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Bonding properties in the crystal of 4,5-di­chloro-l,2,3-di­thia­zolium chloride (Appel's salt) were studied using a combination of single-crystal high-resolution X-ray diffraction data and the orbital-free quantum crystallography approach. A QTAIM-based topological model shows the proximity of S—C and S—N bonds to the sesquialteral type and establishes the low S—S bond order in the l,2,3-di­thia­zolium heterocycle. It is found that the electrostatic potential carries the traces of a common positive area on the junction of interatomic zero-flux surfaces of S1 and S2 atomic basins; meanwhile the exchange energy density per particle shows perfectly here two separate minima through which the two bond paths run. Thus, the pair intermolecular interactions Cl...S1 and Cl...S2 formed by the common chloride anion placed near the center of the S—S bond are categorized as chalcogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520621005928/px5038sup1.cif
Contains datablocks I, Appel_mult

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520621005928/px5038Isup2.hkl
Contains datablock I

CCDC reference: 2088696

Computing details top

Cell refinement: SAINT V8.38A (Bruker AXS Inc., 2013) for (I). Data reduction: SAINT V8.38A (Bruker AXS Inc., 2013) for (I). Program(s) used to solve structure: SHELXT-2018/3 (Sheldrick, 2018) for (I). Program(s) used to refine structure: SHELXL2013/8 (Sheldrick, 2018) for (I); Volkov et al., (2006) for Appel_mult. Molecular graphics: Bruker SHELXTL (Bruker AXS Inc., 2013) for (I); Volkov et al., (2006) for Appel_mult. Software used to prepare material for publication: Volkov et al., (2006) for Appel_mult.

(I) top
Crystal data top
C2Cl2NS2·ClDx = 2.088 Mg m3
Mr = 208.50Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 9877 reflections
a = 5.90947 (10) Åθ = 2.7–39.7°
b = 10.22455 (16) ŵ = 1.89 mm1
c = 10.97838 (18) ÅT = 100 K
V = 663.33 (2) Å3Block-like, dark brown
Z = 40.58 × 0.12 × 0.11 mm
F(000) = 408
Data collection top
Bruker Quest D8
diffractometer with Photon III detector
12387 reflections with I > 2σ(I)
ω–scanRint = 0.024
Absorption correction: multi-scan
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction
θmax = 71.6°, θmin = 2.7°
Tmin = 0.566, Tmax = 0.724h = 1415
102642 measured reflectionsk = 2627
12761 independent reflectionsl = 2929
Refinement top
Refinement on F20 restraints
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0193P)2 + 0.0166P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.014(Δ/σ)max = 0.003
wR(F2) = 0.040Δρmax = 0.49 e Å3
S = 1.07Δρmin = 0.55 e Å3
12761 reflectionsAbsolute structure: Flack x determined using 5383 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
73 parametersAbsolute structure parameter: 0.273 (7)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.28475 (3)0.74344 (2)0.60078 (2)0.01886 (2)
Cl20.03886 (2)0.53741 (2)0.75136 (2)0.01531 (1)
Cl30.48426 (2)0.08785 (2)0.59885 (2)0.01301 (1)
S10.27725 (2)0.33636 (2)0.67299 (2)0.01203 (1)
S20.54906 (2)0.37393 (2)0.56445 (2)0.01248 (1)
N10.51415 (6)0.53003 (3)0.55287 (3)0.01376 (3)
C10.33891 (6)0.57994 (3)0.60914 (3)0.01276 (4)
C20.19775 (6)0.49364 (3)0.67624 (3)0.01212 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02390 (4)0.01003 (2)0.02265 (4)0.00335 (2)0.00101 (4)0.00118 (2)
Cl20.01380 (3)0.01544 (3)0.01668 (3)0.00184 (2)0.00185 (2)0.00338 (2)
Cl30.01313 (2)0.01159 (2)0.01431 (2)0.00126 (2)0.00119 (2)0.00060 (2)
S10.01314 (3)0.00975 (2)0.01320 (2)0.00035 (2)0.00160 (2)0.00013 (2)
S20.01325 (3)0.00998 (2)0.01422 (3)0.00051 (2)0.00215 (2)0.00003 (2)
N10.01559 (9)0.01034 (6)0.01534 (8)0.00005 (6)0.00207 (7)0.00064 (6)
C10.01502 (9)0.00973 (7)0.01352 (9)0.00078 (6)0.00014 (7)0.00002 (6)
C20.01295 (8)0.01117 (7)0.01224 (8)0.00074 (6)0.00017 (7)0.00139 (6)
Geometric parameters (Å, º) top
Cl1—C11.7045 (3)S2—N11.6143 (3)
Cl2—C21.6838 (4)N1—C11.3094 (5)
S1—C21.6757 (3)C1—C21.4203 (5)
S1—S22.0366 (1)
C2—S1—S293.014 (13)C2—C1—Cl1121.80 (3)
N1—S2—S197.570 (13)C1—C2—S1114.87 (3)
C1—N1—S2116.70 (3)C1—C2—Cl2125.21 (3)
N1—C1—C2117.84 (3)S1—C2—Cl2119.89 (2)
N1—C1—Cl1120.36 (3)
(Appel_mult) top
Crystal data top
a = Åα = °
b = Åβ = °
c = Åγ = °
Data collection top
h = l =
k =
Refinement top
Refinement on F29426 reflections
Least-squares matrix: full414 parameters
R[F2 > 2σ(F2)] = 0.0090 restraints
wR(F2) = 0.011 w2 = q/[s2(Fo2) + (0.01 P)2 + 0.00 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2) q = 1.0
S = 1.40(Δ/σ)max < 0.001
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl(1)0.28457 (7)0.74324 (2)0.60055 (4)0.019
Cl(2)0.03844 (5)0.53756 (3)0.75118 (2)0.016
Cl(3)0.48423 (4)0.08786 (2)0.59881 (2)0.013
S(1)0.27720 (4)0.33636 (2)0.67291 (2)0.012
S(2)0.54893 (4)0.37393 (2)0.56454 (2)0.013
N(1)0.51412 (3)0.529971 (16)0.552909 (18)0.014
C(1)0.33882 (4)0.580022 (17)0.609172 (19)0.013
C(2)0.19767 (3)0.493656 (18)0.676274 (18)0.012
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl(1)0.02510 (11)0.01005 (6)0.02313 (10)0.00356 (6)0.00106 (9)0.00108 (6)
Cl(2)0.01443 (7)0.01575 (7)0.01701 (7)0.00192 (5)0.00180 (6)0.00347 (6)
Cl(3)0.01360 (6)0.01152 (5)0.01460 (6)0.00132 (4)0.00135 (5)0.00060 (5)
S(1)0.01368 (7)0.00971 (5)0.01347 (6)0.00036 (5)0.00160 (5)0.00017 (5)
S(2)0.01384 (7)0.00994 (5)0.01443 (6)0.00054 (5)0.00221 (5)0.00009 (5)
N(1)0.01572 (5)0.01029 (4)0.01568 (5)0.00001 (3)0.00242 (4)0.00073 (3)
C(1)0.01503 (5)0.00968 (4)0.01378 (5)0.00083 (3)0.00000 (4)0.00006 (4)
C(2)0.01309 (5)0.01107 (4)0.01247 (4)0.00079 (3)0.00035 (4)0.00131 (3)
 

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