cyclo-Bis­[2-methyl­sulfanyl-6-([1,3,4]­thia­diazol-2-yl­sulfanyl­methyl)­pyridinium] diperchlorate

In the title compound, C₁₈H₁₆N₆S₆²⁺·2ClO₄⁻, the macrocyclic cation shows a twisted conformation and possesses crystallographic twofold symmetry. This conformation is stabilized by intramolecular N—H...N and C—H...N hydrogen bonds. In the crystal, the cations and anions are connected through C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 301 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.080
• wR factor = 0.051
• Data-to-parameter ratio = 13.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
          Tmin and Tmax reported:      0.916     0.999
          Tmin and Tmax expected:      0.727     0.893
          RR =      1.126
          Please check that your absorption correction is appropriate.

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.894
          Tmax scaled      0.893 Tmin scaled      0.819


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C18H16N6S6^2+·2ClO4^2^−	F(000) = 1440.00
Mr = 707.69	Dx = 1.729 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 12.311 (3) Å	θ = 2.5–14°
b = 14.700 (2) Å	µ = 0.76 mm^−1
c = 15.205 (3) Å	T = 301 K
β = 98.79 (2)°	Block, yellow
V = 2719.2 (9) Å^3	0.45 × 0.36 × 0.15 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	2399 reflections with I > 0
Radiation source: X-ray tube	Rint = 0.037
Graphite monochromator	θmax = 25°, θmin = 2°
ω/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→17
Tmin = 0.916, Tmax = 0.999	l = −18→17
2629 measured reflections	3 standard reflections every 250 reflections
2399 independent reflections	intensity decay: 0.1%

Refinement

Refinement on F	H-atom parameters constrained
Least-squares matrix: full	w = 1/[(σ)^2(Fo) + (p/2)^2(Fo)^2] p = 0.016
R[F^2 > 2σ(F^2)] = 0.080	(Δ/σ)max < 0.001
wR(F^2) = 0.051	Δρmax = 0.51 e Å^−3
S = 1.40	Δρmin = −0.32 e Å^−3
2399 reflections	Extinction correction: Zachariasen_type_2_Gaussian_isotropic
183 parameters	Extinction coefficient: 5.8529
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.19844 (8)	−0.38394 (7)	0.33487 (6)	0.0526 (3)
S1	0.0000	−0.10926 (9)	0.2500	0.0590 (5)
S2	0.13640 (10)	−0.05186 (7)	0.42083 (7)	0.0577 (3)
S3	−0.05192 (8)	0.38241 (7)	0.42764 (6)	0.0511 (3)
S4	0.0000	0.43897 (9)	0.2500	0.0643 (5)
O1	0.1958 (3)	−0.2868 (2)	0.3430 (2)	0.083 (1)
O2	0.1213 (3)	−0.4248 (2)	0.3847 (2)	0.077 (1)
O3	0.3052 (3)	−0.4153 (2)	0.3726 (2)	0.094 (1)
O4	0.1762 (3)	−0.4092 (2)	0.2446 (2)	0.097 (1)
N1	0.0323 (2)	0.0578 (2)	0.2915 (2)	0.0462 (9)
N2	0.0825 (2)	0.1636 (2)	0.4615 (2)	0.0353 (8)
N3	−0.0119 (3)	0.2733 (2)	0.2932 (2)	0.054 (1)
C1	0.0556 (3)	−0.0239 (2)	0.3201 (2)	0.043 (1)
C2	0.2206 (3)	0.0499 (2)	0.4376 (2)	0.045 (1)
C3	0.1767 (3)	0.1200 (2)	0.4936 (2)	0.0384 (9)
C4	0.2292 (3)	0.1428 (2)	0.5771 (2)	0.047 (1)
C5	0.1865 (3)	0.2098 (3)	0.6251 (2)	0.052 (1)
C6	0.0899 (3)	0.2515 (2)	0.5908 (2)	0.046 (1)
C7	0.0360 (3)	0.2278 (2)	0.5080 (2)	0.0352 (9)
C8	−0.0704 (3)	0.2691 (2)	0.4688 (2)	0.045 (1)
C9	−0.0214 (3)	0.3548 (2)	0.3227 (2)	0.0387 (10)
H2A	0.2920	0.0329	0.4657	0.0543
H2B	0.2253	0.0759	0.3811	0.0543
H2N	0.0511	0.1469	0.4087	0.0787
H4	0.2950	0.1124	0.6016	0.0558
H5	0.2240	0.2269	0.6819	0.0621
H6	0.0599	0.2971	0.6243	0.0552
H8A	−0.1170	0.2720	0.5131	0.0536
H8B	−0.1037	0.2321	0.4209	0.0536

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0638 (6)	0.0590 (6)	0.0350 (5)	−0.0131 (5)	0.0075 (4)	−0.0029 (4)
S1	0.105 (1)	0.0290 (7)	0.0411 (8)	0.0000	0.0065 (8)	0.0000
S2	0.0853 (8)	0.0363 (5)	0.0481 (6)	0.0035 (5)	−0.0006 (5)	0.0023 (4)
S3	0.0619 (6)	0.0420 (6)	0.0487 (6)	0.0161 (5)	0.0059 (5)	−0.0090 (4)
S4	0.112 (1)	0.0297 (7)	0.0458 (8)	0.0000	−0.0068 (8)	0.0000
O1	0.104 (3)	0.049 (2)	0.097 (3)	−0.003 (2)	0.017 (2)	0.009 (2)
O2	0.108 (3)	0.079 (2)	0.054 (2)	−0.031 (2)	0.040 (2)	−0.012 (2)
O3	0.084 (2)	0.087 (2)	0.103 (3)	0.012 (2)	−0.007 (2)	0.013 (2)
O4	0.120 (3)	0.135 (3)	0.038 (2)	−0.047 (2)	0.021 (2)	−0.017 (2)
N1	0.053 (2)	0.031 (2)	0.053 (2)	0.003 (1)	0.002 (1)	−0.002 (1)
N2	0.038 (2)	0.037 (2)	0.031 (1)	−0.002 (1)	0.007 (1)	−0.005 (1)
N3	0.083 (2)	0.035 (2)	0.052 (2)	0.002 (2)	0.033 (2)	−0.004 (1)
C1	0.057 (2)	0.034 (2)	0.040 (2)	0.000 (2)	0.014 (2)	−0.002 (2)
C2	0.042 (2)	0.043 (2)	0.051 (2)	0.008 (2)	0.008 (2)	−0.004 (2)
C3	0.043 (2)	0.033 (2)	0.039 (2)	−0.001 (2)	0.007 (2)	0.002 (2)
C4	0.050 (2)	0.045 (2)	0.042 (2)	0.002 (2)	−0.002 (2)	0.002 (2)
C5	0.059 (3)	0.058 (2)	0.036 (2)	−0.005 (2)	0.001 (2)	−0.005 (2)
C6	0.057 (2)	0.047 (2)	0.036 (2)	−0.002 (2)	0.012 (2)	−0.011 (2)
C7	0.042 (2)	0.033 (2)	0.033 (2)	−0.007 (2)	0.014 (2)	−0.003 (1)
C8	0.039 (2)	0.051 (2)	0.047 (2)	0.000 (2)	0.015 (2)	−0.008 (2)
C9	0.037 (2)	0.035 (2)	0.042 (2)	0.006 (2)	0.000 (2)	−0.001 (2)

Geometric parameters (Å, º)

Cl1—O1	1.434 (3)	N2—H2N	0.87
Cl1—O2	1.434 (3)	N3—N3^i	1.388 (6)
Cl1—O3	1.428 (3)	N3—C9	1.292 (4)
Cl1—O4	1.408 (3)	C2—C3	1.490 (4)
S1—C1	1.719 (4)	C2—H2A	0.95
S1—C1^i	1.719 (4)	C2—H2B	0.95
S2—C1	1.743 (4)	C3—C4	1.374 (5)
S2—C2	1.816 (4)	C4—C5	1.377 (5)
S3—C8	1.806 (4)	C4—H4	0.95
S3—C9	1.742 (4)	C5—C6	1.369 (5)
S4—C9	1.706 (4)	C5—H5	0.95
S4—C9^i	1.706 (4)	C6—C7	1.375 (4)
N1—N1^i	1.384 (6)	C6—H6	0.95
N1—C1	1.295 (4)	C7—C8	1.484 (5)
N2—C3	1.349 (4)	C8—H8A	0.95
N2—C7	1.357 (4)	C8—H8B	0.95
O1—Cl1—O2	110.2 (2)	N2—C3—C2	119.2 (3)
O1—Cl1—O3	108.5 (2)	N2—C3—C4	118.4 (3)
O1—Cl1—O4	110.1 (2)	C2—C3—C4	122.4 (3)
O2—Cl1—O3	107.2 (2)	C3—C4—C5	120.0 (3)
O2—Cl1—O4	111.0 (2)	C3—C4—H4	120.0
O3—Cl1—O4	109.7 (2)	C5—C4—H4	120.0
C1—S1—C1^i	86.3 (2)	C4—C5—C6	119.9 (3)
C1—S2—C2	99.6 (2)	C4—C5—H5	120.0
C8—S3—C9	99.1 (2)	C6—C5—H5	120.0
C9^i—S4—C9	87.1 (2)	C5—C6—C7	120.3 (3)
N1^i—N1—C1	111.9 (2)	C5—C6—H6	119.8
C3—N2—C7	123.3 (3)	C7—C6—H6	119.8
C3—N2—H2N	115.8	N2—C7—C6	118.0 (3)
C7—N2—H2N	120.8	N2—C7—C8	119.4 (3)
N3^i—N3—C9	111.9 (2)	C6—C7—C8	122.5 (3)
S1—C1—S2	119.5 (2)	S3—C8—C7	111.5 (2)
S1—C1—N1	115.0 (3)	S3—C8—H8A	109.0
S2—C1—N1	125.5 (3)	S3—C8—H8B	109.0
S2—C2—C3	113.6 (2)	C7—C8—H8A	109.0
S2—C2—H2A	108.4	C7—C8—H8B	109.0
S2—C2—H2B	108.4	H8A—C8—H8B	109.5
C3—C2—H2A	108.4	S3—C9—S4	120.1 (2)
C3—C2—H2B	108.4	S3—C9—N3	125.3 (3)
H2A—C2—H2B	109.5	S4—C9—N3	114.6 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1	0.87	2.20	2.999 (4)	153
N2—H2N···N3	0.87	2.59	3.097 (4)	118
C2—H2B···N1	0.95	2.57	2.958 (4)	105
C8—H8B···N3	0.95	2.47	2.870 (4)	105
C2—H2B···O4^ii	0.95	2.42	3.275 (5)	149
C8—H8A···O1^iii	0.95	2.53	3.463 (5)	165
C8—H8B···O1^iv	0.95	2.58	3.307 (5)	133
C8—H8B···O3^iv	0.95	2.50	3.339 (4)	148

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) x−1/2, y+1/2, z.