2) | C8—H16 | 0.98 (2) |
C4—N1 | 1.475 (2) | C9—N2 | 1.328 (2) |
C4—H7 | 0.98 (2) | C9—N1 | 1.329 (2) |
C4—H8 | 0.89 (2) | C9—C10 | 1.510 (2) |
C5—N2 | 1.480 (2) | C10—S1 | 1.6653 (18) |
C5—C6 | 1.524 (2) | C10—S2 | 1.6699 (18) |
C5—H9 | 0.96 (2) | ||
N1—C1—C2 | 110.28 (15) | O2—C6—H11 | 106.0 (12) |
N1—C1—H1 | 109.5 (13) | C5—C6—H11 | 109.8 (13) |
C2—C1—H1 | 113.2 (14) | O2—C6—H12 | 108.4 (13) |
N1—C1—H2 | 107.2 (13) | C5—C6—H12 | 110.0 (13) |
C2—C1—H2 | 112.1 (13) | H11—C6—H12 | 110.2 (18) |
H1—C1—H2 | 104.2 (19) | O2—C7—C8 | 111.07 (14) |
O1—C2—C1 | 110.93 (14) | O2—C7—H13 | 107.7 (14) |
O1—C2—H3 | 111.8 (13) | C8—C7—H13 | 109.1 (15) |
C1—C2—H3 | 109.3 (13) | O2—C7—H14 | 110.9 (13) |
O1—C2—H4 | 107.9 (14) | C8—C7—H14 | 109.3 (13) |
C1—C2—H4 | 108.6 (14) | H13—C7—H14 | 108.6 (19) |
H3—C2—H4 | 108.2 (18) | N2—C8—C7 | 109.93 (14) |
O1—C3—C4 | 112.10 (15) | N2—C8—H15 | 106.3 (12) |
O1—C3—H5 | 110.0 (12) | C7—C8—H15 | 110.8 (12) |
C4—C3—H5 | 109.0 (13) | N2—C8—H16 | 110.1 (12) |
O1—C3—H6 | 106.0 (13) | C7—C8—H16 | 111.2 (13) |
C4—C3—H6 | 109.5 (14) | H15—C8—H16 | 108.4 (17) |
H5—C3—H6 | 110.2 (18) | N2—C9—N1 | 122.62 (14) |
N1—C4—C3 | 108.50 (14) | N2—C9—C10 | 118.53 (14) |
N1—C4—H7 | 107.9 (12) | N1—C9—C10 | 118.85 (14) |
C3—C4—H7 | 108.2 (12) | C9—C10—S1 | 113.87 (12) |
N1—C4—H8 | 109.8 (14) | C9—C10—S2 | 114.71 (12) |
C3—C4—H8 | 110.3 (14) | S1—C10—S2 | 131.42 (10) |
H7—C4—H8 | 112.1 (18) | C9—N1—C4 | 123.99 (14) |
N2—C5—C6 | 108.73 (14) | C9—N1—C1 | 122.63 (13) |
N2—C5—H9 | 108.4 (12) | C4—N1—C1 | 112.44 (13) |
C6—C5—H9 | 111.6 (12) | C9—N2—C8 | 122.36 (14) |
N2—C5—H10 | 109.7 (12) | C9—N2—C5 | 124.66 (14) |
C6—C5—H10 | 106.8 (12) | C8—N2—C5 | 112.72 (13) |
H9—C5—H10 | 111.5 (17) | C2—O1—C3 | 109.80 (13) |
O2—C6—C5 | 112.35 (14) | C6—O2—C7 | 109.49 (13) |
Experimental details
Crystal data | |
Chemical formula | C10H16N2O2S2 |
Mr | 260.37 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 100 |
a, b, c (Å) | 14.991 (1), 10.633 (1), 15.064 (1) |
V (Å3) | 2401.2 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.43 |
Crystal size (mm) | 0.30 × 0.27 × 0.14 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.882, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18623, 3638, 3021 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.724 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.103, 1.09 |
No. of reflections | 3638 |
No. of parameters | 209 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.37, −0.28 |
Computer programs: SMART (Bruker, 1995), SHELXTL (Sheldrick, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
C1—N1 | 1.476 (2) | C9—N1 | 1.329 (2) |
C4—N1 | 1.475 (2) | C9—C10 | 1.510 (2) |
C5—N2 | 1.480 (2) | C10—S1 | 1.6653 (18) |
C8—N2 | 1.476 (2) | C10—S2 | 1.6699 (18) |
C9—N2 | 1.328 (2) | ||
N2—C9—N1 | 122.62 (14) | C9—C10—S2 | 114.71 (12) |
N2—C9—C10 | 118.53 (14) | S1—C10—S2 | 131.42 (10) |
N1—C9—C10 | 118.85 (14) | C4—N1—C1 | 112.44 (13) |
C9—C10—S1 | 113.87 (12) | C9—N2—C8 | 122.36 (14) |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Bis(N,N-disubstituted amino)carbeniumdithiocarboxylates (Scheme 1) are a structurally interesting unique class of inner salts. They have been investigated from the viewpoints of syntheses, structures and reactivities (Nakayama, 1993, 2000, 2002). Their thermodynamic stability apparently comes from localization of the positive and the negative charges on the N—C—N and S—C—S moieties, respectively. The most remarkable structural characteristic of these compounds is that the interplaner angle between the CS2 and CN2 groups is almost perpendicular (Sheldrick et al., 1980; Ziegler et al., 1987; Borer et al., 1989; Kuhn et al., 1994; Nagasawa et al., 1995, 2000). We reporthere the characteristic molecular conformation of the title compound, (I), in the solid state.
Selected bond lengths and angles are given in Table 1. The dihedral angle between the plane of the carbenium and thiocarboxylate moieties is close to being a right angle [7(2)°], probably due to the above-mentioned localization of the charges. The attractive Coulombic interaction is reflected in the reduction of the C—C—S bond angles to about 114°, which also results in the shortening of the non-bonded distances between the carbenium C atom and the S atoms [2.71 Å, sum of the van der Waals radii = 3.50 Å (Bondi, 1964)]. The shortened length of the N2C—CS2 bond [1.510 (2) Å] would also be attributable to the Coulombic interaction. The two C—S distances are not significantly different, indicating that the negative charge is equally spread over these two S atoms. These distances are close to that expected for a C═S double bond rather than a C—S single bond (1.75 Å; Allen et al., 1987). The average C—N bond length is 1.33 Å, which is slightly shorter than the common Csp3—Nsp3 bond length od 1.36 Å (Allen et al., 1987), indicating the contribution of the canonical structure. According to these results, the title compound is considered to maintain the inner-salt structure in the crystal. There is no significant contact among the neighboring molecules. These structural features were confirmed by a theoretical calculation using a natural bond orbital (NBO) analysis (Glendening et al., 2001), with the full optimized structure, and are consistent with the results obtained by GAUSSIAN98 (Frisch et al., 2001), with a B3LYP/6–31G* set of the parameters. According to the NBO analysis, the σ* orbital of the C9—C10 bond and the π* orbital of the C9—N1 bond are occupied by 0.07 and 0.49 e, respectively, and the S atoms are principal lone-pair donors, providing an interaction energy of 31.8 kJ mol-1 for the C9—C10 bond and 30.9 kJ mol-1 for the C9—N1 bond. These electronic interactions by the sulfur lone pairs would contribute to the structural characteristics.