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The self-assembly of 1,3-diiodo­tetra­fluoro­benzene (13DITFB) and bipyridine (44BPY), C10H8N2·C6F4I2, is driven by halogen bonding. It results in infinite wave-like chains, with the two mol­ecules in a 1:1 mole ratio. Both molecules lie on crystallographic mirror planes, bisecting the central 44BPY C—C bond and passing through two opposite CF groups of 13DITFB. The N...I halogen-bonding inter­action is 2.902 (4) Å, and the C—I...N angle is almost linear [175.6 (2)°]. The chain ...13DITFB...44BPY... is polar, with all 13DITFB on the wave crest and all 44BPY at the bottom. This is in contrast to similar complexes obtained on self-assembly of 44BPY with 1,3-dibromo­tetra­fluoro­benzene (13DBrTFB), 1,4-diiodo­tetra­fluoro­benzene (14DITFB) or 1,2-diiodo­tetra­fluoro­benzene (12DITFB), where centrosymmetric wave-like chains are observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047630/fj2045sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047630/fj2045Isup2.hkl
Contains datablock I

CCDC reference: 667297

Key indicators

  • Single-crystal X-ray study
  • T = 297 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.030
  • wR factor = 0.074
  • Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT431_ALERT_2_A Short Inter HL..A Contact I1 .. N1 .. 2.90 Ang.
Author Response: The Contact I...N between iodoperfluorocarbons and amines or pyridines is normally in the range 2.7 - 3.3 A\% as can be seen for example in Fig. 1 of Metrangolo, P., Neukirch, H., Pilati, T., & G. Resnati (2005). Acc. Chem. Res., 38, 386-395.

Alert level B PLAT060_ALERT_3_B Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.52
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.785 1.000 Tmin and Tmax expected: 0.418 0.799 RR = 1.499 Please check that your absorption correction is appropriate. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.80 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.57 PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C7 PLAT410_ALERT_2_C Short Intra H...H Contact H6 .. H6 .. 1.95 Ang.
Alert level G ABSTM02_ALERT_3_G 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 0.799 Tmax scaled 0.799 Tmin scaled 0.627 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.51 From the CIF: _reflns_number_total 2020 Count of symmetry unique reflns 1113 Completeness (_total/calc) 181.49% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 907 Fraction of Friedel pairs measured 0.815 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 15
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The construction of supramolecular architectures by XB is a topic of current interest due to the efficiency and reliability of the interaction (Metrangolo & Resnati, 2001; Metrangolo et al., 2005; Metrangolo et al., 2007). In the present study, we report the first use of 1,3-diiodotetrafluorobenzene (Neenan & Whitesides, 1988) in crystal engineering. Both molecules in the co-crystal lie on a crystallographic mirror (Figure 1). When interacting each other the perfluoroarene acts as a bidentate electron acceptor and 4,4'-bipyridine as a bidentate donor. An halogen bonded system in which the modules alternate is formed (Figure 2). The two rings connected by halogen bonding are twisted each other by an angle of 64.9 (2) °, while 44BPY and 13DITFB, related by the n glide, are nearly parallel. The bipyridine core shows a bent conformation, being 9.2 (2) ° the angle between the two pyridine rings. The crystallographic analysis revealed that the N1···I1 distance is 2.902 (4) Å. This value is shorter than those found in the complex between of 12DITFB and bipyridine (2.909–2.964) Å. The C2—I1···N1 angle slightly deviates from linearity (175.6 (2) °). The 4,4'-bipyridine gives an unlimited 1:1 chain also in the presence of 1,2-diiodotetrafluorobenzene and 1,4-diiodotetrafluorobenzene. The XB properties of the chain in the three complexes are quite similar, the N···I length and N···I—C angles being 2.909–2.964 Å and 172.1–176.2 ° for the complex 44BPY-12DITFB (four independent values, Liantonio et al., 2002), 2.851–2.864 Å and 176.9–177.3 ° for 44BPY-14DITFB (Walsh et al., 2001; Messina et al., 2001). Also in these two complexes the 44BPY and the DITFB mean planes are nearly orthogonal. In these two structures, 44BPY, rather than bent, is slightly twisted, as shown by Figure 3, where the main differences among the waves of the three structures are evidenced. While the 44BPY-14DITFB chain is nearly linear, the 44BPY-12DITFB chain is much more winding than the 44BPY-13DITFB chain. While the structures of 44BPY-12DITFB and 44BPY-14DITFB are both centrosymmetric (as the single chains), in the complex 44BPY-13DITFB both the structure and the chain are polar. This is even more surprising if we consider that 44BPY-13DBrTFB, the complex between 44BPY and 1,3-dibromotetrafluorobenzene, that could be exspected to be isomorphous to 44BPY-14DITFB, is centric with two independent 44BPY-13DBrTFB waves, the first lying along a line of symmetry centres, and the second lined up to a 21 screw axis, but having a conformation very near to the first one (Figure 4, De Santis, Forni,Liantonio, Metrangolo, Pilati & Resnati, 2003).

Related literature top

For related literature, see: De Santis et al. (2003); Liantonio et al. (2002); Messina et al. (2001); Metrangolo & Resnati (2001); Metrangolo et al. (2005, 2007); Neenan & Whitesides (1988); Walsh et al. (2001).

For related literature, see: Altomare et al. (1994).

Experimental top

The starting materials were commercially available from Aldrich. 1,3-Diiodotetrafluorobenzene was prepared as already reported (Neenan & Whitesides, 1988). The 1:1 adduct was obtained by dissolving in chloroform, at room temperature and in a vial, equimolecular amounts of 1,3-diiodotetrafluorobenzene and bipyridine. 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 resulting crystals were filtered. IR (cm-1, selected bands): 3032, 1589, 1459, 1404, 1219, 1067, 1043, 1037, 860,799.

Structure description top

The construction of supramolecular architectures by XB is a topic of current interest due to the efficiency and reliability of the interaction (Metrangolo & Resnati, 2001; Metrangolo et al., 2005; Metrangolo et al., 2007). In the present study, we report the first use of 1,3-diiodotetrafluorobenzene (Neenan & Whitesides, 1988) in crystal engineering. Both molecules in the co-crystal lie on a crystallographic mirror (Figure 1). When interacting each other the perfluoroarene acts as a bidentate electron acceptor and 4,4'-bipyridine as a bidentate donor. An halogen bonded system in which the modules alternate is formed (Figure 2). The two rings connected by halogen bonding are twisted each other by an angle of 64.9 (2) °, while 44BPY and 13DITFB, related by the n glide, are nearly parallel. The bipyridine core shows a bent conformation, being 9.2 (2) ° the angle between the two pyridine rings. The crystallographic analysis revealed that the N1···I1 distance is 2.902 (4) Å. This value is shorter than those found in the complex between of 12DITFB and bipyridine (2.909–2.964) Å. The C2—I1···N1 angle slightly deviates from linearity (175.6 (2) °). The 4,4'-bipyridine gives an unlimited 1:1 chain also in the presence of 1,2-diiodotetrafluorobenzene and 1,4-diiodotetrafluorobenzene. The XB properties of the chain in the three complexes are quite similar, the N···I length and N···I—C angles being 2.909–2.964 Å and 172.1–176.2 ° for the complex 44BPY-12DITFB (four independent values, Liantonio et al., 2002), 2.851–2.864 Å and 176.9–177.3 ° for 44BPY-14DITFB (Walsh et al., 2001; Messina et al., 2001). Also in these two complexes the 44BPY and the DITFB mean planes are nearly orthogonal. In these two structures, 44BPY, rather than bent, is slightly twisted, as shown by Figure 3, where the main differences among the waves of the three structures are evidenced. While the 44BPY-14DITFB chain is nearly linear, the 44BPY-12DITFB chain is much more winding than the 44BPY-13DITFB chain. While the structures of 44BPY-12DITFB and 44BPY-14DITFB are both centrosymmetric (as the single chains), in the complex 44BPY-13DITFB both the structure and the chain are polar. This is even more surprising if we consider that 44BPY-13DBrTFB, the complex between 44BPY and 1,3-dibromotetrafluorobenzene, that could be exspected to be isomorphous to 44BPY-14DITFB, is centric with two independent 44BPY-13DBrTFB waves, the first lying along a line of symmetry centres, and the second lined up to a 21 screw axis, but having a conformation very near to the first one (Figure 4, De Santis, Forni,Liantonio, Metrangolo, Pilati & Resnati, 2003).

For related literature, see: De Santis et al. (2003); Liantonio et al. (2002); Messina et al. (2001); Metrangolo & Resnati (2001); Metrangolo et al. (2005, 2007); Neenan & Whitesides (1988); Walsh et al. (2001).

For related literature, see: Altomare et al. (1994).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular plot of the complex with the numbering scheme, showings 50% probability displacement ellipsoids; H atom not to scale. Dashed lines represent the XB. The view is parallel to the crystallographic mirror planes passing through the atoms C1, C4, F1 and F3 for 1,3-diiodotetrafluorobenzene and at the middle of the N1···N1(-x,y,z) axis for bipyridine.
[Figure 2] Fig. 2. Top: two waves of 44BPY···13DITFB··· projected on the plane of a 44BPY; H atoms omitted for clarity; bottom: the same waves projected along the a axis.
[Figure 3] Fig. 3. Single waves of the complexes 44BPY···14DITF (top), B44BPY···13DITFB (middle), and 44BPY···12DITFB (bottom), showed in the plane defined by the normal to 44BPY and the wave elongation axis.
[Figure 4] Fig. 4. The two independent waves of the complexes 44BPY···14DBrTF both projected parallel to a 44BPY plane. Top: this waves is formed by molecules correlated by centres of symmetry. Bottom: a wave formed by molecules along a screw axis; it may easily seen that also this wave is nearly centro-symmetric.
4,4'-Bipyridine–2,4,5,6-tetrafluoro-1,3-diiodobenzene (1/1) top
Crystal data top
C10H8N2·C6F4I2Dx = 2.179 Mg m3
Mr = 558.04Melting point: 368 K
Orthorhombic, Pmn21Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac -2Cell parameters from 934 reflections
a = 18.069 (3) Åθ = 2.5–23.2°
b = 8.2939 (12) ŵ = 3.74 mm1
c = 5.6759 (8) ÅT = 297 K
V = 850.6 (2) Å3Tabular, yellow
Z = 20.28 × 0.20 × 0.06 mm
F(000) = 520
Data collection top
Bruker SMART 1000 CCD
diffractometer
2020 independent reflections
Radiation source: fine-focus sealed tube1710 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω and φ scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 2323
Tmin = 0.785, Tmax = 1.000k = 1010
7436 measured reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030All H-atom parameters refined
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0395P)2 + 0.0579P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.005
2020 reflectionsΔρmax = 0.77 e Å3
131 parametersΔρmin = 0.30 e Å3
15 restraintsAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (4)
Crystal data top
C10H8N2·C6F4I2V = 850.6 (2) Å3
Mr = 558.04Z = 2
Orthorhombic, Pmn21Mo Kα radiation
a = 18.069 (3) ŵ = 3.74 mm1
b = 8.2939 (12) ÅT = 297 K
c = 5.6759 (8) Å0.28 × 0.20 × 0.06 mm
Data collection top
Bruker SMART 1000 CCD
diffractometer
2020 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
1710 reflections with I > 2σ(I)
Tmin = 0.785, Tmax = 1.000Rint = 0.037
7436 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030All H-atom parameters refined
wR(F2) = 0.074Δρmax = 0.77 e Å3
S = 1.06Δρmin = 0.30 e Å3
2020 reflectionsAbsolute structure: Flack (1983)
131 parametersAbsolute structure parameter: 0.02 (4)
15 restraints
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.

H atoms were refined by SHELX97 with the following restraints: FLAT C5 C6 C7 C8 C9 N1 H5 H6 H8 H9; SADI C5 H5 C6 H6 C8 H8 C9 H9; SADI H5 H6 H8 H9

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.333096 (14)0.22991 (3)0.34245 (12)0.06844 (14)
F10.50000.2934 (6)0.4760 (9)0.0691 (11)
F20.3712 (2)0.0212 (4)0.1240 (7)0.0933 (11)
F30.50000.0625 (6)0.3226 (8)0.1003 (17)
C10.50000.2039 (8)0.2766 (11)0.0526 (17)
C20.4325 (3)0.1604 (5)0.1831 (8)0.0560 (10)
C30.4346 (3)0.0699 (6)0.0198 (8)0.0637 (12)
C40.50000.0246 (8)0.1196 (11)0.0668 (18)
N10.1965 (2)0.3500 (6)0.5460 (8)0.0679 (11)
C50.1578 (3)0.2874 (7)0.7222 (12)0.0699 (14)
H50.181 (3)0.232 (4)0.830 (11)0.071 (14)*
C60.0820 (3)0.2952 (6)0.7403 (9)0.0611 (11)
H60.054 (3)0.251 (4)0.848 (11)0.081 (16)*
C70.0410 (2)0.3727 (5)0.5671 (7)0.0451 (9)
C80.0815 (3)0.4426 (7)0.3889 (8)0.0607 (13)
H80.063 (3)0.498 (5)0.274 (9)0.078 (19)*
C90.1586 (3)0.4285 (8)0.3845 (12)0.0740 (18)
H90.190 (3)0.460 (7)0.275 (11)0.17 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.05658 (18)0.0705 (2)0.0783 (2)0.00068 (10)0.0055 (4)0.0075 (4)
F10.062 (3)0.077 (3)0.068 (3)0.0000.0000.027 (2)
F20.108 (2)0.0919 (19)0.080 (3)0.0149 (16)0.038 (2)0.000 (2)
F30.162 (5)0.089 (3)0.050 (2)0.0000.0000.017 (2)
C10.066 (4)0.042 (3)0.051 (5)0.0000.0000.002 (2)
C20.061 (3)0.050 (2)0.057 (3)0.001 (2)0.009 (2)0.0050 (19)
C30.089 (4)0.050 (2)0.052 (2)0.007 (2)0.015 (3)0.005 (2)
C40.110 (5)0.057 (3)0.033 (4)0.0000.0000.002 (3)
N10.048 (2)0.075 (3)0.081 (3)0.000 (2)0.008 (2)0.002 (2)
C50.061 (3)0.076 (3)0.073 (3)0.004 (2)0.016 (3)0.011 (3)
C60.058 (3)0.071 (3)0.054 (2)0.004 (2)0.005 (2)0.007 (2)
C70.049 (2)0.045 (2)0.042 (2)0.0041 (16)0.0069 (17)0.0112 (16)
C80.053 (2)0.073 (3)0.056 (3)0.0057 (19)0.001 (2)0.014 (2)
C90.052 (2)0.088 (3)0.082 (5)0.003 (2)0.013 (3)0.006 (3)
Geometric parameters (Å, º) top
I1—C22.092 (5)N1—C51.326 (8)
F1—C11.353 (8)C5—C61.375 (8)
F2—C31.350 (5)C5—H50.88 (4)
F3—C41.360 (7)C6—C71.388 (6)
C1—C21.378 (5)C6—H60.88 (5)
C1—C2i1.378 (5)C7—C81.377 (6)
C2—C31.375 (6)C7—C7ii1.482 (8)
C3—C41.364 (6)C8—C91.398 (7)
C4—C3i1.364 (6)C8—H80.87 (4)
N1—C91.316 (8)C9—H90.88 (5)
F1—C1—C2117.8 (3)N1—C5—H5119 (4)
F1—C1—C2i117.8 (3)C6—C5—H5117 (4)
C2—C1—C2i124.5 (6)C5—C6—C7120.0 (5)
C3—C2—C1116.2 (5)C5—C6—H6127 (4)
C3—C2—I1122.4 (4)C7—C6—H6112 (4)
C1—C2—I1121.4 (4)C8—C7—C6115.6 (4)
F2—C3—C4118.1 (4)C8—C7—C7ii122.1 (3)
F2—C3—C2120.5 (5)C6—C7—C7ii122.2 (3)
C4—C3—C2121.4 (5)C7—C8—C9120.5 (5)
F3—C4—C3119.9 (3)C7—C8—H8124 (4)
F3—C4—C3i119.9 (3)C9—C8—H8115 (4)
C3—C4—C3i120.2 (6)N1—C9—C8123.1 (6)
C9—N1—C5116.4 (5)N1—C9—H9108 (5)
N1—C5—C6124.3 (5)C8—C9—H9129 (5)
F1—C1—C2—C3179.8 (5)F2—C3—C4—C3i179.5 (4)
C2i—C1—C2—C31.2 (9)C2—C3—C4—C3i0.5 (9)
F1—C1—C2—I10.0 (7)C9—N1—C5—C62.3 (8)
C2i—C1—C2—I1179.0 (4)N1—C5—C6—C70.1 (8)
C1—C2—C3—F2179.8 (5)C5—C6—C7—C82.2 (6)
I1—C2—C3—F20.4 (6)C5—C6—C7—C7ii174.7 (4)
C1—C2—C3—C40.8 (7)C6—C7—C8—C92.3 (7)
I1—C2—C3—C4179.4 (4)C7ii—C7—C8—C9174.6 (4)
F2—C3—C4—F32.2 (8)C5—N1—C9—C82.2 (9)
C2—C3—C4—F3178.8 (5)C7—C8—C9—N10.1 (9)
Symmetry codes: (i) x+1, y, z; (ii) x, y, z.

Experimental details

Crystal data
Chemical formulaC10H8N2·C6F4I2
Mr558.04
Crystal system, space groupOrthorhombic, Pmn21
Temperature (K)297
a, b, c (Å)18.069 (3), 8.2939 (12), 5.6759 (8)
V3)850.6 (2)
Z2
Radiation typeMo Kα
µ (mm1)3.74
Crystal size (mm)0.28 × 0.20 × 0.06
Data collection
DiffractometerBruker SMART 1000 CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.785, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
7436, 2020, 1710
Rint0.037
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.074, 1.06
No. of reflections2020
No. of parameters131
No. of restraints15
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.77, 0.30
Absolute structureFlack (1983)
Absolute structure parameter0.02 (4)

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002).

 

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