research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1147-1150
doi:10.1107/S2056989015016163

Comparison crystal structure 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-[(S)-2-methyl­pyrrolidin-1-yl]prop-1-yn-1-yl}-1,1′-biphen­yl

CROSSMARK_Color_square_no_text.svg
Anqi Wan,a Narsimha Reddy Penthala,a E. Kim Fifer,a Sean Parkinb and Peter A. Crooksa*

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

Edited by P. C. Healy, Griffith University, Australia (Received 5 August 2015; accepted 28 August 2015; online 12 September 2015)

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 asymmetric unit 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.

CCDC references: 1421219; 1421218

1. Chemical context

The title compounds (I)[link] and (II)[link] 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[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.]), and has shown analgesic effects in various animal pain models (Wala et al., 2012[Wala, E. P., Crooks, P. A., McIntosh, J. M. & Holtman, J. R. (2012). Anesth. Analg. 115, 713-720.]). The terminal aza-aromatic rings were replaced by pyrrolidine and (S)-2-methyl­pyrrolidine moieties in compounds (I)[link] and (II)[link], respectively. We report here the single-crystal X-ray structures of (I)[link] and (II)[link] to determine the conformations of these compounds.

2. Structural commentary

The title compounds, (I) and (II) are shown in Figs. 1[link] and 2[link], 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)[link] is triclinic, space group P[\overline{1}], while crystal (II)[link] is monoclinic, space group P21.

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with ellipsoids drawn at the 50% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], with ellipsoids drawn at the 50% probability level.

In each compound, individual bond lengths and angles are unremarkable. For compound (I)[link], the asymmetric unit contains two half mol­ecules (denoted A and B in Fig. 1[link]) such that the biphenyl rings straddle crystallographic inversion centres. As a result, the biphenyl groups are coplanar. In compound (II)[link], however, the biphenyl rings (C9–C14) and (C15–C20) are non-coplanar, with a dihedral angle of 28.76 (11)°. In crystals of (I)[link], 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)[link], 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)[link] or (II)[link].

4. Database survey

A search of the November 2014 release of the Cambridge Structure Database (Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]), with updates through May 2015, using the program Mogul (Bruno et al., 2004[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.]) 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 bimodal distribution of biphenyl torsion angles with a tight peak at 0° and a broader peak centred at 30°. The biphenyl torsion angles in (I)[link] and (II)[link] are thus not unusual.

5. Synthesis and crystallization

Synthetic procedures: Compound (I)[link], 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)[link]. 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)[link] was purified by column chromatography (di­chloro­methane/methanol, 100:3) (yield: 80%). Compound (II)[link] was prepared using the same experimental conditions as (I)[link] but utilizing (S)-2-methyl­pyrrolidine (66.3 mg, 0.78 mmol) instead of pyrrolidine. Column chromatography (di­chloro­methane/methanol 100:3) was then used for purification of (II)[link] (yield: 80%).

Crystallization: Yellow crystals of compounds (I)[link] and (II)[link] 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. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. In both structures, H atoms were found in difference Fourier maps, but subsequently included in the refinement using riding models. Constrained distances were set to 0.95 Å (Csp2H), 0.98 Å [RCH3, (II)[link] 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)[link] only] of the attached atom.

Table 1
Experimental details

  (I) (II)
Crystal data
Chemical formula C26H28N2 C28H32N2
Mr 368.50 396.55
Crystal system, space group Triclinic, P[\overline{1}] 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 Nonius KappaCCD
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.]) Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
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[Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249-259.])
Absolute structure parameter – −0.3 (10)
Computer programs: APEX2 and SAINT (Bruker, 2006[Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]), SCALEPACK and DENZO-SMN (Otwinowski & Minor, 2006[Otwinowski, Z. & Minor, W. (2006). International Tables for Crystallography, Vol. F, ch. 11.4, pp. 226-235. Chester: International Union of Crystallography.]), SHELXS97, XP in SHELXTL and SHELX (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014/6 and SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]) and CIFFIX (Parkin, 2013[Parkin, S. (2013). CIFFIX, https://xray.uky.edu/people/parkin/programs/ciffix]).

In (II)[link], the Flack parameter, 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 absolute configuration for the model of (II)[link] was dictated by the synthesis.

Refinement progress was checked using PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and by an R-tensor (Parkin, 2000[Parkin, S. (2000). Acta Cryst. A56, 157-162.]). The final models were further checked with the IUCr utility checkCIF.

Supporting information

CCDC references: 1421219; 1421218

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S2056989015016163/hg5457sup1.cif

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

checkCIF report


Chemical context top

\ 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.

Structural commentary top

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, space group P1, while crystal (II) is monoclinic, space group P21. In each compound, individual bond lengths and angles are unremarkable. For compound (I), the asymmetric unit 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.

Supra­molecular features top

Aside from weak van der Waals inter­actions, there are no noteworthy inter­molecular contacts in either (I) or (II).

Database survey top

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 bimodal distribution 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.

Synthesis and crystallization top

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 column chromatography (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. Column chromatography (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.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1. In both structures, H atoms were found in difference Fourier maps, but subsequently included in the refinement 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 Flack parameter, 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 absolute configuration 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.

Related literature top

For related literature, see: Bruno et al. (2004); Groom & Allen (2014); Parkin (2000); Spek (2009); Wala (2012); Zheng et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2006) for (I); COLLECT (Nonius, 1998) for (II). Cell refinement: 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), with ellipsoids drawn at the 50% probability level.
(I) 4,4'-Bis[3-(pyrrolidin-1-yl)prop-1-yn-1-yl]-1,1'-biphenyl top
Crystal data top
C26H28N2Z = 2
Mr = 368.50F(000) = 396
Triclinic, P1Dx = 1.220 Mg m−3
a = 6.2100 (1) ÅCu Kα radiation, λ = 1.54178 Å
b = 10.3089 (2) ÅCell parameters from 9977 reflections
c = 16.3082 (3) Åθ = 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) Å30.23 × 0.19 × 0.10 mm
Data collection top
Bruker X8 Proteum
diffractometer		3586 independent reflections
Radiation source: fine-focus rotating anode3451 reflections with I > 2σ(I)
Detector resolution: 5.6 pixels mm-1Rint = 0.044
φ and ω scansθmax = 68.2°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)		h = −7→7
Tmin = 0.811, Tmax = 0.929k = −12→6
13692 measured reflectionsl = −19→17
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039H-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 reflectionsΔρmax = 0.22 e Å−3
254 parametersΔρmin = −0.20 e Å−3
0 restraintsExtinction correction: SHELXL2014/6 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0061 (11)
Crystal data top
C26H28N2γ = 76.671 (1)°
Mr = 368.50V = 1003.49 (3) Å3
Triclinic, P1Z = 2
a = 6.2100 (1) ÅCu Kα radiation
b = 10.3089 (2) ŵ = 0.54 mm−1
c = 16.3082 (3) ÅT = 90 K
α = 86.317 (1)°0.23 × 0.19 × 0.10 mm
β = 81.202 (1)°
Data collection top
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 = 0.929Rint = 0.044
13692 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.03Δρmax = 0.22 e Å−3
3586 reflectionsΔρmin = −0.20 e Å−3
254 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1A0.90671 (15)0.09727 (9)0.80861 (5)0.0163 (2)
C1A1.11598 (18)0.01531 (11)0.83141 (7)0.0210 (3)
H1A11.23460.00100.78280.025*
H1A21.0951−0.07230.85550.025*
C2A1.1724 (2)0.09853 (12)0.89584 (7)0.0238 (3)
H2A11.26870.15820.86920.029*
H2A21.25000.04060.93810.029*
C3A0.9430 (2)0.17995 (12)0.93527 (7)0.0226 (3)
H3A10.91400.15750.99530.027*
H3A20.93590.27690.92800.027*
C4A0.77498 (18)0.13928 (11)0.88842 (7)0.0187 (2)
H4A10.71590.06510.91800.022*
H4A20.64860.21550.88100.022*
C5A0.79816 (19)0.02600 (11)0.75852 (7)0.0190 (2)
H5A10.7276−0.03790.79480.023*
H5A20.9128−0.02570.71670.023*
C6A0.62761 (18)0.11598 (10)0.71603 (7)0.0175 (2)
C7A0.49421 (18)0.18772 (10)0.67760 (6)0.0168 (2)
C8A0.34803 (18)0.27515 (10)0.62731 (7)0.0160 (2)
C9A0.43797 (18)0.32491 (10)0.55121 (7)0.0160 (2)
H9A0.59420.29930.53310.019*
C10A0.30252 (18)0.41090 (10)0.50192 (6)0.0156 (2)
H10A0.36770.44270.45030.019*
C11A0.07141 (17)0.45231 (9)0.52628 (6)0.0145 (2)
C12A−0.01727 (18)0.39888 (10)0.60194 (7)0.0177 (2)
H12A−0.17380.42320.61970.021*
C13A0.11676 (19)0.31184 (11)0.65140 (7)0.0182 (2)
H13A0.05130.27690.70200.022*
N1B0.65099 (16)0.52088 (9)0.86778 (6)0.0188 (2)
C1B0.84890 (19)0.56666 (12)0.82796 (7)0.0235 (3)
H1B10.81230.63260.78240.028*
H1B20.96880.49110.80560.028*
C2B0.9172 (2)0.63028 (13)0.89876 (8)0.0271 (3)
H2B10.99160.70350.87770.033*
H2B21.01990.56350.92930.033*
C3B0.6947 (2)0.68421 (12)0.95488 (7)0.0253 (3)
H3B10.70200.64981.01270.030*
H3B20.65940.78290.95460.030*
C4B0.51897 (19)0.63353 (11)0.91723 (7)0.0205 (3)
H4B10.41020.60410.96120.025*
H4B20.43730.70360.88180.025*
C5B0.52980 (19)0.47407 (11)0.80985 (7)0.0204 (3)
H5B10.40640.43860.84220.024*
H5B20.63260.39930.77900.024*
C6B0.43522 (19)0.57591 (11)0.74928 (7)0.0199 (3)
C7B0.35385 (19)0.66217 (11)0.70308 (7)0.0190 (3)
C8B0.25131 (18)0.76103 (10)0.64637 (6)0.0170 (2)
C9B0.06171 (19)0.74642 (11)0.61458 (7)0.0180 (2)
H9B−0.00180.67200.63220.022*
C10B−0.03435 (18)0.83874 (10)0.55795 (7)0.0173 (2)
H10B−0.16200.82590.53690.021*
C11B0.05162 (17)0.95096 (10)0.53077 (6)0.0155 (2)
C12B0.23930 (18)0.96591 (10)0.56433 (7)0.0175 (2)
H12B0.30021.04170.54810.021*
C13B0.33793 (18)0.87324 (11)0.62041 (7)0.0180 (2)
H13B0.46580.88580.64150.022*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N1A0.0170 (5)0.0163 (4)0.0157 (5)−0.0032 (4)−0.0031 (4)−0.0010 (3)
C1A0.0179 (5)0.0229 (6)0.0211 (6)−0.0011 (4)−0.0042 (4)−0.0021 (4)
C2A0.0220 (6)0.0290 (6)0.0221 (6)−0.0076 (5)−0.0056 (5)−0.0016 (5)
C3A0.0264 (6)0.0233 (6)0.0192 (6)−0.0064 (5)−0.0039 (5)−0.0032 (4)
C4A0.0191 (5)0.0188 (5)0.0173 (5)−0.0037 (4)−0.0004 (4)−0.0007 (4)
C5A0.0225 (6)0.0151 (5)0.0200 (5)−0.0034 (4)−0.0059 (4)−0.0013 (4)
C6A0.0200 (5)0.0162 (5)0.0174 (5)−0.0064 (4)−0.0019 (4)−0.0028 (4)
C7A0.0207 (5)0.0143 (5)0.0169 (5)−0.0067 (4)−0.0021 (4)−0.0028 (4)
C8A0.0209 (6)0.0111 (5)0.0175 (5)−0.0051 (4)−0.0047 (4)−0.0032 (4)
C9A0.0162 (5)0.0133 (5)0.0198 (5)−0.0053 (4)−0.0021 (4)−0.0034 (4)
C10A0.0190 (5)0.0124 (5)0.0163 (5)−0.0062 (4)−0.0012 (4)−0.0013 (4)
C11A0.0186 (5)0.0099 (5)0.0165 (5)−0.0055 (4)−0.0025 (4)−0.0037 (4)
C12A0.0170 (5)0.0168 (5)0.0186 (5)−0.0035 (4)0.0002 (4)−0.0017 (4)
C13A0.0216 (6)0.0167 (5)0.0162 (5)−0.0055 (4)−0.0008 (4)−0.0002 (4)
N1B0.0192 (5)0.0182 (5)0.0180 (5)−0.0030 (4)−0.0013 (4)−0.0010 (4)
C1B0.0199 (6)0.0284 (6)0.0214 (6)−0.0060 (5)0.0013 (4)−0.0028 (5)
C2B0.0230 (6)0.0339 (7)0.0262 (6)−0.0102 (5)−0.0022 (5)−0.0038 (5)
C3B0.0263 (6)0.0267 (6)0.0233 (6)−0.0063 (5)−0.0026 (5)−0.0054 (5)
C4B0.0201 (6)0.0212 (6)0.0190 (5)−0.0029 (4)−0.0006 (4)−0.0028 (4)
C5B0.0242 (6)0.0171 (5)0.0204 (6)−0.0059 (4)−0.0027 (4)−0.0002 (4)
C6B0.0224 (6)0.0192 (6)0.0190 (6)−0.0073 (4)−0.0013 (4)−0.0030 (4)
C7B0.0214 (6)0.0180 (5)0.0181 (5)−0.0062 (4)−0.0001 (4)−0.0041 (4)
C8B0.0201 (5)0.0153 (5)0.0146 (5)−0.0026 (4)0.0008 (4)−0.0046 (4)
C9B0.0230 (6)0.0141 (5)0.0181 (5)−0.0075 (4)0.0004 (4)−0.0037 (4)
C10B0.0186 (5)0.0157 (5)0.0190 (5)−0.0061 (4)−0.0014 (4)−0.0047 (4)
C11B0.0171 (5)0.0131 (5)0.0159 (5)−0.0037 (4)0.0016 (4)−0.0054 (4)
C12B0.0184 (5)0.0144 (5)0.0204 (5)−0.0067 (4)0.0003 (4)−0.0032 (4)
C13B0.0173 (5)0.0179 (5)0.0191 (5)−0.0044 (4)−0.0012 (4)−0.0047 (4)
Geometric parameters (Å, º) top
N1A—C4A1.4609 (13)N1B—C5B1.4613 (14)
N1A—C5A1.4612 (13)N1B—C1B1.4625 (15)
N1A—C1A1.4637 (14)N1B—C4B1.4663 (14)
C1A—C2A1.5264 (15)C1B—C2B1.5228 (16)
C1A—H1A10.9900C1B—H1B10.9900
C1A—H1A20.9900C1B—H1B20.9900
C2A—C3A1.5442 (16)C2B—C3B1.5430 (17)
C2A—H2A10.9900C2B—H2B10.9900
C2A—H2A20.9900C2B—H2B20.9900
C3A—C4A1.5283 (15)C3B—C4B1.5329 (16)
C3A—H3A10.9900C3B—H3B10.9900
C3A—H3A20.9900C3B—H3B20.9900
C4A—H4A10.9900C4B—H4B10.9900
C4A—H4A20.9900C4B—H4B20.9900
C5A—C6A1.4667 (15)C5B—C6B1.4775 (15)
C5A—H5A10.9900C5B—H5B10.9900
C5A—H5A20.9900C5B—H5B20.9900
C6A—C7A1.2012 (16)C6B—C7B1.1987 (16)
C7A—C8A1.4369 (15)C7B—C8B1.4350 (15)
C8A—C9A1.3976 (15)C8B—C9B1.3986 (16)
C8A—C13A1.3986 (16)C8B—C13B1.4003 (16)
C9A—C10A1.3825 (15)C9B—C10B1.3815 (15)
C9A—H9A0.9500C9B—H9B0.9500
C10A—C11A1.4017 (15)C10B—C11B1.4023 (15)
C10A—H10A0.9500C10B—H10B0.9500
C11A—C12A1.4049 (15)C11B—C12B1.4037 (15)
C11A—C11Ai1.487 (2)C11B—C11Bii1.486 (2)
C12A—C13A1.3844 (15)C12B—C13B1.3834 (15)
C12A—H12A0.9500C12B—H12B0.9500
C13A—H13A0.9500C13B—H13B0.9500
C4A—N1A—C5A114.19 (9)C5B—N1B—C1B114.00 (9)
C4A—N1A—C1A103.63 (8)C5B—N1B—C4B114.41 (9)
C5A—N1A—C1A112.60 (8)C1B—N1B—C4B104.43 (9)
N1A—C1A—C2A102.99 (9)N1B—C1B—C2B102.86 (9)
N1A—C1A—H1A1111.2N1B—C1B—H1B1111.2
C2A—C1A—H1A1111.2C2B—C1B—H1B1111.2
N1A—C1A—H1A2111.2N1B—C1B—H1B2111.2
C2A—C1A—H1A2111.2C2B—C1B—H1B2111.2
H1A1—C1A—H1A2109.1H1B1—C1B—H1B2109.1
C1A—C2A—C3A104.25 (9)C1B—C2B—C3B104.18 (9)
C1A—C2A—H2A1110.9C1B—C2B—H2B1110.9
C3A—C2A—H2A1110.9C3B—C2B—H2B1110.9
C1A—C2A—H2A2110.9C1B—C2B—H2B2110.9
C3A—C2A—H2A2110.9C3B—C2B—H2B2110.9
H2A1—C2A—H2A2108.9H2B1—C2B—H2B2108.9
C4A—C3A—C2A104.34 (9)C4B—C3B—C2B104.86 (9)
C4A—C3A—H3A1110.9C4B—C3B—H3B1110.8
C2A—C3A—H3A1110.9C2B—C3B—H3B1110.8
C4A—C3A—H3A2110.9C4B—C3B—H3B2110.8
C2A—C3A—H3A2110.9C2B—C3B—H3B2110.8
H3A1—C3A—H3A2108.9H3B1—C3B—H3B2108.9
N1A—C4A—C3A103.36 (9)N1B—C4B—C3B103.67 (9)
N1A—C4A—H4A1111.1N1B—C4B—H4B1111.0
C3A—C4A—H4A1111.1C3B—C4B—H4B1111.0
N1A—C4A—H4A2111.1N1B—C4B—H4B2111.0
C3A—C4A—H4A2111.1C3B—C4B—H4B2111.0
H4A1—C4A—H4A2109.1H4B1—C4B—H4B2109.0
N1A—C5A—C6A112.54 (8)N1B—C5B—C6B115.14 (9)
N1A—C5A—H5A1109.1N1B—C5B—H5B1108.5
C6A—C5A—H5A1109.1C6B—C5B—H5B1108.5
N1A—C5A—H5A2109.1N1B—C5B—H5B2108.5
C6A—C5A—H5A2109.1C6B—C5B—H5B2108.5
H5A1—C5A—H5A2107.8H5B1—C5B—H5B2107.5
C7A—C6A—C5A176.79 (11)C7B—C6B—C5B177.04 (11)
C6A—C7A—C8A175.84 (11)C6B—C7B—C8B177.29 (11)
C9A—C8A—C13A118.34 (10)C9B—C8B—C13B118.07 (10)
C9A—C8A—C7A119.38 (10)C9B—C8B—C7B120.32 (10)
C13A—C8A—C7A122.28 (10)C13B—C8B—C7B121.61 (10)
C10A—C9A—C8A120.86 (10)C10B—C9B—C8B120.86 (10)
C10A—C9A—H9A119.6C10B—C9B—H9B119.6
C8A—C9A—H9A119.6C8B—C9B—H9B119.6
C9A—C10A—C11A121.62 (10)C9B—C10B—C11B121.74 (10)
C9A—C10A—H10A119.2C9B—C10B—H10B119.1
C11A—C10A—H10A119.2C11B—C10B—H10B119.1
C10A—C11A—C12A116.84 (10)C10B—C11B—C12B116.87 (10)
C10A—C11A—C11Ai121.06 (12)C10B—C11B—C11Bii121.34 (12)
C12A—C11A—C11Ai122.10 (12)C12B—C11B—C11Bii121.79 (11)
C13A—C12A—C11A121.94 (10)C13B—C12B—C11B121.76 (10)
C13A—C12A—H12A119.0C13B—C12B—H12B119.1
C11A—C12A—H12A119.0C11B—C12B—H12B119.1
C12A—C13A—C8A120.35 (10)C12B—C13B—C8B120.68 (10)
C12A—C13A—H13A119.8C12B—C13B—H13B119.7
C8A—C13A—H13A119.8C8B—C13B—H13B119.7
C4A—N1A—C1A—C2A−45.38 (10)C5B—N1B—C1B—C2B170.74 (9)
C5A—N1A—C1A—C2A−169.28 (9)C4B—N1B—C1B—C2B45.18 (11)
N1A—C1A—C2A—C3A27.96 (11)N1B—C1B—C2B—C3B−30.78 (12)
C1A—C2A—C3A—C4A−1.49 (11)C1B—C2B—C3B—C4B6.22 (12)
C5A—N1A—C4A—C3A167.28 (9)C5B—N1B—C4B—C3B−166.33 (9)
C1A—N1A—C4A—C3A44.43 (10)C1B—N1B—C4B—C3B−41.02 (11)
C2A—C3A—C4A—N1A−25.57 (11)C2B—C3B—C4B—N1B20.48 (12)
C4A—N1A—C5A—C6A78.62 (11)C1B—N1B—C5B—C6B−62.66 (13)
C1A—N1A—C5A—C6A−163.55 (9)C4B—N1B—C5B—C6B57.45 (13)
C13A—C8A—C9A—C10A1.59 (15)C13B—C8B—C9B—C10B1.28 (15)
C7A—C8A—C9A—C10A−178.97 (9)C7B—C8B—C9B—C10B−177.95 (9)
C8A—C9A—C10A—C11A0.51 (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—C11Ai178.33 (10)C9B—C10B—C11B—C11Bii179.42 (11)
C10A—C11A—C12A—C13A1.47 (15)C10B—C11B—C12B—C13B1.19 (15)
C11Ai—C11A—C12A—C13A−178.88 (11)C11Bii—C11B—C12B—C13B−178.74 (11)
C11A—C12A—C13A—C8A0.58 (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—C12A178.46 (9)C7B—C8B—C13B—C12B178.61 (9)
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1.
(II) 4,4'-Bis{3-[(S)-2-methylpyrrolidin-1-yl]prop-1-yn-1-yl}-1,1'-biphenyl top
Crystal data top
C28H32N2F(000) = 428
Mr = 396.55Dx = 1.178 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 8.1411 (4) ÅCell parameters from 2730 reflections
b = 7.3080 (4) Åθ = 1.0–27.5°
c = 18.9840 (9) ŵ = 0.07 mm−1
β = 98.177 (3)°T = 90 K
V = 1117.97 (10) Å3Cut slab, colourless
Z = 20.41 × 0.35 × 0.08 mm
Data collection top
Nonius KappaCCD
diffractometer		4705 independent reflections
Radiation source: fine-focus sealed-tube3548 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1Rint = 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 = 0.971k = −8→9
15874 measured reflectionsl = −24→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054H-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 reflectionsΔρmax = 0.30 e Å−3
273 parametersΔρmin = −0.19 e Å−3
1 restraintAbsolute 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 methodsAbsolute structure parameter: −0.3 (10)
Crystal data top
C28H32N2V = 1117.97 (10) Å3
Mr = 396.55Z = 2
Monoclinic, P21Mo Kα radiation
a = 8.1411 (4) ŵ = 0.07 mm−1
b = 7.3080 (4) ÅT = 90 K
c = 18.9840 (9) Å0.41 × 0.35 × 0.08 mm
β = 98.177 (3)°
Data collection top
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 = 0.971Rint = 0.085
15874 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.144Δρmax = 0.30 e Å−3
S = 1.05Δρmin = −0.19 e Å−3
4705 reflectionsAbsolute structure: Flack x parameter was determined using 1205 quotients of the form [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
273 parametersAbsolute structure parameter: −0.3 (10)
1 restraint
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N1−0.0921 (3)0.5633 (4)0.18120 (12)0.0294 (6)
N21.5991 (3)0.4631 (4)0.82088 (11)0.0288 (6)
C1−0.0274 (4)0.7478 (5)0.17326 (15)0.0333 (7)
H1A0.08460.76190.20080.040*
H1B−0.10210.84130.18920.040*
C2−0.0213 (4)0.7632 (5)0.09382 (16)0.0384 (8)
H2A0.07670.83450.08450.046*
H2B−0.12290.82260.06920.046*
C3−0.0094 (4)0.5640 (5)0.06935 (15)0.0381 (8)
H3A−0.10850.53000.03540.046*
H3B0.09070.54590.04600.046*
C40.0011 (3)0.4496 (5)0.13712 (15)0.0327 (7)
H4A0.11950.44240.15990.039*
C5−0.0680 (5)0.2582 (6)0.12600 (18)0.0533 (10)
H5A−0.05620.19380.17170.080*
H5B−0.00690.19200.09310.080*
H5C−0.18570.26470.10600.080*
C6−0.0833 (3)0.5055 (5)0.25511 (14)0.0336 (8)
H6A−0.13210.38160.25600.040*
H6B−0.15270.58920.27940.040*
C70.0854 (3)0.5015 (4)0.29597 (14)0.0296 (7)
C80.2237 (3)0.5035 (4)0.32840 (13)0.0258 (6)
C90.3832 (3)0.5132 (4)0.37271 (13)0.0251 (6)
C100.5206 (3)0.4133 (4)0.35812 (14)0.0263 (6)
H10A0.51280.34110.31620.032*
C110.6689 (3)0.4188 (4)0.40464 (13)0.0249 (6)
H11A0.76140.35080.39370.030*
C120.6847 (3)0.5219 (4)0.46694 (13)0.0243 (6)
C130.5480 (3)0.6270 (4)0.47988 (14)0.0254 (6)
H13A0.55690.70260.52100.030*
C140.4002 (3)0.6225 (4)0.43367 (13)0.0257 (6)
H14A0.30910.69470.44360.031*
C150.8386 (3)0.5167 (4)0.51885 (13)0.0239 (6)
C160.9931 (4)0.4757 (4)0.49786 (15)0.0261 (6)
H16A1.00100.45930.44880.031*
C171.1338 (3)0.4589 (4)0.54754 (14)0.0271 (7)
H17A1.23690.43200.53190.033*
C181.1278 (3)0.4805 (4)0.61967 (13)0.0247 (6)
C190.9756 (3)0.5261 (4)0.64146 (14)0.0276 (7)
H19A0.96900.54560.69050.033*
C200.8343 (3)0.5429 (4)0.59141 (14)0.0271 (7)
H20A0.73190.57310.60700.033*
C211.2782 (3)0.4600 (5)0.66923 (13)0.0287 (7)
C221.4103 (3)0.4380 (5)0.70559 (14)0.0318 (7)
C231.5765 (3)0.4087 (6)0.74681 (14)0.0388 (9)
H23A1.60340.27690.74460.047*
H23B1.65830.47600.72280.047*
C241.5747 (4)0.6593 (5)0.83087 (16)0.0364 (7)
H24A1.46660.70040.80530.044*
H24B1.66460.73150.81420.044*
C251.5796 (5)0.6761 (6)0.91101 (17)0.0487 (10)
H25A1.50390.77380.92290.058*
H25B1.69340.70340.93460.058*
C261.5222 (4)0.4886 (6)0.93362 (15)0.0439 (9)
H26A1.60960.42980.96780.053*
H26B1.42040.50030.95630.053*
C271.4879 (4)0.3770 (5)0.86523 (16)0.0347 (8)
H27A1.37060.39870.84310.042*
C281.5151 (4)0.1744 (5)0.8746 (2)0.0535 (10)
H28A1.49180.11370.82820.080*
H28C1.44080.12620.90640.080*
H28D1.63060.15130.89520.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0231 (12)0.0336 (16)0.0301 (12)0.0017 (11)−0.0014 (9)−0.0003 (11)
N20.0211 (12)0.0362 (16)0.0283 (12)−0.0022 (11)0.0011 (9)−0.0015 (12)
C10.0264 (15)0.0318 (19)0.0403 (17)0.0012 (14)−0.0002 (12)0.0003 (15)
C20.0305 (17)0.041 (2)0.0421 (17)0.0034 (15)−0.0011 (13)0.0105 (16)
C30.0361 (17)0.047 (2)0.0307 (15)−0.0027 (16)0.0015 (12)−0.0005 (15)
C40.0256 (15)0.038 (2)0.0336 (15)0.0000 (14)−0.0002 (12)−0.0055 (14)
C50.069 (3)0.039 (2)0.051 (2)−0.007 (2)0.0060 (18)−0.0085 (18)
C60.0225 (14)0.044 (2)0.0334 (15)−0.0034 (14)0.0028 (11)0.0003 (15)
C70.0272 (15)0.0339 (19)0.0274 (13)0.0008 (13)0.0034 (11)0.0004 (14)
C80.0279 (14)0.0249 (17)0.0246 (13)0.0006 (12)0.0036 (11)0.0004 (12)
C90.0249 (14)0.0244 (17)0.0259 (13)−0.0009 (12)0.0035 (10)0.0051 (12)
C100.0289 (15)0.0260 (17)0.0239 (13)−0.0005 (13)0.0031 (11)−0.0023 (12)
C110.0223 (14)0.0268 (17)0.0262 (13)0.0014 (12)0.0053 (10)0.0038 (12)
C120.0206 (13)0.0245 (17)0.0274 (13)−0.0017 (12)0.0021 (10)0.0043 (13)
C130.0270 (14)0.0215 (16)0.0279 (14)−0.0007 (12)0.0048 (11)−0.0027 (13)
C140.0224 (13)0.0252 (17)0.0299 (14)0.0030 (12)0.0044 (11)0.0011 (13)
C150.0196 (13)0.0209 (17)0.0304 (13)−0.0036 (12)0.0009 (10)0.0008 (13)
C160.0266 (13)0.0249 (17)0.0271 (12)−0.0010 (13)0.0052 (10)0.0000 (13)
C170.0190 (13)0.0267 (17)0.0358 (14)−0.0007 (12)0.0047 (11)0.0023 (13)
C180.0221 (13)0.0191 (16)0.0318 (14)−0.0039 (12)0.0002 (10)−0.0002 (12)
C190.0245 (14)0.0334 (19)0.0248 (13)−0.0003 (13)0.0024 (10)−0.0033 (13)
C200.0212 (13)0.0303 (18)0.0301 (14)0.0008 (12)0.0041 (10)−0.0001 (13)
C210.0275 (15)0.0292 (19)0.0296 (14)0.0002 (13)0.0042 (11)−0.0007 (13)
C220.0273 (15)0.037 (2)0.0301 (14)0.0024 (14)0.0015 (11)−0.0019 (14)
C230.0223 (15)0.060 (3)0.0331 (15)0.0071 (15)0.0003 (12)−0.0025 (16)
C240.0350 (16)0.0319 (19)0.0395 (17)−0.0074 (14)−0.0047 (13)0.0015 (15)
C250.053 (2)0.048 (3)0.0425 (19)−0.0021 (18)−0.0044 (16)−0.0102 (17)
C260.0386 (18)0.062 (3)0.0307 (15)0.0077 (17)0.0050 (13)0.0041 (17)
C270.0204 (15)0.041 (2)0.0423 (17)−0.0013 (13)0.0015 (13)0.0094 (15)
C280.0384 (19)0.038 (2)0.079 (3)−0.0052 (17)−0.0083 (17)0.0178 (19)
Geometric parameters (Å, º) top
N1—C61.457 (4)C13—C141.385 (3)
N1—C11.463 (4)C13—H13A0.9500
N1—C41.465 (4)C14—H14A0.9500
N2—C231.448 (3)C15—C201.396 (4)
N2—C271.463 (4)C15—C161.405 (4)
N2—C241.464 (4)C16—C171.381 (4)
C1—C21.520 (4)C16—H16A0.9500
C1—H1A0.9900C17—C181.386 (4)
C1—H1B0.9900C17—H17A0.9500
C2—C31.536 (5)C18—C191.401 (4)
C2—H2A0.9900C18—C211.442 (3)
C2—H2B0.9900C19—C201.389 (4)
C3—C41.526 (4)C19—H19A0.9500
C3—H3A0.9900C20—H20A0.9500
C3—H3B0.9900C21—C221.203 (4)
C4—C51.511 (5)C22—C231.479 (4)
C4—H4A1.0000C23—H23A0.9900
C5—H5A0.9800C23—H23B0.9900
C5—H5B0.9800C24—C251.521 (4)
C5—H5C0.9800C24—H24A0.9900
C6—C71.479 (4)C24—H24B0.9900
C6—H6A0.9900C25—C261.529 (6)
C6—H6B0.9900C25—H25A0.9900
C7—C81.204 (3)C25—H25B0.9900
C8—C91.445 (3)C26—C271.525 (5)
C9—C101.396 (4)C26—H26A0.9900
C9—C141.397 (4)C26—H26B0.9900
C10—C111.391 (3)C27—C281.504 (5)
C10—H10A0.9500C27—H27A1.0000
C11—C121.393 (4)C28—H28A0.9800
C11—H11A0.9500C28—H28C0.9800
C12—C131.403 (4)C28—H28D0.9800
C12—C151.480 (3)
C6—N1—C1113.4 (2)C13—C14—C9120.8 (2)
C6—N1—C4115.3 (2)C13—C14—H14A119.6
C1—N1—C4103.9 (2)C9—C14—H14A119.6
C23—N2—C27115.9 (2)C20—C15—C16117.2 (2)
C23—N2—C24113.2 (3)C20—C15—C12121.1 (2)
C27—N2—C24103.9 (2)C16—C15—C12121.6 (2)
N1—C1—C2103.5 (2)C17—C16—C15120.9 (2)
N1—C1—H1A111.1C17—C16—H16A119.5
C2—C1—H1A111.1C15—C16—H16A119.5
N1—C1—H1B111.1C16—C17—C18121.5 (2)
C2—C1—H1B111.1C16—C17—H17A119.3
H1A—C1—H1B109.0C18—C17—H17A119.3
C1—C2—C3104.0 (3)C17—C18—C19118.4 (2)
C1—C2—H2A111.0C17—C18—C21119.1 (2)
C3—C2—H2A111.0C19—C18—C21122.4 (2)
C1—C2—H2B111.0C20—C19—C18120.0 (2)
C3—C2—H2B111.0C20—C19—H19A120.0
H2A—C2—H2B109.0C18—C19—H19A120.0
C4—C3—C2105.2 (3)C19—C20—C15121.9 (2)
C4—C3—H3A110.7C19—C20—H20A119.0
C2—C3—H3A110.7C15—C20—H20A119.0
C4—C3—H3B110.7C22—C21—C18174.2 (3)
C2—C3—H3B110.7C21—C22—C23177.0 (3)
H3A—C3—H3B108.8N2—C23—C22117.0 (2)
N1—C4—C5113.1 (3)N2—C23—H23A108.0
N1—C4—C3101.5 (3)C22—C23—H23A108.0
C5—C4—C3114.5 (3)N2—C23—H23B108.0
N1—C4—H4A109.2C22—C23—H23B108.0
C5—C4—H4A109.2H23A—C23—H23B107.3
C3—C4—H4A109.2N2—C24—C25102.9 (3)
C4—C5—H5A109.5N2—C24—H24A111.2
C4—C5—H5B109.5C25—C24—H24A111.2
H5A—C5—H5B109.5N2—C24—H24B111.2
C4—C5—H5C109.5C25—C24—H24B111.2
H5A—C5—H5C109.5H24A—C24—H24B109.1
H5B—C5—H5C109.5C24—C25—C26104.1 (3)
N1—C6—C7115.2 (2)C24—C25—H25A110.9
N1—C6—H6A108.5C26—C25—H25A110.9
C7—C6—H6A108.5C24—C25—H25B110.9
N1—C6—H6B108.5C26—C25—H25B110.9
C7—C6—H6B108.5H25A—C25—H25B109.0
H6A—C6—H6B107.5C27—C26—C25105.5 (2)
C8—C7—C6177.9 (3)C27—C26—H26A110.7
C7—C8—C9174.7 (3)C25—C26—H26A110.7
C10—C9—C14118.4 (2)C27—C26—H26B110.7
C10—C9—C8122.5 (2)C25—C26—H26B110.7
C14—C9—C8119.0 (2)H26A—C26—H26B108.8
C11—C10—C9120.4 (2)N2—C27—C28113.5 (3)
C11—C10—H10A119.8N2—C27—C26101.9 (3)
C9—C10—H10A119.8C28—C27—C26114.8 (3)
C10—C11—C12121.5 (3)N2—C27—H27A108.8
C10—C11—H11A119.3C28—C27—H27A108.8
C12—C11—H11A119.3C26—C27—H27A108.8
C11—C12—C13117.7 (2)C27—C28—H28A109.5
C11—C12—C15121.3 (2)C27—C28—H28C109.5
C13—C12—C15121.0 (2)H28A—C28—H28C109.5
C14—C13—C12121.0 (2)C27—C28—H28D109.5
C14—C13—H13A119.5H28A—C28—H28D109.5
C12—C13—H13A119.5H28C—C28—H28D109.5
C6—N1—C1—C2170.4 (2)C11—C12—C15—C1626.8 (4)
C4—N1—C1—C244.5 (3)C13—C12—C15—C16−155.0 (3)
N1—C1—C2—C3−24.3 (3)C20—C15—C16—C171.2 (4)
C1—C2—C3—C4−3.3 (3)C12—C15—C16—C17−175.5 (3)
C6—N1—C4—C566.3 (3)C15—C16—C17—C180.4 (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—C21179.5 (3)
C1—N1—C4—C3−45.9 (3)C17—C18—C19—C202.0 (4)
C2—C3—C4—N129.5 (3)C21—C18—C19—C20−179.6 (3)
C2—C3—C4—C5151.6 (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—C759.8 (4)C12—C15—C20—C19175.5 (3)
C14—C9—C10—C112.0 (4)C27—N2—C23—C2257.8 (4)
C8—C9—C10—C11−176.2 (3)C24—N2—C23—C22−62.1 (4)
C9—C10—C11—C120.5 (4)C23—N2—C24—C25172.0 (2)
C10—C11—C12—C13−2.8 (4)C27—N2—C24—C2545.4 (3)
C10—C11—C12—C15175.5 (2)N2—C24—C25—C26−26.8 (3)
C11—C12—C13—C142.6 (4)C24—C25—C26—C27−0.1 (3)
C15—C12—C13—C14−175.7 (3)C23—N2—C27—C2866.2 (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—C13176.1 (3)C24—N2—C27—C26−44.9 (3)
C11—C12—C15—C20−149.7 (3)C25—C26—C27—N226.9 (3)
C13—C12—C15—C2028.5 (4)C25—C26—C27—C28150.0 (3)

Experimental details

(I)(II)
Crystal data
Chemical formulaC26H28N2C28H32N2
Mr368.50396.55
Crystal system, space groupTriclinic, P1Monoclinic, P21
Temperature (K)9090
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)
Z22
Radiation typeCu KαMo Kα
µ (mm−1)0.540.07
Crystal size (mm)0.23 × 0.19 × 0.100.41 × 0.35 × 0.08
Data collection
DiffractometerBruker X8 Proteum
diffractometer		Nonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Krause et al., 2015)		Multi-scan
(SADABS; Krause et al., 2015)
Tmin, Tmax0.811, 0.9290.791, 0.971
No. of measured, independent and
observed [I > 2σ(I)] reflections		13692, 3586, 3451 15874, 4705, 3548
Rint0.0440.085
(sin θ/λ)max (Å−1)0.6020.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.03 0.054, 0.144, 1.05
No. of reflections35864705
No. of parameters254273
No. of restraints01
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.22, −0.200.30, −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

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1147-1150
doi:10.1107/S2056989015016163
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