Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107024420/gg3095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107024420/gg3095Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107024420/gg3095IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107024420/gg3095IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107024420/gg3095IVsup5.hkl |
CCDC references: 655513; 655514; 655515; 655516
A solution of the corresponding 3-(dimethoxyphenyl)-1-(2-hydroxyphenyl)-2-propenone (0.704 mmol) and 1,2-diaminobenzene (1.056 mmol) in methanol (40 ml) was heated to reflux temperatures for 24 h. Concentration in vacuo followed by column chromatographic purification (silica gel 60, ethyl acetate:hexane 1:10) of the reaction mixture afforded a yellow solid that under recrystallization in methanol gave yellow crystals of (I)–(IV) [(I), yield 60%, m.p. 379–382 K. (II), yield 15%, m.p. 427–428 K. (III), yield 21%, m.p. 439.5–440.7 K. (IV) yield 21%, m.p. 429–430 K.
Centroids: Cg1: [C6, C7, C8, C9, C10 and C11]; Cg2: [C12, C13, C14, C15, C16 and C17]; Cg3: [C18, C19, C20, C21, C22 and C23].
H atoms attached to C atoms were included at calculated positions and treated as riding atoms in (I)–(III) using SHELXL97 (Sheldrick, 1997) default values [should this software be listed for these compounds in the following paragraph?]; in (IV), these were refined with the C—H distance restrained to be 0.93 (s.u.?) Å for aromatic and 0.99 (s.u.?) Å for aliphatic H atoms. In all four compounds, hydroxy atom H1 was treated as a riding atom, and amino atom H1N was refined with isotropic displacement parameters. Analysis of the diffraction pattern suggests that the rather high R factor obtained for (III) could be attributed to poor crystal quality.
Data collection: SMART-NT (Bruker, 2001) for (I), (II), (III); SMART (reference?) for (IV). Cell refinement: SAINT-NT (Bruker, 1999) for (I), (II), (III); SAINT (reference?) for (IV). Data reduction: SAINT-NT for (I), (II), (III); SAINT for (IV). Program(s) used to solve structure: SHELXTL-NT (Bruker, 1999 or??2000) for (I), (II), (III); SHELXS97 (Sheldrick, 1997) for (IV). Program(s) used to refine structure: SHELXTL-NT for (I), (II), (III); SHELXL97 (Sheldrick, 1997) for (IV). Molecular graphics: SHELXTL-NT for (I), (II), (III); ORTEP-3 (Farrugia, 1997) for (IV). Software used to prepare material for publication: SHELXTL-NT for (I), (II); SHELXTL-NT) for (III); WinGX (Farrugia, 1999) for (IV).
C21H18N2O | F(000) = 1328 |
Mr = 314.37 | Dx = 1.283 Mg m−3 |
Monoclinic, C2/c | Melting point: 380 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 24.855 (4) Å | Cell parameters from 1020 reflections |
b = 7.6825 (11) Å | θ = 2.2–18.3° |
c = 19.455 (3) Å | µ = 0.08 mm−1 |
β = 118.824 (2)° | T = 298 K |
V = 3254.7 (9) Å3 | Parallelepiped, yellow |
Z = 8 | 0.30 × 0.27 × 0.21 mm |
Siemens SMART CCD area-detector diffractometer | 2893 independent reflections |
Radiation source: fine-focus sealed tube | 1696 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | h = −29→29 |
Tmin = 0.977, Tmax = 0.983 | k = −9→9 |
9815 measured reflections | l = −23→23 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0542P)2 + 0.3684P] where P = (Fo2 + 2Fc2)/3 |
2893 reflections | (Δ/σ)max < 0.001 |
222 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
C21H18N2O | V = 3254.7 (9) Å3 |
Mr = 314.37 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.855 (4) Å | µ = 0.08 mm−1 |
b = 7.6825 (11) Å | T = 298 K |
c = 19.455 (3) Å | 0.30 × 0.27 × 0.21 mm |
β = 118.824 (2)° |
Siemens SMART CCD area-detector diffractometer | 2893 independent reflections |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | 1696 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.983 | Rint = 0.055 |
9815 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.16 e Å−3 |
2893 reflections | Δρmin = −0.12 e Å−3 |
222 parameters |
Experimental. Each frame was mesured during 10 s, using 0.3 /% between frames. |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 3.0880 (0.0508) x + 5.8114 (0.0147) y + 12.1106 (0.0319) z = 2.5763 (0.0060) * 0.0000 (0.0000) C2 * 0.0000 (0.0000) C3 * 0.0000 (0.0000) C4 Rms deviation of fitted atoms = 0.0000 - 9.0494 (0.0165) x + 4.8738 (0.0038) y - 8.2077 (0.0115) z = 0.2682 (0.0028) Angle to previous plane (with approximate e.s.d.) = 85.00 (0.12) * 0.0055 (0.0020) C6 * -0.0102 (0.0021) C7 * -0.0260 (0.0021) C8 * 0.0034 (0.0020) C9 * 0.0510 (0.0020) C10 * 0.0402 (0.0020) C11 * -0.0307 (0.0015) N1 * -0.0332 (0.0014) N5 Rms deviation of fitted atoms = 0.0297 19.5301 (0.0166) x - 0.5079 (0.0055) y + 3.1123 (0.0202) z = 1.6494 (0.0032) * -0.0140 (0.0018) C12 * -0.0049 (0.0021) C13 * -0.0092 (0.0021) C14 * -0.0016 (0.0020) C15 * 0.0105 (0.0022) C16 * 0.0046 (0.0019) C17 * 0.0146 (0.0014) O1 Rms deviation of fitted atoms = 0.0097 24.3581 (0.0063) x - 0.9586 (0.0081) y - 11.8349 (0.0172) z = 3.5606 (0.0072) * 0.0010 (0.0017) C18 * -0.0042 (0.0019) C19 * 0.0034 (0.0020) C20 * 0.0005 (0.0020) C21 * -0.0037 (0.0021) C22 * 0.0029 (0.0019) C23 Rms deviation of fitted atoms = 0.0029 |
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 | ||
N1 | 0.18248 (11) | 0.3724 (3) | −0.00900 (13) | 0.0643 (6) | |
H1N | 0.2102 (11) | 0.382 (3) | −0.0237 (13) | 0.058 (8)* | |
C2 | 0.15942 (11) | 0.5501 (3) | −0.01057 (14) | 0.0597 (7) | |
H2 | 0.1578 | 0.6113 | −0.0557 | 0.072* | |
C3 | 0.09438 (10) | 0.5396 (3) | −0.02214 (14) | 0.0590 (7) | |
H3A | 0.0814 | 0.6552 | −0.0162 | 0.071* | |
H3B | 0.0670 | 0.5009 | −0.0752 | 0.071* | |
C4 | 0.08842 (10) | 0.4186 (3) | 0.03442 (14) | 0.0555 (6) | |
N5 | 0.08771 (9) | 0.2526 (2) | 0.02463 (12) | 0.0603 (6) | |
C6 | 0.06048 (12) | 0.0401 (3) | −0.07624 (16) | 0.0694 (7) | |
H6 | 0.0304 | 0.0015 | −0.0644 | 0.083* | |
C7 | 0.06808 (14) | −0.0445 (3) | −0.13295 (16) | 0.0768 (8) | |
H7 | 0.0427 | −0.1374 | −0.1601 | 0.092* | |
C8 | 0.11330 (14) | 0.0084 (4) | −0.14943 (15) | 0.0762 (8) | |
H8 | 0.1194 | −0.0498 | −0.1870 | 0.091* | |
C9 | 0.14970 (12) | 0.1487 (3) | −0.10984 (15) | 0.0670 (7) | |
H9 | 0.1804 | 0.1839 | −0.1212 | 0.080* | |
C10 | 0.14182 (11) | 0.2385 (3) | −0.05366 (14) | 0.0575 (7) | |
C11 | 0.09635 (11) | 0.1814 (3) | −0.03608 (14) | 0.0573 (7) | |
C12 | 0.08040 (10) | 0.4826 (3) | 0.09969 (14) | 0.0572 (6) | |
C13 | 0.07015 (11) | 0.3679 (4) | 0.14824 (16) | 0.0644 (7) | |
O1 | 0.06828 (9) | 0.1949 (2) | 0.13799 (13) | 0.0870 (6) | |
H1 | 0.0752 | 0.1720 | 0.1018 | 0.101 (12)* | |
C14 | 0.06189 (12) | 0.4302 (4) | 0.20885 (17) | 0.0778 (8) | |
H14 | 0.0545 | 0.3524 | 0.2400 | 0.093* | |
C15 | 0.06440 (13) | 0.6039 (4) | 0.22389 (18) | 0.0829 (9) | |
H15 | 0.0587 | 0.6440 | 0.2651 | 0.100* | |
C16 | 0.07536 (13) | 0.7203 (4) | 0.17803 (18) | 0.0843 (9) | |
H16 | 0.0774 | 0.8391 | 0.1883 | 0.101* | |
C17 | 0.08313 (12) | 0.6598 (3) | 0.11745 (16) | 0.0760 (8) | |
H17 | 0.0905 | 0.7393 | 0.0869 | 0.091* | |
C18 | 0.20220 (11) | 0.6489 (3) | 0.06266 (14) | 0.0565 (6) | |
C19 | 0.23408 (12) | 0.5711 (4) | 0.13502 (16) | 0.0734 (8) | |
H19 | 0.2314 | 0.4514 | 0.1398 | 0.088* | |
C20 | 0.27023 (13) | 0.6706 (5) | 0.20071 (17) | 0.0866 (9) | |
H20 | 0.2920 | 0.6170 | 0.2494 | 0.104* | |
C21 | 0.27412 (14) | 0.8462 (5) | 0.1947 (2) | 0.0898 (10) | |
H21 | 0.2983 | 0.9123 | 0.2391 | 0.108* | |
C22 | 0.24217 (15) | 0.9251 (4) | 0.1230 (2) | 0.0890 (9) | |
H22 | 0.2444 | 1.0451 | 0.1185 | 0.107* | |
C23 | 0.20673 (13) | 0.8262 (3) | 0.05746 (17) | 0.0749 (8) | |
H23 | 0.1855 | 0.8804 | 0.0088 | 0.090* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0590 (14) | 0.0560 (14) | 0.0791 (16) | −0.0052 (11) | 0.0343 (13) | −0.0057 (12) |
C2 | 0.0626 (17) | 0.0502 (15) | 0.0636 (16) | −0.0017 (12) | 0.0282 (14) | 0.0029 (12) |
C3 | 0.0555 (16) | 0.0543 (15) | 0.0567 (15) | 0.0046 (12) | 0.0187 (13) | 0.0019 (12) |
C4 | 0.0451 (15) | 0.0542 (16) | 0.0591 (15) | −0.0002 (11) | 0.0188 (13) | 0.0014 (13) |
N5 | 0.0608 (13) | 0.0487 (13) | 0.0703 (14) | −0.0042 (10) | 0.0307 (12) | −0.0048 (11) |
C6 | 0.0672 (18) | 0.0591 (16) | 0.0773 (18) | −0.0049 (14) | 0.0312 (16) | −0.0062 (15) |
C7 | 0.082 (2) | 0.0643 (17) | 0.0697 (18) | −0.0079 (15) | 0.0247 (17) | −0.0115 (15) |
C8 | 0.095 (2) | 0.0665 (18) | 0.0620 (17) | 0.0044 (17) | 0.0335 (17) | −0.0073 (15) |
C9 | 0.0747 (19) | 0.0635 (17) | 0.0642 (17) | 0.0030 (15) | 0.0346 (15) | 0.0022 (15) |
C10 | 0.0550 (15) | 0.0492 (15) | 0.0579 (16) | 0.0037 (12) | 0.0191 (13) | 0.0043 (13) |
C11 | 0.0556 (16) | 0.0486 (15) | 0.0599 (16) | −0.0006 (12) | 0.0216 (14) | −0.0022 (13) |
C12 | 0.0478 (15) | 0.0578 (16) | 0.0607 (15) | −0.0012 (12) | 0.0221 (13) | 0.0014 (13) |
C13 | 0.0541 (16) | 0.0649 (18) | 0.0708 (18) | −0.0061 (13) | 0.0273 (14) | −0.0026 (15) |
O1 | 0.1097 (16) | 0.0708 (14) | 0.0949 (15) | −0.0204 (11) | 0.0608 (14) | −0.0042 (11) |
C14 | 0.0701 (19) | 0.096 (2) | 0.0694 (19) | −0.0133 (17) | 0.0355 (17) | −0.0084 (17) |
C15 | 0.074 (2) | 0.105 (3) | 0.0727 (19) | −0.0056 (18) | 0.0372 (17) | −0.022 (2) |
C16 | 0.094 (2) | 0.076 (2) | 0.083 (2) | 0.0084 (17) | 0.0425 (19) | −0.0128 (18) |
C17 | 0.089 (2) | 0.0632 (18) | 0.077 (2) | 0.0047 (15) | 0.0414 (17) | −0.0016 (15) |
C18 | 0.0538 (15) | 0.0541 (16) | 0.0604 (16) | −0.0063 (12) | 0.0265 (13) | −0.0032 (13) |
C19 | 0.0737 (19) | 0.0722 (18) | 0.0696 (19) | 0.0037 (15) | 0.0307 (17) | 0.0058 (16) |
C20 | 0.073 (2) | 0.114 (3) | 0.0584 (18) | 0.0016 (19) | 0.0203 (16) | −0.0067 (19) |
C21 | 0.078 (2) | 0.108 (3) | 0.080 (2) | −0.026 (2) | 0.0361 (19) | −0.036 (2) |
C22 | 0.099 (2) | 0.072 (2) | 0.095 (2) | −0.0252 (18) | 0.047 (2) | −0.0218 (19) |
C23 | 0.082 (2) | 0.0628 (18) | 0.0752 (19) | −0.0140 (15) | 0.0338 (17) | −0.0059 (15) |
N1—C10 | 1.410 (3) | C12—C13 | 1.402 (3) |
N1—C2 | 1.475 (3) | C13—O1 | 1.341 (3) |
N1—H1N | 0.87 (2) | C13—C14 | 1.377 (3) |
C2—C18 | 1.509 (3) | O1—H1 | 0.8200 |
C2—C3 | 1.523 (3) | C14—C15 | 1.361 (3) |
C2—H2 | 0.9800 | C14—H14 | 0.9300 |
C3—C4 | 1.501 (3) | C15—C16 | 1.380 (4) |
C3—H3A | 0.9700 | C15—H15 | 0.9300 |
C3—H3B | 0.9700 | C16—C17 | 1.365 (4) |
C4—N5 | 1.288 (3) | C16—H16 | 0.9300 |
C4—C12 | 1.462 (3) | C17—H17 | 0.9300 |
N5—C11 | 1.409 (3) | C18—C23 | 1.374 (3) |
C6—C7 | 1.370 (4) | C18—C19 | 1.375 (3) |
C6—C11 | 1.383 (3) | C19—C20 | 1.385 (4) |
C6—H6 | 0.9300 | C19—H19 | 0.9300 |
C7—C8 | 1.371 (4) | C20—C21 | 1.361 (4) |
C7—H7 | 0.9300 | C20—H20 | 0.9300 |
C8—C9 | 1.379 (3) | C21—C22 | 1.371 (4) |
C8—H8 | 0.9300 | C21—H21 | 0.9300 |
C9—C10 | 1.384 (3) | C22—C23 | 1.376 (4) |
C9—H9 | 0.9300 | C22—H22 | 0.9300 |
C10—C11 | 1.400 (3) | C23—H23 | 0.9300 |
C12—C17 | 1.398 (3) | ||
C10—N1—C2 | 120.4 (2) | C17—C12—C13 | 116.7 (2) |
C10—N1—H1N | 107.6 (15) | C17—C12—C4 | 122.1 (2) |
C2—N1—H1N | 106.3 (15) | C13—C12—C4 | 121.2 (2) |
N1—C2—C18 | 110.9 (2) | O1—C13—C14 | 117.6 (3) |
N1—C2—C3 | 109.2 (2) | O1—C13—C12 | 121.8 (2) |
C18—C2—C3 | 112.4 (2) | C14—C13—C12 | 120.6 (3) |
N1—C2—H2 | 108.1 | C13—O1—H1 | 109.5 |
C18—C2—H2 | 108.1 | C15—C14—C13 | 121.0 (3) |
C3—C2—H2 | 108.1 | C15—C14—H14 | 119.5 |
C4—C3—C2 | 113.39 (19) | C13—C14—H14 | 119.5 |
C4—C3—H3A | 108.9 | C14—C15—C16 | 120.0 (3) |
C2—C3—H3A | 108.9 | C14—C15—H15 | 120.0 |
C4—C3—H3B | 108.9 | C16—C15—H15 | 120.0 |
C2—C3—H3B | 108.9 | C17—C16—C15 | 119.5 (3) |
H3A—C3—H3B | 107.7 | C17—C16—H16 | 120.3 |
N5—C4—C12 | 117.6 (2) | C15—C16—H16 | 120.3 |
N5—C4—C3 | 120.3 (2) | C16—C17—C12 | 122.3 (3) |
C12—C4—C3 | 122.1 (2) | C16—C17—H17 | 118.8 |
C4—N5—C11 | 120.7 (2) | C12—C17—H17 | 118.8 |
C7—C6—C11 | 121.7 (3) | C23—C18—C19 | 118.6 (2) |
C7—C6—H6 | 119.1 | C23—C18—C2 | 118.4 (2) |
C11—C6—H6 | 119.1 | C19—C18—C2 | 122.9 (2) |
C6—C7—C8 | 119.6 (3) | C18—C19—C20 | 120.1 (3) |
C6—C7—H7 | 120.2 | C18—C19—H19 | 119.9 |
C8—C7—H7 | 120.2 | C20—C19—H19 | 119.9 |
C7—C8—C9 | 119.5 (3) | C21—C20—C19 | 120.6 (3) |
C7—C8—H8 | 120.2 | C21—C20—H20 | 119.7 |
C9—C8—H8 | 120.2 | C19—C20—H20 | 119.7 |
C8—C9—C10 | 121.7 (3) | C20—C21—C22 | 119.7 (3) |
C8—C9—H9 | 119.1 | C20—C21—H21 | 120.2 |
C10—C9—H9 | 119.1 | C22—C21—H21 | 120.2 |
C9—C10—C11 | 118.4 (2) | C21—C22—C23 | 119.8 (3) |
C9—C10—N1 | 121.2 (2) | C21—C22—H22 | 120.1 |
C11—C10—N1 | 120.1 (2) | C23—C22—H22 | 120.1 |
C6—C11—C10 | 119.0 (2) | C18—C23—C22 | 121.1 (3) |
C6—C11—N5 | 117.4 (2) | C18—C23—H23 | 119.4 |
C10—C11—N5 | 123.4 (2) | C22—C23—H23 | 119.4 |
C10—N1—C2—C18 | 156.4 (2) | N5—C4—C12—C13 | −2.2 (3) |
C10—N1—C2—C3 | 32.0 (3) | C3—C4—C12—C13 | 175.0 (2) |
N1—C2—C3—C4 | 51.1 (3) | C17—C12—C13—O1 | −178.2 (2) |
C18—C2—C3—C4 | −72.3 (3) | C4—C12—C13—O1 | 1.2 (4) |
C2—C3—C4—N5 | −76.3 (3) | C17—C12—C13—C14 | 1.5 (4) |
C2—C3—C4—C12 | 106.6 (2) | C4—C12—C13—C14 | −179.2 (2) |
C12—C4—N5—C11 | −178.8 (2) | O1—C13—C14—C15 | 178.7 (2) |
C3—C4—N5—C11 | 4.0 (3) | C12—C13—C14—C15 | −1.0 (4) |
C11—C6—C7—C8 | 1.7 (4) | C13—C14—C15—C16 | 0.0 (4) |
C6—C7—C8—C9 | −1.4 (4) | C14—C15—C16—C17 | 0.5 (4) |
C7—C8—C9—C10 | −0.1 (4) | C15—C16—C17—C12 | 0.0 (4) |
C8—C9—C10—C11 | 1.4 (4) | C13—C12—C17—C16 | −1.0 (4) |
C8—C9—C10—N1 | 174.7 (2) | C4—C12—C17—C16 | 179.6 (2) |
C2—N1—C10—C9 | 121.4 (3) | N1—C2—C18—C23 | 149.0 (2) |
C2—N1—C10—C11 | −65.4 (3) | C3—C2—C18—C23 | −88.5 (3) |
C7—C6—C11—C10 | −0.4 (4) | N1—C2—C18—C19 | −34.9 (3) |
C7—C6—C11—N5 | −176.0 (2) | C3—C2—C18—C19 | 87.7 (3) |
C9—C10—C11—C6 | −1.1 (3) | C23—C18—C19—C20 | −0.5 (4) |
N1—C10—C11—C6 | −174.5 (2) | C2—C18—C19—C20 | −176.7 (2) |
C9—C10—C11—N5 | 174.2 (2) | C18—C19—C20—C21 | 0.8 (4) |
N1—C10—C11—N5 | 0.8 (3) | C19—C20—C21—C22 | −0.3 (4) |
C4—N5—C11—C6 | −140.0 (2) | C20—C21—C22—C23 | −0.4 (4) |
C4—N5—C11—C10 | 44.6 (3) | C19—C18—C23—C22 | −0.2 (4) |
N5—C4—C12—C17 | 177.2 (2) | C2—C18—C23—C22 | 176.2 (2) |
C3—C4—C12—C17 | −5.7 (3) | C21—C22—C23—C18 | 0.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.79 | 2.514 (3) | 147 |
C23—H23···Cg1i | 0.93 | 2.62 | 3.480 (2) | 155 |
Symmetry code: (i) x, y+1, z. |
C23H22N2O3 | Z = 2 |
Mr = 374.43 | F(000) = 396 |
Triclinic, P1 | Dx = 1.312 Mg m−3 |
Hall symbol: -P 1 | Melting point: 427 K |
a = 8.250 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.889 (3) Å | Cell parameters from 590 reflections |
c = 12.272 (3) Å | θ = 2.2–20.5° |
α = 108.697 (4)° | µ = 0.09 mm−1 |
β = 90.973 (5)° | T = 298 K |
γ = 90.594 (5)° | Rhombohedral, yellow |
V = 948.1 (4) Å3 | 0.30 × 0.18 × 0.11 mm |
Siemens SMART CCD area-detector diffractometer | 3329 independent reflections |
Radiation source: fine-focus sealed tube | 1625 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | h = −9→9 |
Tmin = 0.974, Tmax = 0.990 | k = −11→11 |
5882 measured reflections | l = −14→14 |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.179 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0776P)2] where P = (Fo2 + 2Fc2)/3 |
3329 reflections | (Δ/σ)max < 0.001 |
259 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C23H22N2O3 | γ = 90.594 (5)° |
Mr = 374.43 | V = 948.1 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.250 (2) Å | Mo Kα radiation |
b = 9.889 (3) Å | µ = 0.09 mm−1 |
c = 12.272 (3) Å | T = 298 K |
α = 108.697 (4)° | 0.30 × 0.18 × 0.11 mm |
β = 90.973 (5)° |
Siemens SMART CCD area-detector diffractometer | 3329 independent reflections |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | 1625 reflections with I > 2σ(I) |
Tmin = 0.974, Tmax = 0.990 | Rint = 0.040 |
5882 measured reflections |
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.179 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.98 | Δρmax = 0.16 e Å−3 |
3329 reflections | Δρmin = −0.20 e Å−3 |
259 parameters |
Experimental. Each frame was mesured during 10 s, using 0.3 /% between frames |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 2.2454 (0.0103) x + 7.1291 (0.0089) y + 4.6739 (0.0145) z = 5.2452 (0.0142) * -0.0055 (0.0021) C18 * 0.0111 (0.0022) C19 * -0.0076 (0.0023) C20 * -0.0016 (0.0024) C21 * 0.0073 (0.0024) C22 * -0.0037 (0.0023) C23 Rms deviation of fitted atoms = 0.0068 1.6961 (0.0080) x - 2.1072 (0.0146) y + 11.8939 (0.0043) z = 8.6201 (0.0052) * 0.0030 (0.0026) C12 * 0.0077 (0.0031) C13 * 0.0029 (0.0030) C14 * -0.0026 (0.0031) C15 * -0.0006 (0.0032) C16 * -0.0032 (0.0026) C17 * -0.0072 (0.0021) O1 Rms deviation of fitted atoms = 0.0046 4.2072 (0.0072) x - 3.4921 (0.0097) y + 10.4063 (0.0071) z = 9.3483 (0.0052) Angle to previous plane (with approximate e.s.d.) = 78.74 (0.21) * 0.0181 (0.0030) C6 * 0.0258 (0.0033) C7 * -0.0039 (0.0034) C8 * -0.0258 (0.0032) C9 * -0.0263 (0.0030) C10 * -0.0275 (0.0030) C11 * 0.0459 (0.0023) N1 * -0.0063 (0.0022) N5 Rms deviation of fitted atoms = 0.0257 - 5.3883 (0.0286) x - 6.3941 (0.0205) y + 7.1566 (0.0422) z = 1.0500 (0.0400) Angle to previous plane (with approximate e.s.d.) = 78.74 (0.21) * 0.0000 (0.0000) C2 * 0.0000 (0.0000) C3 * 0.0000 (0.0000) C4 Rms deviation of fitted atoms = 0.0000 |
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 | ||
N1 | 0.6001 (4) | 0.4398 (3) | 0.8077 (3) | 0.0686 (9) | |
H1N | 0.584 (4) | 0.533 (4) | 0.842 (3) | 0.094 (14)* | |
C2 | 0.4586 (4) | 0.3520 (3) | 0.8064 (3) | 0.0557 (9) | |
H2 | 0.3647 | 0.4147 | 0.8185 | 0.067* | |
C3 | 0.4344 (4) | 0.2398 (4) | 0.6881 (3) | 0.0603 (9) | |
H3A | 0.3243 | 0.2024 | 0.6811 | 0.072* | |
H3B | 0.4480 | 0.2854 | 0.6295 | 0.072* | |
C4 | 0.5492 (5) | 0.1186 (4) | 0.6662 (3) | 0.0565 (9) | |
N5 | 0.7035 (4) | 0.1382 (3) | 0.6597 (2) | 0.0602 (8) | |
C6 | 0.9247 (4) | 0.2576 (4) | 0.6127 (3) | 0.0704 (11) | |
H6 | 0.9587 | 0.1666 | 0.5710 | 0.084* | |
C7 | 1.0197 (5) | 0.3708 (5) | 0.6130 (4) | 0.0891 (13) | |
H7 | 1.1155 | 0.3580 | 0.5723 | 0.107* | |
C8 | 0.9692 (5) | 0.5050 (5) | 0.6756 (4) | 0.0935 (14) | |
H8 | 1.0311 | 0.5846 | 0.6767 | 0.112* | |
C9 | 0.8284 (5) | 0.5225 (4) | 0.7363 (3) | 0.0765 (11) | |
H9 | 0.7974 | 0.6144 | 0.7782 | 0.092* | |
C10 | 0.7304 (4) | 0.4076 (4) | 0.7373 (3) | 0.0568 (9) | |
C11 | 0.7800 (4) | 0.2698 (4) | 0.6709 (3) | 0.0570 (9) | |
C12 | 0.4926 (5) | −0.0272 (4) | 0.6499 (3) | 0.0623 (10) | |
C13 | 0.5973 (6) | −0.1432 (4) | 0.6149 (3) | 0.0738 (11) | |
O1 | 0.7540 (3) | −0.1257 (3) | 0.5944 (2) | 0.0862 (9) | |
H1 | 0.7747 | −0.0404 | 0.6085 | 0.129* | |
C14 | 0.5399 (7) | −0.2817 (4) | 0.5981 (3) | 0.0900 (14) | |
H14 | 0.6101 | −0.3581 | 0.5746 | 0.108* | |
C15 | 0.3815 (8) | −0.3052 (5) | 0.6161 (4) | 0.1051 (17) | |
H15 | 0.3441 | −0.3979 | 0.6045 | 0.126* | |
C16 | 0.2760 (6) | −0.1942 (6) | 0.6509 (4) | 0.0960 (14) | |
H16 | 0.1680 | −0.2110 | 0.6636 | 0.115* | |
C17 | 0.3316 (5) | −0.0590 (4) | 0.6667 (3) | 0.0783 (12) | |
H17 | 0.2589 | 0.0156 | 0.6898 | 0.094* | |
C18 | 0.4614 (4) | 0.2881 (3) | 0.9032 (3) | 0.0502 (8) | |
C19 | 0.3215 (4) | 0.2287 (3) | 0.9302 (3) | 0.0518 (8) | |
O2 | 0.1821 (3) | 0.2256 (2) | 0.86454 (19) | 0.0645 (7) | |
C24 | 0.0645 (4) | 0.3256 (4) | 0.9221 (4) | 0.0871 (13) | |
H24A | 0.0176 | 0.2959 | 0.9819 | 0.131* | |
H24B | −0.0189 | 0.3308 | 0.8681 | 0.131* | |
H24C | 0.1153 | 0.4179 | 0.9551 | 0.131* | |
C20 | 0.3182 (4) | 0.1679 (3) | 1.0174 (3) | 0.0576 (9) | |
O3 | 0.1732 (3) | 0.1093 (3) | 1.0322 (2) | 0.0759 (8) | |
C25 | 0.1575 (5) | 0.0587 (4) | 1.1285 (3) | 0.0844 (12) | |
H25A | 0.2351 | −0.0147 | 1.1233 | 0.127* | |
H25B | 0.0500 | 0.0205 | 1.1285 | 0.127* | |
H25C | 0.1769 | 0.1362 | 1.1985 | 0.127* | |
C21 | 0.4580 (5) | 0.1706 (4) | 1.0816 (3) | 0.0651 (10) | |
H21 | 0.4585 | 0.1315 | 1.1412 | 0.078* | |
C22 | 0.5964 (4) | 0.2320 (4) | 1.0564 (3) | 0.0668 (10) | |
H22 | 0.6900 | 0.2347 | 1.1003 | 0.080* | |
C23 | 0.6012 (4) | 0.2891 (4) | 0.9692 (3) | 0.0605 (9) | |
H23 | 0.6973 | 0.3287 | 0.9537 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.074 (2) | 0.049 (2) | 0.077 (2) | −0.0023 (17) | 0.0261 (17) | 0.0110 (17) |
C2 | 0.055 (2) | 0.054 (2) | 0.057 (2) | 0.0020 (17) | 0.0124 (17) | 0.0153 (18) |
C3 | 0.073 (2) | 0.062 (2) | 0.050 (2) | −0.0006 (19) | 0.0054 (18) | 0.0229 (18) |
C4 | 0.076 (3) | 0.054 (2) | 0.0384 (19) | 0.005 (2) | 0.0085 (17) | 0.0129 (16) |
N5 | 0.068 (2) | 0.060 (2) | 0.0497 (18) | 0.0032 (16) | 0.0096 (15) | 0.0141 (14) |
C6 | 0.065 (2) | 0.078 (3) | 0.066 (3) | 0.009 (2) | 0.010 (2) | 0.020 (2) |
C7 | 0.069 (3) | 0.094 (3) | 0.104 (4) | 0.002 (3) | 0.029 (2) | 0.029 (3) |
C8 | 0.089 (3) | 0.079 (3) | 0.118 (4) | −0.010 (2) | 0.030 (3) | 0.039 (3) |
C9 | 0.085 (3) | 0.059 (2) | 0.087 (3) | −0.004 (2) | 0.024 (2) | 0.025 (2) |
C10 | 0.063 (2) | 0.054 (2) | 0.055 (2) | 0.0016 (18) | 0.0075 (18) | 0.0195 (18) |
C11 | 0.062 (2) | 0.060 (2) | 0.050 (2) | 0.0015 (18) | 0.0052 (17) | 0.0178 (18) |
C12 | 0.084 (3) | 0.057 (2) | 0.041 (2) | −0.006 (2) | 0.0044 (18) | 0.0094 (17) |
C13 | 0.112 (3) | 0.061 (3) | 0.044 (2) | −0.002 (2) | 0.016 (2) | 0.0098 (19) |
O1 | 0.115 (2) | 0.0631 (18) | 0.0755 (19) | 0.0185 (15) | 0.0253 (17) | 0.0133 (14) |
C14 | 0.155 (5) | 0.058 (3) | 0.051 (2) | 0.003 (3) | 0.013 (3) | 0.009 (2) |
C15 | 0.170 (5) | 0.074 (3) | 0.065 (3) | −0.036 (4) | 0.014 (3) | 0.015 (2) |
C16 | 0.118 (4) | 0.086 (4) | 0.075 (3) | −0.030 (3) | 0.002 (3) | 0.014 (3) |
C17 | 0.098 (3) | 0.068 (3) | 0.065 (3) | −0.020 (2) | −0.001 (2) | 0.016 (2) |
C18 | 0.052 (2) | 0.050 (2) | 0.046 (2) | 0.0061 (16) | 0.0125 (16) | 0.0115 (16) |
C19 | 0.055 (2) | 0.054 (2) | 0.046 (2) | 0.0070 (17) | −0.0006 (17) | 0.0150 (17) |
O2 | 0.0513 (15) | 0.0825 (18) | 0.0585 (15) | 0.0036 (12) | −0.0013 (12) | 0.0211 (13) |
C24 | 0.061 (2) | 0.112 (3) | 0.090 (3) | 0.023 (2) | 0.008 (2) | 0.034 (3) |
C20 | 0.063 (2) | 0.053 (2) | 0.056 (2) | 0.0058 (18) | 0.0079 (19) | 0.0147 (18) |
O3 | 0.0771 (18) | 0.0916 (19) | 0.0681 (17) | −0.0176 (14) | 0.0043 (13) | 0.0386 (15) |
C25 | 0.107 (3) | 0.082 (3) | 0.071 (3) | −0.013 (2) | 0.016 (2) | 0.036 (2) |
C21 | 0.078 (3) | 0.068 (3) | 0.051 (2) | 0.016 (2) | 0.005 (2) | 0.0214 (19) |
C22 | 0.058 (2) | 0.085 (3) | 0.054 (2) | 0.013 (2) | 0.0015 (19) | 0.018 (2) |
C23 | 0.052 (2) | 0.065 (2) | 0.059 (2) | 0.0036 (18) | 0.0057 (18) | 0.0119 (19) |
N1—C10 | 1.366 (4) | C14—C15 | 1.359 (6) |
N1—C2 | 1.445 (4) | C14—H14 | 0.9300 |
N1—H1N | 0.90 (4) | C15—C16 | 1.370 (6) |
C2—C18 | 1.514 (4) | C15—H15 | 0.9300 |
C2—C3 | 1.527 (4) | C16—C17 | 1.361 (5) |
C2—H2 | 0.9800 | C16—H16 | 0.9300 |
C3—C4 | 1.493 (4) | C17—H17 | 0.9300 |
C3—H3A | 0.9700 | C18—C19 | 1.383 (4) |
C3—H3B | 0.9700 | C18—C23 | 1.396 (4) |
C4—N5 | 1.294 (4) | C19—C20 | 1.385 (4) |
C4—C12 | 1.462 (5) | C19—O2 | 1.388 (3) |
N5—C11 | 1.405 (4) | O2—C24 | 1.419 (4) |
C6—C7 | 1.358 (5) | C24—H24A | 0.9600 |
C6—C11 | 1.388 (4) | C24—H24B | 0.9600 |
C6—H6 | 0.9300 | C24—H24C | 0.9600 |
C7—C8 | 1.376 (5) | C20—O3 | 1.363 (4) |
C7—H7 | 0.9300 | C20—C21 | 1.381 (4) |
C8—C9 | 1.374 (5) | O3—C25 | 1.432 (4) |
C8—H8 | 0.9300 | C25—H25A | 0.9600 |
C9—C10 | 1.391 (4) | C25—H25B | 0.9600 |
C9—H9 | 0.9300 | C25—H25C | 0.9600 |
C10—C11 | 1.415 (4) | C21—C22 | 1.373 (4) |
C12—C17 | 1.396 (5) | C21—H21 | 0.9300 |
C12—C13 | 1.401 (5) | C22—C23 | 1.361 (4) |
C13—O1 | 1.341 (4) | C22—H22 | 0.9300 |
C13—C14 | 1.395 (5) | C23—H23 | 0.9300 |
O1—H1 | 0.8200 | ||
C10—N1—C2 | 128.1 (3) | C15—C14—C13 | 120.1 (4) |
C10—N1—H1N | 115 (2) | C15—C14—H14 | 120.0 |
C2—N1—H1N | 114 (2) | C13—C14—H14 | 120.0 |
N1—C2—C18 | 112.8 (3) | C14—C15—C16 | 120.9 (4) |
N1—C2—C3 | 110.3 (3) | C14—C15—H15 | 119.5 |
C18—C2—C3 | 112.9 (3) | C16—C15—H15 | 119.5 |
N1—C2—H2 | 106.8 | C17—C16—C15 | 119.1 (5) |
C18—C2—H2 | 106.8 | C17—C16—H16 | 120.4 |
C3—C2—H2 | 106.8 | C15—C16—H16 | 120.4 |
C4—C3—C2 | 113.5 (3) | C16—C17—C12 | 123.0 (4) |
C4—C3—H3A | 108.9 | C16—C17—H17 | 118.5 |
C2—C3—H3A | 108.9 | C12—C17—H17 | 118.5 |
C4—C3—H3B | 108.9 | C19—C18—C23 | 117.8 (3) |
C2—C3—H3B | 108.9 | C19—C18—C2 | 120.0 (3) |
H3A—C3—H3B | 107.7 | C23—C18—C2 | 122.2 (3) |
N5—C4—C12 | 117.0 (3) | C18—C19—C20 | 122.1 (3) |
N5—C4—C3 | 121.2 (3) | C18—C19—O2 | 118.4 (3) |
C12—C4—C3 | 121.8 (3) | C20—C19—O2 | 119.4 (3) |
C4—N5—C11 | 125.2 (3) | C19—O2—C24 | 113.7 (3) |
C7—C6—C11 | 123.9 (4) | O2—C24—H24A | 109.5 |
C7—C6—H6 | 118.1 | O2—C24—H24B | 109.5 |
C11—C6—H6 | 118.1 | H24A—C24—H24B | 109.5 |
C6—C7—C8 | 117.7 (4) | O2—C24—H24C | 109.5 |
C6—C7—H7 | 121.1 | H24A—C24—H24C | 109.5 |
C8—C7—H7 | 121.1 | H24B—C24—H24C | 109.5 |
C9—C8—C7 | 120.6 (4) | O3—C20—C21 | 125.3 (3) |
C9—C8—H8 | 119.7 | O3—C20—C19 | 115.8 (3) |
C7—C8—H8 | 119.7 | C21—C20—C19 | 118.9 (3) |
C8—C9—C10 | 122.3 (4) | C20—O3—C25 | 118.3 (3) |
C8—C9—H9 | 118.8 | O3—C25—H25A | 109.5 |
C10—C9—H9 | 118.8 | O3—C25—H25B | 109.5 |
N1—C10—C9 | 116.0 (3) | H25A—C25—H25B | 109.5 |
N1—C10—C11 | 126.7 (3) | O3—C25—H25C | 109.5 |
C9—C10—C11 | 117.2 (3) | H25A—C25—H25C | 109.5 |
C6—C11—N5 | 113.9 (3) | H25B—C25—H25C | 109.5 |
C6—C11—C10 | 118.3 (3) | C22—C21—C20 | 119.1 (3) |
N5—C11—C10 | 127.7 (3) | C22—C21—H21 | 120.5 |
C17—C12—C13 | 116.4 (4) | C20—C21—H21 | 120.5 |
C17—C12—C4 | 122.1 (4) | C23—C22—C21 | 122.3 (3) |
C13—C12—C4 | 121.5 (4) | C23—C22—H22 | 118.9 |
O1—C13—C14 | 117.9 (4) | C21—C22—H22 | 118.9 |
O1—C13—C12 | 121.6 (4) | C22—C23—C18 | 119.8 (3) |
C14—C13—C12 | 120.5 (4) | C22—C23—H23 | 120.1 |
C13—O1—H1 | 109.5 | C18—C23—H23 | 120.1 |
C10—N1—C2—C18 | 104.5 (4) | C4—C12—C13—C14 | −178.9 (3) |
C10—N1—C2—C3 | −22.7 (5) | O1—C13—C14—C15 | −179.0 (4) |
N1—C2—C3—C4 | 76.0 (4) | C12—C13—C14—C15 | −0.2 (6) |
C18—C2—C3—C4 | −51.1 (4) | C13—C14—C15—C16 | −0.1 (7) |
C2—C3—C4—N5 | −65.1 (4) | C14—C15—C16—C17 | 0.5 (7) |
C2—C3—C4—C12 | 115.5 (3) | C15—C16—C17—C12 | −0.5 (6) |
C12—C4—N5—C11 | 178.8 (3) | C13—C12—C17—C16 | 0.2 (5) |
C3—C4—N5—C11 | −0.6 (5) | C4—C12—C17—C16 | 179.3 (3) |
C11—C6—C7—C8 | 0.5 (6) | N1—C2—C18—C19 | 165.5 (3) |
C6—C7—C8—C9 | 0.7 (7) | C3—C2—C18—C19 | −68.7 (4) |
C7—C8—C9—C10 | −0.4 (7) | N1—C2—C18—C23 | −13.2 (4) |
C2—N1—C10—C9 | 163.6 (4) | C3—C2—C18—C23 | 112.6 (3) |
C2—N1—C10—C11 | −20.1 (6) | C23—C18—C19—C20 | −1.8 (5) |
C8—C9—C10—N1 | 175.6 (4) | C2—C18—C19—C20 | 179.4 (3) |
C8—C9—C10—C11 | −1.1 (6) | C23—C18—C19—O2 | −179.3 (3) |
C7—C6—C11—N5 | −179.1 (4) | C2—C18—C19—O2 | 1.9 (4) |
C7—C6—C11—C10 | −1.9 (6) | C18—C19—O2—C24 | −106.6 (3) |
C4—N5—C11—C6 | −152.7 (3) | C20—C19—O2—C24 | 75.9 (4) |
C4—N5—C11—C10 | 30.5 (5) | C18—C19—C20—O3 | −178.0 (3) |
N1—C10—C11—C6 | −174.1 (3) | O2—C19—C20—O3 | −0.5 (4) |
C9—C10—C11—C6 | 2.2 (5) | C18—C19—C20—C21 | 2.0 (5) |
N1—C10—C11—N5 | 2.6 (6) | O2—C19—C20—C21 | 179.5 (3) |
C9—C10—C11—N5 | 178.9 (3) | C21—C20—O3—C25 | 6.6 (5) |
N5—C4—C12—C17 | 173.2 (3) | C19—C20—O3—C25 | −173.4 (3) |
C3—C4—C12—C17 | −7.4 (5) | O3—C20—C21—C22 | 179.3 (3) |
N5—C4—C12—C13 | −7.7 (5) | C19—C20—C21—C22 | −0.7 (5) |
C3—C4—C12—C13 | 171.7 (3) | C20—C21—C22—C23 | −0.7 (5) |
C17—C12—C13—O1 | 178.9 (3) | C21—C22—C23—C18 | 0.9 (5) |
C4—C12—C13—O1 | −0.1 (5) | C19—C18—C23—C22 | 0.3 (5) |
C17—C12—C13—C14 | 0.2 (5) | C2—C18—C23—C22 | 179.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.78 | 2.514 (4) | 147 |
N1—H1N···Cg2i | 0.90 (4) | 2.60 (4) | 3.445 (4) | 159 (3) |
Symmetry code: (i) −x, −y+1, −z+2. |
C23H22N2O3 | F(000) = 792 |
Mr = 374.43 | Dx = 1.300 Mg m−3 |
Monoclinic, P21/n | Melting point: 439 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 5.5372 (8) Å | Cell parameters from 590 reflections |
b = 23.144 (3) Å | θ = 2.2–20.6° |
c = 15.131 (2) Å | µ = 0.09 mm−1 |
β = 99.520 (3)° | T = 300 K |
V = 1912.4 (4) Å3 | Paralellepiped, yellow |
Z = 4 | 0.37 × 0.07 × 0.06 mm |
Siemens SMART CCD area-detector diffractometer | 3400 independent reflections |
Radiation source: fine-focus sealed tube | 1703 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.105 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.6° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | h = −6→6 |
Tmin = 0.969, Tmax = 0.995 | k = −27→27 |
11881 measured reflections | l = −17→18 |
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)] = 0.086 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0479P)2 + 0.2814P] where P = (Fo2 + 2Fc2)/3 |
3400 reflections | (Δ/σ)max < 0.001 |
259 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C23H22N2O3 | V = 1912.4 (4) Å3 |
Mr = 374.43 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.5372 (8) Å | µ = 0.09 mm−1 |
b = 23.144 (3) Å | T = 300 K |
c = 15.131 (2) Å | 0.37 × 0.07 × 0.06 mm |
β = 99.520 (3)° |
Siemens SMART CCD area-detector diffractometer | 3400 independent reflections |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | 1703 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.995 | Rint = 0.105 |
11881 measured reflections |
R[F2 > 2σ(F2)] = 0.086 | 0 restraints |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.15 e Å−3 |
3400 reflections | Δρmin = −0.16 e Å−3 |
259 parameters |
Experimental. Each frame was mesured during 10 s, using 0.3 /% between frames. |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.1081 (0.0075) x + 5.2479 (0.0357) y - 13.2822 (0.0120) z = 3.3701 (0.0319) * 0.0009 (0.0028) C18 * -0.0080 (0.0027) C19 * 0.0073 (0.0027) C20 * 0.0002 (0.0028) C21 * -0.0070 (0.0030) C22 * 0.0065 (0.0030) C23 Rms deviation of fitted atoms = 0.0059 - 3.1166 (0.0059) x + 9.5144 (0.0332) y + 12.1093 (0.0164) z = 5.9998 (0.0294) * -0.0022 (0.0032) C12 * 0.0004 (0.0037) C13 * -0.0040 (0.0038) C14 * 0.0018 (0.0037) C15 * 0.0014 (0.0039) C16 * 0.0002 (0.0033) C17 * 0.0026 (0.0026) O1 Rms deviation of fitted atoms = 0.0022 - 5.0661 (0.0023) x + 9.2071 (0.0203) y + 3.3077 (0.0176) z = 5.5180 (0.0139) * -0.0291 (0.0033) C6 * 0.0073 (0.0038) C7 * 0.0384 (0.0036) C8 * 0.0215 (0.0032) C9 * -0.0642 (0.0033) C10 * -0.0584 (0.0033) C11 * 0.0126 (0.0024) N1 * 0.0718 (0.0024) N5 Rms deviation of fitted atoms = 0.0443 2.2890 (0.0289) x + 21.0095 (0.0529) y + 0.0250 (0.0463) z = 16.9498 (0.0263) Angle to previous plane (with approximate e.s.d.) = 89.30 (0.29) * 0.0000 (0.0001) C2 * 0.0000 (0.0000) C3 * 0.0000 (0.0000) C4 Rms deviation of fitted atoms = 0.0000 |
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 | ||
N1 | 0.3384 (6) | 0.72297 (14) | 0.1780 (2) | 0.0520 (10) | |
H1N | 0.335 (7) | 0.7169 (15) | 0.237 (2) | 0.062* | |
C2 | 0.5888 (7) | 0.74241 (16) | 0.1711 (3) | 0.0488 (11) | |
H2 | 0.7050 | 0.7160 | 0.2065 | 0.059* | |
C3 | 0.6256 (6) | 0.73852 (16) | 0.0735 (3) | 0.0525 (11) | |
H3A | 0.7722 | 0.7598 | 0.0667 | 0.063* | |
H3B | 0.6519 | 0.6984 | 0.0592 | 0.063* | |
C4 | 0.4141 (8) | 0.76164 (18) | 0.0077 (3) | 0.0522 (11) | |
N5 | 0.2173 (6) | 0.73136 (15) | −0.0129 (2) | 0.0550 (9) | |
C6 | 0.0602 (8) | 0.6347 (2) | −0.0151 (3) | 0.0703 (14) | |
H6 | 0.0248 | 0.6370 | −0.0772 | 0.084* | |
C7 | −0.0072 (8) | 0.5863 (2) | 0.0273 (4) | 0.0828 (16) | |
H7 | −0.0850 | 0.5559 | −0.0061 | 0.099* | |
C8 | 0.0405 (8) | 0.5830 (2) | 0.1190 (4) | 0.0844 (16) | |
H8 | −0.0062 | 0.5504 | 0.1480 | 0.101* | |
C9 | 0.1575 (7) | 0.62790 (19) | 0.1682 (3) | 0.0671 (13) | |
H9 | 0.1850 | 0.6258 | 0.2304 | 0.081* | |
C10 | 0.2349 (7) | 0.67606 (17) | 0.1267 (3) | 0.0511 (11) | |
C11 | 0.1798 (7) | 0.68001 (17) | 0.0331 (3) | 0.0524 (11) | |
C12 | 0.4250 (8) | 0.81744 (19) | −0.0376 (3) | 0.0536 (11) | |
C13 | 0.2287 (8) | 0.8360 (2) | −0.1025 (3) | 0.0636 (12) | |
O1 | 0.0290 (6) | 0.80266 (13) | −0.1275 (2) | 0.0757 (9) | |
H1 | 0.0417 | 0.7730 | −0.0976 | 0.114* | |
C14 | 0.2341 (10) | 0.8893 (2) | −0.1434 (3) | 0.0793 (15) | |
H14 | 0.1038 | 0.9010 | −0.1866 | 0.095* | |
C15 | 0.4313 (10) | 0.9249 (2) | −0.1201 (3) | 0.0840 (16) | |
H15 | 0.4338 | 0.9609 | −0.1473 | 0.101* | |
C16 | 0.6252 (10) | 0.9082 (2) | −0.0571 (4) | 0.0843 (16) | |
H16 | 0.7591 | 0.9326 | −0.0417 | 0.101* | |
C17 | 0.6203 (8) | 0.8553 (2) | −0.0169 (3) | 0.0713 (14) | |
H17 | 0.7528 | 0.8444 | 0.0259 | 0.086* | |
C18 | 0.6308 (7) | 0.80232 (17) | 0.2108 (3) | 0.0469 (10) | |
C19 | 0.4598 (7) | 0.84580 (17) | 0.1886 (3) | 0.0496 (11) | |
H19 | 0.3119 | 0.8374 | 0.1520 | 0.060* | |
C20 | 0.5049 (7) | 0.90070 (17) | 0.2197 (3) | 0.0468 (10) | |
O2 | 0.3493 (5) | 0.94661 (12) | 0.1998 (2) | 0.0656 (8) | |
C24 | 0.1547 (8) | 0.94006 (18) | 0.1259 (3) | 0.0722 (14) | |
H24A | 0.0463 | 0.9100 | 0.1389 | 0.108* | |
H24B | 0.2211 | 0.9301 | 0.0732 | 0.108* | |
H24C | 0.0658 | 0.9757 | 0.1159 | 0.108* | |
C21 | 0.7246 (7) | 0.91336 (18) | 0.2767 (3) | 0.0528 (11) | |
O3 | 0.7498 (5) | 0.96936 (12) | 0.3045 (2) | 0.0738 (9) | |
C25 | 0.9687 (8) | 0.9844 (2) | 0.3635 (3) | 0.0964 (18) | |
H25A | 1.1080 | 0.9741 | 0.3366 | 0.145* | |
H25B | 0.9751 | 0.9640 | 0.4191 | 0.145* | |
H25C | 0.9705 | 1.0253 | 0.3746 | 0.145* | |
C22 | 0.8923 (7) | 0.87055 (19) | 0.2996 (3) | 0.0607 (12) | |
H22 | 1.0380 | 0.8784 | 0.3378 | 0.073* | |
C23 | 0.8456 (7) | 0.81499 (18) | 0.2657 (3) | 0.0580 (12) | |
H23 | 0.9623 | 0.7862 | 0.2806 | 0.070* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.059 (2) | 0.049 (2) | 0.049 (2) | −0.0061 (18) | 0.013 (2) | −0.0009 (19) |
C2 | 0.045 (2) | 0.047 (3) | 0.053 (3) | 0.007 (2) | 0.006 (2) | −0.004 (2) |
C3 | 0.042 (2) | 0.046 (3) | 0.070 (3) | 0.001 (2) | 0.012 (2) | −0.011 (2) |
C4 | 0.057 (3) | 0.056 (3) | 0.047 (3) | 0.002 (2) | 0.019 (2) | −0.007 (2) |
N5 | 0.056 (2) | 0.061 (2) | 0.049 (2) | −0.0044 (19) | 0.0127 (18) | −0.0057 (19) |
C6 | 0.064 (3) | 0.069 (3) | 0.077 (4) | −0.005 (3) | 0.010 (3) | −0.029 (3) |
C7 | 0.062 (3) | 0.049 (3) | 0.133 (5) | −0.013 (3) | 0.005 (4) | −0.023 (4) |
C8 | 0.060 (3) | 0.054 (3) | 0.134 (5) | −0.007 (3) | −0.001 (3) | 0.011 (4) |
C9 | 0.060 (3) | 0.050 (3) | 0.087 (4) | 0.000 (2) | 0.002 (3) | 0.008 (3) |
C10 | 0.045 (2) | 0.035 (3) | 0.074 (3) | 0.001 (2) | 0.008 (2) | 0.001 (2) |
C11 | 0.044 (2) | 0.049 (3) | 0.066 (3) | 0.001 (2) | 0.014 (2) | −0.008 (2) |
C12 | 0.051 (3) | 0.071 (3) | 0.041 (3) | −0.004 (2) | 0.015 (2) | −0.003 (2) |
C13 | 0.066 (3) | 0.072 (3) | 0.054 (3) | −0.011 (3) | 0.015 (3) | −0.005 (3) |
O1 | 0.082 (2) | 0.080 (2) | 0.061 (2) | −0.0054 (19) | −0.0023 (18) | 0.0041 (18) |
C14 | 0.090 (4) | 0.082 (4) | 0.063 (4) | −0.005 (3) | 0.004 (3) | 0.015 (3) |
C15 | 0.097 (4) | 0.074 (4) | 0.083 (4) | −0.002 (3) | 0.021 (3) | 0.016 (3) |
C16 | 0.083 (4) | 0.072 (4) | 0.098 (4) | −0.020 (3) | 0.016 (3) | 0.018 (3) |
C17 | 0.066 (3) | 0.078 (4) | 0.069 (3) | −0.011 (3) | 0.012 (3) | 0.013 (3) |
C18 | 0.046 (2) | 0.052 (3) | 0.044 (3) | −0.001 (2) | 0.009 (2) | −0.001 (2) |
C19 | 0.045 (2) | 0.051 (3) | 0.052 (3) | 0.001 (2) | 0.005 (2) | −0.001 (2) |
C20 | 0.049 (3) | 0.040 (3) | 0.053 (3) | 0.006 (2) | 0.014 (2) | −0.002 (2) |
O2 | 0.068 (2) | 0.0488 (18) | 0.076 (2) | 0.0064 (15) | 0.0000 (17) | −0.0048 (16) |
C24 | 0.066 (3) | 0.066 (3) | 0.077 (4) | 0.011 (2) | −0.008 (3) | 0.008 (3) |
C21 | 0.052 (3) | 0.048 (3) | 0.059 (3) | −0.009 (2) | 0.013 (2) | −0.008 (2) |
O3 | 0.069 (2) | 0.057 (2) | 0.091 (2) | −0.0083 (16) | 0.0003 (18) | −0.0235 (18) |
C25 | 0.066 (3) | 0.085 (4) | 0.132 (5) | −0.008 (3) | 0.000 (3) | −0.048 (4) |
C22 | 0.047 (3) | 0.063 (3) | 0.069 (3) | −0.001 (2) | −0.002 (2) | −0.008 (3) |
C23 | 0.048 (3) | 0.055 (3) | 0.070 (3) | 0.003 (2) | 0.007 (2) | 0.001 (2) |
N1—C10 | 1.401 (5) | C14—C15 | 1.366 (6) |
N1—C2 | 1.477 (5) | C14—H14 | 0.9300 |
N1—H1N | 0.91 (3) | C15—C16 | 1.368 (6) |
C2—C18 | 1.514 (5) | C15—H15 | 0.9300 |
C2—C3 | 1.526 (5) | C16—C17 | 1.369 (6) |
C2—H2 | 0.9800 | C16—H16 | 0.9300 |
C3—C4 | 1.505 (5) | C17—H17 | 0.9300 |
C3—H3A | 0.9700 | C18—C23 | 1.365 (5) |
C3—H3B | 0.9700 | C18—C19 | 1.385 (5) |
C4—N5 | 1.290 (4) | C19—C20 | 1.363 (5) |
C4—C12 | 1.468 (5) | C19—H19 | 0.9300 |
N5—C11 | 1.410 (5) | C20—O2 | 1.370 (4) |
C6—C7 | 1.372 (6) | C20—C21 | 1.400 (5) |
C6—H6 | 0.9300 | O2—C24 | 1.427 (4) |
C6—C11 | 1.382 (5) | C24—H24A | 0.9600 |
C7—C8 | 1.372 (7) | C24—H24B | 0.9600 |
C7—H7 | 0.9300 | C24—H24C | 0.9600 |
C8—C9 | 1.376 (6) | C21—O3 | 1.363 (4) |
C8—H8 | 0.9300 | C21—C22 | 1.363 (5) |
C9—C10 | 1.381 (5) | O3—C25 | 1.425 (5) |
C9—H9 | 0.9300 | C25—H25A | 0.9600 |
C10—C11 | 1.402 (5) | C25—H25B | 0.9600 |
C12—C17 | 1.387 (5) | C25—H25C | 0.9600 |
C12—C13 | 1.406 (5) | C22—C23 | 1.393 (5) |
C13—O1 | 1.350 (5) | C22—H22 | 0.9300 |
O1—H1 | 0.8200 | C23—H23 | 0.9300 |
C13—C14 | 1.383 (6) | ||
C10—N1—C2 | 120.0 (3) | C15—C14—H14 | 120.0 |
N1—C2—C18 | 109.6 (3) | C14—C13—C12 | 120.9 (4) |
N1—C2—C3 | 109.1 (3) | C15—C14—C13 | 119.8 (5) |
C10—N1—H1N | 111 (2) | C14—C15—C16 | 120.7 (5) |
C2—N1—H1N | 107 (2) | C14—C15—H15 | 119.7 |
C18—C2—C3 | 113.7 (3) | C16—C15—H15 | 119.7 |
C4—C3—C2 | 114.0 (3) | C12—C17—H17 | 118.8 |
N1—C2—H2 | 108.1 | C16—C17—H17 | 118.8 |
C18—C2—H2 | 108.1 | C15—C16—H16 | 120.3 |
C3—C2—H2 | 108.1 | C17—C16—H16 | 120.3 |
N5—C4—C12 | 117.6 (4) | C17—C16—C15 | 119.4 (5) |
N5—C4—C3 | 120.0 (4) | C16—C17—C12 | 122.5 (5) |
C12—C4—C3 | 122.3 (4) | C23—C18—C19 | 118.9 (4) |
C4—N5—C11 | 121.8 (4) | C23—C18—C2 | 120.0 (4) |
C4—C3—H3A | 108.8 | C19—C18—C2 | 121.0 (4) |
C2—C3—H3A | 108.7 | C20—C19—C18 | 121.0 (4) |
C4—C3—H3B | 108.8 | C19—C20—O2 | 125.0 (4) |
C2—C3—H3B | 108.7 | C19—C20—C21 | 119.9 (4) |
H3A—C3—H3B | 107.7 | O2—C20—C21 | 115.1 (4) |
C7—C6—C11 | 121.1 (5) | C20—O2—C24 | 117.2 (3) |
C6—C7—C8 | 119.8 (5) | O2—C24—H24A | 109.5 |
C7—C6—H6 | 119.5 | O2—C24—H24B | 109.5 |
C6—C7—H7 | 120.1 | O2—C24—H24C | 109.5 |
C7—C8—C9 | 119.9 (5) | H24A—C24—H24B | 109.5 |
C7—C8—H8 | 120.0 | H24A—C24—H24C | 109.5 |
C9—C8—H8 | 120.0 | H24B—C24—H24C | 109.5 |
C8—C9—C10 | 121.2 (5) | O3—C21—C22 | 125.6 (4) |
C8—C7—H7 | 120.1 | O3—C21—C20 | 115.1 (4) |
C8—C9—H9 | 119.5 | O3—C25—H25A | 109.5 |
C10—C9—H9 | 119.5 | O3—C25—H25B | 109.5 |
C9—C10—N1 | 120.2 (4) | O3—C25—H25C | 109.5 |
C9—C10—C11 | 118.6 (4) | H25A—C25—H25B | 109.5 |
N1—C10—C11 | 120.7 (4) | H25A—C25—H25C | 109.5 |
C11—C6—H6 | 119.5 | H25B—C25—H25C | 109.5 |
C6—C11—C10 | 119.2 (4) | C22—C21—C20 | 119.4 (4) |
C6—C11—N5 | 118.4 (4) | C21—O3—C25 | 117.4 (3) |
C10—C11—N5 | 121.9 (4) | C21—C22—C23 | 120.0 (4) |
C17—C12—C13 | 116.6 (4) | C18—C23—C22 | 120.8 (4) |
C17—C12—C4 | 122.8 (4) | C18—C19—H19 | 119.5 |
C13—C12—C4 | 120.5 (4) | C20—C19—H19 | 119.5 |
C13—O1—H1 | 109.5 | C21—C22—H22 | 120.0 |
O1—C13—C14 | 117.5 (5) | C23—C22—H22 | 120.0 |
O1—C13—C12 | 121.6 (4) | C18—C23—H23 | 119.6 |
C13—C14—H14 | 120.0 | C22—C23—H23 | 119.6 |
C10—N1—C2—C18 | 163.9 (3) | C4—C12—C13—C14 | 177.9 (4) |
C10—N1—C2—C3 | 38.8 (5) | O1—C13—C14—C15 | 179.6 (4) |
N1—C2—C3—C4 | 44.7 (4) | C12—C13—C14—C15 | −0.6 (7) |
C18—C2—C3—C4 | −78.0 (4) | C13—C14—C15—C16 | 0.5 (8) |
C2—C3—C4—N5 | −76.8 (5) | C14—C15—C16—C17 | −0.2 (8) |
C2—C3—C4—C12 | 105.4 (4) | C15—C16—C17—C12 | 0.1 (8) |
C12—C4—N5—C11 | −173.7 (3) | C13—C12—C17—C16 | −0.2 (7) |
C3—C4—N5—C11 | 8.4 (6) | C4—C12—C17—C16 | −177.6 (4) |
C11—C6—C7—C8 | 1.1 (7) | N1—C2—C18—C23 | 136.1 (4) |
C6—C7—C8—C9 | −0.6 (8) | C3—C2—C18—C23 | −101.5 (4) |
C7—C8—C9—C10 | −1.8 (7) | N1—C2—C18—C19 | −47.4 (5) |
C8—C9—C10—N1 | 175.6 (4) | C3—C2—C18—C19 | 75.0 (5) |
C8—C9—C10—C11 | 3.5 (6) | C23—C18—C19—C20 | 0.9 (6) |
C2—N1—C10—C9 | 121.5 (4) | C2—C18—C19—C20 | −175.6 (3) |
C2—N1—C10—C11 | −66.6 (5) | C18—C19—C20—O2 | 178.5 (4) |
C7—C6—C11—C10 | 0.6 (6) | C18—C19—C20—C21 | −1.5 (6) |
C7—C6—C11—N5 | −172.3 (4) | C19—C20—O2—C24 | −15.3 (6) |
C9—C10—C11—C6 | −2.9 (6) | C21—C20—O2—C24 | 164.7 (4) |
N1—C10—C11—C6 | −174.9 (3) | C19—C20—C21—O3 | −179.3 (3) |
C9—C10—C11—N5 | 169.7 (3) | O2—C20—C21—O3 | 0.7 (5) |
N1—C10—C11—N5 | −2.3 (6) | C19—C20—C21—C22 | 0.7 (6) |
C4—N5—C11—C6 | −143.5 (4) | O2—C20—C21—C22 | −179.3 (4) |
C4—N5—C11—C10 | 43.8 (5) | C22—C21—O3—C25 | −0.8 (6) |
N5—C4—C12—C17 | 175.8 (4) | C20—C21—O3—C25 | 179.2 (4) |
C3—C4—C12—C17 | −6.3 (6) | O3—C21—C22—C23 | −179.3 (4) |
N5—C4—C12—C13 | −1.5 (6) | C20—C21—C22—C23 | 0.7 (6) |
C3—C4—C12—C13 | 176.4 (4) | C19—C18—C23—C22 | 0.5 (6) |
C17—C12—C13—O1 | −179.8 (4) | C2—C18—C23—C22 | 177.1 (4) |
C4—C12—C13—O1 | −2.3 (6) | C21—C22—C23—C18 | −1.3 (7) |
C17—C12—C13—C14 | 0.4 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.76 | 2.494 (5) | 148 |
N1—H1N···O1i | 0.91 (3) | 2.20 (3) | 3.017 (4) | 150 (3) |
C8—H8···O3ii | 0.93 | 2.48 | 3.385 (6) | 163 |
C15—H15···O2iii | 0.93 | 2.64 | 3.501 (5) | 154 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z. |
C23H22N2O3 | F(000) = 792 |
Mr = 374.43 | Dx = 1.362 Mg m−3 |
Monoclinic, P21/c | Melting point: 429 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.5071 (3) Å | Cell parameters from 4712 reflections |
b = 20.3901 (6) Å | θ = 2.2–27.5° |
c = 8.7280 (3) Å | µ = 0.09 mm−1 |
β = 102.390 (2)° | T = 296 K |
V = 1826.34 (10) Å3 | Block, yellow |
Z = 4 | 0.50 × 0.50 × 0.35 mm |
Bruker APEX II diffractometer | 4181 independent reflections |
Radiation source: fine-focus sealed tube | 3367 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
CCD rotation images, thin slices scans | θmax = 27.5°, θmin = 2.0° |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | h = −13→13 |
Tmin = 0.956, Tmax = 0.969 | k = −24→26 |
12443 measured reflections | l = −11→11 |
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) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0711P)2 + 0.174P] where P = (Fo2 + 2Fc2)/3 |
4181 reflections | (Δ/σ)max = 0.001 |
338 parameters | Δρmax = 0.30 e Å−3 |
20 restraints | Δρmin = −0.31 e Å−3 |
C23H22N2O3 | V = 1826.34 (10) Å3 |
Mr = 374.43 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.5071 (3) Å | µ = 0.09 mm−1 |
b = 20.3901 (6) Å | T = 296 K |
c = 8.7280 (3) Å | 0.50 × 0.50 × 0.35 mm |
β = 102.390 (2)° |
Bruker APEX II diffractometer | 4181 independent reflections |
Absorption correction: part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | 3367 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.969 | Rint = 0.033 |
12443 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 20 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.30 e Å−3 |
4181 reflections | Δρmin = −0.31 e Å−3 |
338 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 8.3280 (0.0034) x + 7.0500 (0.0097) y - 5.7656 (0.0033) z = 4.3073 (0.0061) * 0.0153 (0.0009) C18 * -0.0129 (0.0009) C19 * 0.0021 (0.0009) C20 * 0.0066 (0.0009) C21 * -0.0042 (0.0009) C22 * -0.0068 (0.0009) C23 Rms deviation of fitted atoms = 0.0092 7.9149 (0.0027) x + 8.0430 (0.0078) y - 5.8970 (0.0034) z = 2.6491 (0.0025) * -0.0094 (0.0009) C12 * -0.0016 (0.0011) C13 * -0.0024 (0.0010) C14 * -0.0039 (0.0010) C15 * 0.0066 (0.0010) C16 * 0.0037 (0.0009) C17 * 0.0071 (0.0007) O1 Rms deviation of fitted atoms = 0.0056 - 1.9131 (0.0040) x - 6.3113 (0.0067) y + 8.2971 (0.0010) z = 2.0337 (0.0034) * 0.0234 (0.0011) C6 * -0.0088 (0.0010) C7 * -0.0414 (0.0010) C8 * -0.0039 (0.0011) C9 * 0.0573 (0.0011) C10 * 0.0563 (0.0011) C11 * -0.0215 (0.0008) N1 * -0.0614 (0.0008) N5 Rms deviation of fitted atoms = 0.0404 4.2130 (0.0092) x - 18.3764 (0.0124) y - 2.1513 (0.0148) z = 0.2915 (0.0070) Angle to previous plane (with approximate e.s.d.) = 86.98 (0.10) * 0.0000 (0.0000) C2 * 0.0000 (0.0000) C3 * 0.0000 (0.0000) C4 Rms deviation of fitted atoms = 0.0000 |
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 | ||
N1 | 0.85059 (10) | 0.17394 (5) | 0.57094 (13) | 0.0175 (2) | |
H1N | 0.9215 (15) | 0.1991 (8) | 0.5834 (19) | 0.024 (4)* | |
C2 | 0.88111 (12) | 0.11011 (6) | 0.64944 (15) | 0.0162 (3) | |
H2 | 0.9185 (12) | 0.0820 (5) | 0.5768 (13) | 0.014 (3)* | |
C3 | 0.75515 (12) | 0.07834 (6) | 0.67415 (15) | 0.0170 (3) | |
H3A | 0.7167 (12) | 0.1069 (6) | 0.7451 (13) | 0.017 (4)* | |
H3B | 0.7738 (13) | 0.0345 (3) | 0.7244 (15) | 0.018 (3)* | |
C4 | 0.65657 (11) | 0.07360 (6) | 0.52160 (16) | 0.0168 (3) | |
N5 | 0.58515 (10) | 0.12372 (5) | 0.46674 (13) | 0.0175 (2) | |
C6 | 0.50620 (12) | 0.22762 (6) | 0.53779 (16) | 0.0195 (3) | |
H6 | 0.4187 (6) | 0.2100 (7) | 0.5092 (18) | 0.026 (4)* | |
C7 | 0.52363 (13) | 0.29193 (7) | 0.58684 (16) | 0.0209 (3) | |
H7 | 0.4497 (9) | 0.3199 (6) | 0.5897 (19) | 0.024 (4)* | |
C8 | 0.64978 (13) | 0.31677 (6) | 0.63090 (17) | 0.0214 (3) | |
H8 | 0.6617 (14) | 0.3616 (3) | 0.6677 (17) | 0.023 (4)* | |
C9 | 0.75553 (12) | 0.27690 (6) | 0.62947 (16) | 0.0193 (3) | |
H9 | 0.8437 (5) | 0.2937 (7) | 0.6582 (17) | 0.023 (4)* | |
C10 | 0.74020 (12) | 0.21091 (6) | 0.58311 (15) | 0.0166 (3) | |
C11 | 0.61195 (12) | 0.18629 (6) | 0.53470 (15) | 0.0172 (3) | |
C12 | 0.64109 (12) | 0.01251 (6) | 0.42990 (15) | 0.0167 (3) | |
C13 | 0.54351 (12) | 0.00694 (6) | 0.29001 (15) | 0.0176 (3) | |
O1 | 0.45796 (8) | 0.05582 (5) | 0.24037 (11) | 0.0220 (2) | |
H1 | 0.4764 | 0.0876 | 0.2983 | 0.056 (6)* | |
C14 | 0.53434 (13) | −0.05007 (7) | 0.20008 (16) | 0.0214 (3) | |
H14 | 0.4681 (11) | −0.0525 (7) | 0.1040 (10) | 0.023 (4)* | |
C15 | 0.62021 (14) | −0.10123 (7) | 0.24581 (17) | 0.0232 (3) | |
H15 | 0.6114 (15) | −0.1404 (4) | 0.1814 (15) | 0.025 (4)* | |
C16 | 0.71797 (13) | −0.09652 (7) | 0.38167 (17) | 0.0222 (3) | |
H16 | 0.7782 (11) | −0.1324 (5) | 0.4139 (18) | 0.022 (4)* | |
C17 | 0.72755 (12) | −0.04024 (6) | 0.47178 (16) | 0.0191 (3) | |
H17 | 0.7956 (10) | −0.0382 (7) | 0.5662 (9) | 0.019 (4)* | |
C18 | 0.97989 (12) | 0.11386 (6) | 0.80489 (15) | 0.0163 (3) | |
C19 | 1.05836 (12) | 0.05875 (6) | 0.85574 (15) | 0.0166 (3) | |
O2 | 1.03426 (9) | 0.00484 (4) | 0.75911 (11) | 0.0205 (2) | |
C24 | 1.11871 (14) | −0.05011 (7) | 0.80086 (17) | 0.0228 (3) | |
H24A | 1.0908 (15) | −0.0829 (6) | 0.7157 (13) | 0.031 (4)* | |
H24B | 1.1117 (14) | −0.0691 (7) | 0.9039 (8) | 0.024 (4)* | |
H24C | 1.2106 (5) | −0.0364 (7) | 0.8068 (18) | 0.024 (4)* | |
C20 | 1.15266 (12) | 0.06164 (6) | 0.99289 (16) | 0.0188 (3) | |
H20 | 1.2113 (11) | 0.0252 (5) | 1.0262 (17) | 0.022 (4)* | |
C21 | 1.16866 (12) | 0.11826 (7) | 1.08444 (16) | 0.0187 (3) | |
H21 | 1.2365 (11) | 0.1203 (7) | 1.1791 (10) | 0.023 (4)* | |
C22 | 1.08938 (12) | 0.17202 (6) | 1.03753 (15) | 0.0172 (3) | |
O3 | 1.09831 (9) | 0.23092 (4) | 1.11742 (11) | 0.0212 (2) | |
C25 | 1.20231 (13) | 0.23626 (7) | 1.25281 (17) | 0.0230 (3) | |
H25A | 1.1910 (15) | 0.2043 (6) | 1.3351 (14) | 0.033 (4)* | |
H25B | 1.1959 (14) | 0.2818 (3) | 1.2919 (18) | 0.027 (4)* | |
H25C | 1.2894 (7) | 0.2289 (7) | 1.2280 (19) | 0.029 (4)* | |
C23 | 0.99466 (11) | 0.16943 (6) | 0.89802 (15) | 0.0171 (3) | |
H23 | 0.9400 (11) | 0.2077 (4) | 0.8693 (17) | 0.018 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0144 (5) | 0.0160 (5) | 0.0210 (6) | −0.0012 (4) | 0.0012 (4) | 0.0040 (4) |
C2 | 0.0168 (6) | 0.0143 (6) | 0.0168 (6) | 0.0006 (5) | 0.0019 (5) | 0.0023 (5) |
C3 | 0.0174 (6) | 0.0148 (6) | 0.0176 (6) | −0.0016 (5) | 0.0010 (5) | 0.0021 (5) |
C4 | 0.0143 (6) | 0.0174 (6) | 0.0185 (6) | −0.0023 (5) | 0.0033 (5) | 0.0026 (5) |
N5 | 0.0164 (5) | 0.0160 (5) | 0.0188 (6) | −0.0015 (4) | 0.0011 (4) | 0.0017 (4) |
C6 | 0.0160 (6) | 0.0202 (7) | 0.0209 (7) | −0.0004 (5) | 0.0005 (5) | 0.0026 (5) |
C7 | 0.0204 (6) | 0.0207 (7) | 0.0219 (7) | 0.0030 (5) | 0.0048 (5) | 0.0023 (5) |
C8 | 0.0252 (7) | 0.0155 (6) | 0.0234 (7) | −0.0015 (5) | 0.0049 (5) | −0.0006 (5) |
C9 | 0.0186 (6) | 0.0181 (6) | 0.0203 (7) | −0.0034 (5) | 0.0019 (5) | 0.0011 (5) |
C10 | 0.0167 (6) | 0.0173 (6) | 0.0149 (6) | 0.0014 (5) | 0.0014 (5) | 0.0044 (5) |
C11 | 0.0196 (6) | 0.0152 (6) | 0.0152 (6) | −0.0009 (5) | −0.0001 (5) | 0.0030 (5) |
C12 | 0.0153 (6) | 0.0167 (6) | 0.0179 (6) | −0.0038 (5) | 0.0030 (5) | 0.0018 (5) |
C13 | 0.0158 (6) | 0.0185 (6) | 0.0184 (6) | −0.0024 (5) | 0.0036 (5) | 0.0024 (5) |
O1 | 0.0196 (5) | 0.0215 (5) | 0.0218 (5) | 0.0006 (4) | −0.0028 (4) | 0.0005 (4) |
C14 | 0.0193 (6) | 0.0259 (7) | 0.0186 (7) | −0.0053 (5) | 0.0034 (5) | −0.0014 (5) |
C15 | 0.0274 (7) | 0.0190 (6) | 0.0243 (7) | −0.0032 (5) | 0.0078 (6) | −0.0048 (5) |
C16 | 0.0236 (7) | 0.0173 (6) | 0.0265 (7) | 0.0008 (5) | 0.0068 (6) | 0.0013 (5) |
C17 | 0.0183 (6) | 0.0188 (6) | 0.0193 (7) | −0.0020 (5) | 0.0020 (5) | 0.0022 (5) |
C18 | 0.0132 (6) | 0.0182 (6) | 0.0176 (6) | −0.0004 (5) | 0.0032 (5) | 0.0022 (5) |
C19 | 0.0157 (6) | 0.0162 (6) | 0.0186 (6) | 0.0000 (5) | 0.0052 (5) | 0.0012 (5) |
O2 | 0.0219 (5) | 0.0151 (4) | 0.0232 (5) | 0.0036 (4) | 0.0020 (4) | 0.0005 (4) |
C24 | 0.0249 (7) | 0.0178 (6) | 0.0266 (7) | 0.0069 (5) | 0.0076 (6) | 0.0031 (5) |
C20 | 0.0151 (6) | 0.0195 (6) | 0.0216 (7) | 0.0033 (5) | 0.0038 (5) | 0.0061 (5) |
C21 | 0.0138 (6) | 0.0244 (7) | 0.0168 (6) | 0.0003 (5) | 0.0006 (5) | 0.0036 (5) |
C22 | 0.0160 (6) | 0.0185 (6) | 0.0174 (6) | −0.0014 (5) | 0.0045 (5) | −0.0003 (5) |
O3 | 0.0197 (5) | 0.0210 (5) | 0.0198 (5) | 0.0015 (4) | −0.0026 (4) | −0.0042 (4) |
C25 | 0.0184 (6) | 0.0292 (7) | 0.0193 (7) | 0.0002 (6) | −0.0008 (5) | −0.0037 (6) |
C23 | 0.0133 (6) | 0.0179 (6) | 0.0193 (7) | 0.0016 (5) | 0.0017 (5) | 0.0030 (5) |
N1—C10 | 1.4064 (16) | C14—C15 | 1.3810 (19) |
N1—C2 | 1.4736 (15) | C14—H14 | 0.969 (10) |
N1—H1N | 0.891 (16) | C15—C16 | 1.396 (2) |
C2—C18 | 1.5231 (17) | C15—H15 | 0.970 (10) |
C2—C3 | 1.5298 (17) | C16—C17 | 1.3827 (19) |
C2—H2 | 0.996 (11) | C16—H16 | 0.969 (11) |
C3—C4 | 1.5044 (17) | C17—H17 | 0.969 (9) |
C3—H3A | 0.997 (12) | C18—C23 | 1.3837 (18) |
C3—H3B | 0.997 (8) | C18—C19 | 1.4080 (17) |
C4—N5 | 1.2972 (16) | C19—O2 | 1.3754 (15) |
C4—C12 | 1.4707 (17) | C19—C20 | 1.3817 (18) |
N5—C11 | 1.4097 (16) | O2—C24 | 1.4272 (16) |
C6—C7 | 1.3794 (18) | C24—H24A | 0.996 (12) |
C6—C11 | 1.3994 (17) | C24—H24B | 0.996 (9) |
C6—H6 | 0.969 (9) | C24—H24C | 0.996 (7) |
C7—C8 | 1.3937 (18) | C20—C21 | 1.3935 (19) |
C7—H7 | 0.968 (11) | C20—H20 | 0.969 (11) |
C8—C9 | 1.3790 (18) | C21—C22 | 1.3845 (18) |
C8—H8 | 0.968 (8) | C21—H21 | 0.969 (10) |
C9—C10 | 1.4043 (18) | C22—O3 | 1.3818 (15) |
C9—H9 | 0.969 (9) | C22—C23 | 1.3985 (17) |
C10—C11 | 1.4149 (17) | O3—C25 | 1.4312 (16) |
C12—C17 | 1.4046 (18) | C25—H25A | 0.996 (12) |
C12—C13 | 1.4205 (17) | C25—H25B | 0.997 (8) |
C13—O1 | 1.3497 (15) | C25—H25C | 0.996 (9) |
C13—C14 | 1.3943 (18) | C23—H23 | 0.969 (10) |
O1—H1 | 0.8200 | ||
C10—N1—C2 | 122.62 (10) | C15—C14—C13 | 120.35 (12) |
C10—N1—H1N | 111.3 (10) | C15—C14—H14 | 121.0 (9) |
C2—N1—H1N | 111.0 (10) | C13—C14—H14 | 118.7 (9) |
N1—C2—C18 | 114.12 (10) | C14—C15—C16 | 120.64 (12) |
N1—C2—C3 | 109.33 (10) | C14—C15—H15 | 118.7 (9) |
C18—C2—C3 | 109.90 (10) | C16—C15—H15 | 120.7 (9) |
N1—C2—H2 | 106.8 (8) | C17—C16—C15 | 119.40 (12) |
C18—C2—H2 | 108.0 (8) | C17—C16—H16 | 119.9 (9) |
C3—C2—H2 | 108.5 (8) | C15—C16—H16 | 120.7 (9) |
C4—C3—C2 | 110.77 (10) | C16—C17—C12 | 121.57 (12) |
C4—C3—H3A | 107.1 (8) | C16—C17—H17 | 118.1 (9) |
C2—C3—H3A | 108.6 (8) | C12—C17—H17 | 120.4 (9) |
C4—C3—H3B | 111.4 (8) | C23—C18—C19 | 118.96 (11) |
C2—C3—H3B | 110.3 (8) | C23—C18—C2 | 122.24 (11) |
H3A—C3—H3B | 108.5 (12) | C19—C18—C2 | 118.80 (11) |
N5—C4—C12 | 118.61 (11) | O2—C19—C20 | 124.67 (11) |
N5—C4—C3 | 120.66 (11) | O2—C19—C18 | 115.22 (11) |
C12—C4—C3 | 120.72 (11) | C20—C19—C18 | 120.10 (12) |
C4—N5—C11 | 120.68 (10) | C19—O2—C24 | 116.63 (10) |
C7—C6—C11 | 121.69 (12) | O2—C24—H24A | 105.6 (9) |
C7—C6—H6 | 119.2 (9) | O2—C24—H24B | 111.9 (9) |
C11—C6—H6 | 119.0 (9) | H24A—C24—H24B | 110.2 (13) |
C6—C7—C8 | 119.08 (12) | O2—C24—H24C | 109.6 (9) |
C6—C7—H7 | 121.0 (9) | H24A—C24—H24C | 110.8 (14) |
C8—C7—H7 | 120.0 (9) | H24B—C24—H24C | 108.7 (13) |
C9—C8—C7 | 120.25 (12) | C19—C20—C21 | 120.53 (11) |
C9—C8—H8 | 120.8 (9) | C19—C20—H20 | 121.3 (9) |
C7—C8—H8 | 118.8 (9) | C21—C20—H20 | 118.2 (9) |
C8—C9—C10 | 121.64 (12) | C22—C21—C20 | 119.70 (11) |
C8—C9—H9 | 121.2 (9) | C22—C21—H21 | 120.2 (9) |
C10—C9—H9 | 117.2 (9) | C20—C21—H21 | 120.0 (9) |
C9—C10—N1 | 119.33 (11) | O3—C22—C21 | 124.57 (11) |
C9—C10—C11 | 117.97 (11) | O3—C22—C23 | 115.51 (11) |
N1—C10—C11 | 122.37 (11) | C21—C22—C23 | 119.89 (12) |
C6—C11—N5 | 117.73 (11) | C22—O3—C25 | 116.11 (10) |
C6—C11—C10 | 119.33 (11) | O3—C25—H25A | 110.9 (9) |
N5—C11—C10 | 122.56 (11) | O3—C25—H25B | 105.0 (9) |
C17—C12—C13 | 118.02 (11) | H25A—C25—H25B | 109.6 (14) |
C17—C12—C4 | 121.14 (11) | O3—C25—H25C | 112.5 (9) |
C13—C12—C4 | 120.70 (11) | H25A—C25—H25C | 108.5 (13) |
O1—C13—C14 | 118.29 (11) | H25B—C25—H25C | 110.3 (13) |
O1—C13—C12 | 121.68 (11) | C18—C23—C22 | 120.76 (11) |
C14—C13—C12 | 120.03 (11) | C18—C23—H23 | 121.4 (9) |
C13—O1—H1 | 109.5 | C22—C23—H23 | 117.8 (9) |
C10—N1—C2—C18 | −97.55 (13) | C4—C12—C13—C14 | 176.71 (11) |
C10—N1—C2—C3 | 25.97 (16) | O1—C13—C14—C15 | 179.65 (12) |
N1—C2—C3—C4 | 54.54 (13) | C12—C13—C14—C15 | −0.3 (2) |
C18—C2—C3—C4 | −179.48 (10) | C13—C14—C15—C16 | −0.5 (2) |
C2—C3—C4—N5 | −81.63 (15) | C14—C15—C16—C17 | 0.7 (2) |
C2—C3—C4—C12 | 97.06 (13) | C15—C16—C17—C12 | 0.0 (2) |
C12—C4—N5—C11 | −168.57 (11) | C13—C12—C17—C16 | −0.83 (19) |
C3—C4—N5—C11 | 10.16 (18) | C4—C12—C17—C16 | −176.53 (12) |
C11—C6—C7—C8 | 1.5 (2) | N1—C2—C18—C23 | 27.89 (17) |
C6—C7—C8—C9 | −1.8 (2) | C3—C2—C18—C23 | −95.32 (14) |
C7—C8—C9—C10 | 0.5 (2) | N1—C2—C18—C19 | −152.40 (11) |
C8—C9—C10—N1 | 174.61 (12) | C3—C2—C18—C19 | 84.39 (14) |
C8—C9—C10—C11 | 1.1 (2) | C23—C18—C19—O2 | 177.77 (11) |
C2—N1—C10—C9 | 127.60 (13) | C2—C18—C19—O2 | −1.95 (17) |
C2—N1—C10—C11 | −59.16 (17) | C23—C18—C19—C20 | −3.06 (19) |
C7—C6—C11—N5 | −173.13 (12) | C2—C18—C19—C20 | 177.22 (11) |
C7—C6—C11—C10 | 0.0 (2) | C20—C19—O2—C24 | −3.80 (18) |
C4—N5—C11—C6 | −145.68 (13) | C18—C19—O2—C24 | 175.33 (11) |
C4—N5—C11—C10 | 41.39 (18) | O2—C19—C20—C21 | −179.08 (12) |
C9—C10—C11—C6 | −1.32 (18) | C18—C19—C20—C21 | 1.83 (19) |
N1—C10—C11—C6 | −174.65 (12) | C19—C20—C21—C22 | 0.01 (19) |
C9—C10—C11—N5 | 171.50 (12) | C20—C21—C22—O3 | −178.70 (11) |
N1—C10—C11—N5 | −1.83 (19) | C20—C21—C22—C23 | −0.60 (19) |
N5—C4—C12—C17 | 171.07 (12) | C21—C22—O3—C25 | 3.53 (18) |
C3—C4—C12—C17 | −7.66 (18) | C23—C22—O3—C25 | −174.64 (11) |
N5—C4—C12—C13 | −4.52 (18) | C19—C18—C23—C22 | 2.49 (19) |
C3—C4—C12—C13 | 176.75 (11) | C2—C18—C23—C22 | −177.80 (11) |
C17—C12—C13—O1 | −178.99 (11) | O3—C22—C23—C18 | 177.59 (11) |
C4—C12—C13—O1 | −3.26 (18) | C21—C22—C23—C18 | −0.68 (19) |
C17—C12—C13—C14 | 0.99 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.81 | 2.5443 (14) | 148 |
N1—H1N···O3i | 0.892 (16) | 2.311 (16) | 3.201 (2) | 177 |
C24—H24B···Cg3ii | 1.00 (1) | 2.74 (1) | 3.5462 (16) | 140 (1) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C21H18N2O | C23H22N2O3 | C23H22N2O3 | C23H22N2O3 |
Mr | 314.37 | 374.43 | 374.43 | 374.43 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 298 | 298 | 300 | 296 |
a, b, c (Å) | 24.855 (4), 7.6825 (11), 19.455 (3) | 8.250 (2), 9.889 (3), 12.272 (3) | 5.5372 (8), 23.144 (3), 15.131 (2) | 10.5071 (3), 20.3901 (6), 8.7280 (3) |
α, β, γ (°) | 90, 118.824 (2), 90 | 108.697 (4), 90.973 (5), 90.594 (5) | 90, 99.520 (3), 90 | 90, 102.390 (2), 90 |
V (Å3) | 3254.7 (9) | 948.1 (4) | 1912.4 (4) | 1826.34 (10) |
Z | 8 | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.30 × 0.27 × 0.21 | 0.30 × 0.18 × 0.11 | 0.37 × 0.07 × 0.06 | 0.50 × 0.50 × 0.35 |
Data collection | ||||
Diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer | Siemens SMART CCD area-detector diffractometer | Bruker APEX II diffractometer |
Absorption correction | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) | Part of the refinement model (ΔF) (SADABS in SAINT-NT; Bruker, 1999) |
Tmin, Tmax | 0.977, 0.983 | 0.974, 0.990 | 0.969, 0.995 | 0.956, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9815, 2893, 1696 | 5882, 3329, 1625 | 11881, 3400, 1703 | 12443, 4181, 3367 |
Rint | 0.055 | 0.040 | 0.105 | 0.033 |
(sin θ/λ)max (Å−1) | 0.597 | 0.596 | 0.597 | 0.649 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.139, 1.02 | 0.062, 0.179, 0.98 | 0.086, 0.167, 1.04 | 0.039, 0.126, 1.10 |
No. of reflections | 2893 | 3329 | 3400 | 4181 |
No. of parameters | 222 | 259 | 259 | 338 |
No. of restraints | 0 | 0 | 0 | 20 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.12 | 0.16, −0.20 | 0.15, −0.16 | 0.30, −0.31 |
Computer programs: SMART-NT (Bruker, 2001), SMART (reference?), SAINT-NT (Bruker, 1999), SAINT (reference?), SAINT-NT, SAINT, SHELXTL-NT (Bruker, 1999 or??2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL-NT), WinGX (Farrugia, 1999).
C10—N1—C2—C3 | 32.0 (3) | C3—C4—N5—C11 | 4.0 (3) |
N1—C2—C3—C4 | 51.1 (3) | N5—C4—C12—C13 | −2.2 (3) |
C2—C3—C4—N5 | −76.3 (3) | N1—C2—C18—C23 | 149.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.785 | 2.514 (3) | 147.3 |
C23—H23···Cg1i | 0.93 | 2.615 | 3.480 (2) | 154.8 |
Symmetry code: (i) x, y+1, z. |
C10—N1—C2—C3 | −22.7 (5) | C3—C4—N5—C11 | −0.6 (5) |
N1—C2—C3—C4 | 76.0 (4) | N5—C4—C12—C13 | −7.7 (5) |
C2—C3—C4—N5 | −65.1 (4) | N1—C2—C18—C23 | −13.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.78 | 2.514 (4) | 147 |
N1—H1N···Cg2i | 0.90 (4) | 2.60 (4) | 3.445 (4) | 159 (3) |
Symmetry code: (i) −x, −y+1, −z+2. |
C10—N1—C2—C3 | 38.8 (5) | C3—C4—N5—C11 | 8.4 (6) |
N1—C2—C3—C4 | 44.7 (4) | N5—C4—C12—C13 | −1.5 (6) |
C2—C3—C4—N5 | −76.8 (5) | N1—C2—C18—C23 | 136.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.76 | 2.494 (5) | 148 |
N1—H1N···O1i | 0.91 (3) | 2.20 (3) | 3.017 (4) | 150 (3) |
C8—H8···O3ii | 0.93 | 2.48 | 3.385 (6) | 163 |
C15—H15···O2iii | 0.93 | 2.64 | 3.501 (5) | 154 |
Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z. |
C10—N1—C2—C3 | 25.97 (16) | C3—C4—N5—C11 | 10.16 (18) |
N1—C2—C3—C4 | 54.54 (13) | N5—C4—C12—C13 | −4.52 (18) |
C2—C3—C4—N5 | −81.63 (15) | N1—C2—C18—C23 | 27.89 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N5 | 0.82 | 1.81 | 2.5443 (14) | 148 |
N1—H1N···O3i | 0.892 (16) | 2.311 (16) | 3.201 (2) | 177 |
C24—H24B···Cg3ii | 0.996 (9) | 2.744 (13) | 3.5462 (16) | 140 (1) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+1/2, z+1/2. |
Continuing with our search of supramolecular synthons of importance in the crystal engineering of substituted aromatic compounds (Donoso-Tauda et al., 2006), our group has focused considerable interest on the crystalline properties of benzodiazepines, particularly in their packing by intermolecular hydrogen bonding. Benzodiazepines are well studied because of their pharmacological properties, with their antifungal, antibacterial, analgesic, tranquilizing and anticonvulsant activities well established (Di Braccio et al., 2001, Michaelifou & Hadjipavlou-Litida or?? Michaelidou & Hadjipavlou-Litina, 2005). Additionally, the chemistry and structure of 1,5-benzodiazepines have become increasingly interesting, owing to their potential as cocrystals in supramolecular chemistry, showing ladder or brick superstructures formed via hydrogen-bonding networks (Thakuria et al., 2006).
The structures of the title compounds, (I)–(IV) (Fig. 1), are constructed around a central benzodiazepine C5N2 seven-membered ring, which is fused with a benzene ring at atoms C10 and C11. The heterocycle is substituted in all cases at position 4 with an o-hydroxyphenyl group, and also with a phenyl [for (I)] or a dimethoxyphenyl [for (II)–(IV)] ring at position 2, as summarized in the scheme. The least-squares plane defined by the aromatic ring (C6–C11) plus atoms N1 and N5 defines an acute angle with the plane defined by C2, C3 and C4 [85.0 (1)° for (I), 78.7 (2)° for (II), 89.3 (3)° for (III) and 87.0 (1)° for (IV)]; the benzodiazepine ring system has a puckered boat–like conformation for all four compounds. This has also been noted in two related benzodiazepines, 2,4-bis(2,5-dipropoxyphenyl)-2,3-dihydro-1H-1,5-benzodiazepine (Hormaza et al., 2004) and 2-methyl-4-p-tolyl-2,3-dihydro-1,5-benzodiazepine (Qi or??? Ci et al., 1985). Bond distances are similar for all four compounds and comparable with literature values (Qi or??? Ci et al., 1985; Braun et al., 2000). Although some significant differences are observed in torsion angles for the benzodiazepine ring, i.e. N1—C2—C3—C4 ranges from 44.7 (4)° in (III) to 76.0 (4)° for (II), the boat-like conformation of the heterocycle is conserved across the series. The substituted phenyl rings occupying positions 2 and 4 in the 1,5-benzodiazepine moiety display, respectively, a pseudo- equatorial–equatorial correlation for compounds (I), (II) and (III), (i.e. Hormaza et al., 2004), while (IV) presents a pseudo-axial–equatorial correlation. The dihedral angle between the phenyl (C18–C23) least-squares plane and the o-hydroxyphenyl plane (C12–C17) is 46.8 (1), 66.1 (1), 37.4 (2) and 4.0 (1)° for (I)–(IV), respectively.
The hydroxyl H atom on the 4-(o–hydroxyphenyl) substituent (H1) forms an intramolecular O—H···N hydrogen bond with atom N5 for (I)–(IV), with O···N distances of 2.514 (3) Å for (I), 2.514 (4) Å for (II), 2.494 (5) Å for (III) and 2.544 (1) Å for (IV). The intramolecular hydrogen bond is rather insensitive to the remainder of the molecule or the different packing modes. This intramolecular bond has been also been described in the synthetic precursor 2–hydroxy chalcone (Srivastava & Verma, 1990). An important consequence of this hydrogen bond is that the six-membered ring N5/C4/C12/C13/O1/H1 is significantly planar in all cases. This planarity is reflected in the low value measured for the N5—C4—C12—C13 torsion angle [-2.2 (3)°, -7.7 (5)°, -1.5 (6)° and -4.5 (2)° for (I)–(IV), respectively].
Despite the close structural similarity between the compounds, their packing modes, arising from N—H···O, N—H···π(arene) or C—H···π(arene) interactions, differ considerably. As in Fig. 2(a), the C—H···π(arene) interactions gives a supramolecular chain along the b axis. Molecules of (II) and (III) form supramolecular dimers by means of N—H···π(arene) and C—H···O—CH3 interactions, respectively, as depicted in Figs. 2(b) and 2(c), respectively. In the case of (III), the dimers are also connected by means of N—H···O hydrogen bonds, leading to a two-dimensional supra-structure. The amine NH group in (IV) interacts with a methoxy substituent in a vecinal molecule, leading to a chain along the c axis (Fig. 2d).
As previously stated (Desiraju, 2002), the relative magnitude of intramolecular interactions could be listed as C—H···π(arene) weaker than N—H···π(arene) and both still weaker than the N—H···O interaction. In this context, the relatively low melting point measured for (I) (379–382 K) could be understood in terms of the weak C—H···π(arene) interaction stabilizing the packing. Conversely, in (III) (with the highest melting point, 440–441 K), stronger N—H···O interactions are present in addition to the C—H···π(arene) interactions. In the same way, (II) and (IV) exhibit intermediate melting points (around 429 K).