Ethyl 4-[2-(3,5-dimethyl-4-oxo-2,6-diphenyl-piperidin-1-yl)-2-oxoeth-yl]piperazine-1-carboxyl-ate.

Abstract

In the title compound, C(28)H(35)N(3)O(4), the piperidine ring adopts a boat conformation while the piperazine ring adopts a chair conformation with an equatorial orientation of the phenyl groups. The dihedral angle between the mean planes of the benzene rings is 74.14 (8)°. The mol-ecular conformation is stabilized by a weak intra-molecular C-H⋯N inter-action and the crystal packing is stabilized by weak inter-molecular C-H⋯O inter-actions.

Full text

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Ethyl 4-[2-(3,5-dimethyl-4-oxo-2,6-
diphenylpiperidin-1-yl)-2-oxoethyl]-
piperazine-1-carboxylate
Mannangatty Rani,aRajamanickam Ramachandran,b
Senthamaraikannan Kabilanaand Yeon Tae Jeongb*
aDepartment of Chemistry, Annamalai University, Annamalai Nagar 608 002, Tamil
Nadu, India, andbDepartment of Image Science and Engineering, Pukyong National
University, Busan 608-737, Republic of Korea
Correspondence e-mail: ytjeong@pknu.ac.kr
Received 13 January 2011; accepted 26 January 2011
Key indicators: single-crystal X-ray study; T = 293 K; mean ?(C–C) = 0.002 A ˚;
R factor = 0.047; wR factor = 0.142; data-to-parameter ratio = 22.0.
In the title compound, C28H35N3O4, the piperidine ring adopts
a boat conformation while the piperazine ring adopts a chair
conformation with an equatorial orientation of the phenyl
groups. The dihedral angle between the mean planes of the
benzene rings is 74.14 (8)?. The molecular conformation is
stabilized by a weak intramolecular C—H???N interaction and
the crystal packing is stabilized by weak intermolecular C—
H???O interactions.
Related literature
For the biological activity of related structures, see: El-
subbagh et al. (2000); Emami et al. (2006); Foroumadi et al.
(2007); Katritzky & Fan (1990); Mobio et al. (1989). For
geometrical analysis, see: Cremer & Pople (1975); Emami et al.
(2006); Foroumadi et al. (2007); Nardelli (1983).
Experimental
Crystal data
C28H35N3O4
Mr= 477.59
Monoclinic, P21=n
a = 10.9073 (3) A˚
b = 19.1940 (6) A˚
c = 12.2246 (3) A˚
? = 91.809 (2)?
V = 2558.00 (12) A˚3
Z = 4
Mo K? radiation
? = 0.08 mm?1
T = 293 K
0.30 ? 0.20 ? 0.20 mm
Data collection
Bruker Kappa APEXII CCD
diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Tmin= 0.975, Tmax= 0.984
31692 measured reflections
6941 independent reflections
4703 reflections with I > 2?(I)
Rint= 0.029
Refinement
R[F2> 2?(F2)] = 0.047
wR(F2) = 0.142
S = 1.01
6941 reflections
316 parameters
H-atom parameters constrained
??max= 0.38 e A˚?3
??min= ?0.18 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
C5—H5???N2
C8—H8???O2i
C24—H24A???O1ii
Symmetry codes: (i) ?x;?y;?z þ 1; (ii) ?x þ 1;?y;?z.
D—HH???AD???AD—H???A
0.98
0.93
0.97
2.51
2.54
2.56
3.1788 (17)
3.4406 (19)
3.520 (2)
125
162
169
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2
and SAINT (Bruker, 2004); data reduction: SAINT and XPREP
(Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare
et al., 1993); program(s) used to refine structure: SHELXL97 (Shel-
drick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software
used to prepare material for publication: SHELXL97.
This study was supported financially by Pukyong National
University in the 2010 post-doc programme. The authors are
thankful to the SAIF, Indian Institute of Technology, Madras,
for the data collection.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: ZQ2086).
References
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl.
Cryst. 26, 343-350.
Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2004). APEX2, SAINT and XPREP. Bruker AXS Inc., Madison,
Wisconsin, USA.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
El-subbagh, H. I., Abu-zaid, S. M., Mahran, M. A., Badria, F. A. & Al-obaid,
A. M. (2000). J. Med. Chem. 43, 2915–2921.
Emami, S., Shafiee, A. & Foroumadi, A. (2006). Mini Rev. Med. Chem. 6, 375–
386.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Foroumadi, A., Emami, S., Mansouri, S., Javidnia, A., Saeid-Adeli, N., Shirazi,
F. H. & Shafiee, A. (2007). Eur. J. Med. Chem. 42, 985–992.
Katritzky, A. R. & Fan, W. (1990). J. Org. Chem. 55, 3205–3209.
Mobio, I. G., Soldatenkov, A. T., Federov, V. O., Ageev, E. A., Sergeeva, N. D.,
Lin, S., Stashenku, E. E., Prostakov, N. S. & Andreeva, E. L. (1989). Khim.
Farm. Zh. 23, 421–427.
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
organic compounds
Acta Cryst. (2011). E67, o541doi:10.1107/S1600536811003412Rani et al.
o541
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
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Acta Cryst. (2011). E67, o541 [ doi:10.1107/S1600536811003412 ]
Ethyl 4-[2-(3,5-dimethyl-4-oxo-2,6-diphenylpiperidin-1-yl)-2-oxoethyl]piperazine-1-carboxylate
M. Rani, R. Ramachandran, S. Kabilan and Y. T. Jeong
Comment
Several interesting investigations have been carried out with piperidine based heterocyclic compounds and these compounds
were found to exhibit numerous pharmacological properties and biological activities such as anticancer, antimicrobial, anti-
inflammatory, antiviral, antimalarial and anesthetics (El-subbagh et al., 2000; Mobio et al., 1989; Katritzky & Fan, 1990).
Similarly, some compounds containing piperazine are used as antibiotic drugs, e.g., Norfloxacin, Ciprofloxacin, Enoxacin,
Ofloxacin and Levofloxacine (Emami et al., 2006; Foroumadi et al., 2007).
In the title compound, C28H35N3O4, the piperidine ring adopts a boat conformation. The corresponding puckering para-
meters (Cremer & Pople, 1975) and smallest displacement asymmetry parameters (Nardelli, 1983) are q1 = 0.6111 (15) Å,
q2 = -0.0839 (15) Å, QT = 0.6168 (15) Å, and θ = 97.81 (14) °. Unlike, the piperazine ring adopts a chair conformation
with q1 = 0.0367 (15), q2 = 0.5606 (15) Å, QT = 0.5618 (15) Å and θ = 3.75 (15)°. The phenyl groups are orientated to
the same side of the piperazine ring. The dihedral angle between the mean planes of the benzene rings is 74.14 (8)°. The
molecular conformation is stabilized by a weak intramolecular C5-H5···N2 interaction and the crystal packing by the weak
intermolecular C8-H8···O2i and C24-H24···O1ii interactions [Table 1; symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z].
Experimental
A mixture of N-chloroacetyl-3,5-dimethyl-2,6-diphenylpiperidin-4-one (0.005 mol), triethylamine (0.01 mol) and N-ethoxy-
carbonylpiperazine (0.005 mol) in toluene were refluxed for about 6–8 h. After the completion of reaction, excess of solvent
was removed under reduced pressure. The obtained residue was column chromatographed on silica gel using benzene:ethyl
acetate (2:1) mixture as an eluent which afforded the title compound in good yield. Colourless crystals were grown by slow
evaporation method using ethanol as solvent.
Refinement
H atoms were positioned and refined using a riding model, with aromatic C—H = 0.93 Å, methine C—H = 0.98 Å, methylene
C—H = 0.97 Å and methyl C—H = 0.96 Å. The displacement parameters were set to Uiso(H) = 1.5Ueq(C) for the methyl
H atoms and to Uiso(H) = 1.2Ueq(C) for the other H atoms.

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Figures
Fig. 1. A view of the molecular structure of the title compound. Displacement ellipsoids are
drawn at the 30% probability level.
Ethyl 4-[2-(3,5-dimethyl-4-oxo-2,6-diphenylpiperidin-1- yl)-2-oxoethyl]piperazine-1-carboxylate
Crystal data
C28H35N3O4
Mr = 477.59
Z = 4
F(000) = 1024
Dx = 1.240 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
θ = 2.0–29.2°
µ = 0.08 mm−1
T = 293 K
Prism, colourless
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 10.9073 (3) Å
b = 19.1940 (6) Å
c = 12.2246 (3) Å
β = 91.809 (2)°
V = 2558.00 (12) Å3
0.30 × 0.20 × 0.20 mm
Data collection
Bruker Kappa APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
ω and φ scans
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
Tmin = 0.975, Tmax = 0.984
31692 measured reflections
6941 independent reflections
4703 reflections with I > 2σ(I)
Rint = 0.029
θmax = 29.2°, θmin = 2.0°
h = −14→14
k = −26→26
l = −16→16
Refinement
Refinement on F2
Primary atom site location: structure-invariant direct
methods
Secondary atom site location: difference Fourier mapLeast-squares matrix: full

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supplementary materials
sup-3
R[F2 > 2σ(F2)] = 0.047
Hydrogen site location: inferred from neighbouring
sites
wR(F2) = 0.142
H-atom parameters constrained
S = 1.01
w = 1/[σ2(Fo2) + (0.0676P)2 + 0.4844P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.38 e Å−3
Δρmin = −0.18 e Å−3
6941 reflections
316 parameters
0 restraints
Special details
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 mat-
rix. 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 of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(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)
x
0.30276 (10)
0.27565 (10)
0.83211 (11)
0.87576 (10)
0.48203 (10)
0.72912 (11)
0.36909 (18)
0.35944 (12)
0.3047
0.3618
0.30991 (11)
0.24946 (13)
0.2739
0.69961 (13)
0.7577
0.7059
0.11293 (13)
0.33470 (14)
0.3107
0.03802 (14)
0.0729
0.18481 (14)
0.28059 (13)
0.3615
y
0.02315 (6)
0.01252 (6)
0.26851 (6)
0.17829 (6)
0.12188 (6)
0.16692 (7)
−0.11603 (8)
0.12158 (7)
0.1482
0.1441
0.04850 (7)
−0.06249 (7)
−0.0741
0.09713 (8)
0.0831
0.0646
−0.07761 (7)
−0.10402 (8)
−0.1532
−0.04948 (8)
−0.0228
0.09997 (7)
0.04335 (7)
0.0648
z
0.45786 (8)
0.27464 (8)
0.33044 (11)
0.44239 (10)
0.31107 (9)
0.31251 (11)
0.02744 (11)
0.35490 (11)
0.3068
0.4260
0.36633 (10)
0.28730 (11)
0.3630
0.34954 (14)
0.4071
0.2893
0.27691 (11)
0.21546 (12)
0.2182
0.35541 (12)
0.4118
0.14324 (11)
0.16348 (10)
0.1569
Uiso*/Ueq
0.0474 (3)
0.0346 (2)
0.0674 (4)
0.0594 (3)
0.0354 (2)
0.0469 (3)
0.1013 (6)
0.0385 (3)
0.046*
0.046*
0.0346 (3)
0.0379 (3)
0.045*
0.0481 (4)
0.058*
0.058*
0.0391 (3)
0.0458 (3)
0.055*
0.0454 (3)
0.054*
0.0414 (3)
0.0380 (3)
0.046*
O2
N1
O3
O4
N2
N3
O1
C21
H21A
H21B
C20
C1
H1
C23
H23A
H23B
C6
C2
H2
C7
H7
C12
C5
H5

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supplementary materials
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C4
H4
C22
H22A
H22B
C11
H11
C3
C13
H13
C25
H25A
H25B
C24
H24A
H24B
C8
H8
C9
H9
C17
H17
C26
C10
H10
C18
H18A
H18B
H18C
C27
H27A
H27B
C16
H16
C14
H14
C15
H15
C19
H19A
H19B
H19C
C28
H28A
H28B
H28C
0.26648 (15)
0.1785
0.57133 (12)
0.5503
0.5682
0.05813 (15)
0.1063
0.32775 (16)
0.06182 (15)
0.0359
0.51477 (13)
0.5134
0.4549
0.64026 (14)
0.6408
0.6616
−0.08692 (14)
−0.1355
−0.13964 (15)
−0.2239
0.21955 (18)
0.3017
0.81377 (13)
−0.06694 (16)
−0.1025
0.46803 (16)
0.4750
0.4943
0.5187
0.97832 (14)
0.9891
0.9616
0.1336 (2)
0.1586
−0.02354 (18)
−0.1063
0.0126 (2)
−0.0450
0.3060 (2)
0.2654
0.2845
0.3932
1.09184 (17)
1.1589
1.0813
1.1090
−0.01210 (8)
−0.0218
0.09542 (7)
0.0479
0.1234
−0.11776 (8)
−0.1380
−0.08057 (9)
0.08840 (9)
0.0452
0.19283 (7)
0.2228
0.2104
0.19466 (9)
0.1670
0.2422
−0.06037 (9)
−0.0410
−0.09967 (9)
−0.1070
0.16440 (9)
0.1731
0.20954 (8)
−0.12810 (9)
−0.1546
−0.09787 (11)
−0.1126
−0.0503
−0.1269
0.21660 (10)
0.2040
0.2662
0.21594 (9)
0.2593
0.14019 (11)
0.1315
0.20387 (11)
0.2388
0.01732 (12)
0.0610
−0.0148
0.0244
0.20086 (12)
0.2266
0.2138
0.1519
0.07262 (11)
0.0642
0.39208 (12)
0.4110
0.4580
0.19519 (13)
0.1424
0.09817 (13)
0.15817 (13)
0.1832
0.28016 (12)
0.3440
0.2266
0.23281 (12)
0.1664
0.2145
0.35137 (14)
0.4046
0.26901 (15)
0.2660
0.10412 (14)
0.0913
0.35904 (13)
0.19096 (15)
0.1347
0.25605 (16)
0.3310
0.2504
0.2122
0.49077 (15)
0.5673
0.4867
0.08396 (15)
0.0590
0.13642 (15)
0.1465
0.10038 (16)
0.0871
−0.03613 (14)
−0.0497
−0.0937
−0.0336
0.43263 (18)
0.4653
0.3571
0.4377
0.0473 (3)
0.057*
0.0405 (3)
0.049*
0.049*
0.0498 (4)
0.060*
0.0540 (4)
0.0518 (4)
0.062*
0.0434 (3)
0.052*
0.052*
0.0490 (4)
0.059*
0.059*
0.0516 (4)
0.062*
0.0560 (4)
0.067*
0.0577 (4)
0.069*
0.0470 (3)
0.0590 (4)
0.071*
0.0661 (5)
0.099*
0.099*
0.099*
0.0575 (4)
0.069*
0.069*
0.0719 (6)
0.086*
0.0678 (5)
0.081*
0.0750 (6)
0.090*
0.0801 (7)
0.120*
0.120*
0.120*
0.0743 (5)
0.111*
0.111*
0.111*

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supplementary materials
sup-5
Atomic displacement parameters (Å2)
U11
0.0544 (6)
0.0375 (6)
0.0553 (7)
0.0454 (6)
0.0334 (5)
0.0357 (6)
0.1630 (17)
0.0356 (7)
0.0284 (6)
0.0429 (7)
0.0386 (7)
0.0447 (7)
0.0509 (8)
0.0473 (8)
0.0502 (8)
0.0400 (7)
0.0538 (9)
0.0381 (7)
0.0549 (9)
0.0638 (10)
0.0530 (9)
0.0416 (7)
0.0485 (8)
0.0465 (8)
0.0439 (8)
0.0710 (11)
0.0344 (7)
0.0600 (10)
0.0532 (10)
0.0483 (9)
0.1107 (17)
0.0632 (11)
0.0996 (16)
0.1185 (18)
0.0501 (10)
U22
0.0553 (6)
0.0359 (6)
0.0542 (7)
0.0619 (7)
0.0359 (6)
0.0506 (7)
0.0893 (10)
0.0385 (7)
0.0408 (7)
0.0350 (7)
0.0415 (8)
0.0325 (6)
0.0414 (7)
0.0467 (8)
0.0430 (7)
0.0436 (7)
0.0560 (9)
0.0391 (7)
0.0421 (8)
0.0560 (9)
0.0537 (9)
0.0406 (7)
0.0568 (9)
0.0525 (9)
0.0526 (9)
0.0515 (9)
0.0501 (9)
0.0494 (9)
0.0853 (13)
0.0631 (10)
0.0461 (10)
0.0812 (13)
0.0673 (12)
0.0870 (14)
0.0823 (14)
U33
0.0324 (5)
0.0303 (5)
0.0916 (9)
0.0702 (8)
0.0368 (6)
0.0544 (7)
0.0528 (8)
0.0414 (7)
0.0347 (7)
0.0359 (7)
0.0642 (10)
0.0402 (7)
0.0454 (8)
0.0423 (8)
0.0308 (6)
0.0306 (6)
0.0323 (7)
0.0439 (7)
0.0525 (9)
0.0426 (8)
0.0491 (9)
0.0475 (8)
0.0415 (8)
0.0563 (9)
0.0710 (11)
0.0501 (9)
0.0565 (9)
0.0665 (11)
0.0599 (10)
0.0605 (10)
0.0582 (11)
0.0598 (11)
0.0581 (11)
0.0359 (9)
0.0905 (14)
U12
−0.0062 (5)
−0.0015 (4)
−0.0118 (5)
−0.0039 (5)
−0.0021 (4)
−0.0048 (5)
0.0586 (11)
0.0010 (5)
0.0021 (5)
0.0000 (5)
0.0019 (6)
−0.0026 (5)
0.0084 (6)
−0.0063 (6)
0.0022 (6)
−0.0016 (6)
0.0098 (7)
−0.0009 (5)
−0.0010 (7)
0.0128 (8)
0.0088 (7)
−0.0032 (6)
−0.0098 (7)
0.0005 (7)
−0.0026 (7)
−0.0067 (8)
−0.0004 (6)
−0.0061 (7)
0.0208 (9)
0.0028 (7)
0.0082 (10)
0.0263 (10)
0.0372 (12)
0.0339 (13)
0.0029 (9)
U13
0.0018 (4)
0.0027 (4)
−0.0117 (6)
−0.0110 (5)
0.0000 (4)
0.0009 (5)
0.0210 (9)
0.0016 (5)
0.0036 (5)
0.0037 (5)
0.0009 (7)
0.0020 (6)
0.0059 (6)
0.0044 (6)
0.0003 (6)
0.0037 (5)
0.0023 (6)
−0.0020 (6)
0.0014 (7)
0.0065 (7)
0.0108 (7)
−0.0077 (6)
−0.0012 (6)
0.0090 (7)
−0.0050 (8)
−0.0075 (8)
0.0049 (6)
−0.0146 (8)
0.0053 (8)
−0.0062 (7)
−0.0092 (11)
0.0130 (8)
0.0015 (11)
0.0186 (10)
0.0049 (9)
U23
0.0037 (4)
0.0030 (4)
0.0157 (7)
0.0083 (6)
0.0029 (4)
0.0106 (6)
−0.0109 (7)
−0.0017 (6)
0.0009 (5)
0.0029 (5)
0.0053 (7)
0.0034 (5)
0.0003 (6)
−0.0023 (6)
0.0038 (5)
0.0061 (5)
−0.0018 (6)
0.0079 (6)
−0.0093 (7)
−0.0071 (7)
0.0091 (7)
0.0109 (6)
0.0114 (7)
0.0049 (7)
0.0072 (8)
0.0152 (7)
0.0050 (7)
−0.0075 (8)
−0.0007 (9)
−0.0116 (8)
0.0140 (8)
0.0089 (10)
0.0078 (9)
0.0095 (9)
−0.0082 (11)
O2
N1
O3
O4
N2
N3
O1
C21
C20
C1
C23
C6
C2
C7
C12
C5
C4
C22
C11
C3
C13
C25
C24
C8
C9
C17
C26
C10
C18
C27
C16
C14
C15
C19
C28
Geometric parameters (Å, °)
O2—C20
N1—C20
N1—C1
N1—C5
O3—C26
O4—C26
O4—C27
1.2250 (15)
1.3590 (17)
1.4768 (17)
1.4846 (16)
1.2032 (19)
1.3460 (18)
1.4491 (19)
C4—H4
C22—H22A
C22—H22B
C11—C10
C11—H11
C13—C14
C13—H13
0.9800
0.9700
0.9700
1.378 (2)
0.9300
1.382 (2)
0.9300

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supplementary materials
sup-6
N2—C21
N2—C22
N2—C25
N3—C26
N3—C23
N3—C24
O1—C3
C21—C20
C21—H21A
C21—H21B
C1—C6
C1—C2
C1—H1
C23—C22
C23—H23A
C23—H23B
C6—C11
C6—C7
C2—C3
C2—C18
C2—H2
C7—C8
C7—H7
C12—C13
C12—C17
C12—C5
C5—C4
C5—H5
C4—C3
C4—C19
1.4561 (17)
1.4583 (16)
1.4606 (17)
1.3461 (19)
1.4534 (19)
1.4535 (18)
1.1995 (19)
1.5111 (19)
0.9700
0.9700
1.519 (2)
1.5240 (19)
0.9800
1.508 (2)
0.9700
0.9700
1.383 (2)
1.389 (2)
1.502 (2)
1.526 (2)
0.9800
1.378 (2)
0.9300
1.378 (2)
1.383 (2)
1.5224 (19)
1.542 (2)
0.9800
1.503 (2)
1.519 (2)
C25—C24
C25—H25A
C25—H25B
C24—H24A
C24—H24B
C8—C9
C8—H8
C9—C10
C9—H9
C17—C16
C17—H17
C10—H10
C18—H18A
C18—H18B
C18—H18C
C27—C28
C27—H27A
C27—H27B
C16—C15
C16—H16
C14—C15
C14—H14
C15—H15
C19—H19A
C19—H19B
C19—H19C
C28—H28A
C28—H28B
C28—H28C
1.503 (2)
0.9700
0.9700
0.9700
0.9700
1.370 (2)
0.9300
1.373 (3)
0.9300
1.380 (3)
0.9300
0.9300
0.9600
0.9600
0.9600
1.478 (2)
0.9700
0.9700
1.362 (3)
0.9300
1.362 (3)
0.9300
0.9300
0.9600
0.9600
0.9600
0.9600
0.9600
0.9600
C20—N1—C1
C20—N1—C5
C1—N1—C5
C26—O4—C27
C21—N2—C22
C21—N2—C25
C22—N2—C25
C26—N3—C23
C26—N3—C24
C23—N3—C24
N2—C21—C20
N2—C21—H21A
C20—C21—H21A
N2—C21—H21B
C20—C21—H21B
H21A—C21—H21B
O2—C20—N1
O2—C20—C21
N1—C20—C21
117.26 (10)
122.37 (11)
119.82 (10)
116.47 (13)
110.50 (10)
109.50 (10)
109.69 (10)
125.75 (13)
119.64 (13)
113.39 (12)
111.89 (11)
109.2
109.2
109.2
109.2
107.9
121.85 (12)
119.11 (12)
119.03 (11)
O1—C3—C2
O1—C3—C4
C2—C3—C4
C12—C13—C14
C12—C13—H13
C14—C13—H13
N2—C25—C24
N2—C25—H25A
C24—C25—H25A
N2—C25—H25B
C24—C25—H25B
H25A—C25—H25B
N3—C24—C25
N3—C24—H24A
C25—C24—H24A
N3—C24—H24B
C25—C24—H24B
H24A—C24—H24B
C9—C8—C7
120.61 (15)
121.42 (15)
117.97 (13)
120.76 (16)
119.6
119.6
110.76 (12)
109.5
109.5
109.5
109.5
108.1
109.23 (12)
109.8
109.8
109.8
109.8
108.3
120.10 (16)

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supplementary materials
sup-7
N1—C1—C6
N1—C1—C2
C6—C1—C2
N1—C1—H1
C6—C1—H1
C2—C1—H1
N3—C23—C22
N3—C23—H23A
C22—C23—H23A
N3—C23—H23B
C22—C23—H23B
H23A—C23—H23B
C11—C6—C7
C11—C6—C1
C7—C6—C1
C3—C2—C1
C3—C2—C18
C1—C2—C18
C3—C2—H2
C1—C2—H2
C18—C2—H2
C8—C7—C6
C8—C7—H7
C6—C7—H7
C13—C12—C17
C13—C12—C5
C17—C12—C5
N1—C5—C12
N1—C5—C4
C12—C5—C4
N1—C5—H5
C12—C5—H5
C4—C5—H5
C3—C4—C19
C3—C4—C5
C19—C4—C5
C3—C4—H4
C19—C4—H4
C5—C4—H4
N2—C22—C23
N2—C22—H22A
C23—C22—H22A
N2—C22—H22B
C23—C22—H22B
H22A—C22—H22B
C10—C11—C6
C10—C11—H11
C6—C11—H11
111.71 (10)
109.03 (11)
117.79 (12)
105.8
105.8
105.8
110.14 (12)
109.6
109.6
109.6
109.6
108.1
117.74 (14)
124.57 (13)
117.68 (12)
112.33 (12)
107.81 (14)
111.38 (13)
108.4
108.4
108.4
121.26 (14)
119.4
119.4
117.94 (14)
121.97 (13)
120.03 (14)
112.88 (11)
112.24 (11)
108.85 (11)
107.5
107.5
107.5
111.72 (14)
114.84 (12)
110.43 (14)
106.4
106.4
106.4
111.42 (12)
109.3
109.3
109.3
109.3
108.0
120.82 (15)
119.6
119.6
C9—C8—H8
C7—C8—H8
C8—C9—C10
C8—C9—H9
C10—C9—H9
C16—C17—C12
C16—C17—H17
C12—C17—H17
O3—C26—O4
O3—C26—N3
O4—C26—N3
C9—C10—C11
C9—C10—H10
C11—C10—H10
C2—C18—H18A
C2—C18—H18B
H18A—C18—H18B
C2—C18—H18C
H18A—C18—H18C
H18B—C18—H18C
O4—C27—C28
O4—C27—H27A
C28—C27—H27A
O4—C27—H27B
C28—C27—H27B
H27A—C27—H27B
C15—C16—C17
C15—C16—H16
C17—C16—H16
C15—C14—C13
C15—C14—H14
C13—C14—H14
C14—C15—C16
C14—C15—H15
C16—C15—H15
C4—C19—H19A
C4—C19—H19B
H19A—C19—H19B
C4—C19—H19C
H19A—C19—H19C
H19B—C19—H19C
C27—C28—H28A
C27—C28—H28B
H28A—C28—H28B
C27—C28—H28C
H28A—C28—H28C
H28B—C28—H28C
120.0
120.0
119.43 (16)
120.3
120.3
120.73 (18)
119.6
119.6
123.71 (14)
124.54 (14)
111.75 (13)
120.64 (15)
119.7
119.7
109.5
109.5
109.5
109.5
109.5
109.5
110.34 (15)
109.6
109.6
109.6
109.6
108.1
120.54 (18)
119.7
119.7
120.53 (19)
119.7
119.7
119.48 (17)
120.3
120.3
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C22—N2—C21—C20−70.96 (14) C25—N2—C22—C23 −57.61 (15)

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supplementary materials
sup-8
C25—N2—C21—C20
C1—N1—C20—O2
C5—N1—C20—O2
C1—N1—C20—C21
C5—N1—C20—C21
N2—C21—C20—O2
N2—C21—C20—N1
C20—N1—C1—C6
C5—N1—C1—C6
C20—N1—C1—C2
C5—N1—C1—C2
C26—N3—C23—C22
C24—N3—C23—C22
N1—C1—C6—C11
C2—C1—C6—C11
N1—C1—C6—C7
C2—C1—C6—C7
N1—C1—C2—C3
C6—C1—C2—C3
N1—C1—C2—C18
C6—C1—C2—C18
C11—C6—C7—C8
C1—C6—C7—C8
C20—N1—C5—C12
C1—N1—C5—C12
C20—N1—C5—C4
C1—N1—C5—C4
C13—C12—C5—N1
C17—C12—C5—N1
C13—C12—C5—C4
C17—C12—C5—C4
N1—C5—C4—C3
C12—C5—C4—C3
N1—C5—C4—C19
C12—C5—C4—C19
C21—N2—C22—C23
168.12 (11)
−10.29 (18)
178.25 (12)
169.07 (11)
−2.39 (17)
107.37 (14)
−72.01 (15)
106.90 (13)
−81.41 (14)
−121.17 (12)
50.52 (15)
113.00 (16)
−54.22 (17)
116.25 (15)
−11.1 (2)
−64.17 (16)
168.49 (12)
−54.18 (16)
74.44 (17)
66.89 (16)
−164.50 (13)
−0.8 (2)
179.55 (13)
−69.90 (15)
118.85 (13)
166.64 (12)
−4.61 (16)
−54.40 (18)
128.50 (14)
70.92 (17)
−106.18 (15)
−37.21 (18)
−162.89 (13)
−164.62 (14)
69.69 (17)
−178.42 (11)
N3—C23—C22—N2
C7—C6—C11—C10
C1—C6—C11—C10
C1—C2—C3—O1
C18—C2—C3—O1
C1—C2—C3—C4
C18—C2—C3—C4
C19—C4—C3—O1
C5—C4—C3—O1
C19—C4—C3—C2
C5—C4—C3—C2
C17—C12—C13—C14
C5—C12—C13—C14
C21—N2—C25—C24
C22—N2—C25—C24
C26—N3—C24—C25
C23—N3—C24—C25
N2—C25—C24—N3
C6—C7—C8—C9
C7—C8—C9—C10
C13—C12—C17—C16
C5—C12—C17—C16
C27—O4—C26—O3
C27—O4—C26—N3
C23—N3—C26—O3
C24—N3—C26—O3
C23—N3—C26—O4
C24—N3—C26—O4
C8—C9—C10—C11
C6—C11—C10—C9
C26—O4—C27—C28
C12—C17—C16—C15
C12—C13—C14—C15
C13—C14—C15—C16
C17—C16—C15—C14
54.42 (16)
1.3 (2)
−179.10 (14)
−164.94 (19)
72.0 (2)
14.4 (2)
−108.69 (17)
−21.7 (3)
−148.50 (19)
158.92 (17)
32.2 (2)
−1.1 (2)
−178.29 (15)
−179.06 (11)
59.52 (15)
−112.15 (15)
55.93 (17)
−57.96 (16)
0.1 (2)
0.1 (2)
1.9 (2)
179.12 (15)
−6.8 (2)
173.41 (13)
−175.88 (16)
−9.4 (2)
3.9 (2)
170.36 (13)
0.4 (3)
−1.1 (3)
−88.67 (19)
−1.2 (3)
−0.4 (3)
1.1 (3)
−0.4 (3)
Hydrogen-bond geometry (Å, °)
D—H···A
C5—H5···N2
C8—H8···O2i
C24—H24A···O1ii
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z.
D—H
0.98
H···A
2.51
D···A
3.1788 (17)
D—H···A
125
0.932.54 3.4406 (19) 162
0.972.56 3.520 (2)169

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supplementary materials
sup-9
Fig. 1