Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052968/fl2170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052968/fl2170Isup2.hkl |
CCDC reference: 672825
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).
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).
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).
Fig. 1. The molecular structure of (I) (thermal ellipsoids are shown at 30% probability levels). |
C20H14F4N4O2 | F(000) = 428 |
Mr = 418.35 | Dx = 1.529 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2571 reflections |
a = 11.5786 (18) Å | θ = 2.6–27.5° |
b = 5.0624 (8) Å | µ = 0.13 mm−1 |
c = 16.259 (3) Å | T = 296 K |
β = 107.542 (2)° | Block, colorless |
V = 908.7 (3) Å3 | 0.30 × 0.22 × 0.20 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1773 independent reflections |
Radiation source: fine-focus sealed tube | 1404 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −14→12 |
Tmin = 0.921, Tmax = 0.975 | k = −6→6 |
6640 measured reflections | l = −20→20 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-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 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C20H14F4N4O2 | V = 908.7 (3) Å3 |
Mr = 418.35 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.5786 (18) Å | µ = 0.13 mm−1 |
b = 5.0624 (8) Å | T = 296 K |
c = 16.259 (3) Å | 0.30 × 0.22 × 0.20 mm |
β = 107.542 (2)° |
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 = 0.975 | Rint = 0.030 |
6640 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.29 e Å−3 |
1773 reflections | Δρmin = −0.21 e Å−3 |
136 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 | ||
C1 | −0.01866 (18) | 0.7509 (4) | 0.42095 (12) | 0.0526 (5) | |
H1 | 0.0435 | 0.6357 | 0.4485 | 0.063* | |
C2 | 0.00636 (15) | 0.9465 (3) | 0.36923 (10) | 0.0407 (4) | |
C3 | −0.08646 (18) | 1.1198 (4) | 0.32969 (13) | 0.0565 (5) | |
H3 | −0.0737 | 1.2565 | 0.2952 | 0.068* | |
C4 | −0.19833 (19) | 1.0860 (5) | 0.34242 (16) | 0.0711 (6) | |
H4 | −0.2624 | 1.1986 | 0.3163 | 0.085* | |
C5 | −0.21302 (19) | 0.8842 (5) | 0.39409 (15) | 0.0679 (6) | |
H5 | −0.2888 | 0.8628 | 0.4018 | 0.081* | |
C6 | 0.12896 (15) | 0.9802 (3) | 0.35843 (9) | 0.0398 (4) | |
C7 | 0.31486 (16) | 0.7658 (4) | 0.35275 (12) | 0.0500 (5) | |
H7A | 0.3118 | 0.8649 | 0.3011 | 0.060* | |
H7B | 0.3386 | 0.5863 | 0.3446 | 0.060* | |
C8 | 0.40972 (14) | 0.8866 (3) | 0.42843 (10) | 0.0416 (4) | |
C9 | 0.48355 (15) | 1.0911 (4) | 0.41885 (10) | 0.0436 (4) | |
C10 | 0.57003 (15) | 1.2033 (3) | 0.48758 (11) | 0.0440 (4) | |
F1 | 0.47180 (10) | 1.1882 (3) | 0.33916 (7) | 0.0647 (4) | |
F2 | 0.63628 (10) | 1.4047 (2) | 0.47259 (7) | 0.0634 (3) | |
N1 | −0.12611 (16) | 0.7170 (4) | 0.43392 (13) | 0.0666 (5) | |
N2 | 0.19512 (12) | 0.7617 (3) | 0.36334 (9) | 0.0446 (4) | |
H2 | 0.1656 | 0.6133 | 0.3731 | 0.053* | |
O1 | 0.16693 (12) | 1.1983 (2) | 0.34513 (8) | 0.0538 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0505 (10) | 0.0499 (11) | 0.0591 (11) | 0.0030 (8) | 0.0188 (8) | 0.0070 (8) |
C2 | 0.0428 (9) | 0.0354 (8) | 0.0418 (8) | −0.0019 (7) | 0.0094 (7) | −0.0051 (6) |
C3 | 0.0541 (11) | 0.0443 (10) | 0.0677 (12) | 0.0037 (8) | 0.0131 (9) | 0.0066 (9) |
C4 | 0.0484 (12) | 0.0623 (13) | 0.0976 (17) | 0.0137 (10) | 0.0143 (11) | 0.0004 (12) |
C5 | 0.0520 (12) | 0.0644 (13) | 0.0943 (16) | −0.0019 (10) | 0.0327 (11) | −0.0092 (12) |
C6 | 0.0469 (9) | 0.0346 (8) | 0.0353 (7) | −0.0031 (7) | 0.0086 (6) | −0.0022 (6) |
C7 | 0.0452 (10) | 0.0524 (11) | 0.0525 (10) | 0.0013 (8) | 0.0150 (8) | −0.0106 (8) |
C8 | 0.0352 (8) | 0.0440 (9) | 0.0468 (9) | 0.0046 (7) | 0.0142 (7) | −0.0024 (7) |
C9 | 0.0415 (9) | 0.0486 (10) | 0.0434 (8) | 0.0060 (7) | 0.0172 (7) | 0.0066 (7) |
C10 | 0.0384 (9) | 0.0434 (9) | 0.0538 (10) | −0.0004 (7) | 0.0194 (7) | 0.0039 (7) |
F1 | 0.0635 (7) | 0.0837 (9) | 0.0476 (6) | −0.0021 (6) | 0.0176 (5) | 0.0156 (5) |
F2 | 0.0598 (7) | 0.0565 (7) | 0.0756 (7) | −0.0147 (5) | 0.0228 (5) | 0.0111 (5) |
N1 | 0.0610 (11) | 0.0634 (11) | 0.0858 (12) | −0.0028 (9) | 0.0378 (9) | 0.0053 (9) |
N2 | 0.0395 (8) | 0.0359 (8) | 0.0553 (8) | −0.0033 (6) | 0.0097 (6) | −0.0026 (6) |
O1 | 0.0645 (8) | 0.0373 (7) | 0.0662 (8) | −0.0054 (6) | 0.0298 (6) | 0.0024 (5) |
C1—N1 | 1.334 (3) | C6—N2 | 1.334 (2) |
C1—C2 | 1.385 (3) | C7—N2 | 1.448 (2) |
C1—H1 | 0.9300 | C7—C8 | 1.510 (2) |
C2—C3 | 1.386 (3) | C7—H7A | 0.9700 |
C2—C6 | 1.492 (2) | C7—H7B | 0.9700 |
C3—C4 | 1.383 (3) | C8—C9 | 1.381 (2) |
C3—H3 | 0.9300 | C8—C10i | 1.391 (2) |
C4—C5 | 1.366 (3) | C9—F1 | 1.3536 (19) |
C4—H4 | 0.9300 | C9—C10 | 1.378 (2) |
C5—N1 | 1.325 (3) | C10—F2 | 1.3416 (19) |
C5—H5 | 0.9300 | C10—C8i | 1.391 (2) |
C6—O1 | 1.231 (2) | N2—H2 | 0.8600 |
N1—C1—C2 | 124.32 (18) | N2—C7—H7A | 108.9 |
N1—C1—H1 | 117.8 | C8—C7—H7A | 108.9 |
C2—C1—H1 | 117.8 | N2—C7—H7B | 108.9 |
C1—C2—C3 | 117.34 (17) | C8—C7—H7B | 108.9 |
C1—C2—C6 | 122.26 (15) | H7A—C7—H7B | 107.7 |
C3—C2—C6 | 120.35 (16) | C9—C8—C10i | 115.43 (15) |
C4—C3—C2 | 118.86 (19) | C9—C8—C7 | 122.33 (15) |
C4—C3—H3 | 120.6 | C10i—C8—C7 | 122.23 (16) |
C2—C3—H3 | 120.6 | F1—C9—C10 | 117.73 (15) |
C5—C4—C3 | 118.7 (2) | F1—C9—C8 | 119.54 (15) |
C5—C4—H4 | 120.6 | C10—C9—C8 | 122.73 (15) |
C3—C4—H4 | 120.6 | F2—C10—C9 | 118.78 (15) |
N1—C5—C4 | 124.17 (19) | F2—C10—C8i | 119.39 (15) |
N1—C5—H5 | 117.9 | C9—C10—C8i | 121.83 (15) |
C4—C5—H5 | 117.9 | C5—N1—C1 | 116.57 (18) |
O1—C6—N2 | 121.66 (15) | C6—N2—C7 | 122.31 (15) |
O1—C6—C2 | 121.73 (15) | C6—N2—H2 | 118.8 |
N2—C6—C2 | 116.61 (14) | C7—N2—H2 | 118.8 |
N2—C7—C8 | 113.35 (14) | ||
N1—C1—C2—C3 | 1.0 (3) | C7—C8—C9—F1 | −0.2 (2) |
N1—C1—C2—C6 | 178.54 (17) | C10i—C8—C9—C10 | −1.2 (3) |
C1—C2—C3—C4 | −1.2 (3) | C7—C8—C9—C10 | 179.73 (16) |
C6—C2—C3—C4 | −178.74 (17) | F1—C9—C10—F2 | 1.2 (2) |
C2—C3—C4—C5 | 0.5 (3) | C8—C9—C10—F2 | −178.75 (15) |
C3—C4—C5—N1 | 0.4 (4) | F1—C9—C10—C8i | −178.73 (15) |
C1—C2—C6—O1 | −149.22 (17) | C8—C9—C10—C8i | 1.3 (3) |
C3—C2—C6—O1 | 28.2 (2) | C4—C5—N1—C1 | −0.6 (3) |
C1—C2—C6—N2 | 31.2 (2) | C2—C1—N1—C5 | −0.1 (3) |
C3—C2—C6—N2 | −151.37 (16) | O1—C6—N2—C7 | −0.5 (2) |
N2—C7—C8—C9 | −126.32 (18) | C2—C6—N2—C7 | 179.06 (14) |
N2—C7—C8—C10i | 54.7 (2) | C8—C7—N2—C6 | 72.3 (2) |
C10i—C8—C9—F1 | 178.81 (14) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1ii | 0.86 | 2.15 | 2.8761 (19) | 142 |
C1—H1···N1iii | 0.93 | 2.58 | 3.407 (3) | 148 |
C7—H7A···O1iv | 0.97 | 2.60 | 3.305 (3) | 129 |
Symmetry codes: (ii) x, y−1, z; (iii) −x, −y+1, −z+1; (iv) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C20H14F4N4O2 |
Mr | 418.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 11.5786 (18), 5.0624 (8), 16.259 (3) |
β (°) | 107.542 (2) |
V (Å3) | 908.7 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.30 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.921, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6640, 1773, 1404 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.114, 1.07 |
No. of reflections | 1773 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.21 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.86 | 2.15 | 2.8761 (19) | 141.8 |
C1—H1···N1ii | 0.93 | 2.58 | 3.407 (3) | 148.0 |
C7—H7A···O1iii | 0.97 | 2.60 | 3.305 (3) | 129.4 |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1; (iii) −x+1/2, y−1/2, −z+1/2. |
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).