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The title compound, C10H16N2O2S2, is considered to maintain an inner-salt structure in the crystal, where the planes of the carbenium and the thio­carboxyl­ate moieties are nearly perpendicular to each other [77 (2)°], and the backbone C-C bond length [N2C-CS2 1.510 (2) Å] is significantly shorter than a normal C-C single-bond length.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102013756/ta1383sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102013756/ta1383Isup2.hkl
Contains datablock I

CCDC reference: 195621

Comment top

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 CS 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.

Experimental top

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.

Refinement top

All H atoms were located from a difference Fourier map and refined isotropically [C—H 0.89 (2)–0.99 (2) Å].

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, shown with 50% probability displacement ellipsoids and the atom-numbering scheme.
2,2-Dimorphorino-2-ethylium-1-dithioate top
Crystal data top
C10H16N2O2S2? # Insert any comments here.
Mr = 260.37Dx = 1.441 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4110 reflections
a = 14.991 (1) Åθ = 2.7–31.0°
b = 10.633 (1) ŵ = 0.43 mm1
c = 15.064 (1) ÅT = 100 K
V = 2401.2 (3) Å3Plate, red
Z = 80.30 × 0.27 × 0.14 mm
F(000) = 1104
Data collection top
Bruker CCD area-detector
diffractometer
3638 independent reflections
Radiation source: fine-focus sealed tube3021 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
Detector resolution: 83.66 pixels mm-1θmax = 31.0°, θmin = 2.7°
η and ω scansh = 2020
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
k = 915
Tmin = 0.882, Tmax = 0.942l = 2021
18623 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: difference Fourier map
wR(F2) = 0.103All 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 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C10H16N2O2S2V = 2401.2 (3) Å3
Mr = 260.37Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 14.991 (1) ŵ = 0.43 mm1
b = 10.633 (1) ÅT = 100 K
c = 15.064 (1) Å0.30 × 0.27 × 0.14 mm
Data collection top
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 = 0.942Rint = 0.055
18623 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.103All H-atom parameters refined
S = 1.09Δρmax = 0.37 e Å3
3638 reflectionsΔρmin = 0.28 e Å3
209 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.28498 (11)0.25376 (18)0.60986 (12)0.0159 (3)
C20.34088 (12)0.37232 (18)0.61439 (12)0.0184 (3)
C30.27008 (12)0.43506 (18)0.74512 (12)0.0182 (3)
C40.21124 (11)0.31897 (18)0.74779 (11)0.0155 (3)
C50.03496 (11)0.18953 (17)0.74419 (11)0.0150 (3)
C60.02966 (11)0.07980 (17)0.73417 (12)0.0173 (3)
C70.10195 (12)0.17133 (18)0.61357 (12)0.0180 (3)
C80.04234 (11)0.28616 (17)0.61723 (11)0.0152 (3)
C90.12116 (10)0.26882 (15)0.61460 (11)0.0123 (3)
C100.11938 (11)0.28218 (17)0.51480 (11)0.0143 (3)
H10.2742 (14)0.227 (2)0.5522 (14)0.021 (5)*
H20.3135 (14)0.185 (2)0.6370 (14)0.020 (5)*
H30.3134 (13)0.436 (2)0.5805 (14)0.014 (5)*
H40.4001 (15)0.355 (2)0.5881 (15)0.026 (6)*
H50.2389 (14)0.502 (2)0.7132 (13)0.019 (5)*
H60.2835 (15)0.462 (2)0.8058 (15)0.025 (6)*
H70.1528 (14)0.344 (2)0.7705 (13)0.016 (5)*
H80.2365 (14)0.259 (2)0.7810 (14)0.020 (5)*
H90.0137 (13)0.2501 (19)0.7867 (13)0.013 (5)*
H100.0908 (14)0.1548 (19)0.7617 (13)0.012 (5)*
H110.0422 (14)0.041 (2)0.7942 (15)0.024 (6)*
H120.0059 (14)0.020 (2)0.6965 (13)0.017 (5)*
H130.1599 (16)0.196 (2)0.5918 (15)0.030 (6)*
H140.0772 (13)0.112 (2)0.5741 (14)0.016 (5)*
H150.0677 (13)0.3493 (19)0.6544 (13)0.010 (5)*
H160.0333 (14)0.322 (2)0.5580 (14)0.019 (5)*
N10.19925 (9)0.27269 (14)0.65624 (9)0.0133 (3)
N20.04439 (9)0.25281 (14)0.65719 (9)0.0127 (3)
O10.35417 (8)0.41056 (13)0.70414 (8)0.0192 (3)
O20.11381 (8)0.11813 (12)0.69987 (8)0.0173 (3)
S10.10528 (3)0.14676 (4)0.46107 (3)0.02035 (12)
S20.13231 (3)0.42912 (5)0.47783 (3)0.02289 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0123 (7)0.0191 (9)0.0164 (8)0.0007 (6)0.0033 (6)0.0008 (6)
C20.0152 (8)0.0235 (9)0.0166 (8)0.0028 (7)0.0024 (6)0.0047 (7)
C30.0155 (8)0.0188 (9)0.0202 (8)0.0013 (7)0.0003 (6)0.0027 (7)
C40.0147 (8)0.0216 (9)0.0102 (7)0.0008 (7)0.0015 (6)0.0016 (6)
C50.0150 (8)0.0186 (8)0.0113 (7)0.0001 (6)0.0000 (6)0.0036 (6)
C60.0139 (8)0.0163 (8)0.0218 (8)0.0003 (6)0.0004 (6)0.0033 (7)
C70.0145 (8)0.0241 (9)0.0154 (8)0.0008 (7)0.0018 (6)0.0002 (7)
C80.0123 (7)0.0180 (8)0.0154 (8)0.0034 (6)0.0013 (6)0.0012 (6)
C90.0137 (7)0.0103 (7)0.0128 (7)0.0011 (6)0.0007 (6)0.0005 (6)
C100.0141 (7)0.0175 (8)0.0112 (7)0.0010 (6)0.0009 (6)0.0028 (6)
N10.0122 (6)0.0161 (7)0.0115 (6)0.0010 (5)0.0018 (5)0.0008 (5)
N20.0126 (6)0.0154 (7)0.0103 (6)0.0001 (5)0.0001 (5)0.0016 (5)
O10.0129 (6)0.0242 (7)0.0204 (6)0.0032 (5)0.0000 (5)0.0005 (5)
O20.0120 (5)0.0211 (6)0.0188 (6)0.0012 (5)0.0014 (5)0.0019 (5)
S10.0297 (2)0.0196 (2)0.01174 (19)0.00058 (18)0.00091 (16)0.00211 (15)
S20.0296 (2)0.0186 (2)0.0205 (2)0.00104 (18)0.00022 (18)0.00820 (17)
Geometric parameters (Å, º) top
C1—N11.476 (2)C5—H100.95 (2)
C1—C21.515 (3)C6—O21.423 (2)
C1—H10.93 (2)C6—H111.01 (2)
C1—H20.94 (2)C6—H120.92 (2)
C2—O11.426 (2)C7—O21.429 (2)
C2—H30.94 (2)C7—C81.514 (3)
C2—H40.99 (2)C7—H130.96 (2)
C3—O11.428 (2)C7—H140.94 (2)
C3—C41.518 (3)C8—N21.476 (2)
C3—H50.98 (2)C8—H150.95 (2)
C3—H60.98 (2)C8—H160.98 (2)
C4—N11.475 (2)C9—N21.328 (2)
C4—H70.98 (2)C9—N11.329 (2)
C4—H80.89 (2)C9—C101.510 (2)
C5—N21.480 (2)C10—S11.6653 (18)
C5—C61.524 (2)C10—S21.6699 (18)
C5—H90.96 (2)
N1—C1—C2110.28 (15)O2—C6—H11106.0 (12)
N1—C1—H1109.5 (13)C5—C6—H11109.8 (13)
C2—C1—H1113.2 (14)O2—C6—H12108.4 (13)
N1—C1—H2107.2 (13)C5—C6—H12110.0 (13)
C2—C1—H2112.1 (13)H11—C6—H12110.2 (18)
H1—C1—H2104.2 (19)O2—C7—C8111.07 (14)
O1—C2—C1110.93 (14)O2—C7—H13107.7 (14)
O1—C2—H3111.8 (13)C8—C7—H13109.1 (15)
C1—C2—H3109.3 (13)O2—C7—H14110.9 (13)
O1—C2—H4107.9 (14)C8—C7—H14109.3 (13)
C1—C2—H4108.6 (14)H13—C7—H14108.6 (19)
H3—C2—H4108.2 (18)N2—C8—C7109.93 (14)
O1—C3—C4112.10 (15)N2—C8—H15106.3 (12)
O1—C3—H5110.0 (12)C7—C8—H15110.8 (12)
C4—C3—H5109.0 (13)N2—C8—H16110.1 (12)
O1—C3—H6106.0 (13)C7—C8—H16111.2 (13)
C4—C3—H6109.5 (14)H15—C8—H16108.4 (17)
H5—C3—H6110.2 (18)N2—C9—N1122.62 (14)
N1—C4—C3108.50 (14)N2—C9—C10118.53 (14)
N1—C4—H7107.9 (12)N1—C9—C10118.85 (14)
C3—C4—H7108.2 (12)C9—C10—S1113.87 (12)
N1—C4—H8109.8 (14)C9—C10—S2114.71 (12)
C3—C4—H8110.3 (14)S1—C10—S2131.42 (10)
H7—C4—H8112.1 (18)C9—N1—C4123.99 (14)
N2—C5—C6108.73 (14)C9—N1—C1122.63 (13)
N2—C5—H9108.4 (12)C4—N1—C1112.44 (13)
C6—C5—H9111.6 (12)C9—N2—C8122.36 (14)
N2—C5—H10109.7 (12)C9—N2—C5124.66 (14)
C6—C5—H10106.8 (12)C8—N2—C5112.72 (13)
H9—C5—H10111.5 (17)C2—O1—C3109.80 (13)
O2—C6—C5112.35 (14)C6—O2—C7109.49 (13)

Experimental details

Crystal data
Chemical formulaC10H16N2O2S2
Mr260.37
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)100
a, b, c (Å)14.991 (1), 10.633 (1), 15.064 (1)
V3)2401.2 (3)
Z8
Radiation typeMo Kα
µ (mm1)0.43
Crystal size (mm)0.30 × 0.27 × 0.14
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.882, 0.942
No. of measured, independent and
observed [I > 2σ(I)] reflections
18623, 3638, 3021
Rint0.055
(sin θ/λ)max1)0.724
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.103, 1.09
No. of reflections3638
No. of parameters209
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.37, 0.28

Computer programs: SMART (Bruker, 1995), SHELXTL (Sheldrick, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
C1—N11.476 (2)C9—N11.329 (2)
C4—N11.475 (2)C9—C101.510 (2)
C5—N21.480 (2)C10—S11.6653 (18)
C8—N21.476 (2)C10—S21.6699 (18)
C9—N21.328 (2)
N2—C9—N1122.62 (14)C9—C10—S2114.71 (12)
N2—C9—C10118.53 (14)S1—C10—S2131.42 (10)
N1—C9—C10118.85 (14)C4—N1—C1112.44 (13)
C9—C10—S1113.87 (12)C9—N2—C8122.36 (14)
 

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