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The crystal structures of N,N'-(1,2-phenylene)bis(pyridine-2-carboxamide), C18H14N4O2, (I), and N,N'-(1,2-cyclohexanediyl)bis(pyridine-2-carboxamide) have been determined, the latter compound as the toluene hemisolvate, C18H20N4O2·0.5C7H8, (II). In (I), the benzene ring is nearly coplanar with one of the pyridine rings and forms a dihedral angle of 59.4 (1)° with the other. However, in (II), the dihedral angle of the two pyridine rings is 70.0 (1)°.
Supporting information
CCDC references: 160000; 160001
Compounds (I) and (II) were synthesized by the reaction of pyridine-2-carboxylic
acid and 2-phenylenediamine (or 1,2-cyclohexanediamine) in the ratio of 2:1 in
the presence of triphenyl phosphite in pyridine at 373 K for 2 h (Leung et
al., 1991). Crystals suitable for X-ray structure analysis were obtained
by slow evaporation of the compounds from toluene at room temperature.
For both compounds (I) and (II), H atoms were placed in calculated positions and
refined with fixed isotropic displacement parameters (N—H 0.8600 and C—H
0.9300 Å - OK?). However, the H atoms of the toluene molecule in (II) were
not located, because of disorder.
Data collection: please provide details for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: please provide details for (I); CAD-4 Software for (II). Data reduction: please provide details for (I); CAD-4 Software for (II). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for (I); SHELXTL (Sheldrick, 1997b) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a) for (I); SHELXTL for (II). Molecular graphics: please provide details for (I); SHELXTL for (II). Software used to prepare material for publication: please provide details for (I); SHELXTL for (II).
(I)
N,
N'-(1,2-phenylene)bis(pyridine-2-carboxamide)
top
Crystal data top
C18H14N4O2 | F(000) = 664 |
Mr = 318.33 | Dx = 1.368 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.346 (2) Å | Cell parameters from 30 reflections |
b = 5.567 (1) Å | θ = 4.9–12.4° |
c = 22.578 (6) Å | µ = 0.09 mm−1 |
β = 95.20 (1)° | T = 293 K |
V = 1545.4 (6) Å3 | Block, colourless |
Z = 4 | 0.5 × 0.2 × 0.2 mm |
Data collection top
Bruker P4 diffractometer | Rint = 0.078 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.8° |
Graphite monochromator | h = −1→14 |
2θ/ω scans | k = −1→6 |
3821 measured reflections | l = −26→26 |
2726 independent reflections | 3 standard reflections every 97 reflections |
1624 reflections with I > 2σ(I) | intensity decay: 5.4% |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.282P] where P = (Fo2 + 2Fc2)/3 |
2726 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C18H14N4O2 | V = 1545.4 (6) Å3 |
Mr = 318.33 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.346 (2) Å | µ = 0.09 mm−1 |
b = 5.567 (1) Å | T = 293 K |
c = 22.578 (6) Å | 0.5 × 0.2 × 0.2 mm |
β = 95.20 (1)° | |
Data collection top
Bruker P4 diffractometer | Rint = 0.078 |
3821 measured reflections | 3 standard reflections every 97 reflections |
2726 independent reflections | intensity decay: 5.4% |
1624 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.16 e Å−3 |
2726 reflections | Δρmin = −0.16 e Å−3 |
217 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.1424 (2) | 0.9104 (5) | 0.4184 (1) | 0.0663 (7) | |
N2 | 0.2666 (2) | 0.5723 (4) | 0.37461 (9) | 0.0519 (6) | |
H2B | 0.2668 | 0.6217 | 0.4107 | 0.062* | |
N3 | 0.3395 (2) | 0.2482 (4) | 0.46983 (8) | 0.0475 (6) | |
H3B | 0.3125 | 0.1202 | 0.4839 | 0.057* | |
N4 | 0.2551 (2) | 0.1948 (4) | 0.57402 (9) | 0.0573 (6) | |
O1 | 0.1829 (2) | 0.6341 (5) | 0.28131 (8) | 0.0814 (7) | |
O2 | 0.3731 (2) | 0.6428 (4) | 0.49015 (7) | 0.0623 (6) | |
C1 | 0.0860 (3) | 1.0908 (7) | 0.4398 (2) | 0.081 (1) | |
H1A | 0.0922 | 1.1138 | 0.4808 | 0.097* | |
C2 | 0.0195 (3) | 1.2442 (7) | 0.4057 (2) | 0.084 (1) | |
H2A | −0.0177 | 1.3673 | 0.4229 | 0.100* | |
C3 | 0.0095 (3) | 1.2105 (7) | 0.3454 (2) | 0.087 (1) | |
H3A | −0.0347 | 1.3106 | 0.3207 | 0.104* | |
C4 | 0.0660 (3) | 1.0265 (6) | 0.3222 (1) | 0.073 (1) | |
H4A | 0.0598 | 0.9995 | 0.2814 | 0.087* | |
C5 | 0.1315 (2) | 0.8821 (5) | 0.3592 (1) | 0.0527 (7) | |
C6 | 0.1961 (2) | 0.6858 (6) | 0.3344 (1) | 0.0545 (7) | |
C7 | 0.3394 (2) | 0.3848 (5) | 0.3652 (1) | 0.0448 (6) | |
C8 | 0.3767 (2) | 0.3474 (6) | 0.3095 (1) | 0.0550 (7) | |
H8A | 0.3565 | 0.4534 | 0.2787 | 0.066* | |
C9 | 0.4429 (2) | 0.1564 (6) | 0.2997 (1) | 0.0603 (8) | |
H9A | 0.4654 | 0.1323 | 0.2619 | 0.072* | |
C10 | 0.4764 (2) | −0.0002 (5) | 0.3449 (1) | 0.0599 (8) | |
H10A | 0.5206 | −0.1305 | 0.3378 | 0.072* | |
C11 | 0.4431 (2) | 0.0398 (5) | 0.4010 (1) | 0.0511 (7) | |
H11A | 0.4664 | −0.0629 | 0.4321 | 0.061* | |
C12 | 0.3756 (2) | 0.2309 (5) | 0.41148 (9) | 0.0436 (6) | |
C13 | 0.3435 (2) | 0.4438 (5) | 0.5048 (1) | 0.0453 (6) | |
C14 | 0.3034 (2) | 0.4023 (5) | 0.5653 (1) | 0.0420 (6) | |
C15 | 0.3183 (2) | 0.5781 (5) | 0.6078 (1) | 0.0596 (8) | |
H15A | 0.3527 | 0.7214 | 0.5997 | 0.072* | |
C16 | 0.2813 (3) | 0.5383 (6) | 0.6628 (1) | 0.0655 (9) | |
H16A | 0.2915 | 0.6528 | 0.6928 | 0.079* | |
C17 | 0.2296 (2) | 0.3282 (6) | 0.6722 (1) | 0.0605 (8) | |
H17A | 0.2024 | 0.2979 | 0.7086 | 0.073* | |
C18 | 0.2181 (3) | 0.1619 (6) | 0.6275 (1) | 0.0676 (9) | |
H18A | 0.1828 | 0.0185 | 0.6346 | 0.081* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.052 (1) | 0.093 (2) | 0.053 (1) | −0.002 (2) | −0.002 (1) | −0.013 (1) |
N2 | 0.055 (1) | 0.071 (2) | 0.029 (1) | −0.006 (1) | −0.001 (1) | 0.001 (1) |
N3 | 0.054 (1) | 0.057 (1) | 0.032 (1) | −0.016 (1) | 0.0063 (9) | 0.002 (1) |
N4 | 0.069 (2) | 0.060 (2) | 0.046 (1) | −0.016 (1) | 0.016 (1) | 0.001 (1) |
O1 | 0.089 (2) | 0.116 (2) | 0.037 (1) | 0.016 (2) | −0.008 (1) | −0.002 (1) |
O2 | 0.087 (1) | 0.062 (1) | 0.037 (1) | −0.028 (1) | 0.0030 (9) | 0.0041 (9) |
C1 | 0.055 (2) | 0.116 (3) | 0.072 (2) | −0.005 (2) | 0.000 (2) | −0.030 (2) |
C2 | 0.050 (2) | 0.087 (3) | 0.113 (3) | 0.004 (2) | 0.005 (2) | −0.017 (2) |
C3 | 0.069 (2) | 0.098 (3) | 0.095 (3) | 0.010 (2) | 0.010 (2) | 0.026 (2) |
C4 | 0.064 (2) | 0.094 (3) | 0.060 (2) | 0.007 (2) | 0.009 (2) | 0.017 (2) |
C5 | 0.043 (1) | 0.068 (2) | 0.047 (2) | −0.010 (2) | 0.001 (1) | 0.004 (2) |
C6 | 0.054 (2) | 0.073 (2) | 0.036 (1) | −0.011 (2) | 0.000 (1) | 0.004 (1) |
C7 | 0.046 (1) | 0.054 (2) | 0.034 (1) | −0.011 (1) | 0.003 (1) | −0.001 (1) |
C8 | 0.061 (2) | 0.071 (2) | 0.033 (1) | −0.009 (2) | 0.004 (1) | 0.004 (2) |
C9 | 0.067 (2) | 0.079 (2) | 0.036 (1) | −0.006 (2) | 0.012 (1) | −0.006 (2) |
C10 | 0.064 (2) | 0.066 (2) | 0.051 (2) | −0.005 (2) | 0.013 (1) | −0.009 (2) |
C11 | 0.055 (2) | 0.054 (2) | 0.044 (2) | −0.012 (2) | 0.006 (1) | 0.004 (1) |
C12 | 0.048 (1) | 0.055 (2) | 0.029 (1) | −0.017 (1) | 0.005 (1) | −0.001 (1) |
C13 | 0.049 (2) | 0.052 (2) | 0.034 (1) | −0.012 (1) | −0.004 (1) | 0.003 (1) |
C14 | 0.045 (1) | 0.048 (2) | 0.032 (1) | −0.005 (1) | 0.001 (1) | 0.004 (1) |
C15 | 0.078 (2) | 0.058 (2) | 0.043 (2) | −0.017 (2) | 0.003 (1) | −0.004 (1) |
C16 | 0.087 (2) | 0.075 (2) | 0.035 (2) | −0.001 (2) | 0.007 (2) | −0.006 (2) |
C17 | 0.065 (2) | 0.081 (2) | 0.038 (1) | 0.011 (2) | 0.016 (1) | 0.009 (2) |
C18 | 0.079 (2) | 0.073 (2) | 0.053 (2) | −0.012 (2) | 0.023 (2) | 0.009 (2) |
Geometric parameters (Å, º) top
N1—C1 | 1.338 (4) | C5—C6 | 1.491 (4) |
N1—C5 | 1.340 (3) | C7—C12 | 1.394 (3) |
N2—C6 | 1.356 (3) | C7—C8 | 1.393 (3) |
N2—C7 | 1.406 (3) | C8—C9 | 1.372 (4) |
N2—H2B | 0.8600 | C8—H8A | 0.9300 |
N3—C13 | 1.343 (3) | C9—C10 | 1.377 (4) |
N3—C12 | 1.432 (3) | C9—H9A | 0.9300 |
N3—H3B | 0.8600 | C10—C11 | 1.386 (4) |
N4—C14 | 1.324 (3) | C10—H10A | 0.9300 |
N4—C18 | 1.342 (3) | C11—C12 | 1.384 (4) |
O1—C6 | 1.229 (3) | C11—H11A | 0.9300 |
O2—C13 | 1.222 (3) | C13—C14 | 1.512 (3) |
C1—C2 | 1.373 (5) | C14—C15 | 1.371 (3) |
C1—H1A | 0.9300 | C15—C16 | 1.381 (4) |
C2—C3 | 1.368 (4) | C15—H15A | 0.9300 |
C2—H2A | 0.9300 | C16—C17 | 1.358 (4) |
C3—C4 | 1.370 (5) | C16—H16A | 0.9300 |
C3—H3A | 0.9300 | C17—C18 | 1.368 (4) |
C4—C5 | 1.370 (4) | C17—H17A | 0.9300 |
C4—H4A | 0.9300 | C18—H18A | 0.9300 |
| | | |
C1—N1—C5 | 116.2 (3) | C7—C8—H8A | 119.6 |
C6—N2—C7 | 128.7 (2) | C8—C9—C10 | 120.9 (2) |
C6—N2—H2B | 115.7 | C8—C9—H9A | 119.5 |
C7—N2—H2B | 115.7 | C10—C9—H9A | 119.5 |
C13—N3—C12 | 126.7 (2) | C9—C10—C11 | 118.8 (3) |
C13—N3—H3B | 116.7 | C9—C10—H10A | 120.6 |
C12—N3—H3B | 116.7 | C11—C10—H10A | 120.6 |
C14—N4—C18 | 116.6 (2) | C12—C11—C10 | 120.8 (3) |
N1—C1—C2 | 124.6 (3) | C12—C11—H11A | 119.6 |
N1—C1—H1A | 117.7 | C10—C11—H11A | 119.6 |
C2—C1—H1A | 117.7 | C11—C12—C7 | 120.1 (2) |
C3—C2—C1 | 118.0 (3) | C11—C12—N3 | 116.8 (2) |
C3—C2—H2A | 121.0 | C7—C12—N3 | 122.9 (2) |
C1—C2—H2A | 121.0 | O2—C13—N3 | 124.9 (2) |
C4—C3—C2 | 118.7 (3) | O2—C13—C14 | 120.9 (2) |
C4—C3—H3A | 120.6 | N3—C13—C14 | 114.2 (2) |
C2—C3—H3A | 120.6 | N4—C14—C15 | 123.5 (2) |
C3—C4—C5 | 119.9 (3) | N4—C14—C13 | 117.2 (2) |
C3—C4—H4A | 120.1 | C15—C14—C13 | 119.3 (2) |
C5—C4—H4A | 120.1 | C14—C15—C16 | 118.8 (3) |
N1—C5—C4 | 122.7 (3) | C14—C15—H15A | 120.6 |
N1—C5—C6 | 116.9 (2) | C16—C15—H15A | 120.6 |
C4—C5—C6 | 120.4 (3) | C17—C16—C15 | 118.5 (3) |
O1—C6—N2 | 124.4 (3) | C17—C16—H16A | 120.7 |
O1—C6—C5 | 120.7 (3) | C15—C16—H16A | 120.7 |
N2—C6—C5 | 115.0 (2) | C16—C17—C18 | 119.1 (3) |
C12—C7—C8 | 118.3 (3) | C16—C17—H17A | 120.4 |
C12—C7—N2 | 120.6 (2) | C18—C17—H17A | 120.4 |
C8—C7—N2 | 121.0 (2) | N4—C18—C17 | 123.4 (3) |
C9—C8—C7 | 120.9 (3) | N4—C18—H18A | 118.3 |
C9—C8—H8A | 119.6 | C17—C18—H18A | 118.3 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2 | 0.86 | 2.13 | 2.840 (3) | 140 |
N2—H2B···N1 | 0.86 | 2.24 | 2.673 (4) | 111 |
N3—H3B···N4 | 0.86 | 2.25 | 2.674 (3) | 110 |
C8—H8A···O1 | 0.93 | 2.37 | 2.898 (4) | 116 |
C11—H11A···O2i | 0.93 | 2.45 | 3.161 (3) | 133 |
Symmetry code: (i) x, y−1, z. |
(II)
N,
N'-(1,2-cyclohexanediyl)bis(pyridine-2-carboxamide)
top
Crystal data top
C18H20N4O2·0.5C7H8 | Z = 2 |
Mr = 370.45 | F(000) = 394 |
Triclinic, P1 | Dx = 1.217 Mg m−3 |
a = 9.899 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.492 (2) Å | Cell parameters from 25 reflections |
c = 10.795 (2) Å | θ = 2.4–15.6° |
α = 88.52 (3)° | µ = 0.08 mm−1 |
β = 64.39 (3)° | T = 293 K |
γ = 89.70 (3)° | Block, colourless |
V = 1010.7 (4) Å3 | 0.30 × 0.26 × 0.24 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.007 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.9° |
Graphite monochromator | h = 0→11 |
2θ/ω scans | k = −12→12 |
3764 measured reflections | l = −11→12 |
3539 independent reflections | 3 standard reflections every 97 reflections |
2552 reflections with I > 2σ(I) | intensity decay: 4.2% |
Refinement top
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.173 | w = 1/[σ2(Fo2) + (0.0904P)2 + 0.3004P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.006 |
3539 reflections | Δρmax = 0.27 e Å−3 |
263 parameters | Δρmin = −0.16 e Å−3 |
10 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.046 (4) |
Crystal data top
C18H20N4O2·0.5C7H8 | γ = 89.70 (3)° |
Mr = 370.45 | V = 1010.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.899 (2) Å | Mo Kα radiation |
b = 10.492 (2) Å | µ = 0.08 mm−1 |
c = 10.795 (2) Å | T = 293 K |
α = 88.52 (3)° | 0.30 × 0.26 × 0.24 mm |
β = 64.39 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.007 |
3764 measured reflections | 3 standard reflections every 97 reflections |
3539 independent reflections | intensity decay: 4.2% |
2552 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 10 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
3539 reflections | Δρmin = −0.16 e Å−3 |
263 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.6317 (2) | 0.1930 (2) | 0.5341 (2) | 0.0804 (6) | |
H1A | 0.7265 | 0.2096 | 0.5284 | 0.096* | |
C2 | 0.6149 (2) | 0.1927 (2) | 0.4146 (2) | 0.0865 (7) | |
H2A | 0.6967 | 0.2067 | 0.3301 | 0.104* | |
C3 | 0.4756 (2) | 0.1714 (3) | 0.4223 (2) | 0.0929 (7) | |
H3A | 0.4606 | 0.1708 | 0.3430 | 0.111* | |
C4 | 0.3578 (2) | 0.1509 (2) | 0.5493 (2) | 0.0768 (6) | |
H4A | 0.2615 | 0.1378 | 0.5573 | 0.092* | |
C5 | 0.3843 (1) | 0.1499 (1) | 0.6640 (1) | 0.0514 (4) | |
C6 | 0.2569 (1) | 0.1259 (1) | 0.8040 (1) | 0.0502 (4) | |
C7 | 0.1855 (1) | 0.1024 (1) | 1.0507 (1) | 0.0462 (3) | |
H7A | 0.0884 | 0.0808 | 1.0525 | 0.055* | |
C8 | 0.1686 (2) | 0.2269 (2) | 1.1246 (2) | 0.0614 (4) | |
H8A | 0.2661 | 0.2550 | 1.1143 | 0.074* | |
H8B | 0.1302 | 0.2916 | 1.0826 | 0.074* | |
C9 | 0.0642 (2) | 0.2129 (2) | 1.2753 (2) | 0.0762 (6) | |
H9A | 0.0570 | 0.2934 | 1.3198 | 0.091* | |
H9B | −0.0351 | 0.1892 | 1.2865 | 0.091* | |
C10 | 0.1228 (2) | 0.1118 (2) | 1.3408 (2) | 0.0783 (6) | |
H10A | 0.0563 | 0.1036 | 1.4380 | 0.094* | |
H10B | 0.2209 | 0.1372 | 1.3316 | 0.094* | |
C11 | 0.1345 (2) | −0.0170 (2) | 1.2734 (1) | 0.0643 (4) | |
H11A | 0.1769 | −0.0791 | 1.3144 | 0.077* | |
H11B | 0.0350 | −0.0463 | 1.2906 | 0.077* | |
C12 | 0.2318 (1) | −0.0079 (1) | 1.1189 (1) | 0.0474 (3) | |
H12A | 0.3357 | 0.0066 | 1.1033 | 0.057* | |
C13 | 0.3371 (1) | −0.2087 (2) | 1.0052 (1) | 0.0514 (4) | |
C14 | 0.3090 (2) | −0.3245 (1) | 0.9399 (1) | 0.0510 (4) | |
C15 | 0.4148 (2) | −0.4191 (2) | 0.8960 (2) | 0.0722 (5) | |
H15A | 0.5031 | −0.4119 | 0.9060 | 0.087* | |
C16 | 0.3872 (2) | −0.5250 (2) | 0.8366 (2) | 0.0859 (6) | |
H16A | 0.4563 | −0.5909 | 0.8069 | 0.103* | |
C17 | 0.2575 (2) | −0.5313 (2) | 0.8222 (2) | 0.0792 (6) | |
H17A | 0.2366 | −0.6013 | 0.7822 | 0.095* | |
C18 | 0.1585 (2) | −0.4327 (2) | 0.8676 (2) | 0.0733 (5) | |
H18A | 0.0707 | −0.4374 | 0.8564 | 0.088* | |
N1 | 0.2255 (1) | −0.1265 (1) | 1.0545 (1) | 0.0525 (3) | |
H1B | 0.1440 | −0.1443 | 1.0481 | 0.063* | |
N2 | 0.2941 (1) | 0.1181 (1) | 0.9076 (1) | 0.0486 (3) | |
H2B | 0.3875 | 0.1226 | 0.8896 | 0.058* | |
N3 | 0.5197 (1) | 0.1708 (1) | 0.6584 (1) | 0.0640 (4) | |
N4 | 0.1808 (1) | −0.3302 (1) | 0.9272 (1) | 0.0607 (4) | |
O1 | 0.4577 (1) | −0.1952 (1) | 1.0105 (1) | 0.0872 (4) | |
O2 | 0.1275 (1) | 0.1167 (2) | 0.8161 (1) | 0.0838 (4) | |
C19 | 0.0952 (3) | −0.5506 (3) | 1.5290 (3) | 0.141 (1) | |
C20 | 0.1656 (5) | −0.4203 (4) | 1.3235 (4) | 0.190 (2) | |
C21 | 0.1998 (7) | −0.4994 (6) | 1.4153 (6) | 0.152 (3) | 0.50 |
C22 | −0.0553 (5) | −0.5336 (4) | 1.5667 (5) | 0.111 (2) | 0.50 |
C23 | 0.0158 (6) | −0.3901 (6) | 1.3510 (6) | 0.127 (2) | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0531 (8) | 0.122 (2) | 0.0588 (9) | −0.0183 (9) | −0.0174 (7) | 0.0099 (9) |
C2 | 0.0641 (9) | 0.131 (2) | 0.0513 (9) | −0.014 (1) | −0.0136 (8) | 0.018 (1) |
C3 | 0.076 (1) | 0.154 (2) | 0.0521 (8) | −0.012 (1) | −0.0317 (7) | 0.014 (1) |
C4 | 0.0575 (8) | 0.123 (2) | 0.0535 (8) | −0.0112 (9) | −0.0273 (6) | 0.0087 (9) |
C5 | 0.0486 (6) | 0.0579 (8) | 0.0475 (6) | −0.0027 (6) | −0.0205 (5) | −0.0015 (6) |
C6 | 0.0444 (6) | 0.0584 (8) | 0.0495 (7) | −0.0040 (6) | −0.0216 (5) | −0.0040 (6) |
C7 | 0.0343 (5) | 0.0610 (8) | 0.0427 (6) | 0.0003 (5) | −0.0160 (5) | −0.0039 (6) |
C8 | 0.0568 (7) | 0.0574 (9) | 0.0610 (8) | 0.0074 (7) | −0.0168 (6) | −0.0083 (7) |
C9 | 0.0687 (9) | 0.085 (1) | 0.0610 (9) | 0.0037 (9) | −0.0139 (8) | −0.0223 (8) |
C10 | 0.0800 (9) | 0.108 (1) | 0.0448 (7) | −0.021 (1) | −0.0245 (7) | −0.0128 (8) |
C11 | 0.0690 (8) | 0.082 (1) | 0.0475 (7) | −0.0127 (8) | −0.0303 (6) | 0.0061 (7) |
C12 | 0.0412 (5) | 0.0557 (8) | 0.0493 (6) | −0.0036 (6) | −0.0232 (5) | −0.0031 (6) |
C13 | 0.0417 (6) | 0.0596 (8) | 0.0524 (7) | −0.0020 (6) | −0.0198 (5) | 0.0010 (6) |
C14 | 0.0487 (6) | 0.0518 (8) | 0.0490 (7) | −0.0022 (6) | −0.0181 (5) | 0.0055 (6) |
C15 | 0.0611 (8) | 0.063 (1) | 0.096 (1) | 0.0067 (7) | −0.0375 (7) | −0.0065 (8) |
C16 | 0.082 (1) | 0.058 (1) | 0.117 (1) | 0.0158 (8) | −0.041 (1) | −0.0170 (9) |
C17 | 0.091 (1) | 0.0543 (9) | 0.101 (1) | 0.0019 (8) | −0.0489 (9) | −0.0126 (8) |
C18 | 0.0756 (8) | 0.060 (1) | 0.098 (1) | −0.0003 (8) | −0.0499 (8) | −0.0095 (8) |
N1 | 0.0441 (5) | 0.0564 (7) | 0.0628 (6) | −0.0033 (5) | −0.0283 (4) | −0.0040 (5) |
N2 | 0.0352 (5) | 0.0642 (7) | 0.0449 (5) | −0.0019 (5) | −0.0158 (4) | −0.0008 (5) |
N3 | 0.0503 (6) | 0.0889 (9) | 0.0497 (6) | −0.0099 (6) | −0.0187 (5) | 0.0008 (6) |
N4 | 0.0577 (6) | 0.0562 (7) | 0.0740 (7) | 0.0003 (5) | −0.0336 (5) | −0.0070 (6) |
O1 | 0.0525 (5) | 0.0950 (9) | 0.1252 (9) | 0.0130 (6) | −0.0472 (5) | −0.0385 (7) |
O2 | 0.0470 (5) | 0.158 (1) | 0.0567 (6) | −0.0147 (6) | −0.0262 (4) | 0.0002 (7) |
C19 | 0.159 (2) | 0.129 (2) | 0.151 (2) | 0.017 (2) | −0.080 (2) | −0.065 (2) |
C20 | 0.239 (4) | 0.152 (3) | 0.167 (3) | −0.036 (3) | −0.077 (3) | 0.001 (3) |
C21 | 0.146 (5) | 0.152 (5) | 0.138 (5) | −0.036 (4) | −0.041 (4) | −0.024 (4) |
C22 | 0.141 (3) | 0.085 (2) | 0.068 (2) | −0.031 (3) | −0.007 (2) | −0.028 (2) |
C23 | 0.152 (4) | 0.108 (4) | 0.115 (4) | −0.034 (3) | −0.053 (3) | −0.011 (3) |
Geometric parameters (Å, º) top
C1—N3 | 1.336 (2) | C14—C15 | 1.375 (2) |
C1—C2 | 1.370 (3) | C15—C16 | 1.383 (3) |
C2—C3 | 1.365 (3) | C16—C17 | 1.361 (3) |
C3—C4 | 1.376 (2) | C17—C18 | 1.368 (3) |
C4—C5 | 1.371 (2) | C18—N4 | 1.335 (2) |
C5—N3 | 1.335 (2) | C19—C21 | 1.319 (5) |
C5—C6 | 1.508 (2) | C19—C22 | 1.376 (5) |
C6—O2 | 1.233 (2) | C19—C23i | 1.417 (6) |
C6—N2 | 1.321 (2) | C19—C22i | 1.519 (7) |
C7—N2 | 1.457 (2) | C20—C22i | 1.299 (5) |
C7—C8 | 1.518 (2) | C20—C23 | 1.417 (6) |
C7—C12 | 1.528 (2) | C20—C21 | 1.425 (7) |
C8—C9 | 1.508 (2) | C21—C22i | 1.401 (8) |
C9—C10 | 1.507 (3) | C22—C20i | 1.299 (5) |
C10—C11 | 1.531 (3) | C22—C23i | 1.358 (8) |
C11—C12 | 1.524 (2) | C22—C21i | 1.401 (8) |
C12—N1 | 1.455 (2) | C22—C19i | 1.519 (7) |
C13—O1 | 1.229 (2) | C22—C22i | 1.538 (9) |
C13—N1 | 1.325 (2) | C23—C22i | 1.358 (8) |
C13—C14 | 1.506 (2) | C23—C19i | 1.417 (6) |
C14—N4 | 1.335 (2) | | |
| | | |
N3—C1—C2 | 123.8 (2) | C5—N3—C1 | 116.9 (2) |
C3—C2—C1 | 118.6 (2) | C14—N4—C18 | 117.0 (1) |
C2—C3—C4 | 118.8 (2) | C21—C19—C22 | 122.6 (5) |
C5—C4—C3 | 119.2 (2) | C21—C19—C23i | 178.0 (5) |
N3—C5—C4 | 122.8 (1) | C22—C19—C23i | 58.1 (3) |
N3—C5—C6 | 117.3 (1) | C21—C19—C22i | 58.6 (4) |
C4—C5—C6 | 119.9 (1) | C22—C19—C22i | 63.9 (3) |
O2—C6—N2 | 124.3 (1) | C23i—C19—C22i | 122.1 (4) |
O2—C6—C5 | 119.9 (1) | C22i—C20—C23 | 59.8 (4) |
N2—C6—C5 | 115.8 (1) | C22i—C20—C21 | 61.7 (4) |
N2—C7—C8 | 110.0 (1) | C23—C20—C21 | 121.5 (4) |
N2—C7—C12 | 109.9 (1) | C19—C21—C22i | 67.8 (4) |
C8—C7—C12 | 112.6 (1) | C19—C21—C20 | 122.5 (5) |
C9—C8—C7 | 111.8 (1) | C22i—C21—C20 | 54.7 (4) |
C10—C9—C8 | 109.4 (1) | C20i—C22—C23i | 64.4 (3) |
C9—C10—C11 | 111.1 (2) | C20i—C22—C19 | 126.8 (5) |
C12—C11—C10 | 111.6 (1) | C23i—C22—C19 | 62.4 (4) |
N1—C12—C11 | 110.6 (1) | C20i—C22—C21i | 63.6 (3) |
N1—C12—C7 | 109.3 (1) | C23i—C22—C21i | 128.0 (4) |
C11—C12—C7 | 112.1 (1) | C19—C22—C21i | 169.5 (5) |
O1—C13—N1 | 124.0 (2) | C20i—C22—C19i | 117.1 (5) |
O1—C13—C14 | 120.1 (1) | C23i—C22—C19i | 178.3 (4) |
N1—C13—C14 | 115.9 (1) | C19—C22—C19i | 116.1 (3) |
N4—C14—C15 | 122.9 (2) | C21i—C22—C19i | 53.5 (3) |
N4—C14—C13 | 117.8 (1) | C20i—C22—C22i | 170.6 (7) |
C15—C14—C13 | 119.3 (2) | C23i—C22—C22i | 125.0 (6) |
C14—C15—C16 | 118.7 (2) | C19—C22—C22i | 62.5 (4) |
C17—C16—C15 | 118.9 (2) | C21i—C22—C22i | 107.0 (6) |
C16—C17—C18 | 118.8 (2) | C19i—C22—C22i | 53.5 (4) |
N4—C18—C17 | 123.7 (2) | C22i—C23—C20 | 55.8 (3) |
C13—N1—C12 | 124.2 (1) | C22i—C23—C19i | 59.4 (3) |
C6—N2—C7 | 123.6 (1) | C20—C23—C19i | 115.2 (5) |
Symmetry code: (i) −x, −y−1, −z+3. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N4 | 0.86 | 2.31 | 2.710 (2) | 108 |
N1—H1B···O2ii | 0.86 | 2.46 | 3.156 (2) | 138 |
N2—H2B···N3 | 0.86 | 2.30 | 2.696 (2) | 108 |
N2—H2B···O1iii | 0.86 | 2.36 | 3.068 (2) | 140 |
C4—H4A···O2 | 0.93 | 2.53 | 2.812 (2) | 98 |
C7—H7A···O2 | 0.98 | 2.43 | 2.828 (2) | 104 |
C8—H8A···O1iii | 0.97 | 2.55 | 3.357 (2) | 140 |
C11—H11B···O2ii | 0.97 | 2.47 | 3.317 (3) | 145 |
C12—H12A···O1 | 0.98 | 2.45 | 2.835 (2) | 103 |
C15—H15A···O1 | 0.93 | 2.51 | 2.799 (3) | 98 |
Symmetry codes: (ii) −x, −y, −z+2; (iii) −x+1, −y, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C18H14N4O2 | C18H20N4O2·0.5C7H8 |
Mr | 318.33 | 370.45 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.346 (2), 5.567 (1), 22.578 (6) | 9.899 (2), 10.492 (2), 10.795 (2) |
α, β, γ (°) | 90, 95.20 (1), 90 | 88.52 (3), 64.39 (3), 89.70 (3) |
V (Å3) | 1545.4 (6) | 1010.7 (4) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.08 |
Crystal size (mm) | 0.5 × 0.2 × 0.2 | 0.30 × 0.26 × 0.24 |
|
Data collection |
Diffractometer | Bruker P4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3821, 2726, 1624 | 3764, 3539, 2552 |
Rint | 0.078 | 0.007 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.139, 1.03 | 0.049, 0.173, 1.06 |
No. of reflections | 2726 | 3539 |
No. of parameters | 217 | 263 |
No. of restraints | 0 | 10 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.16 | 0.27, −0.16 |
Selected geometric parameters (Å, º) for (I) topN1—C1 | 1.338 (4) | N3—C12 | 1.432 (3) |
N1—C5 | 1.340 (3) | N4—C14 | 1.324 (3) |
N2—C6 | 1.356 (3) | N4—C18 | 1.342 (3) |
N2—C7 | 1.406 (3) | O1—C6 | 1.229 (3) |
N3—C13 | 1.343 (3) | O2—C13 | 1.222 (3) |
| | | |
C1—N1—C5 | 116.2 (3) | O1—C6—N2 | 124.4 (3) |
C6—N2—C7 | 128.7 (2) | O1—C6—C5 | 120.7 (3) |
C13—N3—C12 | 126.7 (2) | O2—C13—N3 | 124.9 (2) |
C14—N4—C18 | 116.6 (2) | O2—C13—C14 | 120.9 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2 | 0.86 | 2.13 | 2.840 (3) | 140 |
N2—H2B···N1 | 0.86 | 2.24 | 2.673 (4) | 111 |
N3—H3B···N4 | 0.86 | 2.25 | 2.674 (3) | 110 |
C8—H8A···O1 | 0.93 | 2.37 | 2.898 (4) | 116 |
C11—H11A···O2i | 0.93 | 2.45 | 3.161 (3) | 133 |
Symmetry code: (i) x, y−1, z. |
Selected geometric parameters (Å, º) for (II) topC1—N3 | 1.336 (2) | C12—N1 | 1.455 (2) |
C5—N3 | 1.335 (2) | C13—O1 | 1.229 (2) |
C6—O2 | 1.233 (2) | C13—N1 | 1.325 (2) |
C6—N2 | 1.321 (2) | C14—N4 | 1.335 (2) |
C7—N2 | 1.457 (2) | C18—N4 | 1.335 (2) |
| | | |
O2—C6—N2 | 124.3 (1) | C13—N1—C12 | 124.2 (1) |
O2—C6—C5 | 119.9 (1) | C6—N2—C7 | 123.6 (1) |
O1—C13—N1 | 124.0 (2) | C5—N3—C1 | 116.9 (2) |
O1—C13—C14 | 120.1 (1) | C14—N4—C18 | 117.0 (1) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···N4 | 0.86 | 2.31 | 2.710 (2) | 108 |
N1—H1B···O2i | 0.86 | 2.46 | 3.156 (2) | 138 |
N2—H2B···N3 | 0.86 | 2.30 | 2.696 (2) | 108 |
N2—H2B···O1ii | 0.86 | 2.36 | 3.068 (2) | 140 |
C4—H4A···O2 | 0.93 | 2.53 | 2.812 (2) | 98 |
C7—H7A···O2 | 0.98 | 2.43 | 2.828 (2) | 104 |
C8—H8A···O1ii | 0.97 | 2.55 | 3.357 (2) | 140 |
C11—H11B···O2i | 0.97 | 2.47 | 3.317 (3) | 145 |
C12—H12A···O1 | 0.98 | 2.45 | 2.835 (2) | 103 |
C15—H15A···O1 | 0.93 | 2.51 | 2.799 (3) | 98 |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y, −z+2. |
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Functional mimics of manganese superoxide dismutase (Mn-SOD) are of great potential as therapeutic agents (Riley, 1999), for example, manganese porphyrin derivatives, which show powerful antinflammatory effects due to their multiple scavenging activities (Cuzzocrea et al., 1999), and N-containing macrocyclic manganese complexes, which have high catalytic SOD activity and are chemically and biologically stable in vivo (Salvemini et al., 1999). In the latter case, the introduction of a fused cyclohexane group enhances the kinetic and thermodynamic stabilities of the manganese complexes. Therefore, we designed and synthesized the title compounds, (I) and (II), which each contain two pyridine and two amide moieties. The MnII and MnIII complexes of the title compounds were also synthesized, and preliminary data showed that the MnIII complexes possess potent SOD activity in human blood plasma and platelet. \sch
The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. It is notable that the orientations of the pyridine rings in (I) and (II) are quite different. In compound (I), the N1-pyridine ring is nearly coplanar with the benzene ring, with a dihedral angle of 18.6 (1)°, which may be due to stabilization via an intramolecular C—H···O hydrogen bond between C8 and O1 (see Table 2). The N4-pyridine ring forms a dihedral angle of 59.4 (1)° with the benzene ring. Such an arrangement is similar to that found in N,N'-(4,5-dichloro-o-phenylene)bis(4-tert-butylpyridine-2-carboxamide) (Fun et al., 1999).
In (I), N2–2H acts as a donor in the three-centre (bifurcated) N2—H2B···O2 and N2—H2B···N1 interactions, the former being responsible for the reciprocal orientation of the two oxamide groups that form a dihedral angle of 64.1 (1)°, the latter for the orientation of the O1-carboxamide plane with respect to that of the N1-pyridine, the C4—C5—C6—O1 torsion angle being -7.8 (4)°. The N3—H3B···N4 interaction determines the orientation of the O2-carboxamide plane with respect to that of the N4-pyridine, the N3—C13—C14—N4 and O2—C13—C14—C15 torsion angles being -9.5 (3) and -11.6 (4)°, respectively. The orientation of the two carboxamide-2-pyridine substituents with respect to the benzene plane is defined by the C6—N2—C7—C8 and C13—N3—C12—C11 torsion angles of 23.7 (4) and 130.3 (3)°, respectively. The weak C11—H11A···O2i interaction (Table 2) contributes to the crystal packing [symmetry code: (i) x, y - 1, z].
In compound (II), the two pyridine rings form a dihedral angle of 70.0 (1)° and the cyclohexane ring adopts a chair conformation, with a total puckering amplitude (Cremer & Pople, 1975) QT = 0.559 (2) Å. The two pyridine-2-carboxamide substituents are approximately perpendicular to the cyclohexane ring, the dihedral angles they form with the least-squares plane through cyclohexane being 84.8 (1) and 73.7 (1)° for the N3- and N4-pyridine rings, respectively. The substituents occupy the equatorial position of the cyclohexane ring and adopt a trans conformation, so that the energy of (II) is minimized.
In (II), N1—H1B is involved in two three-centre (bifurcated) interactions. One, N1—H1B···N4, is intramolecular, determining the coplanarity of the N4-pyridine and O1-oxamide [C15—C14—C13—O1 4.9 (2), O1—C13—N1—C12 1.4 (2) and N4—C14—C13—N1 5.2 (2)°]. The other, N1—H1B···O2ii (Table 4), is intermolecular, connecting the molecule to a centrosymmetric one displaced along z [symmetry code: (ii) -x, -y, 2 - z]. Similar behaviour is shown by the N2—H2B group which, with the N2—H2B···N3 interaction, causes coplanarity of the N3-pyridine and O2-oxamide [C4—C5—C6—O2 - 5.4 (2), O2—C6—N2—C7 - 2.4 (2) and N3—C5—C6—N2 - 5.0 (2)°], while the intermolecular N2—H2B···O1iii bond (Table 4) contributes to the crystal packing [symmetry code: (iii) 1 - x, -y, 2 - z]. The weak C4—H4A···O2 and C7—H7A···O2 interactions contribute to the coplanarity of the N3-pyridine with O2-oxamide, which are approximately orthogonal to the cyclohexane ring [C6—N2—C7—C12 129.6 (2)°], and similarly, C12—H12A···O1 and C15—H15A···O1 are responsible for the coplanarity and orthogonality of the N4-pyridine and O1-oxamide system [C13—N1—C12—C11 - 108.1 (2)°]. The weak intermolecular C8—H8A···O1iii and C11—H11B···O2ii interactions (Table 4) contribute to the molecular packing in the crystal. Compound (II) contains a molecule of toluene, disordered over two sites related by centrosymmetry, with occupancy factors of 0.5.
The mean C—N lengths of the pyridine rings are 1.336 (3) and 1.335 (2) Å in (I) and (II), respectively. The amide N—C distances towards the bridging ring [N2—C7 and N3—C12 in (I), and N2—C7 and N1—C12 in (II)] are longer than those towards the pyridine rings [N2—C6 and N3—C13 in (I), and N2—C6 and N1—C13 in (II)] in both compounds. These values are within the normal range expected (Allen et al., 1987).