Bis{5-amino-3-cyano-1-[2,6-di­chloro-4-(tri­fluoro­methyl)­phenyl]-1H-pyrazol-4-yl} di­sulfide aceto­nitrile disolvate

The di­sulfide moiety in the title compound, C₂₂H₈Cl₄F₆N₈S₂·2C₂H₃N, has an overall Z shape. The molecule possesses a crystallographically imposed twofold rotation axis. The pyrazole and adjacent benzene ring make a dihedral angle of 88.16 (12)°. Intermolecular N—H...N hydrogen bonds link the amine groups with the aceto­nitrile solvent mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.060
• wR factor = 0.171
• Data-to-parameter ratio = 13.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for         C1

Author Response: see _publ_section_exptl_refinement

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.13
PLAT213_ALERT_2_C Atom F1      has ADP max/min Ratio .............       3.50 prolat
PLAT213_ALERT_2_C Atom F3      has ADP max/min Ratio .............       3.60 prolat
PLAT230_ALERT_2_C Hirshfeld Test Diff for    F2     -   C1      ..       5.30 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C13
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.49
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C9     ...       1.44 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H4A    ...          ?

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

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

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Bis{5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazol-4- yl}disulfide acetonitrile disolvate

Crystal data

C22H8Cl4F6N8S2·2C2H3N	F(000) = 1576
Mr = 786.39	Dx = 1.557 Mg m^−3
Monoclinic, C2/c	Melting point: 576 K
Hall symbol: -C2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.267 (3) Å	Cell parameters from 3364 reflections
b = 13.083 (3) Å	θ = 2.3–25.0°
c = 20.919 (6) Å	µ = 0.55 mm^−1
β = 92.423 (5)°	T = 298 K
V = 3354.5 (15) Å^3	Block, yellow
Z = 4	0.45 × 0.34 × 0.27 mm

Data collection

Bruker APEX area-detector diffractometer	2961 independent reflections
Radiation source: fine-focus sealed tube	2520 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→8
Tmin = 0.791, Tmax = 0.866	k = −15→15
8406 measured reflections	l = −25→22

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.171	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0937P)^2 + 6.8928P] where P = (Fo^2 + 2Fc^2)/3
2961 reflections	(Δ/σ)max = 0.001
224 parameters	Δρmax = 0.95 e Å^−3
3 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	1.02599 (7)	0.43899 (6)	0.29834 (4)	0.0464 (3)
Cl1	0.80232 (9)	0.58066 (10)	0.51887 (5)	0.0729 (4)
Cl2	0.65557 (9)	0.69557 (8)	0.28458 (4)	0.0617 (3)
F1	0.3882 (3)	0.6716 (5)	0.5299 (2)	0.178 (3)
F2	0.3996 (4)	0.8082 (4)	0.4921 (3)	0.198 (3)
F3	0.3297 (3)	0.7022 (6)	0.4386 (2)	0.203 (3)
N1	0.8191 (2)	0.6163 (2)	0.37915 (13)	0.0434 (6)
N2	0.8996 (2)	0.6884 (2)	0.37329 (15)	0.0490 (7)
N3	1.1596 (3)	0.7237 (3)	0.3201 (2)	0.0780 (11)
N4	0.7771 (3)	0.4435 (2)	0.35485 (19)	0.0579 (8)
N5	1.0281 (4)	0.9578 (3)	0.3522 (3)	0.0956 (14)
C1	0.4071 (4)	0.7112 (4)	0.4774 (2)	0.0753 (13)
C2	0.5168 (3)	0.6883 (3)	0.45207 (18)	0.0517 (9)
C3	0.5324 (3)	0.7034 (3)	0.38815 (17)	0.0468 (8)
H3	0.4764	0.7283	0.3612	0.056*
C4	0.6331 (3)	0.6808 (2)	0.36473 (16)	0.0439 (8)
C5	0.7175 (3)	0.6433 (2)	0.40483 (16)	0.0425 (8)
C6	0.6985 (3)	0.6288 (3)	0.46899 (16)	0.0478 (8)
C7	0.5987 (3)	0.6511 (3)	0.49296 (17)	0.0537 (9)
H7	0.5865	0.6413	0.5361	0.064*
C8	1.0783 (3)	0.6869 (3)	0.33188 (19)	0.0554 (9)
C9	0.9775 (3)	0.6374 (3)	0.34575 (16)	0.0432 (7)
C10	0.9500 (3)	0.5339 (2)	0.33287 (15)	0.0401 (7)
C11	0.8455 (3)	0.5239 (2)	0.35503 (15)	0.0400 (7)
C12	0.8295 (4)	0.9399 (5)	0.3115 (3)	0.0958 (17)
H12A	0.7995	0.8784	0.3286	0.144*
H12B	0.8256	0.9367	0.2656	0.144*
H12C	0.7886	0.9977	0.3254	0.144*
C13	0.9415 (4)	0.9501 (3)	0.3337 (2)	0.0642 (11)
H4A	0.793	0.387	0.339	0.077*
H4B	0.7120	0.450	0.362	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0434 (5)	0.0398 (5)	0.0572 (5)	0.0110 (3)	0.0166 (4)	0.0064 (4)
Cl1	0.0559 (6)	0.1005 (9)	0.0622 (6)	0.0194 (5)	0.0005 (5)	0.0126 (5)
Cl2	0.0713 (7)	0.0689 (6)	0.0461 (5)	0.0125 (5)	0.0178 (5)	0.0062 (4)
F1	0.090 (2)	0.309 (7)	0.142 (3)	0.083 (3)	0.081 (2)	0.110 (4)
F2	0.127 (4)	0.159 (4)	0.318 (8)	0.056 (3)	0.110 (4)	−0.030 (5)
F3	0.0415 (18)	0.449 (10)	0.121 (3)	0.027 (3)	0.0180 (19)	−0.054 (4)
N1	0.0352 (14)	0.0399 (14)	0.0561 (17)	−0.0013 (11)	0.0155 (12)	−0.0063 (12)
N2	0.0445 (16)	0.0432 (15)	0.0605 (18)	−0.0067 (12)	0.0178 (14)	−0.0079 (13)
N3	0.063 (2)	0.083 (3)	0.091 (3)	−0.028 (2)	0.034 (2)	−0.023 (2)
N4	0.0462 (17)	0.0416 (16)	0.087 (2)	−0.0030 (13)	0.0218 (17)	−0.0054 (16)
N5	0.059 (3)	0.075 (3)	0.152 (4)	−0.009 (2)	−0.003 (3)	−0.003 (3)
C1	0.048 (2)	0.112 (4)	0.068 (3)	0.026 (2)	0.022 (2)	0.010 (3)
C2	0.0432 (19)	0.056 (2)	0.057 (2)	0.0057 (16)	0.0160 (16)	0.0014 (16)
C3	0.0421 (18)	0.0473 (18)	0.052 (2)	0.0049 (14)	0.0088 (15)	0.0027 (15)
C4	0.0481 (19)	0.0391 (17)	0.0454 (18)	0.0010 (14)	0.0115 (15)	0.0009 (14)
C5	0.0366 (17)	0.0398 (17)	0.0521 (19)	0.0012 (13)	0.0143 (14)	−0.0047 (14)
C6	0.0426 (18)	0.053 (2)	0.0474 (19)	0.0048 (15)	0.0045 (15)	0.0016 (15)
C7	0.050 (2)	0.069 (2)	0.0433 (19)	0.0076 (18)	0.0146 (16)	0.0029 (17)
C8	0.054 (2)	0.052 (2)	0.061 (2)	−0.0088 (17)	0.0187 (18)	−0.0119 (17)
C9	0.0368 (16)	0.0470 (18)	0.0469 (18)	−0.0029 (14)	0.0133 (14)	−0.0043 (14)
C10	0.0379 (16)	0.0384 (16)	0.0446 (17)	0.0041 (13)	0.0092 (13)	0.0011 (13)
C11	0.0368 (16)	0.0383 (16)	0.0456 (17)	0.0022 (13)	0.0093 (13)	0.0021 (13)
C12	0.064 (3)	0.119 (5)	0.104 (4)	−0.015 (3)	−0.010 (3)	0.019 (3)
C13	0.056 (2)	0.055 (2)	0.082 (3)	−0.0060 (19)	0.010 (2)	0.007 (2)

Geometric parameters (Å, º)

S1—C10	1.729 (3)	C1—C2	1.497 (5)
S1—S1^i	2.0948 (19)	C2—C3	1.373 (5)
Cl1—C6	1.731 (3)	C2—C7	1.381 (5)
Cl2—C4	1.722 (3)	C3—C4	1.380 (5)
F1—C1	1.245 (6)	C3—H3	0.9300
F2—C1	1.311 (7)	C4—C5	1.393 (5)
F3—C1	1.228 (6)	C5—C6	1.385 (5)
N1—C11	1.356 (4)	C6—C7	1.374 (5)
N1—N2	1.374 (4)	C7—H7	0.9300
N1—C5	1.422 (4)	C8—C9	1.436 (5)
N2—C9	1.319 (4)	C9—C10	1.418 (5)
N3—C8	1.143 (5)	C10—C11	1.388 (4)
N4—C11	1.345 (4)	C12—C13	1.438 (7)
N4—H4A	0.83	C12—H12A	0.9600
N4—H4B	0.82	C12—H12B	0.9600
N5—C13	1.120 (6)	C12—H12C	0.9600
C10—S1—S1^i	104.82 (12)	C4—C5—N1	120.0 (3)
C11—N1—N2	113.3 (3)	C7—C6—C5	120.9 (3)
C11—N1—C5	126.1 (3)	C7—C6—Cl1	120.1 (3)
N2—N1—C5	120.5 (3)	C5—C6—Cl1	119.0 (3)
C9—N2—N1	103.2 (3)	C6—C7—C2	119.0 (3)
C11—N4—H4A	122	C6—C7—H7	120.5
C11—N4—H4B	122	C2—C7—H7	120.5
H4A—N4—H4B	114	N3—C8—C9	178.0 (4)
F3—C1—F1	112.1 (5)	N2—C9—C10	113.3 (3)
F3—C1—F2	100.8 (5)	N2—C9—C8	120.4 (3)
F1—C1—F2	100.3 (5)	C10—C9—C8	126.3 (3)
F3—C1—C2	115.3 (4)	C11—C10—C9	104.1 (3)
F1—C1—C2	115.7 (4)	C11—C10—S1	126.4 (3)
F2—C1—C2	110.5 (5)	C9—C10—S1	129.5 (2)
C3—C2—C7	121.7 (3)	N4—C11—N1	122.7 (3)
C3—C2—C1	118.8 (3)	N4—C11—C10	131.1 (3)
C7—C2—C1	119.5 (3)	N1—C11—C10	106.2 (3)
C2—C3—C4	118.6 (3)	C13—C12—H12A	109.5
C2—C3—H3	120.7	C13—C12—H12B	109.5
C4—C3—H3	120.7	H12A—C12—H12B	109.5
C3—C4—C5	121.0 (3)	C13—C12—H12C	109.5
C3—C4—Cl2	120.3 (3)	H12A—C12—H12C	109.5
C5—C4—Cl2	118.7 (3)	H12B—C12—H12C	109.5
C6—C5—C4	118.7 (3)	N5—C13—C12	178.5 (6)
C6—C5—N1	121.2 (3)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···N5^ii	0.82	2.26	3.060 (5)	164

Symmetry code: (ii) x−1/2, y−1/2, z.