3-(4-Hy­droxy­phen­yl)-1,5-bis­(pyridin-2-yl)pentane-1,5-dione

Pan, L.; Shi, H.; Ma, Z.

doi:10.1107/S1600536813025518

organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page o1580

doi:10.1107/S1600536813025518

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3-(4-Hydroxyphenyl)-1,5-bis(pyridin-2-yl)pentane-1,5-dione

Lixia Pan,^a Huaduan Shi ^b and Zhen Ma ^b ^*

^aState Key Laboratory of Non-Food Biomass and Enzyme Technology, National Engineering Research Center for Non-Food Biorefinery, Guangxi Key Laboratory of Biorefinery, Guangxi Academy of Sciences, Nanning, Guangxi 530007, People's Republic of China, and ^bSchool of Chemistry and Chemical Engeneering, Guangxi University, Nanning, Guangxi 530004, People's Republic of China
^*Correspondence e-mail: mzmz2009@sohu.com

(Received 8 August 2013; accepted 13 September 2013; online 21 September 2013)

In the title molecule, C₂₁H₁₈N₂O₃, the pyridine rings make a dihedral angle of 13.1 (1)°. The phenyl ring is approximately perpendicular to both of them, forming dihedral angles of 87.4 (1)and 81.9 (1)°. In the crystal, pairs of O—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers. Additional C—H⋯O, π–π [centroid–centroid distance = 3.971 (2) Å] and C—H⋯π interactions consolidate the dimers into a three-dimensional network.

CCDC reference: 960963

Related literature

For the synthesis of the title compound, see: Constable et al. (1990 , 1998 ); He et al. (2006 ). For the syntheses of terpyridine compounds and their properties and applications, see: Ma et al. (2009 , 2010 , 2012 , 2013 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₁H₁₈N₂O₃
M_r = 346.37
Triclinic, $[P \overline 1]$
a = 8.4392 (6) Å
b = 10.6683 (7) Å
c = 11.0755 (8) Å
α = 100.623 (6)°
β = 103.867 (6)°
γ = 110.550 (6)°
V = 866.05 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.39 × 0.38 × 0.22 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2012 ) T_min = 0.813, T_max = 1.000
6339 measured reflections
3544 independent reflections
2661 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.119
S = 1.03
3544 reflections
308 parameters
All H-atom parameters refined
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C16–C21 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H03A⋯N2ⁱ	0.93 (2)	2.00 (2)	2.8940 (19)	160 (2)
C12—H12A⋯O2ⁱⁱ	0.96 (2)	2.48 (2)	3.312 (3)	145 (2)
C4a—H4a⋯Cg3ⁱⁱⁱ	0.99 (2)	0.98 (2)	3.825 (2)	144 (2)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+2, -z+1; (iii) x, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 960963

Crystal structure: contains datablocks I, C21H18N2O3. DOI: 10.1107/S1600536813025518/ld2113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813025518/ld2113Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813025518/ld2113Isup3.cml

checkCIF report

Comment top

Metal terpyridene complexes is a topic of major current interest because they show very interesting properties, such as photoluminescence, catalytic and antibiological activities (Ma, Xing et al. 2009; Ma, Cao et al. 2010; Ma, Liang et al. 2012; Ma, Lu et al. 2013). Hence, the aim of our current work was to prepare a series of precursors to produce terpyridine ligands, investigate their coordination behavior toward metal ions and study their applications (Constable, Lewis et al. 1990; Constable, Neuburger et al. 1998). Here, we report the structure of a precursor compound for terpyridine synthesis, which was obtained by reaction of 4-hydroxybenzaldehyde with 2-acetylpyridine in a mixed water/ethanol solution of NaOH, and its structure was determined by X-ray crystal analysis.

The molecular structure is shown in Fig. 1. The average bond length C=O for two carbonyls is 1.1212 Å. Other averages are 1.336 Å for N-C bonds, 1.371 Å for C-C bonds of the pyridyl groups and 1.384 Å for C-C bonds of the aryl group. All bond lengths are within normal ranges (Allen et al., 1987). The two pyridyl groups are not parallel, with a dihedral angle of 13.14 (10) °. The plane of aromatic ring with the hydroxyl group (with an r.m.s. deviation of 0.0041 Å) is approximately perpendicular to those of the two pyridyl groups, forming two dihedral angles of 87.36 (5) and 81.90 (6)°, respectively.

Each molecule forms hydrogen bonds (Table 1) involving its hydroxy group and a nitrogen pyridyl atom (N2ⁱⁱ) of a neighboring molecule [symmetry code: (ii) 1-x, 1-y, -z]) and also an H-bond between C(12)-H group and a carbonyl oxygen (O2ⁱⁱⁱ) of a neighboring molecule [symmetry code: (iii) 2-x, 2-y, 1-z] (Table 1). These hydrogen bonds account for the formation of centrosymmetric dimers (see Fig 2). The structure also has one intermolecular π···π interaction with a distance of 3.971 Å between two neighboring pyridyl groups (see Fig 2)[Cg1 and Cg2(iv) or Cg2 and Cg1(v); Cg2 and Cg1 are the two centroids of the two six membered pyridyl rings of C1-C5-N1 or C11-C15-N2, symmetry code: (iv) -1+x, -1+y, z; (v) 1+x, 1+y, z]. Further structural stabilization is provided by an intermolecular C—H···π interaction between C(4)-H and its neighboring aryl group Cg3 (Fig 2) [H..Cg 2.98 Å; Cg(3) is the centroid of the six membered aromatic ring C16ⁱ-C21ⁱ, symmetry code: (i) x, -1+y-1, z]. These π···π and C—H···π interactions help to consolidate the H-bonded dimers into a three-dimensional network (Fig 3).

Related literature top

For the synthesis of the title compound, see: Constable et al. (1990, 1998); He et al. (2006). For the syntheses of terpyridine compounds and their properties and applications, see: Ma et al. (2009, 2010, 2012, 2013). For standard bond lengths, see: Allen et al. (1987).

Experimental top

The title compound was obtained by reaction of 4-hydroxybenzaldehyde with 2-acetylpyridine in a 1.5 M NaOH mixed aqueous/ethanol solution according to a reported procedure (Constable, et al. 1990). In a 250 cm³ flask fitted with a funnel, 4-hydroxybenzaldehyde (5.5 g, 45 mM) and 40 mL of the 1.5 M NaOH aqueous solution were mixed in 60 cm³ of ethanol. To this solution was added dropwise a stoichiometric quantity of 2-acetylpyridine (10 mL, 89 mM) for a period of half an hour with stirring. The mixture was then stirred for 24 h at room temperature. A white solid formed was obtained by filtration and being washed with two times with distilled water (yield 70 %). The product (25 mg) and distilled water (20 mL) were sealed in a 25-mL stainless steel reactor with Teflon liner and heated at 393 K for 1 d. Colourless crystals were obtained, which were suitable for X-ray characterization.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the crystal packing to show the formation of centrosymmetric H-bonded dimers by the help of the hydrogen bonds and the π···π interactions between the pyridyl groups of the compound. The thin dashed lines are used to show the hydrogen bonds. The blue dotted lines are used to show π···π interactions between the pyridyl groups of the compound
	Fig. 3. A view of the crystal packing along the a axis to show the three-dimensional network.

3-(4-Hydroxyphenyl)-1,5-bis(pyridin-2-yl)pentane-1,5-dione top

Crystal data top

C₂₁H₁₈N₂O₃	Z = 2
M_r = 346.37	F(000) = 364
Triclinic, P1	D_x = 1.328 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4392 (6) Å	Cell parameters from 6339 reflections
b = 10.6683 (7) Å	θ = 3.2–26.4°
c = 11.0755 (8) Å	µ = 0.09 mm⁻¹
α = 100.623 (6)°	T = 298 K
β = 103.867 (6)°	Prism, colourless
γ = 110.550 (6)°	0.39 × 0.38 × 0.22 mm
V = 866.05 (10) Å³

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3544 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2661 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.017
Detector resolution: 0 pixels mm^-1	θ_max = 26.4°, θ_min = 3.2°
ω scans	h = −10→9
Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2012)	k = −13→13
T_min = 0.813, T_max = 1.000	l = −13→11
6339 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	All H-atom parameters refined
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0498P)² + 0.1436P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3544 reflections	Δρ_max = 0.18 e Å⁻³
308 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (3)

Crystal data top

C₂₁H₁₈N₂O₃	γ = 110.550 (6)°
M_r = 346.37	V = 866.05 (10) Å³
Triclinic, P1	Z = 2
a = 8.4392 (6) Å	Mo Kα radiation
b = 10.6683 (7) Å	µ = 0.09 mm⁻¹
c = 11.0755 (8) Å	T = 298 K
α = 100.623 (6)°	0.39 × 0.38 × 0.22 mm
β = 103.867 (6)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	3544 independent reflections
Absorption correction: multi-scan (CrysAlis PRO, Agilent, 2012)	2661 reflections with I > 2σ(I)
T_min = 0.813, T_max = 1.000	R_int = 0.017
6339 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.119	All H-atom parameters refined
S = 1.03	Δρ_max = 0.18 e Å⁻³
3544 reflections	Δρ_min = −0.14 e Å⁻³
308 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.71359 (19)	0.30614 (12)	0.46604 (11)	0.0618 (4)
O2	0.91770 (19)	0.78344 (12)	0.42074 (12)	0.0667 (4)
O3	0.08708 (17)	0.40522 (14)	0.08964 (13)	0.0592 (3)
H03A	0.044 (3)	0.351 (3)	0.003 (2)	0.100 (8)*
N1	0.6613 (2)	0.06026 (14)	0.18572 (13)	0.0603 (4)
N2	1.06938 (19)	0.81798 (14)	0.15318 (13)	0.0493 (4)
C1	0.6711 (2)	0.10690 (15)	0.30835 (14)	0.0409 (4)
C2	0.6203 (3)	0.01932 (17)	0.38203 (17)	0.0545 (5)
H2A	0.632 (2)	0.0607 (19)	0.4701 (18)	0.060 (5)*
C3	0.5570 (3)	−0.12308 (18)	0.32835 (19)	0.0639 (5)
H3A	0.524 (3)	−0.184 (2)	0.3782 (19)	0.078 (6)*
C4	0.5449 (3)	−0.17259 (19)	0.20295 (19)	0.0680 (6)
H4A	0.501 (3)	−0.273 (2)	0.159 (2)	0.083 (6)*
C5	0.5963 (4)	−0.07886 (19)	0.1355 (2)	0.0791 (7)
H5A	0.586 (3)	−0.110 (2)	0.044 (2)	0.092 (7)*
C6	0.7379 (2)	0.26254 (15)	0.36597 (14)	0.0414 (4)
C7	0.8359 (2)	0.35918 (16)	0.29975 (17)	0.0432 (4)
H7A	0.966 (3)	0.3793 (18)	0.3406 (17)	0.060 (5)*
H7B	0.798 (2)	0.3108 (17)	0.2046 (16)	0.049 (4)*
C8	0.8128 (2)	0.49738 (14)	0.32322 (14)	0.0378 (3)
H8A	0.847 (2)	0.5387 (15)	0.4188 (15)	0.040 (4)*
C9	0.9371 (2)	0.60196 (15)	0.27268 (16)	0.0409 (4)
H9B	1.059 (2)	0.6076 (17)	0.2993 (15)	0.052 (5)*
H9A	0.897 (2)	0.5730 (17)	0.1737 (17)	0.052 (5)*
C10	0.9588 (2)	0.74944 (15)	0.32631 (15)	0.0426 (4)
C11	1.0436 (2)	0.85928 (15)	0.26587 (15)	0.0428 (4)
C12	1.0940 (3)	0.99903 (18)	0.3296 (2)	0.0623 (5)
H12A	1.072 (3)	1.023 (2)	0.410 (2)	0.075 (6)*
C13	1.1764 (3)	1.0996 (2)	0.2766 (2)	0.0798 (7)
H13A	1.215 (3)	1.200 (3)	0.322 (2)	0.108 (8)*
C14	1.2058 (3)	1.0592 (2)	0.1633 (2)	0.0808 (7)
H14A	1.263 (3)	1.123 (3)	0.122 (2)	0.100 (8)*
C15	1.1504 (3)	0.9187 (2)	0.1043 (2)	0.0665 (5)
H15A	1.167 (3)	0.886 (2)	0.0226 (19)	0.068 (6)*
C16	0.6193 (2)	0.47157 (13)	0.26132 (13)	0.0352 (3)
C17	0.5210 (2)	0.51095 (15)	0.33320 (15)	0.0404 (4)
H17A	0.582 (2)	0.5549 (16)	0.4262 (16)	0.047 (4)*
C18	0.3451 (2)	0.48794 (16)	0.27609 (15)	0.0439 (4)
H18A	0.281 (2)	0.5150 (18)	0.3262 (16)	0.055 (5)*
C19	0.2610 (2)	0.42459 (15)	0.14348 (15)	0.0412 (4)
C20	0.3557 (2)	0.38460 (16)	0.06964 (15)	0.0431 (4)
H20A	0.297 (2)	0.3412 (18)	−0.0231 (17)	0.056 (5)*
C21	0.5317 (2)	0.40803 (15)	0.12846 (14)	0.0412 (4)
H21A	0.598 (2)	0.3788 (17)	0.0732 (16)	0.052 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0992 (11)	0.0463 (6)	0.0503 (7)	0.0314 (7)	0.0388 (7)	0.0165 (5)
O2	0.0913 (11)	0.0402 (6)	0.0726 (8)	0.0205 (6)	0.0498 (8)	0.0096 (6)
O3	0.0476 (8)	0.0696 (8)	0.0573 (8)	0.0270 (6)	0.0158 (6)	0.0081 (6)
N1	0.0922 (13)	0.0422 (8)	0.0493 (8)	0.0227 (8)	0.0355 (8)	0.0142 (6)
N2	0.0491 (9)	0.0450 (7)	0.0508 (8)	0.0142 (6)	0.0180 (6)	0.0160 (6)
C1	0.0478 (10)	0.0381 (8)	0.0402 (8)	0.0191 (7)	0.0162 (7)	0.0144 (6)
C2	0.0769 (13)	0.0433 (9)	0.0463 (9)	0.0213 (9)	0.0281 (9)	0.0168 (8)
C3	0.0923 (16)	0.0427 (9)	0.0621 (11)	0.0231 (10)	0.0357 (11)	0.0241 (9)
C4	0.0978 (17)	0.0371 (9)	0.0669 (12)	0.0208 (10)	0.0369 (11)	0.0125 (9)
C5	0.132 (2)	0.0432 (10)	0.0587 (12)	0.0238 (11)	0.0485 (13)	0.0097 (9)
C6	0.0495 (10)	0.0409 (8)	0.0380 (8)	0.0218 (7)	0.0156 (7)	0.0135 (7)
C7	0.0499 (11)	0.0369 (8)	0.0492 (9)	0.0206 (7)	0.0211 (8)	0.0152 (7)
C8	0.0438 (9)	0.0325 (7)	0.0377 (8)	0.0152 (6)	0.0161 (7)	0.0093 (6)
C9	0.0419 (10)	0.0329 (7)	0.0491 (9)	0.0140 (7)	0.0199 (7)	0.0108 (7)
C10	0.0423 (9)	0.0346 (7)	0.0472 (8)	0.0126 (7)	0.0172 (7)	0.0075 (7)
C11	0.0404 (9)	0.0348 (7)	0.0496 (9)	0.0133 (7)	0.0132 (7)	0.0110 (7)
C12	0.0771 (14)	0.0387 (9)	0.0689 (12)	0.0200 (9)	0.0284 (11)	0.0131 (9)
C13	0.1020 (18)	0.0371 (10)	0.0973 (16)	0.0189 (11)	0.0391 (14)	0.0247 (11)
C14	0.0974 (18)	0.0550 (12)	0.0934 (16)	0.0188 (11)	0.0427 (14)	0.0405 (12)
C15	0.0765 (15)	0.0599 (11)	0.0652 (12)	0.0200 (10)	0.0317 (11)	0.0285 (10)
C16	0.0438 (9)	0.0261 (6)	0.0379 (7)	0.0128 (6)	0.0182 (6)	0.0112 (6)
C17	0.0494 (10)	0.0371 (7)	0.0351 (8)	0.0163 (7)	0.0183 (7)	0.0092 (6)
C18	0.0475 (10)	0.0432 (8)	0.0465 (9)	0.0205 (7)	0.0246 (8)	0.0102 (7)
C19	0.0417 (9)	0.0358 (7)	0.0475 (8)	0.0154 (7)	0.0174 (7)	0.0133 (7)
C20	0.0466 (10)	0.0410 (8)	0.0366 (8)	0.0135 (7)	0.0153 (7)	0.0071 (7)
C21	0.0464 (10)	0.0385 (8)	0.0405 (8)	0.0164 (7)	0.0222 (7)	0.0078 (6)

Geometric parameters (Å, º) top

O1—C6	1.2135 (17)	C8—H8A	0.996 (15)
O2—C10	1.2114 (18)	C9—C10	1.504 (2)
O3—C19	1.3689 (19)	C9—H9B	0.975 (18)
O3—H03A	0.93 (2)	C9—H9A	1.017 (17)
N1—C1	1.3295 (19)	C10—C11	1.504 (2)
N1—C5	1.338 (2)	C11—C12	1.387 (2)
N2—C15	1.339 (2)	C12—C13	1.372 (3)
N2—C11	1.340 (2)	C12—H12A	0.96 (2)
C1—C2	1.375 (2)	C13—C14	1.360 (3)
C1—C6	1.504 (2)	C13—H13A	0.99 (3)
C2—C3	1.375 (2)	C14—C15	1.376 (3)
C2—H2A	0.960 (18)	C14—H14A	0.95 (3)
C3—C4	1.357 (3)	C15—H15A	0.966 (19)
C3—H3A	0.94 (2)	C16—C21	1.389 (2)
C4—C5	1.368 (3)	C16—C17	1.391 (2)
C4—H4A	0.99 (2)	C17—C18	1.378 (2)
C5—H5A	0.99 (2)	C17—H17A	0.971 (16)
C6—C7	1.502 (2)	C18—C19	1.384 (2)
C7—C8	1.538 (2)	C18—H18A	0.938 (18)
C7—H7A	1.006 (19)	C19—C20	1.384 (2)
C7—H7B	1.001 (16)	C20—C21	1.381 (2)
C8—C16	1.513 (2)	C20—H20A	0.967 (17)
C8—C9	1.532 (2)	C21—H21A	0.998 (17)

C19—O3—H03A	109.1 (15)	H9B—C9—H9A	104.6 (13)
C1—N1—C5	116.28 (15)	O2—C10—C9	121.67 (14)
C15—N2—C11	116.90 (15)	O2—C10—C11	119.15 (13)
N1—C1—C2	122.88 (14)	C9—C10—C11	119.08 (13)
N1—C1—C6	117.47 (13)	N2—C11—C12	122.63 (15)
C2—C1—C6	119.64 (14)	N2—C11—C10	118.46 (13)
C1—C2—C3	119.43 (16)	C12—C11—C10	118.91 (15)
C1—C2—H2A	118.1 (11)	C13—C12—C11	119.0 (2)
C3—C2—H2A	122.4 (11)	C13—C12—H12A	121.8 (12)
C4—C3—C2	118.47 (17)	C11—C12—H12A	119.2 (12)
C4—C3—H3A	121.3 (12)	C14—C13—C12	118.97 (19)
C2—C3—H3A	120.2 (12)	C14—C13—H13A	121.0 (15)
C3—C4—C5	118.65 (17)	C12—C13—H13A	120.0 (15)
C3—C4—H4A	122.3 (12)	C13—C14—C15	119.1 (2)
C5—C4—H4A	119.1 (12)	C13—C14—H14A	123.3 (14)
N1—C5—C4	124.27 (18)	C15—C14—H14A	117.6 (15)
N1—C5—H5A	114.4 (13)	N2—C15—C14	123.4 (2)
C4—C5—H5A	121.3 (13)	N2—C15—H15A	115.5 (12)
O1—C6—C7	122.05 (14)	C14—C15—H15A	121.1 (12)
O1—C6—C1	118.79 (14)	C21—C16—C17	116.72 (14)
C7—C6—C1	119.14 (13)	C21—C16—C8	121.07 (13)
C6—C7—C8	112.24 (13)	C17—C16—C8	122.21 (13)
C6—C7—H7A	104.7 (10)	C18—C17—C16	121.93 (14)
C8—C7—H7A	109.3 (10)	C18—C17—H17A	121.3 (9)
C6—C7—H7B	110.5 (9)	C16—C17—H17A	116.7 (10)
C8—C7—H7B	111.5 (9)	C17—C18—C19	120.22 (15)
H7A—C7—H7B	108.3 (14)	C17—C18—H18A	120.7 (10)
C16—C8—C9	110.96 (12)	C19—C18—H18A	119.0 (11)
C16—C8—C7	110.90 (12)	O3—C19—C20	122.26 (14)
C9—C8—C7	110.75 (12)	O3—C19—C18	118.70 (14)
C16—C8—H8A	107.9 (9)	C20—C19—C18	119.04 (15)
C9—C8—H8A	108.1 (9)	C21—C20—C19	119.99 (14)
C7—C8—H8A	108.1 (8)	C21—C20—H20A	121.1 (10)
C10—C9—C8	112.42 (13)	C19—C20—H20A	118.9 (10)
C10—C9—H9B	104.4 (10)	C20—C21—C16	122.10 (14)
C8—C9—H9B	112.2 (10)	C20—C21—H21A	118.6 (9)
C10—C9—H9A	110.8 (9)	C16—C21—H21A	119.3 (10)
C8—C9—H9A	111.9 (10)

C5—N1—C1—C2	0.8 (3)	C9—C10—C11—N2	11.1 (2)
C5—N1—C1—C6	−178.05 (18)	O2—C10—C11—C12	8.4 (3)
N1—C1—C2—C3	0.3 (3)	C9—C10—C11—C12	−168.07 (16)
C6—C1—C2—C3	179.14 (17)	N2—C11—C12—C13	−1.1 (3)
C1—C2—C3—C4	−0.7 (3)	C10—C11—C12—C13	178.02 (18)
C2—C3—C4—C5	0.1 (3)	C11—C12—C13—C14	0.1 (4)
C1—N1—C5—C4	−1.6 (4)	C12—C13—C14—C15	0.7 (4)
C3—C4—C5—N1	1.1 (4)	C11—N2—C15—C14	−0.4 (3)
N1—C1—C6—O1	164.80 (16)	C13—C14—C15—N2	−0.6 (4)
C2—C1—C6—O1	−14.1 (2)	C9—C8—C16—C21	64.71 (16)
N1—C1—C6—C7	−16.5 (2)	C7—C8—C16—C21	−58.83 (17)
C2—C1—C6—C7	164.56 (16)	C9—C8—C16—C17	−114.63 (14)
O1—C6—C7—C8	−30.0 (2)	C7—C8—C16—C17	121.83 (14)
C1—C6—C7—C8	151.38 (14)	C21—C16—C17—C18	0.2 (2)
C6—C7—C8—C16	−65.15 (17)	C8—C16—C17—C18	179.58 (13)
C6—C7—C8—C9	171.20 (13)	C16—C17—C18—C19	−0.3 (2)
C16—C8—C9—C10	72.76 (16)	C17—C18—C19—O3	−179.03 (13)
C7—C8—C9—C10	−163.62 (14)	C17—C18—C19—C20	0.2 (2)
C8—C9—C10—O2	16.4 (2)	O3—C19—C20—C21	179.21 (13)
C8—C9—C10—C11	−167.22 (13)	C18—C19—C20—C21	0.0 (2)
C15—N2—C11—C12	1.2 (3)	C19—C20—C21—C16	−0.1 (2)
C15—N2—C11—C10	−177.89 (16)	C17—C16—C21—C20	0.0 (2)
O2—C10—C11—N2	−172.47 (15)	C8—C16—C21—C20	−179.38 (13)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C16–C21 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H03A···N2ⁱ	0.93 (2)	2.00 (2)	2.8940 (19)	160 (2)
C12—H12A···O2ⁱⁱ	0.96 (2)	2.48 (2)	3.312 (3)	145 (2)
C4a—H4a···Cg3ⁱⁱⁱ	0.99 (2)	0.98 (2)	3.825 (2)	144 (2)

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

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C16–C21 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H03A···N2ⁱ	0.93 (2)	2.00 (2)	2.8940 (19)	160 (2)
C12—H12A···O2ⁱⁱ	0.96 (2)	2.48 (2)	3.312 (3)	145 (2)
C4a—H4a···Cg3ⁱⁱⁱ	0.99 (2)	0.98 (2)	3.825 (2)	144.1 (16)

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

Acknowledgements

The authors are grateful for financial support from the Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (K008).

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