6,6-Dithio­bis(6,7-dihydro-5H-pyrazolo[1,2-a][1,2,4]triazolium) dichloride methanol solvate dihydrate

Song, B.-Z.; Song, J.; Wang, G.-C.; Wang, W.-D.

doi:10.1107/S1600536806004910

6,6-Dithiobis(6,7-dihydro-5H-pyrazolo[1,2-a][1,2,4]triazolium) dichloride methanol solvate dihydrate

B.-Z. Song, J. Song, G.-C. Wang and W.-D. Wang

The title compound, C₁₀H₁₄N₆S₂²⁺·2Cl⁻·CH₄O·2H₂O, was synthesized by the intermolecular cyclization of bis(4-pyrazolidinyl) disulfide dihydrochloride and ethyl formimidate hydrochloride. The water molecules form hydrogen bonds with each other and the chloride counter-ions. One chloride counter-ion is also involved in O—H

Cl hydrogen bonding with the methanol solvent molecule.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806004910/rn6065sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806004910/rn6065Isup2.hkl Contains datablock I

CCDC reference: 601798

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.035
wR factor = 0.091
Data-to-parameter ratio = 17.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT726_ALERT_1_A H...A   Calc     6.02000, Rep     2.32000 Dev...       3.70 Ang.
              H1A  -CL2     1.555   1.555
PLAT726_ALERT_1_A H...A   Calc    10.31000, Rep     1.90000 Dev...       8.41 Ang.
              H2A  -O3      1.555   1.555
PLAT726_ALERT_1_A H...A   Calc    16.41000, Rep     2.29000 Dev...      14.12 Ang.
              H2B  -CL1     1.555   3.656
PLAT727_ALERT_1_A D...A   Calc    5.714(2), Rep     3.13000 Dev...       2.58 Ang.
              O1   -CL2     1.555   1.555
PLAT727_ALERT_1_A D...A   Calc   10.647(4), Rep     2.84000 Dev...       7.81 Ang.
              O2   -O3      1.555   1.555
PLAT727_ALERT_1_A D...A   Calc   15.851(5), Rep     3.17000 Dev...      12.68 Ang.
              O2   -CL1     1.555   3.656
PLAT728_ALERT_1_A D-H..A  Calc       64.00, Rep      166.00 Dev...     102.00 Deg.
              O1   -H1A  -CL2     1.555   1.555   1.555
PLAT728_ALERT_1_A D-H..A  Calc      108.00, Rep      163.00 Dev...      55.00 Deg.
              O2   -H2A  -O3      1.555   1.555   1.555
PLAT728_ALERT_1_A D-H..A  Calc       50.00, Rep      165.00 Dev...     115.00 Deg.
              O2   -H2B  -CL1     1.555   1.555   3.656

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT747_ALERT_1_C D...A   Calc    5.714(2), Rep     3.13000 ......    Missing su
              O1   -CL2     1.555   1.555
PLAT747_ALERT_1_C D...A   Calc   10.647(4), Rep     2.84000 ......    Missing su
              O2   -O3      1.555   1.555
PLAT747_ALERT_1_C D...A   Calc   15.851(5), Rep     3.17000 ......    Missing su
              O2   -CL1     1.555   3.656
PLAT747_ALERT_1_C D...A   Calc    3.079(2), Rep     3.08000 ......    Missing su
              O3   -CL2     1.555   1.555
PLAT747_ALERT_1_C D...A   Calc    3.308(2), Rep     3.31000 ......    Missing su
              O3   -CL1     1.555   1.555

   9 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

  17 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

6,6-Dithiobis(6,7-dihydro-5H-pyrazolo[1,2-a][1,2,4]triazolium) dichloride methanol solvate dihydrate top

Crystal data top

C₁₀H₁₄N₆S₂²⁺·2Cl⁻·CH₄O·2H₂O	D_x = 1.508 Mg m⁻³
M_r = 421.37	Melting point = 556–557 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.942 (3) Å	Cell parameters from 1021 reflections
b = 14.854 (4) Å	θ = 3.4–26.1°
c = 13.175 (4) Å	µ = 0.60 mm⁻¹
β = 107.502 (4)°	T = 293 K
V = 1855.5 (9) Å³	Block, colorless
Z = 4	0.24 × 0.22 × 0.18 mm
F(000) = 880

Data collection top

Bruker SMART CCD area-detector diffractometer	3826 independent reflections
Radiation source: fine-focus sealed tube	2941 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→12
T_min = 0.804, T_max = 0.900	k = −18→16
10653 measured reflections	l = −12→16

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0425P)² + 0.6565P] where P = (F_o² + 2F_c²)/3
3826 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

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
S1	0.13440 (5)	0.42975 (3)	0.42949 (4)	0.03326 (14)
S2	0.12008 (6)	0.56557 (3)	0.42557 (4)	0.03473 (14)
Cl1	0.84584 (8)	0.56541 (4)	0.15276 (5)	0.05313 (18)
Cl2	0.49738 (7)	0.61515 (4)	0.37409 (5)	0.05085 (17)
N1	0.17205 (18)	0.37616 (11)	0.18413 (13)	0.0316 (4)
N2	0.19692 (17)	0.29646 (10)	0.23574 (13)	0.0305 (4)
N3	0.0860 (2)	0.26995 (13)	0.06799 (15)	0.0482 (5)
N4	0.21487 (17)	0.63425 (10)	0.68686 (13)	0.0290 (4)
N5	0.20864 (18)	0.71181 (11)	0.63297 (13)	0.0309 (4)
N6	0.1247 (2)	0.73643 (13)	0.76614 (15)	0.0460 (5)
C1	0.1441 (2)	0.23353 (15)	0.16388 (18)	0.0415 (5)
H1	0.1471	0.1721	0.1782	0.050*
C2	0.1060 (2)	0.35811 (15)	0.08348 (17)	0.0416 (5)
H2	0.0772	0.4013	0.0303	0.050*
C3	0.2371 (3)	0.45135 (13)	0.25406 (17)	0.0387 (5)
H3A	0.1722	0.5014	0.2463	0.046*
H3B	0.3222	0.4720	0.2397	0.046*
C4	0.2705 (2)	0.40891 (13)	0.36478 (16)	0.0322 (4)
H4	0.3621	0.4304	0.4101	0.039*
C5	0.2758 (2)	0.30645 (14)	0.34833 (16)	0.0367 (5)
H5A	0.3721	0.2854	0.3628	0.044*
H5B	0.2308	0.2740	0.3932	0.044*
C6	0.2753 (2)	0.59995 (14)	0.53384 (16)	0.0322 (4)
H6A	0.3614	0.5831	0.5168	0.039*
C7	0.2685 (2)	0.70259 (14)	0.54427 (17)	0.0368 (5)
H7A	0.3616	0.7295	0.5612	0.044*
H7B	0.2078	0.7296	0.4797	0.044*
C8	0.1536 (3)	0.77262 (14)	0.68274 (18)	0.0427 (5)
H8	0.1375	0.8325	0.6621	0.051*
C9	0.1639 (2)	0.65059 (15)	0.76665 (17)	0.0379 (5)
H9	0.1563	0.6080	0.8164	0.045*
C10	0.2794 (2)	0.56134 (14)	0.64242 (16)	0.0366 (5)
H10A	0.2249	0.5062	0.6350	0.044*
H10B	0.3754	0.5497	0.6860	0.044*
O1	0.5171 (2)	0.68523 (11)	0.80478 (13)	0.0525 (4)
H1A	0.5139	0.7399	0.8128	0.079*
C11	0.5222 (3)	0.64162 (18)	0.9004 (2)	0.0571 (7)
H11A	0.6146	0.6483	0.9501	0.086*
H11B	0.5016	0.5788	0.8869	0.086*
H11C	0.4537	0.6680	0.9296	0.086*
O2	0.7674 (2)	0.42709 (12)	0.96100 (15)	0.0616 (5)
H2A	0.6670	0.4254	0.9242	0.074*
H2B	0.7726	0.4661	1.0143	0.074*
O3	0.5191 (2)	0.61592 (13)	0.14583 (14)	0.0672 (5)
H3C	0.5298	0.6123	0.2180	0.081*
H3D	0.6014	0.5985	0.1391	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0345 (3)	0.0335 (3)	0.0337 (3)	−0.0018 (2)	0.0131 (2)	−0.0040 (2)
S2	0.0351 (3)	0.0344 (3)	0.0327 (3)	0.0049 (2)	0.0072 (2)	−0.0043 (2)
Cl1	0.0764 (4)	0.0434 (3)	0.0399 (3)	−0.0083 (3)	0.0179 (3)	−0.0035 (3)
Cl2	0.0598 (4)	0.0531 (4)	0.0447 (3)	0.0020 (3)	0.0233 (3)	0.0042 (3)
N1	0.0391 (10)	0.0286 (9)	0.0279 (9)	−0.0003 (7)	0.0114 (7)	0.0022 (7)
N2	0.0354 (9)	0.0263 (8)	0.0301 (9)	0.0012 (7)	0.0103 (7)	0.0014 (7)
N3	0.0604 (13)	0.0437 (12)	0.0352 (10)	−0.0111 (10)	0.0067 (9)	−0.0045 (9)
N4	0.0320 (9)	0.0267 (8)	0.0283 (9)	0.0002 (7)	0.0088 (7)	0.0006 (7)
N5	0.0368 (9)	0.0269 (8)	0.0292 (9)	−0.0007 (7)	0.0104 (7)	0.0004 (7)
N6	0.0532 (12)	0.0472 (11)	0.0425 (11)	0.0080 (9)	0.0217 (9)	−0.0044 (9)
C1	0.0508 (14)	0.0304 (11)	0.0423 (13)	−0.0062 (10)	0.0125 (11)	−0.0043 (10)
C2	0.0484 (14)	0.0439 (13)	0.0302 (11)	−0.0014 (10)	0.0083 (10)	0.0042 (9)
C3	0.0575 (14)	0.0279 (11)	0.0343 (11)	−0.0074 (9)	0.0192 (10)	−0.0046 (9)
C4	0.0322 (11)	0.0341 (11)	0.0306 (10)	−0.0002 (8)	0.0100 (9)	−0.0033 (8)
C5	0.0423 (12)	0.0364 (11)	0.0282 (10)	0.0081 (9)	0.0058 (9)	0.0012 (9)
C6	0.0311 (11)	0.0367 (11)	0.0305 (11)	0.0013 (8)	0.0118 (9)	−0.0049 (9)
C7	0.0445 (13)	0.0371 (11)	0.0333 (11)	−0.0080 (9)	0.0184 (10)	−0.0021 (9)
C8	0.0578 (15)	0.0304 (11)	0.0395 (12)	0.0072 (10)	0.0141 (11)	−0.0045 (10)
C9	0.0410 (13)	0.0431 (12)	0.0317 (11)	−0.0025 (10)	0.0142 (10)	0.0014 (9)
C10	0.0450 (12)	0.0317 (11)	0.0321 (11)	0.0087 (9)	0.0100 (9)	−0.0035 (9)
O1	0.0651 (12)	0.0500 (10)	0.0470 (10)	−0.0058 (9)	0.0240 (9)	−0.0044 (8)
C11	0.0587 (17)	0.0647 (17)	0.0474 (15)	0.0039 (13)	0.0150 (13)	0.0045 (13)
O2	0.0683 (12)	0.0623 (12)	0.0564 (11)	0.0051 (9)	0.0223 (10)	−0.0123 (9)
O3	0.0755 (14)	0.0856 (15)	0.0415 (11)	−0.0056 (11)	0.0190 (10)	−0.0024 (9)

Geometric parameters (Å, º) top

S1—C4	1.830 (2)	C4—C5	1.540 (3)
S1—S2	2.0220 (9)	C4—H4	0.9800
S2—C6	1.831 (2)	C5—H5A	0.9700
N1—C2	1.318 (3)	C5—H5B	0.9700
N1—N2	1.351 (2)	C6—C10	1.530 (3)
N1—C3	1.468 (3)	C6—C7	1.534 (3)
N2—C1	1.322 (3)	C6—H6A	0.9800
N2—C5	1.462 (3)	C7—H7A	0.9700
N3—C2	1.331 (3)	C7—H7B	0.9700
N3—C1	1.336 (3)	C8—H8	0.9300
N4—C9	1.320 (3)	C9—H9	0.9300
N4—N5	1.345 (2)	C10—H10A	0.9700
N4—C10	1.467 (2)	C10—H10B	0.9700
N5—C8	1.327 (3)	O1—C11	1.404 (3)
N5—C7	1.469 (2)	O1—H1A	0.8200
N6—C8	1.330 (3)	C11—H11A	0.9600
N6—C9	1.333 (3)	C11—H11B	0.9600
C1—H1	0.9300	C11—H11C	0.9600
C2—H2	0.9300	O2—H2A	0.9697
C3—C4	1.531 (3)	O2—H2B	0.8989
C3—H3A	0.9700	O3—H3C	0.9260
C3—H3B	0.9700	O3—H3D	0.8880

C4—S1—S2	102.30 (7)	N2—C5—H5B	111.3
C6—S2—S1	102.83 (7)	C4—C5—H5B	111.3
C2—N1—N2	106.77 (17)	H5A—C5—H5B	109.2
C2—N1—C3	141.08 (18)	C10—C6—C7	106.16 (16)
N2—N1—C3	111.80 (17)	C10—C6—S2	113.75 (15)
C1—N2—N1	106.63 (17)	C7—C6—S2	107.31 (14)
C1—N2—C5	140.80 (18)	C10—C6—H6A	109.8
N1—N2—C5	112.51 (16)	C7—C6—H6A	109.8
C2—N3—C1	104.55 (18)	S2—C6—H6A	109.8
C9—N4—N5	107.17 (16)	N5—C7—C6	101.73 (15)
C9—N4—C10	140.57 (18)	N5—C7—H7A	111.4
N5—N4—C10	112.20 (16)	C6—C7—H7A	111.4
C8—N5—N4	106.42 (17)	N5—C7—H7B	111.4
C8—N5—C7	141.50 (18)	C6—C7—H7B	111.4
N4—N5—C7	112.01 (15)	H7A—C7—H7B	109.3
C8—N6—C9	104.80 (18)	N5—C8—N6	110.90 (19)
N2—C1—N3	110.90 (19)	N5—C8—H8	124.5
N2—C1—H1	124.5	N6—C8—H8	124.5
N3—C1—H1	124.5	N4—C9—N6	110.71 (19)
N1—C2—N3	111.14 (19)	N4—C9—H9	124.6
N1—C2—H2	124.4	N6—C9—H9	124.6
N3—C2—H2	124.4	N4—C10—C6	101.80 (16)
N1—C3—C4	102.31 (16)	N4—C10—H10A	111.4
N1—C3—H3A	111.3	C6—C10—H10A	111.4
C4—C3—H3A	111.3	N4—C10—H10B	111.4
N1—C3—H3B	111.3	C6—C10—H10B	111.4
C4—C3—H3B	111.3	H10A—C10—H10B	109.3
H3A—C3—H3B	109.2	C11—O1—H1A	109.5
C3—C4—C5	106.23 (16)	O1—C11—H11A	109.5
C3—C4—S1	113.29 (15)	O1—C11—H11B	109.5
C5—C4—S1	107.08 (14)	H11A—C11—H11B	109.5
C3—C4—H4	110.0	O1—C11—H11C	109.5
C5—C4—H4	110.0	H11A—C11—H11C	109.5
S1—C4—H4	110.0	H11B—C11—H11C	109.5
N2—C5—C4	102.28 (15)	H2A—O2—H2B	102.6
N2—C5—H5A	111.3	H3C—O3—H3D	105.1
C4—C5—H5A	111.3

C4—S1—S2—C6	−77.55 (10)	C1—N2—C5—C4	−172.2 (3)
C2—N1—N2—C1	−0.3 (2)	N1—N2—C5—C4	11.2 (2)
C3—N1—N2—C1	−174.99 (17)	C3—C4—C5—N2	−20.1 (2)
C2—N1—N2—C5	177.51 (17)	S1—C4—C5—N2	101.21 (16)
C3—N1—N2—C5	2.8 (2)	S1—S2—C6—C10	−58.29 (14)
C9—N4—N5—C8	0.0 (2)	S1—S2—C6—C7	−175.39 (12)
C10—N4—N5—C8	−177.75 (17)	C8—N5—C7—C6	−168.6 (3)
C9—N4—N5—C7	177.62 (17)	N4—N5—C7—C6	15.1 (2)
C10—N4—N5—C7	−0.1 (2)	C10—C6—C7—N5	−23.5 (2)
N1—N2—C1—N3	−0.1 (2)	S2—C6—C7—N5	98.43 (15)
C5—N2—C1—N3	−176.9 (2)	N4—N5—C8—N6	0.0 (2)
C2—N3—C1—N2	0.4 (3)	C7—N5—C8—N6	−176.5 (2)
N2—N1—C2—N3	0.6 (3)	C9—N6—C8—N5	0.1 (3)
C3—N1—C2—N3	172.8 (2)	N5—N4—C9—N6	0.0 (2)
C1—N3—C2—N1	−0.6 (3)	C10—N4—C9—N6	176.8 (2)
C2—N1—C3—C4	172.6 (3)	C8—N6—C9—N4	0.0 (3)
N2—N1—C3—C4	−15.5 (2)	C9—N4—C10—C6	168.5 (2)
N1—C3—C4—C5	21.6 (2)	N5—N4—C10—C6	−14.9 (2)
N1—C3—C4—S1	−95.68 (17)	C7—C6—C10—N4	23.5 (2)
S2—S1—C4—C3	−55.15 (15)	S2—C6—C10—N4	−94.30 (16)
S2—S1—C4—C5	−171.94 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl2	0.82	2.32	3.13	166
O2—H2A···O3	0.97	1.90	2.84	163
O2—H2B···Cl1ⁱ	0.90	2.29	3.17	165
O3—H3C···Cl2	0.93	2.18	3.08	165
O3—H3D···Cl1	0.89	2.43	3.31	169

Symmetry code: (i) −x+1, −y, −z+1.

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

6,6-Dithio­bis(6,7-dihydro-5H-pyrazolo[1,2-a][1,2,4]triazolium) dichloride methanol solvate dihydrate

Supporting information

Key indicators

checkCIF/PLATON results

6,6-Dithiobis(6,7-dihydro-5H-pyrazolo[1,2-a][1,2,4]triazolium) dichloride methanol solvate dihydrate