Tris[2-(2-pyridylsulfan­yl)eth­yl]ammonium perchlorate

An, Y.; Li, X.-F.; Chen, H.-G.; Dong, L.-H.

doi:10.1107/S1600536809052283

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o101

doi:10.1107/S1600536809052283

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Tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate

Yan An,^a Xiao-Feng Li,^a ^* Hui-Guo Chen ^a and Li-Hua Dong ^a

^aInstitute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306, People's Republic of China
^*Correspondence e-mail: lxf_shmtu@yahoo.com.cn

(Received 4 November 2009; accepted 4 December 2009; online 12 December 2009)

In the title molecular salt, C₂₁H₂₅N₄S₃⁺·ClO₄⁻, an intramolecular N—H⋯N hydrogen bond stabilizes the conformation of the cation. The three N—C—C—S torsion angles are 91.7 (2), 100.9 (2) and 167.02 (14)°.

Related literature

For tripodal ligands as recognition reagents towards small molecules or ions, see: Bretonniere et al. (2000 ). For a benzene-based tripodal oxazoline as an efficient recognition system for some alkylammonium ions for clinical applications, see: Kim & Ahn (2000 ). For the complexation structures and Ln/An selectivities of tripodal N-donor ligands, see: Wietzke et al. (1998 ).

Experimental

Crystal data

C₂₁H₂₅N₄S₃⁺·ClO₄⁻
M_r = 529.08
Triclinic, $[P \overline 1]$
a = 8.5480 (7) Å
b = 11.9753 (10) Å
c = 12.9346 (11) Å
α = 110.884 (4)°
β = 99.609 (4)°
γ = 91.774 (4)°
V = 1213.81 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 296 K
0.37 × 0.35 × 0.33 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.846, T_max = 0.862
6994 measured reflections
4726 independent reflections
3936 reflections with I > 2σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.105
S = 1.03
4726 reflections
302 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2	0.85 (2)	1.98 (2)	2.812 (2)	165 (3)

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052283/bx2246sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052283/bx2246Isup2.hkl

checkCIF report

Comment top

A suitably designed tripodal ligand could be an outstanding recognition reagent towards small molecules or ions (Bretonniere et al., 2000). Kim and Ahn developed a benzene-based tripodal oxazoline as an efficient recognition system for some alkylammonium ions for clinical application (Kim & Ahn, 2000). Wietzke et al. investigated the complexation structures and Ln/An selectivities of tripodal N-donor ligands (Wietzke et al., 1998). To develop a new type of tripodal ligands which could have good selectivity towards transition metal ions, we reported here the synthesis and the crystal structure of the title compound, which comprises discrete ions which are not interconected, so Coulombic interaction to stabilize the crystal structure. The molecular structure is stabilized by one N— H··· N intramolecular hydrogen bond, Fig 1, Table 1. In the tris(2-(pyridin-2-ylthio)ethyl)ammonium cation , the dihedral angles N-C-C-S are: 91.7 (2) (N1/C1/C2/S1); 100.9 (2) (N1/C15/C16/S3) and 167.02 (14)° (N1/C8/C9/S2). The mean planes of the phenyl rings (A: N4-C17/C21; B: N3-C10/C14; C: N2-C3/C7) make dihedral angles of : 23.85 (12) (between A/C); 89.74 (13) (between B/C) and 71.81 (12)° (between A/B).Two O atoms of perchlorate anion are slightly disordered; it was not split intro two positions.

Related literature top

For tripodal ligands as recognition reagents towards small molecules or ions, see: Bretonniere et al. (2000). For a benzene-based tripodal oxazoline as an efficient recognition system for some alkylammonium ions for clinical applications, see: Kim & Ahn (2000). For the complexation structures and Ln/An

selectivities of tripodal N-donor ligands, see: Wietzke et al. (1998).

Experimental top

The title compound was obtained , in an attempts to prepare an coordination compound between tris(2-(pyridin-2-ylthio)ethyl)amine (0.214 g, 0.5 mmol) and Cu(ClO₄)₂ (0.132 g, 0.5 mmol) using absolute alcohol (6 ml) as solvent . This mixture was stirred in air for 1 h and the colorless crystals were obtained after evaporating for 5 days. Analysis, calculated for C₂₁H₂₅N₄O₄S₃Cl: C 47.67, H 4.76, N 10.59%; found: C 47.31, H 4.25, N 10.96%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the structure of (I). Displacement ellipsoids are drawn at the 30% probability level.

Tris[2-(2-pyridylsulfanyl)ethyl]ammonium perchlorate top

Crystal data top

C₂₁H₂₅N₄S₃⁺·ClO₄⁻	Z = 2
M_r = 529.08	F(000) = 552
Triclinic, P1	D_x = 1.448 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5480 (7) Å	Cell parameters from 3657 reflections
b = 11.9753 (10) Å	θ = 2.4–28.5°
c = 12.9346 (11) Å	µ = 0.45 mm⁻¹
α = 110.884 (4)°	T = 296 K
β = 99.609 (4)°	Block, yellow
γ = 91.774 (4)°	0.37 × 0.35 × 0.33 mm
V = 1213.81 (18) Å³

Data collection top

Bruker APEXII CCD diffractometer	4726 independent reflections
Radiation source: fine-focus sealed tube	3936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
T_min = 0.846, T_max = 0.862	k = −14→14
6994 measured reflections	l = −15→15

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0436P)² + 0.6528P] where P = (F_o² + 2F_c²)/3
4726 reflections	(Δ/σ)_max = 0.001
302 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₂₁H₂₅N₄S₃⁺·ClO₄⁻	γ = 91.774 (4)°
M_r = 529.08	V = 1213.81 (18) Å³
Triclinic, P1	Z = 2
a = 8.5480 (7) Å	Mo Kα radiation
b = 11.9753 (10) Å	µ = 0.45 mm⁻¹
c = 12.9346 (11) Å	T = 296 K
α = 110.884 (4)°	0.37 × 0.35 × 0.33 mm
β = 99.609 (4)°

Data collection top

Bruker APEXII CCD diffractometer	4726 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	3936 reflections with I > 2σ(I)
T_min = 0.846, T_max = 0.862	R_int = 0.010
6994 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.50 e Å⁻³
4726 reflections	Δρ_min = −0.43 e Å⁻³
302 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.6881 (3)	0.46034 (19)	0.84074 (18)	0.0474 (5)
H1A	0.5787	0.4756	0.8204	0.057*
H1B	0.7181	0.4941	0.9223	0.057*
C2	0.6983 (3)	0.32631 (19)	0.80047 (18)	0.0496 (5)
H2A	0.6785	0.2988	0.8595	0.060*
H2B	0.8064	0.3111	0.7898	0.060*
C3	0.6641 (3)	0.24033 (19)	0.56478 (18)	0.0474 (5)
C4	0.6269 (3)	0.1444 (2)	0.4618 (2)	0.0632 (6)
H4	0.5527	0.0810	0.4512	0.076*
C5	0.7022 (4)	0.1453 (2)	0.3761 (2)	0.0703 (8)
H5	0.6791	0.0825	0.3064	0.084*
C6	0.8115 (3)	0.2394 (2)	0.3942 (2)	0.0656 (7)
H6	0.8643	0.2415	0.3375	0.079*
C7	0.8414 (3)	0.3303 (2)	0.49763 (19)	0.0569 (6)
H7	0.9161	0.3939	0.5097	0.068*
C8	0.9644 (2)	0.53834 (19)	0.85158 (17)	0.0443 (5)
H8A	0.9845	0.4716	0.8762	0.053*
H8B	0.9814	0.6115	0.9181	0.053*
C9	1.0806 (3)	0.5451 (2)	0.77764 (19)	0.0532 (5)
H9A	1.0468	0.5992	0.7394	0.064*
H9B	1.0820	0.4662	0.7208	0.064*
C10	1.2649 (3)	0.7542 (2)	0.91802 (19)	0.0487 (5)
C11	1.3855 (3)	0.8231 (3)	1.0063 (2)	0.0660 (7)
H11	1.4706	0.7883	1.0335	0.079*
C12	1.3746 (4)	0.9446 (3)	1.0520 (2)	0.0781 (9)
H12	1.4517	0.9935	1.1124	0.094*
C13	1.2506 (4)	0.9930 (3)	1.0086 (2)	0.0755 (8)
H13	1.2421	1.0752	1.0380	0.091*
C14	1.1389 (3)	0.9186 (2)	0.9210 (2)	0.0643 (6)
H14	1.0550	0.9525	0.8914	0.077*
C15	0.7377 (3)	0.64094 (18)	0.79479 (18)	0.0481 (5)
H15A	0.8273	0.6933	0.7957	0.058*
H15B	0.6980	0.6784	0.8639	0.058*
C16	0.6077 (3)	0.6288 (2)	0.6955 (2)	0.0555 (6)
H16A	0.5502	0.6998	0.7150	0.067*
H16B	0.5330	0.5602	0.6819	0.067*
C17	0.7470 (2)	0.75988 (19)	0.58998 (17)	0.0447 (5)
C18	0.7867 (3)	0.7806 (2)	0.49839 (19)	0.0523 (5)
H18	0.7791	0.7180	0.4293	0.063*
C19	0.8374 (3)	0.8954 (2)	0.5120 (2)	0.0577 (6)
H19	0.8631	0.9124	0.4518	0.069*
C20	0.8496 (3)	0.9850 (2)	0.6158 (2)	0.0580 (6)
H20	0.8848	1.0636	0.6276	0.070*
C21	0.8088 (3)	0.9557 (2)	0.7016 (2)	0.0565 (6)
H21	0.8176	1.0168	0.7717	0.068*
Cl1	0.81316 (7)	0.76318 (5)	0.16119 (4)	0.05665 (17)
N1	0.7943 (2)	0.52226 (15)	0.79143 (14)	0.0386 (4)
N2	0.7689 (2)	0.33273 (15)	0.58241 (14)	0.0462 (4)
N3	1.1428 (2)	0.79961 (17)	0.87518 (15)	0.0518 (4)
N4	0.7570 (2)	0.84479 (16)	0.69109 (15)	0.0509 (4)
O1	0.9039 (3)	0.73699 (19)	0.25035 (17)	0.0908 (7)
O2	0.6898 (4)	0.6723 (2)	0.0992 (3)	0.1414 (12)
O3	0.9173 (4)	0.7694 (3)	0.0890 (2)	0.1406 (12)
O4	0.7508 (3)	0.87338 (17)	0.20429 (19)	0.0944 (7)
S1	0.56374 (8)	0.23770 (6)	0.67216 (6)	0.06351 (19)
S2	1.27812 (8)	0.59780 (6)	0.86105 (7)	0.0685 (2)
S3	0.67777 (9)	0.61051 (5)	0.56746 (5)	0.06103 (18)
H1N	0.791 (3)	0.475 (2)	0.724 (2)	0.050 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0515 (12)	0.0535 (12)	0.0436 (11)	0.0084 (10)	0.0196 (9)	0.0205 (9)
C2	0.0546 (13)	0.0534 (12)	0.0505 (12)	0.0039 (10)	0.0125 (10)	0.0295 (10)
C3	0.0491 (12)	0.0422 (11)	0.0473 (11)	0.0100 (9)	0.0029 (9)	0.0143 (9)
C4	0.0681 (16)	0.0439 (12)	0.0605 (15)	0.0037 (11)	−0.0066 (12)	0.0071 (11)
C5	0.0872 (19)	0.0593 (15)	0.0434 (13)	0.0265 (14)	−0.0040 (13)	−0.0003 (11)
C6	0.0836 (18)	0.0672 (16)	0.0425 (12)	0.0241 (14)	0.0161 (12)	0.0128 (11)
C7	0.0699 (15)	0.0554 (13)	0.0446 (12)	0.0092 (11)	0.0172 (11)	0.0144 (10)
C8	0.0481 (12)	0.0448 (11)	0.0398 (10)	0.0066 (9)	0.0090 (9)	0.0149 (9)
C9	0.0572 (13)	0.0457 (12)	0.0538 (13)	0.0053 (10)	0.0207 (11)	0.0103 (10)
C10	0.0415 (11)	0.0615 (13)	0.0503 (12)	0.0014 (10)	0.0126 (9)	0.0276 (10)
C11	0.0460 (13)	0.098 (2)	0.0656 (15)	−0.0117 (13)	0.0021 (11)	0.0491 (15)
C12	0.082 (2)	0.088 (2)	0.0523 (15)	−0.0362 (17)	0.0042 (14)	0.0187 (14)
C13	0.093 (2)	0.0581 (16)	0.0667 (17)	−0.0100 (15)	0.0238 (16)	0.0102 (13)
C14	0.0744 (17)	0.0574 (15)	0.0598 (15)	0.0143 (13)	0.0158 (13)	0.0181 (12)
C15	0.0603 (13)	0.0386 (11)	0.0450 (11)	0.0110 (9)	0.0097 (10)	0.0144 (9)
C16	0.0539 (13)	0.0546 (13)	0.0635 (14)	0.0028 (10)	0.0041 (11)	0.0316 (11)
C17	0.0435 (11)	0.0458 (11)	0.0434 (11)	0.0053 (9)	0.0009 (9)	0.0179 (9)
C18	0.0502 (12)	0.0589 (13)	0.0450 (12)	0.0086 (10)	0.0101 (10)	0.0151 (10)
C19	0.0571 (14)	0.0680 (15)	0.0571 (14)	0.0037 (11)	0.0174 (11)	0.0312 (12)
C20	0.0588 (14)	0.0506 (13)	0.0671 (15)	−0.0020 (11)	0.0086 (12)	0.0265 (12)
C21	0.0683 (15)	0.0466 (12)	0.0492 (12)	0.0028 (11)	0.0064 (11)	0.0137 (10)
Cl1	0.0721 (4)	0.0453 (3)	0.0425 (3)	0.0206 (3)	0.0058 (3)	0.0051 (2)
N1	0.0486 (10)	0.0367 (8)	0.0307 (8)	0.0061 (7)	0.0114 (7)	0.0107 (7)
N2	0.0536 (10)	0.0424 (9)	0.0399 (9)	0.0065 (8)	0.0100 (8)	0.0112 (7)
N3	0.0539 (11)	0.0553 (11)	0.0431 (10)	0.0090 (9)	0.0077 (8)	0.0149 (8)
N4	0.0639 (12)	0.0463 (10)	0.0417 (9)	0.0041 (8)	0.0065 (8)	0.0166 (8)
O1	0.1193 (18)	0.0864 (14)	0.0666 (12)	0.0355 (13)	0.0050 (12)	0.0317 (11)
O2	0.126 (2)	0.0691 (15)	0.160 (3)	−0.0060 (14)	−0.041 (2)	−0.0091 (16)
O3	0.174 (3)	0.184 (3)	0.0901 (18)	0.067 (2)	0.075 (2)	0.0556 (19)
O4	0.1193 (18)	0.0551 (11)	0.0962 (15)	0.0403 (11)	0.0168 (13)	0.0118 (10)
S1	0.0563 (4)	0.0638 (4)	0.0661 (4)	−0.0120 (3)	0.0106 (3)	0.0206 (3)
S2	0.0469 (3)	0.0638 (4)	0.1021 (5)	0.0159 (3)	0.0218 (3)	0.0347 (4)
S3	0.0852 (5)	0.0449 (3)	0.0473 (3)	−0.0027 (3)	−0.0015 (3)	0.0172 (2)

Geometric parameters (Å, º) top

C1—N1	1.506 (3)	C12—C13	1.358 (4)
C1—C2	1.511 (3)	C12—H12	0.9300
C1—H1A	0.9700	C13—C14	1.362 (4)
C1—H1B	0.9700	C13—H13	0.9300
C2—S1	1.798 (2)	C14—N3	1.337 (3)
C2—H2A	0.9700	C14—H14	0.9300
C2—H2B	0.9700	C15—N1	1.504 (2)
C3—N2	1.330 (3)	C15—C16	1.512 (3)
C3—C4	1.393 (3)	C15—H15A	0.9700
C3—S1	1.758 (2)	C15—H15B	0.9700
C4—C5	1.375 (4)	C16—S3	1.797 (2)
C4—H4	0.9300	C16—H16A	0.9700
C5—C6	1.368 (4)	C16—H16B	0.9700
C5—H5	0.9300	C17—N4	1.327 (3)
C6—C7	1.368 (3)	C17—C18	1.385 (3)
C6—H6	0.9300	C17—S3	1.772 (2)
C7—N2	1.339 (3)	C18—C19	1.369 (3)
C7—H7	0.9300	C18—H18	0.9300
C8—N1	1.502 (3)	C19—C20	1.372 (3)
C8—C9	1.508 (3)	C19—H19	0.9300
C8—H8A	0.9700	C20—C21	1.369 (3)
C8—H8B	0.9700	C20—H20	0.9300
C9—S2	1.804 (2)	C21—N4	1.339 (3)
C9—H9A	0.9700	C21—H21	0.9300
C9—H9B	0.9700	Cl1—O4	1.3980 (18)
C10—N3	1.323 (3)	Cl1—O2	1.402 (2)
C10—C11	1.389 (3)	Cl1—O3	1.411 (3)
C10—S2	1.766 (2)	Cl1—O1	1.416 (2)
C11—C12	1.375 (4)	N1—H1N	0.85 (2)
C11—H11	0.9300

N1—C1—C2	112.63 (16)	C14—C13—H13	120.7
N1—C1—H1A	109.1	N3—C14—C13	123.9 (3)
C2—C1—H1A	109.1	N3—C14—H14	118.0
N1—C1—H1B	109.1	C13—C14—H14	118.0
C2—C1—H1B	109.1	N1—C15—C16	112.76 (17)
H1A—C1—H1B	107.8	N1—C15—H15A	109.0
C1—C2—S1	116.00 (16)	C16—C15—H15A	109.0
C1—C2—H2A	108.3	N1—C15—H15B	109.0
S1—C2—H2A	108.3	C16—C15—H15B	109.0
C1—C2—H2B	108.3	H15A—C15—H15B	107.8
S1—C2—H2B	108.3	C15—C16—S3	114.41 (17)
H2A—C2—H2B	107.4	C15—C16—H16A	108.7
N2—C3—C4	122.2 (2)	S3—C16—H16A	108.7
N2—C3—S1	120.20 (16)	C15—C16—H16B	108.7
C4—C3—S1	117.62 (19)	S3—C16—H16B	108.7
C5—C4—C3	118.6 (2)	H16A—C16—H16B	107.6
C5—C4—H4	120.7	N4—C17—C18	123.8 (2)
C3—C4—H4	120.7	N4—C17—S3	119.39 (16)
C6—C5—C4	119.4 (2)	C18—C17—S3	116.78 (16)
C6—C5—H5	120.3	C19—C18—C17	118.4 (2)
C4—C5—H5	120.3	C19—C18—H18	120.8
C7—C6—C5	118.4 (2)	C17—C18—H18	120.8
C7—C6—H6	120.8	C18—C19—C20	119.1 (2)
C5—C6—H6	120.8	C18—C19—H19	120.5
N2—C7—C6	123.6 (2)	C20—C19—H19	120.5
N2—C7—H7	118.2	C21—C20—C19	118.3 (2)
C6—C7—H7	118.2	C21—C20—H20	120.8
N1—C8—C9	112.11 (17)	C19—C20—H20	120.8
N1—C8—H8A	109.2	N4—C21—C20	124.3 (2)
C9—C8—H8A	109.2	N4—C21—H21	117.8
N1—C8—H8B	109.2	C20—C21—H21	117.8
C9—C8—H8B	109.2	O4—Cl1—O2	110.19 (16)
H8A—C8—H8B	107.9	O4—Cl1—O3	109.95 (18)
C8—C9—S2	110.37 (16)	O2—Cl1—O3	108.4 (2)
C8—C9—H9A	109.6	O4—Cl1—O1	109.82 (13)
S2—C9—H9A	109.6	O2—Cl1—O1	111.28 (18)
C8—C9—H9B	109.6	O3—Cl1—O1	107.10 (17)
S2—C9—H9B	109.6	C8—N1—C15	110.80 (16)
H9A—C9—H9B	108.1	C8—N1—C1	110.78 (15)
N3—C10—C11	123.5 (2)	C15—N1—C1	111.01 (16)
N3—C10—S2	119.08 (17)	C8—N1—H1N	107.1 (16)
C11—C10—S2	117.41 (19)	C15—N1—H1N	110.9 (16)
C12—C11—C10	117.6 (3)	C1—N1—H1N	106.1 (15)
C12—C11—H11	121.2	C3—N2—C7	117.69 (19)
C10—C11—H11	121.2	C10—N3—C14	116.7 (2)
C13—C12—C11	119.7 (3)	C17—N4—C21	116.07 (19)
C13—C12—H12	120.2	C3—S1—C2	104.27 (10)
C11—C12—H12	120.2	C10—S2—C9	101.18 (11)
C12—C13—C14	118.6 (3)	C17—S3—C16	102.03 (11)
C12—C13—H13	120.7

N1—C1—C2—S1	−88.3 (2)	C16—C15—N1—C1	−84.1 (2)
N2—C3—C4—C5	0.4 (3)	C2—C1—N1—C8	−78.5 (2)
S1—C3—C4—C5	179.12 (19)	C2—C1—N1—C15	157.92 (18)
C3—C4—C5—C6	0.3 (4)	C4—C3—N2—C7	−1.1 (3)
C4—C5—C6—C7	−0.4 (4)	S1—C3—N2—C7	−179.76 (17)
C5—C6—C7—N2	−0.3 (4)	C6—C7—N2—C3	1.1 (3)
N1—C8—C9—S2	167.02 (14)	C11—C10—N3—C14	0.2 (3)
N3—C10—C11—C12	1.1 (3)	S2—C10—N3—C14	−179.71 (17)
S2—C10—C11—C12	−179.07 (18)	C13—C14—N3—C10	−1.0 (4)
C10—C11—C12—C13	−1.5 (4)	C18—C17—N4—C21	0.1 (3)
C11—C12—C13—C14	0.7 (4)	S3—C17—N4—C21	−179.39 (17)
C12—C13—C14—N3	0.6 (4)	C20—C21—N4—C17	0.4 (4)
N1—C15—C16—S3	−79.1 (2)	N2—C3—S1—C2	−27.5 (2)
N4—C17—C18—C19	−0.8 (3)	C4—C3—S1—C2	153.81 (18)
S3—C17—C18—C19	178.63 (18)	C1—C2—S1—C3	85.25 (17)
C17—C18—C19—C20	1.1 (3)	N3—C10—S2—C9	−13.36 (19)
C18—C19—C20—C21	−0.6 (4)	C11—C10—S2—C9	166.76 (17)
C19—C20—C21—N4	−0.2 (4)	C8—C9—S2—C10	−79.99 (17)
C9—C8—N1—C15	−82.6 (2)	N4—C17—S3—C16	9.5 (2)
C9—C8—N1—C1	153.72 (17)	C18—C17—S3—C16	−170.05 (17)
C16—C15—N1—C8	152.34 (18)	C15—C16—S3—C17	−79.31 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H(1N)···N2	0.85 (2)	1.98 (2)	2.812 (2)	165 (3)

Experimental details

Crystal data
Chemical formula	C₂₁H₂₅N₄S₃⁺·ClO₄⁻
M_r	529.08
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.5480 (7), 11.9753 (10), 12.9346 (11)
α, β, γ (°)	110.884 (4), 99.609 (4), 91.774 (4)
V (Å³)	1213.81 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.37 × 0.35 × 0.33

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.846, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	6994, 4726, 3936
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.105, 1.03
No. of reflections	4726
No. of parameters	302
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.43

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H(1N)···N2	0.85 (2)	1.98 (2)	2.812 (2)	165 (3)

Acknowledgements

The authors thank the Project of Shanghai Municipal Education Commission (2008080, 2008068, 09YZ245, 10YZ111, 10ZZ98), the `Chen Guang' project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation (09 C G52), the Innovative Activities of University Students in Shanghai Maritime University Project (090503) and the State Key Laboratory of Pollution Control and Resource Reuse Foundation (PCRRF09001) for financial support.

References

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