Diethyl 6-(4-bromo­phen­yl)-1,4-dioxoperhydro-2,3,4a,6,7a-penta­azacyclo­penta­[cd]indene-2a,7b-dicarboxyl­ate methanol hemisolvate

The title compound, C₁₉H₂₂BrN₅O₆·0.5CH₃OH, is a derivative of glycoluril, with two ethyl acetate substituents on the `convex' face of the glycoluril system. The N atoms from separate rings of the glycouril unit are incorporated into a triazacyclohexane ring, in which the third N atom bears a 4-bromo­benzyl substituent. The title compound, containing two free syn-urea NH groups and two ureidyl C=O, assembles into one-dimensional helical hydrogen-bonded chains in the solid state, running parallel to the [101] direction. One ethyl group is disordered over two positions; the site-occupancy factors are ca 0.52 and 0.48.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.045
• wR factor = 0.136
• Data-to-parameter ratio = 13.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT773_ALERT_2_A Suspect C-C Bond in CIF:      C20    -C20     ..       1.73 Ang.

Author Response: The bond should be omitted as the methanol is disordered.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       4.20 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.43 Ratio

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) .....         14 Ang.
PLAT213_ALERT_2_C Atom C5'     has ADP max/min Ratio .............       3.10 prola
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C5'
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O7
PLAT432_ALERT_2_C Short Inter X...Y Contact  N5     ..  C20     ..       2.99 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          5

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C19.5 H22 Br1 N5 O6.5
            Atom count from _chemical_formula_moiety:C19.5 H24 Br1 N5 O6.5
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         31

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
  12 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

---

S1. Comment

Glycoluril, a biurea compound known for about 130 years, has established an impressive career as building block for molecular and supramolecular chemistry during the recent two decades (Freeman et al., 1981; Rebek, 2005; Rowan et al., 1999; Wu et al., 2002). As a part of our ongoing investigation into glycoluril derivatives (Li et al., 2006), we report here the structure of the title compound (I) (Fig. 1).

The molecular structure of (I) is shown in Fig. 1. It has four fused ring two imidazole and one triazahexane rings. The crystal packing is stabilized by intermolecular non-classical N—H···O hydrogen bonds (Table 1). Interestingly, the two hydrogen-bond donating NH groups and hydrogen-bond accepting ureidyl C═O groups become fully hydrogen-bonded through the formation of R₂²(8) (Bernstein et al. 1995) motifs comprisring N—H···O hydrogen-bonds (Fig 2).

Related literature

For the preparation of the title compound, see: Li et al. (2006). For general background literature regarding glycoluril and its derivatives, see: Freeman et al. (1981); Rebek (2005); Rowan et al. (1999); Wu et al. (2002). For patterns in hydrogen bonding, see: Bernstein et al. (1995).

S2. Experimental

The title compound was synthesized according to the procedure of Li et al. (2006) in 56% isolated yield. Crystals of (I) suitable for X-ray data collection were obtained by slow evaporation of a 1,2-dichloroethane and methanol solution in ratio of 4:1 at 293 K.

S3. Refinement

All H atoms bonded to C atoms were initially located in difference Fourier maps. They were then constrained to their ideal geometry with C–H=0.96 Å (methyl), 0.97 Å (methylene), with their U_iso values being set to 1.5 times of U_eq (methyl C) and 1.2 times of U_eq(methylene). The H atoms of the amine N atoms were found in difference maps and refined with U_iso(H) set to 1.2U_eq(N) and the N—H distances refined freely. The H atoms on the disordered methanol solvate were not included in the model. The occupancies of the disordered atoms C5/C5' and C6/C6' was refined to 0.518 (12)/0.482 (12).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. View of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms are represented by spheres of arbitrary radius. Atoms of the minor disorder components and the solvent molecule have been omitted for clarity.
	Fig. 2. Packing of (I) with hydrogen bonds drawn as dashed lines showing the formation of a right-handed helical hydrogen-bonded R2^2(8) ribbon involving syn-N atoms and C=O. H atoms not involved in hydrogen bonds have been omitted for clarity. Symmetry codes: i. -x + 1/2, -y + 3/2, -z; ii. -x, y, -z - 1/2.

Diethyl 6-(4-bromophenyl)-1,4-dioxoperhydro-2,3,4a,6,7a- pentaazacyclopenta[cd]indene-2a,7 b-dicarboxylate methanol hemisolvate

Crystal data

C19H22BrN5O6·0.5CH4O	F(000) = 2088
Mr = 510.33	Dx = 1.538 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6618 reflections
a = 24.06370 (14) Å	θ = 2.7–23.9°
b = 14.6142 (7) Å	µ = 1.92 mm^−1
c = 15.1014 (7) Å	T = 294 K
β = 123.918 (1)°	Block, colorless
V = 4407.0 (3) Å^3	0.30 × 0.20 × 0.20 mm
Z = 8

Data collection

Bruker SMART 4K CCD area-detector diffractometer	2828 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.081
Graphite monochromator	θmax = 26.0°, θmin = 1.7°
ϕ and ω scans	h = −26→29
22693 measured reflections	k = −18→18
4339 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0787P)^2] where P = (Fo^2 + 2Fc^2)/3
4339 reflections	(Δ/σ)max = 0.002
322 parameters	Δρmax = 0.50 e Å^−3
31 restraints	Δρmin = −0.38 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)
Br1	0.09382 (2)	1.15884 (3)	0.26032 (4)	0.0817 (2)
C1	0.03759 (14)	0.59152 (19)	−0.0950 (2)	0.0388 (6)
C2	0.20106 (13)	0.70999 (18)	0.0667 (2)	0.0377 (6)
C3	0.14998 (13)	0.57862 (18)	−0.0369 (2)	0.0363 (6)
C4	0.18373 (16)	0.4953 (2)	−0.0486 (3)	0.0496 (8)
C5	0.2896 (5)	0.4035 (6)	0.0604 (12)	0.103 (4)	0.518 (12)
H5A	0.3077	0.3821	0.1324	0.123*	0.518 (12)
H5B	0.2652	0.3543	0.0102	0.123*	0.518 (12)
C6	0.3427 (5)	0.4415 (7)	0.0492 (10)	0.106 (4)	0.518 (12)
H6A	0.3236	0.4576	−0.0240	0.159*	0.518 (12)
H6B	0.3771	0.3964	0.0713	0.159*	0.518 (12)
H6C	0.3617	0.4950	0.0931	0.159*	0.518 (12)
C5'	0.2856 (6)	0.4261 (9)	0.0065 (8)	0.097 (4)	0.482 (12)
H5'1	0.2560	0.3833	−0.0495	0.116*	0.482 (12)
H5'2	0.3091	0.4618	−0.0171	0.116*	0.482 (12)
C6'	0.3339 (7)	0.3768 (10)	0.1071 (9)	0.139 (6)	0.482 (12)
H6'1	0.3760	0.4085	0.1445	0.208*	0.482 (12)
H6'2	0.3403	0.3158	0.0907	0.208*	0.482 (12)
H6'3	0.3167	0.3741	0.1511	0.208*	0.482 (12)
C7	0.14412 (13)	0.57875 (17)	0.0619 (2)	0.0331 (6)
C8	0.17281 (14)	0.49725 (19)	0.1388 (2)	0.0418 (7)
C9	0.1625 (2)	0.3379 (2)	0.1509 (3)	0.0704 (11)
H9A	0.2080	0.3427	0.2134	0.084*
H9B	0.1328	0.3296	0.1745	0.084*
C10	0.1570 (3)	0.2609 (3)	0.0866 (4)	0.1003 (15)
H10A	0.1120	0.2568	0.0247	0.150*
H10B	0.1681	0.2057	0.1277	0.150*
H10C	0.1872	0.2689	0.0647	0.150*
C11	0.05125 (14)	0.6256 (2)	0.0780 (2)	0.0398 (6)
H11A	0.0029	0.6327	0.0346	0.048*
H11B	0.0628	0.5857	0.1372	0.048*
C12	0.15451 (14)	0.7051 (2)	0.1800 (2)	0.0396 (6)
H12A	0.1694	0.6682	0.2429	0.047*
H12B	0.1749	0.7651	0.2038	0.047*
C13	0.05662 (15)	0.7874 (2)	0.0380 (2)	0.0472 (7)
H13A	0.0095	0.7770	−0.0159	0.057*
H13B	0.0805	0.7856	0.0034	0.057*
C14	0.06560 (14)	0.8802 (2)	0.0884 (2)	0.0448 (7)
C15	0.12066 (16)	0.9345 (2)	0.1205 (3)	0.0539 (8)
H15	0.1524	0.9155	0.1076	0.065*
C16	0.12924 (17)	1.0173 (2)	0.1718 (3)	0.0578 (8)
H16	0.1673	1.0524	0.1955	0.069*
C17	0.08157 (17)	1.0465 (2)	0.1871 (3)	0.0540 (8)
C18	0.02511 (18)	0.9961 (2)	0.1529 (3)	0.0589 (9)
H18	−0.0078	1.0178	0.1618	0.071*
C19	0.01780 (17)	0.9126 (2)	0.1050 (3)	0.0556 (8)
H19	−0.0199	0.8773	0.0833	0.067*
C20	0.0414 (9)	0.7513 (8)	0.2701 (12)	0.145 (6)	0.50
N1	0.08160 (12)	0.58339 (18)	−0.12421 (18)	0.0457 (6)
H1	0.0683 (15)	0.591 (2)	−0.1891 (11)	0.055*
N2	0.18829 (12)	0.66033 (15)	−0.0188 (2)	0.0416 (6)
H2	0.2078 (14)	0.673 (2)	−0.050 (2)	0.050*
N3	0.07245 (10)	0.58278 (14)	0.01361 (17)	0.0340 (5)
N4	0.17724 (11)	0.66263 (14)	0.11747 (18)	0.0369 (5)
N5	0.08203 (11)	0.71459 (15)	0.11935 (17)	0.0389 (5)
O1	−0.02299 (10)	0.60162 (15)	−0.15411 (15)	0.0513 (5)
O2	0.22887 (10)	0.78421 (13)	0.09463 (17)	0.0487 (5)
O3	0.15792 (14)	0.44551 (19)	−0.1224 (2)	0.0829 (8)
O4	0.24576 (13)	0.4891 (2)	0.0336 (3)	0.0911 (9)
O5	0.21328 (12)	0.50418 (16)	0.23280 (18)	0.0673 (7)
O6	0.14464 (12)	0.42050 (14)	0.08704 (17)	0.0559 (6)
O7	0.0000	0.6840 (8)	0.2500	0.259 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1095 (4)	0.0501 (2)	0.0870 (4)	−0.00416 (19)	0.0558 (3)	−0.00919 (18)
C1	0.0356 (17)	0.0446 (15)	0.0341 (16)	−0.0026 (12)	0.0182 (14)	−0.0042 (12)
C2	0.0352 (15)	0.0418 (16)	0.0393 (17)	−0.0030 (12)	0.0227 (14)	−0.0032 (12)
C3	0.0356 (15)	0.0450 (15)	0.0316 (15)	−0.0021 (12)	0.0208 (13)	−0.0032 (11)
C4	0.052 (2)	0.0520 (18)	0.057 (2)	−0.0044 (15)	0.0381 (18)	−0.0108 (16)
C5	0.081 (6)	0.132 (8)	0.126 (8)	0.021 (5)	0.077 (6)	−0.005 (6)
C6	0.086 (6)	0.105 (7)	0.137 (8)	−0.007 (5)	0.069 (6)	−0.037 (6)
C5'	0.107 (7)	0.102 (7)	0.104 (7)	0.075 (5)	0.072 (6)	0.024 (5)
C6'	0.136 (9)	0.162 (9)	0.117 (8)	0.057 (7)	0.070 (7)	−0.021 (7)
C7	0.0320 (14)	0.0369 (14)	0.0297 (14)	−0.0039 (11)	0.0168 (12)	−0.0024 (11)
C8	0.0374 (16)	0.0472 (17)	0.0387 (18)	0.0026 (13)	0.0201 (15)	−0.0001 (13)
C9	0.090 (3)	0.050 (2)	0.073 (3)	0.0143 (18)	0.047 (2)	0.0213 (17)
C10	0.151 (4)	0.046 (2)	0.126 (4)	0.011 (2)	0.091 (4)	0.007 (2)
C11	0.0394 (16)	0.0507 (16)	0.0359 (16)	−0.0030 (13)	0.0251 (14)	−0.0018 (13)
C12	0.0473 (17)	0.0447 (16)	0.0292 (15)	−0.0055 (13)	0.0228 (14)	−0.0068 (12)
C13	0.0502 (18)	0.0537 (18)	0.0413 (17)	0.0043 (14)	0.0278 (15)	0.0044 (14)
C14	0.0458 (17)	0.0475 (16)	0.0413 (17)	0.0045 (14)	0.0244 (15)	0.0063 (14)
C15	0.0523 (19)	0.0483 (18)	0.072 (2)	0.0076 (14)	0.0412 (19)	0.0126 (16)
C16	0.0521 (19)	0.0439 (18)	0.074 (2)	−0.0026 (14)	0.0331 (18)	0.0085 (16)
C17	0.068 (2)	0.0418 (17)	0.0489 (19)	0.0032 (16)	0.0308 (18)	0.0037 (14)
C18	0.062 (2)	0.060 (2)	0.065 (2)	0.0054 (17)	0.0413 (19)	−0.0040 (17)
C19	0.053 (2)	0.061 (2)	0.059 (2)	−0.0059 (15)	0.0346 (18)	−0.0066 (16)
C20	0.264 (17)	0.088 (7)	0.205 (14)	−0.024 (9)	0.206 (15)	−0.019 (8)
N1	0.0354 (14)	0.0769 (18)	0.0236 (13)	−0.0032 (12)	0.0157 (12)	−0.0052 (12)
N2	0.0499 (15)	0.0457 (13)	0.0437 (15)	−0.0092 (11)	0.0350 (13)	−0.0068 (11)
N3	0.0311 (12)	0.0439 (13)	0.0284 (12)	−0.0023 (9)	0.0174 (10)	−0.0004 (9)
N4	0.0376 (13)	0.0408 (12)	0.0349 (13)	−0.0068 (9)	0.0217 (11)	−0.0069 (9)
N5	0.0408 (14)	0.0434 (13)	0.0363 (13)	−0.0005 (10)	0.0240 (12)	−0.0021 (10)
O1	0.0347 (12)	0.0783 (16)	0.0351 (11)	0.0017 (10)	0.0159 (10)	−0.0034 (10)
O2	0.0554 (13)	0.0481 (12)	0.0547 (13)	−0.0153 (10)	0.0381 (11)	−0.0126 (10)
O3	0.105 (2)	0.0745 (17)	0.089 (2)	−0.0117 (15)	0.0669 (18)	−0.0389 (15)
O4	0.0538 (16)	0.0819 (19)	0.118 (2)	0.0206 (13)	0.0355 (17)	−0.0182 (17)
O5	0.0646 (15)	0.0651 (15)	0.0386 (14)	0.0072 (12)	0.0082 (13)	0.0049 (11)
O6	0.0678 (14)	0.0384 (11)	0.0448 (12)	−0.0010 (10)	0.0211 (12)	0.0051 (9)
O7	0.349 (14)	0.218 (10)	0.433 (17)	0.000	0.356 (15)	0.000

Geometric parameters (Å, º)

Br1—C17	1.908 (3)	C9—O6	1.452 (4)
C1—O1	1.221 (3)	C9—H9A	0.9700
C1—N1	1.361 (4)	C9—H9B	0.9700
C1—N3	1.369 (4)	C10—H10A	0.9600
C2—O2	1.220 (3)	C10—H10B	0.9600
C2—N2	1.359 (3)	C10—H10C	0.9600
C2—N4	1.373 (3)	C11—N5	1.453 (4)
C3—N1	1.425 (4)	C11—N3	1.466 (3)
C3—N2	1.439 (3)	C11—H11A	0.9700
C3—C4	1.528 (4)	C11—H11B	0.9700
C3—C7	1.576 (4)	C12—N5	1.455 (4)
C4—O3	1.177 (4)	C12—N4	1.467 (3)
C4—O4	1.307 (4)	C12—H12A	0.9700
C5—C6	1.487 (9)	C12—H12B	0.9700
C5—O4	1.537 (8)	C13—N5	1.475 (4)
C5—H5A	0.9700	C13—C14	1.512 (4)
C5—H5B	0.9700	C13—H13A	0.9700
C6—H6A	0.9600	C13—H13B	0.9700
C6—H6B	0.9600	C14—C15	1.379 (4)
C6—H6C	0.9600	C14—C19	1.390 (4)
C5'—C6'	1.487 (9)	C15—C16	1.388 (5)
C5'—O4	1.541 (7)	C15—H15	0.9300
C5'—H5'1	0.9700	C16—C17	1.359 (5)
C5'—H5'2	0.9700	C16—H16	0.9300
C6'—H6'1	0.9600	C17—C18	1.368 (5)
C6'—H6'2	0.9600	C18—C19	1.378 (4)
C6'—H6'3	0.9600	C18—H18	0.9300
C7—N4	1.448 (3)	C19—H19	0.9300
C7—N3	1.451 (3)	C20—O7	1.310 (13)
C7—C8	1.532 (4)	C20—C20^i	1.73 (3)
C8—O5	1.197 (3)	N1—H1	0.851 (10)
C8—O6	1.318 (3)	N2—H2	0.85 (4)
C9—C10	1.443 (6)	O7—C20^i	1.310 (13)
O1—C1—N1	126.9 (3)	N5—C11—H11A	109.1
O1—C1—N3	124.8 (2)	N3—C11—H11A	109.1
N1—C1—N3	108.2 (2)	N5—C11—H11B	109.1
O2—C2—N2	126.4 (2)	N3—C11—H11B	109.1
O2—C2—N4	125.1 (2)	H11A—C11—H11B	107.8
N2—C2—N4	108.5 (2)	N5—C12—N4	112.4 (2)
N1—C3—N2	115.0 (2)	N5—C12—H12A	109.1
N1—C3—C4	110.2 (2)	N4—C12—H12A	109.1
N2—C3—C4	111.0 (2)	N5—C12—H12B	109.1
N1—C3—C7	102.07 (19)	N4—C12—H12B	109.1
N2—C3—C7	101.9 (2)	H12A—C12—H12B	107.9
C4—C3—C7	116.4 (2)	N5—C13—C14	110.6 (2)
O3—C4—O4	125.2 (3)	N5—C13—H13A	109.5
O3—C4—C3	124.6 (3)	C14—C13—H13A	109.5
O4—C4—C3	110.1 (3)	N5—C13—H13B	109.5
C6—C5—O4	100.0 (7)	C14—C13—H13B	109.5
C6—C5—H5A	111.8	H13A—C13—H13B	108.1
O4—C5—H5A	111.8	C15—C14—C19	118.0 (3)
C6—C5—H5B	111.8	C15—C14—C13	122.2 (3)
O4—C5—H5B	111.8	C19—C14—C13	119.8 (3)
H5A—C5—H5B	109.5	C14—C15—C16	120.8 (3)
C6'—C5'—O4	105.4 (7)	C14—C15—H15	119.6
C6'—C5'—H5'1	110.7	C16—C15—H15	119.6
O4—C5'—H5'1	110.7	C17—C16—C15	119.4 (3)
C6'—C5'—H5'2	110.7	C17—C16—H16	120.3
O4—C5'—H5'2	110.7	C15—C16—H16	120.3
H5'1—C5'—H5'2	108.8	C16—C17—C18	121.4 (3)
C5'—C6'—H6'1	109.5	C16—C17—Br1	119.8 (3)
C5'—C6'—H6'2	109.5	C18—C17—Br1	118.8 (2)
H6'1—C6'—H6'2	109.5	C17—C18—C19	118.9 (3)
C5'—C6'—H6'3	109.5	C17—C18—H18	120.5
H6'1—C6'—H6'3	109.5	C19—C18—H18	120.5
H6'2—C6'—H6'3	109.5	C18—C19—C14	121.3 (3)
N4—C7—N3	111.9 (2)	C18—C19—H19	119.3
N4—C7—C8	110.5 (2)	C14—C19—H19	119.3
N3—C7—C8	108.6 (2)	O7—C20—C20^i	48.6 (8)
N4—C7—C3	103.8 (2)	C1—N1—C3	114.2 (2)
N3—C7—C3	103.5 (2)	C1—N1—H1	120 (2)
C8—C7—C3	118.4 (2)	C3—N1—H1	125 (2)
O5—C8—O6	125.7 (3)	C2—N2—C3	113.9 (2)
O5—C8—C7	123.9 (3)	C2—N2—H2	121 (2)
O6—C8—C7	110.3 (2)	C3—N2—H2	124 (2)
C10—C9—O6	108.7 (3)	C1—N3—C7	111.6 (2)
C10—C9—H9A	110.0	C1—N3—C11	123.1 (2)
O6—C9—H9A	110.0	C7—N3—C11	116.1 (2)
C10—C9—H9B	110.0	C2—N4—C7	111.7 (2)
O6—C9—H9B	110.0	C2—N4—C12	124.6 (2)
H9A—C9—H9B	108.3	C7—N4—C12	116.7 (2)
C9—C10—H10A	109.5	C11—N5—C12	109.3 (2)
C9—C10—H10B	109.5	C11—N5—C13	114.3 (2)
H10A—C10—H10B	109.5	C12—N5—C13	112.8 (2)
C9—C10—H10C	109.5	C4—O4—C5	123.9 (6)
H10A—C10—H10C	109.5	C4—O4—C5'	109.8 (5)
H10B—C10—H10C	109.5	C8—O6—C9	116.8 (3)
N5—C11—N3	112.6 (2)	C20^i—O7—C20	82.7 (16)
N1—C3—C4—O3	4.3 (4)	C7—C3—N2—C2	−4.5 (3)
N2—C3—C4—O3	−124.3 (3)	O1—C1—N3—C7	−175.6 (3)
C7—C3—C4—O3	119.8 (3)	N1—C1—N3—C7	6.7 (3)
N1—C3—C4—O4	−177.6 (3)	O1—C1—N3—C11	−30.3 (4)
N2—C3—C4—O4	53.8 (3)	N1—C1—N3—C11	152.1 (2)
C7—C3—C4—O4	−62.1 (3)	N4—C7—N3—C1	106.8 (2)
N1—C3—C7—N4	−116.5 (2)	C8—C7—N3—C1	−131.0 (2)
N2—C3—C7—N4	2.6 (2)	C3—C7—N3—C1	−4.4 (3)
C4—C3—C7—N4	123.5 (2)	N4—C7—N3—C11	−41.3 (3)
N1—C3—C7—N3	0.5 (3)	C8—C7—N3—C11	81.0 (3)
N2—C3—C7—N3	119.6 (2)	C3—C7—N3—C11	−152.4 (2)
C4—C3—C7—N3	−119.6 (2)	N5—C11—N3—C1	−93.4 (3)
N1—C3—C7—C8	120.7 (2)	N5—C11—N3—C7	50.6 (3)
N2—C3—C7—C8	−120.2 (2)	O2—C2—N4—C7	177.3 (3)
C4—C3—C7—C8	0.6 (3)	N2—C2—N4—C7	−2.6 (3)
N4—C7—C8—O5	5.2 (4)	O2—C2—N4—C12	27.9 (4)
N3—C7—C8—O5	−117.8 (3)	N2—C2—N4—C12	−152.0 (2)
C3—C7—C8—O5	124.7 (3)	N3—C7—N4—C2	−111.1 (2)
N4—C7—C8—O6	−177.2 (2)	C8—C7—N4—C2	127.8 (2)
N3—C7—C8—O6	59.7 (3)	C3—C7—N4—C2	−0.2 (3)
C3—C7—C8—O6	−57.8 (3)	N3—C7—N4—C12	41.0 (3)
N5—C13—C14—C15	94.6 (3)	C8—C7—N4—C12	−80.2 (3)
N5—C13—C14—C19	−84.5 (3)	C3—C7—N4—C12	151.9 (2)
C19—C14—C15—C16	2.6 (5)	N5—C12—N4—C2	98.4 (3)
C13—C14—C15—C16	−176.5 (3)	N5—C12—N4—C7	−49.7 (3)
C14—C15—C16—C17	−2.3 (5)	N3—C11—N5—C12	−55.9 (3)
C15—C16—C17—C18	−0.1 (5)	N3—C11—N5—C13	71.5 (3)
C15—C16—C17—Br1	178.6 (2)	N4—C12—N5—C11	55.3 (3)
C16—C17—C18—C19	2.1 (5)	N4—C12—N5—C13	−73.1 (3)
Br1—C17—C18—C19	−176.7 (3)	C14—C13—N5—C11	154.6 (2)
C17—C18—C19—C14	−1.7 (5)	C14—C13—N5—C12	−79.8 (3)
C15—C14—C19—C18	−0.6 (5)	O3—C4—O4—C5	−15.6 (7)
C13—C14—C19—C18	178.5 (3)	C3—C4—O4—C5	166.3 (5)
O1—C1—N1—C3	175.9 (3)	O3—C4—O4—C5'	16.1 (7)
N3—C1—N1—C3	−6.5 (3)	C3—C4—O4—C5'	−162.0 (6)
N2—C3—N1—C1	−105.8 (3)	C6—C5—O4—C4	116.7 (8)
C4—C3—N1—C1	127.9 (3)	C6—C5—O4—C5'	45.3 (12)
C7—C3—N1—C1	3.6 (3)	C6'—C5'—O4—C4	−144.8 (11)
O2—C2—N2—C3	−175.3 (3)	C6'—C5'—O4—C5	−21.6 (12)
N4—C2—N2—C3	4.6 (3)	O5—C8—O6—C9	2.6 (5)
N1—C3—N2—C2	105.0 (3)	C7—C8—O6—C9	−174.8 (3)
C4—C3—N2—C2	−129.0 (3)	C10—C9—O6—C8	−151.3 (3)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O5^ii	0.93	2.54	3.222 (4)	130
C9—H9A···O2^iii	0.97	2.56	3.318 (5)	136
N2—H2···O2^iv	0.85 (4)	2.08 (4)	2.914 (3)	168 (3)
N1—H1···O1^v	0.85 (2)	1.98 (1)	2.828 (3)	171 (3)

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