Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802007201/na6158sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802007201/na6158Isup2.hkl |
CCDC reference: 185805
Key indicators
- Single-crystal X-ray study
- T = 290 K
- Mean (C-C) = 0.007 Å
- R factor = 0.038
- wR factor = 0.094
- Data-to-parameter ratio = 15.7
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_731 Alert C Bond Calc 0.93(5), Rep 0.94(2) .... 2.50 s.u-Ratio C2C -H2C 1.555 1.555 PLAT_731 Alert C Bond Calc 0.93(5), Rep 0.93(2) .... 2.50 s.u-Ratio C2D -H2D 1.555 1.555 PLAT_731 Alert C Bond Calc 0.94(5), Rep 0.93(2) .... 2.50 s.u-Ratio C5D -H5D 1.555 1.555 PLAT_735 Alert C D-H Calc 0.93(5), Rep 0.94(2) .... 2.50 s.u-Ratio C2C -H2C 1.555 1.555 PLAT_735 Alert C D-H Calc 0.93(5), Rep 0.93(2) .... 2.50 s.u-Ratio C2D -H2D 1.555 1.555 General Notes
ABSTM_02 When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.673 Tmax scaled 0.662 Tmin scaled 0.450
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
5 Alert Level C = Please check
The starting materials were commercial batchs from Aldrich and Apollo Scientific Ltd. The analysed infinite network was obtained by dissolving in chloroform, at room temperature and in a vial, equimolecular amounts of 4,4'-bpy and F4dIb. The open vial was closed in a cylindrical bottle containing vaseline oil. Volatile solvents were allowed to diffuse at room temperature and after one day the formed crystals were filtered and washed with carbon tetrachloride. M.p. 411–413 K; I·R. (KBr/ν/cm-1, selected bands): 3042, 1592, 1483, 1429, 1407, 1218, 1009, 803, 612. Crystals were obtained as large plastic prisms.
A first data collection on a cut crystal permitted the structure resolution, but the refinement was unsatisfactory, probably because the crystal had a very large mosaic spread due to the cut deformation. To prevent such phenomenon the crystal used for the second data collection was reduced by a partial dissolution in chloroform. H atoms were refined by imposing soft geometric restraints on C—H and closest intramolecular H···H distances. The structure may be described in the standard space group C2/c with a very large β (129.35°), so we preferred the I2/a description. Two diagonals of the I2/a monoclinic cell are the axes of a pseudo-orthorhombic F cell (a = 18.227, b = 33.714, c = 22.045 Å, α = 90.00, b = 89.60, γ = 90.00°), but the Laue symmetry is not orthorhombic, because an attempt to merge the data gave Rave = 0.337.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett and Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983).
C10H8N2·C6F4I2 | F(000) = 4160 |
Mr = 558.04 | Dx = 2.189 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71069 Å |
a = 14.2535 (10) Å | Cell parameters from 2996 reflections |
b = 33.714 (3) Å | θ = 3.1–27.3° |
c = 14.3511 (12) Å | µ = 3.75 mm−1 |
β = 100.831 (6)° | T = 290 K |
V = 6773.5 (10) Å3 | Elongated prism with rounded edges, colourless |
Z = 16 | 0.40 × 0.16 × 0.11 mm |
Bruker SMART-APEX CCD area-detector diffractometer | 7796 independent reflections |
Radiation source: fine-focus sealed tube | 5552 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −18→18 |
Tmin = 0.668, Tmax = 0.983 | k = −43→43 |
15718 measured reflections | l = −18→18 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | All H-atom parameters refined |
wR(F2) = 0.094 | |
S = 0.97 | (Δ/σ)max = 0.008 |
7796 reflections | Δρmax = 0.66 e Å−3 |
498 parameters | Δρmin = −0.60 e Å−3 |
148 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000218 (18) |
C10H8N2·C6F4I2 | V = 6773.5 (10) Å3 |
Mr = 558.04 | Z = 16 |
Monoclinic, I2/a | Mo Kα radiation |
a = 14.2535 (10) Å | µ = 3.75 mm−1 |
b = 33.714 (3) Å | T = 290 K |
c = 14.3511 (12) Å | 0.40 × 0.16 × 0.11 mm |
β = 100.831 (6)° |
Bruker SMART-APEX CCD area-detector diffractometer | 7796 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 5552 reflections with I > 2σ(I) |
Tmin = 0.668, Tmax = 0.983 | Rint = 0.018 |
15718 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 148 restraints |
wR(F2) = 0.094 | All H-atom parameters refined |
S = 0.97 | Δρmax = 0.66 e Å−3 |
7796 reflections | Δρmin = −0.60 e Å−3 |
498 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
I1A | 0.11176 (2) | −0.066462 (9) | 0.00530 (2) | 0.06253 (11) | |
I2A | 0.13725 (2) | −0.070509 (9) | −0.24644 (2) | 0.06673 (12) | |
C1A | 0.1257 (3) | −0.01598 (12) | −0.0766 (3) | 0.0513 (10) | |
C2A | 0.1319 (3) | −0.01726 (12) | −0.1718 (3) | 0.0536 (10) | |
C3A | 0.1374 (3) | 0.01814 (14) | −0.2194 (3) | 0.0625 (12) | |
C4A | 0.1387 (4) | 0.05432 (14) | −0.1745 (4) | 0.0693 (13) | |
C5A | 0.1353 (3) | 0.05542 (14) | −0.0813 (4) | 0.0685 (13) | |
C6A | 0.1288 (3) | 0.02103 (14) | −0.0325 (3) | 0.0578 (11) | |
F1A | 0.1406 (2) | 0.01814 (9) | −0.3133 (2) | 0.0876 (9) | |
F2A | 0.1437 (3) | 0.08798 (9) | −0.2232 (3) | 0.0994 (11) | |
F3A | 0.1390 (2) | 0.09058 (8) | −0.0361 (3) | 0.0946 (10) | |
F4A | 0.1258 (2) | 0.02359 (8) | 0.0602 (2) | 0.0795 (8) | |
I1B | 0.26220 (3) | 0.316354 (11) | 0.13789 (2) | 0.07917 (13) | |
I2B | 0.00046 (3) | 0.321219 (10) | 0.11299 (3) | 0.07737 (13) | |
C1B | 0.1751 (4) | 0.26572 (14) | 0.1216 (3) | 0.0607 (12) | |
C2B | 0.0771 (4) | 0.26780 (14) | 0.1153 (3) | 0.0630 (12) | |
C3B | 0.0255 (4) | 0.23284 (16) | 0.1093 (3) | 0.0693 (14) | |
C4B | 0.0700 (5) | 0.19652 (16) | 0.1076 (4) | 0.0812 (16) | |
C5B | 0.1644 (5) | 0.19500 (16) | 0.1092 (4) | 0.0824 (17) | |
C6B | 0.2175 (4) | 0.22931 (17) | 0.1167 (3) | 0.0721 (14) | |
F1B | −0.0691 (2) | 0.23280 (10) | 0.1039 (2) | 0.1005 (10) | |
F2B | 0.0179 (3) | 0.16290 (10) | 0.1029 (3) | 0.1141 (13) | |
F3B | 0.2078 (3) | 0.15950 (11) | 0.1063 (3) | 0.1204 (13) | |
F4B | 0.3114 (3) | 0.22600 (11) | 0.1226 (3) | 0.1086 (11) | |
C1C | 0.1257 (3) | −0.22460 (12) | 0.1298 (3) | 0.0552 (11) | |
C2C | 0.2039 (4) | −0.20170 (15) | 0.1204 (5) | 0.0777 (15) | |
H2C | 0.259 (3) | −0.2142 (13) | 0.109 (5) | 0.13 (3)* | |
C3C | 0.1938 (5) | −0.16080 (16) | 0.1106 (5) | 0.0832 (16) | |
H3C | 0.246 (2) | −0.1459 (11) | 0.102 (4) | 0.074 (15)* | |
N4C | 0.1127 (4) | −0.14178 (12) | 0.1070 (3) | 0.0765 (12) | |
C5C | 0.0376 (5) | −0.16376 (16) | 0.1160 (4) | 0.0797 (15) | |
H5C | −0.015 (2) | −0.1473 (10) | 0.108 (3) | 0.064 (14)* | |
C6C | 0.0412 (4) | −0.20463 (15) | 0.1275 (4) | 0.0712 (13) | |
H6C | −0.018 (2) | −0.2155 (12) | 0.129 (4) | 0.11 (2)* | |
C7C | 0.1314 (3) | −0.26822 (13) | 0.1404 (3) | 0.0557 (11) | |
C8C | 0.2084 (4) | −0.28952 (15) | 0.1227 (4) | 0.0711 (14) | |
H8C | 0.262 (2) | −0.2758 (12) | 0.111 (4) | 0.092 (18)* | |
C9C | 0.2095 (5) | −0.33094 (16) | 0.1349 (5) | 0.0805 (16) | |
H9C | 0.258 (3) | −0.3445 (11) | 0.114 (3) | 0.081 (17)* | |
N10C | 0.1406 (4) | −0.35109 (12) | 0.1617 (3) | 0.0785 (12) | |
C11C | 0.0686 (5) | −0.33047 (17) | 0.1783 (5) | 0.0863 (17) | |
H11C | 0.017 (3) | −0.3434 (12) | 0.193 (4) | 0.10 (2)* | |
C12C | 0.0592 (4) | −0.28959 (15) | 0.1694 (4) | 0.0719 (14) | |
H12C | 0.007 (2) | −0.2751 (12) | 0.181 (4) | 0.094 (19)* | |
C7D | 0.3859 (3) | 0.51815 (13) | 0.1222 (3) | 0.0582 (11) | |
C12D | 0.3969 (5) | 0.54285 (17) | 0.1992 (4) | 0.0787 (15) | |
H12D | 0.396 (4) | 0.5273 (12) | 0.252 (2) | 0.11 (2)* | |
C11D | 0.4050 (5) | 0.58305 (19) | 0.1880 (5) | 0.0941 (19) | |
H11D | 0.408 (4) | 0.5955 (11) | 0.246 (2) | 0.089 (18)* | |
N10D | 0.4042 (4) | 0.60067 (13) | 0.1079 (4) | 0.0890 (14) | |
C9D | 0.3940 (7) | 0.57799 (19) | 0.0334 (5) | 0.109 (2) | |
H9D | 0.382 (4) | 0.5866 (13) | −0.0289 (19) | 0.10 (2)* | |
C8D | 0.3830 (5) | 0.53684 (17) | 0.0368 (4) | 0.0894 (19) | |
H8D | 0.375 (4) | 0.5185 (12) | −0.012 (3) | 0.11 (2)* | |
C1D | 0.3767 (3) | 0.47456 (14) | 0.1296 (3) | 0.0579 (11) | |
C2D | 0.3811 (5) | 0.44943 (17) | 0.0553 (4) | 0.0891 (18) | |
H2D | 0.377 (7) | 0.4621 (16) | −0.003 (3) | 0.19 (4)* | |
C3D | 0.3725 (6) | 0.40885 (18) | 0.0681 (5) | 0.099 (2) | |
H3D | 0.373 (4) | 0.3940 (14) | 0.014 (3) | 0.11 (2)* | |
N4D | 0.3611 (3) | 0.39215 (14) | 0.1472 (4) | 0.0886 (14) | |
C5D | 0.3587 (5) | 0.4164 (2) | 0.2187 (6) | 0.097 (2) | |
H5D | 0.341 (5) | 0.4024 (14) | 0.269 (3) | 0.15 (3)* | |
C6D | 0.3660 (5) | 0.45641 (19) | 0.2124 (4) | 0.0853 (17) | |
H6D | 0.365 (4) | 0.4703 (12) | 0.268 (2) | 0.11 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1A | 0.0595 (2) | 0.05304 (19) | 0.0771 (2) | 0.00581 (13) | 0.01808 (16) | 0.01005 (14) |
I2A | 0.0715 (2) | 0.05309 (19) | 0.0739 (2) | 0.00423 (15) | 0.00944 (17) | −0.01075 (15) |
C1A | 0.043 (2) | 0.044 (2) | 0.067 (3) | 0.0038 (18) | 0.011 (2) | 0.002 (2) |
C2A | 0.045 (2) | 0.046 (2) | 0.068 (3) | 0.0035 (18) | 0.007 (2) | −0.005 (2) |
C3A | 0.065 (3) | 0.053 (3) | 0.071 (3) | −0.001 (2) | 0.015 (2) | 0.003 (2) |
C4A | 0.069 (3) | 0.048 (3) | 0.093 (4) | 0.002 (2) | 0.019 (3) | 0.007 (3) |
C5A | 0.063 (3) | 0.042 (3) | 0.102 (4) | 0.001 (2) | 0.017 (3) | −0.007 (3) |
C6A | 0.054 (3) | 0.056 (3) | 0.064 (3) | 0.003 (2) | 0.013 (2) | −0.005 (2) |
F1A | 0.115 (3) | 0.079 (2) | 0.0711 (18) | −0.0037 (17) | 0.0232 (17) | 0.0097 (15) |
F2A | 0.120 (3) | 0.0536 (17) | 0.129 (3) | −0.0027 (17) | 0.035 (2) | 0.0256 (18) |
F3A | 0.103 (2) | 0.0512 (17) | 0.131 (3) | −0.0013 (15) | 0.028 (2) | −0.0254 (17) |
F4A | 0.091 (2) | 0.0762 (19) | 0.0731 (18) | 0.0130 (16) | 0.0192 (16) | −0.0142 (15) |
I1B | 0.0874 (3) | 0.0814 (3) | 0.0643 (2) | −0.02539 (19) | 0.00273 (18) | 0.01359 (17) |
I2B | 0.0909 (3) | 0.0667 (2) | 0.0743 (2) | 0.00258 (18) | 0.01497 (19) | 0.00712 (17) |
C1B | 0.077 (3) | 0.061 (3) | 0.040 (2) | −0.013 (2) | 0.002 (2) | 0.006 (2) |
C2B | 0.084 (4) | 0.060 (3) | 0.044 (2) | −0.013 (3) | 0.008 (2) | 0.006 (2) |
C3B | 0.076 (4) | 0.073 (4) | 0.056 (3) | −0.020 (3) | 0.004 (3) | 0.009 (2) |
C4B | 0.119 (5) | 0.060 (3) | 0.063 (3) | −0.023 (3) | 0.011 (3) | 0.001 (3) |
C5B | 0.130 (6) | 0.058 (3) | 0.060 (3) | 0.010 (4) | 0.019 (3) | −0.002 (2) |
C6B | 0.083 (4) | 0.078 (4) | 0.055 (3) | 0.007 (3) | 0.013 (3) | 0.001 (3) |
F1B | 0.085 (2) | 0.099 (2) | 0.114 (3) | −0.0256 (19) | 0.013 (2) | 0.012 (2) |
F2B | 0.158 (3) | 0.067 (2) | 0.109 (3) | −0.038 (2) | 0.003 (2) | 0.0007 (18) |
F3B | 0.180 (4) | 0.074 (2) | 0.107 (3) | 0.028 (2) | 0.026 (3) | −0.008 (2) |
F4B | 0.096 (3) | 0.115 (3) | 0.120 (3) | 0.018 (2) | 0.034 (2) | 0.009 (2) |
C1C | 0.072 (3) | 0.043 (2) | 0.050 (2) | 0.002 (2) | 0.009 (2) | −0.0005 (19) |
C2C | 0.072 (4) | 0.047 (3) | 0.113 (4) | −0.001 (3) | 0.015 (3) | 0.008 (3) |
C3C | 0.094 (4) | 0.051 (3) | 0.102 (4) | −0.017 (3) | 0.011 (4) | 0.002 (3) |
N4C | 0.097 (3) | 0.047 (2) | 0.083 (3) | 0.003 (2) | 0.012 (3) | 0.002 (2) |
C5C | 0.098 (4) | 0.053 (3) | 0.089 (4) | 0.021 (3) | 0.019 (3) | 0.008 (3) |
C6C | 0.074 (4) | 0.057 (3) | 0.088 (4) | 0.002 (3) | 0.029 (3) | 0.007 (3) |
C7C | 0.069 (3) | 0.044 (2) | 0.055 (2) | −0.001 (2) | 0.013 (2) | 0.0011 (19) |
C8C | 0.076 (3) | 0.055 (3) | 0.087 (4) | 0.000 (3) | 0.025 (3) | 0.008 (3) |
C9C | 0.087 (4) | 0.051 (3) | 0.110 (4) | 0.009 (3) | 0.032 (4) | 0.012 (3) |
N10C | 0.100 (4) | 0.044 (2) | 0.094 (3) | 0.002 (2) | 0.024 (3) | 0.007 (2) |
C11C | 0.109 (5) | 0.057 (3) | 0.099 (4) | −0.018 (3) | 0.035 (4) | 0.009 (3) |
C12C | 0.081 (4) | 0.057 (3) | 0.081 (3) | 0.000 (3) | 0.023 (3) | 0.007 (3) |
C7D | 0.056 (3) | 0.052 (3) | 0.068 (3) | −0.001 (2) | 0.017 (2) | −0.005 (2) |
C12D | 0.100 (4) | 0.068 (4) | 0.070 (3) | 0.000 (3) | 0.021 (3) | −0.006 (3) |
C11D | 0.121 (5) | 0.068 (4) | 0.090 (4) | 0.005 (4) | 0.014 (4) | −0.027 (4) |
N10D | 0.105 (4) | 0.054 (3) | 0.108 (4) | 0.004 (2) | 0.021 (3) | −0.010 (3) |
C9D | 0.185 (8) | 0.059 (4) | 0.081 (4) | −0.009 (4) | 0.022 (5) | 0.005 (3) |
C8D | 0.144 (6) | 0.059 (3) | 0.070 (3) | −0.006 (3) | 0.033 (4) | −0.007 (3) |
C1D | 0.050 (3) | 0.058 (3) | 0.068 (3) | 0.004 (2) | 0.017 (2) | 0.001 (2) |
C2D | 0.132 (5) | 0.059 (3) | 0.075 (4) | −0.019 (3) | 0.015 (4) | −0.005 (3) |
C3D | 0.140 (6) | 0.057 (3) | 0.094 (5) | −0.018 (4) | 0.005 (4) | −0.010 (3) |
N4D | 0.085 (3) | 0.066 (3) | 0.113 (4) | −0.014 (2) | 0.014 (3) | 0.013 (3) |
C5D | 0.111 (5) | 0.078 (4) | 0.113 (5) | 0.010 (4) | 0.056 (4) | 0.027 (4) |
C6D | 0.099 (4) | 0.081 (4) | 0.086 (4) | 0.006 (3) | 0.044 (4) | −0.005 (3) |
I1A—C1A | 2.099 (4) | C5C—C6C | 1.388 (7) |
I1A—N4C | 2.928 (4) | C5C—H5C | 0.92 (2) |
I2A—C2A | 2.099 (4) | C6C—H6C | 0.93 (2) |
I2A—N10Ci | 2.958 (4) | C7C—C8C | 1.375 (7) |
C1A—C2A | 1.387 (6) | C7C—C12C | 1.382 (7) |
C1A—C6A | 1.396 (6) | C8C—C9C | 1.407 (7) |
C2A—C3A | 1.385 (6) | C8C—H8C | 0.93 (2) |
C3A—F1A | 1.357 (5) | C9C—N10C | 1.309 (7) |
C3A—C4A | 1.378 (7) | C9C—H9C | 0.93 (2) |
C4A—F2A | 1.342 (6) | N10C—C11C | 1.299 (7) |
C4A—C5A | 1.348 (8) | N10C—I2Aiii | 2.958 (4) |
C5A—F3A | 1.347 (5) | C11C—C12C | 1.388 (8) |
C5A—C6A | 1.366 (7) | C11C—H11C | 0.92 (2) |
C6A—F4A | 1.342 (5) | C12C—H12C | 0.93 (2) |
I1B—C1B | 2.098 (5) | C7D—C12D | 1.369 (7) |
I1B—N4D | 2.909 (5) | C7D—C8D | 1.372 (7) |
I2B—C2B | 2.103 (5) | C7D—C1D | 1.481 (6) |
I2B—N10Dii | 2.964 (5) | C12D—C11D | 1.372 (8) |
C1B—C6B | 1.376 (7) | C12D—H12D | 0.92 (2) |
C1B—C2B | 1.385 (7) | C11D—N10D | 1.292 (8) |
C2B—C3B | 1.383 (6) | C11D—H11D | 0.92 (2) |
C3B—F1B | 1.336 (6) | N10D—C9D | 1.300 (8) |
C3B—C4B | 1.382 (8) | N10D—I2Biv | 2.964 (5) |
C4B—C5B | 1.342 (9) | C9D—C8D | 1.398 (8) |
C4B—F2B | 1.350 (6) | C9D—H9D | 0.92 (2) |
C5B—F3B | 1.351 (6) | C8D—H8D | 0.92 (2) |
C5B—C6B | 1.375 (8) | C1D—C6D | 1.370 (7) |
C6B—F4B | 1.330 (6) | C1D—C2D | 1.373 (7) |
C1C—C6C | 1.375 (7) | C2D—C3D | 1.389 (8) |
C1C—C2C | 1.382 (7) | C2D—H2D | 0.93 (2) |
C1C—C7C | 1.479 (6) | C3D—N4D | 1.304 (8) |
C2C—C3C | 1.391 (7) | C3D—H3D | 0.93 (2) |
C2C—H2C | 0.94 (2) | N4D—C5D | 1.317 (8) |
C3C—N4C | 1.314 (7) | C5D—C6D | 1.357 (9) |
C3C—H3C | 0.93 (2) | C5D—H5D | 0.93 (2) |
N4C—C5C | 1.328 (7) | C6D—H6D | 0.92 (2) |
C1A—I1A—N4C | 172.09 (15) | N4C—C5C—H5C | 107 (3) |
N4C—I1A—C6A | 160.85 (12) | C6C—C5C—H5C | 129 (3) |
C2A—I2A—N10Ci | 175.37 (16) | C1C—C6C—C5C | 120.1 (5) |
C2A—C1A—C6A | 118.1 (4) | C1C—C6C—H6C | 127 (3) |
C2A—C1A—I1A | 123.8 (3) | C5C—C6C—H6C | 112 (3) |
C6A—C1A—I1A | 118.0 (3) | C8C—C7C—C12C | 116.6 (5) |
C3A—C2A—C1A | 118.6 (4) | C8C—C7C—C1C | 122.0 (4) |
C3A—C2A—I2A | 118.3 (3) | C12C—C7C—C1C | 121.3 (4) |
C1A—C2A—I2A | 123.0 (3) | C7C—C8C—C9C | 119.0 (5) |
F1A—C3A—C4A | 117.7 (4) | C7C—C8C—H8C | 119 (3) |
F1A—C3A—C2A | 120.4 (4) | C9C—C8C—H8C | 122 (3) |
C4A—C3A—C2A | 121.9 (5) | N10C—C9C—C8C | 124.1 (5) |
C4A—C3A—I2A | 159.6 (4) | N10C—C9C—H9C | 119 (3) |
F2A—C4A—C5A | 120.6 (5) | C8C—C9C—H9C | 116 (3) |
F2A—C4A—C3A | 120.1 (5) | C11C—N10C—C9C | 116.0 (5) |
C5A—C4A—C3A | 119.2 (5) | C11C—N10C—I2Aiii | 108.5 (4) |
F3A—C5A—C4A | 119.7 (5) | C9C—N10C—I2Aiii | 132.1 (4) |
F3A—C5A—C6A | 120.0 (5) | N10C—C11C—C12C | 125.4 (6) |
C4A—C5A—C6A | 120.2 (4) | N10C—C11C—H11C | 119 (3) |
F4A—C6A—C5A | 118.1 (4) | C12C—C11C—H11C | 115 (3) |
F4A—C6A—C1A | 120.2 (4) | C7C—C12C—C11C | 118.8 (5) |
C5A—C6A—C1A | 121.7 (4) | C7C—C12C—H12C | 116 (3) |
C5A—C6A—I1A | 159.6 (4) | C11C—C12C—H12C | 125 (3) |
C1B—I1B—N4D | 172.45 (17) | C12D—C7D—C8D | 114.9 (5) |
N4D—I1B—C6B | 162.51 (16) | C12D—C7D—C1D | 122.9 (5) |
C2B—I2B—N10Dii | 176.19 (17) | C8D—C7D—C1D | 122.1 (4) |
N10Dii—I2B—C3B | 159.58 (14) | C7D—C12D—C11D | 120.4 (5) |
C6B—C1B—C2B | 119.3 (4) | C7D—C12D—H12D | 108 (3) |
C6B—C1B—I1B | 118.4 (4) | C11D—C12D—H12D | 132 (3) |
C2B—C1B—I1B | 122.3 (4) | N10D—C11D—C12D | 124.8 (6) |
C3B—C2B—C1B | 118.6 (5) | N10D—C11D—H11D | 125 (3) |
C3B—C2B—I2B | 117.4 (4) | C12D—C11D—H11D | 110 (3) |
C1B—C2B—I2B | 124.0 (3) | C11D—N10D—C9D | 116.3 (5) |
F1B—C3B—C4B | 117.4 (5) | C11D—N10D—I2Biv | 117.4 (4) |
F1B—C3B—C2B | 121.6 (5) | C9D—N10D—I2Biv | 121.5 (4) |
C4B—C3B—C2B | 121.0 (5) | N10D—C9D—C8D | 123.4 (6) |
C4B—C3B—I2B | 159.4 (4) | N10D—C9D—H9D | 126 (3) |
C5B—C4B—F2B | 120.6 (6) | C8D—C9D—H9D | 110 (3) |
C5B—C4B—C3B | 119.7 (5) | C7D—C8D—C9D | 120.1 (5) |
F2B—C4B—C3B | 119.6 (6) | C7D—C8D—H8D | 110 (3) |
C4B—C5B—F3B | 119.7 (6) | C9D—C8D—H8D | 130 (3) |
C4B—C5B—C6B | 120.3 (5) | C6D—C1D—C2D | 115.3 (5) |
F3B—C5B—C6B | 120.0 (6) | C6D—C1D—C7D | 122.1 (5) |
F4B—C6B—C5B | 117.8 (5) | C2D—C1D—C7D | 122.6 (5) |
F4B—C6B—C1B | 121.2 (5) | C1D—C2D—C3D | 119.1 (6) |
C5B—C6B—C1B | 120.9 (5) | C1D—C2D—H2D | 114 (4) |
C5B—C6B—I1B | 158.7 (4) | C3D—C2D—H2D | 126 (4) |
C6C—C1C—C2C | 116.2 (4) | N4D—C3D—C2D | 124.7 (6) |
C6C—C1C—C7C | 121.3 (4) | N4D—C3D—H3D | 121 (3) |
C2C—C1C—C7C | 122.4 (4) | C2D—C3D—H3D | 114 (3) |
C1C—C2C—C3C | 119.6 (5) | C3D—N4D—C5D | 115.8 (5) |
C1C—C2C—H2C | 119 (3) | C3D—N4D—I1B | 118.5 (4) |
C3C—C2C—H2C | 120 (3) | C5D—N4D—I1B | 119.9 (4) |
N4C—C3C—C2C | 124.1 (6) | N4D—C5D—C6D | 123.4 (6) |
N4C—C3C—H3C | 117 (3) | N4D—C5D—H5D | 110 (3) |
C2C—C3C—H3C | 119 (3) | C6D—C5D—H5D | 126 (3) |
C3C—N4C—C5C | 116.3 (5) | C5D—C6D—C1D | 121.6 (6) |
C3C—N4C—I1A | 111.3 (4) | C5D—C6D—H6D | 116 (3) |
C5C—N4C—I1A | 127.2 (4) | C1D—C6D—H6D | 123 (3) |
N4C—C5C—C6C | 123.6 (5) | ||
C6A—C1A—C2A—C3A | −2.3 (6) | F3B—C5B—C6B—C1B | −178.7 (4) |
I1A—C1A—C2A—C3A | 177.7 (3) | C4B—C5B—C6B—I1B | 3.0 (14) |
C6A—C1A—C2A—I2A | 175.9 (3) | F3B—C5B—C6B—I1B | −175.0 (7) |
I1A—C1A—C2A—I2A | −4.1 (5) | C2B—C1B—C6B—F4B | −179.9 (4) |
C1A—C2A—C3A—F1A | −177.9 (4) | I1B—C1B—C6B—F4B | 0.4 (6) |
I2A—C2A—C3A—F1A | 3.8 (6) | C2B—C1B—C6B—C5B | −2.5 (7) |
C1A—C2A—C3A—C4A | 1.2 (7) | I1B—C1B—C6B—C5B | 177.8 (4) |
I2A—C2A—C3A—C4A | −177.0 (4) | C2B—C1B—C6B—I1B | 179.7 (6) |
C1A—C2A—C3A—I2A | 178.3 (6) | C6C—C1C—C2C—C3C | 0.8 (8) |
F1A—C3A—C4A—F2A | −0.5 (7) | C7C—C1C—C2C—C3C | 179.9 (5) |
C2A—C3A—C4A—F2A | −179.7 (4) | C1C—C2C—C3C—N4C | −1.8 (10) |
I2A—C3A—C4A—F2A | 175.1 (7) | C2C—C3C—N4C—C5C | 1.7 (9) |
F1A—C3A—C4A—C5A | 179.7 (5) | C3C—N4C—C5C—C6C | −0.7 (9) |
C2A—C3A—C4A—C5A | 0.6 (8) | C2C—C1C—C6C—C5C | 0.2 (8) |
I2A—C3A—C4A—C5A | −4.7 (14) | C7C—C1C—C6C—C5C | −178.9 (5) |
F2A—C4A—C5A—F3A | −1.5 (8) | N4C—C5C—C6C—C1C | −0.3 (9) |
C3A—C4A—C5A—F3A | 178.3 (4) | C6C—C1C—C7C—C8C | 165.7 (5) |
F2A—C4A—C5A—C6A | 179.0 (4) | C2C—C1C—C7C—C8C | −13.3 (7) |
C3A—C4A—C5A—C6A | −1.2 (8) | C6C—C1C—C7C—C12C | −14.7 (7) |
F3A—C5A—C6A—F4A | 0.4 (7) | C2C—C1C—C7C—C12C | 166.3 (5) |
C4A—C5A—C6A—F4A | 179.9 (4) | C12C—C7C—C8C—C9C | −0.1 (8) |
F3A—C5A—C6A—C1A | −179.5 (4) | C1C—C7C—C8C—C9C | 179.5 (5) |
C4A—C5A—C6A—C1A | 0.0 (8) | C7C—C8C—C9C—N10C | 0.6 (9) |
F3A—C5A—C6A—I1A | 177.5 (7) | C8C—C9C—N10C—C11C | −0.7 (9) |
C4A—C5A—C6A—I1A | −3.0 (13) | C9C—N10C—C11C—C12C | 0.4 (10) |
C2A—C1A—C6A—F4A | −178.1 (4) | C8C—C7C—C12C—C11C | −0.2 (8) |
I1A—C1A—C6A—F4A | 1.9 (6) | C1C—C7C—C12C—C11C | −179.8 (5) |
C2A—C1A—C6A—C5A | 1.7 (7) | N10C—C11C—C12C—C7C | 0.1 (10) |
I1A—C1A—C6A—C5A | −178.3 (4) | C8D—C7D—C12D—C11D | −0.6 (8) |
C2A—C1A—C6A—I1A | −180.0 (6) | C1D—C7D—C12D—C11D | −179.9 (6) |
C6B—C1B—C2B—C3B | 3.5 (7) | C7D—C12D—C11D—N10D | −0.8 (11) |
I1B—C1B—C2B—C3B | −176.9 (3) | C12D—C11D—N10D—C9D | 0.7 (11) |
C6B—C1B—C2B—I2B | −176.0 (3) | C12D—C11D—N10D—I2Biv | −155.0 (6) |
I1B—C1B—C2B—I2B | 3.7 (5) | C11D—N10D—C9D—C8D | 0.9 (12) |
C1B—C2B—C3B—F1B | 179.4 (4) | I2Biv—N10D—C9D—C8D | 155.5 (6) |
I2B—C2B—C3B—F1B | −1.1 (6) | C12D—C7D—C8D—C9D | 2.0 (9) |
C1B—C2B—C3B—C4B | −1.4 (7) | C1D—C7D—C8D—C9D | −178.7 (6) |
I2B—C2B—C3B—C4B | 178.1 (4) | N10D—C9D—C8D—C7D | −2.3 (13) |
C1B—C2B—C3B—I2B | −179.5 (6) | C12D—C7D—C1D—C6D | 8.7 (8) |
F1B—C3B—C4B—C5B | 177.5 (5) | C8D—C7D—C1D—C6D | −170.6 (6) |
C2B—C3B—C4B—C5B | −1.7 (8) | C12D—C7D—C1D—C2D | −169.3 (6) |
I2B—C3B—C4B—C5B | 1.7 (14) | C8D—C7D—C1D—C2D | 11.4 (8) |
F1B—C3B—C4B—F2B | −1.6 (7) | C6D—C1D—C2D—C3D | 1.4 (9) |
C2B—C3B—C4B—F2B | 179.2 (4) | C7D—C1D—C2D—C3D | 179.6 (6) |
I2B—C3B—C4B—F2B | −177.4 (7) | C1D—C2D—C3D—N4D | −0.6 (12) |
F2B—C4B—C5B—F3B | −0.1 (8) | C2D—C3D—N4D—C5D | −0.6 (11) |
C3B—C4B—C5B—F3B | −179.2 (4) | C3D—N4D—C5D—C6D | 1.0 (10) |
F2B—C4B—C5B—C6B | −178.2 (5) | I1B—N4D—C5D—C6D | −151.9 (6) |
C3B—C4B—C5B—C6B | 2.8 (9) | N4D—C5D—C6D—C1D | −0.2 (11) |
C4B—C5B—C6B—F4B | 176.8 (5) | C2D—C1D—C6D—C5D | −1.1 (9) |
F3B—C5B—C6B—F4B | −1.2 (7) | C7D—C1D—C6D—C5D | −179.3 (6) |
C4B—C5B—C6B—C1B | −0.7 (8) |
Symmetry codes: (i) x, −y−1/2, z−1/2; (ii) x−1/2, −y+1, z; (iii) x, −y−1/2, z+1/2; (iv) x+1/2, −y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2C—H2C···F1Bv | 0.94 (2) | 2.54 (4) | 3.452 (7) | 165 (4) |
C5C—H5C···F3Avi | 0.92 (2) | 2.68 (3) | 3.557 (7) | 160 (3) |
C6C—H6C···F4Bvii | 0.93 (2) | 2.44 (4) | 3.342 (7) | 165 (3) |
C2D—H2D···F1Aviii | 0.93 (2) | 2.69 (4) | 3.597 (7) | 167 (3) |
C6D—H6D···F4Aix | 0.92 (2) | 2.46 (4) | 3.313 (7) | 154 (3) |
Symmetry codes: (v) x+1/2, −y, z; (vi) −x, −y, −z; (vii) x−1/2, −y, z; (viii) −x+1/2, −y+1/2, −z−1/2; (ix) −x+1/2, −y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H8N2·C6F4I2 |
Mr | 558.04 |
Crystal system, space group | Monoclinic, I2/a |
Temperature (K) | 290 |
a, b, c (Å) | 14.2535 (10), 33.714 (3), 14.3511 (12) |
β (°) | 100.831 (6) |
V (Å3) | 6773.5 (10) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 3.75 |
Crystal size (mm) | 0.40 × 0.16 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART-APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.668, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15718, 7796, 5552 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.094, 0.97 |
No. of reflections | 7796 |
No. of parameters | 498 |
No. of restraints | 148 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.66, −0.60 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett and Johnson, 1996), SHELXL97 and PARST (Nardelli, 1983).
D—H···A | D—H | H···A | D···A | D—H···A |
C2C—H2C···F1Bi | 0.94 (2) | 2.54 (4) | 3.452 (7) | 165 (4) |
C5C—H5C···F3Aii | 0.92 (2) | 2.68 (3) | 3.557 (7) | 160 (3) |
C6C—H6C···F4Biii | 0.93 (2) | 2.44 (4) | 3.342 (7) | 165 (3) |
C2D—H2D···F1Aiv | 0.93 (2) | 2.69 (4) | 3.597 (7) | 167 (3) |
C6D—H6D···F4Av | 0.92 (2) | 2.46 (4) | 3.313 (7) | 154 (3) |
Symmetry codes: (i) x+1/2, −y, z; (ii) −x, −y, −z; (iii) x−1/2, −y, z; (iv) −x+1/2, −y+1/2, −z−1/2; (v) −x+1/2, −y+1/2, −z+1/2. |
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The title structure determination, (I), is part of a study on the halogen bond, which is a powerful intermolecular interaction we have extensively used to produce a variety of structures involving perfluorinated compounds (Cardillo et al., 2000), usually very difficult to crystallize.
In the present structure, 1,2-diiodotetrafluorobenzene (F4dIb) behaves as a bidentate acceptor, as well as 1,4-diiodotetrafluorobenzene, with the same base (Bailey Walsh et al., 2001), towards 4,4'-bipyridine (4,4'-bpy), giving rise to chains extended along the whole crystal, in which the two modules alternate with a 1:1 ratio.
The asymmetric unit contains two independent 4,4'-bpy···F4dIb aggregates, linked by I···N halogen bonds (see Fig. 1). We have assigned the same numbering scheme to chemically equivalent molecules, which are distinguished by the suffix (A and B for F4dIb, and C and D for 4,4'-bpy). The basic aggregates behave as monomers in building two independent, infinite, wave-like chains, in which the F4dIbs represent the crests and 4,4'-bpys the walls; Fig. 2(a) shows a single chain B···D···; the wave A···C··· has the same aspect.
The only strong intermolecular interaction is represented by four independent I···N intermolecular contacts: I1A···N4C 2.928 (4), I1B···N4D 2.909 (5), I2A···N10Ci 2.958 (4) [symmetry code: (i) x, -1/2 - y, -1/2 + z] and I2B···N10Dii 2.964 (5) Å [symmetry code: (ii) -1/2 + x, 1 - y, z]; these distances are not particularly short, if compared, for example, to 2.810 (5) Å found between 1,2-bis(4-pyridyl)ethylene and 1,4-diiodotetrafluorobenzene (Bailey Walsh et al., 2001); the relative C—I···N angles deviate a little from linearity, ranging from 172.1 (2) to 176.2 (2)°.
Within any wave, F4dIbs and 4,4'-bpys are mutually perpendicular because of the second structural motif, namely some H···F contacts shorter than the sum of van der Waals radii (2.7 Å); these attractive interactions, reported in Table 1, act between couples of independent waves. To better understand how these interactions work, see Fig. 2 and 3.
Fig. 2(b) shows the same wave B···D··· projected along c axis as in Fig. 2(a), together a second one related by a screw axis. As can be seen, the two waves, in projections, form large ellipses. In contrast to what would seem from this figure and the following ones, no π–π interaction contributes to the stabilization of the structure; the distance between the partially overlapping F4dIbs in Fig. 2(b) is about 7 Å. Fig. 3 shows the two ways of insertion of the waves A···C··· into the ellipses.
At the bottom, a wave is slipped into the middle of the ellipse; 4,4'-bpyCs are placed exactly at the level of F4dIbBs and form H···F interactions parallel to the sheet, shown as dotted lines. These interactions force the 4,4'-bpyC to be about coplanar with the F4dIbB. The second type of insertion of the wave A···C··· is shown in the top ellipse. Here, two H···F interactions are perpendicular to the sheet and bind 4,4'-bpyD to F4dIbA. BpyD and F4dIbA are also about coplanar.
Figs. 4 and 5 show the whole content of an unit cell viewed along c and b, respectively; it is quite difficult from these two plots to appreciate the contributes to the stability of the structure.
Dunitz & Taylor, (1997) titled their paper `Organic fluorine hardly ever accepts hydrogen bonds'. This is surely true if there is the possibilty of stronger interactions but, in this case, H···F interactions seem quite remarkable for the structure assemblage.