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The title compound, C20H14F4N4O2, has been synthesized as part of our ongoing investigations into three-dimensional supra­molecules or polymers with intriguing structural topologies and properties. The mol­ecule crystallizes around a inversion centre, with one half-mol­ecule in the asymmetric unit and a dihedral angle of 62.26 (9)° between the pyridine ring and the central benzene ring. Inter­molecular N—H...O hydrogen bonds between adjacent mol­ecules result in a one-dimensional chain, and C—H...N and C—H...O inter­actions may be effective in the stabilization of these one-dimensional motifs.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052968/fl2170sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052968/fl2170Isup2.hkl
Contains datablock I

CCDC reference: 672825

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.039
  • wR factor = 0.114
  • Data-to-parameter ratio = 13.0

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Comment top

Bifunctional bridging ligands, such as 4,4'-bipyridine, have been used to construct a wide range of zero-, one-, two- or three-dimensional coordination supramolecules or polymers with intriguing structural topologies and properties (Fujita, 1998; Hagrman et al., 1999; Leininger et al., 2000). The nature of such ligands (e.g. the length and the steric interaction) is crucial to the final observed coordination frameworks (Withersby et al., 1999). In efforts to systematically investigate the syntheses, molecular structures and coordination chemistry of such compounds, we have previously reported on N,N'-[(2,3,5,6-tetrafluoro-1,4-phenylene)-dimethylene] -bis(pyridine-2-carboxamide) (Chen, Yin et al., 2007), N,N'-[(2,3,5,6-tetrafluoro-1,4-phenylene)-dimethylene]-bis(pyridine-4 -carboxamide) (tfpbbp) (He et al., 2006) and the interesting 3-D supramolecular porous compound [Zn(tfpbbp)(Ac)2]n (Chen, He et al., 2007). In this contribution, we report the crystal structure (I).

A perspective view of (I), including the atomic numbering scheme, is shown in Fig. 1. (I) crystallizes around a crystallographic center with a half molecule in the asymmetric unit. The bond lengths and angles are within normal ranges. The pyridine ring forms a dihedral angle of 62.26 (9)° with the central benzene ring. Intermolecular N—H···O interactions exist between adjacent molecules, resulting in a one-dimensional network, and C—H···N, C—H···O hydrogen bonds may be effective in the stabillization of these one-dimensional motifs (Table 1).

Related literature top

For general background, see: Chen, Yin et al. (2007), Chen, He et al. (2007); Fujita (1998); Hagrman et al. (1999); He et al. (2006); Leininger et al. (2000); Withersby et al. (1999).

Experimental top

Compound (I) was prepared according to the reported procedure of He et al. (2006). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol (10 mL) solution of (I) (0.03 g).

Refinement top

The imino H atoms were located in a difference Fourier map and then refined as riding (N—H = 0.86 Å), with Uiso(H) = 1.2Ueq(N). The remaining H atoms were assigned to calculated positions, with C—H = 0.97 (methylene) and 0.93 Å (aromatic), and refined using a riding model, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) (thermal ellipsoids are shown at 30% probability levels).
N,N'-[(2,3,5,6-Tetrafluoro-1,4-phenylene)dimethylene]bis(pyridine-3-carboxamide) top
Crystal data top
C20H14F4N4O2F(000) = 428
Mr = 418.35Dx = 1.529 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2571 reflections
a = 11.5786 (18) Åθ = 2.6–27.5°
b = 5.0624 (8) ŵ = 0.13 mm1
c = 16.259 (3) ÅT = 296 K
β = 107.542 (2)°Block, colorless
V = 908.7 (3) Å30.30 × 0.22 × 0.20 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
1773 independent reflections
Radiation source: fine-focus sealed tube1404 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ϕ and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1412
Tmin = 0.921, Tmax = 0.975k = 66
6640 measured reflectionsl = 2020
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0586P)2 + 0.1844P]
where P = (Fo2 + 2Fc2)/3
1773 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.29 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C20H14F4N4O2V = 908.7 (3) Å3
Mr = 418.35Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.5786 (18) ŵ = 0.13 mm1
b = 5.0624 (8) ÅT = 296 K
c = 16.259 (3) Å0.30 × 0.22 × 0.20 mm
β = 107.542 (2)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
1773 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1404 reflections with I > 2σ(I)
Tmin = 0.921, Tmax = 0.975Rint = 0.030
6640 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.114H-atom parameters constrained
S = 1.07Δρmax = 0.29 e Å3
1773 reflectionsΔρmin = 0.21 e Å3
136 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
C10.01866 (18)0.7509 (4)0.42095 (12)0.0526 (5)
H10.04350.63570.44850.063*
C20.00636 (15)0.9465 (3)0.36923 (10)0.0407 (4)
C30.08646 (18)1.1198 (4)0.32969 (13)0.0565 (5)
H30.07371.25650.29520.068*
C40.19833 (19)1.0860 (5)0.34242 (16)0.0711 (6)
H40.26241.19860.31630.085*
C50.21302 (19)0.8842 (5)0.39409 (15)0.0679 (6)
H50.28880.86280.40180.081*
C60.12896 (15)0.9802 (3)0.35843 (9)0.0398 (4)
C70.31486 (16)0.7658 (4)0.35275 (12)0.0500 (5)
H7A0.31180.86490.30110.060*
H7B0.33860.58630.34460.060*
C80.40972 (14)0.8866 (3)0.42843 (10)0.0416 (4)
C90.48355 (15)1.0911 (4)0.41885 (10)0.0436 (4)
C100.57003 (15)1.2033 (3)0.48758 (11)0.0440 (4)
F10.47180 (10)1.1882 (3)0.33916 (7)0.0647 (4)
F20.63628 (10)1.4047 (2)0.47259 (7)0.0634 (3)
N10.12611 (16)0.7170 (4)0.43392 (13)0.0666 (5)
N20.19512 (12)0.7617 (3)0.36334 (9)0.0446 (4)
H20.16560.61330.37310.053*
O10.16693 (12)1.1983 (2)0.34513 (8)0.0538 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0505 (10)0.0499 (11)0.0591 (11)0.0030 (8)0.0188 (8)0.0070 (8)
C20.0428 (9)0.0354 (8)0.0418 (8)0.0019 (7)0.0094 (7)0.0051 (6)
C30.0541 (11)0.0443 (10)0.0677 (12)0.0037 (8)0.0131 (9)0.0066 (9)
C40.0484 (12)0.0623 (13)0.0976 (17)0.0137 (10)0.0143 (11)0.0004 (12)
C50.0520 (12)0.0644 (13)0.0943 (16)0.0019 (10)0.0327 (11)0.0092 (12)
C60.0469 (9)0.0346 (8)0.0353 (7)0.0031 (7)0.0086 (6)0.0022 (6)
C70.0452 (10)0.0524 (11)0.0525 (10)0.0013 (8)0.0150 (8)0.0106 (8)
C80.0352 (8)0.0440 (9)0.0468 (9)0.0046 (7)0.0142 (7)0.0024 (7)
C90.0415 (9)0.0486 (10)0.0434 (8)0.0060 (7)0.0172 (7)0.0066 (7)
C100.0384 (9)0.0434 (9)0.0538 (10)0.0004 (7)0.0194 (7)0.0039 (7)
F10.0635 (7)0.0837 (9)0.0476 (6)0.0021 (6)0.0176 (5)0.0156 (5)
F20.0598 (7)0.0565 (7)0.0756 (7)0.0147 (5)0.0228 (5)0.0111 (5)
N10.0610 (11)0.0634 (11)0.0858 (12)0.0028 (9)0.0378 (9)0.0053 (9)
N20.0395 (8)0.0359 (8)0.0553 (8)0.0033 (6)0.0097 (6)0.0026 (6)
O10.0645 (8)0.0373 (7)0.0662 (8)0.0054 (6)0.0298 (6)0.0024 (5)
Geometric parameters (Å, º) top
C1—N11.334 (3)C6—N21.334 (2)
C1—C21.385 (3)C7—N21.448 (2)
C1—H10.9300C7—C81.510 (2)
C2—C31.386 (3)C7—H7A0.9700
C2—C61.492 (2)C7—H7B0.9700
C3—C41.383 (3)C8—C91.381 (2)
C3—H30.9300C8—C10i1.391 (2)
C4—C51.366 (3)C9—F11.3536 (19)
C4—H40.9300C9—C101.378 (2)
C5—N11.325 (3)C10—F21.3416 (19)
C5—H50.9300C10—C8i1.391 (2)
C6—O11.231 (2)N2—H20.8600
N1—C1—C2124.32 (18)N2—C7—H7A108.9
N1—C1—H1117.8C8—C7—H7A108.9
C2—C1—H1117.8N2—C7—H7B108.9
C1—C2—C3117.34 (17)C8—C7—H7B108.9
C1—C2—C6122.26 (15)H7A—C7—H7B107.7
C3—C2—C6120.35 (16)C9—C8—C10i115.43 (15)
C4—C3—C2118.86 (19)C9—C8—C7122.33 (15)
C4—C3—H3120.6C10i—C8—C7122.23 (16)
C2—C3—H3120.6F1—C9—C10117.73 (15)
C5—C4—C3118.7 (2)F1—C9—C8119.54 (15)
C5—C4—H4120.6C10—C9—C8122.73 (15)
C3—C4—H4120.6F2—C10—C9118.78 (15)
N1—C5—C4124.17 (19)F2—C10—C8i119.39 (15)
N1—C5—H5117.9C9—C10—C8i121.83 (15)
C4—C5—H5117.9C5—N1—C1116.57 (18)
O1—C6—N2121.66 (15)C6—N2—C7122.31 (15)
O1—C6—C2121.73 (15)C6—N2—H2118.8
N2—C6—C2116.61 (14)C7—N2—H2118.8
N2—C7—C8113.35 (14)
N1—C1—C2—C31.0 (3)C7—C8—C9—F10.2 (2)
N1—C1—C2—C6178.54 (17)C10i—C8—C9—C101.2 (3)
C1—C2—C3—C41.2 (3)C7—C8—C9—C10179.73 (16)
C6—C2—C3—C4178.74 (17)F1—C9—C10—F21.2 (2)
C2—C3—C4—C50.5 (3)C8—C9—C10—F2178.75 (15)
C3—C4—C5—N10.4 (4)F1—C9—C10—C8i178.73 (15)
C1—C2—C6—O1149.22 (17)C8—C9—C10—C8i1.3 (3)
C3—C2—C6—O128.2 (2)C4—C5—N1—C10.6 (3)
C1—C2—C6—N231.2 (2)C2—C1—N1—C50.1 (3)
C3—C2—C6—N2151.37 (16)O1—C6—N2—C70.5 (2)
N2—C7—C8—C9126.32 (18)C2—C6—N2—C7179.06 (14)
N2—C7—C8—C10i54.7 (2)C8—C7—N2—C672.3 (2)
C10i—C8—C9—F1178.81 (14)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1ii0.862.152.8761 (19)142
C1—H1···N1iii0.932.583.407 (3)148
C7—H7A···O1iv0.972.603.305 (3)129
Symmetry codes: (ii) x, y1, z; (iii) x, y+1, z+1; (iv) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC20H14F4N4O2
Mr418.35
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)11.5786 (18), 5.0624 (8), 16.259 (3)
β (°) 107.542 (2)
V3)908.7 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.30 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.921, 0.975
No. of measured, independent and
observed [I > 2σ(I)] reflections
6640, 1773, 1404
Rint0.030
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.114, 1.07
No. of reflections1773
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.29, 0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.862.152.8761 (19)141.8
C1—H1···N1ii0.932.583.407 (3)148.0
C7—H7A···O1iii0.972.603.305 (3)129.4
Symmetry codes: (i) x, y1, z; (ii) x, y+1, z+1; (iii) x+1/2, y1/2, z+1/2.
 

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