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 1132-1135
doi:10.1107/S2056989015015352

Comparison of the crystal structures of 4,4′-bis­­[3-(4-methyl­piperidin-1-yl)prop-1-yn-1-yl]-1,1′-bi­phenyl and 4,4′-bis­­[3-(2,2,6,6-tetra­methyl­piperidin-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*

aDepartment of Pharmaceutical Sciences, College of Pharmacy, University of Arkansas for Medical Sciences, Little Rock, AR 72205, USA, and bDepartment of Chemistry, University of Kentucky, Lexington KY 40506, USA
*Correspondence e-mail: pacrooks@uams.edu

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 1 July 2015; accepted 17 August 2015; online 12 September 2015)

As part of a comprehensive program to discover α9α10 nicotinic acetyl­choline receptor antagonists, the title compounds C30H36N2, (I), and C36H48N2, (II), were synthesized by coupling 4,4′-bis­(3-bromo­prop-1-yn-1-yl)-1,1′-biphenyl with 4-methyl­piperidine and 2,2,6,6-tetra­methyl­piperidine, respectively, in aceto­nitrile at room temperature. In compound (I), the biphenyl system has a twisted conformation with a dihedral angle of 26.57 (6)° between the two phenyl rings of the biphenyl moiety, while in compound (II), the biphenyl moiety sits on a crystallographic inversion centre so the two phenyl rings are exactly coplanar. The terminal piperidine rings in both compound (I) and compound (II) are in the chair conformation. In compound (I), the dihedral angles about the ethynyl groups between the planes of the phenyl rings and the piperidine ring N atoms are 37.16 (16) and 14.20 (17)°. In compound (II), the corresponding dihedral angles are both 61.48 (17)°. There are no noteworthy inter­molecular inter­actions in (I), but in (II) there is a small π-overlap between inversion-related mol­ecules (1 − x, 1 − y, 1 − z), with an inter­planar spacing of 3.553 (3) Å and centroid-to-centroid separation of 3.859 (4) Å.

CCDC references: 1419252; 1419251

1. Chemical context

Previous studies have shown that the bis-quaternary ammonium compound 1′-[(1,1′-biphen­yl)-4,4′-diylbis(prop-2-yne-3,1-di­yl)]bis­(3,4-di­methyl­pyridin-1-ium) bromide (ZZ161C) is a potent and selective α9α10 nicotinic acetyl­choline receptor antagonist (Zheng et al., 2011[Zheng, G., Zhang, Z., Dowell, C., Wala, E., Dwoskin, L. P., Holtman, J. R., McIntosh, J. M. & Crooks, P. A. (2011). Bioorg. Med. Chem. Lett. 21, 2476-2479.]). ZZ161C has been reported to have analgesic effects in various animal pain models (Wala et al., 2012[Wala, E. P., Crooks, P. A., McIntosh, J. M. & Holtman, J. R. Jr (2012). Anesth. Analg. 115, 713-720.]). In order to improve the pharmacological and pharmacokinetic profile of ZZ161C, we have replaced the terminal aza­aromatic rings with fully reduced piperidine rings to obtain the title compounds (I)[link] and (II)[link]. Single-crystal X-ray structure determinations were carried out to determine the conformations of these compounds.

2. Structural commentary

The title compounds, C30H36N2 (I)[link] and C36H48N2 (II)[link] are shown in Figs. 1[link] and 2[link], respectively. The present X-ray crystallographic study was carried out in order to ascertain the geometry of the piperidine rings and the biphenyl ring systems, as well as to obtain more detailed information about the conformation of the title compounds. Crystals of both (I)[link] and (II)[link] are monoclinic, space group P21/c, with Z′ = 1 and 0.5, respectively. In each compound, individual bond lengths and angles are unremarkable.

[Scheme 1]
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with displacement ellipsoids drawn at the 50% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are generated by the symmetry operator (1 − x, 2 − y, 1 − z).

The piperidine rings in both of the title mol­ecules are in the chair conformation. In (I)[link], the biphenyl rings (C20-C21-C22-C23-C30-C29) and (C16-C17-C18-C19-C28-C27) are non-coplanar, with a dihedral angle of 26.57 (6)°. For compound (II)[link], however, the biphenyl group is strictly coplanar because the mol­ecule sits on a crystallographic inversion centre. In compound (I)[link], the dihedral angles about the ethynyl groups between the planes of the phenyl rings and the piperidine ring N atoms are 37.16 (16) and 14.20 (17)°. In compound (II)[link], the corresponding dihedral angles are both 61.48 (17)°.

3. Supra­molecular features

Other than weak van der Waals inter­actions, there are no noteworthy inter­molecular contacts in (I)[link]. In (II)[link] there is a small π-overlap between inversion-related mol­ecules (1 − x, 1 − y, 1 − z), giving an inter­planar spacing of 3.553 (3) Å and centroid-to-centroid separation of 3.859 (4) Å.

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 hits, which gave a bimodal distribution of biphenyl dihedral angles with a tight peak at 0° and a broader peak centred at 30°. The biphenyl dihedral angles in (I)[link] and (II)[link] are thus not unusual.

5. Synthesis and crystallization

In the synthesis of 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. Bis-(tri­phenyl­phos­phine)palladium(II) dichloride and copper(I) iodide were used as catalysts. The mixture 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 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 4-methyl­piperidine (77.2 mg, 0.78 mmol) and the reaction mixture stirred for two hours 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 and combined. The extract (organic layer) was dried over anhydrous sodium sulfate, filtered, and the filtrate concentrated under reduced pressure. The resulting crude sample of compound (I)[link] was purified by column chromatography (di­chloro­methane/methanol, 100:2 v/v). Yield: 80%.

A crude sample of compound (II)[link] was prepared using the same experimental conditions for the preparation of compound (I)[link] but utilizing 2,2,6,6-tetra­methyl­piperidine (110.0 mg, 0.78 mmol) instead of 4-methyl­piperidine. Column chromatography (dichlormethane/methanol 100:2 v/v) was then used for purification of (II)[link]. Yield: 80%.

Compound (I)[link] and (II)[link] were each dissolved separately in a mixture of di­chloro­methane/methanol (2:1 v/v). Yellow crystals of both compounds were obtained by slow evaporation of the solution at room temperature over 24 h.

Compound (I)[link] 1H-NMR (400 Mz, CDCl3): δ 7.49 (q, 8H), 3.52 (s, 4H), 2.97 (d, 4H), 2.26 (t, 4H) p.p.m.; 13C-NMR (100 Mz, CDCl3): δ 132.92, 132.19, 126.76, 122.36, 85.13, 52.83, 48.09, 34.02, 30.20, 21.74 p.p.m.

Compound (II)[link] 1H-NMR (400 Mz, CDCl3): δ 7.50 (q, 8H), 3.62 (s, 4H), 1.61–1.60 (m, 8H), 1.52–1.51 (m, 4H), 1.22 (s, 24H) p.p.m. 13C-NMR (100 Mz, CDCl3): δ 139.47, 131.88, 126.61, 123.42, 94.00, 80.78, 55.00, 41.16, 33.87, 27.49, 17.81 p.p.m.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1[link]. H atoms were found in difference Fourier maps, but subsequently included in the refinement using riding models, with constrained distances set to 0.95 Å (Csp2H), 0.98 Å (RCH3), 0.99 Å (R2CH2) and 1.00 Å (R3CH). Uiso(H) parameters were set to values of either 1.2Ueq(C) or 1.5Ueq(C) (RCH3 only) of the attached atom. The final models were checked using an R-tensor (Parkin, 2000[Parkin, S. (2000). Acta Cryst. A56, 157-162.]) and by PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Table 1
Experimental details

  (I) (II)
Crystal data
Chemical formula C30H36N2 C36H48N2
Mr 424.61 508.76
Crystal system, space group Monoclinic, P21/c Monoclinic, P21/c
Temperature (K) 90 90
a, b, c (Å) 21.9870 (6), 7.0390 (3), 15.7840 (11) 16.0591 (3), 6.2267 (1), 15.5921 (3)
β (°) 99.0310 (19) 100.895 (1)
V (Å3) 2412.6 (2) 1531.03 (5)
Z 4 2
Radiation type Mo Kα Cu Kα
μ (mm−1) 0.07 0.47
Crystal size (mm) 0.32 × 0.30 × 0.03 0.22 × 0.04 × 0.03
 
Data collection
Diffractometer Nonius KappaCCD Bruker X8 Proteum
Absorption correction Multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.]) Multi-scan (SADABS; Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.764, 0.958 0.767, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections 54455, 5546, 3347 19631, 2797, 2405
Rint 0.066 0.053
(sin θ/λ)max (Å−1) 0.650 0.602
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.144, 1.02 0.050, 0.137, 1.05
No. of reflections 5546 2797
No. of parameters 291 176
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.22, −0.22 0.24, −0.24
Computer programs: COLLECT (Nonius, 1998[Nonius (1998). Collect Nonius BV, Delft, The Netherlands.]), APEX2 and SAINT (Bruker, 2006[Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SCALEPACK and DENZO-SMN (Otwinowski & Minor, 2006[Otwinowski, Z. & Minor, W. (2006). International Tables for Crystallography, Vol. F, ch. 11.4, 226-235. Dordrecht: Kluwer Academic Publishers.]), SHELXS97, SHELXTL and XP in SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]), 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]).

Supporting information

CCDC references: 1419252; 1419251

Crystal structure: contains datablocks global, I, II. DOI: 10.1107/S2056989015015352/rz5164sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015015352/rz5164Isup2.hkl

Structure factors: contains datablock II. DOI: 10.1107/S2056989015015352/rz5164IIsup3.hkl

Supporting information file. DOI: 10.1107/S2056989015015352/rz5164Isup4.cml

Supporting information file. DOI: 10.1107/S2056989015015352/rz5164IIsup5.cml

checkCIF report


Chemical context top

\ Previous studies have shown that the bis-quaternary ammonium compound 1'-[(1,1'-bi­phenyl)-4,4'-diylbis(prop-2-yne-3,1-diyl)]-bis­(3,4-\ di­methyl­pyridin-1-ium) bromide (ZZ161C) is a potent and selective α9α10 nicotinic acetyl­choline receptor antagonist (Zheng et al., 2011). ZZ161C has been reported to have analgesic effects in various animal pain models (Wala et al., 2012). In order to improve the pharmacological and pharmacokinetic profile of ZZ161C, we have replaced the terminal aza­aromatic rings with fully reduced piperidine rings to obtain the title compounds (I) and (II). Single-crystal X-ray structure determinations were carried out to determine the conformations of these compounds.

Structural commentary top

The title compounds, C30H36N2 (I) and C36H48N2 (II) are shown in Figs. 1 and 2, respectively. The present X-ray crystallographic study was carried out in order to ascertain the geometry of the piperidine rings and the bi­phenyl ring systems, as well as to obtain more detailed information about the conformation of the title compounds. Crystals of both (I) and (II) are monoclinic, space group P21/c, with Z' = 1 and 0.5, respectively. In each compound, individual bond lengths and angles are unremarkable. The piperidine rings in both of the title molecules are in the chair conformation. In (I), the bi­phenyl rings (C20—C21—C22—C23—C30—C29) and (C16—C17—C18—C19—C28—C27) are non-coplanar, with a dihedral angle of 26.57 (6)°. For compound (II), however, the bi­phenyl group is strictly coplanar because the molecule sits on a crystallographic inversion centre. In compound (I), the dihedral angles about the ethynyl groups between the planes of the phenyl rings and the piperidine ring N atoms are 37.16 (16) and 14.20 (17)°. In compound (II), the corresponding dihedral angles are both 61.48 (17)°.

Supra­molecular features top

Other than weak van der Waals inter­actions, there are no noteworthy inter­molecular contacts in (I). In (II) there is a small π-overlap between inversion-related molecules (1- x, 1- y, 1- z), giving an inter­planar spacing of 3.553 (3) Å and centroid-to-centroid separation of 3.859 (4) Å.

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 hits, which gave a bimodal distribution of bi­phenyl dihedral angles with a tight peak at 0° and a broader peak centred at ~30°. The bi­phenyl dihedral angles in (I) and (II) are thus not unusual.

Synthesis and crystallization top

In the synthesis of 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. Bis-(tri­phenyl­phosphine)palladium(II) dichloride and copper(I) iodide were used as catalysts. The mixture 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 4-methyl­piperidine (77.2 mg, 0.78 mmol) and the reaction mixture stirred for two 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 and combined. The extract (organic layer) was dried over anhydrous sodium sulfate, filtered, and the filtrate concentrated under reduced pressure. The resulting crude sample of compound (I) was purified by column chromatography (di­chloro­methane/methanol, 100:2 v/v). Yield: 80%.

A crude sample of compound (II) was prepared using the same experimental conditions for the preparation of compound (I) but utilizing 2,2,6,6-tetra­methyl­piperidine (110.0 mg, 0.78 mmol) instead of 4-methyl­piperidine. Column chromatography (dichlormethane/methanol 100:2 v/v) was then used for purification of (II). Yield: 80%.

Compound (I) and (II) were each dissolved separately in a mixture of di­chloro­methane/methanol (2:1 v/v). Yellow crystals of both compounds were obtained by slow evaporation of the solution at room temperature over 24 hours.

Compound (I) 1H-NMR (400 Mz, CDCl3): δ 7.49 (q, 8H), 3.52 (s, 4H), 2.97 (d, 4H), 2.26 (t, 4H) p.p.m.; 13C-NMR (100 Mz, CDCl3): δ 132.92, 132.19, 126.76, 122.36, 85.13, 52.83, 48.09, 34.02, 30.20, 21.74 p.p.m.

Compound (II) 1H-NMR (400 Mz, CDCl3): δ 7.50 (q, 8H), 3.62 (s, 4H), 1.61–1.60 (m, 8H), 1.52–1.51 (m, 4H), 1.22 (s, 24H) p.p.m. 13C-NMR (100 Mz, CDCl3): δ 139.47, 131.88, 126.61, 123.42, 94.00, 80.78, 55.00, 41.16, 33.87, 27.49, 17.81 p.p.m.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were found in difference Fourier maps, but subsequently included in the refinement using riding models, with constrained distances set to 0.95 Å (Csp2H), 0.98 Å (RCH3), 0.99 Å (R2CH2) and 1.00 Å (R3CH). Uiso(H) parameters were set to values of either 1.2Ueq(C) or 1.5Ueq(C) (RCH3 only) of the attached atom. The final models were checked using an R-tensor (Parkin, 2000) and by PLATON (Spek, 2009).

Related literature top

For related literature, see: Bruno et al. (2004); Bruno et al. (2004); Groom & Allen (2014); Parkin (2000); Spek (2009); Wala et al. (2012); Zheng et al. (2011).

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I); APEX2 (Bruker, 2006) for (II). Cell refinement: SCALEPACK (Otwinowski & Minor, 2006) for (I); SAINT (Bruker, 2006) for (II). Data reduction: DENZO-SMN (Otwinowski & Minor, 2006) for (I); SAINT (Bruker, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b) and CIFFIX (Parkin, 2013).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. The molecular structure of (II), with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are generated by the symmetry operator (1 - x, 2 -y, 1 - z).
(I) 4,4'-Bis[3-(4-methylpiperidin-1-yl)prop-1-yn-1-yl]-1,1'-biphenyl top
Crystal data top
C30H36N2F(000) = 920
Mr = 424.61Dx = 1.169 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 21.9870 (6) ÅCell parameters from 5987 reflections
b = 7.0390 (3) Åθ = 1.0–27.5°
c = 15.7840 (11) ŵ = 0.07 mm−1
β = 99.0310 (19)°T = 90 K
V = 2412.6 (2) Å3Plate, colourless
Z = 40.32 × 0.30 × 0.03 mm
Data collection top
Nonius KappaCCD
diffractometer		5546 independent reflections
Radiation source: fine-focus sealed-tube3347 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm-1Rint = 0.066
φ and ω scans at fixed χ = 55°θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		h = −28→28
Tmin = 0.764, Tmax = 0.958k = −9→9
54455 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: difference Fourier map
wR(F2) = 0.144H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0706P)2 + 0.3882P]
where P = (Fo2 + 2Fc2)/3
5546 reflections(Δ/σ)max < 0.001
291 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
C30H36N2V = 2412.6 (2) Å3
Mr = 424.61Z = 4
Monoclinic, P21/cMo Kα radiation
a = 21.9870 (6) ŵ = 0.07 mm−1
b = 7.0390 (3) ÅT = 90 K
c = 15.7840 (11) Å0.32 × 0.30 × 0.03 mm
β = 99.0310 (19)°
Data collection top
Nonius KappaCCD
diffractometer		5546 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)		3347 reflections with I > 2σ(I)
Tmin = 0.764, Tmax = 0.958Rint = 0.066
54455 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.144H-atom parameters constrained
S = 1.02Δρmax = 0.22 e Å−3
5546 reflectionsΔρmin = −0.22 e Å−3
291 parameters
Special details top

Experimental. The crystal was mounted with polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid nitrogen based cryostat, according to published methods (Hope, 1994; Parkin & Hope, 1998).

Diffraction data were collected with the crystal at 90 K, which is standard practice in this laboratory for the majority of flash-cooled crystals.

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
N10.20730 (5)0.24205 (18)0.41351 (8)0.0245 (3)
N20.79153 (5)0.22850 (18)−0.16448 (8)0.0234 (3)
C10.19401 (7)0.4165 (2)0.36333 (10)0.0255 (4)
H1A0.21710.41530.31430.031*
H1B0.20800.52770.39960.031*
C20.12538 (7)0.4349 (2)0.33012 (10)0.0268 (4)
H2A0.11790.55100.29460.032*
H2B0.10270.44780.37930.032*
C30.10128 (7)0.2625 (2)0.27674 (10)0.0246 (4)
H3A0.12310.25690.22580.030*
C40.11755 (6)0.0832 (2)0.32978 (10)0.0259 (4)
H4A0.09470.08220.37910.031*
H4B0.1049−0.03000.29410.031*
C50.18653 (6)0.0736 (2)0.36255 (10)0.0250 (4)
H5A0.1957−0.04160.39820.030*
H5B0.20920.06440.31320.030*
C60.03225 (7)0.2769 (2)0.24399 (10)0.0304 (4)
H6A0.01880.16500.20910.046*
H6B0.02390.39180.20900.046*
H6C0.00980.28330.29290.046*
C70.80978 (7)0.0602 (2)−0.11219 (10)0.0251 (4)
H7A0.7993−0.0555−0.14700.030*
H7B0.78670.0566−0.06310.030*
C80.87867 (7)0.0625 (2)−0.07886 (10)0.0263 (4)
H8A0.90170.0561−0.12790.032*
H8B0.8897−0.0505−0.04240.032*
C90.89727 (7)0.2419 (2)−0.02685 (10)0.0248 (4)
H9A0.87560.24100.02430.030*
C100.87516 (7)0.4146 (2)−0.08094 (10)0.0264 (4)
H10A0.89810.4233−0.13000.032*
H10B0.88380.5309−0.04590.032*
C110.80634 (7)0.4027 (2)−0.11454 (10)0.0253 (4)
H11A0.78310.4048−0.06570.030*
H11B0.79360.5146−0.15110.030*
C120.96641 (7)0.2486 (2)0.00546 (10)0.0308 (4)
H12A0.97860.13620.04070.046*
H12B0.97630.36350.04000.046*
H12C0.98880.2505−0.04360.046*
C130.27358 (6)0.2281 (2)0.44724 (10)0.0266 (4)
H13A0.28070.11320.48360.032*
H13B0.28580.33970.48420.032*
C140.31350 (7)0.2189 (2)0.38025 (10)0.0254 (4)
C150.34323 (7)0.2140 (2)0.32287 (10)0.0237 (3)
C160.38357 (6)0.2046 (2)0.25885 (9)0.0215 (3)
C170.37212 (6)0.3064 (2)0.18216 (9)0.0229 (3)
H17A0.33540.37880.16910.027*
C180.41397 (6)0.3028 (2)0.12486 (9)0.0214 (3)
H18A0.40540.37310.07300.026*
C190.46856 (6)0.1975 (2)0.14209 (9)0.0198 (3)
C200.51543 (6)0.2019 (2)0.08399 (9)0.0199 (3)
C210.57773 (6)0.1686 (2)0.11555 (9)0.0236 (4)
H21A0.58980.14230.17480.028*
C220.62205 (7)0.1732 (2)0.06218 (9)0.0250 (4)
H22A0.66400.15050.08520.030*
C230.60560 (7)0.2107 (2)−0.02488 (10)0.0225 (3)
C240.64979 (7)0.2140 (2)−0.08346 (10)0.0247 (4)
C250.68349 (7)0.2177 (2)−0.13613 (10)0.0244 (4)
C260.72570 (6)0.2217 (2)−0.20057 (9)0.0256 (4)
H26A0.71810.1073−0.23720.031*
H26B0.71570.3341−0.23790.031*
C270.43683 (6)0.0935 (2)0.27488 (9)0.0226 (3)
H27A0.44460.01930.32570.027*
C280.47825 (6)0.0904 (2)0.21758 (9)0.0223 (3)
H28A0.51410.01380.22970.027*
C290.49939 (7)0.2415 (2)−0.00348 (10)0.0214 (3)
H29A0.45760.2659−0.02660.026*
C300.54362 (7)0.2455 (2)−0.05680 (9)0.0221 (3)
H30A0.53170.2723−0.11610.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0214 (6)0.0309 (8)0.0216 (7)−0.0012 (5)0.0049 (5)−0.0001 (6)
N20.0216 (6)0.0271 (8)0.0218 (7)−0.0004 (5)0.0045 (5)−0.0014 (5)
C10.0259 (8)0.0268 (9)0.0243 (8)−0.0011 (7)0.0061 (7)−0.0036 (7)
C20.0278 (8)0.0273 (9)0.0255 (8)0.0033 (7)0.0053 (7)−0.0013 (7)
C30.0228 (8)0.0299 (9)0.0216 (8)0.0002 (6)0.0051 (6)−0.0005 (7)
C40.0244 (8)0.0274 (9)0.0257 (8)−0.0029 (7)0.0037 (7)0.0010 (7)
C50.0256 (8)0.0253 (9)0.0247 (8)−0.0018 (6)0.0053 (7)0.0016 (7)
C60.0267 (8)0.0352 (10)0.0284 (9)0.0020 (7)0.0014 (7)0.0009 (7)
C70.0271 (8)0.0243 (9)0.0250 (8)−0.0010 (7)0.0071 (7)−0.0026 (7)
C80.0263 (8)0.0263 (9)0.0263 (9)0.0036 (7)0.0044 (7)−0.0008 (7)
C90.0262 (8)0.0287 (9)0.0202 (8)−0.0008 (7)0.0059 (6)−0.0006 (7)
C100.0294 (8)0.0242 (9)0.0252 (8)−0.0028 (7)0.0028 (7)0.0013 (7)
C110.0284 (8)0.0234 (9)0.0244 (8)0.0008 (7)0.0048 (7)0.0014 (7)
C120.0283 (8)0.0347 (10)0.0285 (9)0.0005 (7)0.0024 (7)−0.0014 (7)
C130.0210 (8)0.0367 (10)0.0226 (8)−0.0013 (7)0.0048 (6)0.0010 (7)
C140.0227 (8)0.0276 (9)0.0257 (8)−0.0022 (7)0.0036 (7)−0.0007 (7)
C150.0219 (8)0.0221 (8)0.0263 (8)−0.0016 (6)0.0014 (7)−0.0010 (7)
C160.0219 (7)0.0205 (8)0.0222 (8)−0.0036 (6)0.0040 (6)−0.0024 (6)
C170.0200 (7)0.0214 (8)0.0270 (8)0.0011 (6)0.0031 (6)−0.0007 (7)
C180.0224 (7)0.0207 (8)0.0207 (8)−0.0002 (6)0.0019 (6)0.0020 (6)
C190.0209 (7)0.0180 (8)0.0206 (8)−0.0032 (6)0.0033 (6)−0.0027 (6)
C200.0219 (7)0.0152 (8)0.0232 (8)−0.0004 (6)0.0053 (6)−0.0018 (6)
C210.0261 (8)0.0231 (9)0.0213 (8)0.0035 (6)0.0030 (7)0.0015 (7)
C220.0210 (8)0.0269 (9)0.0271 (8)0.0023 (6)0.0041 (7)0.0001 (7)
C230.0250 (8)0.0181 (8)0.0257 (8)0.0013 (6)0.0083 (7)−0.0008 (7)
C240.0252 (8)0.0225 (9)0.0260 (8)0.0009 (6)0.0030 (7)0.0004 (7)
C250.0221 (8)0.0254 (9)0.0259 (8)−0.0001 (6)0.0044 (7)0.0000 (7)
C260.0231 (8)0.0320 (9)0.0224 (8)−0.0001 (7)0.0059 (6)−0.0020 (7)
C270.0251 (8)0.0213 (9)0.0213 (8)−0.0012 (6)0.0034 (6)0.0012 (6)
C280.0213 (7)0.0205 (8)0.0247 (8)0.0018 (6)0.0026 (6)−0.0004 (6)
C290.0217 (7)0.0178 (8)0.0240 (8)0.0001 (6)0.0019 (6)−0.0015 (6)
C300.0267 (8)0.0197 (8)0.0199 (8)−0.0007 (6)0.0034 (6)0.0009 (6)
Geometric parameters (Å, º) top
N1—C51.4647 (19)C11—H11B0.9900
N1—C11.4657 (19)C12—H12A0.9800
N1—C131.4741 (18)C12—H12B0.9800
N2—C71.4631 (19)C12—H12C0.9800
N2—C111.4666 (19)C13—C141.478 (2)
N2—C261.4707 (18)C13—H13A0.9900
C1—C21.523 (2)C13—H13B0.9900
C1—H1A0.9900C14—C151.198 (2)
C1—H1B0.9900C15—C161.447 (2)
C2—C31.524 (2)C16—C171.395 (2)
C2—H2A0.9900C16—C271.398 (2)
C2—H2B0.9900C17—C181.3880 (19)
C3—C41.526 (2)C17—H17A0.9500
C3—C61.5280 (19)C18—C191.401 (2)
C3—H3A1.0000C18—H18A0.9500
C4—C51.5252 (19)C19—C281.3976 (19)
C4—H4A0.9900C19—C201.483 (2)
C4—H4B0.9900C20—C291.398 (2)
C5—H5A0.9900C20—C211.4019 (19)
C5—H5B0.9900C21—C221.3848 (19)
C6—H6A0.9800C21—H21A0.9500
C6—H6B0.9800C22—C231.390 (2)
C6—H6C0.9800C22—H22A0.9500
C7—C81.523 (2)C23—C301.3984 (19)
C7—H7A0.9900C23—C241.443 (2)
C7—H7B0.9900C24—C251.197 (2)
C8—C91.527 (2)C25—C261.481 (2)
C8—H8A0.9900C26—H26A0.9900
C8—H8B0.9900C26—H26B0.9900
C9—C101.520 (2)C27—C281.3807 (19)
C9—C121.526 (2)C27—H27A0.9500
C9—H9A1.0000C28—H28A0.9500
C10—C111.525 (2)C29—C301.383 (2)
C10—H10A0.9900C29—H29A0.9500
C10—H10B0.9900C30—H30A0.9500
C11—H11A0.9900
C5—N1—C1111.28 (11)H10A—C10—H10B108.0
C5—N1—C13110.47 (12)N2—C11—C10110.91 (12)
C1—N1—C13110.65 (12)N2—C11—H11A109.5
C7—N2—C11110.83 (11)C10—C11—H11A109.5
C7—N2—C26110.99 (12)N2—C11—H11B109.5
C11—N2—C26110.93 (12)C10—C11—H11B109.5
N1—C1—C2111.08 (12)H11A—C11—H11B108.0
N1—C1—H1A109.4C9—C12—H12A109.5
C2—C1—H1A109.4C9—C12—H12B109.5
N1—C1—H1B109.4H12A—C12—H12B109.5
C2—C1—H1B109.4C9—C12—H12C109.5
H1A—C1—H1B108.0H12A—C12—H12C109.5
C1—C2—C3111.25 (12)H12B—C12—H12C109.5
C1—C2—H2A109.4N1—C13—C14114.15 (12)
C3—C2—H2A109.4N1—C13—H13A108.7
C1—C2—H2B109.4C14—C13—H13A108.7
C3—C2—H2B109.4N1—C13—H13B108.7
H2A—C2—H2B108.0C14—C13—H13B108.7
C2—C3—C4108.91 (12)H13A—C13—H13B107.6
C2—C3—C6112.03 (13)C15—C14—C13176.56 (16)
C4—C3—C6112.04 (13)C14—C15—C16175.24 (15)
C2—C3—H3A107.9C17—C16—C27118.45 (13)
C4—C3—H3A107.9C17—C16—C15122.39 (13)
C6—C3—H3A107.9C27—C16—C15119.14 (13)
C5—C4—C3110.95 (12)C18—C17—C16120.54 (13)
C5—C4—H4A109.4C18—C17—H17A119.7
C3—C4—H4A109.4C16—C17—H17A119.7
C5—C4—H4B109.4C17—C18—C19121.25 (14)
C3—C4—H4B109.4C17—C18—H18A119.4
H4A—C4—H4B108.0C19—C18—H18A119.4
N1—C5—C4110.99 (12)C28—C19—C18117.53 (13)
N1—C5—H5A109.4C28—C19—C20120.70 (13)
C4—C5—H5A109.4C18—C19—C20121.75 (13)
N1—C5—H5B109.4C29—C20—C21117.70 (13)
C4—C5—H5B109.4C29—C20—C19121.51 (13)
H5A—C5—H5B108.0C21—C20—C19120.79 (13)
C3—C6—H6A109.5C22—C21—C20121.44 (14)
C3—C6—H6B109.5C22—C21—H21A119.3
H6A—C6—H6B109.5C20—C21—H21A119.3
C3—C6—H6C109.5C21—C22—C23120.46 (14)
H6A—C6—H6C109.5C21—C22—H22A119.8
H6B—C6—H6C109.5C23—C22—H22A119.8
N2—C7—C8110.85 (12)C22—C23—C30118.49 (13)
N2—C7—H7A109.5C22—C23—C24122.66 (13)
C8—C7—H7A109.5C30—C23—C24118.85 (14)
N2—C7—H7B109.5C25—C24—C23175.97 (16)
C8—C7—H7B109.5C24—C25—C26179.41 (16)
H7A—C7—H7B108.1N2—C26—C25114.80 (12)
C7—C8—C9111.25 (12)N2—C26—H26A108.6
C7—C8—H8A109.4C25—C26—H26A108.6
C9—C8—H8A109.4N2—C26—H26B108.6
C7—C8—H8B109.4C25—C26—H26B108.6
C9—C8—H8B109.4H26A—C26—H26B107.5
H8A—C8—H8B108.0C28—C27—C16120.67 (14)
C10—C9—C12112.14 (13)C28—C27—H27A119.7
C10—C9—C8108.91 (12)C16—C27—H27A119.7
C12—C9—C8111.96 (12)C27—C28—C19121.47 (14)
C10—C9—H9A107.9C27—C28—H28A119.3
C12—C9—H9A107.9C19—C28—H28A119.3
C8—C9—H9A107.9C30—C29—C20120.84 (14)
C9—C10—C11111.35 (12)C30—C29—H29A119.6
C9—C10—H10A109.4C20—C29—H29A119.6
C11—C10—H10A109.4C29—C30—C23121.06 (14)
C9—C10—H10B109.4C29—C30—H30A119.5
C11—C10—H10B109.4C23—C30—H30A119.5
C5—N1—C1—C258.26 (15)C16—C17—C18—C190.1 (2)
C13—N1—C1—C2−178.52 (12)C17—C18—C19—C282.4 (2)
N1—C1—C2—C3−56.80 (17)C17—C18—C19—C20−176.17 (13)
C1—C2—C3—C454.60 (16)C28—C19—C20—C29154.84 (14)
C1—C2—C3—C6179.11 (12)C18—C19—C20—C29−26.7 (2)
C2—C3—C4—C5−54.81 (16)C28—C19—C20—C21−26.0 (2)
C6—C3—C4—C5−179.30 (12)C18—C19—C20—C21152.48 (14)
C1—N1—C5—C4−58.59 (15)C29—C20—C21—C22−0.5 (2)
C13—N1—C5—C4178.08 (12)C19—C20—C21—C22−179.67 (14)
C3—C4—C5—N157.36 (17)C20—C21—C22—C23−0.2 (2)
C11—N2—C7—C8−59.31 (15)C21—C22—C23—C300.7 (2)
C26—N2—C7—C8176.95 (12)C21—C22—C23—C24−178.97 (14)
N2—C7—C8—C957.45 (17)C7—N2—C26—C2561.28 (17)
C7—C8—C9—C10−54.19 (16)C11—N2—C26—C25−62.40 (17)
C7—C8—C9—C12−178.78 (12)C17—C16—C27—C282.4 (2)
C12—C9—C10—C11178.51 (12)C15—C16—C27—C28−176.02 (13)
C8—C9—C10—C1154.03 (16)C16—C27—C28—C190.0 (2)
C7—N2—C11—C1059.11 (15)C18—C19—C28—C27−2.4 (2)
C26—N2—C11—C10−177.12 (12)C20—C19—C28—C27176.14 (13)
C9—C10—C11—N2−57.14 (17)C21—C20—C29—C300.7 (2)
C5—N1—C13—C1461.90 (17)C19—C20—C29—C30179.85 (13)
C1—N1—C13—C14−61.79 (17)C20—C29—C30—C23−0.2 (2)
C27—C16—C17—C18−2.5 (2)C22—C23—C30—C29−0.5 (2)
C15—C16—C17—C18175.94 (14)C24—C23—C30—C29179.17 (13)
(II) 4,4'-Bis[3-(2,2,6,6-tetramethylpiperidin-1-yl)prop-1-yn-1-yl]-1,1'-biphenyl top
Crystal data top
C36H48N2F(000) = 556
Mr = 508.76Dx = 1.104 Mg m−3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 16.0591 (3) ÅCell parameters from 8231 reflections
b = 6.2267 (1) Åθ = 2.8–67.9°
c = 15.5921 (3) ŵ = 0.47 mm−1
β = 100.895 (1)°T = 90 K
V = 1531.03 (5) Å3Needle, colourless
Z = 20.22 × 0.04 × 0.03 mm
Data collection top
Bruker X8 Proteum
diffractometer		2797 independent reflections
Radiation source: fine-focus rotating anode2405 reflections with I > 2σ(I)
Detector resolution: 5.6 pixels mm-1Rint = 0.053
φ and ω scansθmax = 68.2°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		h = −19→18
Tmin = 0.767, Tmax = 0.929k = −7→7
19631 measured reflectionsl = −7→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: difference Fourier map
wR(F2) = 0.137H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0655P)2 + 0.6795P]
where P = (Fo2 + 2Fc2)/3
2797 reflections(Δ/σ)max < 0.001
176 parametersΔρmax = 0.24 e Å−3
0 restraintsΔρmin = −0.24 e Å−3
Crystal data top
C36H48N2V = 1531.03 (5) Å3
Mr = 508.76Z = 2
Monoclinic, P21/cCu Kα radiation
a = 16.0591 (3) ŵ = 0.47 mm−1
b = 6.2267 (1) ÅT = 90 K
c = 15.5921 (3) Å0.22 × 0.04 × 0.03 mm
β = 100.895 (1)°
Data collection top
Bruker X8 Proteum
diffractometer		2797 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		2405 reflections with I > 2σ(I)
Tmin = 0.767, Tmax = 0.929Rint = 0.053
19631 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.05Δρmax = 0.24 e Å−3
2797 reflectionsΔρmin = −0.24 e Å−3
176 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
N10.78341 (8)0.0593 (2)0.79190 (7)0.0251 (3)
C10.83571 (10)−0.0569 (3)0.73835 (10)0.0282 (4)
C20.92701 (10)0.0213 (3)0.76309 (11)0.0362 (4)
H2A0.9634−0.06960.73330.043*
H2B0.93030.17030.74180.043*
C30.96116 (11)0.0163 (3)0.86058 (12)0.0459 (5)
H3A1.01970.07340.87320.055*
H3B0.9623−0.13340.88220.055*
C40.90420 (12)0.1523 (3)0.90597 (11)0.0450 (5)
H4A0.90720.30340.88690.054*
H4B0.92580.14720.96980.054*
C50.81150 (11)0.0802 (3)0.88750 (9)0.0344 (4)
C60.69196 (10)0.0225 (3)0.76398 (11)0.0311 (4)
H6A0.6669−0.01100.81580.037*
H6B0.6829−0.10310.72440.037*
C70.64850 (9)0.2102 (3)0.71880 (10)0.0315 (4)
C80.61556 (10)0.3635 (3)0.68003 (10)0.0321 (4)
C90.58105 (9)0.5448 (3)0.62925 (10)0.0306 (4)
C100.52059 (11)0.6782 (3)0.65485 (12)0.0408 (4)
H10A0.50070.64870.70730.049*
C110.48936 (11)0.8531 (3)0.60457 (12)0.0401 (4)
H11A0.44780.94090.62320.048*
C120.51674 (9)0.9061 (3)0.52692 (10)0.0301 (4)
C130.57751 (13)0.7705 (4)0.50380 (12)0.0497 (5)
H13A0.59810.79970.45170.060*
C140.60900 (12)0.5960 (4)0.55329 (12)0.0478 (5)
H14A0.65090.50860.53490.057*
C150.80502 (11)0.0062 (3)0.64265 (10)0.0361 (4)
H15A0.80230.16300.63770.054*
H15B0.7485−0.05450.62170.054*
H15C0.8446−0.04960.60730.054*
C160.83244 (12)−0.3037 (3)0.74548 (12)0.0384 (4)
H16A0.8630−0.34870.80310.058*
H16B0.8590−0.36850.70010.058*
H16C0.7732−0.35050.73780.058*
C170.80193 (14)−0.1264 (3)0.93930 (11)0.0456 (5)
H17A0.8451−0.23070.93010.068*
H17B0.7454−0.18750.91900.068*
H17C0.8092−0.09221.00160.068*
C180.75837 (15)0.2577 (3)0.91871 (11)0.0477 (5)
H18A0.75860.38500.88180.072*
H18B0.78250.29450.97940.072*
H18C0.70000.20710.91490.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0261 (6)0.0330 (7)0.0174 (6)−0.0037 (5)0.0076 (5)0.0001 (5)
C10.0288 (8)0.0347 (8)0.0231 (7)0.0026 (6)0.0103 (6)0.0023 (6)
C20.0262 (8)0.0442 (10)0.0398 (9)0.0021 (7)0.0102 (7)0.0145 (8)
C30.0311 (9)0.0553 (12)0.0456 (10)−0.0071 (8)−0.0075 (8)0.0224 (9)
C40.0568 (11)0.0472 (11)0.0241 (8)−0.0167 (9)−0.0104 (7)0.0098 (7)
C50.0508 (10)0.0364 (9)0.0169 (7)−0.0088 (7)0.0088 (6)0.0027 (6)
C60.0267 (8)0.0330 (8)0.0359 (8)−0.0049 (6)0.0120 (6)−0.0015 (7)
C70.0241 (7)0.0389 (9)0.0335 (8)−0.0034 (7)0.0103 (6)−0.0075 (7)
C80.0243 (7)0.0387 (9)0.0347 (8)−0.0037 (7)0.0092 (6)−0.0092 (7)
C90.0217 (7)0.0372 (9)0.0325 (8)−0.0017 (6)0.0040 (6)−0.0091 (7)
C100.0374 (9)0.0434 (10)0.0475 (10)0.0033 (8)0.0227 (8)−0.0001 (8)
C110.0343 (9)0.0417 (10)0.0500 (10)0.0072 (7)0.0222 (8)−0.0021 (8)
C120.0222 (7)0.0376 (9)0.0306 (8)−0.0012 (6)0.0048 (6)−0.0111 (7)
C130.0514 (11)0.0697 (14)0.0335 (9)0.0281 (10)0.0221 (8)0.0066 (9)
C140.0464 (11)0.0649 (13)0.0363 (9)0.0264 (9)0.0186 (8)0.0009 (9)
C150.0453 (10)0.0444 (10)0.0203 (7)0.0054 (8)0.0105 (7)−0.0009 (7)
C160.0436 (10)0.0342 (9)0.0400 (9)0.0042 (7)0.0148 (7)0.0009 (7)
C170.0688 (13)0.0434 (11)0.0286 (8)−0.0070 (9)0.0193 (8)0.0090 (8)
C180.0838 (15)0.0393 (10)0.0254 (8)−0.0073 (10)0.0239 (9)−0.0047 (7)
Geometric parameters (Å, º) top
N1—C61.4688 (19)C9—C101.392 (2)
N1—C51.4793 (18)C10—C111.380 (3)
N1—C11.4804 (19)C10—H10A0.9500
C1—C21.524 (2)C11—C121.403 (2)
C1—C151.532 (2)C11—H11A0.9500
C1—C161.542 (2)C12—C131.389 (2)
C2—C31.516 (2)C12—C12i1.480 (3)
C2—H2A0.9900C13—C141.373 (3)
C2—H2B0.9900C13—H13A0.9500
C3—C41.517 (3)C14—H14A0.9500
C3—H3A0.9900C15—H15A0.9800
C3—H3B0.9900C15—H15B0.9800
C4—C51.529 (2)C15—H15C0.9800
C4—H4A0.9900C16—H16A0.9800
C4—H4B0.9900C16—H16B0.9800
C5—C181.531 (3)C16—H16C0.9800
C5—C171.542 (2)C17—H17A0.9800
C6—C71.471 (2)C17—H17B0.9800
C6—H6A0.9900C17—H17C0.9800
C6—H6B0.9900C18—H18A0.9800
C7—C81.198 (2)C18—H18B0.9800
C8—C91.429 (2)C18—H18C0.9800
C9—C141.381 (2)
C6—N1—C5114.19 (12)C14—C9—C8120.16 (15)
C6—N1—C1113.49 (12)C10—C9—C8122.07 (15)
C5—N1—C1120.92 (13)C11—C10—C9120.43 (16)
N1—C1—C2108.79 (13)C11—C10—H10A119.8
N1—C1—C15108.16 (12)C9—C10—H10A119.8
C2—C1—C15106.36 (13)C10—C11—C12122.43 (15)
N1—C1—C16114.57 (13)C10—C11—H11A118.8
C2—C1—C16110.15 (14)C12—C11—H11A118.8
C15—C1—C16108.47 (14)C13—C12—C11115.55 (16)
C3—C2—C1113.30 (13)C13—C12—C12i122.06 (18)
C3—C2—H2A108.9C11—C12—C12i122.39 (17)
C1—C2—H2A108.9C14—C13—C12122.53 (16)
C3—C2—H2B108.9C14—C13—H13A118.7
C1—C2—H2B108.9C12—C13—H13A118.7
H2A—C2—H2B107.7C13—C14—C9121.32 (16)
C2—C3—C4108.70 (14)C13—C14—H14A119.3
C2—C3—H3A109.9C9—C14—H14A119.3
C4—C3—H3A109.9C1—C15—H15A109.5
C2—C3—H3B109.9C1—C15—H15B109.5
C4—C3—H3B109.9H15A—C15—H15B109.5
H3A—C3—H3B108.3C1—C15—H15C109.5
C3—C4—C5113.55 (15)H15A—C15—H15C109.5
C3—C4—H4A108.9H15B—C15—H15C109.5
C5—C4—H4A108.9C1—C16—H16A109.5
C3—C4—H4B108.9C1—C16—H16B109.5
C5—C4—H4B108.9H16A—C16—H16B109.5
H4A—C4—H4B107.7C1—C16—H16C109.5
N1—C5—C4108.43 (12)H16A—C16—H16C109.5
N1—C5—C18107.54 (14)H16B—C16—H16C109.5
C4—C5—C18108.02 (15)C5—C17—H17A109.5
N1—C5—C17114.40 (14)C5—C17—H17B109.5
C4—C5—C17109.65 (15)H17A—C17—H17B109.5
C18—C5—C17108.61 (14)C5—C17—H17C109.5
N1—C6—C7112.04 (13)H17A—C17—H17C109.5
N1—C6—H6A109.2H17B—C17—H17C109.5
C7—C6—H6A109.2C5—C18—H18A109.5
N1—C6—H6B109.2C5—C18—H18B109.5
C7—C6—H6B109.2H18A—C18—H18B109.5
H6A—C6—H6B107.9C5—C18—H18C109.5
C8—C7—C6177.40 (16)H18A—C18—H18C109.5
C7—C8—C9175.42 (16)H18B—C18—H18C109.5
C14—C9—C10117.74 (16)
C6—N1—C1—C2170.72 (12)C1—N1—C5—C17−75.06 (19)
C5—N1—C1—C2−47.93 (18)C3—C4—C5—N1−50.81 (19)
C6—N1—C1—C1555.59 (17)C3—C4—C5—C18−167.07 (14)
C5—N1—C1—C15−163.06 (14)C3—C4—C5—C1774.74 (17)
C6—N1—C1—C16−65.52 (17)C5—N1—C6—C7109.77 (15)
C5—N1—C1—C1675.83 (18)C1—N1—C6—C7−106.21 (15)
N1—C1—C2—C351.04 (19)C14—C9—C10—C111.0 (3)
C15—C1—C2—C3167.34 (15)C8—C9—C10—C11179.33 (16)
C16—C1—C2—C3−75.31 (19)C9—C10—C11—C12−0.6 (3)
C1—C2—C3—C4−57.6 (2)C10—C11—C12—C130.0 (3)
C2—C3—C4—C557.58 (19)C10—C11—C12—C12i−179.94 (18)
C6—N1—C5—C4−171.25 (14)C11—C12—C13—C140.0 (3)
C1—N1—C5—C447.65 (19)C12i—C12—C13—C14180.0 (2)
C6—N1—C5—C18−54.69 (17)C12—C13—C14—C90.5 (3)
C1—N1—C5—C18164.21 (14)C10—C9—C14—C13−0.9 (3)
C6—N1—C5—C1766.04 (19)C8—C9—C14—C13−179.33 (18)
Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC30H36N2C36H48N2
Mr424.61508.76
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)9090
a, b, c (Å)21.9870 (6), 7.0390 (3), 15.7840 (11)16.0591 (3), 6.2267 (1), 15.5921 (3)
β (°) 99.0310 (19) 100.895 (1)
V (Å3)2412.6 (2)1531.03 (5)
Z42
Radiation typeMo KαCu Kα
µ (mm−1)0.070.47
Crystal size (mm)0.32 × 0.30 × 0.030.22 × 0.04 × 0.03
Data collection
DiffractometerNonius KappaCCD
diffractometer		Bruker X8 Proteum
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)		Multi-scan
(SADABS; Bruker, 2006)
Tmin, Tmax0.764, 0.9580.767, 0.929
No. of measured, independent and
observed [I > 2σ(I)] reflections		54455, 5546, 3347 19631, 2797, 2405
Rint0.0660.053
(sin θ/λ)max (Å−1)0.6500.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.144, 1.02 0.050, 0.137, 1.05
No. of reflections55462797
No. of parameters291176
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.22, −0.220.24, −0.24

Computer programs: COLLECT (Nonius, 1998), APEX2 (Bruker, 2006), SCALEPACK (Otwinowski & Minor, 2006), SAINT (Bruker, 2006), DENZO-SMN (Otwinowski & Minor, 2006), SHELXS97 (Sheldrick, 2008b), SHELXL2014 (Sheldrick, 2015), XP in SHELXTL (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b) and CIFFIX (Parkin, 2013).

 

Acknowledgements

This investigation was supported by ARA (Arkansas Research Alliance).

References

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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.

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ISSN: 2056-9890
Volume 71| Part 10| October 2015| Pages 1132-1135
doi:10.1107/S2056989015015352
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