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A new organic charge-transfer complex, C18H7N5O8·C6H4S4, has been prepared using TTF (tetrathiafulvalene) as a donor (D) and MeDC2TNF (9-dicyanomethylene-4,5,7-trinitro-fluorene-2-carboxylic acid methyl ester) as an acceptor (A). Two monoclinic polymorphs of the 1:1 salt were crystallized and characterized by X-ray diffraction. Form α crystallizes in space group P21/n with Z′ = 1, while form β crystallizes in space group C2/c with Z′ = 1\over 2 and the MeDC2TNF moiety disordered across a twofold axis. Both phases have mixed-stack crystal packings, which are characteristic of semiconducting one-dimensional organic complexes. However, the observed crystal packings are significantly different, with a single D...A interlayer separation of 3.452 Å for the disordered β polymorph and interlayer separations of 3.378 and 3.483 Å in the case of the ordered α form. These variations are reflected in the degree of charge transfer, δ, which was estimated on the basis of the b2u stretching-mode frequency shift observed in the IR spectra for the cyano groups of the MeDC2TNF radical anion. The fact that the charge transfer is more efficient for α-(TTF-MeDC2TNF) than for β-(TTF-MeDC2TNF) (δ = 0.35 and 0.31, respectively) is consistent with the structural features observed for each crystalline form.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768103011893/sn5000sup1.cif
Contains datablocks cdc2tnf, cdc2tnfb, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103011893/sn5000cdc2tnfsup2.hkl
Contains datablock cdc2tnf

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768103011893/sn5000cdc2tnfbsup3.hkl
Contains datablock cdc2tnfb

CCDC references: 219305; 219306

Computing details top

For both compounds, data collection: XSCANS 2.21 (Siemens, 1996); cell refinement: XSCANS 2.21 (Siemens, 1996); data reduction: XSCANS 2.21 (Siemens, 1996); program(s) used to solve structure: SHELXTL 5.10 (Sheldrick, 1998); program(s) used to refine structure: SHELX97 (Sheldrick, 1997); molecular graphics: SHELXTL 5.10 (Sheldrick, 1998); software used to prepare material for publication: SHELX97 (Sheldrick, 1997).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
(cdc2tnf) [2,2'-Bis-1,3-dithiole][9-dicyanomethylene-4,5,7- trinitro-fluorene-2-carboxylic acid methyl ester] top
Crystal data top
C18H7N5O8·C6H4S4F(000) = 1272
Mr = 625.62Dx = 1.616 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 60 reflections
a = 6.7816 (17) Åθ = 4.7–11.1°
b = 30.572 (4) ŵ = 0.43 mm1
c = 12.4381 (13) ÅT = 296 K
β = 94.304 (11)°Needle, dark brown
V = 2571.5 (8) Å30.70 × 0.16 × 0.08 mm
Z = 4
Data collection top
Bruker P4
diffractometer
θmax = 25.0°, θmin = 1.8°
Graphite monochromatorh = 81
2θ/ω scansk = 136
5958 measured reflectionsl = 1414
4503 independent reflections2 standard reflections every 48 reflections
3133 reflections with I > 2σ(I) intensity decay: 1%
Rint = 0.041
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0585P)2 + 5.5383P]
where P = (Fo2 + 2Fc2)/3
4503 reflections(Δ/σ)max = 0.001
370 parametersΔρmax = 0.66 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
C18H7N5O8·C6H4S4V = 2571.5 (8) Å3
Mr = 625.62Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.7816 (17) ŵ = 0.43 mm1
b = 30.572 (4) ÅT = 296 K
c = 12.4381 (13) Å0.70 × 0.16 × 0.08 mm
β = 94.304 (11)°
Data collection top
Bruker P4
diffractometer
Rint = 0.041
5958 measured reflections2 standard reflections every 48 reflections
4503 independent reflections intensity decay: 1%
3133 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.169H-atom parameters constrained
S = 1.06Δρmax = 0.66 e Å3
4503 reflectionsΔρmin = 0.35 e Å3
370 parameters
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
xyzUiso*/Ueq
C10.2976 (7)0.55190 (15)0.2132 (3)0.0367 (11)
H1A0.31700.54230.28420.044*
C20.2778 (7)0.52171 (14)0.1290 (4)0.0357 (11)
C30.2453 (7)0.53659 (15)0.0241 (4)0.0409 (12)
H3A0.22980.51650.03210.049*
C40.2354 (7)0.58046 (16)0.0019 (3)0.0387 (11)
C4A0.2669 (6)0.61197 (15)0.0839 (3)0.0317 (10)
C4B0.2786 (7)0.66021 (15)0.0875 (3)0.0333 (10)
C50.2852 (8)0.69395 (16)0.0124 (4)0.0433 (12)
C60.2846 (8)0.73740 (17)0.0417 (4)0.0474 (13)
H6A0.28510.75930.01010.057*
C70.2833 (8)0.74778 (16)0.1505 (4)0.0444 (12)
C80.2890 (7)0.71643 (14)0.2293 (4)0.0372 (11)
H8A0.29380.72410.30180.045*
C8A0.2875 (7)0.67244 (14)0.1973 (3)0.0325 (10)
C90.2953 (7)0.63326 (14)0.2656 (3)0.0316 (10)
C9A0.2883 (7)0.59582 (14)0.1907 (3)0.0317 (10)
C100.3050 (7)0.63167 (15)0.3760 (4)0.0371 (11)
C110.3050 (8)0.59168 (18)0.4366 (4)0.0437 (12)
N120.3027 (7)0.56037 (16)0.4868 (4)0.0593 (13)
C130.3087 (9)0.67029 (17)0.4438 (4)0.0509 (14)
N140.3088 (11)0.69944 (19)0.4987 (4)0.095 (2)
C150.2863 (8)0.47399 (16)0.1481 (4)0.0437 (12)
O160.2636 (8)0.44730 (12)0.0774 (3)0.0776 (14)
O170.3190 (7)0.46362 (11)0.2507 (3)0.0637 (11)
C180.3325 (13)0.4170 (2)0.2796 (5)0.085 (2)
H18A0.35640.41410.35630.128*
H18B0.43920.40380.24480.128*
H18C0.21070.40260.25650.128*
N190.1603 (8)0.59223 (17)0.1088 (3)0.0603 (13)
O200.0540 (6)0.62625 (15)0.1203 (3)0.0646 (11)
O210.1964 (8)0.56729 (14)0.1819 (3)0.0788 (14)
N220.3245 (9)0.68566 (17)0.1014 (4)0.0666 (15)
O230.4336 (7)0.65394 (17)0.1197 (3)0.0735 (13)
O240.2499 (9)0.71146 (14)0.1688 (3)0.0909 (17)
N250.2803 (8)0.79436 (15)0.1820 (4)0.0630 (13)
O260.2897 (10)0.82204 (14)0.1126 (4)0.1025 (19)
O270.2651 (8)0.80272 (13)0.2769 (4)0.0840 (15)
S280.7867 (2)0.54576 (4)0.22884 (10)0.0437 (3)
C290.7882 (8)0.51976 (17)0.3516 (5)0.0536 (14)
H29A0.78690.48940.35600.064*
C300.7911 (9)0.5443 (2)0.4401 (5)0.0610 (16)
H30A0.79020.53170.50820.073*
S310.7969 (2)0.60078 (4)0.42341 (9)0.0473 (4)
C320.7880 (7)0.59870 (16)0.2825 (4)0.0378 (11)
C330.7832 (7)0.63553 (15)0.2216 (3)0.0346 (10)
S340.79314 (19)0.68820 (4)0.27898 (9)0.0386 (3)
C350.7895 (7)0.71523 (17)0.1555 (4)0.0430 (12)
H35A0.79380.74560.15200.052*
C360.7806 (8)0.69119 (17)0.0670 (4)0.0447 (12)
H36A0.78000.70410.00070.054*
S370.7699 (2)0.63441 (4)0.08083 (9)0.0412 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.048 (3)0.035 (3)0.026 (2)0.000 (2)0.002 (2)0.0002 (19)
C20.042 (3)0.029 (2)0.037 (3)0.000 (2)0.004 (2)0.0026 (19)
C30.054 (3)0.036 (3)0.032 (3)0.006 (2)0.003 (2)0.011 (2)
C40.055 (3)0.042 (3)0.019 (2)0.000 (2)0.001 (2)0.0034 (19)
C4A0.031 (2)0.036 (3)0.028 (2)0.000 (2)0.0017 (18)0.0009 (19)
C4B0.037 (3)0.034 (2)0.028 (2)0.001 (2)0.0010 (19)0.0002 (19)
C50.060 (3)0.037 (3)0.033 (3)0.005 (2)0.000 (2)0.004 (2)
C60.061 (3)0.040 (3)0.040 (3)0.000 (2)0.003 (2)0.012 (2)
C70.047 (3)0.030 (3)0.055 (3)0.003 (2)0.003 (2)0.003 (2)
C80.047 (3)0.032 (3)0.033 (2)0.001 (2)0.005 (2)0.007 (2)
C8A0.035 (2)0.033 (2)0.029 (2)0.0006 (19)0.0002 (19)0.0017 (18)
C90.037 (3)0.033 (2)0.025 (2)0.001 (2)0.0015 (19)0.0019 (18)
C9A0.038 (3)0.034 (3)0.023 (2)0.001 (2)0.0015 (18)0.0026 (18)
C100.047 (3)0.037 (3)0.027 (2)0.001 (2)0.001 (2)0.0075 (19)
C110.054 (3)0.050 (3)0.027 (2)0.002 (2)0.002 (2)0.004 (2)
N120.077 (3)0.058 (3)0.043 (3)0.003 (3)0.004 (2)0.015 (2)
C130.084 (4)0.043 (3)0.025 (2)0.004 (3)0.003 (2)0.005 (2)
N140.178 (7)0.063 (4)0.042 (3)0.009 (4)0.005 (3)0.023 (3)
C150.060 (3)0.033 (3)0.038 (3)0.001 (2)0.002 (2)0.005 (2)
O160.150 (4)0.035 (2)0.046 (2)0.009 (2)0.005 (2)0.0126 (18)
O170.115 (3)0.035 (2)0.040 (2)0.000 (2)0.007 (2)0.0005 (16)
C180.144 (7)0.046 (4)0.064 (4)0.006 (4)0.007 (4)0.002 (3)
N190.092 (4)0.057 (3)0.030 (2)0.005 (3)0.004 (2)0.002 (2)
O200.072 (3)0.083 (3)0.037 (2)0.006 (2)0.0092 (19)0.011 (2)
O210.141 (4)0.068 (3)0.0272 (19)0.004 (3)0.003 (2)0.0154 (19)
N220.113 (5)0.051 (3)0.036 (3)0.012 (3)0.008 (3)0.004 (2)
O230.088 (3)0.097 (4)0.038 (2)0.006 (3)0.018 (2)0.008 (2)
O240.175 (5)0.057 (3)0.038 (2)0.001 (3)0.010 (3)0.023 (2)
N250.076 (4)0.037 (3)0.075 (4)0.001 (2)0.000 (3)0.003 (3)
O260.189 (6)0.036 (2)0.080 (3)0.006 (3)0.006 (3)0.015 (2)
O270.129 (4)0.043 (2)0.082 (3)0.007 (3)0.017 (3)0.016 (2)
S280.0540 (8)0.0377 (7)0.0397 (7)0.0009 (6)0.0049 (6)0.0042 (5)
C290.069 (4)0.036 (3)0.057 (4)0.000 (3)0.009 (3)0.010 (3)
C300.078 (4)0.059 (4)0.045 (3)0.005 (3)0.003 (3)0.019 (3)
S310.0636 (9)0.0484 (8)0.0295 (6)0.0016 (6)0.0009 (6)0.0008 (5)
C320.040 (3)0.043 (3)0.030 (2)0.001 (2)0.002 (2)0.004 (2)
C330.038 (3)0.039 (3)0.026 (2)0.002 (2)0.0008 (19)0.0054 (19)
S340.0495 (7)0.0373 (7)0.0290 (6)0.0028 (5)0.0026 (5)0.0040 (5)
C350.053 (3)0.040 (3)0.036 (3)0.002 (2)0.002 (2)0.007 (2)
C360.054 (3)0.045 (3)0.035 (3)0.005 (2)0.002 (2)0.012 (2)
S370.0529 (8)0.0437 (7)0.0269 (6)0.0005 (6)0.0024 (5)0.0054 (5)
Geometric parameters (Å, º) top
C1—C9A1.372 (6)N19—O201.268 (6)
C1—C21.395 (6)N22—O241.232 (6)
C2—C31.384 (6)N22—O231.251 (7)
C2—C151.479 (7)N25—O261.213 (6)
C3—C41.370 (7)N25—O271.220 (6)
C4—C4A1.407 (6)S28—C291.721 (5)
C4—N191.476 (6)S28—C321.750 (5)
C4A—C9A1.415 (6)C29—C301.330 (8)
C4A—C4B1.478 (6)C30—S311.740 (6)
C4B—C51.395 (6)S31—C321.751 (5)
C4B—C8A1.413 (6)C32—C331.356 (6)
C5—C61.378 (7)C33—S371.747 (4)
C5—N221.481 (7)C33—S341.760 (4)
C6—C71.390 (7)S34—C351.743 (5)
C7—C81.370 (7)C35—C361.321 (7)
C7—N251.478 (7)C36—S371.746 (5)
C8—C8A1.403 (6)C1—H1A0.9300
C8A—C91.467 (6)C3—H3A0.9300
C9—C101.371 (6)C6—H6A0.9300
C9—C9A1.474 (6)C8—H8A0.9300
C10—C111.436 (7)C18—H18A0.9600
C10—C131.451 (7)C18—H18B0.9600
C11—N121.144 (6)C18—H18C0.9600
C13—N141.122 (7)C29—H29A0.9300
C15—O161.201 (6)C30—H30A0.9300
C15—O171.318 (6)C35—H35A0.9300
O17—C181.471 (7)C36—H36A0.9300
N19—O211.225 (6)
C9A—C1—C2119.6 (4)O24—N22—O23126.2 (5)
C3—C2—C1119.3 (4)O24—N22—C5116.5 (5)
C3—C2—C15118.5 (4)O23—N22—C5117.3 (5)
C1—C2—C15122.1 (4)O26—N25—O27123.7 (5)
C4—C3—C2120.9 (4)O26—N25—C7118.7 (5)
C3—C4—C4A121.4 (4)O27—N25—C7117.6 (5)
C3—C4—N19115.8 (4)C29—S28—C3295.1 (2)
C4A—C4—N19122.1 (4)C30—C29—S28118.2 (4)
C4—C4A—C9A116.2 (4)C29—C30—S31117.4 (4)
C4—C4A—C4B135.2 (4)C30—S31—C3294.8 (3)
C9A—C4A—C4B108.6 (4)C33—C32—S28123.8 (3)
C5—C4B—C8A116.8 (4)C33—C32—S31121.8 (4)
C5—C4B—C4A136.2 (4)S28—C32—S31114.5 (3)
C8A—C4B—C4A107.0 (4)C32—C33—S37122.7 (3)
C6—C5—C4B122.3 (4)C32—C33—S34122.3 (3)
C6—C5—N22115.0 (4)S37—C33—S34114.9 (3)
C4B—C5—N22122.0 (4)C35—S34—C3394.5 (2)
C5—C6—C7118.6 (4)C36—C35—S34117.8 (4)
C8—C7—C6122.4 (4)C35—C36—S37118.1 (4)
C8—C7—N25119.0 (5)C36—S37—C3394.6 (2)
C6—C7—N25118.6 (5)C9A—C1—H1A120.2
C7—C8—C8A117.9 (4)C2—C1—H1A120.2
C8—C8A—C4B121.8 (4)C4—C3—H3A119.5
C8—C8A—C9128.2 (4)C2—C3—H3A119.5
C4B—C8A—C9109.9 (4)C5—C6—H6A120.7
C10—C9—C8A127.3 (4)C7—C6—H6A120.7
C10—C9—C9A127.0 (4)C7—C8—H8A121.0
C8A—C9—C9A105.7 (3)C8A—C8—H8A121.0
C1—C9A—C4A122.2 (4)O17—C18—H18A109.5
C1—C9A—C9129.2 (4)O17—C18—H18B109.5
C4A—C9A—C9108.6 (4)H18A—C18—H18B109.5
C9—C10—C11123.7 (4)O17—C18—H18C109.5
C9—C10—C13123.5 (4)H18A—C18—H18C109.5
C11—C10—C13112.8 (4)H18B—C18—H18C109.5
N12—C11—C10178.3 (5)C30—C29—H29A120.9
N14—C13—C10177.9 (6)S28—C29—H29A120.9
O16—C15—O17123.3 (5)C29—C30—H30A121.3
O16—C15—C2123.4 (5)S31—C30—H30A121.3
O17—C15—C2113.2 (4)C36—C35—H35A121.1
C15—O17—C18118.2 (4)S34—C35—H35A121.1
O21—N19—O20124.8 (5)C35—C36—H36A121.0
O21—N19—C4117.8 (5)S37—C36—H36A121.0
O20—N19—C4117.3 (4)
C9A—C1—C2—C31.2 (7)C8A—C9—C10—C11177.6 (5)
C9A—C1—C2—C15180.0 (5)C9A—C9—C10—C111.7 (8)
C1—C2—C3—C41.0 (7)C8A—C9—C10—C130.2 (8)
C15—C2—C3—C4179.8 (5)C9A—C9—C10—C13179.1 (5)
C2—C3—C4—C4A3.0 (8)C9—C10—C11—N1215E1 (2)
C2—C3—C4—N19167.9 (5)C13—C10—C11—N123E1 (2)
C3—C4—C4A—C9A6.4 (7)C9—C10—C13—N14152 (19)
N19—C4—C4A—C9A163.9 (4)C11—C10—C13—N1425 (19)
C3—C4—C4A—C4B175.8 (5)C3—C2—C15—O161.1 (8)
N19—C4—C4A—C4B13.9 (8)C1—C2—C15—O16177.6 (5)
C4—C4A—C4B—C58.7 (10)C3—C2—C15—O17179.7 (5)
C9A—C4A—C4B—C5173.3 (5)C1—C2—C15—O171.6 (7)
C4—C4A—C4B—C8A172.3 (5)O16—C15—O17—C181.4 (9)
C9A—C4A—C4B—C8A5.6 (5)C2—C15—O17—C18179.4 (5)
C8A—C4B—C5—C65.0 (7)C3—C4—N19—O2132.5 (7)
C4A—C4B—C5—C6176.1 (5)C4A—C4—N19—O21156.6 (5)
C8A—C4B—C5—N22165.3 (5)C3—C4—N19—O20143.7 (5)
C4A—C4B—C5—N2213.6 (9)C4A—C4—N19—O2027.1 (7)
C4B—C5—C6—C71.9 (8)C6—C5—N22—O2438.5 (8)
N22—C5—C6—C7169.0 (5)C4B—C5—N22—O24150.5 (5)
C5—C6—C7—C82.2 (8)C6—C5—N22—O23139.9 (5)
C5—C6—C7—N25179.3 (5)C4B—C5—N22—O2331.1 (8)
C6—C7—C8—C8A2.8 (8)C8—C7—N25—O26174.7 (6)
N25—C7—C8—C8A178.7 (4)C6—C7—N25—O263.9 (8)
C7—C8—C8A—C4B0.5 (7)C8—C7—N25—O276.4 (8)
C7—C8—C8A—C9179.1 (5)C6—C7—N25—O27175.0 (5)
C5—C4B—C8A—C84.3 (7)C32—S28—C29—C300.5 (5)
C4A—C4B—C8A—C8176.5 (4)S28—C29—C30—S310.9 (7)
C5—C4B—C8A—C9175.4 (4)C29—C30—S31—C321.8 (5)
C4A—C4B—C8A—C93.8 (5)C29—S28—C32—C33178.5 (5)
C8—C8A—C9—C100.3 (8)C29—S28—C32—S311.7 (3)
C4B—C8A—C9—C10179.9 (5)C30—S31—C32—C33178.2 (4)
C8—C8A—C9—C9A179.7 (5)C30—S31—C32—S282.1 (3)
C4B—C8A—C9—C9A0.6 (5)S28—C32—C33—S371.4 (6)
C2—C1—C9A—C4A2.6 (7)S31—C32—C33—S37178.8 (3)
C2—C1—C9A—C9176.7 (4)S28—C32—C33—S34177.8 (3)
C4—C4A—C9A—C16.2 (7)S31—C32—C33—S342.0 (6)
C4B—C4A—C9A—C1175.4 (4)C32—C33—S34—C35178.0 (4)
C4—C4A—C9A—C9173.1 (4)S37—C33—S34—C351.3 (3)
C4B—C4A—C9A—C95.3 (5)C33—S34—C35—C360.3 (5)
C10—C9—C9A—C12.8 (8)S34—C35—C36—S370.8 (6)
C8A—C9—C9A—C1177.8 (5)C35—C36—S37—C331.4 (5)
C10—C9—C9A—C4A176.5 (5)C32—C33—S37—C36177.7 (4)
C8A—C9—C9A—C4A2.9 (5)S34—C33—S37—C361.6 (3)
(cdc2tnfb) [2,2'-Bis-1,3-dithiole][9-dicyanomethylene-4,5,7- trinitro-fluorene-2-carboxylic acid methyl ester] top
Crystal data top
C18H7N5O8·C6H4S4F(000) = 1272
Mr = 625.62Dx = 1.607 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 70 reflections
a = 15.2489 (14) Åθ = 4.3–11.9°
b = 12.692 (1) ŵ = 0.43 mm1
c = 13.7950 (13) ÅT = 296 K
β = 104.350 (7)°Block, dark brown
V = 2586.6 (4) Å30.40 × 0.20 × 0.18 mm
Z = 4
Data collection top
Bruker P4
diffractometer
Rint = 0.020
Graphite monochromatorθmax = 25.0°, θmin = 2.1°
2θ/ω scansh = 186
Absorption correction: ψ scan
XSCANS 2.21 (Siemens, 1996)
k = 151
Tmin = 0.890, Tmax = 0.926l = 1616
3590 measured reflections2 standard reflections every 48 reflections
2274 independent reflections intensity decay: 1%
1768 reflections with I > 2σ(I)
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0359P)2 + 3.2371P]
where P = (Fo2 + 2Fc2)/3
2274 reflections(Δ/σ)max < 0.001
218 parametersΔρmax = 0.25 e Å3
7 restraintsΔρmin = 0.26 e Å3
Crystal data top
C18H7N5O8·C6H4S4V = 2586.6 (4) Å3
Mr = 625.62Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.2489 (14) ŵ = 0.43 mm1
b = 12.692 (1) ÅT = 296 K
c = 13.7950 (13) Å0.40 × 0.20 × 0.18 mm
β = 104.350 (7)°
Data collection top
Bruker P4
diffractometer
1768 reflections with I > 2σ(I)
Absorption correction: ψ scan
XSCANS 2.21 (Siemens, 1996)
Rint = 0.020
Tmin = 0.890, Tmax = 0.9262 standard reflections every 48 reflections
3590 measured reflections intensity decay: 1%
2274 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0417 restraints
wR(F2) = 0.098H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
2274 reflectionsΔρmin = 0.26 e Å3
218 parameters
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
xyzUiso*/UeqOcc. (<1)
C10.33426 (18)0.4681 (2)0.66201 (19)0.0366 (6)
H1A0.31740.53820.64990.044*
C20.27175 (18)0.3887 (2)0.6318 (2)0.0421 (7)
C30.29481 (19)0.2842 (2)0.6552 (2)0.0444 (7)
H3A0.25140.23150.63760.053*
C40.38232 (19)0.2593 (2)0.70446 (19)0.0375 (6)
C50.45035 (17)0.3354 (2)0.72824 (18)0.0321 (6)
C60.42279 (16)0.4420 (2)0.71072 (17)0.0298 (6)
C70.50000.5113 (3)0.75000.0307 (8)
C80.50000.6200 (3)0.75000.0356 (9)
C90.4190 (2)0.6819 (2)0.7201 (2)0.0439 (7)
N100.3560 (2)0.7330 (2)0.6981 (2)0.0689 (8)
N110.1810 (9)0.4095 (10)0.5688 (18)0.048 (5)0.50
O120.1321 (11)0.3341 (15)0.5386 (15)0.076 (4)0.50
O130.1638 (13)0.5072 (15)0.5662 (18)0.078 (6)0.50
C140.1751 (11)0.4175 (18)0.583 (2)0.074 (9)0.50
O150.1159 (13)0.3513 (16)0.5616 (19)0.114 (7)0.50
O160.1603 (10)0.5098 (11)0.5415 (16)0.045 (2)0.50
C170.0699 (5)0.5295 (7)0.4845 (6)0.086 (3)0.50
H17A0.06160.60380.47270.129*0.50
H17B0.02780.50480.52080.129*0.50
H17C0.05950.49320.42160.129*0.50
N180.39646 (18)0.1501 (2)0.7409 (2)0.0510 (7)
O190.35021 (18)0.08123 (18)0.6914 (2)0.0835 (8)
O200.45130 (16)0.13580 (17)0.82109 (17)0.0601 (6)
S210.46610 (5)0.66761 (6)0.48993 (6)0.0444 (2)
C220.3510 (2)0.6833 (3)0.4384 (2)0.0505 (8)
H22A0.32490.74990.43120.061*
C230.3010 (2)0.5978 (3)0.4095 (2)0.0491 (8)
H23A0.23920.60260.38040.059*
S240.35557 (5)0.47723 (6)0.42836 (5)0.0405 (2)
C250.46282 (17)0.5302 (2)0.48226 (18)0.0330 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0321 (15)0.0393 (15)0.0386 (14)0.0020 (14)0.0090 (12)0.0007 (12)
C20.0282 (15)0.0562 (19)0.0409 (15)0.0015 (14)0.0065 (12)0.0004 (14)
C30.0342 (16)0.0536 (19)0.0438 (16)0.0168 (14)0.0068 (13)0.0052 (14)
C40.0399 (16)0.0352 (15)0.0382 (14)0.0075 (13)0.0113 (12)0.0023 (12)
C50.0315 (14)0.0349 (15)0.0298 (13)0.0011 (12)0.0074 (11)0.0012 (11)
C60.0258 (14)0.0340 (14)0.0299 (12)0.0005 (11)0.0076 (11)0.0012 (11)
C70.0257 (19)0.036 (2)0.0306 (17)0.0000.0067 (15)0.000
C80.037 (2)0.032 (2)0.039 (2)0.0000.0110 (17)0.000
C90.0474 (19)0.0347 (16)0.0485 (17)0.0031 (15)0.0101 (14)0.0008 (13)
N100.064 (2)0.0557 (18)0.084 (2)0.0246 (17)0.0127 (16)0.0071 (16)
N110.040 (8)0.051 (7)0.054 (8)0.007 (5)0.016 (5)0.003 (4)
O120.032 (7)0.071 (5)0.107 (6)0.019 (6)0.019 (5)0.014 (4)
O130.044 (6)0.112 (9)0.067 (12)0.023 (6)0.005 (5)0.002 (7)
C140.017 (7)0.15 (2)0.053 (9)0.006 (10)0.003 (7)0.011 (10)
O150.033 (6)0.105 (12)0.187 (18)0.009 (6)0.003 (7)0.049 (10)
O160.027 (4)0.053 (5)0.045 (7)0.001 (3)0.010 (3)0.001 (3)
C170.054 (4)0.101 (6)0.084 (5)0.021 (5)0.016 (4)0.037 (5)
N180.0488 (16)0.0401 (15)0.0642 (17)0.0090 (13)0.0145 (14)0.0027 (13)
O190.0759 (18)0.0430 (14)0.118 (2)0.0217 (13)0.0014 (16)0.0135 (14)
O200.0711 (16)0.0480 (13)0.0597 (14)0.0025 (12)0.0136 (13)0.0122 (11)
S210.0432 (4)0.0358 (4)0.0533 (4)0.0010 (3)0.0106 (3)0.0002 (3)
C220.0489 (19)0.0477 (19)0.0571 (18)0.0130 (16)0.0170 (15)0.0101 (15)
C230.0367 (17)0.059 (2)0.0506 (17)0.0066 (16)0.0095 (14)0.0114 (15)
S240.0325 (4)0.0463 (4)0.0406 (4)0.0047 (3)0.0052 (3)0.0022 (3)
C250.0298 (13)0.0364 (15)0.0329 (13)0.0022 (11)0.0081 (11)0.0019 (11)
Geometric parameters (Å, º) top
C1—C21.379 (4)N11—O121.222 (13)
C1—C61.391 (4)N11—O131.266 (17)
C1—H1A0.9300C14—O151.214 (16)
C2—C31.389 (4)C14—O161.301 (17)
C2—N111.464 (12)O16—C171.431 (15)
C2—C141.505 (14)C17—H17A0.9600
C3—C41.376 (4)C17—H17B0.9600
C3—H3A0.9300C17—H17C0.9600
C4—C51.396 (4)N18—O191.220 (3)
C4—N181.471 (4)N18—O201.224 (3)
C5—C61.419 (4)S21—C221.734 (3)
C5—C5i1.484 (5)S21—C251.747 (3)
C6—C71.462 (3)C22—C231.329 (4)
C7—C81.379 (5)C22—H22A0.9300
C7—C6i1.462 (3)C23—S241.731 (3)
C8—C9i1.436 (4)C23—H23A0.9300
C8—C91.436 (4)S24—C251.754 (3)
C9—N101.137 (4)C25—C25ii1.356 (5)
C2—C1—C6119.2 (3)O12—N11—O13130.7 (16)
C2—C1—H1A120.4O12—N11—C2117.9 (13)
C6—C1—H1A120.4O13—N11—C2110.7 (12)
C1—C2—C3120.8 (3)O15—C14—O16118.5 (18)
C1—C2—N11121.9 (5)O15—C14—C2121.8 (18)
C3—C2—N11117.2 (5)O16—C14—C2117.3 (15)
C1—C2—C14119.0 (9)C14—O16—C17116.0 (12)
C3—C2—C14119.9 (9)O16—C17—H17A109.5
N11—C2—C1410 (2)O16—C17—H17B109.5
C4—C3—C2119.5 (3)H17A—C17—H17B109.5
C4—C3—H3A120.2O16—C17—H17C109.5
C2—C3—H3A120.2H17A—C17—H17C109.5
C3—C4—C5122.0 (3)H17B—C17—H17C109.5
C3—C4—N18115.3 (2)O19—N18—O20124.8 (3)
C5—C4—N18122.3 (2)O19—N18—C4117.9 (3)
C4—C5—C6116.6 (2)O20—N18—C4117.2 (2)
C4—C5—C5i135.98 (16)C22—S21—C2594.51 (14)
C6—C5—C5i107.36 (14)C23—C22—S21118.5 (2)
C1—C6—C5121.4 (2)C23—C22—H22A120.8
C1—C6—C7129.2 (3)S21—C22—H22A120.8
C5—C6—C7109.5 (2)C22—C23—S24117.3 (2)
C8—C7—C6127.01 (15)C22—C23—H23A121.4
C8—C7—C6i127.01 (15)S24—C23—H23A121.4
C6—C7—C6i106.0 (3)C23—S24—C2595.03 (14)
C7—C8—C9i123.21 (17)C25ii—C25—S21122.3 (3)
C7—C8—C9123.21 (17)C25ii—C25—S24123.0 (3)
C9i—C8—C9113.6 (3)S21—C25—S24114.72 (15)
N10—C9—C8178.2 (3)
C6—C1—C2—C34.1 (4)C9i—C8—C9—N1031 (11)
C6—C1—C2—N11171.7 (12)C1—C2—N11—O12174.2 (17)
C6—C1—C2—C14177.2 (17)C3—C2—N11—O122 (3)
C1—C2—C3—C43.4 (4)C14—C2—N11—O12110 (8)
N11—C2—C3—C4172.6 (12)C1—C2—N11—O1314 (2)
C14—C2—C3—C4176.4 (17)C3—C2—N11—O13169.8 (15)
C2—C3—C4—C52.9 (4)C14—C2—N11—O1362 (7)
C2—C3—C4—N18170.0 (3)C1—C2—C14—O15175 (3)
C3—C4—C5—C67.8 (4)C3—C2—C14—O152 (4)
N18—C4—C5—C6164.5 (2)N11—C2—C14—O1575 (7)
C3—C4—C5—C5i174.0 (3)C1—C2—C14—O1623 (3)
N18—C4—C5—C5i13.6 (5)C3—C2—C14—O16163.8 (19)
C2—C1—C6—C51.2 (4)N11—C2—C14—O1687 (8)
C2—C1—C6—C7179.5 (2)O15—C14—O16—C179 (4)
C4—C5—C6—C17.0 (4)C2—C14—O16—C17172 (2)
C5i—C5—C6—C1174.4 (2)C3—C4—N18—O1933.4 (4)
C4—C5—C6—C7173.57 (19)C5—C4—N18—O19153.8 (3)
C5i—C5—C6—C75.1 (3)C3—C4—N18—O20143.6 (3)
C1—C6—C7—C82.6 (3)C5—C4—N18—O2029.3 (4)
C5—C6—C7—C8177.98 (13)C25—S21—C22—C231.6 (3)
C1—C6—C7—C6i177.4 (3)S21—C22—C23—S241.2 (4)
C5—C6—C7—C6i2.02 (13)C22—C23—S24—C250.1 (3)
C6—C7—C8—C9i172.74 (18)C22—S21—C25—C25ii177.0 (3)
C6i—C7—C8—C9i7.26 (18)C22—S21—C25—S241.40 (17)
C6—C7—C8—C97.26 (18)C23—S24—C25—C25ii177.4 (3)
C6i—C7—C8—C9172.74 (18)C23—S24—C25—S210.93 (17)
C7—C8—C9—N10149 (11)
Symmetry codes: (i) x+1, y, z+3/2; (ii) x+1, y+1, z+1.

Experimental details

(cdc2tnf)(cdc2tnfb)
Crystal data
Chemical formulaC18H7N5O8·C6H4S4C18H7N5O8·C6H4S4
Mr625.62625.62
Crystal system, space groupMonoclinic, P21/nMonoclinic, C2/c
Temperature (K)296296
a, b, c (Å)6.7816 (17), 30.572 (4), 12.4381 (13)15.2489 (14), 12.692 (1), 13.7950 (13)
β (°) 94.304 (11) 104.350 (7)
V3)2571.5 (8)2586.6 (4)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.430.43
Crystal size (mm)0.70 × 0.16 × 0.080.40 × 0.20 × 0.18
Data collection
DiffractometerBruker P4
diffractometer
Bruker P4
diffractometer
Absorption correctionψ scan
XSCANS 2.21 (Siemens, 1996)
Tmin, Tmax0.890, 0.926
No. of measured, independent and
observed [I > 2σ(I)] reflections
5958, 4503, 3133 3590, 2274, 1768
Rint0.0410.020
(sin θ/λ)max1)0.5950.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.169, 1.06 0.041, 0.098, 1.05
No. of reflections45032274
No. of parameters370218
No. of restraints07
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.66, 0.350.25, 0.26

Computer programs: XSCANS 2.21 (Siemens, 1996), SHELXTL 5.10 (Sheldrick, 1998), SHELX97 (Sheldrick, 1997).

 

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