Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113023792/sk3507sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023792/sk3507Isup2.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113023792/sk3507Isup4.mol | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113023792/sk3507IIsup3.hkl | |
MDL mol file https://doi.org/10.1107/S0108270113023792/sk3507IIsup5.mol |
CCDC references: 969467; 969468
Nitrogen-containing heterocycles (N-heterocycles) are ubiquitous in natural products, pharmaceuticals and materials science. Their synthesis represents a substantial chemical research effort that includes the total synthesis of natural products and medicinal chemistry (Behenna et al., 2012). To the best of our knowledge, there are no reported examples of 1,2-diaza heterocycles with seven-membered rings (Pettersson, 2011). As part of an on-going project on the syntheses of N-heterocycles (Shi et al., 2006a,b,c; Shi, Sui & Zhu, 2006; Shi, Zhu & Ng, 2007; Shi, Sui, Cheng et al., 2007; Shi, Cheng, Sui et al., 2007; Zhu, Shi, Shen et al., 2011), in this article we describe the syntheses and crystal structures of two seven-membered N-heterocycles. Reactions of 1,5-diketones ArCOCH2CHPhCH2COAr with hydrazine hydrate in the presence of HOAc afford the title compounds, (I) (Ar = C6H5) and (II) (Ar = 2-HOC6H4).
A mixture of ArCOCH2CHPhCH2COAr (4 mmol) and 80% N2H4.H2O (4 mmol) in the presence of HOAc (2 drops) in EtOH (25 ml) was refluxed for 12 h. The solvent was removed in vacuo and the resulting residue was isolated by chromatography on silica gel. Elution with petroleum ether–THF (2:1 v/v) gave one colorless band which was recrystallized from petroleum ether (333–363 K) and CH2Cl2 to afford a white solid of (I) (yield 0.701 g, 54%; m.p. 433–435 K). For (II), the resulting solid was collected, washed with EtOH, air-dried and recrystallized from petroleum ether (333–363 K) and CH2Cl2 to give a yellow solid (yield 0.713 g, 50%; m.p. 510–512 K).
Analysis calculated for C23H20N2, (I): C 85.15, H 6.21, N 8.63%; found: C 85.11, H 6.34, N 8.57%; m.p. 433–435 K. Spectroscopic analysis: IR (KBr disk, ν, cm-1): 3029 (m), 2921 (m), 1667 (m), 1590 (m), 1547 (m), 1492 (s), 1446 (s), 1344 (m), 1254 (m), 1187 (m), 1065 (m), 1020 (m), 919 (m), 761 (vs), 697 (vs); UV (ελ × 104, in DMF): 290.00 (1.02), 375.00 (0.86) nm; 1H NMR (600 MHz, CDCl3, TMS) δ 6.797–7.804 (m, 15H, 3C6H5), 4.045–4.087 (m, 1H, CH), 3.002–3.018 (m, 4H, 2CH2).
Analysis calculated for C23H20N2O2, (II): C 77.51, H 5.66, N 7.86%; found: C 77.75, H 5.69, N 7.67%; m.p. 510–512 K. Spectroscopic analysis: IR (KBr disk, ν, cm-1): 3434 (m), 3030 (m), 2921 (m), 1668 (m), 1590 (m), 1548 (m), 1493 (s), 1447 (s), 1344 (s), 1300 (m), 1255 (m), 1187 (m), 1020 (m), 919 (m), 762 (vs), 698 (vs); UV (ελ × 104, in DMF): 290.00 (1.16), 377.00 (0.76) nm; 1H NMR (600 MHz, CDCl3, TMS): δ 12.956 (s, 2H, 2OH), 6.765–7.364 (m, 14H, 2C6H5, C6H4), 4.083–4.124 (m, 1H, CH), 3.053–3.105 (m, 4H, 2CH2).
H atoms attached to C atoms were placed at calculated positions and treated as riding atoms, with C—H = 0.93 (CH, aromatic), 0.97 (CH2) and 0.98 (CH) Å, and with Uiso(H) = 1.2Ueq(C). For (II), H atoms attached to O atoms were located in a difference Fourier map and freely refined isotropically.
Compound (I) crystallizes in the space group P1, with two independent molecules in the asymmetric unit, labelled (Ia) and (Ib) (Fig. 1, Table 1). A quaternion fit plot of (Ia) on inverted (Ib) (Spek, 2009) (Fig. 2) shows that molecules (Ia) and (Ib) are conformers, differing mainly in the rotation of one of the phenyl groups with respect to the rest of the molecule. The C1–C6 and C10–C15 planes form a dihedral angle of 59.15 (9)° for (Ia). The corresponding angle in (Ib) for the C24–C29 and C33–C38 planes is 51.88 (10)°. Atoms C7, C17, C30 and C40 each adopt sp2-hybridization (Table 2). However, the C═N bonds are not conjugated with the respective phenyl groups, the dihedral angles between the C1–C6 and N1/C7/C8 planes, and the C18–C23 and N2/C16/C17 planes, being 26.9 (2) and 28.2 (2)°, respectively, for (Ia), and the corresponding dihedral angles being 33.0 (2) and 17.9 (2)° for (Ib). Furthermore, the two C═N bonds are not involved in conjugation with each other, with C—N—N—C torsion angles of -60.5 (2)° for (Ia) and 61.8 (2)° for (Ib). The seven-membered ring in (Ia) displays a twist-boat conformation, with puckering parameters (Cremer & Pople, 1975; Zotov et al., 1997) q2 = 1.1007 (17) Å, q3 = 0.0974 (17) Å, φ2 = 39.77 (9)°, φ3 = 196.9 (10)° and Q = 1.1049 (17) Å, and this is also indicated by the dihedral angles of 62.4 (2) and 63.0 (2)° generated by the C8/C9/C16 plane with the N1/C7/C8 and N2/C16/C17 planes, respectively. The seven-membered ring in (Ib) also exhibits a similar twist-boat conformation, with puckering parameters q2 = 1.1194 (17) Å, q3 = 0.0983 (17) Å, φ2 = 219.87 (9)°, φ3 = 18.2 (10)° and Q = 1.1238 (18) Å, the C31/C32/C39 plane forming dihedral angles with the N3/C30/C31 and N4/C39/C40 planes of 63.0 (2) and 64.0 (2)°, respectively.
Compound (II) crystallizes in the space group C2/c (Fig. 3). Both atoms C7 and C17 adopt sp2-hybridization (Table 2). Although the two C═N bonds are not conjugated with each other, with a C—N—N—C torsion angle of -59.8 (3)°, they partly participate in conjugation with their attached phenyl rings, as shown by the small dihedral angles of 3.6 (2)° between the C1–C6 and N1/C7/C8 planes and 4.8 (3)° between the C18–C23 and N2/C16/C17 planes. Thus, the C6—C7 and C17—C18 bonds are shorter in (II) than in (I), the latter being typical single bonds (Csp2—Csp2). The C8/C9/C16 plane forms dihedral angles of 64.2 (3) and 60.3 (3)° with the N1/C7/C8 and N2/C16/C17 planes, respectively. This indicates that the seven-membered ring has a twist-boat conformation similar to (Ia), with puckering parameters q2 = 1.087 (2) Å, q3 = 0.116 (2) Å, φ2 = 36.36 (13)°, φ3 = 179.3 (12)° and Q = 1.093 (2) Å. Additionally, the C1–C6 and C10–C15 planes make a dihedral angle of 63.11 (13)°.
No π–π stacking interactions or C—H···π interactions are present in (I). The only supramolecular interaction in (II) is C21—H21···Cg2i (π), where Cg2 is the centroid of the C10–C15 phenyl ring [symmetry code: (i) x, y - 1, z]. Molecules of (II) join into an infinite chain in the b-axis direction (Table 4; Fig. 4).
In the crystalline state of (II), a low-field signal of the OH group at 12.956 p.p.m. confirms the presence of intramolecular O—H···N hydrogen bonds in a CDCl3 solution of (II) (Shi, Zhang, Cheng et al., 2006; Shi & Zhang, 2007; Shi et al., 2012).
For related literature, see: Behenna et al. (2012); Cremer & Pople (1975); Pettersson (2011); Shi & Zhang (2007); Shi et al. (2006a, 2006b, 2006c, 2012); Shi, Cheng, Sui & Zhu (2007); Shi, Sui & Zhu (2006); Shi, Sui, Cheng & Zhu (2007); Shi, Zhang, Cheng & Sun (2006); Shi, Zhu & Ng (2007); Spek (2009); Zhu et al. (2011); Zotov et al. (1997).
For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).
C23H20N2 | Z = 4 |
Mr = 324.41 | F(000) = 688 |
Triclinic, P1 | Dx = 1.210 Mg m−3 |
a = 9.4245 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6605 (16) Å | Cell parameters from 5062 reflections |
c = 18.405 (3) Å | θ = 2.0–27.7° |
α = 80.2989 (19)° | µ = 0.07 mm−1 |
β = 85.094 (2)° | T = 296 K |
γ = 78.1155 (19)° | Block, white |
V = 1781.1 (5) Å3 | 0.24 × 0.20 × 0.15 mm |
Bruker SMART APEX CCD area-detector diffractometer | 8141 independent reflections |
Radiation source: fine-focus sealed tube | 5062 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and φ scans | θmax = 27.7°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −11→12 |
Tmin = 0.967, Tmax = 0.982 | k = −13→13 |
15860 measured reflections | l = −24→24 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0725P)2 + 0.0625P] where P = (Fo2 + 2Fc2)/3 |
8141 reflections | (Δ/σ)max < 0.001 |
451 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C23H20N2 | γ = 78.1155 (19)° |
Mr = 324.41 | V = 1781.1 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.4245 (14) Å | Mo Kα radiation |
b = 10.6605 (16) Å | µ = 0.07 mm−1 |
c = 18.405 (3) Å | T = 296 K |
α = 80.2989 (19)° | 0.24 × 0.20 × 0.15 mm |
β = 85.094 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 8141 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 5062 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.982 | Rint = 0.030 |
15860 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.18 e Å−3 |
8141 reflections | Δρmin = −0.21 e Å−3 |
451 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.45206 (19) | 0.35100 (18) | 0.06052 (10) | 0.0567 (5) | |
H1 | 0.4049 | 0.4128 | 0.0240 | 0.068* | |
C2 | 0.5909 (2) | 0.2851 (2) | 0.04550 (11) | 0.0630 (5) | |
H2 | 0.6366 | 0.3030 | −0.0008 | 0.076* | |
C3 | 0.6618 (2) | 0.19324 (19) | 0.09872 (12) | 0.0650 (5) | |
H3 | 0.7548 | 0.1481 | 0.0883 | 0.078* | |
C4 | 0.5946 (2) | 0.1683 (2) | 0.16752 (13) | 0.0693 (6) | |
H4 | 0.6432 | 0.1071 | 0.2039 | 0.083* | |
C5 | 0.4549 (2) | 0.23370 (17) | 0.18309 (11) | 0.0589 (5) | |
H5 | 0.4102 | 0.2154 | 0.2296 | 0.071* | |
C6 | 0.38163 (17) | 0.32626 (15) | 0.12960 (9) | 0.0459 (4) | |
C7 | 0.23121 (17) | 0.39697 (16) | 0.14432 (9) | 0.0461 (4) | |
C8 | 0.12814 (18) | 0.33644 (16) | 0.19997 (9) | 0.0478 (4) | |
H8A | 0.0805 | 0.3993 | 0.2311 | 0.057* | |
H8B | 0.1826 | 0.2630 | 0.2312 | 0.057* | |
C9 | 0.01134 (17) | 0.29026 (15) | 0.16181 (9) | 0.0442 (4) | |
H9 | −0.0735 | 0.2906 | 0.1965 | 0.053* | |
C10 | 0.05610 (17) | 0.15394 (15) | 0.14295 (9) | 0.0444 (4) | |
C11 | 0.1572 (2) | 0.12425 (17) | 0.08598 (11) | 0.0596 (5) | |
H11 | 0.2032 | 0.1885 | 0.0597 | 0.071* | |
C12 | 0.1908 (2) | 0.00012 (19) | 0.06769 (12) | 0.0703 (6) | |
H12 | 0.2587 | −0.0179 | 0.0292 | 0.084* | |
C13 | 0.1246 (2) | −0.09664 (18) | 0.10582 (12) | 0.0658 (5) | |
H13 | 0.1455 | −0.1792 | 0.0926 | 0.079* | |
C14 | 0.0278 (2) | −0.06981 (17) | 0.16334 (11) | 0.0619 (5) | |
H14 | −0.0157 | −0.1352 | 0.1902 | 0.074* | |
C15 | −0.00653 (18) | 0.05436 (17) | 0.18225 (10) | 0.0517 (4) | |
H15 | −0.0723 | 0.0708 | 0.2218 | 0.062* | |
C16 | −0.03654 (18) | 0.39067 (15) | 0.09335 (9) | 0.0474 (4) | |
H16A | 0.0364 | 0.3792 | 0.0533 | 0.057* | |
H16B | −0.1269 | 0.3767 | 0.0776 | 0.057* | |
C17 | −0.05721 (18) | 0.52700 (15) | 0.11026 (9) | 0.0463 (4) | |
C18 | −0.20589 (18) | 0.60540 (16) | 0.11874 (9) | 0.0475 (4) | |
C19 | −0.32386 (19) | 0.54717 (19) | 0.14197 (11) | 0.0592 (5) | |
H19 | −0.3103 | 0.4572 | 0.1529 | 0.071* | |
C20 | −0.4617 (2) | 0.6214 (2) | 0.14902 (12) | 0.0688 (5) | |
H20 | −0.5402 | 0.5814 | 0.1649 | 0.083* | |
C21 | −0.4828 (2) | 0.7542 (2) | 0.13257 (11) | 0.0690 (6) | |
H21 | −0.5757 | 0.8038 | 0.1372 | 0.083* | |
C22 | −0.3676 (2) | 0.8138 (2) | 0.10936 (11) | 0.0650 (5) | |
H22 | −0.3827 | 0.9037 | 0.0980 | 0.078* | |
C23 | −0.2289 (2) | 0.74058 (17) | 0.10276 (10) | 0.0553 (4) | |
H23 | −0.1509 | 0.7816 | 0.0877 | 0.066* | |
C24 | 0.64207 (19) | 0.85674 (17) | 0.43180 (10) | 0.0542 (4) | |
H24 | 0.5895 | 0.8962 | 0.4698 | 0.065* | |
C25 | 0.7791 (2) | 0.78340 (18) | 0.44365 (11) | 0.0612 (5) | |
H25 | 0.8178 | 0.7736 | 0.4895 | 0.073* | |
C26 | 0.8592 (2) | 0.72444 (18) | 0.38795 (12) | 0.0638 (5) | |
H26 | 0.9515 | 0.6750 | 0.3962 | 0.077* | |
C27 | 0.8017 (2) | 0.73931 (19) | 0.32052 (12) | 0.0664 (5) | |
H27 | 0.8558 | 0.7007 | 0.2826 | 0.080* | |
C28 | 0.6633 (2) | 0.81159 (18) | 0.30837 (10) | 0.0594 (5) | |
H28 | 0.6247 | 0.8195 | 0.2626 | 0.071* | |
C29 | 0.58134 (18) | 0.87253 (16) | 0.36372 (9) | 0.0473 (4) | |
C30 | 0.43378 (18) | 0.95174 (16) | 0.35081 (9) | 0.0472 (4) | |
C31 | 0.33390 (18) | 0.91588 (17) | 0.30130 (9) | 0.0492 (4) | |
H31A | 0.3893 | 0.8541 | 0.2714 | 0.059* | |
H31B | 0.2906 | 0.9927 | 0.2684 | 0.059* | |
C32 | 0.21158 (18) | 0.85520 (15) | 0.34815 (9) | 0.0455 (4) | |
H32 | 0.1286 | 0.8720 | 0.3169 | 0.055* | |
C33 | 0.25497 (17) | 0.70859 (15) | 0.36832 (9) | 0.0458 (4) | |
C34 | 0.2912 (2) | 0.64605 (18) | 0.43816 (11) | 0.0702 (6) | |
H34 | 0.2901 | 0.6944 | 0.4759 | 0.084* | |
C35 | 0.3293 (3) | 0.5110 (2) | 0.45268 (13) | 0.0803 (6) | |
H35 | 0.3527 | 0.4704 | 0.5001 | 0.096* | |
C36 | 0.3329 (2) | 0.43795 (19) | 0.39851 (14) | 0.0700 (6) | |
H36 | 0.3590 | 0.3480 | 0.4085 | 0.084* | |
C37 | 0.2974 (2) | 0.4986 (2) | 0.32940 (13) | 0.0720 (6) | |
H37 | 0.2996 | 0.4495 | 0.2919 | 0.086* | |
C38 | 0.2583 (2) | 0.63236 (19) | 0.31423 (11) | 0.0625 (5) | |
H38 | 0.2337 | 0.6717 | 0.2667 | 0.075* | |
C39 | 0.16124 (19) | 0.92650 (16) | 0.41463 (9) | 0.0510 (4) | |
H39A | 0.0696 | 0.9055 | 0.4359 | 0.061* | |
H39B | 0.2323 | 0.8984 | 0.4521 | 0.061* | |
C40 | 0.14324 (19) | 1.07091 (16) | 0.39051 (9) | 0.0478 (4) | |
C41 | −0.00265 (18) | 1.15585 (16) | 0.38144 (9) | 0.0465 (4) | |
C42 | −0.1257 (2) | 1.10590 (18) | 0.37626 (10) | 0.0570 (5) | |
H42 | −0.1177 | 1.0166 | 0.3806 | 0.068* | |
C43 | −0.2598 (2) | 1.1862 (2) | 0.36478 (12) | 0.0700 (6) | |
H43 | −0.3410 | 1.1507 | 0.3617 | 0.084* | |
C44 | −0.2728 (2) | 1.3181 (2) | 0.35797 (12) | 0.0739 (6) | |
H44 | −0.3623 | 1.3724 | 0.3491 | 0.089* | |
C45 | −0.1526 (2) | 1.36985 (19) | 0.36436 (11) | 0.0679 (5) | |
H45 | −0.1619 | 1.4593 | 0.3605 | 0.082* | |
C46 | −0.0187 (2) | 1.29029 (17) | 0.37643 (10) | 0.0543 (4) | |
H46 | 0.0612 | 1.3263 | 0.3813 | 0.065* | |
N1 | 0.19129 (15) | 0.50891 (14) | 0.10536 (8) | 0.0554 (4) | |
N2 | 0.05077 (15) | 0.57917 (13) | 0.11899 (9) | 0.0547 (4) | |
N3 | 0.39270 (16) | 1.04815 (14) | 0.38622 (8) | 0.0543 (4) | |
N4 | 0.25420 (15) | 1.12582 (13) | 0.37384 (8) | 0.0514 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0509 (11) | 0.0633 (12) | 0.0548 (11) | −0.0083 (9) | −0.0072 (8) | −0.0070 (9) |
C2 | 0.0505 (11) | 0.0795 (14) | 0.0624 (12) | −0.0121 (10) | −0.0010 (9) | −0.0225 (10) |
C3 | 0.0481 (11) | 0.0632 (13) | 0.0866 (15) | −0.0011 (9) | −0.0098 (10) | −0.0279 (11) |
C4 | 0.0582 (12) | 0.0601 (12) | 0.0836 (15) | −0.0014 (10) | −0.0164 (11) | −0.0009 (10) |
C5 | 0.0550 (11) | 0.0534 (11) | 0.0650 (12) | −0.0087 (9) | −0.0076 (9) | 0.0000 (9) |
C6 | 0.0441 (9) | 0.0425 (9) | 0.0546 (10) | −0.0130 (7) | −0.0082 (7) | −0.0090 (7) |
C7 | 0.0454 (9) | 0.0448 (9) | 0.0504 (9) | −0.0134 (7) | −0.0042 (7) | −0.0070 (7) |
C8 | 0.0502 (10) | 0.0491 (10) | 0.0445 (9) | −0.0110 (8) | −0.0026 (7) | −0.0069 (7) |
C9 | 0.0428 (9) | 0.0434 (9) | 0.0463 (9) | −0.0112 (7) | 0.0026 (7) | −0.0060 (7) |
C10 | 0.0430 (9) | 0.0414 (9) | 0.0486 (9) | −0.0091 (7) | −0.0064 (7) | −0.0033 (7) |
C11 | 0.0628 (11) | 0.0466 (10) | 0.0699 (12) | −0.0158 (9) | 0.0144 (9) | −0.0132 (9) |
C12 | 0.0742 (13) | 0.0548 (12) | 0.0814 (14) | −0.0092 (10) | 0.0142 (11) | −0.0226 (10) |
C13 | 0.0676 (13) | 0.0435 (10) | 0.0878 (15) | −0.0076 (9) | −0.0116 (11) | −0.0148 (10) |
C14 | 0.0664 (12) | 0.0436 (10) | 0.0767 (13) | −0.0210 (9) | −0.0164 (10) | 0.0069 (9) |
C15 | 0.0498 (10) | 0.0514 (10) | 0.0527 (10) | −0.0135 (8) | −0.0073 (8) | 0.0018 (8) |
C16 | 0.0480 (9) | 0.0452 (9) | 0.0494 (9) | −0.0062 (7) | −0.0049 (7) | −0.0108 (7) |
C17 | 0.0496 (10) | 0.0416 (9) | 0.0467 (9) | −0.0092 (8) | −0.0022 (7) | −0.0035 (7) |
C18 | 0.0487 (10) | 0.0470 (10) | 0.0476 (9) | −0.0058 (8) | −0.0070 (7) | −0.0113 (7) |
C19 | 0.0520 (11) | 0.0558 (11) | 0.0716 (12) | −0.0107 (9) | 0.0001 (9) | −0.0165 (9) |
C20 | 0.0516 (11) | 0.0788 (15) | 0.0807 (14) | −0.0135 (10) | 0.0033 (10) | −0.0277 (11) |
C21 | 0.0540 (12) | 0.0847 (16) | 0.0662 (13) | 0.0106 (11) | −0.0097 (10) | −0.0324 (11) |
C22 | 0.0721 (14) | 0.0549 (11) | 0.0639 (12) | 0.0058 (10) | −0.0127 (10) | −0.0149 (9) |
C23 | 0.0574 (11) | 0.0481 (10) | 0.0602 (11) | −0.0065 (9) | −0.0081 (9) | −0.0096 (8) |
C24 | 0.0575 (11) | 0.0530 (11) | 0.0543 (10) | −0.0146 (9) | −0.0031 (8) | −0.0099 (8) |
C25 | 0.0620 (12) | 0.0569 (11) | 0.0665 (12) | −0.0160 (9) | −0.0165 (10) | −0.0027 (9) |
C26 | 0.0508 (11) | 0.0505 (11) | 0.0872 (15) | −0.0095 (9) | −0.0068 (10) | −0.0017 (10) |
C27 | 0.0614 (12) | 0.0599 (12) | 0.0740 (14) | −0.0066 (10) | 0.0123 (10) | −0.0139 (10) |
C28 | 0.0632 (12) | 0.0630 (12) | 0.0515 (10) | −0.0114 (9) | −0.0018 (9) | −0.0092 (9) |
C29 | 0.0495 (10) | 0.0440 (9) | 0.0499 (10) | −0.0143 (8) | −0.0007 (8) | −0.0064 (7) |
C30 | 0.0520 (10) | 0.0442 (9) | 0.0470 (9) | −0.0146 (8) | −0.0015 (7) | −0.0055 (7) |
C31 | 0.0558 (10) | 0.0499 (10) | 0.0424 (9) | −0.0112 (8) | −0.0014 (7) | −0.0078 (7) |
C32 | 0.0475 (9) | 0.0455 (9) | 0.0455 (9) | −0.0116 (7) | −0.0052 (7) | −0.0076 (7) |
C33 | 0.0406 (9) | 0.0437 (9) | 0.0554 (10) | −0.0121 (7) | −0.0008 (7) | −0.0099 (8) |
C34 | 0.1031 (16) | 0.0477 (11) | 0.0613 (12) | −0.0147 (11) | −0.0170 (11) | −0.0067 (9) |
C35 | 0.1083 (18) | 0.0515 (12) | 0.0784 (15) | −0.0149 (12) | −0.0161 (13) | 0.0026 (11) |
C36 | 0.0651 (13) | 0.0423 (11) | 0.1010 (17) | −0.0113 (9) | 0.0053 (12) | −0.0101 (11) |
C37 | 0.0768 (14) | 0.0593 (13) | 0.0890 (16) | −0.0194 (11) | 0.0038 (12) | −0.0340 (12) |
C38 | 0.0697 (13) | 0.0589 (12) | 0.0612 (11) | −0.0102 (10) | −0.0049 (9) | −0.0178 (9) |
C39 | 0.0580 (10) | 0.0457 (10) | 0.0477 (9) | −0.0094 (8) | 0.0025 (8) | −0.0058 (7) |
C40 | 0.0567 (10) | 0.0416 (9) | 0.0450 (9) | −0.0094 (8) | 0.0012 (8) | −0.0086 (7) |
C41 | 0.0530 (10) | 0.0446 (9) | 0.0423 (9) | −0.0118 (8) | 0.0047 (7) | −0.0092 (7) |
C42 | 0.0567 (11) | 0.0503 (10) | 0.0646 (12) | −0.0125 (9) | 0.0048 (9) | −0.0121 (9) |
C43 | 0.0530 (12) | 0.0730 (14) | 0.0861 (15) | −0.0146 (10) | 0.0016 (10) | −0.0181 (11) |
C44 | 0.0553 (12) | 0.0725 (15) | 0.0855 (15) | 0.0038 (11) | 0.0031 (11) | −0.0126 (11) |
C45 | 0.0683 (13) | 0.0482 (11) | 0.0821 (14) | −0.0042 (10) | 0.0078 (11) | −0.0102 (10) |
C46 | 0.0572 (11) | 0.0457 (10) | 0.0590 (11) | −0.0097 (8) | 0.0054 (8) | −0.0101 (8) |
N1 | 0.0458 (8) | 0.0458 (9) | 0.0715 (10) | −0.0101 (7) | 0.0000 (7) | −0.0009 (7) |
N2 | 0.0477 (8) | 0.0429 (8) | 0.0719 (10) | −0.0101 (7) | −0.0020 (7) | −0.0035 (7) |
N3 | 0.0531 (9) | 0.0462 (8) | 0.0660 (10) | −0.0096 (7) | −0.0065 (7) | −0.0137 (7) |
N4 | 0.0524 (9) | 0.0442 (8) | 0.0592 (9) | −0.0085 (7) | −0.0068 (7) | −0.0116 (7) |
C1—C2 | 1.381 (2) | C24—C29 | 1.392 (2) |
C1—C6 | 1.393 (2) | C24—H24 | 0.9300 |
C1—H1 | 0.9300 | C25—C26 | 1.380 (3) |
C2—C3 | 1.373 (3) | C25—H25 | 0.9300 |
C2—H2 | 0.9300 | C26—C27 | 1.368 (3) |
C3—C4 | 1.376 (3) | C26—H26 | 0.9300 |
C3—H3 | 0.9300 | C27—C28 | 1.387 (3) |
C4—C5 | 1.388 (3) | C27—H27 | 0.9300 |
C4—H4 | 0.9300 | C28—C29 | 1.392 (2) |
C5—C6 | 1.389 (2) | C28—H28 | 0.9300 |
C5—H5 | 0.9300 | C29—C30 | 1.486 (2) |
C6—C7 | 1.488 (2) | C30—N3 | 1.284 (2) |
C7—N1 | 1.286 (2) | C30—C31 | 1.508 (2) |
C7—C8 | 1.508 (2) | C31—C32 | 1.562 (2) |
C8—C9 | 1.555 (2) | C31—H31A | 0.9700 |
C8—H8A | 0.9700 | C31—H31B | 0.9700 |
C8—H8B | 0.9700 | C32—C33 | 1.521 (2) |
C9—C10 | 1.517 (2) | C32—C39 | 1.538 (2) |
C9—C16 | 1.543 (2) | C32—H32 | 0.9800 |
C9—H9 | 0.9800 | C33—C34 | 1.380 (2) |
C10—C15 | 1.387 (2) | C33—C38 | 1.382 (2) |
C10—C11 | 1.387 (2) | C34—C35 | 1.395 (3) |
C11—C12 | 1.387 (3) | C34—H34 | 0.9300 |
C11—H11 | 0.9300 | C35—C36 | 1.359 (3) |
C12—C13 | 1.375 (3) | C35—H35 | 0.9300 |
C12—H12 | 0.9300 | C36—C37 | 1.362 (3) |
C13—C14 | 1.365 (3) | C36—H36 | 0.9300 |
C13—H13 | 0.9300 | C37—C38 | 1.384 (3) |
C14—C15 | 1.392 (3) | C37—H37 | 0.9300 |
C14—H14 | 0.9300 | C38—H38 | 0.9300 |
C15—H15 | 0.9300 | C39—C40 | 1.507 (2) |
C16—C17 | 1.508 (2) | C39—H39A | 0.9700 |
C16—H16A | 0.9700 | C39—H39B | 0.9700 |
C16—H16B | 0.9700 | C40—N4 | 1.291 (2) |
C17—N2 | 1.289 (2) | C40—C41 | 1.488 (2) |
C17—C18 | 1.487 (2) | C41—C42 | 1.388 (2) |
C18—C19 | 1.385 (2) | C41—C46 | 1.398 (2) |
C18—C23 | 1.396 (2) | C42—C43 | 1.384 (3) |
C19—C20 | 1.384 (3) | C42—H42 | 0.9300 |
C19—H19 | 0.9300 | C43—C44 | 1.371 (3) |
C20—C21 | 1.372 (3) | C43—H43 | 0.9300 |
C20—H20 | 0.9300 | C44—C45 | 1.380 (3) |
C21—C22 | 1.370 (3) | C44—H44 | 0.9300 |
C21—H21 | 0.9300 | C45—C46 | 1.380 (2) |
C22—C23 | 1.385 (2) | C45—H45 | 0.9300 |
C22—H22 | 0.9300 | C46—H46 | 0.9300 |
C23—H23 | 0.9300 | N1—N2 | 1.4056 (19) |
C24—C25 | 1.379 (2) | N3—N4 | 1.4083 (19) |
C2—C1—C6 | 120.96 (17) | C29—C24—H24 | 119.6 |
C2—C1—H1 | 119.5 | C24—C25—C26 | 120.53 (18) |
C6—C1—H1 | 119.5 | C24—C25—H25 | 119.7 |
C3—C2—C1 | 120.23 (18) | C26—C25—H25 | 119.7 |
C3—C2—H2 | 119.9 | C27—C26—C25 | 119.50 (18) |
C1—C2—H2 | 119.9 | C27—C26—H26 | 120.2 |
C2—C3—C4 | 119.67 (18) | C25—C26—H26 | 120.2 |
C2—C3—H3 | 120.2 | C26—C27—C28 | 120.37 (19) |
C4—C3—H3 | 120.2 | C26—C27—H27 | 119.8 |
C3—C4—C5 | 120.53 (18) | C28—C27—H27 | 119.8 |
C3—C4—H4 | 119.7 | C27—C28—C29 | 120.92 (18) |
C5—C4—H4 | 119.7 | C27—C28—H28 | 119.5 |
C4—C5—C6 | 120.38 (18) | C29—C28—H28 | 119.5 |
C4—C5—H5 | 119.8 | C24—C29—C28 | 117.80 (16) |
C6—C5—H5 | 119.8 | C24—C29—C30 | 120.94 (15) |
C5—C6—C1 | 118.22 (16) | C28—C29—C30 | 121.26 (16) |
C5—C6—C7 | 121.65 (15) | N3—C30—C29 | 117.17 (15) |
C1—C6—C7 | 120.12 (15) | N3—C30—C31 | 121.53 (15) |
N1—C7—C6 | 117.17 (14) | C29—C30—C31 | 121.22 (15) |
N1—C7—C8 | 121.65 (15) | C30—C31—C32 | 110.55 (13) |
C6—C7—C8 | 121.11 (14) | C30—C31—H31A | 109.5 |
C7—C8—C9 | 111.65 (13) | C32—C31—H31A | 109.5 |
C7—C8—H8A | 109.3 | C30—C31—H31B | 109.5 |
C9—C8—H8A | 109.3 | C32—C31—H31B | 109.5 |
C7—C8—H8B | 109.3 | H31A—C31—H31B | 108.1 |
C9—C8—H8B | 109.3 | C33—C32—C39 | 114.17 (13) |
H8A—C8—H8B | 108.0 | C33—C32—C31 | 112.31 (13) |
C10—C9—C16 | 111.73 (13) | C39—C32—C31 | 109.82 (13) |
C10—C9—C8 | 114.79 (13) | C33—C32—H32 | 106.7 |
C16—C9—C8 | 109.01 (13) | C39—C32—H32 | 106.7 |
C10—C9—H9 | 107.0 | C31—C32—H32 | 106.7 |
C16—C9—H9 | 107.0 | C34—C33—C38 | 117.41 (17) |
C8—C9—H9 | 107.0 | C34—C33—C32 | 123.80 (16) |
C15—C10—C11 | 117.68 (16) | C38—C33—C32 | 118.78 (16) |
C15—C10—C9 | 120.10 (15) | C33—C34—C35 | 120.62 (19) |
C11—C10—C9 | 122.21 (14) | C33—C34—H34 | 119.7 |
C12—C11—C10 | 120.91 (17) | C35—C34—H34 | 119.7 |
C12—C11—H11 | 119.5 | C36—C35—C34 | 121.0 (2) |
C10—C11—H11 | 119.5 | C36—C35—H35 | 119.5 |
C13—C12—C11 | 120.68 (19) | C34—C35—H35 | 119.5 |
C13—C12—H12 | 119.7 | C35—C36—C37 | 118.90 (19) |
C11—C12—H12 | 119.7 | C35—C36—H36 | 120.6 |
C14—C13—C12 | 119.08 (18) | C37—C36—H36 | 120.6 |
C14—C13—H13 | 120.5 | C36—C37—C38 | 120.83 (19) |
C12—C13—H13 | 120.5 | C36—C37—H37 | 119.6 |
C13—C14—C15 | 120.72 (17) | C38—C37—H37 | 119.6 |
C13—C14—H14 | 119.6 | C33—C38—C37 | 121.25 (19) |
C15—C14—H14 | 119.6 | C33—C38—H38 | 119.4 |
C10—C15—C14 | 120.88 (17) | C37—C38—H38 | 119.4 |
C10—C15—H15 | 119.6 | C40—C39—C32 | 109.97 (13) |
C14—C15—H15 | 119.6 | C40—C39—H39A | 109.7 |
C17—C16—C9 | 110.90 (13) | C32—C39—H39A | 109.7 |
C17—C16—H16A | 109.5 | C40—C39—H39B | 109.7 |
C9—C16—H16A | 109.5 | C32—C39—H39B | 109.7 |
C17—C16—H16B | 109.5 | H39A—C39—H39B | 108.2 |
C9—C16—H16B | 109.5 | N4—C40—C41 | 116.91 (14) |
H16A—C16—H16B | 108.0 | N4—C40—C39 | 121.36 (15) |
N2—C17—C18 | 117.66 (15) | C41—C40—C39 | 121.68 (14) |
N2—C17—C16 | 122.19 (15) | C42—C41—C46 | 117.92 (16) |
C18—C17—C16 | 120.14 (14) | C42—C41—C40 | 121.87 (15) |
C19—C18—C23 | 118.65 (16) | C46—C41—C40 | 120.19 (15) |
C19—C18—C17 | 121.36 (15) | C43—C42—C41 | 121.42 (18) |
C23—C18—C17 | 119.99 (15) | C43—C42—H42 | 119.3 |
C20—C19—C18 | 120.67 (18) | C41—C42—H42 | 119.3 |
C20—C19—H19 | 119.7 | C44—C43—C42 | 119.85 (19) |
C18—C19—H19 | 119.7 | C44—C43—H43 | 120.1 |
C21—C20—C19 | 120.03 (19) | C42—C43—H43 | 120.1 |
C21—C20—H20 | 120.0 | C43—C44—C45 | 119.79 (19) |
C19—C20—H20 | 120.0 | C43—C44—H44 | 120.1 |
C22—C21—C20 | 120.26 (18) | C45—C44—H44 | 120.1 |
C22—C21—H21 | 119.9 | C44—C45—C46 | 120.65 (19) |
C20—C21—H21 | 119.9 | C44—C45—H45 | 119.7 |
C21—C22—C23 | 120.28 (19) | C46—C45—H45 | 119.7 |
C21—C22—H22 | 119.9 | C45—C46—C41 | 120.33 (17) |
C23—C22—H22 | 119.9 | C45—C46—H46 | 119.8 |
C22—C23—C18 | 120.11 (18) | C41—C46—H46 | 119.8 |
C22—C23—H23 | 119.9 | C7—N1—N2 | 118.48 (13) |
C18—C23—H23 | 119.9 | C17—N2—N1 | 117.55 (14) |
C25—C24—C29 | 120.87 (17) | C30—N3—N4 | 118.10 (14) |
C25—C24—H24 | 119.6 | C40—N4—N3 | 117.54 (14) |
C6—C1—C2—C3 | 0.2 (3) | C25—C24—C29—C30 | −179.90 (16) |
C1—C2—C3—C4 | −0.8 (3) | C27—C28—C29—C24 | −1.0 (3) |
C2—C3—C4—C5 | 1.0 (3) | C27—C28—C29—C30 | 179.10 (16) |
C3—C4—C5—C6 | −0.6 (3) | C24—C29—C30—N3 | 31.3 (2) |
C4—C5—C6—C1 | 0.0 (3) | C28—C29—C30—N3 | −148.76 (17) |
C4—C5—C6—C7 | 179.31 (17) | C24—C29—C30—C31 | −145.51 (16) |
C2—C1—C6—C5 | 0.2 (3) | C28—C29—C30—C31 | 34.4 (2) |
C2—C1—C6—C7 | −179.12 (16) | N3—C30—C31—C32 | −71.6 (2) |
C5—C6—C7—N1 | 155.10 (17) | C29—C30—C31—C32 | 105.09 (17) |
C1—C6—C7—N1 | −25.6 (2) | C30—C31—C32—C33 | −89.81 (17) |
C5—C6—C7—C8 | −27.9 (2) | C30—C31—C32—C39 | 38.37 (18) |
C1—C6—C7—C8 | 151.36 (16) | C39—C32—C33—C34 | −19.5 (2) |
N1—C7—C8—C9 | 71.8 (2) | C31—C32—C33—C34 | 106.31 (19) |
C6—C7—C8—C9 | −105.05 (17) | C39—C32—C33—C38 | 160.18 (16) |
C7—C8—C9—C10 | 87.21 (17) | C31—C32—C33—C38 | −73.96 (19) |
C7—C8—C9—C16 | −38.97 (18) | C38—C33—C34—C35 | 0.0 (3) |
C16—C9—C10—C15 | −126.52 (16) | C32—C33—C34—C35 | 179.74 (18) |
C8—C9—C10—C15 | 108.72 (17) | C33—C34—C35—C36 | 0.5 (3) |
C16—C9—C10—C11 | 52.3 (2) | C34—C35—C36—C37 | −0.4 (3) |
C8—C9—C10—C11 | −72.5 (2) | C35—C36—C37—C38 | −0.1 (3) |
C15—C10—C11—C12 | 2.0 (3) | C34—C33—C38—C37 | −0.5 (3) |
C9—C10—C11—C12 | −176.81 (17) | C32—C33—C38—C37 | 179.76 (16) |
C10—C11—C12—C13 | −0.2 (3) | C36—C37—C38—C33 | 0.5 (3) |
C11—C12—C13—C14 | −1.6 (3) | C33—C32—C39—C40 | 171.24 (14) |
C12—C13—C14—C15 | 1.6 (3) | C31—C32—C39—C40 | 44.09 (18) |
C11—C10—C15—C14 | −2.1 (2) | C32—C39—C40—N4 | −72.9 (2) |
C9—C10—C15—C14 | 176.75 (15) | C32—C39—C40—C41 | 104.24 (17) |
C13—C14—C15—C10 | 0.3 (3) | N4—C40—C41—C42 | 160.69 (16) |
C10—C9—C16—C17 | −170.82 (13) | C39—C40—C41—C42 | −16.5 (2) |
C8—C9—C16—C17 | −42.90 (17) | N4—C40—C41—C46 | −18.1 (2) |
C9—C16—C17—N2 | 72.4 (2) | C39—C40—C41—C46 | 164.70 (15) |
C9—C16—C17—C18 | −106.57 (16) | C46—C41—C42—C43 | 1.5 (3) |
N2—C17—C18—C19 | −151.71 (17) | C40—C41—C42—C43 | −177.30 (17) |
C16—C17—C18—C19 | 27.3 (2) | C41—C42—C43—C44 | 0.3 (3) |
N2—C17—C18—C23 | 28.7 (2) | C42—C43—C44—C45 | −1.5 (3) |
C16—C17—C18—C23 | −152.37 (16) | C43—C44—C45—C46 | 1.0 (3) |
C23—C18—C19—C20 | 0.2 (3) | C44—C45—C46—C41 | 0.8 (3) |
C17—C18—C19—C20 | −179.48 (17) | C42—C41—C46—C45 | −2.0 (3) |
C18—C19—C20—C21 | 0.3 (3) | C40—C41—C46—C45 | 176.79 (16) |
C19—C20—C21—C22 | −0.2 (3) | C6—C7—N1—N2 | −178.77 (14) |
C20—C21—C22—C23 | −0.4 (3) | C8—C7—N1—N2 | 4.2 (2) |
C21—C22—C23—C18 | 0.9 (3) | C18—C17—N2—N1 | −175.19 (14) |
C19—C18—C23—C22 | −0.8 (3) | C16—C17—N2—N1 | 5.9 (2) |
C17—C18—C23—C22 | 178.86 (16) | C7—N1—N2—C17 | −60.5 (2) |
C29—C24—C25—C26 | 0.3 (3) | C29—C30—N3—N4 | 178.94 (13) |
C24—C25—C26—C27 | 0.1 (3) | C31—C30—N3—N4 | −4.2 (2) |
C25—C26—C27—C28 | −0.9 (3) | C41—C40—N4—N3 | 176.38 (14) |
C26—C27—C28—C29 | 1.3 (3) | C39—C40—N4—N3 | −6.4 (2) |
C25—C24—C29—C28 | 0.2 (2) | C30—N3—N4—C40 | 61.8 (2) |
C23H20N2O2 | F(000) = 1504 |
Mr = 356.41 | Dx = 1.298 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 23.9715 (14) Å | Cell parameters from 1649 reflections |
b = 9.5669 (16) Å | θ = 2.0–25.0° |
c = 18.2303 (12) Å | µ = 0.08 mm−1 |
β = 119.256 (3)° | T = 296 K |
V = 3647.5 (7) Å3 | Block, yellow |
Z = 8 | 0.30 × 0.28 × 0.26 mm |
Bruker SMART APEX CCD area-detector diffractometer | 3224 independent reflections |
Radiation source: fine-focus sealed tube | 1647 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.071 |
ω and φ scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −27→28 |
Tmin = 0.967, Tmax = 0.972 | k = −11→11 |
12998 measured reflections | l = −21→21 |
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0426P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max < 0.001 |
3224 reflections | Δρmax = 0.13 e Å−3 |
253 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0014 (2) |
C23H20N2O2 | V = 3647.5 (7) Å3 |
Mr = 356.41 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 23.9715 (14) Å | µ = 0.08 mm−1 |
b = 9.5669 (16) Å | T = 296 K |
c = 18.2303 (12) Å | 0.30 × 0.28 × 0.26 mm |
β = 119.256 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 3224 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1647 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.972 | Rint = 0.071 |
12998 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.13 e Å−3 |
3224 reflections | Δρmin = −0.14 e Å−3 |
253 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.37760 (14) | 0.7121 (3) | 0.13321 (16) | 0.0607 (7) | |
C2 | 0.42387 (14) | 0.8122 (4) | 0.14804 (18) | 0.0827 (10) | |
H2 | 0.4647 | 0.7840 | 0.1606 | 0.099* | |
C3 | 0.41027 (18) | 0.9513 (4) | 0.14444 (19) | 0.0923 (11) | |
H3 | 0.4421 | 1.0168 | 0.1552 | 0.111* | |
C4 | 0.34995 (17) | 0.9960 (3) | 0.12501 (17) | 0.0795 (9) | |
H4 | 0.3406 | 1.0909 | 0.1217 | 0.095* | |
C5 | 0.30379 (13) | 0.8978 (3) | 0.11052 (14) | 0.0595 (7) | |
H5 | 0.2631 | 0.9280 | 0.0973 | 0.071* | |
C6 | 0.31590 (12) | 0.7540 (3) | 0.11501 (14) | 0.0500 (6) | |
C7 | 0.26667 (11) | 0.6507 (3) | 0.10285 (13) | 0.0450 (6) | |
C8 | 0.20110 (11) | 0.6912 (2) | 0.08683 (14) | 0.0479 (6) | |
H8A | 0.1692 | 0.6360 | 0.0408 | 0.058* | |
H8B | 0.1933 | 0.7890 | 0.0709 | 0.058* | |
C9 | 0.19542 (10) | 0.6666 (2) | 0.16681 (14) | 0.0420 (6) | |
H9 | 0.2233 | 0.7356 | 0.2084 | 0.050* | |
C10 | 0.12857 (11) | 0.6920 (2) | 0.15289 (15) | 0.0415 (6) | |
C11 | 0.12080 (12) | 0.7586 (2) | 0.21469 (16) | 0.0545 (7) | |
H11 | 0.1567 | 0.7863 | 0.2641 | 0.065* | |
C12 | 0.06055 (14) | 0.7850 (3) | 0.20441 (19) | 0.0654 (8) | |
H12 | 0.0564 | 0.8293 | 0.2469 | 0.079* | |
C13 | 0.00712 (14) | 0.7458 (3) | 0.1318 (2) | 0.0647 (8) | |
H13 | −0.0334 | 0.7644 | 0.1245 | 0.078* | |
C14 | 0.01365 (13) | 0.6789 (3) | 0.06980 (17) | 0.0626 (7) | |
H14 | −0.0226 | 0.6514 | 0.0207 | 0.075* | |
C15 | 0.07382 (13) | 0.6522 (2) | 0.07994 (17) | 0.0576 (7) | |
H15 | 0.0776 | 0.6070 | 0.0374 | 0.069* | |
C16 | 0.22259 (11) | 0.5200 (2) | 0.20419 (13) | 0.0451 (6) | |
H16A | 0.2685 | 0.5272 | 0.2400 | 0.054* | |
H16B | 0.2044 | 0.4902 | 0.2389 | 0.054* | |
C17 | 0.20836 (11) | 0.4110 (2) | 0.13753 (14) | 0.0435 (6) | |
C18 | 0.16451 (11) | 0.2931 (2) | 0.12071 (14) | 0.0425 (6) | |
C19 | 0.12935 (11) | 0.2789 (2) | 0.16312 (15) | 0.0523 (7) | |
H19 | 0.1327 | 0.3478 | 0.2011 | 0.063* | |
C20 | 0.09007 (12) | 0.1661 (3) | 0.15024 (16) | 0.0640 (7) | |
H20 | 0.0677 | 0.1584 | 0.1798 | 0.077* | |
C21 | 0.08399 (13) | 0.0638 (3) | 0.09293 (17) | 0.0646 (8) | |
H21 | 0.0576 | −0.0128 | 0.0841 | 0.077* | |
C22 | 0.11670 (13) | 0.0752 (3) | 0.04939 (17) | 0.0648 (8) | |
H22 | 0.1119 | 0.0066 | 0.0106 | 0.078* | |
C23 | 0.15679 (12) | 0.1872 (2) | 0.06208 (16) | 0.0535 (7) | |
H1O | 0.3599 (15) | 0.519 (3) | 0.1286 (18) | 0.105 (12)* | |
H2O | 0.2146 (13) | 0.272 (3) | 0.0362 (18) | 0.098 (10)* | |
N1 | 0.28238 (9) | 0.5199 (2) | 0.10805 (12) | 0.0511 (5) | |
N2 | 0.23654 (9) | 0.41738 (19) | 0.09215 (12) | 0.0506 (5) | |
O1 | 0.39492 (9) | 0.5766 (3) | 0.13736 (12) | 0.0776 (6) | |
O2 | 0.18745 (11) | 0.1904 (2) | 0.01661 (13) | 0.0808 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (2) | 0.080 (2) | 0.0454 (18) | −0.0123 (17) | 0.0258 (15) | 0.0017 (14) |
C2 | 0.061 (2) | 0.113 (3) | 0.070 (2) | −0.027 (2) | 0.0293 (17) | −0.0015 (19) |
C3 | 0.093 (3) | 0.111 (3) | 0.073 (2) | −0.057 (2) | 0.040 (2) | −0.014 (2) |
C4 | 0.106 (3) | 0.077 (2) | 0.064 (2) | −0.033 (2) | 0.048 (2) | −0.0091 (16) |
C5 | 0.072 (2) | 0.0653 (18) | 0.0450 (17) | −0.0161 (16) | 0.0318 (15) | −0.0030 (13) |
C6 | 0.0528 (18) | 0.0622 (16) | 0.0366 (16) | −0.0098 (14) | 0.0232 (14) | −0.0013 (12) |
C7 | 0.0452 (17) | 0.0569 (16) | 0.0330 (15) | −0.0032 (13) | 0.0191 (13) | −0.0001 (12) |
C8 | 0.0475 (16) | 0.0485 (14) | 0.0474 (16) | −0.0001 (12) | 0.0229 (13) | 0.0071 (11) |
C9 | 0.0419 (15) | 0.0406 (13) | 0.0412 (15) | −0.0041 (11) | 0.0186 (12) | −0.0032 (11) |
C10 | 0.0382 (15) | 0.0380 (13) | 0.0462 (16) | −0.0021 (11) | 0.0190 (13) | 0.0007 (11) |
C11 | 0.0516 (18) | 0.0677 (16) | 0.0495 (17) | −0.0051 (13) | 0.0288 (15) | −0.0052 (13) |
C12 | 0.065 (2) | 0.0805 (19) | 0.070 (2) | −0.0008 (16) | 0.0474 (19) | −0.0015 (16) |
C13 | 0.054 (2) | 0.0690 (18) | 0.083 (2) | 0.0010 (15) | 0.042 (2) | 0.0118 (17) |
C14 | 0.0443 (18) | 0.0701 (18) | 0.065 (2) | −0.0063 (14) | 0.0197 (16) | −0.0028 (15) |
C15 | 0.0498 (18) | 0.0599 (16) | 0.0629 (19) | −0.0030 (14) | 0.0274 (16) | −0.0118 (14) |
C16 | 0.0449 (15) | 0.0500 (14) | 0.0377 (14) | 0.0002 (12) | 0.0181 (12) | 0.0001 (11) |
C17 | 0.0422 (16) | 0.0469 (14) | 0.0406 (15) | 0.0086 (12) | 0.0195 (13) | 0.0044 (11) |
C18 | 0.0435 (15) | 0.0420 (13) | 0.0395 (15) | 0.0028 (11) | 0.0184 (13) | 0.0038 (11) |
C19 | 0.0556 (18) | 0.0541 (15) | 0.0464 (17) | −0.0047 (13) | 0.0242 (15) | 0.0023 (12) |
C20 | 0.067 (2) | 0.0693 (18) | 0.0589 (19) | −0.0088 (16) | 0.0328 (16) | 0.0064 (15) |
C21 | 0.064 (2) | 0.0550 (17) | 0.064 (2) | −0.0111 (14) | 0.0231 (17) | 0.0076 (15) |
C22 | 0.078 (2) | 0.0436 (15) | 0.069 (2) | −0.0040 (15) | 0.0328 (17) | −0.0041 (14) |
C23 | 0.0638 (18) | 0.0455 (15) | 0.0562 (18) | 0.0039 (13) | 0.0331 (16) | −0.0023 (13) |
N1 | 0.0500 (14) | 0.0574 (13) | 0.0521 (14) | −0.0032 (12) | 0.0300 (11) | −0.0019 (11) |
N2 | 0.0545 (14) | 0.0487 (12) | 0.0572 (14) | −0.0033 (11) | 0.0339 (12) | −0.0040 (10) |
O1 | 0.0528 (14) | 0.0947 (16) | 0.0912 (16) | 0.0010 (13) | 0.0398 (12) | 0.0054 (12) |
O2 | 0.1081 (17) | 0.0676 (13) | 0.1017 (16) | −0.0172 (12) | 0.0786 (15) | −0.0309 (11) |
C1—O1 | 1.351 (3) | C12—H12 | 0.9300 |
C1—C2 | 1.389 (4) | C13—C14 | 1.372 (3) |
C1—C6 | 1.407 (3) | C13—H13 | 0.9300 |
C2—C3 | 1.364 (4) | C14—C15 | 1.386 (3) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.378 (4) | C15—H15 | 0.9300 |
C3—H3 | 0.9300 | C16—C17 | 1.509 (3) |
C4—C5 | 1.375 (3) | C16—H16A | 0.9700 |
C4—H4 | 0.9300 | C16—H16B | 0.9700 |
C5—C6 | 1.400 (3) | C17—N2 | 1.300 (3) |
C5—H5 | 0.9300 | C17—C18 | 1.468 (3) |
C6—C7 | 1.471 (3) | C18—C19 | 1.401 (3) |
C7—N1 | 1.297 (3) | C18—C23 | 1.418 (3) |
C7—C8 | 1.503 (3) | C19—C20 | 1.375 (3) |
C8—C9 | 1.547 (3) | C19—H19 | 0.9300 |
C8—H8A | 0.9700 | C20—C21 | 1.386 (3) |
C8—H8B | 0.9700 | C20—H20 | 0.9300 |
C9—C10 | 1.514 (3) | C21—C22 | 1.366 (3) |
C9—C16 | 1.556 (3) | C21—H21 | 0.9300 |
C9—H9 | 0.9800 | C22—C23 | 1.381 (3) |
C10—C11 | 1.384 (3) | C22—H22 | 0.9300 |
C10—C15 | 1.389 (3) | C23—O2 | 1.351 (3) |
C11—C12 | 1.386 (3) | N1—N2 | 1.394 (2) |
C11—H11 | 0.9300 | O1—H1O | 0.95 (3) |
C12—C13 | 1.370 (3) | O2—H2O | 0.97 (3) |
O1—C1—C2 | 117.2 (3) | C11—C12—H12 | 120.0 |
O1—C1—C6 | 123.1 (2) | C12—C13—C14 | 119.6 (3) |
C2—C1—C6 | 119.8 (3) | C12—C13—H13 | 120.2 |
C3—C2—C1 | 121.0 (3) | C14—C13—H13 | 120.2 |
C3—C2—H2 | 119.5 | C13—C14—C15 | 120.4 (3) |
C1—C2—H2 | 119.5 | C13—C14—H14 | 119.8 |
C2—C3—C4 | 120.7 (3) | C15—C14—H14 | 119.8 |
C2—C3—H3 | 119.6 | C14—C15—C10 | 120.8 (2) |
C4—C3—H3 | 119.6 | C14—C15—H15 | 119.6 |
C5—C4—C3 | 118.9 (3) | C10—C15—H15 | 119.6 |
C5—C4—H4 | 120.6 | C17—C16—C9 | 112.89 (18) |
C3—C4—H4 | 120.6 | C17—C16—H16A | 109.0 |
C4—C5—C6 | 122.4 (3) | C9—C16—H16A | 109.0 |
C4—C5—H5 | 118.8 | C17—C16—H16B | 109.0 |
C6—C5—H5 | 118.8 | C9—C16—H16B | 109.0 |
C5—C6—C1 | 117.3 (2) | H16A—C16—H16B | 107.8 |
C5—C6—C7 | 121.6 (2) | N2—C17—C18 | 116.4 (2) |
C1—C6—C7 | 121.2 (2) | N2—C17—C16 | 119.8 (2) |
N1—C7—C6 | 117.0 (2) | C18—C17—C16 | 123.8 (2) |
N1—C7—C8 | 120.1 (2) | C19—C18—C23 | 117.0 (2) |
C6—C7—C8 | 122.8 (2) | C19—C18—C17 | 121.4 (2) |
C7—C8—C9 | 110.07 (18) | C23—C18—C17 | 121.5 (2) |
C7—C8—H8A | 109.6 | C20—C19—C18 | 121.9 (2) |
C9—C8—H8A | 109.6 | C20—C19—H19 | 119.1 |
C7—C8—H8B | 109.6 | C18—C19—H19 | 119.1 |
C9—C8—H8B | 109.6 | C19—C20—C21 | 119.6 (2) |
H8A—C8—H8B | 108.2 | C19—C20—H20 | 120.2 |
C10—C9—C8 | 113.01 (18) | C21—C20—H20 | 120.2 |
C10—C9—C16 | 113.57 (17) | C22—C21—C20 | 120.2 (2) |
C8—C9—C16 | 109.80 (17) | C22—C21—H21 | 119.9 |
C10—C9—H9 | 106.7 | C20—C21—H21 | 119.9 |
C8—C9—H9 | 106.7 | C21—C22—C23 | 121.0 (2) |
C16—C9—H9 | 106.7 | C21—C22—H22 | 119.5 |
C11—C10—C15 | 117.7 (2) | C23—C22—H22 | 119.5 |
C11—C10—C9 | 119.3 (2) | O2—C23—C22 | 117.2 (2) |
C15—C10—C9 | 122.9 (2) | O2—C23—C18 | 122.5 (2) |
C10—C11—C12 | 121.3 (2) | C22—C23—C18 | 120.3 (2) |
C10—C11—H11 | 119.3 | C7—N1—N2 | 119.52 (19) |
C12—C11—H11 | 119.3 | C17—N2—N1 | 120.17 (19) |
C13—C12—C11 | 120.1 (3) | C1—O1—H1O | 108.9 (18) |
C13—C12—H12 | 120.0 | C23—O2—H2O | 105.1 (16) |
O1—C1—C2—C3 | 179.5 (3) | C13—C14—C15—C10 | 0.2 (4) |
C6—C1—C2—C3 | −0.6 (4) | C11—C10—C15—C14 | 0.2 (3) |
C1—C2—C3—C4 | −0.8 (5) | C9—C10—C15—C14 | −179.4 (2) |
C2—C3—C4—C5 | 1.0 (4) | C10—C9—C16—C17 | 91.1 (2) |
C3—C4—C5—C6 | 0.2 (4) | C8—C9—C16—C17 | −36.5 (3) |
C4—C5—C6—C1 | −1.5 (4) | C9—C16—C17—N2 | 69.7 (3) |
C4—C5—C6—C7 | 177.4 (2) | C9—C16—C17—C18 | −111.5 (2) |
O1—C1—C6—C5 | −178.4 (2) | N2—C17—C18—C19 | −177.2 (2) |
C2—C1—C6—C5 | 1.7 (4) | C16—C17—C18—C19 | 4.0 (3) |
O1—C1—C6—C7 | 2.7 (4) | N2—C17—C18—C23 | 4.1 (3) |
C2—C1—C6—C7 | −177.1 (2) | C16—C17—C18—C23 | −174.7 (2) |
C5—C6—C7—N1 | 179.9 (2) | C23—C18—C19—C20 | 1.4 (3) |
C1—C6—C7—N1 | −1.3 (3) | C17—C18—C19—C20 | −177.4 (2) |
C5—C6—C7—C8 | −1.4 (3) | C18—C19—C20—C21 | −0.9 (4) |
C1—C6—C7—C8 | 177.4 (2) | C19—C20—C21—C22 | −0.2 (4) |
N1—C7—C8—C9 | 73.4 (3) | C20—C21—C22—C23 | 0.7 (4) |
C6—C7—C8—C9 | −105.2 (2) | C21—C22—C23—O2 | 179.9 (2) |
C7—C8—C9—C10 | −174.46 (18) | C21—C22—C23—C18 | −0.2 (4) |
C7—C8—C9—C16 | −46.5 (2) | C19—C18—C23—O2 | 179.1 (2) |
C8—C9—C10—C11 | −140.0 (2) | C17—C18—C23—O2 | −2.1 (4) |
C16—C9—C10—C11 | 94.1 (2) | C19—C18—C23—C22 | −0.8 (3) |
C8—C9—C10—C15 | 39.5 (3) | C17—C18—C23—C22 | 178.0 (2) |
C16—C9—C10—C15 | −86.4 (3) | C6—C7—N1—N2 | −176.21 (19) |
C15—C10—C11—C12 | 0.0 (3) | C8—C7—N1—N2 | 5.0 (3) |
C9—C10—C11—C12 | 179.5 (2) | C18—C17—N2—N1 | −175.34 (19) |
C10—C11—C12—C13 | −0.4 (4) | C16—C17—N2—N1 | 3.5 (3) |
C11—C12—C13—C14 | 0.8 (4) | C7—N1—N2—C17 | −59.8 (3) |
C12—C13—C14—C15 | −0.6 (4) |
Cg2 is the centroid of the C10–C15 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.95 (3) | 1.71 (3) | 2.539 (3) | 144 (3) |
O2—H2O···N2 | 0.97 (3) | 1.65 (3) | 2.532 (3) | 150 (2) |
C21—H21···Cg2i | 0.93 | 2.74 | 3.495 (3) | 138 |
Symmetry code: (i) x, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C23H20N2 | C23H20N2O2 |
Mr | 324.41 | 356.41 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 9.4245 (14), 10.6605 (16), 18.405 (3) | 23.9715 (14), 9.5669 (16), 18.2303 (12) |
α, β, γ (°) | 80.2989 (19), 85.094 (2), 78.1155 (19) | 90, 119.256 (3), 90 |
V (Å3) | 1781.1 (5) | 3647.5 (7) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.08 |
Crystal size (mm) | 0.24 × 0.20 × 0.15 | 0.30 × 0.28 × 0.26 |
Data collection | ||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.967, 0.982 | 0.967, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15860, 8141, 5062 | 12998, 3224, 1647 |
Rint | 0.030 | 0.071 |
(sin θ/λ)max (Å−1) | 0.654 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.149, 1.02 | 0.045, 0.109, 0.96 |
No. of reflections | 8141 | 3224 |
No. of parameters | 451 | 253 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.21 | 0.13, −0.14 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SIR2004 (Burla et al., 2005), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 2012), publCIF (Westrip, 2010).
C6—C7 | 1.488 (2) | C30—N3 | 1.284 (2) |
C7—N1 | 1.286 (2) | C40—N4 | 1.291 (2) |
C17—N2 | 1.289 (2) | C40—C41 | 1.488 (2) |
C17—C18 | 1.487 (2) | N1—N2 | 1.4056 (19) |
C29—C30 | 1.486 (2) | N3—N4 | 1.4083 (19) |
N1—C7—C6 | 117.17 (14) | N3—C30—C29 | 117.17 (15) |
N1—C7—C8 | 121.65 (15) | N3—C30—C31 | 121.53 (15) |
C6—C7—C8 | 121.11 (14) | C29—C30—C31 | 121.22 (15) |
N2—C17—C18 | 117.66 (15) | N4—C40—C41 | 116.91 (14) |
N2—C17—C16 | 122.19 (15) | N4—C40—C39 | 121.36 (15) |
C18—C17—C16 | 120.14 (14) | C41—C40—C39 | 121.68 (14) |
C7—N1—N2—C17 | −60.5 (2) | C30—N3—N4—C40 | 61.8 (2) |
C6—C7 | 1.471 (3) | C17—C18 | 1.468 (3) |
C7—N1 | 1.297 (3) | N1—N2 | 1.394 (2) |
C17—N2 | 1.300 (3) | ||
N1—C7—C6 | 117.0 (2) | N2—C17—C18 | 116.4 (2) |
N1—C7—C8 | 120.1 (2) | N2—C17—C16 | 119.8 (2) |
C6—C7—C8 | 122.8 (2) | C18—C17—C16 | 123.8 (2) |
C7—N1—N2—C17 | −59.8 (3) |
Cg2 is the centroid of the C10–C15 benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···N1 | 0.95 (3) | 1.71 (3) | 2.539 (3) | 144 (3) |
O2—H2O···N2 | 0.97 (3) | 1.65 (3) | 2.532 (3) | 150 (2) |
C21—H21···Cg2i | 0.93 | 2.74 | 3.495 (3) | 138 |
Symmetry code: (i) x, y−1, z. |
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