Tris[2-(2-pyridylsulfan-yl)eth-yl]ammonium perchlorate.

In the title molecular salt, C(21)H(25)N(4)S(3) (+)·ClO(4) (-), an intra-molecular 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 +·n class="Chemical">ClO4 −

M = 529.08

Triclinic,

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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.105

S = 1.03

4726 reflections

302 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.43 e Å−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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H25N4S3+·ClO4−	Z = 2
Mr = 529.08	F(000) = 552
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0436P)2 + 0.6528P] where P = (Fo2 + 2Fc2)/3
4726 reflections	(Δ/σ)max = 0.001
302 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

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)