organic compounds
2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)
aDepartment of Chemistry, Graduate School of Science and Engineering , Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan, and bComprehensive Analysis Center for Science, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan
*Correspondence e-mail: fuji@chem.saitama-u.ac.jp
The title salt, C20H42N4S22+·2ClO4−, was obtained from the reaction of bis(diethylamino)carbeniumdithiocarboxylate, (Et2N)2C2S2, with Fe(ClO4)2·6H2O in CH2Cl2. The title compound, in which one of the S atoms of (Et2N)2C2S2 is bound to a 1,1-bis(diethylamino)ethane moiety, has two carbenium C atoms, and the charge compensation is provided by two perchlorate anions. The N2C—CS2 bond length is 1.512 (4) Å, corresponding to a C—C single bond, and the dihedral angle between N2C– and –CS2 planes [72.0 (2)°] is smaller than that of (Et2N)2C2S2 [82.0 (1)°]. The features C—H⋯S hydrogen bonds.
Related literature
For general background to bis(N,N-disubstituted amino)carbeniumdithiocarboxylates, see: Winberg & Coffman (1965); Nagasawa et al. (1995); Nakayama & Akiyama (1992); Nakayama et al. (1997, 2000); Nakayama (2000, 2002); Miller et al. (2000); Fujihara et al. (2002); Siemeling et al. (2012). For transition metal complexes, see: Miyashita et al. (1998); Banerjee et al. (2002); Fujihara et al. (2004); Sugaya et al. (2009). For the cationic dimer of bis(N,N-disubstituted amino)carbeniumdithiocarboxylates, see: Otani et al. (1998); Banerjee & Zubieta (2004). For reference bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
10.1107/S1600536812035453/rk2371sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035453/rk2371Isup2.hkl
All the processes were carried out under an argon atmosphere using standard Schlenk techniques. Fe(ClO4)2.6H2O (0.076 g, 0.21 mmol) was dissolved in CH3CN (15 cm3). After stirring for 1 h at room temperature, the solvent was removed by evaporation under reduced pressure. The resulting powder (white) and II (0.141 g, 0.60 mmol) were dissolved in CH2Cl2 (30 cm3) and stirred for 1 h at room temperature. The insoluble salt was then filtered off, and the solvent of the filtrate was removed by evaporation under reduced pressure. The resulting powder was dissolved in CH2Cl2, layered with Et2O, and set aside for several months at room temperature. The red-purple crystals were obtained and dried in vacuo. Yield 0.011 g. (6.2% based on the II). 1H NMR, CD3CN δ 4.62 (s, 2H, -S–CH2-), 3.55 (dq, 16H, CH3–CH2-) 1.27 (q, 24H, CH3-). 13C NMR, CD3CN δ 213.3 (S-C-S), 167.0 (N–C–N), 163.6 (N–C–N), 49.1 (CH3–CH2-), 48.7 (CH3–CH2-), 36.9 (S-CH2-), 13.7 (CH3). Analysis found: C 39.72, H 7.04, N 9.16%; calculated for C20H42Cl2N4O8S2: C 39.93, H 7.04, N 9.31%.
All the non-hydrogen atoms were refined anisotropically. All H atoms were placed in geometrically idealized positions and treated as riding on their parent atoms with C–H = 0.99Å, Uiso(H) = 1.2Ueq(C) for methylene atoms and C–H = 0.98Å, Uiso(H) = 1.5Ueq(C) for methyl atoms.
Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The chemical structure of (II). Fig. 2. The molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Fig. 3. A view of the crystal packing, showing the hydrogen bonding (dashed lines). All counter ions (ClO4-) have been omitted for clarity. |
C20H42N4S22+·2ClO4− | F(000) = 1280 |
Mr = 601.62 | Dx = 1.350 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3791 reflections |
a = 8.4158 (7) Å | θ = 2.3–25.2° |
b = 16.1889 (13) Å | µ = 0.41 mm−1 |
c = 21.7213 (18) Å | T = 150 K |
V = 2959.4 (4) Å3 | Block, red |
Z = 4 | 0.32 × 0.21 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 7058 independent reflections |
Radiation source: fine-focus sealed tube | 5641 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 8.366 pixels mm-1 | θmax = 27.9°, θmin = 1.6° |
ϕ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −20→21 |
Tmin = 0.881, Tmax = 0.923 | l = −18→28 |
21803 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)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.0814P)2P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.003 |
7058 reflections | Δρmax = 0.70 e Å−3 |
333 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 3081 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (7) |
C20H42N4S22+·2ClO4− | V = 2959.4 (4) Å3 |
Mr = 601.62 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.4158 (7) Å | µ = 0.41 mm−1 |
b = 16.1889 (13) Å | T = 150 K |
c = 21.7213 (18) Å | 0.32 × 0.21 × 0.20 mm |
Bruker SMART APEX CCD diffractometer | 7058 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5641 reflections with I > 2σ(I) |
Tmin = 0.881, Tmax = 0.923 | Rint = 0.046 |
21803 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.140 | Δρmax = 0.70 e Å−3 |
S = 1.02 | Δρmin = −0.26 e Å−3 |
7058 reflections | Absolute structure: Flack (1983), 3081 Friedel pairs |
333 parameters | Absolute structure parameter: 0.00 (7) |
0 restraints |
Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.5375 (0.0177) x + 3.5865 (0.0590) y + 12.8042 (0.0841) z = 5.1962 (0.0328) * 0.0000 (0.0000) N1 * 0.0000 (0.0000) C2 * 0.0000 (0.0000) N2 Rms deviation of fitted atoms = 0.0000 6.1258 (0.0105) x + 10.6803 (0.0361) y + 4.0595 (0.0680) z = 11.1638 (0.0232) Angle to previous plane (with approximate e.s.d.) = 71.99 (0.22) * 0.0000 (0.0000) S1 * 0.0000 (0.0000) C1 * 0.0000 (0.0000) S2 Rms deviation of fitted atoms = 0.0000 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0803 (3) | 0.92906 (17) | 0.18456 (13) | 0.0266 (6) | |
C2 | 0.1428 (3) | 0.87247 (17) | 0.23435 (13) | 0.0275 (6) | |
C3 | −0.0518 (4) | 0.7694 (2) | 0.20201 (15) | 0.0402 (8) | |
H3A | −0.0328 | 0.7193 | 0.1769 | 0.048* | |
H3B | −0.0864 | 0.8142 | 0.1741 | 0.048* | |
C4 | −0.1802 (6) | 0.7523 (4) | 0.2484 (2) | 0.0905 (19) | |
H4A | −0.1428 | 0.7108 | 0.2779 | 0.136* | |
H4B | −0.2750 | 0.7315 | 0.2272 | 0.136* | |
H4C | −0.2066 | 0.8033 | 0.2703 | 0.136* | |
C5 | 0.1951 (5) | 0.7249 (2) | 0.25762 (18) | 0.0510 (9) | |
H5A | 0.1389 | 0.6720 | 0.2506 | 0.061* | |
H5B | 0.2093 | 0.7319 | 0.3026 | 0.061* | |
C6 | 0.3555 (7) | 0.7219 (3) | 0.2270 (2) | 0.0891 (19) | |
H6A | 0.3418 | 0.7134 | 0.1826 | 0.134* | |
H6B | 0.4176 | 0.6762 | 0.2443 | 0.134* | |
H6C | 0.4116 | 0.7741 | 0.2341 | 0.134* | |
C7 | 0.2630 (4) | 0.8720 (2) | 0.33875 (14) | 0.0381 (8) | |
H7A | 0.3331 | 0.9100 | 0.3619 | 0.046* | |
H7B | 0.3157 | 0.8174 | 0.3369 | 0.046* | |
C8 | 0.1063 (5) | 0.8636 (2) | 0.37214 (16) | 0.0456 (8) | |
H8A | 0.0482 | 0.9160 | 0.3698 | 0.068* | |
H8B | 0.1260 | 0.8496 | 0.4154 | 0.068* | |
H8C | 0.0432 | 0.8198 | 0.3529 | 0.068* | |
C9 | 0.3319 (4) | 0.98111 (19) | 0.26184 (16) | 0.0378 (7) | |
H9A | 0.3147 | 1.0217 | 0.2953 | 0.045* | |
H9B | 0.2930 | 1.0058 | 0.2230 | 0.045* | |
C10 | 0.5082 (5) | 0.9627 (3) | 0.2561 (2) | 0.0628 (11) | |
H10A | 0.5488 | 0.9430 | 0.2958 | 0.094* | |
H10B | 0.5649 | 1.0131 | 0.2442 | 0.094* | |
H10C | 0.5247 | 0.9201 | 0.2248 | 0.094* | |
C11 | 0.1161 (3) | 0.98670 (17) | 0.06450 (13) | 0.0274 (6) | |
H11A | 0.1500 | 1.0391 | 0.0841 | 0.033* | |
H11B | 0.1794 | 0.9803 | 0.0264 | 0.033* | |
C12 | −0.0572 (3) | 0.99655 (17) | 0.04567 (12) | 0.0258 (6) | |
C13 | −0.3217 (4) | 0.9369 (2) | 0.04633 (17) | 0.0427 (8) | |
H13A | −0.3786 | 0.9335 | 0.0065 | 0.051* | |
H13B | −0.3464 | 0.9911 | 0.0652 | 0.051* | |
C14 | −0.3781 (5) | 0.8689 (3) | 0.0880 (2) | 0.0585 (11) | |
H14A | −0.3607 | 0.8154 | 0.0680 | 0.088* | |
H14B | −0.4917 | 0.8761 | 0.0964 | 0.088* | |
H14C | −0.3187 | 0.8708 | 0.1268 | 0.088* | |
C15 | −0.0855 (4) | 0.85068 (19) | 0.01460 (15) | 0.0334 (7) | |
H15A | −0.1061 | 0.8083 | 0.0465 | 0.040* | |
H15B | 0.0309 | 0.8551 | 0.0090 | 0.040* | |
C16 | −0.1614 (5) | 0.8243 (2) | −0.04533 (17) | 0.0479 (9) | |
H16A | −0.2754 | 0.8154 | −0.0390 | 0.072* | |
H16B | −0.1123 | 0.7728 | −0.0595 | 0.072* | |
H16C | −0.1457 | 0.8675 | −0.0763 | 0.072* | |
C17 | −0.2247 (5) | 1.0945 (3) | −0.01183 (18) | 0.0527 (10) | |
H17A | −0.2348 | 1.1554 | −0.0140 | 0.063* | |
H17B | −0.3297 | 1.0719 | −0.0001 | 0.063* | |
C18 | −0.1813 (5) | 1.0624 (3) | −0.07407 (18) | 0.0593 (11) | |
H18A | −0.0680 | 1.0720 | −0.0816 | 0.089* | |
H18B | −0.2440 | 1.0912 | −0.1055 | 0.089* | |
H18C | −0.2035 | 1.0031 | −0.0760 | 0.089* | |
C19 | −0.0413 (5) | 1.1461 (2) | 0.06844 (18) | 0.0482 (9) | |
H19A | 0.0134 | 1.1278 | 0.1064 | 0.058* | |
H19B | −0.1296 | 1.1830 | 0.0807 | 0.058* | |
C20 | 0.0738 (6) | 1.1938 (2) | 0.0293 (2) | 0.0675 (13) | |
H20A | 0.1609 | 1.1574 | 0.0166 | 0.101* | |
H20B | 0.1165 | 1.2402 | 0.0530 | 0.101* | |
H20C | 0.0188 | 1.2148 | −0.0073 | 0.101* | |
N1 | 0.0976 (3) | 0.79387 (15) | 0.23329 (12) | 0.0338 (6) | |
N2 | 0.2405 (3) | 0.90405 (16) | 0.27537 (11) | 0.0304 (5) | |
N3 | −0.1489 (3) | 0.93085 (14) | 0.03540 (12) | 0.0282 (5) | |
N4 | −0.1076 (3) | 1.07317 (15) | 0.03665 (13) | 0.0372 (7) | |
O1 | 0.6764 (4) | 0.61374 (17) | 0.34864 (12) | 0.0564 (7) | |
O2 | 0.4000 (4) | 0.6153 (3) | 0.35918 (17) | 0.0945 (12) | |
O3 | 0.5508 (5) | 0.73360 (19) | 0.37979 (16) | 0.0918 (12) | |
O4 | 0.5645 (4) | 0.6189 (2) | 0.44602 (13) | 0.0710 (9) | |
O5 | 0.6992 (4) | 0.53757 (17) | 0.07763 (13) | 0.0663 (9) | |
O6 | 0.9442 (4) | 0.58632 (19) | 0.11349 (17) | 0.0749 (9) | |
O7 | 0.7235 (4) | 0.6719 (2) | 0.11376 (18) | 0.0878 (11) | |
O8 | 0.8378 (4) | 0.6359 (2) | 0.02204 (14) | 0.0705 (9) | |
Cl1 | 0.54701 (11) | 0.64601 (6) | 0.38326 (4) | 0.0490 (2) | |
Cl2 | 0.80215 (10) | 0.60677 (5) | 0.08213 (4) | 0.0389 (2) | |
S1 | 0.16983 (8) | 0.90400 (4) | 0.11539 (3) | 0.02782 (16) | |
S2 | −0.05125 (11) | 0.99911 (6) | 0.19878 (4) | 0.0407 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0269 (15) | 0.0247 (14) | 0.0283 (14) | −0.0014 (11) | −0.0026 (12) | −0.0001 (12) |
C2 | 0.0311 (15) | 0.0273 (14) | 0.0242 (14) | 0.0008 (12) | −0.0004 (12) | 0.0014 (12) |
C3 | 0.0454 (19) | 0.0397 (17) | 0.0354 (17) | −0.0164 (16) | −0.0078 (15) | 0.0043 (15) |
C4 | 0.072 (3) | 0.147 (5) | 0.053 (3) | −0.055 (4) | 0.005 (3) | 0.008 (3) |
C5 | 0.078 (3) | 0.0277 (16) | 0.047 (2) | 0.0047 (18) | −0.012 (2) | 0.0011 (15) |
C6 | 0.121 (5) | 0.085 (3) | 0.061 (3) | 0.061 (3) | 0.021 (3) | 0.016 (3) |
C7 | 0.0467 (19) | 0.0410 (18) | 0.0266 (15) | 0.0019 (15) | −0.0076 (14) | 0.0004 (14) |
C8 | 0.060 (2) | 0.0443 (19) | 0.0328 (18) | −0.0042 (17) | 0.0051 (16) | 0.0030 (16) |
C9 | 0.0430 (18) | 0.0341 (16) | 0.0362 (17) | −0.0109 (15) | −0.0032 (15) | −0.0036 (14) |
C10 | 0.046 (2) | 0.083 (3) | 0.059 (3) | −0.014 (2) | 0.0002 (19) | 0.000 (2) |
C11 | 0.0263 (14) | 0.0280 (14) | 0.0279 (15) | −0.0055 (11) | 0.0043 (11) | 0.0046 (12) |
C12 | 0.0285 (14) | 0.0261 (13) | 0.0228 (13) | 0.0040 (12) | 0.0070 (12) | 0.0036 (12) |
C13 | 0.0271 (16) | 0.052 (2) | 0.049 (2) | 0.0059 (15) | −0.0021 (15) | −0.0039 (17) |
C14 | 0.0356 (19) | 0.075 (3) | 0.065 (3) | −0.0094 (19) | 0.0131 (19) | 0.005 (2) |
C15 | 0.0310 (16) | 0.0314 (16) | 0.0377 (16) | −0.0018 (13) | −0.0020 (13) | −0.0010 (13) |
C16 | 0.050 (2) | 0.048 (2) | 0.046 (2) | 0.0013 (18) | −0.0098 (18) | −0.0121 (17) |
C17 | 0.048 (2) | 0.052 (2) | 0.058 (2) | 0.0180 (19) | 0.0010 (18) | 0.0167 (19) |
C18 | 0.047 (2) | 0.083 (3) | 0.047 (2) | 0.017 (2) | −0.0052 (19) | 0.021 (2) |
C19 | 0.065 (2) | 0.0273 (16) | 0.052 (2) | 0.0037 (17) | 0.012 (2) | −0.0016 (16) |
C20 | 0.097 (4) | 0.036 (2) | 0.069 (3) | −0.011 (2) | 0.008 (3) | 0.0147 (19) |
N1 | 0.0466 (16) | 0.0240 (12) | 0.0306 (14) | −0.0041 (11) | −0.0069 (12) | 0.0060 (11) |
N2 | 0.0334 (13) | 0.0315 (13) | 0.0263 (12) | 0.0000 (11) | −0.0033 (10) | 0.0040 (11) |
N3 | 0.0217 (12) | 0.0288 (12) | 0.0342 (13) | 0.0015 (10) | −0.0012 (10) | 0.0016 (11) |
N4 | 0.0410 (15) | 0.0299 (13) | 0.0407 (16) | 0.0100 (12) | 0.0044 (13) | 0.0078 (12) |
O1 | 0.0625 (17) | 0.0525 (15) | 0.0543 (16) | 0.0216 (14) | 0.0191 (14) | 0.0003 (13) |
O2 | 0.0563 (19) | 0.143 (3) | 0.084 (2) | 0.002 (2) | −0.0089 (17) | 0.042 (2) |
O3 | 0.143 (3) | 0.0545 (17) | 0.078 (2) | 0.049 (2) | 0.012 (3) | 0.0031 (17) |
O4 | 0.0634 (19) | 0.102 (2) | 0.0473 (16) | 0.0145 (18) | 0.0108 (14) | 0.0237 (17) |
O5 | 0.093 (2) | 0.0591 (16) | 0.0472 (15) | −0.0381 (17) | −0.0234 (16) | 0.0195 (13) |
O6 | 0.0643 (19) | 0.0660 (17) | 0.094 (2) | 0.0070 (16) | −0.0421 (19) | 0.0015 (18) |
O7 | 0.066 (2) | 0.096 (2) | 0.102 (3) | 0.0200 (18) | −0.016 (2) | −0.057 (2) |
O8 | 0.071 (2) | 0.086 (2) | 0.0544 (16) | −0.0347 (18) | −0.0061 (15) | 0.0210 (16) |
Cl1 | 0.0517 (5) | 0.0519 (5) | 0.0434 (5) | 0.0224 (4) | 0.0125 (4) | 0.0125 (4) |
Cl2 | 0.0420 (4) | 0.0345 (4) | 0.0402 (4) | −0.0056 (3) | −0.0080 (3) | 0.0004 (3) |
S1 | 0.0269 (3) | 0.0302 (3) | 0.0263 (3) | 0.0038 (3) | −0.0007 (3) | 0.0006 (3) |
S2 | 0.0430 (5) | 0.0411 (4) | 0.0380 (4) | 0.0119 (4) | 0.0069 (4) | 0.0016 (4) |
C1—C2 | 1.512 (4) | C12—N3 | 1.333 (4) |
C1—S2 | 1.615 (3) | C13—N3 | 1.476 (4) |
C1—S1 | 1.729 (3) | C13—C14 | 1.503 (5) |
C2—N2 | 1.316 (4) | C13—H13A | 0.9900 |
C2—N1 | 1.328 (4) | C13—H13B | 0.9900 |
C3—N1 | 1.483 (4) | C14—H14A | 0.9800 |
C3—C4 | 1.504 (6) | C14—H14B | 0.9800 |
C3—H3A | 0.9900 | C14—H14C | 0.9800 |
C3—H3B | 0.9900 | C15—N3 | 1.474 (4) |
C4—H4A | 0.9800 | C15—C16 | 1.512 (5) |
C4—H4B | 0.9800 | C15—H15A | 0.9900 |
C4—H4C | 0.9800 | C15—H15B | 0.9900 |
C5—N1 | 1.483 (4) | C16—H16A | 0.9800 |
C5—C6 | 1.506 (7) | C16—H16B | 0.9800 |
C5—H5A | 0.9900 | C16—H16C | 0.9800 |
C5—H5B | 0.9900 | C17—N4 | 1.483 (5) |
C6—H6A | 0.9800 | C17—C18 | 1.494 (5) |
C6—H6B | 0.9800 | C17—H17A | 0.9900 |
C6—H6C | 0.9800 | C17—H17B | 0.9900 |
C7—N2 | 1.483 (4) | C18—H18A | 0.9800 |
C7—C8 | 1.511 (5) | C18—H18B | 0.9800 |
C7—H7A | 0.9900 | C18—H18C | 0.9800 |
C7—H7B | 0.9900 | C19—N4 | 1.477 (4) |
C8—H8A | 0.9800 | C19—C20 | 1.503 (5) |
C8—H8B | 0.9800 | C19—H19A | 0.9900 |
C8—H8C | 0.9800 | C19—H19B | 0.9900 |
C9—N2 | 1.495 (4) | C20—H20A | 0.9800 |
C9—C10 | 1.518 (5) | C20—H20B | 0.9800 |
C9—H9A | 0.9900 | C20—H20C | 0.9800 |
C9—H9B | 0.9900 | Cl1—O3 | 1.420 (3) |
C10—H10A | 0.9800 | Cl1—O1 | 1.423 (3) |
C10—H10B | 0.9800 | Cl1—O2 | 1.432 (4) |
C10—H10C | 0.9800 | Cl1—O4 | 1.439 (3) |
C11—C12 | 1.523 (4) | Cl2—O6 | 1.415 (3) |
C11—S1 | 1.794 (3) | Cl2—O5 | 1.420 (3) |
C11—H11A | 0.9900 | Cl2—O8 | 1.420 (3) |
C11—H11B | 0.9900 | Cl2—O7 | 1.422 (3) |
C12—N4 | 1.326 (4) | ||
C2—C1—S2 | 121.8 (2) | H13A—C13—H13B | 108.0 |
C2—C1—S1 | 109.1 (2) | C13—C14—H14A | 109.5 |
S2—C1—S1 | 129.03 (18) | C13—C14—H14B | 109.5 |
N2—C2—N1 | 124.3 (3) | H14A—C14—H14B | 109.5 |
N2—C2—C1 | 117.8 (2) | C13—C14—H14C | 109.5 |
N1—C2—C1 | 117.9 (3) | H14A—C14—H14C | 109.5 |
N1—C3—C4 | 110.6 (3) | H14B—C14—H14C | 109.5 |
N1—C3—H3A | 109.5 | N3—C15—C16 | 111.1 (3) |
C4—C3—H3A | 109.5 | N3—C15—H15A | 109.4 |
N1—C3—H3B | 109.5 | C16—C15—H15A | 109.4 |
C4—C3—H3B | 109.5 | N3—C15—H15B | 109.4 |
H3A—C3—H3B | 108.1 | C16—C15—H15B | 109.4 |
C3—C4—H4A | 109.5 | H15A—C15—H15B | 108.0 |
C3—C4—H4B | 109.5 | C15—C16—H16A | 109.5 |
H4A—C4—H4B | 109.5 | C15—C16—H16B | 109.5 |
C3—C4—H4C | 109.5 | H16A—C16—H16B | 109.5 |
H4A—C4—H4C | 109.5 | C15—C16—H16C | 109.5 |
H4B—C4—H4C | 109.5 | H16A—C16—H16C | 109.5 |
N1—C5—C6 | 111.3 (3) | H16B—C16—H16C | 109.5 |
N1—C5—H5A | 109.4 | N4—C17—C18 | 113.5 (3) |
C6—C5—H5A | 109.4 | N4—C17—H17A | 108.9 |
N1—C5—H5B | 109.4 | C18—C17—H17A | 108.9 |
C6—C5—H5B | 109.4 | N4—C17—H17B | 108.9 |
H5A—C5—H5B | 108.0 | C18—C17—H17B | 108.9 |
C5—C6—H6A | 109.5 | H17A—C17—H17B | 107.7 |
C5—C6—H6B | 109.5 | C17—C18—H18A | 109.5 |
H6A—C6—H6B | 109.5 | C17—C18—H18B | 109.5 |
C5—C6—H6C | 109.5 | H18A—C18—H18B | 109.5 |
H6A—C6—H6C | 109.5 | C17—C18—H18C | 109.5 |
H6B—C6—H6C | 109.5 | H18A—C18—H18C | 109.5 |
N2—C7—C8 | 111.4 (3) | H18B—C18—H18C | 109.5 |
N2—C7—H7A | 109.3 | N4—C19—C20 | 112.9 (3) |
C8—C7—H7A | 109.3 | N4—C19—H19A | 109.0 |
N2—C7—H7B | 109.3 | C20—C19—H19A | 109.0 |
C8—C7—H7B | 109.3 | N4—C19—H19B | 109.0 |
H7A—C7—H7B | 108.0 | C20—C19—H19B | 109.0 |
C7—C8—H8A | 109.5 | H19A—C19—H19B | 107.8 |
C7—C8—H8B | 109.5 | C19—C20—H20A | 109.5 |
H8A—C8—H8B | 109.5 | C19—C20—H20B | 109.5 |
C7—C8—H8C | 109.5 | H20A—C20—H20B | 109.5 |
H8A—C8—H8C | 109.5 | C19—C20—H20C | 109.5 |
H8B—C8—H8C | 109.5 | H20A—C20—H20C | 109.5 |
N2—C9—C10 | 110.8 (3) | H20B—C20—H20C | 109.5 |
N2—C9—H9A | 109.5 | O3—Cl1—O1 | 108.8 (2) |
C10—C9—H9A | 109.5 | O3—Cl1—O2 | 110.2 (3) |
N2—C9—H9B | 109.5 | O1—Cl1—O2 | 109.9 (2) |
C10—C9—H9B | 109.5 | O3—Cl1—O4 | 110.6 (2) |
H9A—C9—H9B | 108.1 | O1—Cl1—O4 | 108.10 (18) |
C9—C10—H10A | 109.5 | O2—Cl1—O4 | 109.2 (2) |
C9—C10—H10B | 109.5 | O6—Cl2—O5 | 111.35 (18) |
H10A—C10—H10B | 109.5 | O6—Cl2—O8 | 110.0 (2) |
C9—C10—H10C | 109.5 | O5—Cl2—O8 | 109.14 (17) |
H10A—C10—H10C | 109.5 | O6—Cl2—O7 | 109.5 (2) |
H10B—C10—H10C | 109.5 | O5—Cl2—O7 | 109.5 (2) |
C12—C11—S1 | 119.01 (19) | O8—Cl2—O7 | 107.2 (2) |
C12—C11—H11A | 107.6 | C2—N1—C5 | 123.8 (3) |
S1—C11—H11A | 107.6 | C2—N1—C3 | 120.5 (3) |
C12—C11—H11B | 107.6 | C5—N1—C3 | 115.5 (3) |
S1—C11—H11B | 107.6 | C2—N2—C7 | 124.9 (3) |
H11A—C11—H11B | 107.0 | C2—N2—C9 | 120.8 (3) |
N4—C12—N3 | 122.4 (3) | C7—N2—C9 | 114.1 (3) |
N4—C12—C11 | 116.4 (3) | C12—N3—C15 | 122.9 (2) |
N3—C12—C11 | 121.1 (2) | C12—N3—C13 | 119.4 (3) |
N3—C13—C14 | 111.1 (3) | C15—N3—C13 | 117.7 (2) |
N3—C13—H13A | 109.4 | C12—N4—C19 | 123.9 (3) |
C14—C13—H13A | 109.4 | C12—N4—C17 | 122.4 (3) |
N3—C13—H13B | 109.4 | C19—N4—C17 | 113.4 (3) |
C14—C13—H13B | 109.4 | C1—S1—C11 | 104.50 (14) |
S2—C1—C2—N2 | −73.0 (3) | C10—C9—N2—C7 | 72.0 (4) |
S1—C1—C2—N2 | 107.7 (3) | N4—C12—N3—C15 | 148.3 (3) |
S2—C1—C2—N1 | 108.1 (3) | C11—C12—N3—C15 | −27.5 (4) |
S1—C1—C2—N1 | −71.2 (3) | N4—C12—N3—C13 | −33.0 (4) |
S1—C11—C12—N4 | 146.7 (2) | C11—C12—N3—C13 | 151.1 (3) |
S1—C11—C12—N3 | −37.2 (4) | C16—C15—N3—C12 | −122.3 (3) |
N2—C2—N1—C5 | −27.7 (5) | C16—C15—N3—C13 | 59.0 (4) |
C1—C2—N1—C5 | 151.2 (3) | C14—C13—N3—C12 | −127.1 (3) |
N2—C2—N1—C3 | 157.5 (3) | C14—C13—N3—C15 | 51.6 (4) |
C1—C2—N1—C3 | −23.6 (4) | N3—C12—N4—C19 | 155.1 (3) |
C6—C5—N1—C2 | −57.2 (5) | C11—C12—N4—C19 | −28.8 (4) |
C6—C5—N1—C3 | 117.8 (4) | N3—C12—N4—C17 | −31.9 (4) |
C4—C3—N1—C2 | −103.8 (4) | C11—C12—N4—C17 | 144.2 (3) |
C4—C3—N1—C5 | 81.1 (5) | C20—C19—N4—C12 | 100.6 (4) |
N1—C2—N2—C7 | −26.8 (5) | C20—C19—N4—C17 | −72.9 (4) |
C1—C2—N2—C7 | 154.3 (3) | C18—C17—N4—C12 | −51.3 (5) |
N1—C2—N2—C9 | 157.3 (3) | C18—C17—N4—C19 | 122.4 (4) |
C1—C2—N2—C9 | −21.6 (4) | C2—C1—S1—C11 | −169.24 (19) |
C8—C7—N2—C2 | −52.6 (4) | S2—C1—S1—C11 | 11.5 (3) |
C8—C7—N2—C9 | 123.5 (3) | C12—C11—S1—C1 | −67.1 (3) |
C10—C9—N2—C2 | −111.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14B···S1i | 0.98 | 2.91 | 3.893 (4) | 177 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C20H42N4S22+·2ClO4− |
Mr | 601.62 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 8.4158 (7), 16.1889 (13), 21.7213 (18) |
V (Å3) | 2959.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.32 × 0.21 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.881, 0.923 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21803, 7058, 5641 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.140, 1.02 |
No. of reflections | 7058 |
No. of parameters | 333 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −0.26 |
Absolute structure | Flack (1983), 3081 Friedel pairs |
Absolute structure parameter | 0.00 (7) |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14B···S1i | 0.98 | 2.9138 | 3.8925 (38) | 176.69 |
Symmetry code: (i) x−1, y, z. |
Acknowledgements
This work was supported by a Grant-in-Aid for Scientific Research(C) (11005897 to TF) from the Japan Society for the Promotion of Science (JSPS).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Bis(N,N-disubsituted amino)carbeniumdithiocarboxylates [(R2N)2C2S2], which have a zwitterionic (inner-salt) form and a neutral form as canonical structures (Nagasawa et al., 1995; Fujihara et al., 2002), are structurally and reactively interesting (Winberg & Coffman, 1965; Otani et al., 1998; Nakayama & Akiyama, 1992; Nakayama et al., 2000; Nakayama, 2000, 2002; Banerjee & Zubieta, 2004; Siemeling et al., 2012). We have reported the syntheses, structures, and properties of the various transition metal complexes using (R2N)2C2S2 as ligands (Miyashita et al., 1998; Banerjee et al., 2002; Fujihara et al., 2004; Sugaya et al., 2009), and the ligands act as neutral monodentate, bridging, and chelating ligands maintaining the characteristic zwitterionic form.
In the process of a preparation of iron(II) complex with bis(N,N-diethylamino)carbeniumdithiocarboxylate [(Et2N)2C2S2] (II) (Fig 1), we obtained the unexpectedly bis(diethylamino)-methylium bis(diethylamino)-2-ethyliumcarbodithioate perchlorate [(C10H20N2S2)(C10H20N2)](ClO4)2 (I) and report here its molecular structure. We suppose that I was formed through an oxidation of II, which has taken place under gentle conditions for several months in solution. The molecular structure of I is shown in Fig. 2. The C11–S1 bond length is 1.794 (3) Å, which corresponds to the C–S single bond [1.79 (1)–1.82 (1)Å; Miller et al., 2000; 1.78 (4)Å; Nakayama et al., 1997]. The N–C(CS2) bond lengths in the range of 1.316 (4)–1.333 (4) Å are slightly shorter than the normal C(sp3)–N(sp3) bond length (1.36Å; Allen et al., 1987) suggesting that the C2 and C12 atoms are carbenium carbons. The bond lengths of C1–S2 [1.615 (3) Å] and C1–S1 [1.729 (3) Å] are close to those of the CS terminal and the –C–S– bridging bonds of methylated species of I, respectively [1.608 (14)Å and 1.714 (13)Å, respectively; Nakayama et al., 1997], indicating localization of electron on S–C–S moiety. The C1–C2 bond length [1.512 (4) Å] and dihedral angle between N2C– and –CS2 planes [71.99 (22)°] are slightly longer and smaller, respectively, than those of II [1.477Å–1.506 (2)Å and 82.0 (1)°, respectively; Nagasawa et al., 1995], and these change mean that decrease of interaction between the unfilled p orbital of carbenium carbon (C2) and electrons on S–C–S moiety. The C11–C12 bond length 1.523 (4)Å is slightly longer than that of C1–C2. The S1–C1–S2, N1–C2–N2, and N3–C12–N4 bond angles are similar values for those of II [S–C–S: 129.4 (8)° and N–C–N: 122 (1)°; Nagasawa et al., 1995]. Two ClO4- per one I exist as counter ions in the crystal. The crystal structure consists of a chain structure through intermolecular weak C—H···S hydrogen bonding [H14B···S1': 2.9138 Å, C14–H14B···S1': 176.69°] (Fig. 3 and Hydrogen-bond geometry).