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The title compound, C26H23NO2, (Ia) and (Ib), shows polymorphism with crystals obtained from different solvents displaying different crystal structures. However, it is not the geometry of the single molecules nor the hydrogen-bond pattern that is different in (Ia) and (Ib), but the way in which the hydrogen-bonded chains, running along the a-axis direction, are arranged with respect to each other.
Supporting information
CCDC references: 167004; 167005
Compound (I) was synthesized according to the reaction described by Weiss
(1952). Crystals of (Ia) were obtained from ethyl acetate and of (Ib) from
acetone. Having discovered that (Ib) was a polymorph of (Ia), the cell
parameters of several further crystals out of the charge of (Ib) were checked
at room temperature and at 163 K. They all turned out to be identical with
those found for the first crystal of (Ib).
All H atoms were located by difference Fourier synthesis and refined with fixed
individual displacement parameters [U(H) = 1.5Ueq(Cmethyl), U(H) =
1.2Ueq(C) or U(H) = 1.2Ueq(N)] using a riding model with
N—H = 0.86 for (Ia) and 0.88 for (Ib), C—H(aromatic) = 0.93 for (Ia) and
0.95 for (Ib), C—H(methyl) = 0.96 for (Ia) and 0.98 for (Ib),
C—H(secondary) = 0.97 for (Ia) and 0.99 for (Ib), and C—H(tertiary) = 0.98
for (Ia) and 1.00 Å for (Ib).
For both compounds, data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990) and XP in SHELXTL-Plus (Siemens, 1991).
(Ia) Ethyl 1,4-dihydro-2,4,6-triphenylpyridine-3-carboxylate
top
Crystal data top
C26H23NO2 | Z = 2 |
Mr = 381.45 | F(000) = 404 |
Triclinic, P1 | Dx = 1.168 Mg m−3 |
a = 7.5083 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.6140 (3) Å | Cell parameters from 6287 reflections |
c = 12.6644 (3) Å | θ = 1–26° |
α = 93.862 (1)° | µ = 0.07 mm−1 |
β = 98.759 (1)° | T = 293 K |
γ = 94.527 (1)° | Block, colourless |
V = 1084.53 (5) Å3 | 0.5 × 0.4 × 0.3 mm |
Data collection top
Siemens CCD three-circle diffractometer | 3332 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.038 |
Highly oriented graphite crystal monochromator | θmax = 26.1°, θmin = 1.8° |
ω scans | h = −9→9 |
9841 measured reflections | k = −14→14 |
3961 independent reflections | l = −15→15 |
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) = 0.141 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.051P)2 + 0.3729P] where P = (Fo2 + 2Fc2)/3 |
3961 reflections | (Δ/σ)max < 0.001 |
262 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C26H23NO2 | γ = 94.527 (1)° |
Mr = 381.45 | V = 1084.53 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5083 (2) Å | Mo Kα radiation |
b = 11.6140 (3) Å | µ = 0.07 mm−1 |
c = 12.6644 (3) Å | T = 293 K |
α = 93.862 (1)° | 0.5 × 0.4 × 0.3 mm |
β = 98.759 (1)° | |
Data collection top
Siemens CCD three-circle diffractometer | 3332 reflections with I > 2σ(I) |
9841 measured reflections | Rint = 0.038 |
3961 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.22 e Å−3 |
3961 reflections | Δρmin = −0.28 e Å−3 |
262 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 | 0.61677 (19) | 0.39930 (13) | 0.67560 (12) | 0.0509 (4) | |
H1 | 0.7302 | 0.4224 | 0.6885 | 0.061* | |
C2 | 0.4994 (2) | 0.45399 (14) | 0.73286 (13) | 0.0409 (4) | |
C3 | 0.3233 (2) | 0.40740 (14) | 0.72714 (13) | 0.0427 (4) | |
C4 | 0.2561 (2) | 0.29000 (15) | 0.66396 (14) | 0.0472 (4) | |
H4 | 0.1384 | 0.2988 | 0.6212 | 0.057* | |
C5 | 0.3838 (2) | 0.25907 (16) | 0.58692 (14) | 0.0503 (4) | |
H5 | 0.3416 | 0.2043 | 0.5298 | 0.060* | |
C6 | 0.5557 (2) | 0.30705 (15) | 0.59695 (14) | 0.0464 (4) | |
C21 | 0.5803 (2) | 0.56875 (14) | 0.78956 (13) | 0.0407 (4) | |
C22 | 0.6013 (3) | 0.66294 (17) | 0.72779 (16) | 0.0558 (5) | |
H22 | 0.5712 | 0.6528 | 0.6536 | 0.067* | |
C23 | 0.6675 (3) | 0.77210 (18) | 0.7775 (2) | 0.0684 (6) | |
H23 | 0.6790 | 0.8347 | 0.7361 | 0.082* | |
C24 | 0.7160 (3) | 0.78797 (18) | 0.8874 (2) | 0.0661 (6) | |
H24 | 0.7589 | 0.8611 | 0.9200 | 0.079* | |
C25 | 0.7005 (3) | 0.69455 (19) | 0.94912 (16) | 0.0604 (5) | |
H25 | 0.7353 | 0.7048 | 1.0231 | 0.073* | |
C26 | 0.6326 (2) | 0.58501 (16) | 0.90038 (14) | 0.0482 (4) | |
H26 | 0.6222 | 0.5227 | 0.9421 | 0.058* | |
C31 | 0.1820 (2) | 0.46706 (15) | 0.77272 (15) | 0.0475 (4) | |
O31 | 0.01969 (17) | 0.43771 (14) | 0.74637 (13) | 0.0733 (5) | |
O32 | 0.24286 (16) | 0.55464 (12) | 0.84743 (12) | 0.0604 (4) | |
C33 | 0.1088 (3) | 0.6185 (2) | 0.8921 (2) | 0.0700 (6) | |
H33A | 0.0248 | 0.5656 | 0.9203 | 0.084* | |
H33B | 0.0408 | 0.6585 | 0.8367 | 0.084* | |
C34 | 0.2045 (4) | 0.7038 (2) | 0.9793 (3) | 0.0930 (9) | |
H34A | 0.1177 | 0.7466 | 1.0096 | 0.140* | |
H34B | 0.2866 | 0.7562 | 0.9506 | 0.140* | |
H34C | 0.2709 | 0.6635 | 1.0339 | 0.140* | |
C41 | 0.2283 (3) | 0.19255 (16) | 0.73806 (15) | 0.0537 (5) | |
C42 | 0.3725 (4) | 0.1390 (2) | 0.78806 (18) | 0.0744 (6) | |
H42 | 0.4898 | 0.1634 | 0.7790 | 0.089* | |
C43 | 0.3420 (6) | 0.0472 (3) | 0.8530 (2) | 0.1054 (11) | |
H43 | 0.4386 | 0.0104 | 0.8861 | 0.127* | |
C44 | 0.1649 (7) | 0.0123 (2) | 0.8666 (3) | 0.1127 (13) | |
H44 | 0.1436 | −0.0486 | 0.9086 | 0.135* | |
C45 | 0.0245 (6) | 0.0663 (3) | 0.8194 (3) | 0.1054 (11) | |
H45 | −0.0923 | 0.0435 | 0.8304 | 0.126* | |
C46 | 0.0531 (3) | 0.1550 (2) | 0.7551 (2) | 0.0763 (7) | |
H46 | −0.0453 | 0.1906 | 0.7224 | 0.092* | |
C61 | 0.6873 (2) | 0.27183 (17) | 0.52594 (14) | 0.0501 (4) | |
C62 | 0.6968 (3) | 0.1548 (2) | 0.49578 (19) | 0.0735 (6) | |
H62 | 0.6245 | 0.0987 | 0.5227 | 0.088* | |
C63 | 0.8136 (4) | 0.1207 (2) | 0.4257 (2) | 0.0938 (9) | |
H63 | 0.8171 | 0.0426 | 0.4056 | 0.113* | |
C64 | 0.9238 (4) | 0.2031 (3) | 0.3864 (2) | 0.0886 (8) | |
H64 | 1.0018 | 0.1803 | 0.3401 | 0.106* | |
C65 | 0.9179 (3) | 0.3189 (2) | 0.41596 (17) | 0.0727 (6) | |
H65 | 0.9922 | 0.3741 | 0.3894 | 0.087* | |
C66 | 0.8012 (3) | 0.35408 (19) | 0.48547 (15) | 0.0575 (5) | |
H66 | 0.7988 | 0.4325 | 0.5051 | 0.069* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0318 (7) | 0.0595 (9) | 0.0578 (9) | −0.0026 (6) | 0.0069 (6) | −0.0137 (7) |
C2 | 0.0329 (8) | 0.0443 (9) | 0.0440 (9) | 0.0016 (7) | 0.0032 (7) | 0.0025 (7) |
C3 | 0.0346 (8) | 0.0447 (9) | 0.0482 (9) | 0.0005 (7) | 0.0056 (7) | 0.0047 (7) |
C4 | 0.0361 (9) | 0.0528 (10) | 0.0494 (10) | −0.0051 (7) | 0.0023 (7) | 0.0009 (8) |
C5 | 0.0485 (10) | 0.0536 (10) | 0.0445 (9) | −0.0073 (8) | 0.0043 (8) | −0.0052 (8) |
C6 | 0.0442 (9) | 0.0492 (10) | 0.0434 (9) | −0.0014 (7) | 0.0053 (7) | −0.0026 (7) |
C21 | 0.0277 (8) | 0.0453 (9) | 0.0485 (9) | 0.0012 (6) | 0.0075 (7) | −0.0008 (7) |
C22 | 0.0548 (11) | 0.0554 (11) | 0.0559 (11) | −0.0014 (9) | 0.0066 (9) | 0.0066 (9) |
C23 | 0.0686 (13) | 0.0469 (11) | 0.0895 (16) | −0.0041 (9) | 0.0153 (12) | 0.0090 (11) |
C24 | 0.0550 (12) | 0.0522 (12) | 0.0877 (16) | −0.0058 (9) | 0.0167 (11) | −0.0197 (11) |
C25 | 0.0459 (10) | 0.0775 (14) | 0.0547 (11) | −0.0002 (9) | 0.0109 (9) | −0.0180 (10) |
C26 | 0.0387 (9) | 0.0574 (11) | 0.0488 (10) | 0.0023 (7) | 0.0101 (7) | 0.0016 (8) |
C31 | 0.0347 (9) | 0.0500 (10) | 0.0579 (10) | 0.0009 (7) | 0.0080 (7) | 0.0069 (8) |
O31 | 0.0321 (7) | 0.0855 (10) | 0.0982 (11) | −0.0025 (6) | 0.0097 (7) | −0.0135 (9) |
O32 | 0.0353 (7) | 0.0631 (8) | 0.0817 (9) | 0.0061 (6) | 0.0132 (6) | −0.0143 (7) |
C33 | 0.0470 (11) | 0.0807 (15) | 0.0856 (15) | 0.0173 (10) | 0.0212 (11) | −0.0077 (12) |
C34 | 0.0763 (16) | 0.0746 (16) | 0.125 (2) | 0.0246 (13) | 0.0133 (15) | −0.0283 (15) |
C41 | 0.0658 (12) | 0.0431 (10) | 0.0503 (10) | −0.0060 (9) | 0.0132 (9) | −0.0067 (8) |
C42 | 0.1002 (18) | 0.0671 (14) | 0.0591 (13) | 0.0189 (13) | 0.0157 (12) | 0.0078 (11) |
C43 | 0.177 (3) | 0.0748 (18) | 0.0718 (17) | 0.043 (2) | 0.0237 (19) | 0.0114 (14) |
C44 | 0.210 (4) | 0.0534 (15) | 0.084 (2) | −0.007 (2) | 0.063 (2) | 0.0066 (14) |
C45 | 0.149 (3) | 0.0641 (17) | 0.106 (2) | −0.0335 (18) | 0.055 (2) | 0.0029 (16) |
C46 | 0.0807 (15) | 0.0646 (14) | 0.0821 (16) | −0.0237 (11) | 0.0275 (13) | −0.0025 (12) |
C61 | 0.0467 (10) | 0.0588 (11) | 0.0423 (9) | −0.0014 (8) | 0.0065 (8) | −0.0062 (8) |
C62 | 0.0780 (15) | 0.0637 (13) | 0.0785 (15) | −0.0060 (11) | 0.0269 (12) | −0.0148 (11) |
C63 | 0.102 (2) | 0.0826 (18) | 0.0974 (19) | 0.0040 (15) | 0.0378 (16) | −0.0349 (15) |
C64 | 0.0774 (16) | 0.117 (2) | 0.0708 (15) | −0.0010 (15) | 0.0312 (13) | −0.0280 (15) |
C65 | 0.0607 (13) | 0.1041 (19) | 0.0523 (12) | −0.0090 (12) | 0.0167 (10) | 0.0001 (12) |
C66 | 0.0521 (11) | 0.0664 (12) | 0.0517 (11) | −0.0023 (9) | 0.0073 (8) | −0.0010 (9) |
Geometric parameters (Å, º) top
N1—C2 | 1.388 (2) | C33—H33A | 0.9700 |
N1—C6 | 1.411 (2) | C33—H33B | 0.9700 |
N1—H1 | 0.8600 | C34—H34A | 0.9600 |
C2—C3 | 1.378 (2) | C34—H34B | 0.9600 |
C2—C21 | 1.507 (2) | C34—H34C | 0.9600 |
C3—C31 | 1.479 (2) | C41—C42 | 1.382 (3) |
C3—C4 | 1.541 (2) | C41—C46 | 1.406 (3) |
C4—C5 | 1.514 (3) | C42—C43 | 1.415 (4) |
C4—C41 | 1.540 (3) | C42—H42 | 0.9300 |
C4—H4 | 0.9800 | C43—C44 | 1.399 (5) |
C5—C6 | 1.349 (2) | C43—H43 | 0.9300 |
C5—H5 | 0.9300 | C44—C45 | 1.351 (5) |
C6—C61 | 1.496 (2) | C44—H44 | 0.9300 |
C21—C26 | 1.394 (2) | C45—C46 | 1.380 (4) |
C21—C22 | 1.400 (2) | C45—H45 | 0.9300 |
C22—C23 | 1.396 (3) | C46—H46 | 0.9300 |
C22—H22 | 0.9300 | C61—C62 | 1.397 (3) |
C23—C24 | 1.381 (3) | C61—C66 | 1.406 (3) |
C23—H23 | 0.9300 | C62—C63 | 1.398 (3) |
C24—C25 | 1.387 (3) | C62—H62 | 0.9300 |
C24—H24 | 0.9300 | C63—C64 | 1.383 (4) |
C25—C26 | 1.398 (3) | C63—H63 | 0.9300 |
C25—H25 | 0.9300 | C64—C65 | 1.377 (4) |
C26—H26 | 0.9300 | C64—H64 | 0.9300 |
C31—O31 | 1.228 (2) | C65—C66 | 1.397 (3) |
C31—O32 | 1.343 (2) | C65—H65 | 0.9300 |
O32—C33 | 1.455 (2) | C66—H66 | 0.9300 |
C33—C34 | 1.488 (3) | | |
| | | |
C2—N1—C6 | 122.03 (14) | O32—C33—H33B | 110.0 |
C2—N1—H1 | 119.0 | C34—C33—H33B | 110.0 |
C6—N1—H1 | 119.0 | H33A—C33—H33B | 108.4 |
C3—C2—N1 | 120.25 (15) | C33—C34—H34A | 109.5 |
C3—C2—C21 | 126.23 (15) | C33—C34—H34B | 109.5 |
N1—C2—C21 | 113.31 (13) | H34A—C34—H34B | 109.5 |
C2—C3—C31 | 124.07 (15) | C33—C34—H34C | 109.5 |
C2—C3—C4 | 121.10 (15) | H34A—C34—H34C | 109.5 |
C31—C3—C4 | 114.69 (14) | H34B—C34—H34C | 109.5 |
C5—C4—C41 | 111.36 (15) | C42—C41—C46 | 118.4 (2) |
C5—C4—C3 | 110.26 (13) | C42—C41—C4 | 121.51 (19) |
C41—C4—C3 | 112.34 (14) | C46—C41—C4 | 120.1 (2) |
C5—C4—H4 | 107.6 | C41—C42—C43 | 120.2 (3) |
C41—C4—H4 | 107.6 | C41—C42—H42 | 119.9 |
C3—C4—H4 | 107.6 | C43—C42—H42 | 119.9 |
C6—C5—C4 | 123.29 (16) | C44—C43—C42 | 119.2 (3) |
C6—C5—H5 | 118.4 | C44—C43—H43 | 120.4 |
C4—C5—H5 | 118.4 | C42—C43—H43 | 120.4 |
C5—C6—N1 | 119.41 (16) | C45—C44—C43 | 120.5 (3) |
C5—C6—C61 | 123.93 (16) | C45—C44—H44 | 119.8 |
N1—C6—C61 | 116.60 (14) | C43—C44—H44 | 119.8 |
C26—C21—C22 | 118.99 (16) | C44—C45—C46 | 120.6 (3) |
C26—C21—C2 | 122.84 (15) | C44—C45—H45 | 119.7 |
C22—C21—C2 | 118.16 (15) | C46—C45—H45 | 119.7 |
C23—C22—C21 | 120.08 (19) | C45—C46—C41 | 121.1 (3) |
C23—C22—H22 | 120.0 | C45—C46—H46 | 119.5 |
C21—C22—H22 | 120.0 | C41—C46—H46 | 119.5 |
C24—C23—C22 | 120.6 (2) | C62—C61—C66 | 118.00 (18) |
C24—C23—H23 | 119.7 | C62—C61—C6 | 120.26 (17) |
C22—C23—H23 | 119.7 | C66—C61—C6 | 121.73 (17) |
C23—C24—C25 | 119.81 (19) | C61—C62—C63 | 120.9 (2) |
C23—C24—H24 | 120.1 | C61—C62—H62 | 119.5 |
C25—C24—H24 | 120.1 | C63—C62—H62 | 119.5 |
C24—C25—C26 | 120.14 (19) | C64—C63—C62 | 120.1 (2) |
C24—C25—H25 | 119.9 | C64—C63—H63 | 119.9 |
C26—C25—H25 | 119.9 | C62—C63—H63 | 119.9 |
C21—C26—C25 | 120.37 (18) | C65—C64—C63 | 119.8 (2) |
C21—C26—H26 | 119.8 | C65—C64—H64 | 120.1 |
C25—C26—H26 | 119.8 | C63—C64—H64 | 120.1 |
O31—C31—O32 | 121.66 (17) | C64—C65—C66 | 120.6 (2) |
O31—C31—C3 | 122.81 (17) | C64—C65—H65 | 119.7 |
O32—C31—C3 | 115.51 (14) | C66—C65—H65 | 119.7 |
C31—O32—C33 | 117.53 (14) | C65—C66—C61 | 120.5 (2) |
O32—C33—C34 | 108.48 (17) | C65—C66—H66 | 119.8 |
O32—C33—H33A | 110.0 | C61—C66—H66 | 119.8 |
C34—C33—H33A | 110.0 | | |
| | | |
C6—N1—C2—C3 | 10.7 (3) | C2—C3—C31—O32 | −18.9 (3) |
C6—N1—C2—C21 | −164.16 (15) | C4—C3—C31—O32 | 165.37 (15) |
N1—C2—C3—C31 | −171.19 (16) | O31—C31—O32—C33 | −3.5 (3) |
C21—C2—C3—C31 | 3.0 (3) | C3—C31—O32—C33 | 177.98 (17) |
N1—C2—C3—C4 | 4.3 (2) | C31—O32—C33—C34 | 175.0 (2) |
C21—C2—C3—C4 | 178.47 (15) | C5—C4—C41—C42 | 45.6 (2) |
C2—C3—C4—C5 | −17.8 (2) | C3—C4—C41—C42 | −78.6 (2) |
C31—C3—C4—C5 | 158.05 (15) | C5—C4—C41—C46 | −133.53 (18) |
C2—C3—C4—C41 | 107.03 (19) | C3—C4—C41—C46 | 102.2 (2) |
C31—C3—C4—C41 | −77.11 (19) | C46—C41—C42—C43 | 1.2 (3) |
C41—C4—C5—C6 | −106.0 (2) | C4—C41—C42—C43 | −177.97 (19) |
C3—C4—C5—C6 | 19.4 (2) | C41—C42—C43—C44 | −0.6 (4) |
C4—C5—C6—N1 | −6.9 (3) | C42—C43—C44—C45 | −0.7 (4) |
C4—C5—C6—C61 | 175.76 (17) | C43—C44—C45—C46 | 1.4 (5) |
C2—N1—C6—C5 | −9.6 (3) | C44—C45—C46—C41 | −0.9 (4) |
C2—N1—C6—C61 | 167.91 (16) | C42—C41—C46—C45 | −0.4 (3) |
C3—C2—C21—C26 | 78.1 (2) | C4—C41—C46—C45 | 178.7 (2) |
N1—C2—C21—C26 | −107.36 (18) | C5—C6—C61—C62 | −41.7 (3) |
C3—C2—C21—C22 | −101.1 (2) | N1—C6—C61—C62 | 140.9 (2) |
N1—C2—C21—C22 | 73.4 (2) | C5—C6—C61—C66 | 136.7 (2) |
C26—C21—C22—C23 | −2.4 (3) | N1—C6—C61—C66 | −40.7 (2) |
C2—C21—C22—C23 | 176.90 (17) | C66—C61—C62—C63 | −1.3 (3) |
C21—C22—C23—C24 | 1.2 (3) | C6—C61—C62—C63 | 177.2 (2) |
C22—C23—C24—C25 | 0.6 (3) | C61—C62—C63—C64 | 1.0 (4) |
C23—C24—C25—C26 | −1.3 (3) | C62—C63—C64—C65 | −0.3 (4) |
C22—C21—C26—C25 | 1.7 (2) | C63—C64—C65—C66 | 0.0 (4) |
C2—C21—C26—C25 | −177.54 (15) | C64—C65—C66—C61 | −0.3 (3) |
C24—C25—C26—C21 | 0.1 (3) | C62—C61—C66—C65 | 0.9 (3) |
C2—C3—C31—O31 | 162.60 (19) | C6—C61—C66—C65 | −177.53 (18) |
C4—C3—C31—O31 | −13.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O31i | 0.86 | 2.17 | 3.0103 (19) | 164 |
Symmetry code: (i) x+1, y, z. |
(Ib) Ethyl 1,4-dihydro-2,4,6-triphenylpyridine-3-carboxylate
top
Crystal data top
C26H23NO2 | Z = 2 |
Mr = 381.45 | F(000) = 404 |
Triclinic, P1 | Dx = 1.215 Mg m−3 |
a = 7.5178 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.0669 (2) Å | Cell parameters from 5616 reflections |
c = 14.6364 (2) Å | θ = 1–25° |
α = 73.534 (1)° | µ = 0.08 mm−1 |
β = 80.826 (1)° | T = 163 K |
γ = 81.478 (1)° | Block, colourless |
V = 1042.46 (3) Å3 | 0.6 × 0.4 × 0.2 mm |
Data collection top
Siemens CCD three-circle diffractometer | 3545 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.022 |
Highly oriented graphite crystal monochromator | θmax = 26.5°, θmin = 2.1° |
ω scans | h = −9→9 |
15858 measured reflections | k = −12→12 |
4188 independent reflections | l = −18→17 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0462P)2 + 0.2564P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
4188 reflections | Δρmax = 0.27 e Å−3 |
263 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
Crystal data top
C26H23NO2 | γ = 81.478 (1)° |
Mr = 381.45 | V = 1042.46 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.5178 (1) Å | Mo Kα radiation |
b = 10.0669 (2) Å | µ = 0.08 mm−1 |
c = 14.6364 (2) Å | T = 163 K |
α = 73.534 (1)° | 0.6 × 0.4 × 0.2 mm |
β = 80.826 (1)° | |
Data collection top
Siemens CCD three-circle diffractometer | 3545 reflections with I > 2σ(I) |
15858 measured reflections | Rint = 0.022 |
4188 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
4188 reflections | Δρmin = −0.15 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 | |
N1 | 0.17355 (12) | 0.42261 (10) | 0.29186 (7) | 0.0258 (2) | |
H1 | 0.0666 | 0.4506 | 0.2716 | 0.031* | |
C2 | 0.32475 (14) | 0.47502 (11) | 0.23455 (8) | 0.0220 (2) | |
C3 | 0.49454 (14) | 0.41688 (11) | 0.25628 (8) | 0.0217 (2) | |
C4 | 0.52015 (14) | 0.28176 (11) | 0.33604 (8) | 0.0226 (2) | |
H4 | 0.6190 | 0.2900 | 0.3718 | 0.027* | |
C5 | 0.34763 (15) | 0.26333 (11) | 0.40605 (8) | 0.0235 (2) | |
H5 | 0.3551 | 0.2055 | 0.4694 | 0.028* | |
C6 | 0.18528 (15) | 0.32570 (11) | 0.38167 (8) | 0.0231 (2) | |
C21 | 0.27833 (14) | 0.60015 (11) | 0.15455 (8) | 0.0215 (2) | |
C22 | 0.29812 (15) | 0.59304 (12) | 0.05950 (8) | 0.0268 (3) | |
H22 | 0.3406 | 0.5071 | 0.0445 | 0.032* | |
C23 | 0.25585 (16) | 0.71133 (14) | −0.01315 (9) | 0.0322 (3) | |
H23 | 0.2695 | 0.7061 | −0.0777 | 0.039* | |
C24 | 0.19353 (16) | 0.83754 (13) | 0.00826 (9) | 0.0332 (3) | |
H24 | 0.1677 | 0.9189 | −0.0418 | 0.040* | |
C25 | 0.16920 (17) | 0.84427 (12) | 0.10285 (9) | 0.0318 (3) | |
H25 | 0.1244 | 0.9300 | 0.1177 | 0.038* | |
C26 | 0.21028 (15) | 0.72589 (12) | 0.17599 (8) | 0.0263 (2) | |
H26 | 0.1919 | 0.7307 | 0.2408 | 0.032* | |
C31 | 0.66345 (14) | 0.47569 (11) | 0.20746 (8) | 0.0228 (2) | |
O31 | 0.81311 (10) | 0.42368 (9) | 0.22958 (6) | 0.0332 (2) | |
O32 | 0.64183 (10) | 0.59177 (8) | 0.13489 (6) | 0.0315 (2) | |
C33 | 0.80527 (15) | 0.64381 (12) | 0.07695 (9) | 0.0286 (3) | |
H33A | 0.8784 | 0.5707 | 0.0497 | 0.034* | |
H33B | 0.8798 | 0.6729 | 0.1164 | 0.034* | |
C34 | 0.74374 (18) | 0.76695 (14) | −0.00232 (10) | 0.0394 (3) | |
H34A | 0.8499 | 0.8062 | −0.0434 | 0.059* | |
H34B | 0.6709 | 0.8380 | 0.0258 | 0.059* | |
H34C | 0.6705 | 0.7365 | −0.0408 | 0.059* | |
C41 | 0.57537 (15) | 0.15349 (11) | 0.29692 (8) | 0.0239 (2) | |
C42 | 0.46160 (17) | 0.11522 (13) | 0.24453 (9) | 0.0309 (3) | |
H42 | 0.3508 | 0.1713 | 0.2308 | 0.037* | |
C43 | 0.5083 (2) | −0.00404 (14) | 0.21212 (10) | 0.0387 (3) | |
H43 | 0.4301 | −0.0281 | 0.1758 | 0.046* | |
C44 | 0.6678 (2) | −0.08763 (14) | 0.23247 (10) | 0.0440 (4) | |
H44 | 0.6985 | −0.1700 | 0.2113 | 0.053* | |
C45 | 0.7820 (2) | −0.05047 (17) | 0.28364 (11) | 0.0528 (4) | |
H45 | 0.8922 | −0.1073 | 0.2975 | 0.063* | |
C46 | 0.73683 (19) | 0.06995 (15) | 0.31525 (10) | 0.0406 (3) | |
H46 | 0.8175 | 0.0951 | 0.3497 | 0.049* | |
C61 | 0.01142 (15) | 0.30883 (12) | 0.44657 (8) | 0.0247 (2) | |
C62 | −0.02433 (17) | 0.17820 (13) | 0.50662 (9) | 0.0322 (3) | |
H62 | 0.0614 | 0.0993 | 0.5045 | 0.039* | |
C63 | −0.18452 (19) | 0.16211 (16) | 0.56968 (10) | 0.0431 (3) | |
H63 | −0.2083 | 0.0724 | 0.6094 | 0.052* | |
C64 | −0.30907 (18) | 0.27711 (17) | 0.57435 (9) | 0.0433 (4) | |
H64 | −0.4177 | 0.2665 | 0.6176 | 0.052* | |
C65 | −0.27432 (17) | 0.40758 (16) | 0.51558 (10) | 0.0396 (3) | |
H65 | −0.3586 | 0.4866 | 0.5195 | 0.048* | |
C66 | −0.11695 (16) | 0.42351 (13) | 0.45090 (9) | 0.0312 (3) | |
H66 | −0.0964 | 0.5128 | 0.4094 | 0.037* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0158 (4) | 0.0282 (5) | 0.0289 (5) | −0.0036 (4) | −0.0056 (4) | 0.0017 (4) |
C2 | 0.0196 (5) | 0.0214 (5) | 0.0248 (5) | −0.0039 (4) | −0.0038 (4) | −0.0046 (4) |
C3 | 0.0192 (5) | 0.0215 (5) | 0.0242 (5) | −0.0022 (4) | −0.0044 (4) | −0.0047 (4) |
C4 | 0.0189 (5) | 0.0240 (5) | 0.0242 (5) | −0.0013 (4) | −0.0067 (4) | −0.0036 (4) |
C5 | 0.0250 (6) | 0.0224 (5) | 0.0215 (5) | −0.0019 (4) | −0.0038 (4) | −0.0028 (4) |
C6 | 0.0229 (5) | 0.0214 (5) | 0.0245 (5) | −0.0043 (4) | −0.0030 (4) | −0.0043 (4) |
C21 | 0.0134 (5) | 0.0236 (5) | 0.0264 (6) | −0.0045 (4) | −0.0035 (4) | −0.0028 (4) |
C22 | 0.0193 (5) | 0.0317 (6) | 0.0291 (6) | −0.0028 (5) | −0.0023 (4) | −0.0081 (5) |
C23 | 0.0244 (6) | 0.0455 (7) | 0.0237 (6) | −0.0080 (5) | −0.0025 (5) | −0.0022 (5) |
C24 | 0.0246 (6) | 0.0318 (6) | 0.0346 (7) | −0.0077 (5) | −0.0088 (5) | 0.0100 (5) |
C25 | 0.0279 (6) | 0.0227 (6) | 0.0432 (7) | −0.0027 (5) | −0.0100 (5) | −0.0030 (5) |
C26 | 0.0248 (6) | 0.0266 (6) | 0.0279 (6) | −0.0033 (5) | −0.0062 (5) | −0.0060 (5) |
C31 | 0.0198 (5) | 0.0232 (5) | 0.0264 (6) | −0.0018 (4) | −0.0054 (4) | −0.0070 (4) |
O31 | 0.0174 (4) | 0.0396 (5) | 0.0373 (5) | −0.0029 (3) | −0.0077 (3) | 0.0007 (4) |
O32 | 0.0170 (4) | 0.0291 (4) | 0.0404 (5) | −0.0055 (3) | −0.0041 (3) | 0.0053 (4) |
C33 | 0.0184 (5) | 0.0309 (6) | 0.0344 (6) | −0.0085 (5) | −0.0021 (5) | −0.0033 (5) |
C34 | 0.0313 (7) | 0.0372 (7) | 0.0436 (8) | −0.0130 (6) | −0.0081 (6) | 0.0055 (6) |
C41 | 0.0246 (6) | 0.0230 (5) | 0.0196 (5) | −0.0019 (4) | −0.0008 (4) | 0.0002 (4) |
C42 | 0.0275 (6) | 0.0311 (6) | 0.0336 (6) | −0.0055 (5) | −0.0034 (5) | −0.0068 (5) |
C43 | 0.0468 (8) | 0.0372 (7) | 0.0346 (7) | −0.0146 (6) | 0.0019 (6) | −0.0125 (6) |
C44 | 0.0646 (10) | 0.0311 (7) | 0.0326 (7) | 0.0026 (6) | 0.0033 (6) | −0.0114 (6) |
C45 | 0.0571 (10) | 0.0500 (9) | 0.0484 (9) | 0.0269 (7) | −0.0154 (7) | −0.0202 (7) |
C46 | 0.0373 (7) | 0.0455 (8) | 0.0401 (7) | 0.0134 (6) | −0.0147 (6) | −0.0169 (6) |
C61 | 0.0223 (6) | 0.0300 (6) | 0.0234 (5) | −0.0048 (5) | −0.0039 (4) | −0.0083 (5) |
C62 | 0.0312 (6) | 0.0342 (6) | 0.0275 (6) | −0.0054 (5) | −0.0009 (5) | −0.0027 (5) |
C63 | 0.0377 (7) | 0.0570 (9) | 0.0291 (7) | −0.0164 (7) | 0.0026 (6) | −0.0007 (6) |
C64 | 0.0256 (6) | 0.0776 (11) | 0.0300 (7) | −0.0129 (7) | 0.0046 (5) | −0.0201 (7) |
C65 | 0.0238 (6) | 0.0575 (9) | 0.0463 (8) | 0.0007 (6) | −0.0052 (5) | −0.0298 (7) |
C66 | 0.0241 (6) | 0.0339 (6) | 0.0388 (7) | −0.0025 (5) | −0.0069 (5) | −0.0138 (5) |
Geometric parameters (Å, º) top
N1—C2 | 1.3773 (14) | C33—H33A | 0.9900 |
N1—C6 | 1.4042 (14) | C33—H33B | 0.9900 |
N1—H1 | 0.8800 | C34—H34A | 0.9800 |
C2—C3 | 1.3696 (15) | C34—H34B | 0.9800 |
C2—C21 | 1.4979 (15) | C34—H34C | 0.9800 |
C3—C31 | 1.4722 (15) | C41—C46 | 1.3878 (17) |
C3—C4 | 1.5310 (15) | C41—C42 | 1.3936 (17) |
C4—C5 | 1.5186 (15) | C42—C43 | 1.3909 (18) |
C4—C41 | 1.5336 (15) | C42—H42 | 0.9500 |
C4—H4 | 1.0000 | C43—C44 | 1.381 (2) |
C5—C6 | 1.3401 (15) | C43—H43 | 0.9500 |
C5—H5 | 0.9500 | C44—C45 | 1.377 (2) |
C6—C61 | 1.4893 (15) | C44—H44 | 0.9500 |
C21—C26 | 1.3944 (16) | C45—C46 | 1.395 (2) |
C21—C22 | 1.3964 (16) | C45—H45 | 0.9500 |
C22—C23 | 1.3884 (17) | C46—H46 | 0.9500 |
C22—H22 | 0.9500 | C61—C62 | 1.3958 (17) |
C23—C24 | 1.3909 (19) | C61—C66 | 1.4000 (16) |
C23—H23 | 0.9500 | C62—C63 | 1.3953 (18) |
C24—C25 | 1.3870 (19) | C62—H62 | 0.9500 |
C24—H24 | 0.9500 | C63—C64 | 1.387 (2) |
C25—C26 | 1.3909 (17) | C63—H63 | 0.9500 |
C25—H25 | 0.9500 | C64—C65 | 1.387 (2) |
C26—H26 | 0.9500 | C64—H64 | 0.9500 |
C31—O31 | 1.2208 (13) | C65—C66 | 1.3910 (18) |
C31—O32 | 1.3473 (14) | C65—H65 | 0.9500 |
O32—C33 | 1.4526 (13) | C66—H66 | 0.9500 |
C33—C34 | 1.5109 (17) | | |
| | | |
C2—N1—C6 | 121.81 (9) | O32—C33—H33B | 110.4 |
C2—N1—H1 | 119.1 | C34—C33—H33B | 110.4 |
C6—N1—H1 | 119.1 | H33A—C33—H33B | 108.6 |
C3—C2—N1 | 120.25 (10) | C33—C34—H34A | 109.5 |
C3—C2—C21 | 127.01 (10) | C33—C34—H34B | 109.5 |
N1—C2—C21 | 112.67 (9) | H34A—C34—H34B | 109.5 |
C2—C3—C31 | 124.43 (10) | C33—C34—H34C | 109.5 |
C2—C3—C4 | 120.69 (9) | H34A—C34—H34C | 109.5 |
C31—C3—C4 | 114.88 (9) | H34B—C34—H34C | 109.5 |
C5—C4—C3 | 109.82 (9) | C46—C41—C42 | 118.20 (11) |
C5—C4—C41 | 110.29 (9) | C46—C41—C4 | 121.04 (10) |
C3—C4—C41 | 112.55 (9) | C42—C41—C4 | 120.73 (10) |
C5—C4—H4 | 108.0 | C43—C42—C41 | 120.80 (12) |
C3—C4—H4 | 108.0 | C43—C42—H42 | 119.6 |
C41—C4—H4 | 108.0 | C41—C42—H42 | 119.6 |
C6—C5—C4 | 122.36 (10) | C44—C43—C42 | 120.36 (13) |
C6—C5—H5 | 118.8 | C44—C43—H43 | 119.8 |
C4—C5—H5 | 118.8 | C42—C43—H43 | 119.8 |
C5—C6—N1 | 119.72 (10) | C45—C44—C43 | 119.40 (13) |
C5—C6—C61 | 124.64 (10) | C45—C44—H44 | 120.3 |
N1—C6—C61 | 115.47 (9) | C43—C44—H44 | 120.3 |
C26—C21—C22 | 119.36 (10) | C44—C45—C46 | 120.46 (13) |
C26—C21—C2 | 119.07 (10) | C44—C45—H45 | 119.8 |
C22—C21—C2 | 121.56 (10) | C46—C45—H45 | 119.8 |
C23—C22—C21 | 120.14 (11) | C41—C46—C45 | 120.76 (13) |
C23—C22—H22 | 119.9 | C41—C46—H46 | 119.6 |
C21—C22—H22 | 119.9 | C45—C46—H46 | 119.6 |
C22—C23—C24 | 120.24 (11) | C62—C61—C66 | 118.59 (11) |
C22—C23—H23 | 119.9 | C62—C61—C6 | 120.36 (10) |
C24—C23—H23 | 119.9 | C66—C61—C6 | 121.02 (10) |
C25—C24—C23 | 119.80 (11) | C63—C62—C61 | 120.77 (12) |
C25—C24—H24 | 120.1 | C63—C62—H62 | 119.6 |
C23—C24—H24 | 120.1 | C61—C62—H62 | 119.6 |
C24—C25—C26 | 120.19 (11) | C64—C63—C62 | 120.00 (13) |
C24—C25—H25 | 119.9 | C64—C63—H63 | 120.0 |
C26—C25—H25 | 119.9 | C62—C63—H63 | 120.0 |
C25—C26—C21 | 120.22 (11) | C63—C64—C65 | 119.73 (12) |
C25—C26—H26 | 119.9 | C63—C64—H64 | 120.1 |
C21—C26—H26 | 119.9 | C65—C64—H64 | 120.1 |
O31—C31—O32 | 121.74 (10) | C64—C65—C66 | 120.44 (13) |
O31—C31—C3 | 123.24 (10) | C64—C65—H65 | 119.8 |
O32—C31—C3 | 115.01 (9) | C66—C65—H65 | 119.8 |
C31—O32—C33 | 117.01 (8) | C65—C66—C61 | 120.43 (12) |
O32—C33—C34 | 106.40 (9) | C65—C66—H66 | 119.8 |
O32—C33—H33A | 110.4 | C61—C66—H66 | 119.8 |
C34—C33—H33A | 110.4 | | |
| | | |
C6—N1—C2—C3 | 10.91 (16) | C2—C3—C31—O32 | −2.43 (16) |
C6—N1—C2—C21 | −166.12 (10) | C4—C3—C31—O32 | 177.66 (9) |
N1—C2—C3—C31 | −171.75 (10) | O31—C31—O32—C33 | 6.75 (16) |
C21—C2—C3—C31 | 4.81 (18) | C3—C31—O32—C33 | −172.58 (9) |
N1—C2—C3—C4 | 8.15 (16) | C31—O32—C33—C34 | 176.21 (10) |
C21—C2—C3—C4 | −175.28 (10) | C5—C4—C41—C46 | −116.43 (12) |
C2—C3—C4—C5 | −23.09 (14) | C3—C4—C41—C46 | 120.54 (12) |
C31—C3—C4—C5 | 156.82 (9) | C5—C4—C41—C42 | 61.48 (13) |
C2—C3—C4—C41 | 100.19 (12) | C3—C4—C41—C42 | −61.54 (13) |
C31—C3—C4—C41 | −79.90 (11) | C46—C41—C42—C43 | 0.43 (18) |
C3—C4—C5—C6 | 22.45 (14) | C4—C41—C42—C43 | −177.54 (11) |
C41—C4—C5—C6 | −102.16 (12) | C41—C42—C43—C44 | 0.80 (19) |
C4—C5—C6—N1 | −6.51 (16) | C42—C43—C44—C45 | −1.2 (2) |
C4—C5—C6—C61 | 178.54 (10) | C43—C44—C45—C46 | 0.4 (2) |
C2—N1—C6—C5 | −11.92 (16) | C42—C41—C46—C45 | −1.3 (2) |
C2—N1—C6—C61 | 163.47 (10) | C4—C41—C46—C45 | 176.71 (13) |
C3—C2—C21—C26 | −105.30 (13) | C44—C45—C46—C41 | 0.9 (2) |
N1—C2—C21—C26 | 71.48 (13) | C5—C6—C61—C62 | −40.99 (16) |
C3—C2—C21—C22 | 76.02 (15) | N1—C6—C61—C62 | 143.87 (11) |
N1—C2—C21—C22 | −107.19 (12) | C5—C6—C61—C66 | 137.09 (12) |
C26—C21—C22—C23 | 2.07 (16) | N1—C6—C61—C66 | −38.05 (15) |
C2—C21—C22—C23 | −179.26 (10) | C66—C61—C62—C63 | −0.01 (18) |
C21—C22—C23—C24 | −0.02 (17) | C6—C61—C62—C63 | 178.12 (11) |
C22—C23—C24—C25 | −1.65 (18) | C61—C62—C63—C64 | −1.1 (2) |
C23—C24—C25—C26 | 1.25 (18) | C62—C63—C64—C65 | 0.5 (2) |
C24—C25—C26—C21 | 0.81 (17) | C63—C64—C65—C66 | 1.1 (2) |
C22—C21—C26—C25 | −2.46 (16) | C64—C65—C66—C61 | −2.19 (18) |
C2—C21—C26—C25 | 178.83 (10) | C62—C61—C66—C65 | 1.64 (17) |
C2—C3—C31—O31 | 178.25 (11) | C6—C61—C66—C65 | −176.48 (11) |
C4—C3—C31—O31 | −1.66 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O31i | 0.88 | 2.17 | 2.9912 (12) | 155 |
Symmetry code: (i) x−1, y, z. |
Experimental details
| (Ia) | (Ib) |
Crystal data |
Chemical formula | C26H23NO2 | C26H23NO2 |
Mr | 381.45 | 381.45 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 163 |
a, b, c (Å) | 7.5083 (2), 11.6140 (3), 12.6644 (3) | 7.5178 (1), 10.0669 (2), 14.6364 (2) |
α, β, γ (°) | 93.862 (1), 98.759 (1), 94.527 (1) | 73.534 (1), 80.826 (1), 81.478 (1) |
V (Å3) | 1084.53 (5) | 1042.46 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.08 |
Crystal size (mm) | 0.5 × 0.4 × 0.3 | 0.6 × 0.4 × 0.2 |
|
Data collection |
Diffractometer | Siemens CCD three-circle diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9841, 3961, 3332 | 15858, 4188, 3545 |
Rint | 0.038 | 0.022 |
(sin θ/λ)max (Å−1) | 0.619 | 0.627 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.141, 1.10 | 0.036, 0.095, 1.03 |
No. of reflections | 3961 | 4188 |
No. of parameters | 262 | 263 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.28 | 0.27, −0.15 |
Selected geometric parameters (Å, º) for (Ia) topN1—C2 | 1.388 (2) | C3—C4 | 1.541 (2) |
N1—C6 | 1.411 (2) | C4—C5 | 1.514 (3) |
C2—C3 | 1.378 (2) | C5—C6 | 1.349 (2) |
| | | |
C2—N1—C6 | 122.03 (14) | C5—C4—C3 | 110.26 (13) |
C3—C2—N1 | 120.25 (15) | C6—C5—C4 | 123.29 (16) |
C2—C3—C4 | 121.10 (15) | C5—C6—N1 | 119.41 (16) |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O31i | 0.86 | 2.17 | 3.0103 (19) | 163.8 |
Symmetry code: (i) x+1, y, z. |
Selected geometric parameters (Å, º) for (Ib) topN1—C2 | 1.3773 (14) | C3—C4 | 1.5310 (15) |
N1—C6 | 1.4042 (14) | C4—C5 | 1.5186 (15) |
C2—C3 | 1.3696 (15) | C5—C6 | 1.3401 (15) |
| | | |
C2—N1—C6 | 121.81 (9) | C5—C4—C3 | 109.82 (9) |
C3—C2—N1 | 120.25 (10) | C6—C5—C4 | 122.36 (10) |
C2—C3—C4 | 120.69 (9) | C5—C6—N1 | 119.72 (10) |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O31i | 0.88 | 2.17 | 2.9912 (12) | 155.2 |
Symmetry code: (i) x−1, y, z. |
Comparative table of reduced (Niggli) cell parameters of the two polymorphs topPolymorph | a.a | b.b | c.c | b.c | a.c | a.b |
(Ia) | 56.370 | 134.890 | 160.390 | -9.905 | -14.480 | -6.885 |
(Ib) | 56.520 | 101.340 | 214.220 | 41.765 | 17.545 | 11.215 |
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The 1,4-dihydropyridine ring system is of biological importance because it occurs in the reduced forms of nicotinamide adenine dinucleotide (NADH) and NADPH (Kosower & Sorensen, 1962). Since very little information is available on the geometry of aryl-substituted 1,4-dihydropyridines, the title compound, (I), was synthesized and its conformation was determined by means of an X-ray structure analysis. Surprisingly, crystals of (I) obtained from two different solvents showed two different crystal structures, (Ia) and (Ib). Thus, compound (I) shows polymorphism. However, since only two polymorphs have been characterized to date, one might speak of dimorphism. \sch
Polymorphism is a well known phenomenon in crystallography (Mitscherlich, 1822) and it is extensively described in crystallographic textbooks (e.g. Dunitz, 1979; Glusker, 1994). In the case of (I), two polymorphs, (Ia) (Fig. 1) and (Ib) (Fig. 2), were obtained via crystallization from different solvents. Although both polymorphs crystallize in space group P1 (No. 2) with Z = 2, they have slightly different unit-cell volumes and their unit-cell dimensions, apart from the a axis, are significantly different.
The Niggli values (Spek, 1990; Table 5) demonstrate clearly that the reduced cells are definitely different. The molecular structures of (I) found in the two polymorphs are very similar, indeed nearly identical. A least-squares fit of all non-H atoms in (Ia) and (Ib) gives an r.m.s. deviation of 0.263 Å. Bond lengths and angles are typical of their types (Allen et al., 1987). The 1,4-dihydropyridine ring system is essentially planar [r.m.s. deviations 0.082 and 0.098 Å for (Ia) and (Ib), respectively]. The phenyl ring in the para position to the NH group is almost perpendicular to the heterocycle [80.54 (5)° in (Ia) and 87.13 (3)° in (Ib)]. The phenyl rings in the ortho positions with respect to the NH group enclose smaller dihedral angles with the central ring: C21—C26 71.37 (6)° in (Ia) and 68.07 (4)° in (Ib), and C61—C66 36.96 (9)° in (Ia) and 35.58 (5)° in (Ib). Since the aryl ring C21—C26 is in the ortho position with respect to the ester group, it is obvious that its dihedral angle with the heterocycle is increased due to steric repulsion with the ester group. This ester group is also planar [r.m.s. deviation 0.040 Å in (Ia) and 0.021 Å in (Ib)] and more or less coplanar with the heterocycle [17.6 (1)° in (Ia) and 7.57 (6)° in (Ib)].
In the crystal, the molecules form infinite chains which are stabilized by a hydrogen bond from the NH group to the carbonyl O atom. The remarkable feature of (Ia) and (Ib), however, is their different crystal packing (Figs. 3 and 4).