Crystal structure of 2,4,6-tris­(cyclo­hex­yloxy)-1,3,5-triazine

Sankolli, R.; Hauser, J.; Row, T.N.G.; Hulliger, J.

doi:10.1107/S2056989015018782

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages 1328-1331

https://doi.org/10.1107/S2056989015018782

Open

access

Crystal structure of 2,4,6-tris(cyclohexyloxy)-1,3,5-triazine

Ravish Sankolli,^a Jürg Hauser,^a T. N. Guru Row ^b and Jürg Hulliger ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland, and ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India
^*Correspondence e-mail: juerg.hulliger@dcb.unibe.ch

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 13 September 2015; accepted 6 October 2015; online 14 October 2015)

The title compound, C₂₁H₃₃N₃O₃, is a tri-substituted cyclohexyloxy triazine. In the crystal, the triazine rings form (C3i-PU) Piedfort units. The inter-centroid distance of the π–π interaction involving the triazine rings is 3.3914 (10) Å. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming ribbons propagating along [1-10]. There are also weak C—H⋯N and C—H⋯O contacts present, linking inversion-related ribbons, forming a three-dimensional structure.

Keywords: crystal structure; triazine; cyclohexanol; channel inclusion; Piedfort units; hydrogen bonding.

CCDC reference: 1430153

1. Chemical content

Cyclohexyl derivatives are known to have applications in various fields of chemistry. The mono- and di-substituted derivatives of triazine with cyclohexanol show antiviral activity (Mibu et al., 2013 ), wherein cyclohexyl esters show the properties of traction fluids (Baldwin et al., 1997 ). Partially substituted menthoxy triazines can be used as enantio-differentiating reagents in organic synthesis (Kamiński et al., 1998 ). The cyclohexyl trimer, perhydrotriphenelene (PHTP) can form inclusion compounds showing non-linear optical properties (Hoss et al., 1996 ). In particular, PHTP as a renowned host in the literature, forms variable inclusions with functional molecules (Allegra et al., 1967 ; König et al., 1997 ; Couderc & Hulliger, 2010 ). Most triazines also exhibit various types of inclusion properties (Süss et al., 2002 , 2005 ; Reichenbächer et al., 2004 ). Thus, the title compound was synthesized to study the supramolecular features in comparison to PHTP. Symmetrically substituted triazines with three cyclohexanol units through an oxygen linkage shows a trigonal symmetry in its trans racemic form and a planar geometry in its crystal structure. So far, the crystallization of the title compound with conventional solvents did not form any inclusions. To the best of our knowledge, this is the first tri-substituted cyclohexyloxy triazine to be described.

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The molecule has threefold rotation symmetry, but there are small variation in the C—O—C=N torsion angles; C4—O1—C1—N1 = 3.6 (2), C10—O2—C2—N2 = −1.2 (2) and C16—O3—C3—N3 = −3.1 (2)°.

Figure 1
The molecular structure of the title compound, with atom labelling. Displacement ellipsoids drawn at the 50% probability level. The C—O—C=N torsion angles are C4—O1—C1—N1 = 3.6 (2), C10—O2—C2—N2 = −1.2 (2) and C16—O3—C3—N3 = −3.1 (2)°.

3. Supramolecular features

In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming ribbons propagating along [1 $[\overline{1}]$ 0] (Fig. 2 and Table 1). Inversion-related ribbons are linked by weak C—H⋯N and C—H⋯O contacts, forming a three-dimensional structure (Table 1). There are Piedfort units (C3i-PU) present (Jessiman et al., 1990 ), as shown in Fig. 3. The inter-centroid distance of the slightly slipped parallel π–π interaction involving inversion-related triazine rings is 3.3914 (10) Å. The inter-planar distance is 3.3315 (7) Å, while the slippage is 0.634 Å. There are three C—H⋯H—C van der Waals contacts, 2.28, 2.28 and 2.37 Å (Fig. 4), which are longer than those in the crystal structure of PHTP (measured 2.13, 2.14 and 2.16 Å; Harlow & Desiraju, 1990 ).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O1ⁱ	0.99	2.45	3.413 (2)	164
C9—H9A⋯O3ⁱⁱ	0.99	2.60	3.528 (2)	156
C10—H10⋯O1ⁱⁱ	1.00	2.95	3.787 (2)	142
C5—H5B⋯N1ⁱⁱⁱ	0.99	2.77	3.684 (2)	154
Symmetry codes: (i) x-1, y-1, z; (ii) -x+2, -y+2, -z+1; (iii) -x+3, -y+2, -z+1.

Figure 2
A view along the c axis of the crystal packing of the title compound. The most significant C—H⋯O hydrogen bonds (see Table 1

) are shown as dashed lines, and the only H atoms shown are H12A and H9A (grey balls) for clarity.

Figure 3
A view of the Piedfort unit (C3i-PU), with the two triazine rings stacking one above the other, forming an hexagonal symmetry unit. The N atoms are shown as red and blue balls.

Figure 4
A view of the short C—H⋯H⋯C contacts (orange dashed lines) and some C—H⋯O hydrogen bonds (green dashed lines; see Table 1

) in the crystal structure of the title compound.

The perhydrogenated outer wall resembles the structural features of PHTP (pehydrotriphenylene) in its crystal structure with C—H⋯H—C short contacts (Harlow & Desiraju, 1990). In comparison, PHTP is a highly symmetrical chiral molecule, which is used for inclusions in its all-trans racemic form (König et al., 1997). Thus, the title compound is a perhydrogenated triazine analogue of PHTP. However, the triazine rings which form Piedfort units (Jessiman et al., 1990) and the C—H⋯O and C—H⋯N hydrogen bonds (Table 1) contribute to the stabilization of the structure as compared to PHTP.

4. Synthesis and crystallization

Cyclohexanol (10.4 ml, 10.02 g, 100 mmol) and sodium hydride (2.88 g, 120 mmol) were taken in a round bottom flask containing 50 ml of THF at 273 K. The mixture was stirred at room temperature for 30 min, then cyanuric chloride (4.6 g, 25 mmol) was carefully added in one portion. The mixture was stirred overnight at 323 K. The solvent was then removed under reduced pressure and the oily mixture was transferred in to a separating funnel and extracted with CH₂Cl₂ (3 × 100 ml). Again, the solvent was removed under reduced pressure and the crude product was further purified through column chromatography (SiO₂ 60, eluent: diethyl ether/pentane 1:1) to yield the pure product as a white powder. Colourless prismatic crystals were obtained by isothermal evaporation of a solution in THF.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.99–1.00 Å with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₁H₃₃N₃O₃
M_r	375.50
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.7020 (2), 10.1456 (3), 11.2064 (3)
α, β, γ (°)	96.528 (2), 95.982 (2), 112.110 (2)
V (Å³)	1002.30 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.47 × 0.24 × 0.10

Data collection
Diffractometer	Agilent SuperNova, Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.657, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	24791, 4106, 3603
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.142, 1.04
No. of reflections	4106
No. of parameters	244
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.21
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXS2014/7 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), POV-RAY (POV-RAY Team, 2004 ), Mercury (Macrae et al., 2008 ), and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1430153

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018782/su5213sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018782/su5213Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018782/su5213Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2014/7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: POV-RAY (POV-RAY Team, 2004) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015) and PLATON (Spek, 2009).

2,4,6-Tris(cyclohexyloxy)-1,3,5-triazine top

Crystal data top

C₂₁H₃₃N₃O₃	Z = 2
M_r = 375.50	F(000) = 408
Triclinic, P1	D_x = 1.244 Mg m⁻³
a = 9.7020 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1456 (3) Å	Cell parameters from 9471 reflections
c = 11.2064 (3) Å	θ = 2.2–27.7°
α = 96.528 (2)°	µ = 0.08 mm⁻¹
β = 95.982 (2)°	T = 100 K
γ = 112.110 (2)°	Prism, colourless
V = 1002.30 (5) Å³	0.47 × 0.24 × 0.10 mm

Data collection top

Agilent SuperNova, Eos diffractometer	4106 independent reflections
Radiation source: Mo X-ray Source	3603 reflections with I > 2σ(I)
Detector resolution: 16.0965 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 26.4°, θ_min = 1.9°
Absorption correction: multi-scan (CrysAlis Pro; Agilent, 2014)	h = −12→12
T_min = 0.657, T_max = 1	k = −12→12
24791 measured reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.142	w = 1/[σ²(F_o²) + (0.0651P)² + 0.7913P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4106 reflections	Δρ_max = 0.61 e Å⁻³
244 parameters	Δρ_min = −0.21 e Å⁻³

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.24843 (18)	1.05014 (17)	0.49190 (14)	0.0195 (3)
C2	1.05411 (17)	0.83773 (16)	0.45059 (14)	0.0188 (3)
C3	1.07636 (18)	1.00085 (17)	0.32811 (14)	0.0194 (3)
C4	1.44642 (19)	1.10652 (17)	0.66284 (14)	0.0225 (4)
H4	1.4372	1.0047	0.6426	0.027*
C5	1.61162 (19)	1.20826 (19)	0.68357 (16)	0.0256 (4)
H5A	1.6204	1.3094	0.6976	0.031*
H5B	1.6569	1.1941	0.6105	0.031*
C6	1.6957 (2)	1.1792 (2)	0.79337 (17)	0.0295 (4)
H6A	1.6956	1.0813	0.7755	0.035*
H6B	1.8018	1.2495	0.8091	0.035*
C7	1.6240 (2)	1.19059 (19)	0.90564 (16)	0.0284 (4)
H7A	1.6353	1.2916	0.9295	0.034*
H7B	1.6765	1.1642	0.9737	0.034*
C8	1.4568 (2)	1.0913 (2)	0.88254 (16)	0.0277 (4)
H8A	1.4459	0.9896	0.8677	0.033*
H8B	1.4114	1.1055	0.9556	0.033*
C9	1.3732 (2)	1.1221 (2)	0.77312 (16)	0.0271 (4)
H9A	1.2663	1.0536	0.7574	0.033*
H9B	1.3763	1.2212	0.7902	0.033*
C10	0.83931 (18)	0.61278 (17)	0.40889 (15)	0.0220 (3)
H10	0.7850	0.6696	0.3740	0.026*
C11	0.7472 (2)	0.5209 (2)	0.49280 (16)	0.0293 (4)
H11A	0.7268	0.5829	0.5575	0.035*
H11B	0.8038	0.4697	0.5319	0.035*
C12	0.5979 (2)	0.4112 (2)	0.41799 (17)	0.0330 (4)
H12A	0.5375	0.3498	0.4718	0.040*
H12B	0.5395	0.4630	0.3826	0.040*
C13	0.6271 (2)	0.31714 (19)	0.31667 (17)	0.0317 (4)
H13A	0.5300	0.2477	0.2689	0.038*
H13B	0.6814	0.2618	0.3520	0.038*
C14	0.7213 (2)	0.4114 (2)	0.23329 (16)	0.0297 (4)
H14A	0.6643	0.4622	0.1941	0.036*
H14B	0.7422	0.3498	0.1685	0.036*
C15	0.87075 (19)	0.52219 (18)	0.30727 (15)	0.0243 (4)
H15A	0.9311	0.4715	0.3417	0.029*
H15B	0.9295	0.5851	0.2535	0.029*
C16	1.09447 (19)	1.17766 (17)	0.19788 (15)	0.0219 (3)
H16	1.1439	1.2490	0.2743	0.026*
C17	0.9714 (2)	1.2129 (2)	0.13237 (19)	0.0314 (4)
H17A	0.8992	1.2163	0.1877	0.038*
H17B	0.9159	1.1367	0.0612	0.038*
C18	1.0407 (2)	1.3590 (2)	0.09008 (19)	0.0338 (4)
H18A	0.9602	1.3788	0.0434	0.041*
H18B	1.0872	1.4361	0.1620	0.041*
C19	1.1586 (2)	1.36119 (19)	0.01149 (16)	0.0310 (4)
H19A	1.2046	1.4582	−0.0110	0.037*
H19B	1.1103	1.2906	−0.0643	0.037*
C20	1.2807 (2)	1.3241 (2)	0.07840 (19)	0.0350 (4)
H20A	1.3352	1.3995	0.1503	0.042*
H20B	1.3542	1.3216	0.0241	0.042*
C21	1.2106 (2)	1.17700 (19)	0.11921 (17)	0.0292 (4)
H21A	1.1629	1.1006	0.0469	0.035*
H21B	1.2903	1.1557	0.1653	0.035*
N1	1.18158 (15)	0.92270 (14)	0.52567 (12)	0.0202 (3)
N2	0.99553 (15)	0.86893 (14)	0.35006 (12)	0.0203 (3)
N3	1.20286 (15)	1.09706 (14)	0.39485 (12)	0.0208 (3)
O1	1.37668 (13)	1.14586 (12)	0.55837 (10)	0.0244 (3)
O2	0.98237 (13)	0.71122 (12)	0.48406 (10)	0.0227 (3)
O3	1.01921 (13)	1.03331 (12)	0.22770 (10)	0.0230 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0179 (7)	0.0191 (8)	0.0164 (7)	0.0030 (6)	0.0012 (6)	−0.0001 (6)
C2	0.0186 (7)	0.0166 (7)	0.0189 (7)	0.0042 (6)	0.0042 (6)	0.0024 (6)
C3	0.0224 (8)	0.0219 (8)	0.0154 (7)	0.0098 (6)	0.0041 (6)	0.0042 (6)
C4	0.0239 (8)	0.0199 (8)	0.0180 (8)	0.0039 (7)	−0.0038 (6)	0.0036 (6)
C5	0.0223 (8)	0.0265 (9)	0.0236 (8)	0.0046 (7)	0.0038 (7)	0.0047 (7)
C6	0.0204 (8)	0.0332 (10)	0.0304 (9)	0.0062 (7)	−0.0004 (7)	0.0063 (7)
C7	0.0308 (9)	0.0273 (9)	0.0211 (8)	0.0080 (7)	−0.0067 (7)	0.0020 (7)
C8	0.0290 (9)	0.0344 (10)	0.0206 (8)	0.0120 (8)	0.0051 (7)	0.0091 (7)
C9	0.0220 (8)	0.0340 (9)	0.0238 (9)	0.0089 (7)	0.0023 (7)	0.0075 (7)
C10	0.0201 (8)	0.0168 (8)	0.0218 (8)	0.0004 (6)	0.0006 (6)	0.0019 (6)
C11	0.0282 (9)	0.0278 (9)	0.0198 (8)	−0.0018 (7)	0.0013 (7)	0.0032 (7)
C12	0.0284 (9)	0.0279 (9)	0.0286 (9)	−0.0044 (7)	0.0026 (7)	0.0056 (7)
C13	0.0323 (10)	0.0191 (8)	0.0309 (9)	−0.0001 (7)	−0.0077 (8)	0.0008 (7)
C14	0.0334 (10)	0.0279 (9)	0.0226 (8)	0.0104 (8)	−0.0032 (7)	−0.0032 (7)
C15	0.0238 (8)	0.0244 (8)	0.0208 (8)	0.0066 (7)	0.0006 (6)	0.0014 (6)
C16	0.0260 (8)	0.0182 (8)	0.0186 (8)	0.0055 (6)	0.0007 (6)	0.0054 (6)
C17	0.0253 (9)	0.0287 (9)	0.0407 (11)	0.0093 (7)	0.0038 (8)	0.0138 (8)
C18	0.0337 (10)	0.0292 (10)	0.0416 (11)	0.0135 (8)	0.0046 (8)	0.0152 (8)
C19	0.0426 (11)	0.0223 (8)	0.0223 (8)	0.0061 (8)	0.0024 (8)	0.0076 (7)
C20	0.0330 (10)	0.0318 (10)	0.0415 (11)	0.0098 (8)	0.0145 (8)	0.0143 (8)
C21	0.0306 (9)	0.0261 (9)	0.0344 (10)	0.0122 (7)	0.0099 (8)	0.0110 (7)
N1	0.0195 (7)	0.0196 (7)	0.0167 (6)	0.0031 (5)	−0.0001 (5)	0.0030 (5)
N2	0.0191 (7)	0.0202 (7)	0.0177 (6)	0.0046 (5)	0.0003 (5)	0.0018 (5)
N3	0.0228 (7)	0.0183 (7)	0.0175 (7)	0.0041 (6)	0.0019 (5)	0.0038 (5)
O1	0.0228 (6)	0.0209 (6)	0.0204 (6)	−0.0001 (5)	−0.0041 (5)	0.0056 (5)
O2	0.0220 (6)	0.0188 (6)	0.0202 (6)	0.0009 (5)	−0.0012 (4)	0.0041 (4)
O3	0.0233 (6)	0.0203 (6)	0.0202 (6)	0.0037 (5)	−0.0025 (5)	0.0051 (4)

Geometric parameters (Å, º) top

C1—N1	1.329 (2)	C11—H11A	0.9900
C1—O1	1.3338 (19)	C11—H11B	0.9900
C1—N3	1.334 (2)	C12—C13	1.518 (3)
C2—O2	1.3281 (19)	C12—H12A	0.9900
C2—N2	1.333 (2)	C12—H12B	0.9900
C2—N1	1.340 (2)	C13—C14	1.532 (3)
C3—N3	1.326 (2)	C13—H13A	0.9900
C3—O3	1.3318 (19)	C13—H13B	0.9900
C3—N2	1.339 (2)	C14—C15	1.537 (2)
C4—O1	1.4601 (19)	C14—H14A	0.9900
C4—C9	1.510 (2)	C14—H14B	0.9900
C4—C5	1.520 (2)	C15—H15A	0.9900
C4—H4	1.0000	C15—H15B	0.9900
C5—C6	1.524 (2)	C16—O3	1.4652 (19)
C5—H5A	0.9900	C16—C21	1.502 (2)
C5—H5B	0.9900	C16—C17	1.514 (2)
C6—C7	1.513 (3)	C16—H16	1.0000
C6—H6A	0.9900	C17—C18	1.533 (2)
C6—H6B	0.9900	C17—H17A	0.9900
C7—C8	1.529 (2)	C17—H17B	0.9900
C7—H7A	0.9900	C18—C19	1.510 (3)
C7—H7B	0.9900	C18—H18A	0.9900
C8—C9	1.526 (2)	C18—H18B	0.9900
C8—H8A	0.9900	C19—C20	1.524 (3)
C8—H8B	0.9900	C19—H19A	0.9900
C9—H9A	0.9900	C19—H19B	0.9900
C9—H9B	0.9900	C20—C21	1.535 (2)
C10—O2	1.4680 (18)	C20—H20A	0.9900
C10—C15	1.510 (2)	C20—H20B	0.9900
C10—C11	1.516 (2)	C21—H21A	0.9900
C10—H10	1.0000	C21—H21B	0.9900
C11—C12	1.536 (2)

N1—C1—O1	119.36 (14)	H12A—C12—H12B	108.1
N1—C1—N3	127.33 (14)	C12—C13—C14	109.90 (15)
O1—C1—N3	113.31 (14)	C12—C13—H13A	109.7
O2—C2—N2	119.16 (14)	C14—C13—H13A	109.7
O2—C2—N1	114.21 (14)	C12—C13—H13B	109.7
N2—C2—N1	126.63 (14)	C14—C13—H13B	109.7
N3—C3—O3	119.32 (14)	H13A—C13—H13B	108.2
N3—C3—N2	126.75 (14)	C13—C14—C15	110.08 (14)
O3—C3—N2	113.93 (14)	C13—C14—H14A	109.6
O1—C4—C9	111.01 (14)	C15—C14—H14A	109.6
O1—C4—C5	105.24 (13)	C13—C14—H14B	109.6
C9—C4—C5	111.64 (14)	C15—C14—H14B	109.6
O1—C4—H4	109.6	H14A—C14—H14B	108.2
C9—C4—H4	109.6	C10—C15—C14	109.76 (14)
C5—C4—H4	109.6	C10—C15—H15A	109.7
C4—C5—C6	109.90 (14)	C14—C15—H15A	109.7
C4—C5—H5A	109.7	C10—C15—H15B	109.7
C6—C5—H5A	109.7	C14—C15—H15B	109.7
C4—C5—H5B	109.7	H15A—C15—H15B	108.2
C6—C5—H5B	109.7	O3—C16—C21	109.68 (13)
H5A—C5—H5B	108.2	O3—C16—C17	105.89 (13)
C7—C6—C5	111.39 (15)	C21—C16—C17	111.75 (14)
C7—C6—H6A	109.3	O3—C16—H16	109.8
C5—C6—H6A	109.3	C21—C16—H16	109.8
C7—C6—H6B	109.3	C17—C16—H16	109.8
C5—C6—H6B	109.3	C16—C17—C18	109.82 (15)
H6A—C6—H6B	108.0	C16—C17—H17A	109.7
C6—C7—C8	111.16 (14)	C18—C17—H17A	109.7
C6—C7—H7A	109.4	C16—C17—H17B	109.7
C8—C7—H7A	109.4	C18—C17—H17B	109.7
C6—C7—H7B	109.4	H17A—C17—H17B	108.2
C8—C7—H7B	109.4	C19—C18—C17	111.37 (16)
H7A—C7—H7B	108.0	C19—C18—H18A	109.4
C9—C8—C7	111.15 (14)	C17—C18—H18A	109.4
C9—C8—H8A	109.4	C19—C18—H18B	109.4
C7—C8—H8A	109.4	C17—C18—H18B	109.4
C9—C8—H8B	109.4	H18A—C18—H18B	108.0
C7—C8—H8B	109.4	C18—C19—C20	110.83 (15)
H8A—C8—H8B	108.0	C18—C19—H19A	109.5
C4—C9—C8	109.41 (14)	C20—C19—H19A	109.5
C4—C9—H9A	109.8	C18—C19—H19B	109.5
C8—C9—H9A	109.8	C20—C19—H19B	109.5
C4—C9—H9B	109.8	H19A—C19—H19B	108.1
C8—C9—H9B	109.8	C19—C20—C21	110.28 (16)
H9A—C9—H9B	108.2	C19—C20—H20A	109.6
O2—C10—C15	109.31 (13)	C21—C20—H20A	109.6
O2—C10—C11	106.48 (13)	C19—C20—H20B	109.6
C15—C10—C11	111.73 (14)	C21—C20—H20B	109.6
O2—C10—H10	109.8	H20A—C20—H20B	108.1
C15—C10—H10	109.8	C16—C21—C20	110.14 (15)
C11—C10—H10	109.8	C16—C21—H21A	109.6
C10—C11—C12	108.91 (14)	C20—C21—H21A	109.6
C10—C11—H11A	109.9	C16—C21—H21B	109.6
C12—C11—H11A	109.9	C20—C21—H21B	109.6
C10—C11—H11B	109.9	H21A—C21—H21B	108.1
C12—C11—H11B	109.9	C1—N1—C2	112.84 (13)
H11A—C11—H11B	108.3	C2—N2—C3	113.31 (14)
C13—C12—C11	110.63 (16)	C3—N3—C1	113.12 (13)
C13—C12—H12A	109.5	C1—O1—C4	119.74 (12)
C11—C12—H12A	109.5	C2—O2—C10	117.91 (12)
C13—C12—H12B	109.5	C3—O3—C16	118.62 (12)
C11—C12—H12B	109.5

C4—O1—C1—N1	3.6 (2)	O1—C4—C5—C6	178.67 (14)
C4—O1—C1—N3	−175.80 (14)	C9—C4—C5—C6	58.2 (2)
C1—O1—C4—C5	157.44 (15)	O1—C4—C9—C8	−175.68 (14)
C1—O1—C4—C9	−81.64 (18)	C5—C4—C9—C8	−58.60 (19)
C2—O2—C10—C15	87.08 (17)	C4—C5—C6—C7	−55.8 (2)
C10—O2—C2—N1	178.32 (14)	C5—C6—C7—C8	55.0 (2)
C10—O2—C2—N2	−1.2 (2)	C6—C7—C8—C9	−55.5 (2)
C2—O2—C10—C11	−152.09 (15)	C7—C8—C9—C4	56.8 (2)
C3—O3—C16—C17	−148.75 (15)	O2—C10—C11—C12	−177.83 (14)
C16—O3—C3—N2	177.09 (15)	C11—C10—C15—C14	58.48 (19)
C16—O3—C3—N3	−3.1 (2)	C15—C10—C11—C12	−58.6 (2)
C3—O3—C16—C21	90.51 (18)	O2—C10—C15—C14	176.06 (13)
C2—N1—C1—O1	−179.98 (15)	C10—C11—C12—C13	58.4 (2)
C1—N1—C2—O2	−178.09 (15)	C11—C12—C13—C14	−58.9 (2)
C2—N1—C1—N3	−0.7 (3)	C12—C13—C14—C15	58.0 (2)
C1—N1—C2—N2	1.4 (3)	C13—C14—C15—C10	−57.36 (19)
C2—N2—C3—N3	0.1 (3)	O3—C16—C17—C18	−176.46 (14)
C3—N2—C2—O2	178.35 (15)	C21—C16—C17—C18	−57.1 (2)
C3—N2—C2—N1	−1.1 (3)	O3—C16—C21—C20	175.18 (14)
C2—N2—C3—O3	179.86 (14)	C17—C16—C21—C20	58.1 (2)
C1—N3—C3—O3	−179.28 (15)	C16—C17—C18—C19	55.9 (2)
C3—N3—C1—N1	−0.2 (3)	C17—C18—C19—C20	−56.4 (2)
C3—N3—C1—O1	179.16 (15)	C18—C19—C20—C21	56.6 (2)
C1—N3—C3—N2	0.5 (3)	C19—C20—C21—C16	−57.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O1ⁱ	0.99	2.45	3.413 (2)	164
C9—H9A···O3ⁱⁱ	0.99	2.60	3.528 (2)	156
C10—H10···O1ⁱⁱ	1.00	2.95	3.787 (2)	142
C5—H5B···N1ⁱⁱⁱ	0.99	2.77	3.684 (2)	154

Symmetry codes: (i) x−1, y−1, z; (ii) −x+2, −y+2, −z+1; (iii) −x+3, −y+2, −z+1.

Acknowledgements

This work was supported by the Swiss National Science Foundation through the Indo-Swiss Joint Research Program (project number ISJRP 138 860).

References

Agilent (2014). CrysAlis PRO. Agilent Technologies, Yarnton, UK. Google Scholar
Allegra, G., Farina, M., Immirzi, A., Colombo, A., Rossi, U., Broggi, I. & Natta, G. (1967). J. Chem. Soc. B, pp. 1020–1028. Google Scholar
Baldwin, C. R., Britton, M. M., Davies, S. C., Gillies, D. G., Hughes, D. L., Smith, G. W. & Sutcliffe, L. H. (1997). J. Mol. Struct. 403, 1–16. CSD CrossRef CAS Web of Science Google Scholar
Couderc, G. & Hulliger, J. (2010). Chem. Soc. Rev. 39, 1545–1554. Web of Science CrossRef CAS PubMed Google Scholar
Harlow, R. L. & Desiraju, G. R. (1990). Acta Cryst. C46, 1054–1055. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Hoss, R., König, O., Kramer-Hoss, V., Berger, P., Rogin, P. & Hulliger, J. (1996). Angew. Chem. Int. Ed. Engl. 35, 1664–1666. CrossRef CAS Web of Science Google Scholar
Jessiman, A. S., MacNicol, D. D., Mallinson, P. R. & Vallance, I. (1990). J. Chem. Soc. Chem. Commun. pp. 1619–1621. CrossRef Web of Science Google Scholar
Kamiński, Z. J., Markowicz, S. W., Kolesińska, B., Martynowski, D. & Główka, M. L. (1998). Synth. Commun. 28, 2689–2696. Google Scholar
König, O., Bürgi, H. B., Armbruster, T., Hulliger, J. & Weber, T. (1997). J. Am. Chem. Soc. 119, 10632–10640. CSD CrossRef Web of Science Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mibu, N., Yokomizo, K., Takemura, S., Ueki, N., Itohara, S., Zhou, J., Miyata, T. & Sumoto, K. (2013). Chem. Pharm. Bull. 61, 823–833. CrossRef CAS PubMed Google Scholar
POV-RAY Team (2004). POV-RAY – The Persistance of Vision Raytracer. http://www.povray.org Google Scholar
Reichenbächer, K., Süss, H. I., Stoeckli-Evans, H., Bracco, S., Sozzani, P., Weber, E. & Hulliger, J. (2004). New J. Chem. 28, 393–397. 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
Süss, H. I., Lutz, M. & Hulliger, J. (2002). CrystEngComm, 4, 610–612. Google Scholar
Süss, H. I., Neels, A. & Hulliger, J. (2005). CrystEngComm, 7, 370–373. Google Scholar