2-{[2,2-Bis(diethyl­amino)­ethan-2-ylium­thio­yl]sulfan­yl}-1,1-bis­(diethyl­amino)­ethyl­ium bis­(perchlorate)

Ohno, K.; Sugaya, T.; Fujihara, T.; Nagasawa, A.

doi:10.1107/S1600536812035453

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages o2753-o2754

doi:10.1107/S1600536812035453

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2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)

Keiji Ohno,^a Tomoaki Sugaya,^a Takashi Fujihara ^b ^* and Akira Nagasawa ^a

^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

(Received 5 July 2012; accepted 10 August 2012; online 23 August 2012)

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 crystal structure 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

C₂₀H₄₂N₄S₂²⁺·2ClO₄⁻
M_r = 601.62
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.4158 (7) Å
b = 16.1889 (13) Å
c = 21.7213 (18) Å
V = 2959.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 150 K
0.32 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.881, T_max = 0.923
21803 measured reflections
7058 independent reflections
5641 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.140
S = 1.02
7058 reflections
333 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ), 3081 Friedel pairs
Flack parameter: 0.00 (7)

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: SMART (Bruker, 2003 ); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812035453/rk2371sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035453/rk2371Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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%.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: 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).

Figures top

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.

2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1- bis(diethylamino)ethylium bis(perchlorate) top

Crystal data top

C₂₀H₄₂N₄S₂²⁺·2ClO₄⁻	F(000) = 1280
M_r = 601.62	D_x = 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

Data collection top

Bruker SMART APEX CCD diffractometer	7058 independent reflections
Radiation source: fine-focus sealed tube	5641 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 8.366 pixels mm^-1	θ_max = 27.9°, θ_min = 1.6°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −20→21
T_min = 0.881, T_max = 0.923	l = −18→28
21803 measured reflections

Refinement top

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(F_o²) + (0.0814P)²P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.003
7058 reflections	Δρ_max = 0.70 e Å⁻³
333 parameters	Δρ_min = −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)

Crystal data top

C₂₀H₄₂N₄S₂²⁺·2ClO₄⁻	V = 2959.4 (4) Å³
M_r = 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

Data collection top

Bruker SMART APEX CCD diffractometer	7058 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5641 reflections with I > 2σ(I)
T_min = 0.881, T_max = 0.923	R_int = 0.046
21803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.140	Δρ_max = 0.70 e Å⁻³
S = 1.02	Δρ_min = −0.26 e Å⁻³
7058 reflections	Absolute structure: Flack (1983), 3081 Friedel pairs
333 parameters	Absolute structure parameter: 0.00 (7)
0 restraints

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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⁻
M_r	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)
T_min, T_max	0.881, 0.923
No. of measured, independent and observed [I > 2σ(I)] reflections	21803, 7058, 5641
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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).

References

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Volume 68| Part 9| September 2012| Pages o2753-o2754

doi:10.1107/S1600536812035453

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-{[2,2-Bis(di­ethyl­amino)­ethan-2-ylium­thio­yl]sulfan­yl}-1,1-bis­­(di­ethyl­amino)­ethyl­ium bis­­(perchlorate)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-{[2,2-Bis(diethylamino)ethan-2-yliumthioyl]sulfanyl}-1,1-bis(diethylamino)ethylium bis(perchlorate)