3,7-Di-tert-butyl-1,5-di­nitro-3,7-di­aza­bi­cyclo­[3.3.1]­nonane

The conformation of the title compound, C₁₅H₂₈N₄O₄, was determined. The tricyclic nine-membered ring has a boat-shaped aza­cyclo­hexane ring on one side of the bridge and a chair-shaped ring on the other side.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.064
• wR factor = 0.195
• Data-to-parameter ratio = 13.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.622     0.929
          Tmin' and Tmax expected:      0.743     0.957
          RR' =      0.863
          Please check that your absorption correction is appropriate.

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           67.00
         From the CIF: _reflns_number_total               5860
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         6367
         Completeness (_total/calc)             92.04%
          Alert C: < 95% complete

PLAT_301  Alert C Main Residue Disorder ........................       4.00 Perc.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

The development of synthetic routes to new cyclic energetic materials with performance properties superior to HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane), but with less sensitivity toward certain stimuli, is a continuing effort. Although they would be expected to be chemically equivalent, the bridged nine-membered ring of the title compound, (I), has a boat-shaped azacyclohexane on one side and and a chair-shaped azacyclohexane ring on the other side. This must be due to steric hindrance between the two tert-butyl groups. The all-nitro version (1,3,5,7-tetranitro-3,7,-diazabicyclo[3.3.1]nonane; Gilardi, 2001) of this molecule does have two chair-shaped rings. A least-squares fit of the two independent molcules, using all atoms except the nitro O atoms, gives a weighted r.m.s. deviation of 0.08 Å.

S2. Experimental

The title compound was the minor reaction product formed by the Mannnich condensation of nitromethane with formaldehyde and tert-butylamine. The major product formed was the corresponding six-membered analog 1,2-di-tert-butyl-5-(tert-butylaminomethyl)-5-nitro-1,3-diazacyclohexane.

S3. Refinement

Of the four nitro groups in the asymmetric unit only one is disordered (66:34).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL 5.1 (Sheldrick, 1997); program(s) used to refine structure: SHELXTL 5.1; molecular graphics: SHELXTL 5.1; software used to prepare material for publication: SHELXTL 5.1.

Figures

Fig. 1. View of 3,7-di-tert-butyl-1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane with 20% probability ellipsoids. Only one of the two molecules in the asymmetric unit is shown.

(I)

Crystal data

C15H28N4O4	F(000) = 1424
Mr = 328.41	Dx = 1.223 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.9782 (2) Å	Cell parameters from 5644 reflections
b = 9.9382 (1) Å	θ = 3.0–67.0°
c = 30.5174 (4) Å	µ = 0.73 mm^−1
β = 100.812 (1)°	T = 293 K
V = 3568.35 (8) Å^3	Plate, colorless
Z = 8	0.36 × 0.30 × 0.06 mm

Data collection

Bruker SMART 6000 diffractometer	5860 independent reflections
Radiation source: normal-focus sealed tube	4673 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 8.3 pixels mm^-1	θmax = 67.0°, θmin = 3.8°
ω scans	h = −12→13
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −10→11
Tmin = 0.622, Tmax = 0.929	l = −36→33
17521 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: calc
R[F^2 > 2σ(F^2)] = 0.064	H-atom parameters constrained
wR(F^2) = 0.195	w = 1/[σ^2(Fo^2) + (0.1273P)^2 + 0.8387P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.028
5860 reflections	Δρmax = 0.26 e Å^−3
436 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0080 (5)

Special details

Experimental. Only 92.5% of the data in a sphere of diffraction 2θ < 134 was collected. This is due to the use of a CCD diffractometer on a rotating anode with Cu Kα radiation. This made it impossible to collect the entire sphere of data, but losses were only in the highest resolution data (126.0 <2θ < 136.0°).

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)
C1	0.83944 (16)	0.5913 (2)	0.14230 (7)	0.0555 (5)
N1	0.95918 (15)	0.5579 (2)	0.16679 (7)	0.0684 (5)
O1A	0.97063 (15)	0.4675 (2)	0.19359 (7)	0.0924 (6)
O1B	1.03794 (17)	0.6216 (3)	0.15866 (10)	0.1284 (9)
C2	0.79255 (17)	0.4631 (2)	0.11731 (7)	0.0586 (5)
H2A	0.8374	0.4400	0.0950	0.070*
H2B	0.7957	0.3885	0.1380	0.070*
N3	0.67561 (14)	0.48948 (16)	0.09611 (5)	0.0553 (4)
C4	0.67060 (19)	0.5974 (2)	0.06361 (7)	0.0632 (5)
H4A	0.5926	0.6125	0.0488	0.076*
H4B	0.7148	0.5736	0.0412	0.076*
C5	0.71908 (19)	0.7253 (2)	0.08847 (7)	0.0614 (5)
N5	0.7107 (2)	0.8363 (2)	0.05395 (7)	0.0793 (6)
O5A	0.6212 (2)	0.8526 (3)	0.02938 (10)	0.1374 (11)
O5B	0.7925 (2)	0.9024 (3)	0.05126 (9)	0.1373 (11)
C6	0.64818 (19)	0.7680 (2)	0.12365 (7)	0.0623 (5)
H6A	0.6198	0.8588	0.1173	0.075*
H6B	0.5835	0.7084	0.1221	0.075*
N7	0.71785 (14)	0.76288 (15)	0.16843 (5)	0.0541 (4)
C8	0.76895 (17)	0.63034 (19)	0.17792 (7)	0.0562 (5)
H8A	0.7097	0.5641	0.1782	0.067*
H8B	0.8177	0.6310	0.2071	0.067*
C9	0.84245 (18)	0.7043 (2)	0.10969 (7)	0.0635 (5)
H9A	0.8870	0.6795	0.0875	0.076*
H9B	0.8744	0.7851	0.1249	0.076*
C10	0.60524 (19)	0.3679 (2)	0.08069 (7)	0.0657 (5)
C11	0.4825 (2)	0.4118 (3)	0.06512 (10)	0.0887 (8)
H11A	0.4762	0.4621	0.0379	0.133*
H11B	0.4593	0.4671	0.0876	0.133*
H11C	0.4345	0.3338	0.0600	0.133*
C12	0.6482 (3)	0.2945 (3)	0.04321 (11)	0.1034 (10)
H12A	0.6502	0.3558	0.0191	0.155*
H12B	0.5981	0.2211	0.0328	0.155*
H12C	0.7233	0.2605	0.0541	0.155*
C13	0.6073 (3)	0.2750 (3)	0.12080 (10)	0.0917 (8)
H13A	0.6810	0.2344	0.1288	0.138*
H13B	0.5509	0.2060	0.1132	0.138*
H13C	0.5913	0.3263	0.1455	0.138*
C14	0.66080 (17)	0.8145 (2)	0.20441 (7)	0.0589 (5)
C15	0.6188 (3)	0.9569 (3)	0.19258 (10)	0.0879 (8)
H15A	0.5559	0.9540	0.1680	0.132*
H15B	0.6792	1.0092	0.1845	0.132*
H15C	0.5949	0.9973	0.2179	0.132*
C16	0.7496 (2)	0.8238 (3)	0.24764 (8)	0.0798 (7)
H16A	0.8147	0.8727	0.2421	0.120*
H16B	0.7724	0.7348	0.2579	0.120*
H16C	0.7174	0.8697	0.2700	0.120*
C17	0.5629 (2)	0.7257 (3)	0.21249 (10)	0.0874 (8)
H17A	0.5097	0.7141	0.1850	0.131*
H17B	0.5255	0.7675	0.2342	0.131*
H17C	0.5920	0.6395	0.2234	0.131*
C21	0.1409 (2)	0.2309 (2)	0.08824 (7)	0.0659 (6)
N21	0.1218 (2)	0.3469 (3)	0.05507 (8)	0.0897 (7)
O21A	0.1967 (4)	0.3735 (5)	0.03516 (16)	0.1091 (13)	0.66
O21B	0.0296 (4)	0.4085 (5)	0.05044 (17)	0.1285 (16)	0.66
O21C	0.0843 (11)	0.4464 (13)	0.0648 (4)	0.142 (4)*	0.34
O21D	0.1547 (10)	0.3387 (12)	0.0200 (4)	0.131 (4)*	0.34
C32	0.1493 (3)	−0.1915 (4)	0.03585 (12)	0.1100 (11)
H32A	0.0773	−0.2096	0.0441	0.165*
H32B	0.1807	−0.2737	0.0269	0.165*
H32C	0.1389	−0.1288	0.0115	0.165*
C22	0.1610 (2)	0.1047 (2)	0.06200 (7)	0.0678 (6)
H22A	0.0950	0.0867	0.0390	0.081*
H22B	0.2261	0.1179	0.0478	0.081*
N23	0.18150 (15)	−0.00794 (17)	0.09286 (6)	0.0595 (4)
C24	0.08313 (17)	−0.0312 (2)	0.11364 (7)	0.0611 (5)
H24A	0.0967	−0.1078	0.1336	0.073*
H24B	0.0165	−0.0498	0.0910	0.073*
C25	0.06445 (17)	0.0962 (2)	0.13970 (7)	0.0592 (5)
N25	−0.03516 (17)	0.0648 (2)	0.16273 (8)	0.0744 (5)
O25A	−0.02339 (17)	−0.0237 (2)	0.19057 (7)	0.1005 (6)
O25B	−0.1221 (2)	0.1252 (3)	0.15154 (12)	0.1500 (12)
C26	0.16799 (18)	0.1288 (2)	0.17632 (7)	0.0601 (5)
H26A	0.1457	0.1272	0.2053	0.072*
H26B	0.2263	0.0612	0.1763	0.072*
N27	0.21343 (14)	0.26158 (16)	0.16863 (6)	0.0571 (4)
C28	0.24474 (19)	0.2660 (2)	0.12463 (7)	0.0652 (5)
H28A	0.3055	0.2023	0.1235	0.078*
H28B	0.2721	0.3552	0.1192	0.078*
C29	0.03539 (19)	0.2131 (2)	0.10824 (8)	0.0677 (6)
H29A	0.0198	0.2934	0.1241	0.081*
H29B	−0.0302	0.1929	0.0853	0.081*
C30	0.2297 (2)	−0.1321 (2)	0.07527 (8)	0.0713 (6)
C31	0.2563 (3)	−0.2341 (3)	0.11302 (12)	0.1118 (12)
H31A	0.2931	−0.1896	0.1398	0.168*
H31B	0.3057	−0.3025	0.1052	0.168*
H31C	0.1870	−0.2747	0.1179	0.168*
C33	0.3422 (2)	−0.0938 (3)	0.06174 (10)	0.0897 (8)
H33A	0.3865	−0.0401	0.0848	0.134*
H33B	0.3272	−0.0433	0.0345	0.134*
H33C	0.3836	−0.1740	0.0575	0.134*
C34	0.30185 (17)	0.3110 (2)	0.20612 (7)	0.0600 (5)
C35	0.2497 (2)	0.3203 (3)	0.24807 (8)	0.0797 (7)
H35A	0.1790	0.3684	0.2413	0.120*
H35B	0.3010	0.3669	0.2710	0.120*
H35C	0.2362	0.2313	0.2582	0.120*
C36	0.3360 (3)	0.4535 (3)	0.19522 (10)	0.0874 (8)
H36A	0.2689	0.5061	0.1851	0.131*
H36B	0.3808	0.4499	0.1723	0.131*
H36C	0.3796	0.4941	0.2215	0.131*
C37	0.4067 (2)	0.2201 (3)	0.21579 (10)	0.0827 (7)
H37A	0.4369	0.2084	0.1890	0.124*
H37B	0.3857	0.1340	0.2260	0.124*
H37C	0.4633	0.2607	0.2384	0.124*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0470 (10)	0.0598 (11)	0.0605 (11)	0.0037 (8)	0.0121 (8)	0.0005 (8)
N1	0.0519 (10)	0.0726 (11)	0.0810 (12)	0.0025 (8)	0.0136 (8)	−0.0044 (10)
O1A	0.0691 (11)	0.1038 (13)	0.1000 (13)	0.0184 (9)	0.0047 (9)	0.0272 (11)
O1B	0.0559 (11)	0.153 (2)	0.172 (2)	−0.0095 (12)	0.0099 (12)	0.0535 (18)
C2	0.0564 (11)	0.0581 (11)	0.0637 (12)	0.0047 (8)	0.0176 (9)	−0.0036 (9)
N3	0.0540 (9)	0.0579 (9)	0.0551 (9)	−0.0019 (7)	0.0129 (7)	−0.0011 (7)
C4	0.0654 (12)	0.0735 (13)	0.0514 (11)	−0.0030 (10)	0.0127 (9)	0.0044 (9)
C5	0.0662 (13)	0.0621 (12)	0.0569 (11)	0.0002 (9)	0.0140 (9)	0.0122 (9)
N5	0.0867 (14)	0.0792 (13)	0.0708 (12)	−0.0069 (11)	0.0120 (11)	0.0216 (10)
O5A	0.1161 (18)	0.144 (2)	0.138 (2)	−0.0127 (15)	−0.0135 (15)	0.0841 (18)
O5B	0.130 (2)	0.135 (2)	0.135 (2)	−0.0484 (16)	−0.0065 (15)	0.0721 (17)
C6	0.0638 (12)	0.0594 (11)	0.0628 (12)	0.0098 (9)	0.0095 (9)	0.0063 (9)
N7	0.0563 (9)	0.0493 (9)	0.0574 (9)	0.0055 (6)	0.0126 (7)	0.0007 (7)
C8	0.0603 (11)	0.0552 (11)	0.0542 (10)	0.0085 (8)	0.0131 (8)	0.0028 (8)
C9	0.0598 (12)	0.0668 (12)	0.0669 (12)	−0.0070 (9)	0.0200 (10)	0.0022 (10)
C10	0.0658 (13)	0.0663 (13)	0.0656 (13)	−0.0087 (10)	0.0138 (10)	−0.0062 (10)
C11	0.0662 (15)	0.1025 (19)	0.0938 (19)	−0.0171 (13)	0.0059 (12)	0.0068 (15)
C12	0.118 (2)	0.095 (2)	0.103 (2)	−0.0207 (17)	0.0374 (18)	−0.0419 (17)
C13	0.0874 (18)	0.0852 (17)	0.099 (2)	−0.0225 (14)	0.0091 (14)	0.0210 (14)
C14	0.0602 (12)	0.0525 (11)	0.0668 (12)	0.0050 (8)	0.0189 (9)	−0.0055 (9)
C15	0.104 (2)	0.0643 (14)	0.0974 (18)	0.0250 (13)	0.0254 (15)	−0.0053 (13)
C16	0.0846 (16)	0.0827 (16)	0.0712 (15)	0.0105 (12)	0.0118 (12)	−0.0186 (12)
C17	0.0776 (17)	0.0928 (18)	0.1016 (19)	−0.0114 (13)	0.0417 (14)	−0.0125 (14)
C21	0.0689 (13)	0.0638 (12)	0.0646 (13)	0.0031 (10)	0.0113 (10)	0.0128 (10)
N21	0.1098 (19)	0.0800 (15)	0.0803 (14)	0.0104 (13)	0.0206 (13)	0.0158 (12)
O21A	0.103 (3)	0.122 (3)	0.109 (3)	0.006 (2)	0.036 (2)	0.062 (2)
O21B	0.102 (3)	0.125 (3)	0.162 (4)	0.051 (3)	0.035 (3)	0.085 (3)
C32	0.098 (2)	0.112 (2)	0.123 (3)	−0.0032 (17)	0.0285 (19)	−0.052 (2)
C22	0.0689 (13)	0.0764 (14)	0.0591 (12)	0.0015 (10)	0.0142 (10)	0.0060 (10)
N23	0.0587 (10)	0.0617 (10)	0.0610 (10)	0.0020 (7)	0.0188 (8)	0.0012 (7)
C24	0.0543 (11)	0.0611 (12)	0.0698 (12)	−0.0044 (8)	0.0164 (9)	−0.0036 (9)
C25	0.0507 (11)	0.0592 (12)	0.0701 (12)	−0.0030 (8)	0.0178 (9)	−0.0017 (9)
N25	0.0572 (11)	0.0733 (12)	0.0983 (15)	−0.0044 (9)	0.0291 (10)	−0.0101 (11)
O25A	0.0853 (13)	0.1180 (16)	0.1073 (14)	−0.0142 (11)	0.0412 (11)	0.0225 (13)
O25B	0.0811 (15)	0.151 (2)	0.237 (3)	0.0339 (15)	0.0779 (18)	0.061 (2)
C26	0.0629 (12)	0.0573 (11)	0.0620 (12)	−0.0075 (9)	0.0168 (9)	0.0023 (9)
N27	0.0557 (10)	0.0539 (9)	0.0634 (10)	−0.0057 (7)	0.0156 (7)	−0.0003 (7)
C28	0.0642 (13)	0.0649 (12)	0.0694 (13)	−0.0092 (9)	0.0197 (10)	0.0069 (10)
C29	0.0574 (12)	0.0664 (13)	0.0777 (14)	0.0069 (9)	0.0086 (10)	−0.0006 (10)
C30	0.0704 (14)	0.0729 (14)	0.0751 (14)	0.0089 (10)	0.0248 (11)	−0.0037 (11)
C31	0.135 (3)	0.0863 (19)	0.131 (3)	0.0465 (18)	0.068 (2)	0.0316 (18)
C33	0.0757 (16)	0.108 (2)	0.0932 (18)	0.0152 (14)	0.0354 (14)	−0.0006 (15)
C34	0.0537 (11)	0.0581 (11)	0.0688 (12)	−0.0058 (8)	0.0129 (9)	−0.0041 (9)
C35	0.0815 (16)	0.0853 (17)	0.0747 (15)	−0.0118 (12)	0.0209 (12)	−0.0154 (12)
C36	0.0955 (19)	0.0687 (15)	0.0972 (19)	−0.0240 (13)	0.0161 (14)	−0.0050 (13)
C37	0.0631 (14)	0.0890 (17)	0.0928 (18)	0.0037 (12)	0.0063 (12)	−0.0061 (13)

Geometric parameters (Å, º)

C1—C9	1.506 (3)	C21—C22	1.532 (3)
C1—N1	1.524 (3)	C21—N21	1.522 (3)
C1—C2	1.536 (3)	C21—C28	1.544 (3)
C1—C8	1.546 (3)	N21—O21C	1.149 (13)
N1—O1B	1.200 (3)	N21—O21A	1.203 (4)
N1—O1A	1.205 (3)	N21—O21B	1.248 (4)
C2—N3	1.453 (3)	N21—O21D	1.212 (13)
N3—C4	1.454 (3)	C32—C30	1.513 (4)
N3—C10	1.498 (3)	C22—N23	1.454 (3)
C4—C5	1.537 (3)	N23—C24	1.458 (3)
C5—C9	1.512 (3)	N23—C30	1.504 (3)
C5—N5	1.516 (3)	C24—C25	1.534 (3)
C5—C6	1.548 (3)	C25—C29	1.506 (3)
N5—O5B	1.194 (3)	C25—N25	1.526 (3)
N5—O5A	1.198 (3)	C25—C26	1.540 (3)
C6—N7	1.462 (3)	N25—O25B	1.194 (3)
N7—C8	1.458 (2)	N25—O25A	1.213 (3)
N7—C14	1.489 (2)	C26—N27	1.463 (3)
C10—C11	1.522 (3)	N27—C28	1.461 (3)
C10—C12	1.525 (4)	N27—C34	1.489 (3)
C10—C13	1.530 (3)	C30—C33	1.529 (4)
C14—C15	1.522 (3)	C30—C31	1.523 (4)
C14—C17	1.524 (3)	C34—C35	1.529 (3)
C14—C16	1.534 (3)	C34—C36	1.528 (3)
C21—C29	1.513 (3)	C34—C37	1.531 (3)
C9—C1—N1	110.45 (16)	C29—C21—C28	110.95 (19)
C9—C1—C2	110.03 (17)	C22—C21—C28	112.08 (19)
N1—C1—C2	106.59 (16)	N21—C21—C28	107.91 (19)
C9—C1—C8	111.20 (16)	O21C—N21—O21A	107.8 (7)
N1—C1—C8	107.33 (16)	O21A—N21—O21B	124.2 (3)
C2—C1—C8	111.11 (16)	O21C—N21—O21D	119.7 (9)
O1B—N1—O1A	122.7 (2)	O21B—N21—O21D	111.1 (6)
O1B—N1—C1	119.2 (2)	O21C—N21—C21	119.8 (7)
O1A—N1—C1	118.15 (18)	O21A—N21—C21	118.0 (3)
N3—C2—C1	107.66 (15)	O21B—N21—C21	117.8 (3)
C2—N3—C4	110.49 (16)	O21D—N21—C21	120.3 (6)
C2—N3—C10	115.65 (16)	N23—C22—C21	108.44 (17)
C4—N3—C10	115.59 (16)	C22—N23—C24	110.61 (17)
N3—C4—C5	108.04 (16)	C22—N23—C30	115.48 (17)
C9—C5—N5	109.25 (17)	C24—N23—C30	114.91 (17)
C9—C5—C4	110.22 (18)	N23—C24—C25	107.63 (16)
N5—C5—C4	106.82 (17)	C29—C25—N25	110.12 (18)
C9—C5—C6	111.10 (17)	C29—C25—C24	110.19 (18)
N5—C5—C6	107.99 (17)	N25—C25—C24	105.83 (16)
C4—C5—C6	111.32 (18)	C29—C25—C26	111.01 (17)
O5B—N5—O5A	122.1 (2)	N25—C25—C26	107.55 (17)
O5B—N5—C5	120.0 (2)	C24—C25—C26	111.97 (17)
O5A—N5—C5	117.9 (2)	O25B—N25—O25A	123.0 (2)
N7—C6—C5	110.32 (17)	O25B—N25—C25	118.7 (2)
C8—N7—C6	111.22 (15)	O25A—N25—C25	118.20 (19)
C8—N7—C14	113.48 (15)	N27—C26—C25	110.29 (16)
C6—N7—C14	114.62 (16)	C28—N27—C26	109.99 (16)
N7—C8—C1	110.57 (16)	C28—N27—C34	115.34 (16)
C1—C9—C5	104.08 (16)	C26—N27—C34	114.00 (16)
N3—C10—C11	108.69 (19)	N27—C28—C21	110.06 (17)
N3—C10—C12	111.86 (19)	C25—C29—C21	103.71 (17)
C11—C10—C12	110.2 (2)	N23—C30—C32	112.0 (2)
N3—C10—C13	108.17 (18)	N23—C30—C33	108.0 (2)
C11—C10—C13	107.0 (2)	C32—C30—C33	110.1 (2)
C12—C10—C13	110.8 (2)	N23—C30—C31	108.4 (2)
N7—C14—C15	108.81 (18)	C32—C30—C31	110.7 (3)
N7—C14—C17	113.14 (17)	C33—C30—C31	107.5 (2)
C15—C14—C17	110.3 (2)	N27—C34—C35	108.63 (17)
N7—C14—C16	108.34 (17)	N27—C34—C36	108.62 (19)
C15—C14—C16	107.04 (19)	C35—C34—C36	107.12 (19)
C17—C14—C16	109.0 (2)	N27—C34—C37	113.15 (18)
C29—C21—C22	109.89 (19)	C35—C34—C37	108.9 (2)
C29—C21—N21	108.95 (19)	C36—C34—C37	110.3 (2)
C22—C21—N21	106.92 (19)
C9—C1—N1—O1B	1.0 (3)	C29—C21—N21—O21A	−178.5 (4)
C2—C1—N1—O1B	120.5 (3)	C22—C21—N21—O21A	−59.7 (4)
C8—C1—N1—O1B	−120.4 (3)	C28—C21—N21—O21A	61.0 (4)
C9—C1—N1—O1A	−178.8 (2)	C29—C21—N21—O21B	1.9 (5)
C2—C1—N1—O1A	−59.3 (2)	C22—C21—N21—O21B	120.6 (4)
C8—C1—N1—O1A	59.8 (2)	C28—C21—N21—O21B	−118.7 (4)
C9—C1—C2—N3	−64.0 (2)	C29—C21—N21—O21D	−139.4 (6)
N1—C1—C2—N3	176.23 (15)	C22—C21—N21—O21D	−20.6 (7)
C8—C1—C2—N3	59.6 (2)	C28—C21—N21—O21D	100.1 (6)
C1—C2—N3—C4	62.3 (2)	C29—C21—C22—N23	−62.9 (2)
C1—C2—N3—C10	−163.99 (16)	N21—C21—C22—N23	179.03 (18)
C2—N3—C4—C5	−61.7 (2)	C28—C21—C22—N23	61.0 (2)
C10—N3—C4—C5	164.56 (17)	C21—C22—N23—C24	61.2 (2)
N3—C4—C5—C9	62.5 (2)	C21—C22—N23—C30	−166.16 (18)
N3—C4—C5—N5	−178.97 (17)	C22—N23—C24—C25	−61.2 (2)
N3—C4—C5—C6	−61.3 (2)	C30—N23—C24—C25	165.86 (18)
C9—C5—N5—O5B	−9.2 (3)	N23—C24—C25—C29	63.8 (2)
C4—C5—N5—O5B	−128.4 (3)	N23—C24—C25—N25	−177.21 (17)
C6—C5—N5—O5B	111.8 (3)	N23—C24—C25—C26	−60.3 (2)
C9—C5—N5—O5A	169.2 (3)	C29—C25—N25—O25B	5.3 (3)
C4—C5—N5—O5A	50.0 (3)	C24—C25—N25—O25B	−113.7 (3)
C6—C5—N5—O5A	−69.8 (3)	C26—C25—N25—O25B	126.4 (3)
C9—C5—C6—N7	−5.8 (2)	C29—C25—N25—O25A	−177.1 (2)
N5—C5—C6—N7	−125.61 (18)	C24—C25—N25—O25A	63.8 (3)
C4—C5—C6—N7	117.43 (19)	C26—C25—N25—O25A	−56.0 (3)
C5—C6—N7—C8	−55.1 (2)	C29—C25—C26—N27	−3.5 (2)
C5—C6—N7—C14	174.52 (16)	N25—C25—C26—N27	−123.99 (18)
C6—N7—C8—C1	56.3 (2)	C24—C25—C26—N27	120.15 (18)
C14—N7—C8—C1	−172.71 (16)	C25—C26—N27—C28	−57.9 (2)
C9—C1—C8—N7	3.9 (2)	C25—C26—N27—C34	170.77 (16)
N1—C1—C8—N7	124.84 (17)	C26—N27—C28—C21	57.1 (2)
C2—C1—C8—N7	−118.99 (18)	C34—N27—C28—C21	−172.26 (17)
N1—C1—C9—C5	−179.92 (16)	C29—C21—C28—N27	4.4 (2)
C2—C1—C9—C5	62.7 (2)	C22—C21—C28—N27	−118.8 (2)
C8—C1—C9—C5	−60.9 (2)	N21—C21—C28—N27	123.7 (2)
N5—C5—C9—C1	−179.02 (17)	N25—C25—C29—C21	−179.78 (18)
C4—C5—C9—C1	−61.9 (2)	C24—C25—C29—C21	−63.4 (2)
C6—C5—C9—C1	61.9 (2)	C26—C25—C29—C21	61.2 (2)
C2—N3—C10—C11	172.56 (18)	C22—C21—C29—C25	62.7 (2)
C4—N3—C10—C11	−56.1 (2)	N21—C21—C29—C25	179.49 (19)
C2—N3—C10—C12	−65.6 (3)	C28—C21—C29—C25	−61.9 (2)
C4—N3—C10—C12	65.8 (3)	C22—N23—C30—C32	−63.0 (3)
C2—N3—C10—C13	56.7 (2)	C24—N23—C30—C32	67.7 (3)
C4—N3—C10—C13	−171.9 (2)	C22—N23—C30—C33	58.5 (3)
C8—N7—C14—C15	175.74 (19)	C24—N23—C30—C33	−170.9 (2)
C6—N7—C14—C15	−55.0 (2)	C22—N23—C30—C31	174.6 (2)
C8—N7—C14—C17	−61.3 (2)	C24—N23—C30—C31	−54.7 (3)
C6—N7—C14—C17	68.0 (2)	C28—N27—C34—C35	171.32 (19)
C8—N7—C14—C16	59.7 (2)	C26—N27—C34—C35	−60.0 (2)
C6—N7—C14—C16	−171.03 (18)	C28—N27—C34—C36	55.1 (2)
C29—C21—N21—O21C	46.8 (8)	C26—N27—C34—C36	−176.20 (19)
C22—C21—N21—O21C	165.5 (7)	C28—N27—C34—C37	−67.6 (2)
C28—C21—N21—O21C	−73.7 (8)	C26—N27—C34—C37	61.0 (2)