Hexahydro­cyclo­octa­[b]quinoxaline formation from 1,2-diacet­oxycyclo­octa-5,6-dione

The reaction of 1,2-diacet­oxycyclo­octane-5,6-dione with ortho-phenyl­enediamine in acetic acid gave trans-6,7,8,9,10,11-hexa­hydro­cyclo­octa­[b]quinoxaline-8,9-diyl diacetate, C₁₈H₂₀N₂O₄. The saturated H atoms in the structure display almost perfect gauche orientations and the two acet­oxy groups are oriented almost perfectly anti­periplanar. There are C—H...N bonding inter­actions linking the mol­ecules into chains and inter­molecular π–π stacking inter­actions between pyrazine rings [centroid–centroid distance = 3.6569 (9) Å and perpendicular distance = 3.426 Å].

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.041
• wR factor = 0.089
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.58 Ratio
PLAT301_ALERT_3_C Main Residue  Disorder .........................      17.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      25.40 Deg.
              C4B  -C3   -C4      1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      38.40 Deg.
              C5   -C6   -C5B     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      22.10 Deg.
              O1   -C15  -O1B     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      29.90 Deg.
              O3B  -C17  -O3      1.555   1.555   1.555

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C4     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C5     = ...          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

We have been interested in exploiting the potential of the readily available cis,cis-1,5-cyclooctadiene (1) for the synthesis of heterocycles. Following earlier work (Yates et al., 1972) we dihydroxylated the diene with hydrogen peroxide and formic acid, diacetylated the resulting diol (2) giving (3) and oxidized the remaining double bond to the 5,6-dione (4) using KMnO₄, CuSO₄, Cu(OAc)₂. Condensation of this diketone with ortho-phenylenediamine produced the corresponding quinoxaline (5) cleanly, and significantly, with no ammonolytic loss of the acetoxy groups. A crystal structure of the quinoxaline-diacetate (Figure 1) revealed a trans disposition of the acetoxy groups confirming the trans orientation of the two alcoholic groups in the initial dihydroxylation product. The two (CH₂CH₂) chains which lead away from the quinoxaline 2- and 3-positions align to place the H atoms in a close-to-perfect gauche relationship: the relevant torsion angles for the H atoms on carbons C2 and C3 are, to the nearest whole number, 49, 67, 51, and 166° and those for C7 and C6, 35, 81, 82, and 163°.

The dihedral angle between the two acetoxy groups is 155.9° - remarkably close to the 180° required for these two groups to be perfectly antiperiplanar.

One other significant aspect of the structure is intermolecular C—H···N hydrogen bonding of the two acetyl methyl groups to an adjacent quinoxaline nitrogen, linking the molecules into chains (Figure 2, Table 1). There is also intermolecular π–π-stacking of the N1—C1—C8—N2—C14—C9 rings linking pairs of molecules in adjacent H bonded chains, with a centroid-centroid distance of 3.6569 (9) Å and a perpendicular distance of 3.426 Å (symmetry operation 2 - x,2 - y,-z; Figure 2).

Also of interest is that in the solid-state, one of the methyl groups lies directly over the pyrazine ring and close enough that one would anticipate the ¹H NMR chemical shift of that methyl group to be under the influence of the aromatic ring current. The methyl C16 lies just 4.14 Å from C9 and 4.16 Å from N1. However, solution-state ¹H NMR measurement showed only one, six-proton signal for the two acetyl methyl groups at δ 1.72 indicating that rapid ring flipping in solution must cause averaging of the stereochemical situation and hence magnetic environment of these two groups.

Related literature

For related literature, see: Yates et al. (1972).

S2. Experimental

1,2-Bis(acetoxy)cyclooctane-5,6-dione (0.5 g, 1.95 mmol) and ortho-phenylenediamine (0.21 g, 1.95 mmol) in acetic acid (10 ml) were heated at 368 K for 1 h. Water (20 ml) was added to the hot solution and, after cooling, the product was extracted with dichloromethane (3 x 15 ml). The solvent was evaporated from the extract giving trans-6,7,8,9,10,11-hexahydrocycloocta[b]quinoxaline-8,9-diyl diacetate (0.48 g, 75 percent) which was recrystallized from ethanol, m.p. 391–392 K.

S3. Refinement

H atoms were included in calculated positions with C—H distances ranging from 0.95 to 1.00 Å and methyl H atoms allowed to rotate to give the best fit with the electron density. There is disorder of the atoms O1, O2, O3, C4 and C5 whose occupancies were constrained to sum to 1.0; the final occupancy of the highest occupancy component was 0.768 (4). The atoms of the lower occupancy fraction were refined isotropically. Restraints were applied to the C15—O1 and C15—O1B bond lengths.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Plot of the title compound with ellipsoids drawn at the 50% probability level; disordered atoms from the lower occupancy fraction have been omitted for clarity.
	Fig. 2. Packing diagram viewed down the a axis with intermolecular C—H···N hydrogen bonds shown with dashed lines. Only H atoms involved in H bonding have been included.
	Fig. 3. The synthesis of trans-6,7,8,9,10,11-hexahydrocycloocta [b]quinoxaline-8,9-diyl diacetate.

trans-6,7,8,9,10,11-Hexahydrocycloocta[b]quinoxaline-8,9-diyl diacetate

Crystal data

C18H20N2O4	Dx = 1.328 Mg m^−3
Mr = 328.36	Melting point = 391–392 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4108 (8) Å	Cell parameters from 1632 reflections
b = 12.6470 (11) Å	θ = 2.3–24.0°
c = 14.5249 (13) Å	µ = 0.10 mm^−1
β = 108.177 (2)°	T = 100 K
V = 1642.5 (2) Å^3	Plate, colourless
Z = 4	0.40 × 0.30 × 0.10 mm
F(000) = 696

Data collection

Bruker SMART CCD area-detector diffractometer	1960 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 26.4°, θmin = 2.2°
φ and ω scans	h = −11→11
9291 measured reflections	k = −8→15
3356 independent reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 0.84	w = 1/[σ^2(Fo^2) + (0.0357P)^2] where P = (Fo^2 + 2Fc^2)/3
3356 reflections	(Δ/σ)max = 0.001
240 parameters	Δρmax = 0.21 e Å^−3
1 restraint	Δρmin = −0.20 e Å^−3

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 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 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	1.0620 (2)	0.89998 (18)	0.34648 (13)	0.0291 (5)	0.768 (4)
O2	1.0940 (2)	0.75700 (19)	0.44192 (15)	0.0550 (8)	0.768 (4)
O3	0.72848 (19)	1.05380 (19)	0.32464 (12)	0.0277 (5)	0.768 (4)
O1B	1.1075 (8)	0.9328 (5)	0.3444 (5)	0.024 (2)*	0.232 (4)
O2B	1.1174 (6)	0.8335 (6)	0.4743 (4)	0.037 (2)*	0.232 (4)
O3B	0.7117 (7)	0.9997 (6)	0.3176 (5)	0.0285 (19)*	0.232 (4)
O4	0.69096 (16)	0.97625 (11)	0.45751 (10)	0.0554 (4)
N1	0.98120 (15)	0.83903 (11)	0.10558 (10)	0.0268 (4)
N2	1.10797 (15)	1.04284 (11)	0.13626 (10)	0.0267 (4)
C1	0.91975 (18)	0.91665 (14)	0.13993 (11)	0.0249 (4)
C2	0.77806 (18)	0.89132 (15)	0.16289 (12)	0.0308 (5)
H2A	0.7211	0.8376	0.1163	0.037*
H2B	0.7158	0.9559	0.1538	0.037*
C3	0.80500 (19)	0.84975 (14)	0.26634 (12)	0.0305 (4)
H3A	0.7067	0.8452	0.2776	0.037*
H3B	0.8441	0.7768	0.2691	0.037*
C4	0.9107 (3)	0.9117 (2)	0.35072 (18)	0.0304 (7)	0.768 (4)
H4	0.9074	0.8774	0.4120	0.037*	0.768 (4)
C5	0.8866 (3)	1.03003 (19)	0.36028 (16)	0.0301 (7)	0.768 (4)
H5	0.9214	1.0470	0.4311	0.036*	0.768 (4)
C4B	0.8414 (10)	0.9287 (8)	0.3417 (7)	0.025 (3)*	0.232 (4)
H4B	0.8461	0.8922	0.4036	0.030*	0.232 (4)
C5B	0.9849 (9)	0.9962 (6)	0.3616 (5)	0.020 (2)*	0.232 (4)
H5B	1.0179	1.0113	0.4327	0.024*	0.232 (4)
C6	0.96715 (19)	1.10592 (14)	0.31121 (12)	0.0293 (4)
H6A	1.0752	1.0890	0.3350	0.035*
H6B	0.9552	1.1784	0.3334	0.035*
C7	0.91850 (18)	1.10711 (14)	0.20033 (12)	0.0285 (4)
H7A	0.8081	1.1017	0.1754	0.034*
H7B	0.9471	1.1759	0.1788	0.034*
C8	0.98452 (17)	1.02016 (14)	0.15627 (11)	0.0243 (4)
C9	1.11112 (18)	0.86141 (14)	0.08546 (11)	0.0244 (4)
C10	1.18255 (19)	0.78094 (15)	0.04906 (12)	0.0296 (4)
H10	1.1418	0.7116	0.0396	0.036*
C11	1.31064 (19)	0.80316 (15)	0.02752 (12)	0.0323 (5)
H11	1.3592	0.7487	0.0036	0.039*
C12	1.37116 (18)	0.90505 (16)	0.04022 (12)	0.0319 (5)
H12	1.4598	0.9192	0.0242	0.038*
C13	1.30442 (18)	0.98434 (15)	0.07531 (12)	0.0310 (5)
H13	1.3461	1.0534	0.0833	0.037*
C14	1.17343 (18)	0.96348 (14)	0.09967 (11)	0.0237 (4)
C15	1.1460 (2)	0.8237 (2)	0.39717 (15)	0.0515 (6)
C16	1.29052 (19)	0.80853 (15)	0.38052 (13)	0.0368 (5)
H16A	1.3247	0.7357	0.3970	0.055*
H16B	1.3640	0.8578	0.4213	0.055*
H16C	1.2794	0.8220	0.3122	0.055*
C17	0.6419 (2)	1.02199 (16)	0.38171 (14)	0.0356 (5)
C18	0.4911 (2)	1.06620 (16)	0.34063 (14)	0.0440 (5)
H18A	0.4299	1.0464	0.3815	0.066*
H18B	0.4454	1.0383	0.2751	0.066*
H18C	0.4974	1.1434	0.3379	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0267 (12)	0.0302 (13)	0.0305 (10)	0.0069 (10)	0.0091 (9)	0.0072 (9)
O2	0.0547 (13)	0.0587 (18)	0.0618 (15)	0.0211 (12)	0.0330 (11)	0.0354 (13)
O3	0.0290 (10)	0.0312 (13)	0.0259 (10)	0.0015 (10)	0.0129 (7)	0.0005 (9)
O4	0.0803 (11)	0.0572 (11)	0.0385 (9)	0.0237 (9)	0.0327 (8)	0.0129 (8)
N1	0.0276 (8)	0.0302 (9)	0.0226 (8)	−0.0031 (7)	0.0077 (7)	−0.0002 (7)
N2	0.0297 (8)	0.0258 (9)	0.0262 (8)	−0.0013 (7)	0.0111 (7)	0.0033 (7)
C1	0.0250 (10)	0.0310 (11)	0.0178 (9)	−0.0021 (9)	0.0053 (7)	0.0027 (8)
C2	0.0269 (10)	0.0361 (12)	0.0301 (10)	−0.0065 (9)	0.0099 (8)	−0.0017 (9)
C3	0.0320 (10)	0.0275 (11)	0.0376 (11)	−0.0008 (9)	0.0189 (9)	0.0040 (9)
C4	0.0341 (18)	0.0317 (18)	0.0269 (14)	0.0038 (14)	0.0114 (13)	0.0082 (12)
C5	0.0313 (16)	0.0350 (16)	0.0217 (12)	0.0046 (13)	0.0050 (10)	0.0023 (12)
C6	0.0322 (10)	0.0232 (10)	0.0287 (10)	0.0001 (9)	0.0039 (8)	−0.0008 (9)
C7	0.0317 (10)	0.0270 (11)	0.0283 (10)	0.0031 (9)	0.0113 (8)	0.0046 (9)
C8	0.0256 (10)	0.0272 (11)	0.0192 (9)	0.0025 (9)	0.0054 (7)	0.0064 (8)
C9	0.0242 (10)	0.0294 (11)	0.0183 (9)	−0.0004 (8)	0.0049 (7)	0.0033 (8)
C10	0.0374 (11)	0.0281 (11)	0.0249 (10)	−0.0003 (9)	0.0119 (8)	0.0006 (8)
C11	0.0358 (11)	0.0383 (13)	0.0232 (10)	0.0095 (10)	0.0100 (8)	0.0026 (9)
C12	0.0247 (10)	0.0466 (13)	0.0252 (10)	0.0001 (9)	0.0090 (8)	0.0018 (9)
C13	0.0283 (10)	0.0353 (12)	0.0290 (10)	−0.0065 (9)	0.0084 (8)	−0.0001 (9)
C14	0.0249 (9)	0.0255 (10)	0.0196 (9)	0.0003 (8)	0.0052 (7)	0.0039 (8)
C15	0.0469 (13)	0.0754 (18)	0.0350 (13)	0.0269 (13)	0.0170 (10)	0.0208 (13)
C16	0.0370 (11)	0.0346 (12)	0.0385 (12)	0.0096 (10)	0.0113 (9)	0.0053 (9)
C17	0.0449 (12)	0.0364 (12)	0.0322 (11)	0.0029 (10)	0.0215 (9)	−0.0044 (10)
C18	0.0459 (13)	0.0441 (13)	0.0512 (13)	0.0050 (11)	0.0284 (11)	−0.0039 (11)

Geometric parameters (Å, º)

O1—C15	1.317 (2)	C4B—C5B	1.546 (12)
O1—C4	1.452 (4)	C4B—H4B	1.0000
O2—C15	1.253 (3)	C5B—C6	1.553 (7)
O3—C17	1.390 (2)	C5B—H5B	1.0000
O3—C5	1.447 (3)	C6—C7	1.531 (2)
O1B—C5B	1.489 (10)	C6—H6A	0.9900
O1B—C15	1.566 (7)	C6—H6B	0.9900
O2B—C15	1.237 (6)	C7—C8	1.501 (2)
O3B—C17	1.326 (7)	C7—H7A	0.9900
O3B—C4B	1.467 (11)	C7—H7B	0.9900
O4—C17	1.201 (2)	C9—C14	1.406 (2)
N1—C1	1.314 (2)	C9—C10	1.410 (2)
N1—C9	1.372 (2)	C10—C11	1.366 (2)
N2—C8	1.314 (2)	C10—H10	0.9500
N2—C14	1.369 (2)	C11—C12	1.398 (2)
C1—C8	1.432 (2)	C11—H11	0.9500
C1—C2	1.506 (2)	C12—C13	1.364 (2)
C2—C3	1.537 (2)	C12—H12	0.9500
C2—H2A	0.9900	C13—C14	1.409 (2)
C2—H2B	0.9900	C13—H13	0.9500
C3—C4B	1.442 (10)	C15—C16	1.467 (3)
C3—C4	1.532 (3)	C16—H16A	0.9800
C3—H3A	0.9900	C16—H16B	0.9800
C3—H3B	0.9900	C16—H16C	0.9800
C4—C5	1.526 (4)	C17—C18	1.468 (2)
C4—H4	1.0000	C18—H18A	0.9800
C5—C6	1.530 (3)	C18—H18B	0.9800
C5—H5	1.0000	C18—H18C	0.9800
C15—O1—C4	118.5 (2)	C5B—C6—H6B	132.9
C17—O3—C5	117.07 (17)	H6A—C6—H6B	107.2
C5B—O1B—C15	117.7 (5)	C8—C7—C6	114.43 (14)
C17—O3B—C4B	121.4 (6)	C8—C7—H7A	108.7
C1—N1—C9	116.98 (15)	C6—C7—H7A	108.7
C8—N2—C14	117.50 (15)	C8—C7—H7B	108.7
N1—C1—C8	122.05 (15)	C6—C7—H7B	108.7
N1—C1—C2	116.74 (16)	H7A—C7—H7B	107.6
C8—C1—C2	121.20 (16)	N2—C8—C1	121.52 (16)
C1—C2—C3	113.70 (13)	N2—C8—C7	116.51 (15)
C1—C2—H2A	108.8	C1—C8—C7	121.94 (15)
C3—C2—H2A	108.8	N1—C9—C14	121.09 (16)
C1—C2—H2B	108.8	N1—C9—C10	119.45 (16)
C3—C2—H2B	108.8	C14—C9—C10	119.46 (15)
H2A—C2—H2B	107.7	C11—C10—C9	119.70 (17)
C4B—C3—C4	25.4 (3)	C11—C10—H10	120.2
C4B—C3—C2	115.7 (4)	C9—C10—H10	120.2
C4—C3—C2	118.38 (16)	C10—C11—C12	120.79 (18)
C4B—C3—H3A	85.8	C10—C11—H11	119.6
C4—C3—H3A	107.7	C12—C11—H11	119.6
C2—C3—H3A	107.7	C13—C12—C11	120.74 (17)
C4B—C3—H3B	128.2	C13—C12—H12	119.6
C4—C3—H3B	107.7	C11—C12—H12	119.6
C2—C3—H3B	107.7	C12—C13—C14	119.81 (17)
H3A—C3—H3B	107.1	C12—C13—H13	120.1
O1—C4—C5	106.2 (2)	C14—C13—H13	120.1
O1—C4—C3	108.3 (2)	N2—C14—C9	120.83 (15)
C5—C4—C3	119.8 (2)	N2—C14—C13	119.68 (16)
O1—C4—H4	107.3	C9—C14—C13	119.49 (16)
C5—C4—H4	107.3	O2B—C15—O2	50.8 (3)
C3—C4—H4	107.3	O2B—C15—O1	99.8 (3)
O3—C5—C4	109.7 (2)	O2—C15—O1	121.3 (2)
O3—C5—C6	107.86 (17)	O2B—C15—C16	129.6 (3)
C4—C5—C6	117.6 (2)	O2—C15—C16	122.0 (2)
O3—C5—H5	107.1	O1—C15—C16	115.4 (2)
C4—C5—H5	107.1	O2B—C15—O1B	105.8 (4)
C6—C5—H5	107.1	O2—C15—O1B	141.2 (3)
C3—C4B—O3B	105.0 (6)	O1—C15—O1B	22.1 (2)
C3—C4B—C5B	120.7 (7)	C16—C15—O1B	96.8 (3)
O3B—C4B—C5B	108.7 (8)	C15—C16—H16A	109.5
C3—C4B—H4B	107.2	C15—C16—H16B	109.5
O3B—C4B—H4B	107.2	H16A—C16—H16B	109.5
C5B—C4B—H4B	107.2	C15—C16—H16C	109.5
O1B—C5B—C4B	110.4 (7)	H16A—C16—H16C	109.5
O1B—C5B—C6	112.2 (5)	H16B—C16—H16C	109.5
C4B—C5B—C6	116.5 (6)	O4—C17—O3B	114.1 (3)
O1B—C5B—H5B	105.6	O4—C17—O3	123.84 (18)
C4B—C5B—H5B	105.6	O3B—C17—O3	29.9 (3)
C6—C5B—H5B	105.6	O4—C17—C18	127.03 (18)
C5—C6—C7	117.86 (15)	O3B—C17—C18	115.1 (3)
C5—C6—C5B	38.4 (3)	O3—C17—C18	108.62 (17)
C7—C6—C5B	117.2 (3)	C17—C18—H18A	109.5
C5—C6—H6A	107.8	C17—C18—H18B	109.5
C7—C6—H6A	107.8	H18A—C18—H18B	109.5
C5B—C6—H6A	72.2	C17—C18—H18C	109.5
C5—C6—H6B	107.8	H18A—C18—H18C	109.5
C7—C6—H6B	107.8	H18B—C18—H18C	109.5
C9—N1—C1—C8	−0.2 (2)	C5B—C6—C7—C8	−37.7 (4)
C9—N1—C1—C2	−179.36 (14)	C14—N2—C8—C1	−0.4 (2)
N1—C1—C2—C3	88.39 (19)	C14—N2—C8—C7	177.43 (14)
C8—C1—C2—C3	−90.8 (2)	N1—C1—C8—N2	1.0 (2)
C1—C2—C3—C4B	78.1 (4)	C2—C1—C8—N2	−179.89 (14)
C1—C2—C3—C4	49.6 (2)	N1—C1—C8—C7	−176.75 (15)
C15—O1—C4—C5	136.7 (2)	C2—C1—C8—C7	2.4 (2)
C15—O1—C4—C3	−93.4 (2)	C6—C7—C8—N2	−93.89 (18)
C4B—C3—C4—O1	−160.1 (11)	C6—C7—C8—C1	84.0 (2)
C2—C3—C4—O1	−69.6 (2)	C1—N1—C9—C14	−1.0 (2)
C4B—C3—C4—C5	−38.2 (10)	C1—N1—C9—C10	179.58 (15)
C2—C3—C4—C5	52.4 (3)	N1—C9—C10—C11	179.01 (15)
C17—O3—C5—C4	72.6 (2)	C14—C9—C10—C11	−0.4 (2)
C17—O3—C5—C6	−158.2 (2)	C9—C10—C11—C12	−0.6 (3)
O1—C4—C5—O3	155.86 (18)	C10—C11—C12—C13	0.6 (3)
C3—C4—C5—O3	32.9 (3)	C11—C12—C13—C14	0.4 (3)
O1—C4—C5—C6	32.2 (3)	C8—N2—C14—C9	−0.8 (2)
C3—C4—C5—C6	−90.8 (3)	C8—N2—C14—C13	178.79 (15)
C4—C3—C4B—O3B	163.3 (14)	N1—C9—C14—N2	1.6 (2)
C2—C3—C4B—O3B	60.7 (6)	C10—C9—C14—N2	−179.01 (15)
C4—C3—C4B—C5B	40.2 (7)	N1—C9—C14—C13	−178.00 (15)
C2—C3—C4B—C5B	−62.4 (9)	C10—C9—C14—C13	1.4 (2)
C17—O3B—C4B—C3	126.7 (7)	C12—C13—C14—N2	179.01 (15)
C17—O3B—C4B—C5B	−102.8 (8)	C12—C13—C14—C9	−1.4 (2)
C15—O1B—C5B—C4B	−52.7 (8)	C4—O1—C15—O2B	−44.0 (4)
C15—O1B—C5B—C6	175.6 (4)	C4—O1—C15—O2	5.8 (4)
C3—C4B—C5B—O1B	−34.3 (10)	C4—O1—C15—C16	173.0 (2)
O3B—C4B—C5B—O1B	−155.6 (6)	C4—O1—C15—O1B	−152.0 (9)
C3—C4B—C5B—C6	95.1 (9)	C5B—O1B—C15—O2B	−30.8 (7)
O3B—C4B—C5B—C6	−26.2 (9)	C5B—O1B—C15—O2	15.1 (9)
O3—C5—C6—C7	−57.0 (2)	C5B—O1B—C15—O1	46.2 (6)
C4—C5—C6—C7	67.6 (3)	C5B—O1B—C15—C16	−165.3 (5)
O3—C5—C6—C5B	−156.5 (5)	C4B—O3B—C17—O4	−2.7 (8)
C4—C5—C6—C5B	−31.9 (5)	C4B—O3B—C17—O3	113.8 (10)
O1B—C5B—C6—C5	166.2 (8)	C4B—O3B—C17—C18	−162.3 (6)
C4B—C5B—C6—C5	37.6 (5)	C5—O3—C17—O4	−0.3 (3)
O1B—C5B—C6—C7	64.8 (6)	C5—O3—C17—O3B	−79.9 (6)
C4B—C5B—C6—C7	−63.8 (7)	C5—O3—C17—C18	172.02 (19)
C5—C6—C7—C8	−81.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···N2^i	0.98	2.60	3.523 (2)	156
C18—H18C···N1^ii	0.98	2.59	3.529 (2)	160

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2.