research communications
One molecule, three crystal structures: conformational trimorphism of N-[(1S)-1-phenylethyl]benzamide
aFacultad de Ciencias Químicas, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico, and bInstituto de Física, Benemérita Universidad Autónoma de Puebla, 72570 Puebla, Pue., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title compound, C15H15NO, is an enantiopure small molecule, which has been synthesized many times, although its was never determined. By recrystallization from a variety of solvent mixtures (pure acetonitrile, ethanol–water, toluene–ethanol, THF–methanol), we obtained three unsolvated polymorphs, in space groups P21 and P212121. Form I is obtained from acetonitrile, without admixture of other forms, whereas forms II and III are obtained simultaneously by concomitant crystallizations from alcohol-based solvent mixtures. All forms share the same supramolecular structure, based on infinite C11(4) chain motifs formed by N—H⋯O intermolecular hydrogen bonds, as usual for non-sterically hindered However, a conformational modification of the molecular structure, related to the rotation of the phenyl rings, alters the packing of the chains in the crystal structures. The orientation of the chain axis is perpendicular and parallel to the crystallographic twofold screw axis of P21 in forms I and II, respectively. As for form III, the contains two independent molecules forming parallel chains in P212121, and the combines features of monoclinic forms I and II.
1. Chemical context
The study of ) famously stated more than 50 years ago that `the number of [polymorphic] forms known for a given compound is proportional to the time and money spent in research on that compound'. Today, it seems that this statement still holds true, and that a large proportion of the discovered polymorphs are obtained in a non-planned way. In the current situation, the rules allowing (or avoiding) a molecular system to crystallize with several forms are not fully understood, although assessing the risk of is workable to some extent. For example, the CSD-Materials module available in Mercury can perform predictions on a polymorphic target compound, through an estimation of its hydrogen-bonding landscape (Feeder et al., 2015; Macrae et al., 2020).
is paramount in the field of organic materials, especially in the design of new active pharmaceutical ingredients, either for tailoring their bioavailability, or for legal reasons related to patent rights and intellectual property. Walter McCrone (1965A recent survey of the CSD (Groom et al., 2016) showed that prevalence among single-component organic anhydrates constitutes about 1.22% of compounds for which at least one is known (Kersten et al., 2018). A similar figure was obtained using the Merck index as a source of data: for 10330 compounds present in the 12th edition (1996), 1.4% were polymorphic (Stahly, 2007).
However, compounds appearing only once in the CSD might exist in other polymorphic forms that have still not been crystallized. It also seems hard to believe that all molecules should be necessarily polymorphous, as sometimes claimed. For example, huge amounts of ibuprofen [2-(4-isobutylphenyl)propanoic acid] have been produced since its introduction as a painkiller in 1969. Notwithstanding the numerous studies carried out on this small molecule, only one crystalline form is known. But there is no doubt that from a statistical point of view, trimorphic systems are much less common than dimorphic systems, tetramorphic systems are in turn much less common than trimorphic systems, etc. A rule of thumb is that a tenfold drop is observed for the prevalence of n-morphism in comparison to (n-1)-morphism (n ≥ 3). It is not surprising that, for example, well-characterized hexamorphism is exceptional (Yu et al., 2000). Another empirical observation is that more polymorphs are reported for small molecules (less than 30 C atoms per formula) compared to large ones, because of the correlation between molecular complexity and the difficulty of synthesizing large molecules. These observations are in line with McCrone's statement, and today there is a consensus that is a pervasive phenomenon, which occurs on a random basis and remains poorly predictable (Cruz-Cabeza et al., 2015).
Within this context, we report a case of trimorphism, for a low-molecular-weight chiral molecule, for which the et al., 1967).
was never established, even though many researchers have used it as a reagent since its first reported synthesis (Bezruchko2. Molecular and crystal structures
We used N-[(1S)-1-phenylethyl]benzamide as a component for co-crystallization with other small molecules having a high hydrogen-bond propensity. While probing a variety of solvents for the crystallization of the free amide, we recovered three non-solvated polymorphs, in a reproducible manner. Form I (P21) was obtained from acetonitrile, and its measured melting point and angle of match data reported by other groups (e.g. Karnik & Kamath, 2008). Forms II (P21) and III (P212121) were obtained as concomitant crystals, by using ethanol–water, toluene–ethanol or THF–methanol mixtures. Simulated X-ray powder patterns are clearly different for each form, confirming that true polymorphs were crystallized.
Forms I and II share the same crystal symmetry (Table 5), but have very different densities, 1.157 and 1.208 g cm−3, respectively. It can therefore be predicted that molecules are packed in the solid state in a more efficient manner for II, compared to I. However, both forms display the same supramolecular structure, based on the classical C11(4) chain motif, which is the most common for amide derivatives (Figs. 1 and 2). The N—H⋯O hydrogen bond is stronger for I, while an opposite situation should be expected if one considers crystal densities (Tables 1 and 2). The factor triggering is, in this case, related to the molecular structure. The conformation of the molecule is modified by rotation of the phenyl ring C3–C8 bonded to the chiral centre, while the position of the other peripheral phenyl group, C10–C15, remains almost unchanged with respect to the amide group. Dihedral angles involved in the molecular conformation are given in Table 4: angle N1—C9—C10—C15 is modified by ca 3° between the two forms, while the other angle, N1—C2—C3—C4, is modified by ca 14°. As a consequence, the dihedral angle between the phenyl rings is 23.1 (2) and 56.2 (1)° in I and II, respectively.
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The conformational modification leads to different arrangements for the infinite C(4) chains in the crystals. In I, the 1D motif is running in the [100] direction, and is thus normal to the twofold screw axis (Fig. 1, inset). The 21 relates neighbouring chains in the crystal, resulting in a relative orientation of the chains that is unfavourable for the packing of the phenyl rings: inter-chain dihedral angles between phenyl groups are close to 90°: δ1→1′ = 88.4 (3)°, δ1→2′ = 84.9 (2)° and δ2→2′ = 70.8 (2)°, where 1 and 2 stand for rings C3–C8 and C10–C15, while a primed ring is related to a non-primed ring through the 21. These angles were calculated using PLATON (Spek, 2020), and only non-parallel rings are considered. In contrast, the of form II is built on C(4) chains parallel to the screw axis, in the [010] direction. As in the previous case, two neighbouring chains are related through the 21 axis. However, given that chains and symmetry elements share the same direction, some inter-chain interactions feature phenyl rings in a less perpendicular arrangement: δ1→1′ = 85.2 (2)°, δ1→2′ = 80.3 (2)°, δ2→1′ = 56.2 (2)° and δ2→2′ = 64.7 (1)°. Chains are then more densely packed, to afford a material with higher density (Fig. 2, inset). These different packing structures, in the same are also reflected in different Kitaigorodskii packing index: 0.638 for I and 0.670 for II (Spek, 2020).
The third polymorph, III, includes two independent molecules in the of an orthorhombic cell, each one forming a supramolecular structure identical to those of forms I and II [infinite C11(4) chains parallel to the a axis for molecules A and B, see Table 3 and Fig. 3]. The molecular conformation is similar for A and B molecules, and can be described as intermediary between conformations stabilized in crystals I and II: the phenyl ring bonded to the chiral C atom is configured as in crystal II, while the other phenyl group is oriented as in crystal I (Table 4). The intramolecular dihedral angle between phenyl rings is therefore also midway: 47.0 (1)° for molecules A and 47.4 (1)° for molecules B.
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With such a configuration, it is not surprising to obtain a III in P212121 simultaneously reminiscent of those observed for I and II (Fig. 4). The twofold screw axis parallel to [100] gives an arrangement similar to that described in form II, with two neighbouring C(4) chains including molecules from the same family, A/A or B/B, closely packed around this On the other hand, the packing in directions perpendicular to the chain axis is based on screw axes along [010] and [001], and is thus similar to that observed in form I with regard to neighbouring crystallographically independent molecules, A/B or B/A. The orthorhombic form III with Z′ = 2 can be seen as a mixture combining features of Z′ = 1 monoclinic forms I and II. This is consistent with metrics directly related to packing efficiency, which fall between those of phases I and II: the calculated density for III is 1.199 g cm−3, the Kitaigorodskii packing index is 0.666, and large intermolecular dihedral angles δp→q′ between phenyl rings in neighbouring chains are in the range 70.1 (2) to 89.7 (2)°.
for3. Database survey
From the previous description, it is clear that the conformational trimorphism for the title compound is a consequence of the rotation of the peripheral phenyl rings, which changes their environment, affecting the packing of the C(4) chains. This molecular flexibility is confirmed by the crystal-structure determination of the unique reported to date including the title molecule (Tinsley et al., 2017): the conformation is far from that observed in the free amide we report, and one phenyl is even disordered by rotation.
Polymorphism can then occur, although the hydrogen-bonded pattern remains unaltered. Such a behaviour has been invoked to rationalize the crystallization of the highly metastable orthorhombic form of benzamide, for which the Pba2: Blagden et al., 2005; Fdd2: Johansson & van de Streek, 2016). In the same way, the twisting between the nitrophenyl and the thiophene rings in the pharmaceutical intermediate 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile is related to the rich of this compound: six forms have been structurally characterized in this case, with a variety of colours and shapes (Yu et al., 2000; Price et al., 2005).
is still controversial (Regarding the supramolecular structure observed in the title compound, the imposed supramolecular motif limits the scope for i.e. non-enantiogenic) space groups reveals that for 449 hits, 83% are reported in space groups P21 and P212121, while the combined frequency of these groups over the whole CSD database is only 12%. It thus seems that any including rototranslations can fit a polymorphic form of a small amide, either enantiopure or achiral, regardless of the rigidity of the supramolecular structure. We could anticipate that crystallization of other forms of the title compound could be achieved, for example, in space groups P21212, or P31, among others.
Indeed, the frequency of infinite chains in the crystal structures of is as high as 28.2% in the CSD (version 5.41, updated May 2020; both organic and metal–organic were considered), and is probably higher for non-sterically hindered such as the title compound. Moreover, the title amide having only one donor and one acceptor sites, any variation of the supramolecular structure is very unlikely. However, it should be noted that this 1D structure is easily propagated through a screw axis in the crystal state. A survey of the organic crystallizing in Sohncke (4. Synthesis and crystallization
The title compound was synthesized using a literature method (Tang, 2005). A solution of benzoic acid was prepared (1 g, 8.18 mmol in 50 mL toluene), and 50 mg of boric acid, B(OH)3, was added, followed by (S)-1-phenylethylamine (0.9 g, 7.44 mmol). This mixture was refluxed for 36 h, after which the reaction was complete (TLC, SiO2, hexane:AcOEt 1:1). After cooling to room temperature, 200 mL of hexane were added, affording the title compound as a white precipitate, which was separated. Yield, 90%. Single crystals were obtained by slow evaporation of solutions (0.01 g in 10 mL): with acetonitrile at 298 K, pure form I was recrystallized; [α]D −17.1 (c 1, CHCl3), m.p. 395 K [literature: −17.9 (c 1, CHCl3), 395–396 K; Karnik & Kamath, 2008]. Concomitant crystallizations of forms II and III were realized at 298 K in ethanol–water (97:3 v/v) or ethanol–toluene (1:1, v/v). Given that all of the crystals are colourless and prism-shaped, the crystal form can not be assigned visually.
5. Refinement
Crystal data, data collection and structure . C-bound hydrogen atoms were placed in calculated positions and refined using a riding model with Uiso(H) = 1.2Ueq(C), C—H = 0.93 Å, and C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C), for aromatic and methyl hydrogen atoms, respectively. Amide hydrogen atoms (H1 in I and II; H1A and H1B in III) were found in difference maps and their coordinates were freely refined with Uiso(H) = 1.2Ueq(N).
details are summarized in Table 5Supporting information
https://doi.org/10.1107/S2056989020008877/yk2134sup1.cif
contains datablocks I, II, III, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020008877/yk2134Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989020008877/yk2134IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989020008877/yk2134IIIsup4.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020008877/yk2134Isup5.cml
For all structures, data collection: X-AREA (Stoe & Cie, 2019); cell
X-AREA (Stoe & Cie, 2019); data reduction: X-RED32 (Stoe & Cie, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).C15H15NO | Dx = 1.157 Mg m−3 |
Mr = 225.28 | Melting point: 395 K |
Monoclinic, P21 | Ag Kα radiation, λ = 0.56083 Å |
a = 5.0472 (4) Å | Cell parameters from 7505 reflections |
b = 9.3118 (7) Å | θ = 2.9–21.0° |
c = 13.9581 (15) Å | µ = 0.05 mm−1 |
β = 99.708 (8)° | T = 295 K |
V = 646.62 (10) Å3 | Prism, colourless |
Z = 2 | 0.37 × 0.12 × 0.09 mm |
F(000) = 240 |
Stoe Stadivari diffractometer | 2833 independent reflections |
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source | 1573 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.066 |
Detector resolution: 5.81 pixels mm-1 | θmax = 21.0°, θmin = 2.9° |
ω scans | h = −5→6 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019) | k = −11→11 |
Tmin = 0.313, Tmax = 1.000 | l = −17→17 |
15392 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0482P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.84 | (Δ/σ)max < 0.001 |
2833 reflections | Δρmax = 0.11 e Å−3 |
159 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Extinction correction: SHELXL-2018/3 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.110 (15) |
Primary atom site location: dual |
x | y | z | Uiso*/Ueq | ||
O1 | 0.0514 (3) | 0.4480 (2) | 0.20994 (15) | 0.0634 (7) | |
N1 | 0.4967 (5) | 0.4138 (3) | 0.24782 (19) | 0.0552 (7) | |
H1 | 0.648 (6) | 0.434 (4) | 0.232 (2) | 0.066* | |
C1 | 0.5907 (9) | 0.1568 (5) | 0.2590 (3) | 0.0930 (13) | |
H1A | 0.775962 | 0.172744 | 0.254262 | 0.140* | |
H1B | 0.488542 | 0.143158 | 0.195139 | 0.140* | |
H1C | 0.575931 | 0.072839 | 0.297644 | 0.140* | |
C2 | 0.4818 (6) | 0.2871 (4) | 0.3067 (2) | 0.0644 (10) | |
H2 | 0.291287 | 0.268881 | 0.308304 | 0.077* | |
C3 | 0.6215 (6) | 0.3062 (4) | 0.4109 (2) | 0.0607 (9) | |
C4 | 0.8300 (8) | 0.3981 (5) | 0.4371 (3) | 0.0897 (13) | |
H4 | 0.889422 | 0.454313 | 0.389872 | 0.108* | |
C5 | 0.9556 (10) | 0.4096 (7) | 0.5331 (3) | 0.1221 (18) | |
H5 | 1.099463 | 0.472265 | 0.549813 | 0.147* | |
C6 | 0.8674 (14) | 0.3286 (9) | 0.6029 (4) | 0.125 (2) | |
H6 | 0.946930 | 0.337460 | 0.667740 | 0.150* | |
C7 | 0.6669 (16) | 0.2373 (8) | 0.5769 (4) | 0.143 (2) | |
H7 | 0.609507 | 0.180178 | 0.624109 | 0.171* | |
C8 | 0.5405 (10) | 0.2247 (6) | 0.4809 (3) | 0.1114 (17) | |
H8 | 0.399651 | 0.160002 | 0.464684 | 0.134* | |
C9 | 0.2809 (5) | 0.4846 (3) | 0.20237 (19) | 0.0465 (7) | |
C10 | 0.3311 (5) | 0.6101 (3) | 0.1421 (2) | 0.0476 (8) | |
C11 | 0.1515 (6) | 0.6394 (4) | 0.0594 (2) | 0.0674 (10) | |
H11 | 0.000363 | 0.581618 | 0.042805 | 0.081* | |
C12 | 0.1920 (9) | 0.7537 (5) | 0.0002 (3) | 0.0898 (14) | |
H12 | 0.072176 | 0.770246 | −0.057018 | 0.108* | |
C13 | 0.4068 (10) | 0.8418 (5) | 0.0258 (4) | 0.0922 (15) | |
H13 | 0.431123 | 0.920152 | −0.013150 | 0.111* | |
C14 | 0.5853 (8) | 0.8160 (4) | 0.1077 (4) | 0.0855 (13) | |
H14 | 0.731981 | 0.876693 | 0.124659 | 0.103* | |
C15 | 0.5512 (6) | 0.6993 (4) | 0.1667 (3) | 0.0646 (10) | |
H15 | 0.675967 | 0.681326 | 0.222472 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0432 (9) | 0.0760 (17) | 0.0717 (14) | −0.0023 (11) | 0.0114 (9) | 0.0127 (13) |
N1 | 0.0412 (12) | 0.0636 (18) | 0.0604 (15) | −0.0008 (13) | 0.0074 (11) | 0.0189 (14) |
C1 | 0.130 (3) | 0.060 (3) | 0.081 (3) | 0.000 (2) | −0.006 (2) | 0.007 (2) |
C2 | 0.0567 (17) | 0.061 (2) | 0.074 (2) | −0.0070 (17) | 0.0069 (17) | 0.020 (2) |
C3 | 0.0590 (17) | 0.067 (2) | 0.058 (2) | 0.0136 (18) | 0.0154 (16) | 0.0182 (19) |
C4 | 0.095 (3) | 0.113 (4) | 0.057 (2) | −0.011 (3) | 0.0018 (19) | 0.008 (2) |
C5 | 0.136 (4) | 0.146 (5) | 0.073 (3) | −0.007 (4) | −0.015 (3) | −0.013 (4) |
C6 | 0.148 (5) | 0.162 (6) | 0.057 (3) | 0.064 (4) | −0.006 (3) | 0.009 (4) |
C7 | 0.177 (6) | 0.178 (7) | 0.075 (4) | 0.021 (5) | 0.032 (4) | 0.061 (4) |
C8 | 0.119 (3) | 0.137 (4) | 0.078 (3) | −0.013 (3) | 0.015 (3) | 0.049 (3) |
C9 | 0.0449 (15) | 0.054 (2) | 0.0411 (16) | 0.0003 (14) | 0.0097 (12) | −0.0029 (15) |
C10 | 0.0457 (14) | 0.051 (2) | 0.0483 (17) | 0.0075 (14) | 0.0149 (13) | 0.0019 (15) |
C11 | 0.0660 (18) | 0.077 (3) | 0.059 (2) | 0.0056 (19) | 0.0087 (16) | 0.013 (2) |
C12 | 0.095 (3) | 0.104 (4) | 0.070 (3) | 0.021 (3) | 0.016 (2) | 0.031 (3) |
C13 | 0.101 (3) | 0.078 (3) | 0.108 (4) | 0.023 (3) | 0.050 (3) | 0.044 (3) |
C14 | 0.081 (2) | 0.060 (3) | 0.121 (4) | −0.006 (2) | 0.033 (3) | 0.015 (3) |
C15 | 0.064 (2) | 0.060 (2) | 0.069 (2) | 0.0007 (17) | 0.0097 (17) | 0.0092 (19) |
O1—C9 | 1.229 (3) | C6—H6 | 0.9300 |
N1—C9 | 1.338 (3) | C7—C8 | 1.388 (8) |
N1—C2 | 1.448 (4) | C7—H7 | 0.9300 |
N1—H1 | 0.85 (3) | C8—H8 | 0.9300 |
C1—C2 | 1.530 (5) | C9—C10 | 1.486 (4) |
C1—H1A | 0.9600 | C10—C11 | 1.370 (4) |
C1—H1B | 0.9600 | C10—C15 | 1.383 (4) |
C1—H1C | 0.9600 | C11—C12 | 1.384 (5) |
C2—C3 | 1.515 (5) | C11—H11 | 0.9300 |
C2—H2 | 0.9800 | C12—C13 | 1.358 (6) |
C3—C8 | 1.354 (5) | C12—H12 | 0.9300 |
C3—C4 | 1.358 (5) | C13—C14 | 1.352 (6) |
C4—C5 | 1.386 (5) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.392 (5) |
C5—C6 | 1.365 (8) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C7 | 1.325 (8) | ||
C9—N1—C2 | 123.7 (2) | C6—C7—C8 | 121.6 (5) |
C9—N1—H1 | 118 (2) | C6—C7—H7 | 119.2 |
C2—N1—H1 | 118 (2) | C8—C7—H7 | 119.2 |
C2—C1—H1A | 109.5 | C3—C8—C7 | 120.2 (5) |
C2—C1—H1B | 109.5 | C3—C8—H8 | 119.9 |
H1A—C1—H1B | 109.5 | C7—C8—H8 | 119.9 |
C2—C1—H1C | 109.5 | O1—C9—N1 | 121.7 (3) |
H1A—C1—H1C | 109.5 | O1—C9—C10 | 121.3 (3) |
H1B—C1—H1C | 109.5 | N1—C9—C10 | 116.9 (2) |
N1—C2—C3 | 112.9 (3) | C11—C10—C15 | 118.7 (3) |
N1—C2—C1 | 110.0 (3) | C11—C10—C9 | 118.8 (3) |
C3—C2—C1 | 111.6 (3) | C15—C10—C9 | 122.6 (3) |
N1—C2—H2 | 107.4 | C10—C11—C12 | 120.8 (4) |
C3—C2—H2 | 107.4 | C10—C11—H11 | 119.6 |
C1—C2—H2 | 107.4 | C12—C11—H11 | 119.6 |
C8—C3—C4 | 118.3 (4) | C13—C12—C11 | 120.0 (4) |
C8—C3—C2 | 118.6 (4) | C13—C12—H12 | 120.0 |
C4—C3—C2 | 123.1 (3) | C11—C12—H12 | 120.0 |
C3—C4—C5 | 121.1 (4) | C14—C13—C12 | 120.2 (4) |
C3—C4—H4 | 119.5 | C14—C13—H13 | 119.9 |
C5—C4—H4 | 119.5 | C12—C13—H13 | 119.9 |
C6—C5—C4 | 119.8 (6) | C13—C14—C15 | 120.5 (4) |
C6—C5—H5 | 120.1 | C13—C14—H14 | 119.7 |
C4—C5—H5 | 120.1 | C15—C14—H14 | 119.7 |
C7—C6—C5 | 119.0 (5) | C10—C15—C14 | 119.7 (3) |
C7—C6—H6 | 120.5 | C10—C15—H15 | 120.1 |
C5—C6—H6 | 120.5 | C14—C15—H15 | 120.1 |
C9—N1—C2—C3 | −120.7 (3) | C2—N1—C9—O1 | 2.0 (5) |
C9—N1—C2—C1 | 114.0 (3) | C2—N1—C9—C10 | −178.1 (3) |
N1—C2—C3—C8 | 154.8 (3) | O1—C9—C10—C11 | −33.8 (4) |
C1—C2—C3—C8 | −80.7 (4) | N1—C9—C10—C11 | 146.2 (3) |
N1—C2—C3—C4 | −27.3 (5) | O1—C9—C10—C15 | 145.7 (3) |
C1—C2—C3—C4 | 97.1 (4) | N1—C9—C10—C15 | −34.2 (4) |
C8—C3—C4—C5 | −0.6 (6) | C15—C10—C11—C12 | 1.5 (5) |
C2—C3—C4—C5 | −178.5 (4) | C9—C10—C11—C12 | −179.0 (3) |
C3—C4—C5—C6 | −0.7 (8) | C10—C11—C12—C13 | −2.4 (6) |
C4—C5—C6—C7 | 1.8 (9) | C11—C12—C13—C14 | 1.7 (6) |
C5—C6—C7—C8 | −1.6 (10) | C12—C13—C14—C15 | −0.1 (6) |
C4—C3—C8—C7 | 0.8 (7) | C11—C10—C15—C14 | 0.2 (4) |
C2—C3—C8—C7 | 178.8 (5) | C9—C10—C15—C14 | −179.4 (3) |
C6—C7—C8—C3 | 0.3 (9) | C13—C14—C15—C10 | −0.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.85 (3) | 2.11 (3) | 2.952 (3) | 169 (3) |
Symmetry code: (i) x+1, y, z. |
C15H15NO | F(000) = 240 |
Mr = 225.28 | Dx = 1.208 Mg m−3 |
Monoclinic, P21 | Ag Kα radiation, λ = 0.56083 Å |
a = 8.3496 (6) Å | Cell parameters from 15127 reflections |
b = 5.2632 (2) Å | θ = 2.7–24.3° |
c = 14.2969 (10) Å | µ = 0.05 mm−1 |
β = 99.800 (6)° | T = 295 K |
V = 619.12 (7) Å3 | Prism, colourless |
Z = 2 | 0.34 × 0.19 × 0.14 mm |
Stoe Stadivari diffractometer | 2456 independent reflections |
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source | 1847 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.037 |
Detector resolution: 5.81 pixels mm-1 | θmax = 21.0°, θmin = 2.7° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019) | k = −6→6 |
Tmin = 0.574, Tmax = 1.000 | l = −18→18 |
14738 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
2456 reflections | Δρmax = 0.12 e Å−3 |
159 parameters | Δρmin = −0.14 e Å−3 |
1 restraint | Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.076 (15) |
Primary atom site location: dual |
x | y | z | Uiso*/Ueq | ||
O1 | 0.4368 (2) | 0.7962 (3) | 0.72214 (11) | 0.0587 (5) | |
N1 | 0.4801 (2) | 0.3812 (3) | 0.75328 (12) | 0.0469 (5) | |
H1 | 0.463 (3) | 0.230 (5) | 0.7361 (17) | 0.056* | |
C1 | 0.5445 (4) | 0.2070 (5) | 0.91253 (17) | 0.0634 (7) | |
H1A | 0.431636 | 0.203287 | 0.918240 | 0.095* | |
H1B | 0.609341 | 0.231415 | 0.974081 | 0.095* | |
H1C | 0.573648 | 0.049095 | 0.886292 | 0.095* | |
C2 | 0.5745 (3) | 0.4245 (4) | 0.84752 (14) | 0.0477 (5) | |
H2 | 0.533500 | 0.580228 | 0.872634 | 0.057* | |
C3 | 0.7537 (3) | 0.4647 (4) | 0.84452 (15) | 0.0513 (5) | |
C4 | 0.8339 (4) | 0.3259 (8) | 0.7885 (2) | 0.0915 (10) | |
H4 | 0.777746 | 0.203331 | 0.749040 | 0.110* | |
C5 | 0.9981 (4) | 0.3612 (11) | 0.7883 (2) | 0.1148 (15) | |
H5 | 1.050709 | 0.260491 | 0.749457 | 0.138* | |
C6 | 1.0820 (4) | 0.5382 (9) | 0.8431 (2) | 0.0947 (11) | |
H6 | 1.191933 | 0.563011 | 0.841941 | 0.114* | |
C7 | 1.0040 (4) | 0.6813 (8) | 0.9005 (4) | 0.1196 (15) | |
H7 | 1.060842 | 0.805082 | 0.939071 | 0.144* | |
C8 | 0.8399 (4) | 0.6433 (6) | 0.9018 (3) | 0.0898 (10) | |
H8 | 0.787916 | 0.740396 | 0.941994 | 0.108* | |
C9 | 0.4209 (2) | 0.5733 (4) | 0.69593 (14) | 0.0417 (5) | |
C10 | 0.3338 (2) | 0.5054 (4) | 0.59924 (14) | 0.0395 (5) | |
C11 | 0.2133 (3) | 0.6681 (4) | 0.55550 (16) | 0.0487 (5) | |
H11 | 0.186538 | 0.811620 | 0.587523 | 0.058* | |
C12 | 0.1325 (3) | 0.6186 (5) | 0.46458 (17) | 0.0572 (6) | |
H12 | 0.050761 | 0.727543 | 0.436194 | 0.069* | |
C13 | 0.1725 (3) | 0.4090 (5) | 0.41606 (16) | 0.0528 (6) | |
H13 | 0.118548 | 0.376985 | 0.354762 | 0.063* | |
C14 | 0.2928 (3) | 0.2463 (4) | 0.45841 (15) | 0.0501 (6) | |
H14 | 0.320498 | 0.105115 | 0.425418 | 0.060* | |
C15 | 0.3725 (3) | 0.2925 (4) | 0.54998 (14) | 0.0463 (5) | |
H15 | 0.452280 | 0.180724 | 0.578634 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0812 (12) | 0.0348 (7) | 0.0555 (9) | 0.0003 (7) | −0.0011 (8) | −0.0023 (7) |
N1 | 0.0578 (11) | 0.0363 (9) | 0.0433 (10) | 0.0003 (8) | −0.0009 (8) | 0.0004 (8) |
C1 | 0.0814 (17) | 0.0588 (13) | 0.0495 (14) | 0.0020 (13) | 0.0091 (12) | 0.0091 (11) |
C2 | 0.0601 (14) | 0.0403 (10) | 0.0406 (11) | 0.0053 (9) | 0.0031 (10) | −0.0026 (9) |
C3 | 0.0588 (14) | 0.0488 (12) | 0.0419 (11) | 0.0040 (10) | −0.0038 (10) | 0.0036 (10) |
C4 | 0.0678 (18) | 0.134 (3) | 0.0759 (18) | −0.018 (2) | 0.0215 (15) | −0.049 (2) |
C5 | 0.071 (2) | 0.200 (5) | 0.078 (2) | −0.015 (3) | 0.0245 (16) | −0.046 (3) |
C6 | 0.0579 (17) | 0.131 (3) | 0.091 (2) | −0.012 (2) | 0.0007 (17) | 0.013 (2) |
C7 | 0.065 (2) | 0.099 (2) | 0.177 (4) | −0.0025 (19) | −0.030 (2) | −0.042 (3) |
C8 | 0.0617 (17) | 0.080 (2) | 0.116 (2) | 0.0118 (14) | −0.0177 (16) | −0.0407 (18) |
C9 | 0.0412 (10) | 0.0358 (9) | 0.0483 (12) | 0.0010 (8) | 0.0082 (9) | 0.0019 (9) |
C10 | 0.0379 (10) | 0.0370 (9) | 0.0438 (11) | −0.0016 (8) | 0.0074 (8) | 0.0047 (8) |
C11 | 0.0477 (12) | 0.0392 (10) | 0.0581 (13) | 0.0030 (9) | 0.0059 (10) | 0.0015 (9) |
C12 | 0.0530 (14) | 0.0547 (14) | 0.0592 (15) | 0.0043 (10) | −0.0042 (11) | 0.0078 (11) |
C13 | 0.0527 (13) | 0.0589 (13) | 0.0452 (11) | −0.0118 (11) | 0.0039 (10) | 0.0040 (11) |
C14 | 0.0518 (12) | 0.0500 (13) | 0.0503 (13) | −0.0043 (9) | 0.0141 (10) | −0.0052 (10) |
C15 | 0.0466 (12) | 0.0415 (10) | 0.0501 (12) | 0.0034 (9) | 0.0059 (10) | 0.0025 (10) |
O1—C9 | 1.232 (3) | C6—H6 | 0.9300 |
N1—C9 | 1.342 (3) | C7—C8 | 1.388 (5) |
N1—C2 | 1.459 (3) | C7—H7 | 0.9300 |
N1—H1 | 0.84 (3) | C8—H8 | 0.9300 |
C1—C2 | 1.522 (3) | C9—C10 | 1.492 (3) |
C1—H1A | 0.9600 | C10—C11 | 1.387 (3) |
C1—H1B | 0.9600 | C10—C15 | 1.390 (3) |
C1—H1C | 0.9600 | C11—C12 | 1.383 (3) |
C2—C3 | 1.519 (3) | C11—H11 | 0.9300 |
C2—H2 | 0.9800 | C12—C13 | 1.374 (4) |
C3—C4 | 1.343 (4) | C12—H12 | 0.9300 |
C3—C8 | 1.368 (3) | C13—C14 | 1.379 (3) |
C4—C5 | 1.385 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—C15 | 1.386 (3) |
C5—C6 | 1.336 (5) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C7 | 1.359 (5) | ||
C9—N1—C2 | 122.11 (18) | C6—C7—C8 | 120.3 (3) |
C9—N1—H1 | 120.7 (17) | C6—C7—H7 | 119.9 |
C2—N1—H1 | 117.1 (17) | C8—C7—H7 | 119.9 |
C2—C1—H1A | 109.5 | C3—C8—C7 | 120.7 (3) |
C2—C1—H1B | 109.5 | C3—C8—H8 | 119.6 |
H1A—C1—H1B | 109.5 | C7—C8—H8 | 119.6 |
C2—C1—H1C | 109.5 | O1—C9—N1 | 121.50 (19) |
H1A—C1—H1C | 109.5 | O1—C9—C10 | 121.34 (18) |
H1B—C1—H1C | 109.5 | N1—C9—C10 | 117.16 (17) |
N1—C2—C3 | 112.09 (17) | C11—C10—C15 | 118.86 (19) |
N1—C2—C1 | 109.10 (18) | C11—C10—C9 | 118.16 (18) |
C3—C2—C1 | 112.80 (19) | C15—C10—C9 | 122.93 (18) |
N1—C2—H2 | 107.5 | C12—C11—C10 | 120.5 (2) |
C3—C2—H2 | 107.5 | C12—C11—H11 | 119.7 |
C1—C2—H2 | 107.5 | C10—C11—H11 | 119.7 |
C4—C3—C8 | 117.7 (3) | C13—C12—C11 | 120.3 (2) |
C4—C3—C2 | 122.3 (2) | C13—C12—H12 | 119.9 |
C8—C3—C2 | 119.9 (2) | C11—C12—H12 | 119.9 |
C3—C4—C5 | 121.5 (3) | C12—C13—C14 | 119.9 (2) |
C3—C4—H4 | 119.2 | C12—C13—H13 | 120.1 |
C5—C4—H4 | 119.2 | C14—C13—H13 | 120.1 |
C6—C5—C4 | 120.8 (4) | C13—C14—C15 | 120.2 (2) |
C6—C5—H5 | 119.6 | C13—C14—H14 | 119.9 |
C4—C5—H5 | 119.6 | C15—C14—H14 | 119.9 |
C5—C6—C7 | 118.9 (3) | C14—C15—C10 | 120.3 (2) |
C5—C6—H6 | 120.6 | C14—C15—H15 | 119.8 |
C7—C6—H6 | 120.6 | C10—C15—H15 | 119.8 |
C9—N1—C2—C3 | −85.6 (2) | C2—N1—C9—O1 | −3.7 (3) |
C9—N1—C2—C1 | 148.7 (2) | C2—N1—C9—C10 | 176.80 (18) |
N1—C2—C3—C4 | −41.1 (3) | O1—C9—C10—C11 | −28.1 (3) |
C1—C2—C3—C4 | 82.5 (3) | N1—C9—C10—C11 | 151.43 (19) |
N1—C2—C3—C8 | 140.4 (2) | O1—C9—C10—C15 | 149.3 (2) |
C1—C2—C3—C8 | −95.9 (3) | N1—C9—C10—C15 | −31.2 (3) |
C8—C3—C4—C5 | 0.0 (5) | C15—C10—C11—C12 | 0.3 (3) |
C2—C3—C4—C5 | −178.5 (3) | C9—C10—C11—C12 | 177.8 (2) |
C3—C4—C5—C6 | −1.0 (6) | C10—C11—C12—C13 | −0.9 (4) |
C4—C5—C6—C7 | 1.0 (7) | C11—C12—C13—C14 | 0.5 (3) |
C5—C6—C7—C8 | 0.0 (6) | C12—C13—C14—C15 | 0.5 (3) |
C4—C3—C8—C7 | 1.0 (5) | C13—C14—C15—C10 | −1.1 (3) |
C2—C3—C8—C7 | 179.5 (3) | C11—C10—C15—C14 | 0.7 (3) |
C6—C7—C8—C3 | −1.0 (6) | C9—C10—C15—C14 | −176.71 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.84 (3) | 2.30 (3) | 3.123 (2) | 168 (2) |
Symmetry code: (i) x, y−1, z. |
C15H15NO | Dx = 1.199 Mg m−3 |
Mr = 225.28 | Ag Kα radiation, λ = 0.56083 Å |
Orthorhombic, P212121 | Cell parameters from 15625 reflections |
a = 5.2133 (3) Å | θ = 2.5–24.4° |
b = 18.3625 (12) Å | µ = 0.05 mm−1 |
c = 26.0799 (19) Å | T = 295 K |
V = 2496.6 (3) Å3 | Prism, colourless |
Z = 8 | 0.27 × 0.25 × 0.08 mm |
F(000) = 960 |
Stoe Stadivari diffractometer | 5439 independent reflections |
Radiation source: Sealed X-ray tube, Axo Astix-f Microfocus source | 2319 reflections with I > 2σ(I) |
Graded multilayer mirror monochromator | Rint = 0.132 |
Detector resolution: 5.81 pixels mm-1 | θmax = 21.0°, θmin = 2.6° |
ω scans | h = −6→6 |
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2019) | k = −23→23 |
Tmin = 0.361, Tmax = 1.000 | l = −33→33 |
46311 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.74 | (Δ/σ)max < 0.001 |
5439 reflections | Δρmax = 0.11 e Å−3 |
316 parameters | Δρmin = −0.10 e Å−3 |
0 restraints | Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.0132 (13) |
Primary atom site location: dual |
x | y | z | Uiso*/Ueq | ||
O1A | 0.4387 (3) | 0.69302 (12) | 0.38661 (8) | 0.0630 (6) | |
N1A | 0.0203 (5) | 0.70377 (15) | 0.36724 (11) | 0.0568 (8) | |
H1A | −0.136 (5) | 0.6967 (16) | 0.3772 (11) | 0.068* | |
C1A | −0.1440 (6) | 0.70880 (18) | 0.27970 (13) | 0.0720 (10) | |
H1AA | −0.143954 | 0.656603 | 0.277663 | 0.108* | |
H1AB | −0.112684 | 0.728890 | 0.246299 | 0.108* | |
H1AC | −0.307634 | 0.725268 | 0.291994 | 0.108* | |
C2A | 0.0663 (6) | 0.73371 (17) | 0.31654 (13) | 0.0588 (9) | |
H2A | 0.229586 | 0.713993 | 0.304120 | 0.071* | |
C3A | 0.0901 (5) | 0.81724 (18) | 0.31768 (13) | 0.0557 (9) | |
C4A | −0.0701 (7) | 0.8593 (2) | 0.34610 (15) | 0.0764 (11) | |
H4A | −0.195949 | 0.837185 | 0.366024 | 0.092* | |
C5A | −0.0493 (8) | 0.9346 (2) | 0.34597 (15) | 0.0847 (12) | |
H5A | −0.160183 | 0.962224 | 0.366004 | 0.102* | |
C6A | 0.1311 (7) | 0.9684 (2) | 0.31689 (16) | 0.0800 (11) | |
H6A | 0.143867 | 1.018943 | 0.316643 | 0.096* | |
C7A | 0.2924 (7) | 0.9271 (2) | 0.28823 (16) | 0.0868 (13) | |
H7A | 0.417606 | 0.949590 | 0.268377 | 0.104* | |
C8A | 0.2729 (6) | 0.8514 (2) | 0.28814 (14) | 0.0772 (11) | |
H8A | 0.383777 | 0.823801 | 0.268047 | 0.093* | |
C9A | 0.2110 (6) | 0.68623 (16) | 0.39947 (13) | 0.0526 (9) | |
C10A | 0.1348 (5) | 0.65628 (17) | 0.45033 (12) | 0.0498 (8) | |
C11A | 0.2833 (6) | 0.60179 (19) | 0.47200 (15) | 0.0702 (10) | |
H11A | 0.428210 | 0.584939 | 0.454929 | 0.084* | |
C12A | 0.2167 (7) | 0.5726 (2) | 0.51869 (16) | 0.0845 (12) | |
H12A | 0.314346 | 0.535028 | 0.532549 | 0.101* | |
C13A | 0.0064 (7) | 0.5985 (2) | 0.54520 (14) | 0.0759 (11) | |
H13A | −0.036474 | 0.578974 | 0.576969 | 0.091* | |
C14A | −0.1383 (6) | 0.6530 (2) | 0.52434 (15) | 0.0712 (10) | |
H14A | −0.279492 | 0.670892 | 0.542129 | 0.085* | |
C15A | −0.0758 (6) | 0.68183 (17) | 0.47688 (14) | 0.0620 (9) | |
H15A | −0.176383 | 0.718594 | 0.462823 | 0.074* | |
O1B | 0.9295 (3) | 0.77969 (11) | 0.14990 (9) | 0.0670 (7) | |
N1B | 0.5075 (5) | 0.75516 (14) | 0.14882 (12) | 0.0616 (8) | |
H1B | 0.354 (5) | 0.7718 (16) | 0.1493 (12) | 0.074* | |
C1B | 0.3496 (6) | 0.63517 (17) | 0.17383 (14) | 0.0746 (11) | |
H1BA | 0.384355 | 0.646314 | 0.209113 | 0.112* | |
H1BB | 0.370027 | 0.583818 | 0.168261 | 0.112* | |
H1BC | 0.176985 | 0.649170 | 0.165628 | 0.112* | |
C2B | 0.5365 (6) | 0.67688 (16) | 0.13957 (14) | 0.0601 (9) | |
H2B | 0.710627 | 0.663219 | 0.149944 | 0.072* | |
C3B | 0.5075 (6) | 0.65798 (17) | 0.08365 (14) | 0.0558 (8) | |
C4B | 0.3156 (7) | 0.6867 (2) | 0.05320 (17) | 0.0809 (12) | |
H4B | 0.201052 | 0.719768 | 0.067555 | 0.097* | |
C5B | 0.2882 (7) | 0.6682 (2) | 0.00274 (18) | 0.0905 (13) | |
H5B | 0.156648 | 0.688641 | −0.016579 | 0.109* | |
C6B | 0.4541 (8) | 0.6197 (2) | −0.01948 (17) | 0.0871 (12) | |
H6B | 0.436818 | 0.607068 | −0.053830 | 0.105* | |
C7B | 0.6442 (8) | 0.5905 (2) | 0.00953 (19) | 0.0933 (13) | |
H7B | 0.756746 | 0.557102 | −0.005069 | 0.112* | |
C8B | 0.6727 (7) | 0.60959 (19) | 0.06030 (16) | 0.0787 (11) | |
H8B | 0.806240 | 0.589440 | 0.079221 | 0.094* | |
C9B | 0.7071 (6) | 0.80071 (17) | 0.15121 (12) | 0.0534 (8) | |
C10B | 0.6444 (6) | 0.88026 (17) | 0.15614 (13) | 0.0548 (9) | |
C11B | 0.8059 (7) | 0.92343 (19) | 0.18443 (15) | 0.0763 (11) | |
H11B | 0.948339 | 0.902977 | 0.200342 | 0.092* | |
C12B | 0.7580 (9) | 0.9974 (2) | 0.18947 (18) | 0.0956 (14) | |
H12B | 0.864493 | 1.026153 | 0.209710 | 0.115* | |
C13B | 0.5537 (9) | 1.0280 (2) | 0.16455 (18) | 0.0940 (15) | |
H13B | 0.523360 | 1.077740 | 0.167155 | 0.113* | |
C14B | 0.3948 (8) | 0.9854 (2) | 0.13589 (18) | 0.0943 (14) | |
H14B | 0.256023 | 1.006218 | 0.118964 | 0.113* | |
C15B | 0.4386 (6) | 0.91134 (19) | 0.13184 (15) | 0.0718 (11) | |
H15B | 0.328058 | 0.882535 | 0.112564 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0482 (11) | 0.0706 (16) | 0.0702 (17) | −0.0008 (11) | 0.0031 (12) | 0.0003 (13) |
N1A | 0.0446 (13) | 0.0673 (19) | 0.059 (2) | −0.0003 (15) | 0.0043 (14) | 0.0115 (16) |
C1A | 0.077 (2) | 0.072 (2) | 0.066 (3) | 0.003 (2) | −0.005 (2) | 0.002 (2) |
C2A | 0.0524 (18) | 0.066 (2) | 0.058 (2) | 0.0073 (17) | 0.0101 (19) | 0.005 (2) |
C3A | 0.0477 (17) | 0.063 (2) | 0.056 (2) | 0.0047 (17) | 0.0012 (17) | 0.0087 (19) |
C4A | 0.076 (2) | 0.066 (3) | 0.087 (3) | 0.000 (2) | 0.025 (2) | 0.008 (2) |
C5A | 0.100 (3) | 0.065 (3) | 0.090 (3) | 0.007 (2) | 0.022 (3) | 0.000 (2) |
C6A | 0.088 (2) | 0.064 (3) | 0.088 (3) | −0.010 (2) | −0.002 (3) | 0.005 (2) |
C7A | 0.075 (2) | 0.076 (3) | 0.110 (4) | −0.008 (2) | 0.012 (3) | 0.026 (3) |
C8A | 0.069 (2) | 0.077 (3) | 0.085 (3) | 0.003 (2) | 0.019 (2) | 0.014 (2) |
C9A | 0.0512 (17) | 0.040 (2) | 0.066 (3) | −0.0008 (16) | −0.0018 (18) | −0.0050 (17) |
C10A | 0.0493 (17) | 0.049 (2) | 0.051 (2) | −0.0044 (16) | −0.0011 (17) | −0.0017 (18) |
C11A | 0.067 (2) | 0.076 (3) | 0.068 (3) | 0.012 (2) | 0.001 (2) | 0.009 (2) |
C12A | 0.092 (3) | 0.084 (3) | 0.078 (3) | 0.018 (2) | −0.001 (3) | 0.019 (2) |
C13A | 0.082 (2) | 0.084 (3) | 0.062 (3) | −0.013 (2) | −0.001 (2) | 0.008 (2) |
C14A | 0.068 (2) | 0.080 (3) | 0.065 (3) | −0.003 (2) | 0.004 (2) | −0.001 (2) |
C15A | 0.0582 (18) | 0.059 (2) | 0.068 (3) | 0.0051 (17) | −0.004 (2) | 0.008 (2) |
O1B | 0.0433 (11) | 0.0619 (15) | 0.096 (2) | 0.0017 (11) | 0.0019 (12) | −0.0003 (13) |
N1B | 0.0428 (13) | 0.0458 (18) | 0.096 (2) | 0.0002 (14) | 0.0010 (16) | −0.0044 (16) |
C1B | 0.076 (2) | 0.055 (2) | 0.093 (3) | −0.0052 (19) | 0.002 (2) | 0.006 (2) |
C2B | 0.0505 (17) | 0.044 (2) | 0.086 (3) | 0.0020 (15) | −0.0057 (19) | −0.0008 (19) |
C3B | 0.0479 (17) | 0.0464 (19) | 0.073 (3) | −0.0015 (16) | 0.0007 (19) | 0.002 (2) |
C4B | 0.069 (2) | 0.087 (3) | 0.087 (3) | 0.015 (2) | −0.007 (2) | −0.009 (3) |
C5B | 0.082 (3) | 0.103 (3) | 0.086 (4) | 0.007 (3) | −0.010 (3) | 0.006 (3) |
C6B | 0.085 (3) | 0.103 (3) | 0.073 (3) | −0.007 (3) | −0.005 (3) | −0.006 (3) |
C7B | 0.099 (3) | 0.094 (3) | 0.088 (4) | 0.015 (3) | 0.004 (3) | −0.013 (3) |
C8B | 0.075 (2) | 0.076 (3) | 0.085 (3) | 0.015 (2) | −0.008 (2) | −0.004 (2) |
C9B | 0.0466 (16) | 0.057 (2) | 0.057 (2) | −0.0022 (17) | −0.0001 (16) | −0.0032 (18) |
C10B | 0.0516 (17) | 0.049 (2) | 0.064 (2) | −0.0046 (17) | 0.0087 (18) | 0.0032 (19) |
C11B | 0.070 (2) | 0.062 (3) | 0.097 (3) | −0.007 (2) | 0.004 (2) | −0.009 (2) |
C12B | 0.105 (3) | 0.061 (3) | 0.121 (4) | −0.021 (2) | 0.023 (3) | −0.015 (3) |
C13B | 0.111 (3) | 0.049 (3) | 0.122 (4) | 0.002 (3) | 0.040 (3) | 0.011 (3) |
C14B | 0.090 (3) | 0.068 (3) | 0.125 (4) | 0.009 (2) | 0.012 (3) | 0.030 (3) |
C15B | 0.068 (2) | 0.056 (3) | 0.091 (3) | 0.0047 (19) | −0.001 (2) | 0.011 (2) |
O1A—C9A | 1.240 (3) | O1B—C9B | 1.223 (3) |
N1A—C9A | 1.341 (4) | N1B—C9B | 1.336 (3) |
N1A—C2A | 1.452 (4) | N1B—C2B | 1.465 (4) |
N1A—H1A | 0.87 (3) | N1B—H1B | 0.85 (3) |
C1A—C2A | 1.528 (4) | C1B—C2B | 1.528 (4) |
C1A—H1AA | 0.9600 | C1B—H1BA | 0.9600 |
C1A—H1AB | 0.9600 | C1B—H1BB | 0.9600 |
C1A—H1AC | 0.9600 | C1B—H1BC | 0.9600 |
C2A—C3A | 1.539 (4) | C2B—C3B | 1.507 (4) |
C2A—H2A | 0.9800 | C2B—H2B | 0.9800 |
C3A—C4A | 1.357 (4) | C3B—C8B | 1.379 (4) |
C3A—C8A | 1.376 (4) | C3B—C4B | 1.382 (4) |
C4A—C5A | 1.387 (4) | C4B—C5B | 1.367 (5) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—C6A | 1.359 (5) | C5B—C6B | 1.370 (5) |
C5A—H5A | 0.9300 | C5B—H5B | 0.9300 |
C6A—C7A | 1.357 (5) | C6B—C7B | 1.357 (5) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.395 (4) | C7B—C8B | 1.378 (5) |
C7A—H7A | 0.9300 | C7B—H7B | 0.9300 |
C8A—H8A | 0.9300 | C8B—H8B | 0.9300 |
C9A—C10A | 1.490 (4) | C9B—C10B | 1.502 (4) |
C10A—C15A | 1.380 (4) | C10B—C15B | 1.370 (4) |
C10A—C11A | 1.386 (4) | C10B—C11B | 1.372 (4) |
C11A—C12A | 1.375 (5) | C11B—C12B | 1.388 (4) |
C11A—H11A | 0.9300 | C11B—H11B | 0.9300 |
C12A—C13A | 1.381 (4) | C12B—C13B | 1.368 (5) |
C12A—H12A | 0.9300 | C12B—H12B | 0.9300 |
C13A—C14A | 1.367 (4) | C13B—C14B | 1.363 (5) |
C13A—H13A | 0.9300 | C13B—H13B | 0.9300 |
C14A—C15A | 1.385 (4) | C14B—C15B | 1.382 (4) |
C14A—H14A | 0.9300 | C14B—H14B | 0.9300 |
C15A—H15A | 0.9300 | C15B—H15B | 0.9300 |
C9A—N1A—C2A | 122.6 (3) | C9B—N1B—C2B | 122.8 (2) |
C9A—N1A—H1A | 118 (2) | C9B—N1B—H1B | 120 (2) |
C2A—N1A—H1A | 119 (2) | C2B—N1B—H1B | 117 (2) |
C2A—C1A—H1AA | 109.5 | C2B—C1B—H1BA | 109.5 |
C2A—C1A—H1AB | 109.5 | C2B—C1B—H1BB | 109.5 |
H1AA—C1A—H1AB | 109.5 | H1BA—C1B—H1BB | 109.5 |
C2A—C1A—H1AC | 109.5 | C2B—C1B—H1BC | 109.5 |
H1AA—C1A—H1AC | 109.5 | H1BA—C1B—H1BC | 109.5 |
H1AB—C1A—H1AC | 109.5 | H1BB—C1B—H1BC | 109.5 |
N1A—C2A—C1A | 109.9 (3) | N1B—C2B—C3B | 112.0 (3) |
N1A—C2A—C3A | 111.9 (3) | N1B—C2B—C1B | 109.3 (3) |
C1A—C2A—C3A | 111.6 (3) | C3B—C2B—C1B | 112.7 (3) |
N1A—C2A—H2A | 107.7 | N1B—C2B—H2B | 107.5 |
C1A—C2A—H2A | 107.7 | C3B—C2B—H2B | 107.5 |
C3A—C2A—H2A | 107.7 | C1B—C2B—H2B | 107.5 |
C4A—C3A—C8A | 118.2 (3) | C8B—C3B—C4B | 116.4 (4) |
C4A—C3A—C2A | 121.8 (3) | C8B—C3B—C2B | 120.9 (3) |
C8A—C3A—C2A | 119.9 (3) | C4B—C3B—C2B | 122.7 (3) |
C3A—C4A—C5A | 121.2 (3) | C5B—C4B—C3B | 122.3 (4) |
C3A—C4A—H4A | 119.4 | C5B—C4B—H4B | 118.9 |
C5A—C4A—H4A | 119.4 | C3B—C4B—H4B | 118.9 |
C6A—C5A—C4A | 120.8 (4) | C4B—C5B—C6B | 120.2 (4) |
C6A—C5A—H5A | 119.6 | C4B—C5B—H5B | 119.9 |
C4A—C5A—H5A | 119.6 | C6B—C5B—H5B | 119.9 |
C7A—C6A—C5A | 118.7 (4) | C7B—C6B—C5B | 118.8 (4) |
C7A—C6A—H6A | 120.6 | C7B—C6B—H6B | 120.6 |
C5A—C6A—H6A | 120.6 | C5B—C6B—H6B | 120.6 |
C6A—C7A—C8A | 120.9 (4) | C6B—C7B—C8B | 120.9 (4) |
C6A—C7A—H7A | 119.6 | C6B—C7B—H7B | 119.5 |
C8A—C7A—H7A | 119.6 | C8B—C7B—H7B | 119.5 |
C3A—C8A—C7A | 120.2 (4) | C7B—C8B—C3B | 121.4 (4) |
C3A—C8A—H8A | 119.9 | C7B—C8B—H8B | 119.3 |
C7A—C8A—H8A | 119.9 | C3B—C8B—H8B | 119.3 |
O1A—C9A—N1A | 121.1 (3) | O1B—C9B—N1B | 122.6 (3) |
O1A—C9A—C10A | 122.2 (3) | O1B—C9B—C10B | 121.0 (3) |
N1A—C9A—C10A | 116.7 (3) | N1B—C9B—C10B | 116.3 (3) |
C15A—C10A—C11A | 119.0 (3) | C15B—C10B—C11B | 119.2 (3) |
C15A—C10A—C9A | 122.2 (3) | C15B—C10B—C9B | 122.4 (3) |
C11A—C10A—C9A | 118.7 (3) | C11B—C10B—C9B | 118.3 (3) |
C12A—C11A—C10A | 120.1 (3) | C10B—C11B—C12B | 120.4 (4) |
C12A—C11A—H11A | 119.9 | C10B—C11B—H11B | 119.8 |
C10A—C11A—H11A | 119.9 | C12B—C11B—H11B | 119.8 |
C11A—C12A—C13A | 120.6 (4) | C13B—C12B—C11B | 119.8 (4) |
C11A—C12A—H12A | 119.7 | C13B—C12B—H12B | 120.1 |
C13A—C12A—H12A | 119.7 | C11B—C12B—H12B | 120.1 |
C14A—C13A—C12A | 119.4 (4) | C14B—C13B—C12B | 119.9 (4) |
C14A—C13A—H13A | 120.3 | C14B—C13B—H13B | 120.0 |
C12A—C13A—H13A | 120.3 | C12B—C13B—H13B | 120.0 |
C13A—C14A—C15A | 120.4 (3) | C13B—C14B—C15B | 120.4 (4) |
C13A—C14A—H14A | 119.8 | C13B—C14B—H14B | 119.8 |
C15A—C14A—H14A | 119.8 | C15B—C14B—H14B | 119.8 |
C10A—C15A—C14A | 120.4 (3) | C10B—C15B—C14B | 120.2 (4) |
C10A—C15A—H15A | 119.8 | C10B—C15B—H15B | 119.9 |
C14A—C15A—H15A | 119.8 | C14B—C15B—H15B | 119.9 |
C9A—N1A—C2A—C1A | 147.9 (3) | C9B—N1B—C2B—C3B | −94.7 (4) |
C9A—N1A—C2A—C3A | −87.5 (3) | C9B—N1B—C2B—C1B | 139.6 (3) |
N1A—C2A—C3A—C4A | −42.5 (4) | N1B—C2B—C3B—C8B | 136.4 (3) |
C1A—C2A—C3A—C4A | 81.1 (4) | C1B—C2B—C3B—C8B | −99.8 (3) |
N1A—C2A—C3A—C8A | 139.4 (3) | N1B—C2B—C3B—C4B | −44.4 (4) |
C1A—C2A—C3A—C8A | −97.0 (3) | C1B—C2B—C3B—C4B | 79.3 (4) |
C8A—C3A—C4A—C5A | −0.7 (5) | C8B—C3B—C4B—C5B | 0.4 (5) |
C2A—C3A—C4A—C5A | −178.8 (3) | C2B—C3B—C4B—C5B | −178.8 (3) |
C3A—C4A—C5A—C6A | 0.6 (6) | C3B—C4B—C5B—C6B | −0.1 (6) |
C4A—C5A—C6A—C7A | −0.5 (6) | C4B—C5B—C6B—C7B | 0.2 (6) |
C5A—C6A—C7A—C8A | 0.5 (6) | C5B—C6B—C7B—C8B | −0.7 (6) |
C4A—C3A—C8A—C7A | 0.7 (5) | C6B—C7B—C8B—C3B | 1.1 (6) |
C2A—C3A—C8A—C7A | 178.8 (3) | C4B—C3B—C8B—C7B | −0.9 (5) |
C6A—C7A—C8A—C3A | −0.6 (6) | C2B—C3B—C8B—C7B | 178.3 (3) |
C2A—N1A—C9A—O1A | −2.1 (5) | C2B—N1B—C9B—O1B | −5.9 (5) |
C2A—N1A—C9A—C10A | 179.8 (3) | C2B—N1B—C9B—C10B | 174.6 (3) |
O1A—C9A—C10A—C15A | 144.0 (3) | O1B—C9B—C10B—C15B | 143.9 (3) |
N1A—C9A—C10A—C15A | −37.9 (4) | N1B—C9B—C10B—C15B | −36.6 (4) |
O1A—C9A—C10A—C11A | −34.9 (4) | O1B—C9B—C10B—C11B | −33.5 (5) |
N1A—C9A—C10A—C11A | 143.2 (3) | N1B—C9B—C10B—C11B | 146.0 (3) |
C15A—C10A—C11A—C12A | 1.6 (5) | C15B—C10B—C11B—C12B | 1.6 (5) |
C9A—C10A—C11A—C12A | −179.4 (3) | C9B—C10B—C11B—C12B | 179.1 (3) |
C10A—C11A—C12A—C13A | −1.9 (5) | C10B—C11B—C12B—C13B | −2.4 (6) |
C11A—C12A—C13A—C14A | 0.8 (5) | C11B—C12B—C13B—C14B | 1.5 (7) |
C12A—C13A—C14A—C15A | 0.4 (5) | C12B—C13B—C14B—C15B | 0.0 (6) |
C11A—C10A—C15A—C14A | −0.4 (5) | C11B—C10B—C15B—C14B | 0.0 (5) |
C9A—C10A—C15A—C14A | −179.3 (3) | C9B—C10B—C15B—C14B | −177.4 (3) |
C13A—C14A—C15A—C10A | −0.7 (5) | C13B—C14B—C15B—C10B | −0.8 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O1Ai | 0.87 (3) | 2.23 (3) | 3.080 (3) | 167 (3) |
N1B—H1B···O1Bi | 0.85 (3) | 2.22 (3) | 3.047 (3) | 163 (3) |
Symmetry code: (i) x−1, y, z. |
Dihedral angle (°) | P21 form I | P21 form II | P212121 form IIIa |
N1—C2—C3—C4 | -27.3 (5) | -41.1 (3) | -42.5 (4), -44.4 (4) |
N1—C9—C10—C15 | -34.2 (4) | -31.2 (3) | -37.9 (4), -36.6 (4) |
Phenyl···phenyl | 23.1 (2) | 56.2 (1) | 47.0 (1), 47.4 (1) |
Note: (a) Z' = 2 |
Funding information
Funding for this research was provided by: Consejo Nacional de Ciencia y Tecnología (grant No. 268178; scholarship No. 000536).
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