research communications
Comparison S)-2-methylpyrrolidin-1-yl]prop-1-yn-1-yl}-1,1′-biphenyl
conformations of two structurally related biphenyl analogues: 4,4′-bis[3-(pyrrolidin-1-yl)prop-1-yn-1-yl]-1,1′-biphenyl and 4,4′-bis{3-[(aDept. of Pharm. Sciences, College of Pharmacy, University of Arkansas for Medical Sciences, Little Rock, AR 72205, USA, and bDept. of Chemistry, University of Kentucky, Lexington KY 40506, USA
*Correspondence e-mail: pacrooks@uams.edu
The title compounds, C26H28N2, (I), and C28H32N2, (II), were designed based on the structure of the potent α9α10 nicotinic acetylcholine receptor antagonist ZZ161C {1,1′-[[1,1′-biphenyl]-4,4′-diylbis(prop-2-yne-3,1-diyl)]bis(3,4-dimethylpyridin-1-ium) bromide}. In order to improve the druglikeness properties of ZZ161C for potential oral administration, the title compounds (I) and (II) were prepared by coupling 4,4′-bis(3-bromoprop-1-yn-1-yl)-1,1′-biphenyl with pyrrolidine, (I), and (S)-2-methylpyrrolidine, (II), respectively, in acetonitrile at room temperature. The of (I) contains two half molecules that each sit on sites of crystallographic inversion. As a result, the biphenyl ring systems in compound (I) are coplanar. The biphenyl ring system in compound (II), however, has a dihedral angle of 28.76 (11)°. In (I), the two independent molecules differ in the orientation of the pyrrolidine ring (the nitrogen lone pair points towards the biphenyl rings in one molecule, but away from the rings in the other). The torsion angles about the ethynyl groups between the planes of the phenyl rings and the pyrrolidine ring N atoms are 84.15 (10) and −152.89 (10)°. In compound (II), the corresponding torsion angles are 122.0 (3) and 167.0 (3)°, with the nitrogen lone pairs at both ends of the molecule directed away from the central biphenyl rings.
1. Chemical context
The title compounds (I) and (II) are structural analogue precursors of the bis-quaternary ammonium salt, ZZ161C {1′-[(1,1′-biphenyl)-4,4′-diylbis(prop-2-yne-3,1-diyl)]bis(3,4-dimethylpyridin-1-ium) bromide}, designed to improve druglikeness properties. ZZ161C is a potent and selective nicotinic acetylcholine receptor antagonist for α9α10 subunits (Zheng et al., 2007), and has shown analgesic effects in various animal pain models (Wala et al., 2012). The terminal aza-aromatic rings were replaced by pyrrolidine and (S)-2-methylpyrrolidine moieties in compounds (I) and (II), respectively. We report here the single-crystal X-ray structures of (I) and (II) to determine the conformations of these compounds.
2. Structural commentary
The title compounds, (I) and (II) are shown in Figs. 1 and 2, respectively. X-ray crystallographic studies were carried out in order to determine the geometry of the biphenyl ring systems, as well as to obtain more detailed information about the conformation of the pyrrolidino headgroups. Structure (I) is triclinic, P, while crystal (II) is monoclinic, P21.
In each compound, individual bond lengths and angles are unremarkable. For compound (I), the contains two half molecules (denoted A and B in Fig. 1) such that the biphenyl rings straddle crystallographic inversion centres. As a result, the biphenyl groups are coplanar. In compound (II), however, the biphenyl rings (C9–C14) and (C15–C20) are non-coplanar, with a dihedral angle of 28.76 (11)°. In crystals of (I), the two independent molecules differ in the orientation of the pyrrolidine ring. In molecule A, the nitrogen lone pair points inward towards the biphenyl rings, but in molecule B the nitrogen lone pair is directed away from the rings). The torsion angles about the ethynyl groups between the planes of the phenyl rings and the pyrrolidine ring N atoms are 84.15 (10)° and −152.89 (10)° (defined by atoms N1A—C5A—C8A—C9A and N1B—C5B—C8B—C9B, respectively). In compound (II), the corresponding torsion angles are 122.0 (3)° and 167.0 (3)° (defined by atoms N1—C6—C9—C14 and N2—C23—C18—C17, respectively), with the nitrogen lone pair directed away from the biphenyl rings at both ends of the molecule.
3. Supramolecular features
Aside from weak van der Waals interactions, there are no noteworthy intermolecular contacts in either (I) or (II).
4. Database survey
A search of the November 2014 release of the Cambridge Structure Database (Groom & Allen, 2014), with updates through May 2015, using the program Mogul (Bruno et al., 2004) for 4,4′ substituted biphenyl fragments was conducted. The search was restricted to non-organometallic, solvent-free structures with R < 5% and Cl as the heaviest element. There were over 1000 matches, which gave a of biphenyl torsion angles with a tight peak at 0° and a broader peak centred at 30°. The biphenyl torsion angles in (I) and (II) are thus not unusual.
5. Synthesis and crystallization
Synthetic procedures: Compound (I), 3,3′-([1,1′-biphenyl]-4,4′-diyl)bis (prop-2-yn-1-ol) was synthesized by coupling 1,2,4,5-tetraiodobenzene with 4-pentyn-1-ol in the presence of bis-(triphenylphosphine)palladium(II)dichloride and copper(I) iodide as catalysts. A mixture of 1,2,4,5-tetraiodobenzene, 4-pentyn-1-ol, bis-(triphenylphosphine)palladium(II)dichloride and copper(I) iodide was stirred at room temperature for 24 h under argon. The obtained 3,3′-([1,1′-biphenyl]-4,4′-diyl)bis(prop-2-yn-1-ol) was converted to 4,4′-bis-(3-bromoprop-1-yn-1-yl)-1,1′-biphenyl using bromomethane and triphenylphosphine in anhydrous methylene chloride at room temperature. To a suspension of 4,4′-bis(3-bromoprop-1-yn-1-yl)-1,1′-biphenyl (100.0 mg, 0.26 mmol) in acetonitrile (7 mL) was added pyrrolidine (55.4 mg, 0.78 mmol) and the reaction mixture was stirred for 2 h at room temperature to obtain compound (I). Acetonitrile was removed from the reaction mixture under reduced pressure and the resulting residue was partitioned between water and dichloromethane. The organic layers were collected, combined, dried over anhydrous sodium sulfate, filtered, and the filtrate concentrated under reduced pressure. The resulting crude sample of (I) was purified by (dichloromethane/methanol, 100:3) (yield: 80%). Compound (II) was prepared using the same experimental conditions as (I) but utilizing (S)-2-methylpyrrolidine (66.3 mg, 0.78 mmol) instead of pyrrolidine. (dichloromethane/methanol 100:3) was then used for purification of (II) (yield: 80%).
Crystallization: Yellow crystals of compounds (I) and (II) suitable for X-ray analysis were grown from a mixture of dichloromethane/methanol (2:1) by slow evaporation of the solution at room temperature over 24 h.
Compound (I)
1H NMR (400 Mz, CDCl3): δ 7.49 (q, 8H), 3.67 (s, 4H), 2.75 (s, 8H), 1.86 (s, 8H) p.p.m.
13C NMR (100 Mz, CDCl3): δ 139.94. 132.19, 126.77, 122.32, 85.67, 84.55, 52.65, 43.85, 23.83 p.p.m.
Compound (II)
1H NMR (400 Mz, CDCl3): δ 7.21 (q, 8H), 3.69 (dd, 4H), 3.16–3.11 (m, 2H), 2.69–2.59 (m, 4H), 2.01–1.43 (m, 8H), 1.15 (d, 6H) p.p.m.
13C NMR (100 Mz, CDCl3): δ 139.86, 132.18, 126.74, 122.43, 85.53, 84.61, 57.31, 53.00, 41.18, 32.79, 21.55, 18.51 p.p.m.
6. details
Crystal data, data collection and structure . In both structures, H atoms were found in difference Fourier maps, but subsequently included in the using riding models. Constrained distances were set to 0.95 Å (Csp2H), 0.98 Å [RCH3, (II) only], 0.99 Å (R2CH2) and 1.00 Å (R3CH). Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq [RCH3 in (II) only] of the attached atom.
details are summarized in Table 1In (II), the x = −0.3 (10) is indeterminate, which is to be expected for a light-atom structure refined against Mo Kα data. However, the synthesis used pure (S)-2-methylpyrrolidine, so the for the model of (II) was dictated by the synthesis.
Refinement progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final models were further checked with the IUCr utility checkCIF.
Supporting information
10.1107/S2056989015016163/hg5457sup1.cif
contains datablocks global, I, II. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015016163/hg5457Isup2.hkl
Structure factors: contains datablock II. DOI: 10.1107/S2056989015016163/hg5457IIsup3.hkl
Supporting information file. DOI: 10.1107/S2056989015016163/hg5457Isup4.cml
Supporting information file. DOI: 10.1107/S2056989015016163/hg5457IIsup5.cml
\ The title compounds (I) and (II) are structural analogue precursors of the bis-quaternary ammonium salt, ZZ161C (1'-([1,1'-biphenyl]-4,4'-diylbis(prop-2-yne-3,1-diyl))bis(3,4-\ dimethylpyridin-1-ium) bromide), designed to improve druglikeness properties. ZZ161C is a potent and selective nicotinic acetylcholine receptor antagonist for α9α10 subunits (Zheng et al., 2007), and has shown analgesic effects in various animal pain models (Wala et al., 2012). The terminal aza-aromatic rings were replaced by pyrrolidine and (S)-2-methylpyrrolidine moieties in compounds (I) and (II), respectively. We report here the single-crystal X-ray structures of (I) and (II) to determine the conformations of these compounds.
The title compounds, I and II are shown in Figs. 1 and 2, respectively. X-ray crystallographic studies were carried out in order to determine the geometry of the biphenyl ring systems, as well as to obtain more detailed information about the conformation of the pyrrolidino headgroups. Structure (I) is triclinic, 1, while crystal (II) is monoclinic, P21. In each compound, individual bond lengths and angles are unremarkable. For compound (I), the contains two half molecules (denoted A and B in Fig. 1) such that the biphenyl rings straddle crystallographic inversion centres. As a result, the biphenyl groups are coplanar. In compound (II), however, the biphenyl rings (C9–C14) and (C15–C20) are non-coplanar, with a dihedral angle of 28.76 (11)°. In crystals of (I), the two independent molecules differ in the orientation of the pyrrolidine ring. In molecule A, the nitrogen lone pair points inward towards the biphenyl rings, but in molecule B the nitrogen lone pair is directed away from the rings). The torsion angles about the ethynyl groups between the planes of the phenyl rings and the pyrrolidine ring N atoms are 84.15 (10)° and -152.89 (10)° (defined by atoms N1A—C5A—C8A—C9A and N1B—C5B—C8B—C9B, respectively). In compound (II), the corresponding torsion angles are 122.0 (3)° and 167.0 (3)° (defined by atoms N1—C6—C9—C14 and N2—C23—C18—C17, respectively), with the nitrogen lone pair directed away from the biphenyl rings at both ends of the molecule.
PAside from weak van der Waals interactions, there are no noteworthy intermolecular contacts in either (I) or (II).
A search of the November 2014 release of the Cambridge Structure Database (Groom & Allen, 2014), with updates through May 2015, using the program Mogul (Bruno et al., 2004) for 4,4' substituted biphenyl fragments was conducted. The search was restricted to non-organometallic, solvent-free structures with R < 5% and Cl as the heaviest element. There were over 1000 matches, which gave a
of biphenyl torsion angles with a tight peak at 0° and a broader peak centred at ~30°. The biphenyl torsion angles in (I) and (II) are thus not unusual.Synthetic procedures: Compound (I), 3,3'-([1,1'-biphenyl]-4,4'-diyl)bis (prop-2-yn-1-ol) was synthesized by coupling 1,2,4,5-tetraiodobenzene with 4-pentyn-1-ol in the presence of bis-(triphenylphosphine)palladium(II)dichloride and copper(I) iodide as catalysts. A mixture of 1,2,4,5-tetraiodobenzene, 4-pentyn-1-ol, bis-(triphenylphosphine)palladium(II)dichloride and copper(I) iodide was stirred at room temperature for 24 hours under argon. The obtained 3,3'-([1,1'-biphenyl]-4,4'-diyl)bis(prop-2-yn-1-ol) was converted to 4,4'-bis-(3-bromoprop-1-yn-1-yl)-1,1'-biphenyl using bromomethane and triphenylphosphine in anhydrous methylene chloride at room temperature. To a suspension of the 4,4'-bis(3-bromoprop-1-yn-1-yl)-1,1'-biphenyl (100.0 mg, 0.26 mmol) in acetonitrile (7 mL) was added pyrrolidine (55.4 mg, 0.78 mmol) and the reaction mixture was stirred for 2 hours at room temperature to obtain compound (I). Acetonitrile was removed from the reaction mixture under reduced pressure and the resulting residue was partitioned between water and dichloromethane. The organic layers were collected, combined, dried over anhydrous sodium sulfate, filtered, and the filtrate concentrated under reduced pressure. The resulting crude sample of (I) was purified by
(dichloromethane/methanol, 100:3) (yield: 80%). Compound (II) was prepared using the same experimental conditions as (I) but utilizing (S)-2-methylpyrrolidine (66.3 mg, 0.78 mmol) instead of pyrrolidine. (dichloromethane/methanol 100:3) was then used for purification of (II) (yield: 80%).Crystallization: Yellow crystals of compounds (I) and (II) suitable for X-ray analysis were grown from a mixture of dichloromethane/methanol (2:1) by slow evaporation of the solution at room temperature over 24 hours.
Compound (I)
1H NMR (400 Mz, CDCl3): δ 7.49 (q, 8H), 3.67 (s, 4H), 2.75 (s, 8H), 1.86 (s, 8H) p.p.m.
13C NMR (100 Mz, CDCl3): δ 139.94. 132.19, 126.77, 122.32, 85.67, 84.55, 52.65, 43.85, 23.83 p.p.m.
Compound (II)
1H NMR (400 Mz, CDCl3): δ 7.21 (q, 8H), 3.69 (dd, 4H), 3.16–3.11 (m, 2H), 2.69–2.59 (m, 4H), 2.01–1.43 (m, 8H), 1.15 (d, 6H) p.p.m.
13C NMR (100 Mz, CDCl3): δ 139.86, 132.18, 126.74, 122.43, 85.53, 84.61, 57.31, 53.00, 41.18, 32.79, 21.55, 18.51 p.p.m.
Crystal data, data collection and structure
details are summarized in Table 1. In both structures, H atoms were found in difference Fourier maps, but subsequently included in the using riding models. Constrained distances were set to 0.95 Å (Csp2H), 0.98 Å [RCH3, (II) only], 0.99 Å (R2CH2) and 1.00 Å (R3CH). Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq [RCH3 in (II) only] of the attached atom.In (II), the α data. However, the synthesis used pure (S)-2-methylpyrrolidine, so the for the model of (II) was dictated by the synthesis.
x = -0.3 (10) is indeterminate, which is to be expected for a light-atom structure refined against Mo KRefinement progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final models were further checked with the IUCr utility checkCIF.
Data collection: APEX2 (Bruker, 2006) for (I); COLLECT (Nonius, 1998) for (II). Cell
SAINT (Bruker, 2006) for (I); SCALEPACK (Otwinowski & Minor, 2006) for (II). Data reduction: SAINT (Bruker, 2006) for (I); DENZO-SMN (Otwinowski & Minor, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015) for (I); SHELXL2014 (Sheldrick, 2015) for (II). Molecular graphics: XP in SHELXTL (Sheldrick, 2008) for (I); XP in SHELXTL (Sheldrick, 2008) for (II). For both compounds, software used to prepare material for publication: SHELX (Sheldrick, 2008) and CIFFIX (Parkin, 2013).Fig. 1. The molecular structure of (I), with ellipsoids drawn at the 50% probability level. | |
Fig. 2. The molecular structure of (II), with ellipsoids drawn at the 50% probability level. |
C26H28N2 | Z = 2 |
Mr = 368.50 | F(000) = 396 |
Triclinic, P1 | Dx = 1.220 Mg m−3 |
a = 6.2100 (1) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 10.3089 (2) Å | Cell parameters from 9977 reflections |
c = 16.3082 (3) Å | θ = 2.7–68.2° |
α = 86.317 (1)° | µ = 0.54 mm−1 |
β = 81.202 (1)° | T = 90 K |
γ = 76.671 (1)° | Shard, colourless |
V = 1003.49 (3) Å3 | 0.23 × 0.19 × 0.10 mm |
Bruker X8 Proteum diffractometer | 3586 independent reflections |
Radiation source: fine-focus rotating anode | 3451 reflections with I > 2σ(I) |
Detector resolution: 5.6 pixels mm-1 | Rint = 0.044 |
φ and ω scans | θmax = 68.2°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −7→7 |
Tmin = 0.811, Tmax = 0.929 | k = −12→6 |
13692 measured reflections | l = −19→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0577P)2 + 0.3125P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3586 reflections | Δρmax = 0.22 e Å−3 |
254 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL2014/6 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0061 (11) |
C26H28N2 | γ = 76.671 (1)° |
Mr = 368.50 | V = 1003.49 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.2100 (1) Å | Cu Kα radiation |
b = 10.3089 (2) Å | µ = 0.54 mm−1 |
c = 16.3082 (3) Å | T = 90 K |
α = 86.317 (1)° | 0.23 × 0.19 × 0.10 mm |
β = 81.202 (1)° |
Bruker X8 Proteum diffractometer | 3586 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 3451 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.929 | Rint = 0.044 |
13692 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.22 e Å−3 |
3586 reflections | Δρmin = −0.20 e Å−3 |
254 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 progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
N1A | 0.90671 (15) | 0.09727 (9) | 0.80861 (5) | 0.0163 (2) | |
C1A | 1.11598 (18) | 0.01531 (11) | 0.83141 (7) | 0.0210 (3) | |
H1A1 | 1.2346 | 0.0010 | 0.7828 | 0.025* | |
H1A2 | 1.0951 | −0.0723 | 0.8555 | 0.025* | |
C2A | 1.1724 (2) | 0.09853 (12) | 0.89584 (7) | 0.0238 (3) | |
H2A1 | 1.2687 | 0.1582 | 0.8692 | 0.029* | |
H2A2 | 1.2500 | 0.0406 | 0.9381 | 0.029* | |
C3A | 0.9430 (2) | 0.17995 (12) | 0.93527 (7) | 0.0226 (3) | |
H3A1 | 0.9140 | 0.1575 | 0.9953 | 0.027* | |
H3A2 | 0.9359 | 0.2769 | 0.9280 | 0.027* | |
C4A | 0.77498 (18) | 0.13928 (11) | 0.88842 (7) | 0.0187 (2) | |
H4A1 | 0.7159 | 0.0651 | 0.9180 | 0.022* | |
H4A2 | 0.6486 | 0.2155 | 0.8810 | 0.022* | |
C5A | 0.79816 (19) | 0.02600 (11) | 0.75852 (7) | 0.0190 (2) | |
H5A1 | 0.7276 | −0.0379 | 0.7948 | 0.023* | |
H5A2 | 0.9128 | −0.0257 | 0.7167 | 0.023* | |
C6A | 0.62761 (18) | 0.11598 (10) | 0.71603 (7) | 0.0175 (2) | |
C7A | 0.49421 (18) | 0.18772 (10) | 0.67760 (6) | 0.0168 (2) | |
C8A | 0.34803 (18) | 0.27515 (10) | 0.62731 (7) | 0.0160 (2) | |
C9A | 0.43797 (18) | 0.32491 (10) | 0.55121 (7) | 0.0160 (2) | |
H9A | 0.5942 | 0.2993 | 0.5331 | 0.019* | |
C10A | 0.30252 (18) | 0.41090 (10) | 0.50192 (6) | 0.0156 (2) | |
H10A | 0.3677 | 0.4427 | 0.4503 | 0.019* | |
C11A | 0.07141 (17) | 0.45231 (9) | 0.52628 (6) | 0.0145 (2) | |
C12A | −0.01727 (18) | 0.39888 (10) | 0.60194 (7) | 0.0177 (2) | |
H12A | −0.1738 | 0.4232 | 0.6197 | 0.021* | |
C13A | 0.11676 (19) | 0.31184 (11) | 0.65140 (7) | 0.0182 (2) | |
H13A | 0.0513 | 0.2769 | 0.7020 | 0.022* | |
N1B | 0.65099 (16) | 0.52088 (9) | 0.86778 (6) | 0.0188 (2) | |
C1B | 0.84890 (19) | 0.56666 (12) | 0.82796 (7) | 0.0235 (3) | |
H1B1 | 0.8123 | 0.6326 | 0.7824 | 0.028* | |
H1B2 | 0.9688 | 0.4911 | 0.8056 | 0.028* | |
C2B | 0.9172 (2) | 0.63028 (13) | 0.89876 (8) | 0.0271 (3) | |
H2B1 | 0.9916 | 0.7035 | 0.8777 | 0.033* | |
H2B2 | 1.0199 | 0.5635 | 0.9293 | 0.033* | |
C3B | 0.6947 (2) | 0.68421 (12) | 0.95488 (7) | 0.0253 (3) | |
H3B1 | 0.7020 | 0.6498 | 1.0127 | 0.030* | |
H3B2 | 0.6594 | 0.7829 | 0.9546 | 0.030* | |
C4B | 0.51897 (19) | 0.63353 (11) | 0.91723 (7) | 0.0205 (3) | |
H4B1 | 0.4102 | 0.6041 | 0.9612 | 0.025* | |
H4B2 | 0.4373 | 0.7036 | 0.8818 | 0.025* | |
C5B | 0.52980 (19) | 0.47407 (11) | 0.80985 (7) | 0.0204 (3) | |
H5B1 | 0.4064 | 0.4386 | 0.8422 | 0.024* | |
H5B2 | 0.6326 | 0.3993 | 0.7790 | 0.024* | |
C6B | 0.43522 (19) | 0.57591 (11) | 0.74928 (7) | 0.0199 (3) | |
C7B | 0.35385 (19) | 0.66217 (11) | 0.70308 (7) | 0.0190 (3) | |
C8B | 0.25131 (18) | 0.76103 (10) | 0.64637 (6) | 0.0170 (2) | |
C9B | 0.06171 (19) | 0.74642 (11) | 0.61458 (7) | 0.0180 (2) | |
H9B | −0.0018 | 0.6720 | 0.6322 | 0.022* | |
C10B | −0.03435 (18) | 0.83874 (10) | 0.55795 (7) | 0.0173 (2) | |
H10B | −0.1620 | 0.8259 | 0.5369 | 0.021* | |
C11B | 0.05162 (17) | 0.95096 (10) | 0.53077 (6) | 0.0155 (2) | |
C12B | 0.23930 (18) | 0.96591 (10) | 0.56433 (7) | 0.0175 (2) | |
H12B | 0.3002 | 1.0417 | 0.5481 | 0.021* | |
C13B | 0.33793 (18) | 0.87324 (11) | 0.62041 (7) | 0.0180 (2) | |
H13B | 0.4658 | 0.8858 | 0.6415 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0170 (5) | 0.0163 (4) | 0.0157 (5) | −0.0032 (4) | −0.0031 (4) | −0.0010 (3) |
C1A | 0.0179 (5) | 0.0229 (6) | 0.0211 (6) | −0.0011 (4) | −0.0042 (4) | −0.0021 (4) |
C2A | 0.0220 (6) | 0.0290 (6) | 0.0221 (6) | −0.0076 (5) | −0.0056 (5) | −0.0016 (5) |
C3A | 0.0264 (6) | 0.0233 (6) | 0.0192 (6) | −0.0064 (5) | −0.0039 (5) | −0.0032 (4) |
C4A | 0.0191 (5) | 0.0188 (5) | 0.0173 (5) | −0.0037 (4) | −0.0004 (4) | −0.0007 (4) |
C5A | 0.0225 (6) | 0.0151 (5) | 0.0200 (5) | −0.0034 (4) | −0.0059 (4) | −0.0013 (4) |
C6A | 0.0200 (5) | 0.0162 (5) | 0.0174 (5) | −0.0064 (4) | −0.0019 (4) | −0.0028 (4) |
C7A | 0.0207 (5) | 0.0143 (5) | 0.0169 (5) | −0.0067 (4) | −0.0021 (4) | −0.0028 (4) |
C8A | 0.0209 (6) | 0.0111 (5) | 0.0175 (5) | −0.0051 (4) | −0.0047 (4) | −0.0032 (4) |
C9A | 0.0162 (5) | 0.0133 (5) | 0.0198 (5) | −0.0053 (4) | −0.0021 (4) | −0.0034 (4) |
C10A | 0.0190 (5) | 0.0124 (5) | 0.0163 (5) | −0.0062 (4) | −0.0012 (4) | −0.0013 (4) |
C11A | 0.0186 (5) | 0.0099 (5) | 0.0165 (5) | −0.0055 (4) | −0.0025 (4) | −0.0037 (4) |
C12A | 0.0170 (5) | 0.0168 (5) | 0.0186 (5) | −0.0035 (4) | 0.0002 (4) | −0.0017 (4) |
C13A | 0.0216 (6) | 0.0167 (5) | 0.0162 (5) | −0.0055 (4) | −0.0008 (4) | −0.0002 (4) |
N1B | 0.0192 (5) | 0.0182 (5) | 0.0180 (5) | −0.0030 (4) | −0.0013 (4) | −0.0010 (4) |
C1B | 0.0199 (6) | 0.0284 (6) | 0.0214 (6) | −0.0060 (5) | 0.0013 (4) | −0.0028 (5) |
C2B | 0.0230 (6) | 0.0339 (7) | 0.0262 (6) | −0.0102 (5) | −0.0022 (5) | −0.0038 (5) |
C3B | 0.0263 (6) | 0.0267 (6) | 0.0233 (6) | −0.0063 (5) | −0.0026 (5) | −0.0054 (5) |
C4B | 0.0201 (6) | 0.0212 (6) | 0.0190 (5) | −0.0029 (4) | −0.0006 (4) | −0.0028 (4) |
C5B | 0.0242 (6) | 0.0171 (5) | 0.0204 (6) | −0.0059 (4) | −0.0027 (4) | −0.0002 (4) |
C6B | 0.0224 (6) | 0.0192 (6) | 0.0190 (6) | −0.0073 (4) | −0.0013 (4) | −0.0030 (4) |
C7B | 0.0214 (6) | 0.0180 (5) | 0.0181 (5) | −0.0062 (4) | −0.0001 (4) | −0.0041 (4) |
C8B | 0.0201 (5) | 0.0153 (5) | 0.0146 (5) | −0.0026 (4) | 0.0008 (4) | −0.0046 (4) |
C9B | 0.0230 (6) | 0.0141 (5) | 0.0181 (5) | −0.0075 (4) | 0.0004 (4) | −0.0037 (4) |
C10B | 0.0186 (5) | 0.0157 (5) | 0.0190 (5) | −0.0061 (4) | −0.0014 (4) | −0.0047 (4) |
C11B | 0.0171 (5) | 0.0131 (5) | 0.0159 (5) | −0.0037 (4) | 0.0016 (4) | −0.0054 (4) |
C12B | 0.0184 (5) | 0.0144 (5) | 0.0204 (5) | −0.0067 (4) | 0.0003 (4) | −0.0032 (4) |
C13B | 0.0173 (5) | 0.0179 (5) | 0.0191 (5) | −0.0044 (4) | −0.0012 (4) | −0.0047 (4) |
N1A—C4A | 1.4609 (13) | N1B—C5B | 1.4613 (14) |
N1A—C5A | 1.4612 (13) | N1B—C1B | 1.4625 (15) |
N1A—C1A | 1.4637 (14) | N1B—C4B | 1.4663 (14) |
C1A—C2A | 1.5264 (15) | C1B—C2B | 1.5228 (16) |
C1A—H1A1 | 0.9900 | C1B—H1B1 | 0.9900 |
C1A—H1A2 | 0.9900 | C1B—H1B2 | 0.9900 |
C2A—C3A | 1.5442 (16) | C2B—C3B | 1.5430 (17) |
C2A—H2A1 | 0.9900 | C2B—H2B1 | 0.9900 |
C2A—H2A2 | 0.9900 | C2B—H2B2 | 0.9900 |
C3A—C4A | 1.5283 (15) | C3B—C4B | 1.5329 (16) |
C3A—H3A1 | 0.9900 | C3B—H3B1 | 0.9900 |
C3A—H3A2 | 0.9900 | C3B—H3B2 | 0.9900 |
C4A—H4A1 | 0.9900 | C4B—H4B1 | 0.9900 |
C4A—H4A2 | 0.9900 | C4B—H4B2 | 0.9900 |
C5A—C6A | 1.4667 (15) | C5B—C6B | 1.4775 (15) |
C5A—H5A1 | 0.9900 | C5B—H5B1 | 0.9900 |
C5A—H5A2 | 0.9900 | C5B—H5B2 | 0.9900 |
C6A—C7A | 1.2012 (16) | C6B—C7B | 1.1987 (16) |
C7A—C8A | 1.4369 (15) | C7B—C8B | 1.4350 (15) |
C8A—C9A | 1.3976 (15) | C8B—C9B | 1.3986 (16) |
C8A—C13A | 1.3986 (16) | C8B—C13B | 1.4003 (16) |
C9A—C10A | 1.3825 (15) | C9B—C10B | 1.3815 (15) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C10A—C11A | 1.4017 (15) | C10B—C11B | 1.4023 (15) |
C10A—H10A | 0.9500 | C10B—H10B | 0.9500 |
C11A—C12A | 1.4049 (15) | C11B—C12B | 1.4037 (15) |
C11A—C11Ai | 1.487 (2) | C11B—C11Bii | 1.486 (2) |
C12A—C13A | 1.3844 (15) | C12B—C13B | 1.3834 (15) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C4A—N1A—C5A | 114.19 (9) | C5B—N1B—C1B | 114.00 (9) |
C4A—N1A—C1A | 103.63 (8) | C5B—N1B—C4B | 114.41 (9) |
C5A—N1A—C1A | 112.60 (8) | C1B—N1B—C4B | 104.43 (9) |
N1A—C1A—C2A | 102.99 (9) | N1B—C1B—C2B | 102.86 (9) |
N1A—C1A—H1A1 | 111.2 | N1B—C1B—H1B1 | 111.2 |
C2A—C1A—H1A1 | 111.2 | C2B—C1B—H1B1 | 111.2 |
N1A—C1A—H1A2 | 111.2 | N1B—C1B—H1B2 | 111.2 |
C2A—C1A—H1A2 | 111.2 | C2B—C1B—H1B2 | 111.2 |
H1A1—C1A—H1A2 | 109.1 | H1B1—C1B—H1B2 | 109.1 |
C1A—C2A—C3A | 104.25 (9) | C1B—C2B—C3B | 104.18 (9) |
C1A—C2A—H2A1 | 110.9 | C1B—C2B—H2B1 | 110.9 |
C3A—C2A—H2A1 | 110.9 | C3B—C2B—H2B1 | 110.9 |
C1A—C2A—H2A2 | 110.9 | C1B—C2B—H2B2 | 110.9 |
C3A—C2A—H2A2 | 110.9 | C3B—C2B—H2B2 | 110.9 |
H2A1—C2A—H2A2 | 108.9 | H2B1—C2B—H2B2 | 108.9 |
C4A—C3A—C2A | 104.34 (9) | C4B—C3B—C2B | 104.86 (9) |
C4A—C3A—H3A1 | 110.9 | C4B—C3B—H3B1 | 110.8 |
C2A—C3A—H3A1 | 110.9 | C2B—C3B—H3B1 | 110.8 |
C4A—C3A—H3A2 | 110.9 | C4B—C3B—H3B2 | 110.8 |
C2A—C3A—H3A2 | 110.9 | C2B—C3B—H3B2 | 110.8 |
H3A1—C3A—H3A2 | 108.9 | H3B1—C3B—H3B2 | 108.9 |
N1A—C4A—C3A | 103.36 (9) | N1B—C4B—C3B | 103.67 (9) |
N1A—C4A—H4A1 | 111.1 | N1B—C4B—H4B1 | 111.0 |
C3A—C4A—H4A1 | 111.1 | C3B—C4B—H4B1 | 111.0 |
N1A—C4A—H4A2 | 111.1 | N1B—C4B—H4B2 | 111.0 |
C3A—C4A—H4A2 | 111.1 | C3B—C4B—H4B2 | 111.0 |
H4A1—C4A—H4A2 | 109.1 | H4B1—C4B—H4B2 | 109.0 |
N1A—C5A—C6A | 112.54 (8) | N1B—C5B—C6B | 115.14 (9) |
N1A—C5A—H5A1 | 109.1 | N1B—C5B—H5B1 | 108.5 |
C6A—C5A—H5A1 | 109.1 | C6B—C5B—H5B1 | 108.5 |
N1A—C5A—H5A2 | 109.1 | N1B—C5B—H5B2 | 108.5 |
C6A—C5A—H5A2 | 109.1 | C6B—C5B—H5B2 | 108.5 |
H5A1—C5A—H5A2 | 107.8 | H5B1—C5B—H5B2 | 107.5 |
C7A—C6A—C5A | 176.79 (11) | C7B—C6B—C5B | 177.04 (11) |
C6A—C7A—C8A | 175.84 (11) | C6B—C7B—C8B | 177.29 (11) |
C9A—C8A—C13A | 118.34 (10) | C9B—C8B—C13B | 118.07 (10) |
C9A—C8A—C7A | 119.38 (10) | C9B—C8B—C7B | 120.32 (10) |
C13A—C8A—C7A | 122.28 (10) | C13B—C8B—C7B | 121.61 (10) |
C10A—C9A—C8A | 120.86 (10) | C10B—C9B—C8B | 120.86 (10) |
C10A—C9A—H9A | 119.6 | C10B—C9B—H9B | 119.6 |
C8A—C9A—H9A | 119.6 | C8B—C9B—H9B | 119.6 |
C9A—C10A—C11A | 121.62 (10) | C9B—C10B—C11B | 121.74 (10) |
C9A—C10A—H10A | 119.2 | C9B—C10B—H10B | 119.1 |
C11A—C10A—H10A | 119.2 | C11B—C10B—H10B | 119.1 |
C10A—C11A—C12A | 116.84 (10) | C10B—C11B—C12B | 116.87 (10) |
C10A—C11A—C11Ai | 121.06 (12) | C10B—C11B—C11Bii | 121.34 (12) |
C12A—C11A—C11Ai | 122.10 (12) | C12B—C11B—C11Bii | 121.79 (11) |
C13A—C12A—C11A | 121.94 (10) | C13B—C12B—C11B | 121.76 (10) |
C13A—C12A—H12A | 119.0 | C13B—C12B—H12B | 119.1 |
C11A—C12A—H12A | 119.0 | C11B—C12B—H12B | 119.1 |
C12A—C13A—C8A | 120.35 (10) | C12B—C13B—C8B | 120.68 (10) |
C12A—C13A—H13A | 119.8 | C12B—C13B—H13B | 119.7 |
C8A—C13A—H13A | 119.8 | C8B—C13B—H13B | 119.7 |
C4A—N1A—C1A—C2A | −45.38 (10) | C5B—N1B—C1B—C2B | 170.74 (9) |
C5A—N1A—C1A—C2A | −169.28 (9) | C4B—N1B—C1B—C2B | 45.18 (11) |
N1A—C1A—C2A—C3A | 27.96 (11) | N1B—C1B—C2B—C3B | −30.78 (12) |
C1A—C2A—C3A—C4A | −1.49 (11) | C1B—C2B—C3B—C4B | 6.22 (12) |
C5A—N1A—C4A—C3A | 167.28 (9) | C5B—N1B—C4B—C3B | −166.33 (9) |
C1A—N1A—C4A—C3A | 44.43 (10) | C1B—N1B—C4B—C3B | −41.02 (11) |
C2A—C3A—C4A—N1A | −25.57 (11) | C2B—C3B—C4B—N1B | 20.48 (12) |
C4A—N1A—C5A—C6A | 78.62 (11) | C1B—N1B—C5B—C6B | −62.66 (13) |
C1A—N1A—C5A—C6A | −163.55 (9) | C4B—N1B—C5B—C6B | 57.45 (13) |
C13A—C8A—C9A—C10A | 1.59 (15) | C13B—C8B—C9B—C10B | 1.28 (15) |
C7A—C8A—C9A—C10A | −178.97 (9) | C7B—C8B—C9B—C10B | −177.95 (9) |
C8A—C9A—C10A—C11A | 0.51 (15) | C8B—C9B—C10B—C11B | −0.73 (16) |
C9A—C10A—C11A—C12A | −2.01 (14) | C9B—C10B—C11B—C12B | −0.51 (15) |
C9A—C10A—C11A—C11Ai | 178.33 (10) | C9B—C10B—C11B—C11Bii | 179.42 (11) |
C10A—C11A—C12A—C13A | 1.47 (15) | C10B—C11B—C12B—C13B | 1.19 (15) |
C11Ai—C11A—C12A—C13A | −178.88 (11) | C11Bii—C11B—C12B—C13B | −178.74 (11) |
C11A—C12A—C13A—C8A | 0.58 (16) | C11B—C12B—C13B—C8B | −0.65 (16) |
C9A—C8A—C13A—C12A | −2.12 (15) | C9B—C8B—C13B—C12B | −0.60 (15) |
C7A—C8A—C13A—C12A | 178.46 (9) | C7B—C8B—C13B—C12B | 178.61 (9) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
C28H32N2 | F(000) = 428 |
Mr = 396.55 | Dx = 1.178 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.1411 (4) Å | Cell parameters from 2730 reflections |
b = 7.3080 (4) Å | θ = 1.0–27.5° |
c = 18.9840 (9) Å | µ = 0.07 mm−1 |
β = 98.177 (3)° | T = 90 K |
V = 1117.97 (10) Å3 | Cut slab, colourless |
Z = 2 | 0.41 × 0.35 × 0.08 mm |
Nonius KappaCCD diffractometer | 4705 independent reflections |
Radiation source: fine-focus sealed-tube | 3548 reflections with I > 2σ(I) |
Detector resolution: 9.1 pixels mm-1 | Rint = 0.085 |
φ and ω scans at fixed χ = 55° | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −10→10 |
Tmin = 0.791, Tmax = 0.971 | k = −8→9 |
15874 measured reflections | l = −24→24 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.144 | w = 1/[σ2(Fo2) + (0.0742P)2 + 0.0409P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4705 reflections | Δρmax = 0.30 e Å−3 |
273 parameters | Δρmin = −0.19 e Å−3 |
1 restraint | Absolute structure: Flack x parameter was determined using 1205 quotients of the form [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.3 (10) |
C28H32N2 | V = 1117.97 (10) Å3 |
Mr = 396.55 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.1411 (4) Å | µ = 0.07 mm−1 |
b = 7.3080 (4) Å | T = 90 K |
c = 18.9840 (9) Å | 0.41 × 0.35 × 0.08 mm |
β = 98.177 (3)° |
Nonius KappaCCD diffractometer | 4705 independent reflections |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | 3548 reflections with I > 2σ(I) |
Tmin = 0.791, Tmax = 0.971 | Rint = 0.085 |
15874 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.144 | Δρmax = 0.30 e Å−3 |
S = 1.05 | Δρmin = −0.19 e Å−3 |
4705 reflections | Absolute structure: Flack x parameter was determined using 1205 quotients of the form [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
273 parameters | Absolute structure parameter: −0.3 (10) |
1 restraint |
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 progress was checked using PLATON (Spek, 2009) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. Absolute structure analysis: The Flack x parameter was determined using 1205 quotients of the form [(I+)-(I-)]/[(I+)+(I-)], but since the anomalous signal was so small the result is thoroughly inconclusive. This is to be expected, and merely confirms what we already know about light atom non-centrosymmetric structures that are determined with MoKα radiation. The quotient method has been described by Parsons et al. (2013). However, the synthesis used pure (S)-2-methylpyrrolidine, so the absolute configuration for the model of (II) was dictated by the synthesis. |
x | y | z | Uiso*/Ueq | ||
N1 | −0.0921 (3) | 0.5633 (4) | 0.18120 (12) | 0.0294 (6) | |
N2 | 1.5991 (3) | 0.4631 (4) | 0.82088 (11) | 0.0288 (6) | |
C1 | −0.0274 (4) | 0.7478 (5) | 0.17326 (15) | 0.0333 (7) | |
H1A | 0.0846 | 0.7619 | 0.2008 | 0.040* | |
H1B | −0.1021 | 0.8413 | 0.1892 | 0.040* | |
C2 | −0.0213 (4) | 0.7632 (5) | 0.09382 (16) | 0.0384 (8) | |
H2A | 0.0767 | 0.8345 | 0.0845 | 0.046* | |
H2B | −0.1229 | 0.8226 | 0.0692 | 0.046* | |
C3 | −0.0094 (4) | 0.5640 (5) | 0.06935 (15) | 0.0381 (8) | |
H3A | −0.1085 | 0.5300 | 0.0354 | 0.046* | |
H3B | 0.0907 | 0.5459 | 0.0460 | 0.046* | |
C4 | 0.0011 (3) | 0.4496 (5) | 0.13712 (15) | 0.0327 (7) | |
H4A | 0.1195 | 0.4424 | 0.1599 | 0.039* | |
C5 | −0.0680 (5) | 0.2582 (6) | 0.12600 (18) | 0.0533 (10) | |
H5A | −0.0562 | 0.1938 | 0.1717 | 0.080* | |
H5B | −0.0069 | 0.1920 | 0.0931 | 0.080* | |
H5C | −0.1857 | 0.2647 | 0.1060 | 0.080* | |
C6 | −0.0833 (3) | 0.5055 (5) | 0.25511 (14) | 0.0336 (8) | |
H6A | −0.1321 | 0.3816 | 0.2560 | 0.040* | |
H6B | −0.1527 | 0.5892 | 0.2794 | 0.040* | |
C7 | 0.0854 (3) | 0.5015 (4) | 0.29597 (14) | 0.0296 (7) | |
C8 | 0.2237 (3) | 0.5035 (4) | 0.32840 (13) | 0.0258 (6) | |
C9 | 0.3832 (3) | 0.5132 (4) | 0.37271 (13) | 0.0251 (6) | |
C10 | 0.5206 (3) | 0.4133 (4) | 0.35812 (14) | 0.0263 (6) | |
H10A | 0.5128 | 0.3411 | 0.3162 | 0.032* | |
C11 | 0.6689 (3) | 0.4188 (4) | 0.40464 (13) | 0.0249 (6) | |
H11A | 0.7614 | 0.3508 | 0.3937 | 0.030* | |
C12 | 0.6847 (3) | 0.5219 (4) | 0.46694 (13) | 0.0243 (6) | |
C13 | 0.5480 (3) | 0.6270 (4) | 0.47988 (14) | 0.0254 (6) | |
H13A | 0.5569 | 0.7026 | 0.5210 | 0.030* | |
C14 | 0.4002 (3) | 0.6225 (4) | 0.43367 (13) | 0.0257 (6) | |
H14A | 0.3091 | 0.6947 | 0.4436 | 0.031* | |
C15 | 0.8386 (3) | 0.5167 (4) | 0.51885 (13) | 0.0239 (6) | |
C16 | 0.9931 (4) | 0.4757 (4) | 0.49786 (15) | 0.0261 (6) | |
H16A | 1.0010 | 0.4593 | 0.4488 | 0.031* | |
C17 | 1.1338 (3) | 0.4589 (4) | 0.54754 (14) | 0.0271 (7) | |
H17A | 1.2369 | 0.4320 | 0.5319 | 0.033* | |
C18 | 1.1278 (3) | 0.4805 (4) | 0.61967 (13) | 0.0247 (6) | |
C19 | 0.9756 (3) | 0.5261 (4) | 0.64146 (14) | 0.0276 (7) | |
H19A | 0.9690 | 0.5456 | 0.6905 | 0.033* | |
C20 | 0.8343 (3) | 0.5429 (4) | 0.59141 (14) | 0.0271 (7) | |
H20A | 0.7319 | 0.5731 | 0.6070 | 0.033* | |
C21 | 1.2782 (3) | 0.4600 (5) | 0.66923 (13) | 0.0287 (7) | |
C22 | 1.4103 (3) | 0.4380 (5) | 0.70559 (14) | 0.0318 (7) | |
C23 | 1.5765 (3) | 0.4087 (6) | 0.74681 (14) | 0.0388 (9) | |
H23A | 1.6034 | 0.2769 | 0.7446 | 0.047* | |
H23B | 1.6583 | 0.4760 | 0.7228 | 0.047* | |
C24 | 1.5747 (4) | 0.6593 (5) | 0.83087 (16) | 0.0364 (7) | |
H24A | 1.4666 | 0.7004 | 0.8053 | 0.044* | |
H24B | 1.6646 | 0.7315 | 0.8142 | 0.044* | |
C25 | 1.5796 (5) | 0.6761 (6) | 0.91101 (17) | 0.0487 (10) | |
H25A | 1.5039 | 0.7738 | 0.9229 | 0.058* | |
H25B | 1.6934 | 0.7034 | 0.9346 | 0.058* | |
C26 | 1.5222 (4) | 0.4886 (6) | 0.93362 (15) | 0.0439 (9) | |
H26A | 1.6096 | 0.4298 | 0.9678 | 0.053* | |
H26B | 1.4204 | 0.5003 | 0.9563 | 0.053* | |
C27 | 1.4879 (4) | 0.3770 (5) | 0.86523 (16) | 0.0347 (8) | |
H27A | 1.3706 | 0.3987 | 0.8431 | 0.042* | |
C28 | 1.5151 (4) | 0.1744 (5) | 0.8746 (2) | 0.0535 (10) | |
H28A | 1.4918 | 0.1137 | 0.8282 | 0.080* | |
H28C | 1.4408 | 0.1262 | 0.9064 | 0.080* | |
H28D | 1.6306 | 0.1513 | 0.8952 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0231 (12) | 0.0336 (16) | 0.0301 (12) | 0.0017 (11) | −0.0014 (9) | −0.0003 (11) |
N2 | 0.0211 (12) | 0.0362 (16) | 0.0283 (12) | −0.0022 (11) | 0.0011 (9) | −0.0015 (12) |
C1 | 0.0264 (15) | 0.0318 (19) | 0.0403 (17) | 0.0012 (14) | −0.0002 (12) | 0.0003 (15) |
C2 | 0.0305 (17) | 0.041 (2) | 0.0421 (17) | 0.0034 (15) | −0.0011 (13) | 0.0105 (16) |
C3 | 0.0361 (17) | 0.047 (2) | 0.0307 (15) | −0.0027 (16) | 0.0015 (12) | −0.0005 (15) |
C4 | 0.0256 (15) | 0.038 (2) | 0.0336 (15) | 0.0000 (14) | −0.0002 (12) | −0.0055 (14) |
C5 | 0.069 (3) | 0.039 (2) | 0.051 (2) | −0.007 (2) | 0.0060 (18) | −0.0085 (18) |
C6 | 0.0225 (14) | 0.044 (2) | 0.0334 (15) | −0.0034 (14) | 0.0028 (11) | 0.0003 (15) |
C7 | 0.0272 (15) | 0.0339 (19) | 0.0274 (13) | 0.0008 (13) | 0.0034 (11) | 0.0004 (14) |
C8 | 0.0279 (14) | 0.0249 (17) | 0.0246 (13) | 0.0006 (12) | 0.0036 (11) | 0.0004 (12) |
C9 | 0.0249 (14) | 0.0244 (17) | 0.0259 (13) | −0.0009 (12) | 0.0035 (10) | 0.0051 (12) |
C10 | 0.0289 (15) | 0.0260 (17) | 0.0239 (13) | −0.0005 (13) | 0.0031 (11) | −0.0023 (12) |
C11 | 0.0223 (14) | 0.0268 (17) | 0.0262 (13) | 0.0014 (12) | 0.0053 (10) | 0.0038 (12) |
C12 | 0.0206 (13) | 0.0245 (17) | 0.0274 (13) | −0.0017 (12) | 0.0021 (10) | 0.0043 (13) |
C13 | 0.0270 (14) | 0.0215 (16) | 0.0279 (14) | −0.0007 (12) | 0.0048 (11) | −0.0027 (13) |
C14 | 0.0224 (13) | 0.0252 (17) | 0.0299 (14) | 0.0030 (12) | 0.0044 (11) | 0.0011 (13) |
C15 | 0.0196 (13) | 0.0209 (17) | 0.0304 (13) | −0.0036 (12) | 0.0009 (10) | 0.0008 (13) |
C16 | 0.0266 (13) | 0.0249 (17) | 0.0271 (12) | −0.0010 (13) | 0.0052 (10) | 0.0000 (13) |
C17 | 0.0190 (13) | 0.0267 (17) | 0.0358 (14) | −0.0007 (12) | 0.0047 (11) | 0.0023 (13) |
C18 | 0.0221 (13) | 0.0191 (16) | 0.0318 (14) | −0.0039 (12) | 0.0002 (10) | −0.0002 (12) |
C19 | 0.0245 (14) | 0.0334 (19) | 0.0248 (13) | −0.0003 (13) | 0.0024 (10) | −0.0033 (13) |
C20 | 0.0212 (13) | 0.0303 (18) | 0.0301 (14) | 0.0008 (12) | 0.0041 (10) | −0.0001 (13) |
C21 | 0.0275 (15) | 0.0292 (19) | 0.0296 (14) | 0.0002 (13) | 0.0042 (11) | −0.0007 (13) |
C22 | 0.0273 (15) | 0.037 (2) | 0.0301 (14) | 0.0024 (14) | 0.0015 (11) | −0.0019 (14) |
C23 | 0.0223 (15) | 0.060 (3) | 0.0331 (15) | 0.0071 (15) | 0.0003 (12) | −0.0025 (16) |
C24 | 0.0350 (16) | 0.0319 (19) | 0.0395 (17) | −0.0074 (14) | −0.0047 (13) | 0.0015 (15) |
C25 | 0.053 (2) | 0.048 (3) | 0.0425 (19) | −0.0021 (18) | −0.0044 (16) | −0.0102 (17) |
C26 | 0.0386 (18) | 0.062 (3) | 0.0307 (15) | 0.0077 (17) | 0.0050 (13) | 0.0041 (17) |
C27 | 0.0204 (15) | 0.041 (2) | 0.0423 (17) | −0.0013 (13) | 0.0015 (13) | 0.0094 (15) |
C28 | 0.0384 (19) | 0.038 (2) | 0.079 (3) | −0.0052 (17) | −0.0083 (17) | 0.0178 (19) |
N1—C6 | 1.457 (4) | C13—C14 | 1.385 (3) |
N1—C1 | 1.463 (4) | C13—H13A | 0.9500 |
N1—C4 | 1.465 (4) | C14—H14A | 0.9500 |
N2—C23 | 1.448 (3) | C15—C20 | 1.396 (4) |
N2—C27 | 1.463 (4) | C15—C16 | 1.405 (4) |
N2—C24 | 1.464 (4) | C16—C17 | 1.381 (4) |
C1—C2 | 1.520 (4) | C16—H16A | 0.9500 |
C1—H1A | 0.9900 | C17—C18 | 1.386 (4) |
C1—H1B | 0.9900 | C17—H17A | 0.9500 |
C2—C3 | 1.536 (5) | C18—C19 | 1.401 (4) |
C2—H2A | 0.9900 | C18—C21 | 1.442 (3) |
C2—H2B | 0.9900 | C19—C20 | 1.389 (4) |
C3—C4 | 1.526 (4) | C19—H19A | 0.9500 |
C3—H3A | 0.9900 | C20—H20A | 0.9500 |
C3—H3B | 0.9900 | C21—C22 | 1.203 (4) |
C4—C5 | 1.511 (5) | C22—C23 | 1.479 (4) |
C4—H4A | 1.0000 | C23—H23A | 0.9900 |
C5—H5A | 0.9800 | C23—H23B | 0.9900 |
C5—H5B | 0.9800 | C24—C25 | 1.521 (4) |
C5—H5C | 0.9800 | C24—H24A | 0.9900 |
C6—C7 | 1.479 (4) | C24—H24B | 0.9900 |
C6—H6A | 0.9900 | C25—C26 | 1.529 (6) |
C6—H6B | 0.9900 | C25—H25A | 0.9900 |
C7—C8 | 1.204 (3) | C25—H25B | 0.9900 |
C8—C9 | 1.445 (3) | C26—C27 | 1.525 (5) |
C9—C10 | 1.396 (4) | C26—H26A | 0.9900 |
C9—C14 | 1.397 (4) | C26—H26B | 0.9900 |
C10—C11 | 1.391 (3) | C27—C28 | 1.504 (5) |
C10—H10A | 0.9500 | C27—H27A | 1.0000 |
C11—C12 | 1.393 (4) | C28—H28A | 0.9800 |
C11—H11A | 0.9500 | C28—H28C | 0.9800 |
C12—C13 | 1.403 (4) | C28—H28D | 0.9800 |
C12—C15 | 1.480 (3) | ||
C6—N1—C1 | 113.4 (2) | C13—C14—C9 | 120.8 (2) |
C6—N1—C4 | 115.3 (2) | C13—C14—H14A | 119.6 |
C1—N1—C4 | 103.9 (2) | C9—C14—H14A | 119.6 |
C23—N2—C27 | 115.9 (2) | C20—C15—C16 | 117.2 (2) |
C23—N2—C24 | 113.2 (3) | C20—C15—C12 | 121.1 (2) |
C27—N2—C24 | 103.9 (2) | C16—C15—C12 | 121.6 (2) |
N1—C1—C2 | 103.5 (2) | C17—C16—C15 | 120.9 (2) |
N1—C1—H1A | 111.1 | C17—C16—H16A | 119.5 |
C2—C1—H1A | 111.1 | C15—C16—H16A | 119.5 |
N1—C1—H1B | 111.1 | C16—C17—C18 | 121.5 (2) |
C2—C1—H1B | 111.1 | C16—C17—H17A | 119.3 |
H1A—C1—H1B | 109.0 | C18—C17—H17A | 119.3 |
C1—C2—C3 | 104.0 (3) | C17—C18—C19 | 118.4 (2) |
C1—C2—H2A | 111.0 | C17—C18—C21 | 119.1 (2) |
C3—C2—H2A | 111.0 | C19—C18—C21 | 122.4 (2) |
C1—C2—H2B | 111.0 | C20—C19—C18 | 120.0 (2) |
C3—C2—H2B | 111.0 | C20—C19—H19A | 120.0 |
H2A—C2—H2B | 109.0 | C18—C19—H19A | 120.0 |
C4—C3—C2 | 105.2 (3) | C19—C20—C15 | 121.9 (2) |
C4—C3—H3A | 110.7 | C19—C20—H20A | 119.0 |
C2—C3—H3A | 110.7 | C15—C20—H20A | 119.0 |
C4—C3—H3B | 110.7 | C22—C21—C18 | 174.2 (3) |
C2—C3—H3B | 110.7 | C21—C22—C23 | 177.0 (3) |
H3A—C3—H3B | 108.8 | N2—C23—C22 | 117.0 (2) |
N1—C4—C5 | 113.1 (3) | N2—C23—H23A | 108.0 |
N1—C4—C3 | 101.5 (3) | C22—C23—H23A | 108.0 |
C5—C4—C3 | 114.5 (3) | N2—C23—H23B | 108.0 |
N1—C4—H4A | 109.2 | C22—C23—H23B | 108.0 |
C5—C4—H4A | 109.2 | H23A—C23—H23B | 107.3 |
C3—C4—H4A | 109.2 | N2—C24—C25 | 102.9 (3) |
C4—C5—H5A | 109.5 | N2—C24—H24A | 111.2 |
C4—C5—H5B | 109.5 | C25—C24—H24A | 111.2 |
H5A—C5—H5B | 109.5 | N2—C24—H24B | 111.2 |
C4—C5—H5C | 109.5 | C25—C24—H24B | 111.2 |
H5A—C5—H5C | 109.5 | H24A—C24—H24B | 109.1 |
H5B—C5—H5C | 109.5 | C24—C25—C26 | 104.1 (3) |
N1—C6—C7 | 115.2 (2) | C24—C25—H25A | 110.9 |
N1—C6—H6A | 108.5 | C26—C25—H25A | 110.9 |
C7—C6—H6A | 108.5 | C24—C25—H25B | 110.9 |
N1—C6—H6B | 108.5 | C26—C25—H25B | 110.9 |
C7—C6—H6B | 108.5 | H25A—C25—H25B | 109.0 |
H6A—C6—H6B | 107.5 | C27—C26—C25 | 105.5 (2) |
C8—C7—C6 | 177.9 (3) | C27—C26—H26A | 110.7 |
C7—C8—C9 | 174.7 (3) | C25—C26—H26A | 110.7 |
C10—C9—C14 | 118.4 (2) | C27—C26—H26B | 110.7 |
C10—C9—C8 | 122.5 (2) | C25—C26—H26B | 110.7 |
C14—C9—C8 | 119.0 (2) | H26A—C26—H26B | 108.8 |
C11—C10—C9 | 120.4 (2) | N2—C27—C28 | 113.5 (3) |
C11—C10—H10A | 119.8 | N2—C27—C26 | 101.9 (3) |
C9—C10—H10A | 119.8 | C28—C27—C26 | 114.8 (3) |
C10—C11—C12 | 121.5 (3) | N2—C27—H27A | 108.8 |
C10—C11—H11A | 119.3 | C28—C27—H27A | 108.8 |
C12—C11—H11A | 119.3 | C26—C27—H27A | 108.8 |
C11—C12—C13 | 117.7 (2) | C27—C28—H28A | 109.5 |
C11—C12—C15 | 121.3 (2) | C27—C28—H28C | 109.5 |
C13—C12—C15 | 121.0 (2) | H28A—C28—H28C | 109.5 |
C14—C13—C12 | 121.0 (2) | C27—C28—H28D | 109.5 |
C14—C13—H13A | 119.5 | H28A—C28—H28D | 109.5 |
C12—C13—H13A | 119.5 | H28C—C28—H28D | 109.5 |
C6—N1—C1—C2 | 170.4 (2) | C11—C12—C15—C16 | 26.8 (4) |
C4—N1—C1—C2 | 44.5 (3) | C13—C12—C15—C16 | −155.0 (3) |
N1—C1—C2—C3 | −24.3 (3) | C20—C15—C16—C17 | 1.2 (4) |
C1—C2—C3—C4 | −3.3 (3) | C12—C15—C16—C17 | −175.5 (3) |
C6—N1—C4—C5 | 66.3 (3) | C15—C16—C17—C18 | 0.4 (4) |
C1—N1—C4—C5 | −169.0 (3) | C16—C17—C18—C19 | −2.1 (4) |
C6—N1—C4—C3 | −170.6 (2) | C16—C17—C18—C21 | 179.5 (3) |
C1—N1—C4—C3 | −45.9 (3) | C17—C18—C19—C20 | 2.0 (4) |
C2—C3—C4—N1 | 29.5 (3) | C21—C18—C19—C20 | −179.6 (3) |
C2—C3—C4—C5 | 151.6 (3) | C18—C19—C20—C15 | −0.4 (4) |
C1—N1—C6—C7 | −59.8 (3) | C16—C15—C20—C19 | −1.2 (4) |
C4—N1—C6—C7 | 59.8 (4) | C12—C15—C20—C19 | 175.5 (3) |
C14—C9—C10—C11 | 2.0 (4) | C27—N2—C23—C22 | 57.8 (4) |
C8—C9—C10—C11 | −176.2 (3) | C24—N2—C23—C22 | −62.1 (4) |
C9—C10—C11—C12 | 0.5 (4) | C23—N2—C24—C25 | 172.0 (2) |
C10—C11—C12—C13 | −2.8 (4) | C27—N2—C24—C25 | 45.4 (3) |
C10—C11—C12—C15 | 175.5 (2) | N2—C24—C25—C26 | −26.8 (3) |
C11—C12—C13—C14 | 2.6 (4) | C24—C25—C26—C27 | −0.1 (3) |
C15—C12—C13—C14 | −175.7 (3) | C23—N2—C27—C28 | 66.2 (3) |
C12—C13—C14—C9 | −0.1 (4) | C24—N2—C27—C28 | −169.0 (2) |
C10—C9—C14—C13 | −2.2 (4) | C23—N2—C27—C26 | −169.8 (3) |
C8—C9—C14—C13 | 176.1 (3) | C24—N2—C27—C26 | −44.9 (3) |
C11—C12—C15—C20 | −149.7 (3) | C25—C26—C27—N2 | 26.9 (3) |
C13—C12—C15—C20 | 28.5 (4) | C25—C26—C27—C28 | 150.0 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C26H28N2 | C28H32N2 |
Mr | 368.50 | 396.55 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 90 | 90 |
a, b, c (Å) | 6.2100 (1), 10.3089 (2), 16.3082 (3) | 8.1411 (4), 7.3080 (4), 18.9840 (9) |
α, β, γ (°) | 86.317 (1), 81.202 (1), 76.671 (1) | 90, 98.177 (3), 90 |
V (Å3) | 1003.49 (3) | 1117.97 (10) |
Z | 2 | 2 |
Radiation type | Cu Kα | Mo Kα |
µ (mm−1) | 0.54 | 0.07 |
Crystal size (mm) | 0.23 × 0.19 × 0.10 | 0.41 × 0.35 × 0.08 |
Data collection | ||
Diffractometer | Bruker X8 Proteum diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Krause et al., 2015) | Multi-scan (SADABS; Krause et al., 2015) |
Tmin, Tmax | 0.811, 0.929 | 0.791, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13692, 3586, 3451 | 15874, 4705, 3548 |
Rint | 0.044 | 0.085 |
(sin θ/λ)max (Å−1) | 0.602 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.03 | 0.054, 0.144, 1.05 |
No. of reflections | 3586 | 4705 |
No. of parameters | 254 | 273 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.20 | 0.30, −0.19 |
Absolute structure | ? | Flack x parameter was determined using 1205 quotients of the form [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | ? | −0.3 (10) |
Computer programs: APEX2 (Bruker, 2006), COLLECT (Nonius, 1998), SAINT (Bruker, 2006), SCALEPACK (Otwinowski & Minor, 2006), DENZO-SMN (Otwinowski & Minor, 2006), SHELXS97 (Sheldrick, 2008), SHELXL2014/6 (Sheldrick, 2015), SHELXL2014 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELX (Sheldrick, 2008) and CIFFIX (Parkin, 2013).
Acknowledgements
This investigation was supported by ARA (Arkansas Research Alliance).
References
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruno, I. J., Cole, J. C., Kessler, M., Luo, J., Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004). J. Chem. Inf. Model. 44, 2133–2144. CSD CrossRef CAS Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (2006). International Tables for Crystallography, Vol. F, ch. 11.4, pp. 226–235. Chester: International Union of Crystallography. Google Scholar
Parkin, S. (2000). Acta Cryst. A56, 157–162. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parkin, S. (2013). CIFFIX, https://xray.uky.edu/people/parkin/programs/ciffix Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wala, E. P., Crooks, P. A., McIntosh, J. M. & Holtman, J. R. (2012). Anesth. Analg. 115, 713–720. CAS PubMed Google Scholar
Zheng, G., Zhang, Z., Dowell, C., Wala, E., Dwoskin, L. P., Holton, J. R., McIntosh, J. M. & Crooks, P. A. (2007). Bioorg. Med. Chem. Lett., 21, 2476–2479. CrossRef Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.