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The crystal structures of four polymorphs of the pesticide dithianon (5,10-dihydro-5,10-dioxonaphtho[2,3-b]-1,4-dithiine-2,3-dicarbonitrile) have been solved from powder diffraction data and refined using the Rietveld method. Three polymorphs crystallize in non-centrosymmetric space groups. Two polymorphs have Z' > 1. The structures are assembled via interactions between carbonyl groups of quinoid fragments into layers which further interact only by weak interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768112036191/kd5066sup1.cif
Contains datablocks global, I, II, III, IV

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768112036191/kd5066Isup2.rtv
Contains datablock I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768112036191/kd5066IIsup3.rtv
Contains datablock II

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768112036191/kd5066IIIsup4.rtv
Contains datablock III

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768112036191/kd5066IVsup5.rtv
Contains datablock IV

CCDC references: 914865; 914866; 914867; 914868

Computing details top

For all compounds, data collection: Bruker; cell refinement: Topas; data reduction: none; program(s) used to solve structure: Topas; program(s) used to refine structure: Topas.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
(I) top
Crystal data top
C14H4N2O2S2V = 1287.44 (7) Å3
Mr = 296.33Z = 4
Orthorhombic, Pna21Dx = 1.53 Mg m3
a = 8.49373 (19) ÅCu Kα_1 radiation, λ = 1.54059 Å
b = 6.2466 (2) ÅT = 293 K
c = 24.2652 (10) Å?, ? × ? × ? mm
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 2°, 2θmax = 70°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Refinement on F2? data points
Rp = 0.030106 parameters
Rwp = 0.03965 restraints
Rexp = 0.002All H-atom parameters refined
χ2 = 1.742(Δ/σ)max < 0.01
Crystal data top
C14H4N2O2S2V = 1287.44 (7) Å3
Mr = 296.33Z = 4
Orthorhombic, Pna21Cu Kα_1 radiation, λ = 1.54059 Å
a = 8.49373 (19) ÅT = 293 K
b = 6.2466 (2) Å?, ? × ? × ? mm
c = 24.2652 (10) Å
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 2°, 2θmax = 70°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Rp = 0.030? data points
Rwp = 0.039106 parameters
Rexp = 0.00265 restraints
χ2 = 1.742All H-atom parameters refined
Special details top

Refinement. The crystal structure (all atoms) was refined with restraints on bond lenghts and angles as well as planarity restraints.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.52082 (15)0.29473 (16)0.40146 (3)
C20.43823 (15)0.49291 (13)0.39346 (3)
C30.39941 (16)0.62139 (14)0.43888 (3)
C40.43982 (12)0.55590 (14)0.49181 (3)
C50.52256 (11)0.35672 (15)0.49938 (3)
C60.56098 (16)0.22917 (17)0.45404 (3)
C70.39736 (13)0.69230 (14)0.53969 (3)
C80.44316 (19)0.61527 (18)0.59496 (4)
C90.52280 (16)0.4204 (2)0.60217 (4)
C100.56754 (16)0.28214 (18)0.55424 (4)
S110.39236 (16)0.7890 (2)0.65055 (6)
C120.36056 (9)0.61133 (13)0.70560 (3)
C130.44338 (10)0.41415 (13)0.71205 (3)
S140.58569 (14)0.3234 (2)0.66626 (6)
C150.41128 (10)0.28177 (16)0.75714 (4)
N160.38425 (16)0.1722 (3)0.79460 (6)
C170.24786 (11)0.67302 (15)0.74425 (4)
N180.1541 (2)0.7238 (3)0.77649 (6)
O190.6351 (3)0.1180 (4)0.56135 (6)
O200.3289 (3)0.8570 (4)0.53481 (6)
H210.5489 (5)0.2011 (7)0.3684 (2)
H220.4098 (6)0.5415 (7)0.3555 (3)
H230.3437 (6)0.7601 (8)0.43311 (15)
H240.6173 (5)0.0902 (8)0.45962 (14)
(II) top
Crystal data top
C14H4N2O2S2γ = 90.975 (2)°
Mr = 296.33V = 612.02 (5) Å3
Triclinic, P1Z = 2
a = 3.89671 (11) ÅDx = 1.61 Mg m3
b = 12.1707 (3) ÅCu Kα_1 radiation, λ = 1.54059 Å
c = 13.0436 (9) ÅT = 293 K
α = 90.710 (9)°?, ? × ? × ? mm
β = 81.707 (10)°
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 2°, 2θmax = 65°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Refinement on F2? data points
Rp = 0.034129 parameters
Rwp = 0.04865 restraints
Rexp = 0.014All H-atom parameters refined
χ2 = 3.349(Δ/σ)max < 0.01
Crystal data top
C14H4N2O2S2β = 81.707 (10)°
Mr = 296.33γ = 90.975 (2)°
Triclinic, P1V = 612.02 (5) Å3
a = 3.89671 (11) ÅZ = 2
b = 12.1707 (3) ÅCu Kα_1 radiation, λ = 1.54059 Å
c = 13.0436 (9) ÅT = 293 K
α = 90.710 (9)°?, ? × ? × ? mm
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 2°, 2θmax = 65°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Rp = 0.034? data points
Rwp = 0.048129 parameters
Rexp = 0.01465 restraints
χ2 = 3.349All H-atom parameters refined
Special details top

Refinement. The crystal structure (all atoms) was refined with restraints on bond lenghts and angles as well as planarity restraints.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.2537 (5)0.22960 (9)0.46146 (8)
C20.4345 (5)0.33349 (9)0.45351 (8)
C30.5494 (6)0.37813 (12)0.35717 (8)
C40.4979 (5)0.31968 (9)0.26565 (7)
C50.3161 (6)0.21521 (12)0.27402 (8)
C60.2000 (5)0.17076 (10)0.37119 (8)
C70.6305 (3)0.36684 (7)0.16218 (5)
C80.5630 (6)0.30206 (11)0.06900 (8)
C90.3851 (6)0.20211 (12)0.07624 (8)
C100.2486 (3)0.15142 (7)0.17806 (5)
S110.7273 (9)0.36386 (16)0.04496 (18)
C120.6500 (5)0.28853 (11)0.15550 (9)
C130.4719 (5)0.18531 (13)0.14883 (9)
S140.3004 (9)0.12675 (16)0.02973 (19)
C150.4090 (3)0.12679 (11)0.23632 (13)
N160.3565 (7)0.07788 (19)0.3089 (2)
C170.7740 (3)0.33682 (11)0.24984 (13)
N180.8782 (6)0.3779 (2)0.3284 (2)
O190.0980 (11)0.0652 (3)0.18184 (5)
O200.7847 (11)0.4525 (3)0.15235 (5)
H210.171 (2)0.1973 (4)0.5316 (4)
H220.4721 (18)0.3755 (4)0.5177 (5)
H230.6741 (17)0.4504 (4)0.3523 (3)
H240.0752 (18)0.0984 (3)0.3767 (3)
(III) top
Crystal data top
C14H4N2O2S2V = 1908.57 (19) Å3
Mr = 296.33Z = 6
Monoclinic, P21Dx = 1.55 Mg m3
a = 12.4934 (8) ÅCu Kα_1 radiation, λ = 1.54059 Å
b = 24.6720 (12) ÅT = 293 K
c = 6.2769 (3) Å?, ? × ? × ? mm
β = 99.442 (4)°
Data collection top
Stoe Stadi-P
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 5°, 2θmax = 70°, 2θstep = 0.012°
Data collection mode: transmission
Refinement top
Refinement on F2? data points
Rp = 0.020260 parameters
Rwp = 0.027204 restraints
Rexp = 0.007All H-atom parameters refined
χ2 = 3.572(Δ/σ)max < 0.01
Crystal data top
C14H4N2O2S2β = 99.442 (4)°
Mr = 296.33V = 1908.57 (19) Å3
Monoclinic, P21Z = 6
a = 12.4934 (8) ÅCu Kα_1 radiation, λ = 1.54059 Å
b = 24.6720 (12) ÅT = 293 K
c = 6.2769 (3) Å?, ? × ? × ? mm
Data collection top
Stoe Stadi-P
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 5°, 2θmax = 70°, 2θstep = 0.012°
Data collection mode: transmission
Refinement top
Rp = 0.020? data points
Rwp = 0.027260 parameters
Rexp = 0.007204 restraints
χ2 = 3.572All H-atom parameters refined
Special details top

Refinement. The crystal structure (all atoms) was refined with restraints on bond lenghts and angles as well as planarity restraints.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
C10.50963 (18)0.6329 (2)0.5234 (4)
C30.6218 (2)0.6447 (3)0.6376 (6)
C40.6365 (2)0.6719 (2)0.8152 (5)
C50.41060 (19)0.64666 (17)0.6207 (5)
C20.5391 (2)0.6867 (2)0.9185 (5)
C60.42505 (19)0.67318 (16)0.8110 (5)
O10.4969 (3)0.6132 (6)0.3538 (15)
O20.5520 (3)0.7058 (6)1.0900 (15)
C70.30225 (19)0.63424 (18)0.5068 (5)
C80.3400 (2)0.6861 (2)0.9063 (6)
C90.2150 (2)0.64478 (18)0.6010 (4)
C100.2293 (2)0.67546 (18)0.7946 (5)
S10.7266 (5)0.6254 (3)0.5109 (7)
S20.7705 (4)0.6849 (2)0.9716 (7)
C110.8545 (2)0.61566 (15)0.7009 (5)
C120.8723 (2)0.63987 (13)0.8878 (5)
C130.9310 (3)0.58090 (14)0.6246 (6)
N10.9937 (5)0.5528 (3)0.5640 (11)
C140.9699 (3)0.63320 (12)1.0427 (5)
N21.0513 (5)0.6273 (2)1.1708 (9)
H70.2931 (13)0.6165 (7)0.376 (4)
H80.3511 (13)0.7049 (7)1.036 (3)
H90.1445 (13)0.6335 (9)0.531 (3)
H100.1705 (13)0.6852 (7)0.859 (4)
C210.4950 (3)0.4708 (2)0.4316 (5)
C230.6024 (3)0.4817 (3)0.3678 (6)
C240.6076 (2)0.5103 (2)0.1927 (5)
C250.3903 (2)0.4859 (2)0.2872 (6)
C220.5039 (2)0.5243 (2)0.0403 (4)
C260.3948 (2)0.51269 (18)0.0981 (5)
O210.4910 (4)0.4539 (6)0.5963 (15)
O220.5084 (3)0.5453 (5)0.1252 (16)
C270.2913 (2)0.4749 (2)0.3540 (5)
C280.2992 (2)0.52837 (18)0.0421 (6)
C290.1943 (2)0.4866 (2)0.2193 (5)
C300.1982 (2)0.5184 (2)0.0148 (5)
S210.7215 (5)0.4547 (2)0.5441 (6)
S220.7297 (4)0.5256 (2)0.1038 (7)
C310.8303 (2)0.44696 (15)0.3847 (5)
C320.8321 (2)0.47550 (13)0.2009 (5)
C330.9082 (3)0.40954 (15)0.4675 (6)
N210.9756 (5)0.3775 (3)0.5386 (10)
C340.9117 (3)0.46929 (12)0.0685 (6)
N220.9785 (5)0.4638 (2)0.0429 (9)
H270.2901 (13)0.4570 (7)0.482 (3)
H280.3039 (13)0.5461 (8)0.166 (4)
H290.1279 (16)0.4771 (8)0.263 (4)
H300.1295 (14)0.5264 (7)0.094 (3)
C410.5160 (3)0.35216 (19)0.9253 (5)
C430.4080 (3)0.3472 (2)0.7828 (7)
C440.3997 (3)0.3212 (2)0.6063 (6)
C450.6181 (3)0.32947 (15)0.8581 (6)
C420.4996 (3)0.2997 (2)0.5348 (5)
C460.6094 (2)0.30389 (19)0.6751 (5)
O410.5244 (4)0.3772 (6)1.0933 (18)
O420.4933 (4)0.2782 (5)0.3684 (16)
C470.7249 (2)0.33453 (18)0.9966 (5)
C480.7042 (2)0.2821 (2)0.5987 (6)
C490.8231 (2)0.31233 (18)0.9203 (5)
C500.8104 (2)0.28454 (17)0.7313 (5)
S410.2915 (5)0.3712 (2)0.8865 (7)
S420.2694 (5)0.3071 (3)0.4305 (6)
C510.1827 (2)0.32760 (13)0.7957 (6)
C520.1730 (2)0.30032 (16)0.5961 (5)
C530.1123 (3)0.32254 (12)0.9398 (6)
N410.0523 (6)0.3179 (2)1.0634 (10)
C540.0880 (3)0.26578 (15)0.5123 (6)
N420.0171 (5)0.2373 (3)0.4434 (10)
H470.7324 (15)0.3538 (7)1.127 (3)
H480.6962 (14)0.2651 (6)0.469 (4)
H490.8961 (17)0.3136 (8)1.018 (3)
H500.8702 (15)0.2714 (6)0.677 (4)
(IV) top
Crystal data top
C14H4N2O2S2V = 1269.02 (11) Å3
Mr = 296.33Z = 4
Monoclinic, P21Dx = 1.55 Mg m3
a = 13.0945 (6) ÅCu Kα_1 radiation, λ = 1.54059 Å
b = 6.0103 (4) ÅT = 293 K
c = 17.1209 (6) Å?, ? × ? × ? mm
β = 109.646 (4)°
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 5°, 2θmax = 60°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Refinement on F2? data points
Rp = 0.048177 parameters
Rwp = 0.065139 restraints
Rexp = 0.007All H-atom parameters refined
χ2 = 9.000(Δ/σ)max < 0.01
Crystal data top
C14H4N2O2S2β = 109.646 (4)°
Mr = 296.33V = 1269.02 (11) Å3
Monoclinic, P21Z = 4
a = 13.0945 (6) ÅCu Kα_1 radiation, λ = 1.54059 Å
b = 6.0103 (4) ÅT = 293 K
c = 17.1209 (6) Å?, ? × ? × ? mm
Data collection top
Bruker D8
diffractometer
Scan method: step
Specimen mounting: capillary2θmin = 5°, 2θmax = 60°, 2θstep = 0.009°
Data collection mode: transmission
Refinement top
Rp = 0.048? data points
Rwp = 0.065177 parameters
Rexp = 0.007139 restraints
χ2 = 9.000All H-atom parameters refined
Special details top

Refinement. The crystal structure (all atoms) was refined with restraints on bond lenghts and angles as well as planarity restraints.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzBiso*/Beq
S10.2615 (7)0.2641 (16)0.1099 (5)
S20.2664 (7)0.7363 (10)0.0107 (5)
S30.2794 (6)1.2616 (11)0.3754 (5)
S40.2627 (7)0.8021 (14)0.2600 (5)
O10.4779 (7)0.115 (2)0.1976 (10)
O20.4873 (6)0.867 (2)0.0525 (9)
O30.5050 (6)1.367 (2)0.4526 (8)
O40.4755 (6)0.604 (2)0.2938 (8)
N10.0322 (9)0.041 (2)0.0613 (5)
N20.0327 (10)0.553 (3)0.1818 (6)
N30.0516 (8)1.107 (2)0.4515 (8)
N40.0426 (7)0.524 (2)0.3096 (6)
C10.0922 (5)0.1588 (15)0.0331 (3)
C20.1756 (5)0.3224 (18)0.0054 (3)
C30.3844 (3)0.3995 (15)0.1151 (4)
C40.4850 (4)0.2803 (12)0.1644 (4)
C50.5904 (3)0.3907 (14)0.1755 (5)
C60.6903 (3)0.2898 (14)0.2217 (5)
H60.6908 (19)0.142 (9)0.2467 (15)
C70.7859 (3)0.4068 (13)0.2345 (4)
H70.851 (2)0.349 (10)0.2677 (14)
C80.7852 (4)0.6301 (13)0.1953 (4)
H80.851 (2)0.717 (10)0.2051 (14)
C90.6951 (3)0.7154 (13)0.1509 (5)
H90.6959 (19)0.857 (9)0.1265 (15)
C100.5937 (3)0.5942 (12)0.1386 (5)
C110.4894 (5)0.7033 (11)0.0865 (6)
C120.3887 (3)0.5859 (13)0.0784 (5)
C130.1781 (6)0.5077 (14)0.0327 (4)
C140.0964 (5)0.5410 (18)0.1166 (4)
C150.1055 (7)1.0754 (17)0.4079 (5)
C160.1786 (4)1.0485 (15)0.3569 (4)
C170.3948 (3)1.0957 (13)0.3695 (5)
C180.5009 (5)1.1923 (10)0.4166 (5)
C190.6001 (3)1.0672 (14)0.4172 (3)
C200.7101 (3)1.1640 (13)0.4634 (5)
H200.7218 (18)1.311 (10)0.4925 (17)
C210.7939 (3)1.0302 (14)0.4567 (3)
H210.8695 (19)1.078 (10)0.4884 (19)
C220.7740 (3)0.8128 (14)0.4165 (3)
H220.8356 (18)0.705 (11)0.4190 (14)
C230.6748 (3)0.7467 (13)0.3747 (4)
H230.6644 (19)0.610 (10)0.3467 (15)
C240.5889 (3)0.8630 (13)0.3749 (3)
C250.4868 (4)0.7745 (12)0.3299 (4)
C260.3886 (4)0.9054 (14)0.3286 (4)
C270.1766 (3)0.8599 (16)0.3123 (4)
C280.1005 (5)0.6753 (15)0.3113 (3)

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC14H4N2O2S2C14H4N2O2S2C14H4N2O2S2C14H4N2O2S2
Mr296.33296.33296.33296.33
Crystal system, space groupOrthorhombic, Pna21Triclinic, P1Monoclinic, P21Monoclinic, P21
Temperature (K)293293293293
a, b, c (Å)8.49373 (19), 6.2466 (2), 24.2652 (10)3.89671 (11), 12.1707 (3), 13.0436 (9)12.4934 (8), 24.6720 (12), 6.2769 (3)13.0945 (6), 6.0103 (4), 17.1209 (6)
α, β, γ (°)90, 90, 9090.710 (9), 81.707 (10), 90.975 (2)90, 99.442 (4), 9090, 109.646 (4), 90
V3)1287.44 (7)612.02 (5)1908.57 (19)1269.02 (11)
Z4264
Radiation typeCu Kα_1, λ = 1.54059 ÅCu Kα_1, λ = 1.54059 ÅCu Kα_1, λ = 1.54059 ÅCu Kα_1, λ = 1.54059 Å
µ (mm1)????
Specimen shape, size (mm)?, ? × ? × ??, ? × ? × ??, ? × ? × ??, ? × ? × ?
Data collection
DiffractometerBruker D8
diffractometer
Bruker D8
diffractometer
Stoe Stadi-P
diffractometer
Bruker D8
diffractometer
Specimen mountingCapillaryCapillaryCapillaryCapillary
Data collection modeTransmissionTransmissionTransmissionTransmission
Scan methodStepStepStepStep
2θ values (°)2θmin = 2 2θmax = 70 2θstep = 0.0092θmin = 2 2θmax = 65 2θstep = 0.0092θmin = 5 2θmax = 70 2θstep = 0.0122θmin = 5 2θmax = 60 2θstep = 0.009
Refinement
R factors and goodness of fitRp = 0.030, Rwp = 0.039, Rexp = 0.002, χ2 = 1.742Rp = 0.034, Rwp = 0.048, Rexp = 0.014, χ2 = 3.349Rp = 0.020, Rwp = 0.027, Rexp = 0.007, χ2 = 3.572Rp = 0.048, Rwp = 0.065, Rexp = 0.007, χ2 = 9.000
No. of data points????
No. of parameters106129260177
No. of restraints6565204139
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refined

Computer programs: Bruker, Topas, none.

 

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