Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004604/lh6033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004604/lh6033Isup2.hkl |
CCDC reference: 209917
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.006 Å
- R factor = 0.089
- wR factor = 0.181
- Data-to-parameter ratio = 17.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
RINTA_01 Alert C The value of Rint is greater than 0.10 Rint given 0.137
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was synthesized from 2,6-pyridinedicarboxylic acid and 4-toluidine by following a published procedure (Ray et al., 1997). The crystal used for the data collection was obtained by slow evaporation from a dimethylformamide/water saturated solution at room temperature.
The H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding-model approximation. The percentage of observed data, collected by our diffractometer, was only 35% of the unique data available to a θmax of 27.5°. Inclusion of such a high percentage of essentially unobserved data into the structure refinement restricts the precision of the results. The weak data also leads to a high value of Rint of 0.137.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
C21H19N3O2 | F(000) = 728 |
Mr = 345.39 | Dx = 1.251 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2125 reflections |
a = 25.140 (5) Å | θ = 1–27.5° |
b = 8.5779 (17) Å | µ = 0.08 mm−1 |
c = 8.5295 (17) Å | T = 294 K |
β = 94.46 (3)° | Prism, yellow |
V = 1833.8 (6) Å3 | 0.22 × 0.20 × 0.10 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 2084 independent reflections |
Radiation source: fine-focus sealed tube | 734 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.137 |
ϕ and ω scans | θmax = 27.6°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −32→25 |
Tmin = 0.982, Tmax = 0.992 | k = −10→11 |
5712 measured reflections | l = −11→11 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.089 | H-atom parameters constrained |
wR(F2) = 0.181 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2084 reflections | Δρmax = 0.22 e Å−3 |
120 parameters | Δρmin = −0.25 e Å−3 |
C21H19N3O2 | V = 1833.8 (6) Å3 |
Mr = 345.39 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.140 (5) Å | µ = 0.08 mm−1 |
b = 8.5779 (17) Å | T = 294 K |
c = 8.5295 (17) Å | 0.22 × 0.20 × 0.10 mm |
β = 94.46 (3)° |
Bruker CCD area-detector diffractometer | 2084 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 734 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.992 | Rint = 0.137 |
5712 measured reflections |
R[F2 > 2σ(F2)] = 0.089 | 0 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
2084 reflections | Δρmin = −0.25 e Å−3 |
120 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 | ||
O1 | 0.07266 (11) | 0.1728 (3) | −0.0835 (3) | 0.0712 (9) | |
N1 | 0.07286 (11) | −0.0329 (3) | 0.0855 (3) | 0.0479 (8) | |
H1 | 0.0586 | −0.0656 | 0.1678 | 0.058* | |
N2 | 0.0000 | 0.1195 (4) | 0.2500 | 0.0437 (10) | |
C1 | 0.21858 (19) | −0.4737 (6) | −0.1486 (6) | 0.130 (2) | |
H1A | 0.2469 | −0.4873 | −0.0674 | 0.195* | |
H1B | 0.2329 | −0.4325 | −0.2411 | 0.195* | |
H1C | 0.2020 | −0.5725 | −0.1728 | 0.195* | |
C2 | 0.17732 (17) | −0.3609 (6) | −0.0922 (5) | 0.0796 (14) | |
C3 | 0.17786 (18) | −0.2080 (6) | −0.1422 (5) | 0.0873 (15) | |
H3 | 0.2018 | −0.1791 | −0.2148 | 0.105* | |
C4 | 0.14395 (15) | −0.0954 (5) | −0.0882 (4) | 0.0675 (12) | |
H4 | 0.1456 | 0.0071 | −0.1228 | 0.081* | |
C5 | 0.10785 (13) | −0.1386 (4) | 0.0178 (4) | 0.0466 (9) | |
C6 | 0.10708 (15) | −0.2910 (5) | 0.0688 (4) | 0.0638 (11) | |
H6 | 0.0836 | −0.3211 | 0.1421 | 0.077* | |
C7 | 0.14110 (17) | −0.3980 (5) | 0.0112 (5) | 0.0791 (14) | |
H7 | 0.1392 | −0.5009 | 0.0446 | 0.095* | |
C8 | 0.05902 (14) | 0.1121 (4) | 0.0376 (4) | 0.0479 (9) | |
C9 | 0.02741 (13) | 0.2001 (4) | 0.1502 (4) | 0.0426 (9) | |
C10 | 0.02767 (14) | 0.3605 (4) | 0.1440 (4) | 0.0569 (10) | |
H10 | 0.0462 | 0.4126 | 0.0697 | 0.068* | |
C11 | 0.0000 | 0.4418 (6) | 0.2500 | 0.080 (2) | |
H11 | 0.0000 | 0.5503 | 0.2500 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.117 (2) | 0.0570 (17) | 0.0430 (16) | −0.0104 (13) | 0.0277 (16) | 0.0098 (12) |
N1 | 0.068 (2) | 0.0464 (18) | 0.0313 (17) | 0.0017 (14) | 0.0145 (16) | 0.0002 (13) |
N2 | 0.052 (3) | 0.044 (2) | 0.035 (2) | 0.000 | 0.001 (2) | 0.000 |
C1 | 0.104 (4) | 0.175 (5) | 0.111 (5) | 0.053 (4) | 0.003 (4) | −0.065 (4) |
C2 | 0.059 (3) | 0.115 (4) | 0.063 (3) | 0.019 (3) | −0.006 (2) | −0.041 (3) |
C3 | 0.066 (3) | 0.142 (4) | 0.056 (3) | 0.002 (3) | 0.021 (2) | −0.023 (3) |
C4 | 0.055 (3) | 0.095 (3) | 0.054 (3) | 0.001 (2) | 0.018 (2) | 0.007 (2) |
C5 | 0.044 (2) | 0.062 (3) | 0.034 (2) | −0.0009 (17) | 0.0055 (18) | −0.0124 (18) |
C6 | 0.063 (3) | 0.066 (3) | 0.065 (3) | 0.007 (2) | 0.023 (2) | −0.002 (2) |
C7 | 0.083 (4) | 0.073 (3) | 0.083 (4) | 0.010 (2) | 0.020 (3) | −0.024 (2) |
C8 | 0.060 (2) | 0.045 (2) | 0.039 (2) | −0.0084 (18) | 0.0027 (19) | −0.0040 (18) |
C9 | 0.059 (2) | 0.042 (2) | 0.0253 (18) | −0.0063 (17) | −0.0073 (17) | 0.0017 (16) |
C10 | 0.087 (3) | 0.037 (2) | 0.047 (2) | −0.0024 (18) | 0.005 (2) | 0.0042 (18) |
C11 | 0.137 (6) | 0.026 (3) | 0.078 (5) | 0.000 | 0.010 (4) | 0.000 |
O1—C8 | 1.229 (3) | C3—H3 | 0.9300 |
N1—C8 | 1.346 (4) | C4—C5 | 1.380 (4) |
N1—C5 | 1.417 (4) | C4—H4 | 0.9300 |
N1—H1 | 0.8600 | C5—C6 | 1.378 (4) |
N2—C9i | 1.330 (3) | C6—C7 | 1.372 (5) |
N2—C9 | 1.330 (3) | C6—H6 | 0.9300 |
C1—C2 | 1.524 (5) | C7—H7 | 0.9300 |
C1—H1A | 0.9600 | C8—C9 | 1.497 (4) |
C1—H1B | 0.9600 | C9—C10 | 1.377 (4) |
C1—H1C | 0.9600 | C10—C11 | 1.373 (4) |
C2—C7 | 1.353 (5) | C10—H10 | 0.9300 |
C2—C3 | 1.380 (5) | C11—C10i | 1.373 (4) |
C3—C4 | 1.390 (5) | C11—H11 | 0.9300 |
C8—N1—C5 | 128.4 (3) | C6—C5—N1 | 117.0 (3) |
C8—N1—H1 | 115.8 | C4—C5—N1 | 123.8 (4) |
C5—N1—H1 | 115.8 | C7—C6—C5 | 119.8 (3) |
C9i—N2—C9 | 117.3 (4) | C7—C6—H6 | 120.1 |
C2—C1—H1A | 109.5 | C5—C6—H6 | 120.1 |
C2—C1—H1B | 109.5 | C2—C7—C6 | 123.1 (4) |
H1A—C1—H1B | 109.5 | C2—C7—H7 | 118.5 |
C2—C1—H1C | 109.5 | C6—C7—H7 | 118.5 |
H1A—C1—H1C | 109.5 | O1—C8—N1 | 124.3 (3) |
H1B—C1—H1C | 109.5 | O1—C8—C9 | 121.5 (3) |
C7—C2—C3 | 116.6 (4) | N1—C8—C9 | 114.1 (3) |
C7—C2—C1 | 124.4 (5) | N2—C9—C10 | 123.2 (3) |
C3—C2—C1 | 118.9 (4) | N2—C9—C8 | 118.4 (3) |
C2—C3—C4 | 122.4 (4) | C10—C9—C8 | 118.3 (3) |
C2—C3—H3 | 118.8 | C11—C10—C9 | 118.6 (4) |
C4—C3—H3 | 118.8 | C11—C10—H10 | 120.7 |
C5—C4—C3 | 118.8 (4) | C9—C10—H10 | 120.7 |
C5—C4—H4 | 120.6 | C10—C11—C10i | 118.9 (5) |
C3—C4—H4 | 120.6 | C10—C11—H11 | 120.5 |
C6—C5—C4 | 119.2 (3) | C10i—C11—H11 | 120.5 |
C7—C2—C3—C4 | 1.3 (6) | C5—N1—C8—O1 | 5.3 (6) |
C1—C2—C3—C4 | −175.6 (4) | C5—N1—C8—C9 | −171.4 (3) |
C2—C3—C4—C5 | −1.0 (6) | C9i—N2—C9—C10 | −1.3 (2) |
C3—C4—C5—C6 | 1.1 (5) | C9i—N2—C9—C8 | 179.4 (3) |
C3—C4—C5—N1 | 177.4 (4) | O1—C8—C9—N2 | 159.4 (3) |
C8—N1—C5—C6 | −167.0 (4) | N1—C8—C9—N2 | −23.9 (4) |
C8—N1—C5—C4 | 16.6 (5) | O1—C8—C9—C10 | −19.9 (5) |
C4—C5—C6—C7 | −1.6 (5) | N1—C8—C9—C10 | 156.9 (3) |
N1—C5—C6—C7 | −178.1 (3) | N2—C9—C10—C11 | 2.6 (5) |
C3—C2—C7—C6 | −1.7 (6) | C8—C9—C10—C11 | −178.2 (3) |
C1—C2—C7—C6 | 175.0 (4) | C9—C10—C11—C10i | −1.2 (2) |
C5—C6—C7—C2 | 2.0 (6) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1ii | 0.86 | 2.31 | 3.068 (4) | 147 |
Symmetry code: (ii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C21H19N3O2 |
Mr | 345.39 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 294 |
a, b, c (Å) | 25.140 (5), 8.5779 (17), 8.5295 (17) |
β (°) | 94.46 (3) |
V (Å3) | 1833.8 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.22 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.982, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5712, 2084, 734 |
Rint | 0.137 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.089, 0.181, 1.02 |
No. of reflections | 2084 |
No. of parameters | 120 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL-NT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.31 | 3.068 (4) | 147 |
Symmetry code: (i) x, −y, z+1/2. |
Our research has shown that the previously reported ligands (II) and (III) (Qi et al., 2001; Yang et al., 2001) easily form CoIII complexes via the coordination of the pyridine N and the amide N atoms. However, these CoIII complexes are difficult to crystallize and this may be due to the steric effect of the bulky naphthyl ring of ligand (II) or the 2-methoxy group on the phenyl ring of ligand (III). Therefore, ligand (I), with less steric hindrance of the coordinated amide N atom, was prepared. We expect that it will be easier to form metal complexes of this ligand and grow single crystals for X-ray analysis.
Compound (I) has the similar plane structures to those in (II) and (III). The two phenyl rings are twisted from coplanarity with the pyridine-ring plane and form dihedral angles of 15.7 (14)°. The dihedral angle between the two phenyl rings is 25.0 (15)°. Intermolecular N—H···O, hydrogen bonds, formed via the carbonyl O and amide H atoms, link molecules into chains in the c direction (see Table 1).