Crystal structure of ethyl 2-[(4-bromo­phen­yl)amino]-3,4-di­methyl­pent-3-enoate

In the title compound, C₁₅H₂₀BrNO₂, there are two independent mol­ecules (A and B) comprising the asymmetric unit and these adopt very similar conformations. In A, the dihedral angle between the CO₂ and MeC=CMe₂ groups is 80.7 (3)°, and these make dihedral angles of 3.5 (3) and 84.09 (16)°, respectively, with the bromo­benzene ring. The equivalent dihedral angles for mol­ecule B are 78.4 (3), 2.1 (3) and 78.37 (12)°, respectively. The most prominent inter­actions in the crystal packing are amine-N—H...O(carbon­yl) hydrogen bonds between the two independent mol­ecules, resulting in non-centrosymmetric ten-membered {...OC₂NH}₂ synthons. Statistical disorder is noted for each of the terminal methyl groups of the ethyl residues.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.045
• wR factor = 0.129
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT220_ALERT_2_C Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        3.7 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H    Uiso(max)/Uiso(min) ..        4.2 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     --  C17     ..        6.5 su
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         N1 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         C6 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C13 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        C21 Check
PLAT334_ALERT_2_C Small Average Benzene  C-C Dist. C10    -C15           1.37 Ang.
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H7A    ..  H8A     ..       1.88 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         34 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          4 Note
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         11 Note
PLAT793_ALERT_4_G The Model has Chirality at C1      .............          S Verify
PLAT793_ALERT_4_G The Model has Chirality at C16     .............          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         22 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
  10 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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

---

S1. Synthesis and crystallization

Ytterbium triflate (10 mol%) was added to a stirred solution of (E)-ethyl 2-(4-bromo­phenyl­imino)­acetate (0.5 mmol) in CH₂Cl₂ (5 mL). Potassium 3-methyl-2-buten-2-yltri­fluoro­borate (0.6 mmol) was then added and reaction mixture was stirred at room temperature until there was total consumption of the starting material. The reaction mixture was extracted with NaOH (0.5 N). The organic phase was dried using MgSO₄, and the solvent was removed under reduced pressure. Suitable crystals were obtained by slow evaporation from its EtOAc solution.

¹H NMR (CDCl₃, 300 MHz): δ 7.18 (d, J = 8.7 Hz, 2H), 6.35 (d, J = 8.7 Hz, 2H), 4.86 (s,1H), 4.59 (bs, NH), 4.17-4.08 (m, 2H), 1.87 (s, 3H), 1.65 (s, 3H), 1.42 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H) ppm. ¹³C NMR (CDCl₃, 75 MHz) δ =171.9, 145.3, 131.8 (2C), 131.6, 123.6, 114.7 (2C), 109.2, 61.4, 57.7, 21.4, 20.5, 14.1, 12.6 ppm. HRMS: calcd. for C₁₅H₂₀BrNO₂ [M + H]⁺ 325.0677; found: 325.0671.

S2. Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.93 to 0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The N—H H atoms were refined with N—H = 0.86±0.01 Å, and with U_iso(H) = 1.2U_eq(N). The terminal methyl group of each ethyl residue was found to be statistically disordered over two positions. These were refined so that equivalent pairs of atoms in each residue had the same anisotropic displacement parameters. Disorder in the C10–C15 benzene ring, manifested in a short average C—C bond length, i.e. 1.37 Å, could not be resolved.

Related literature

For background to the study into new and simpler synthetic routes for β,γ-unsaturated α-amino acid derivatives, see: Stefani et al. (2013). For the use of potassium organotrifluoroborate in synthesis, see: Caracelli et al. (2007).

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (Chemaxon, 2010) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structures of the two independent molecules in the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Overlay diagram of the two crystallographically independent molecules of the title compound. The N1- and N2-containing molecules are shown in red and blue, respectively.

Ethyl 2-[(4-bromophenyl)amino]-3,4-dimethylpent-3-enoate

Crystal data

C15H20BrNO2	Z = 4
Mr = 326.22	F(000) = 672
Triclinic, P1	Dx = 1.337 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.8746 (6) Å	Cell parameters from 6830 reflections
b = 12.2023 (5) Å	θ = 2.8–24.5°
c = 13.7760 (6) Å	µ = 2.54 mm^−1
α = 97.557 (3)°	T = 290 K
β = 110.520 (2)°	Irregular, colourless
γ = 113.866 (2)°	0.50 × 0.34 × 0.28 mm
V = 1620.20 (14) Å^3

Data collection

Bruker Kappa APEXII CCD diffractometer	5927 independent reflections
Radiation source: fine-focus sealed tube	4054 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and ϕ scans	θmax = 25.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
Tmin = 0.552, Tmax = 0.745	k = −14→14
18794 measured reflections	l = −16→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0596P)^2 + 0.9501P] where P = (Fo^2 + 2Fc^2)/3
5927 reflections	(Δ/σ)max < 0.001
377 parameters	Δρmax = 0.70 e Å^−3
2 restraints	Δρmin = −0.73 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.40749 (8)	0.86878 (7)	0.59824 (4)	0.1400 (3)
O1	1.0407 (3)	0.8284 (3)	1.1303 (2)	0.0801 (8)
O2	1.0548 (2)	0.9633 (3)	1.2646 (2)	0.0763 (7)
N1	0.8516 (4)	0.8629 (4)	0.9787 (3)	0.0780 (10)
H1N	0.889 (4)	0.819 (3)	0.966 (3)	0.094*
C1	0.8827 (3)	0.9110 (3)	1.0912 (3)	0.0566 (8)
H1	0.9102	1.0012	1.1093	0.068*
C2	1.0017 (3)	0.8954 (3)	1.1617 (3)	0.0613 (9)
C3	1.1615 (4)	0.9495 (4)	1.3454 (3)	0.0851 (12)	0.50
H3A	1.2353	0.9647	1.3248	0.102*	0.50
H3B	1.1241	0.8643	1.3495	0.102*	0.50
C4	1.2124 (17)	1.0377 (15)	1.4481 (16)	0.095 (5)	0.50
H4A	1.2291	1.1189	1.4397	0.143*	0.50
H4B	1.2968	1.0441	1.4979	0.143*	0.50
H4C	1.1460	1.0101	1.4763	0.143*	0.50
C3'	1.1615 (4)	0.9495 (4)	1.3454 (3)	0.0851 (12)	0.50
H3C	1.2506	1.0009	1.3483	0.102*	0.50
H3D	1.1412	0.8620	1.3300	0.102*	0.50
C4'	1.157 (2)	0.998 (2)	1.4551 (17)	0.191 (14)	0.50
H4D	1.1003	1.0376	1.4427	0.286*	0.50
H4E	1.2485	1.0579	1.5098	0.286*	0.50
H4F	1.1195	0.9276	1.4797	0.286*	0.50
C5	0.7633 (3)	0.8432 (3)	1.1185 (3)	0.0526 (8)
C6	0.7384 (3)	0.9023 (3)	1.1894 (3)	0.0576 (8)
C7	0.6809 (4)	0.7015 (3)	1.0618 (3)	0.0844 (12)
H7A	0.6281	0.6623	1.0985	0.127*
H7B	0.7424	0.6686	1.0637	0.127*
H7C	0.6200	0.6839	0.9871	0.127*
C8	0.6271 (4)	0.8335 (5)	1.2224 (4)	0.0909 (13)
H8A	0.5672	0.7488	1.1726	0.136*
H8B	0.5751	0.8770	1.2204	0.136*
H8C	0.6684	0.8310	1.2951	0.136*
C9	0.8196 (4)	1.0425 (4)	1.2481 (3)	0.0801 (11)
H9A	0.8852	1.0590	1.3207	0.120*
H9B	0.7583	1.0736	1.2520	0.120*
H9C	0.8671	1.0844	1.2090	0.120*
C10	0.7498 (4)	0.8649 (3)	0.8936 (3)	0.0547 (8)
C11	0.6902 (4)	0.9391 (3)	0.9089 (3)	0.0610 (9)
H11	0.7187	0.9884	0.9792	0.073*
C12	0.5895 (4)	0.9404 (3)	0.8214 (3)	0.0646 (9)
H12	0.5513	0.9912	0.8324	0.077*
C13	0.5462 (4)	0.8675 (4)	0.7189 (3)	0.0696 (10)
C14	0.6019 (4)	0.7914 (4)	0.7010 (3)	0.0709 (10)
H14	0.5709	0.7407	0.6307	0.085*
C15	0.7030 (4)	0.7917 (3)	0.7878 (3)	0.0614 (9)
H15	0.7414	0.7414	0.7756	0.074*
Br2	0.49175 (4)	0.41287 (4)	−0.39558 (3)	0.07843 (18)
O3	1.0151 (3)	0.2650 (2)	0.13441 (19)	0.0672 (6)
O4	1.0539 (3)	0.4148 (3)	0.27261 (18)	0.0744 (7)
N2	0.8714 (3)	0.3402 (3)	−0.0138 (2)	0.0595 (7)
H2N	0.888 (4)	0.280 (2)	−0.031 (3)	0.071*
C16	0.9097 (3)	0.3973 (3)	0.0989 (2)	0.0481 (7)
H16	0.9642	0.4892	0.1181	0.058*
C17	0.9983 (3)	0.3501 (3)	0.1685 (3)	0.0524 (8)
C18	1.1336 (4)	0.3766 (4)	0.3526 (3)	0.0819 (12)	0.50
H18A	1.2144	0.3865	0.3438	0.098*	0.50
H18B	1.0790	0.2890	0.3457	0.098*	0.50
C19	1.1732 (15)	0.4617 (17)	0.4594 (11)	0.126 (6)	0.50
H19A	1.2409	0.5454	0.4705	0.189*	0.50
H19B	1.2107	0.4314	0.5166	0.189*	0.50
H19C	1.0936	0.4636	0.4605	0.189*	0.50
C18'	1.1336 (4)	0.3766 (4)	0.3526 (3)	0.0819 (12)	0.50
H18C	1.2309	0.4325	0.3777	0.098*	0.50
H18D	1.1129	0.2913	0.3197	0.098*	0.50
C19'	1.0989 (17)	0.3819 (14)	0.4482 (13)	0.117 (5)	0.50
H19D	1.1248	0.4675	0.4831	0.175*	0.50
H19E	1.1482	0.3524	0.4997	0.175*	0.50
H19F	1.0019	0.3292	0.4225	0.175*	0.50
C20	0.7878 (3)	0.3681 (3)	0.1252 (2)	0.0484 (7)
C21	0.7868 (3)	0.4541 (3)	0.1947 (3)	0.0550 (8)
C22	0.6735 (4)	0.2335 (3)	0.0699 (3)	0.0700 (10)
H22A	0.6291	0.2086	0.1156	0.105*
H22B	0.7108	0.1793	0.0576	0.105*
H22C	0.6078	0.2266	0.0011	0.105*
C23	0.9035 (4)	0.5876 (4)	0.2554 (3)	0.0807 (11)
H23A	0.9629	0.5913	0.3257	0.121*
H23B	0.8670	0.6433	0.2649	0.121*
H23C	0.9547	0.6130	0.2143	0.121*
C24	0.6692 (4)	0.4254 (4)	0.2237 (3)	0.0864 (12)
H24A	0.5903	0.3479	0.1715	0.130*
H24B	0.6474	0.4930	0.2227	0.130*
H24C	0.6950	0.4169	0.2955	0.130*
C25	0.7873 (3)	0.3598 (3)	−0.0999 (2)	0.0471 (7)
C26	0.7547 (3)	0.4562 (3)	−0.0847 (2)	0.0520 (8)
H26	0.7915	0.5107	−0.0146	0.062*
C27	0.6683 (3)	0.4717 (3)	−0.1726 (2)	0.0532 (8)
H27	0.6465	0.5360	−0.1614	0.064*
C28	0.6147 (3)	0.3936 (3)	−0.2755 (2)	0.0498 (7)
C29	0.6476 (3)	0.2985 (3)	−0.2934 (3)	0.0560 (8)
H29	0.6119	0.2460	−0.3640	0.067*
C30	0.7330 (3)	0.2825 (3)	−0.2061 (3)	0.0542 (8)
H30	0.7550	0.2186	−0.2183	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.1954 (7)	0.2199 (7)	0.0665 (3)	0.1728 (6)	0.0380 (3)	0.0441 (4)
O1	0.0827 (18)	0.110 (2)	0.0766 (17)	0.0718 (17)	0.0375 (15)	0.0241 (15)
O2	0.0632 (15)	0.1006 (19)	0.0620 (16)	0.0502 (14)	0.0184 (13)	0.0091 (14)
N1	0.093 (2)	0.121 (3)	0.0558 (18)	0.083 (2)	0.0354 (17)	0.0231 (18)
C1	0.061 (2)	0.070 (2)	0.0554 (19)	0.0412 (18)	0.0312 (17)	0.0200 (16)
C2	0.052 (2)	0.077 (2)	0.062 (2)	0.0338 (18)	0.0294 (17)	0.0218 (19)
C3	0.057 (2)	0.098 (3)	0.077 (3)	0.040 (2)	0.008 (2)	0.014 (2)
C4	0.082 (8)	0.103 (7)	0.086 (10)	0.055 (6)	0.020 (6)	−0.001 (6)
C3'	0.057 (2)	0.098 (3)	0.077 (3)	0.040 (2)	0.008 (2)	0.014 (2)
C4'	0.22 (3)	0.36 (4)	0.056 (8)	0.21 (3)	0.033 (14)	0.049 (15)
C5	0.0490 (18)	0.0557 (18)	0.0530 (18)	0.0303 (15)	0.0173 (15)	0.0164 (15)
C6	0.054 (2)	0.072 (2)	0.0556 (19)	0.0354 (17)	0.0268 (16)	0.0246 (17)
C7	0.079 (3)	0.063 (2)	0.089 (3)	0.033 (2)	0.020 (2)	0.013 (2)
C8	0.064 (3)	0.128 (4)	0.091 (3)	0.041 (3)	0.048 (2)	0.047 (3)
C9	0.100 (3)	0.075 (2)	0.080 (3)	0.048 (2)	0.053 (2)	0.017 (2)
C10	0.070 (2)	0.0635 (19)	0.0572 (19)	0.0426 (17)	0.0411 (18)	0.0254 (16)
C11	0.080 (2)	0.073 (2)	0.0539 (19)	0.052 (2)	0.0379 (18)	0.0191 (17)
C12	0.089 (3)	0.076 (2)	0.066 (2)	0.060 (2)	0.046 (2)	0.0313 (19)
C13	0.097 (3)	0.088 (3)	0.059 (2)	0.065 (2)	0.042 (2)	0.037 (2)
C14	0.106 (3)	0.084 (2)	0.052 (2)	0.065 (2)	0.043 (2)	0.0235 (18)
C15	0.087 (3)	0.071 (2)	0.063 (2)	0.056 (2)	0.048 (2)	0.0292 (18)
Br2	0.0834 (3)	0.0954 (3)	0.0568 (2)	0.0548 (2)	0.01649 (19)	0.0287 (2)
O3	0.0790 (17)	0.0841 (16)	0.0601 (14)	0.0583 (14)	0.0297 (13)	0.0270 (13)
O4	0.0727 (16)	0.1072 (19)	0.0448 (13)	0.0582 (15)	0.0137 (12)	0.0153 (13)
N2	0.0765 (19)	0.0811 (19)	0.0456 (15)	0.0580 (17)	0.0288 (14)	0.0222 (14)
C16	0.0514 (18)	0.0561 (17)	0.0445 (17)	0.0303 (15)	0.0236 (14)	0.0185 (14)
C17	0.0427 (18)	0.069 (2)	0.0476 (18)	0.0255 (16)	0.0226 (15)	0.0216 (16)
C18	0.065 (2)	0.120 (3)	0.057 (2)	0.051 (2)	0.0153 (19)	0.030 (2)
C19	0.123 (13)	0.23 (2)	0.051 (6)	0.124 (13)	0.023 (8)	0.043 (11)
C18'	0.065 (2)	0.120 (3)	0.057 (2)	0.051 (2)	0.0153 (19)	0.030 (2)
C19'	0.144 (15)	0.153 (14)	0.063 (7)	0.079 (10)	0.045 (10)	0.038 (9)
C20	0.0478 (18)	0.0601 (18)	0.0423 (16)	0.0306 (15)	0.0189 (14)	0.0197 (14)
C21	0.057 (2)	0.069 (2)	0.0473 (17)	0.0355 (17)	0.0266 (16)	0.0196 (16)
C22	0.057 (2)	0.067 (2)	0.076 (2)	0.0245 (18)	0.0259 (19)	0.0204 (19)
C23	0.092 (3)	0.075 (2)	0.073 (3)	0.045 (2)	0.035 (2)	0.008 (2)
C24	0.083 (3)	0.121 (3)	0.081 (3)	0.061 (3)	0.052 (2)	0.029 (3)
C25	0.0487 (18)	0.0571 (17)	0.0464 (17)	0.0295 (15)	0.0261 (14)	0.0219 (14)
C26	0.065 (2)	0.0538 (17)	0.0441 (17)	0.0350 (16)	0.0241 (15)	0.0148 (14)
C27	0.068 (2)	0.0529 (17)	0.0511 (18)	0.0365 (16)	0.0285 (16)	0.0221 (15)
C28	0.0492 (18)	0.0592 (18)	0.0470 (17)	0.0289 (15)	0.0225 (14)	0.0232 (15)
C29	0.062 (2)	0.070 (2)	0.0398 (17)	0.0363 (17)	0.0232 (15)	0.0134 (15)
C30	0.062 (2)	0.0629 (19)	0.0507 (19)	0.0393 (17)	0.0292 (16)	0.0152 (15)

Geometric parameters (Å, º)

Br1—C13	1.894 (4)	Br2—C28	1.900 (3)
O1—C2	1.194 (4)	O3—C17	1.201 (4)
O2—C2	1.318 (4)	O4—C17	1.317 (4)
O2—C3	1.451 (4)	O4—C18	1.445 (4)
N1—C10	1.369 (4)	N2—C25	1.378 (4)
N1—C1	1.438 (4)	N2—C16	1.437 (4)
N1—H1N	0.858 (10)	N2—H2N	0.856 (10)
C1—C2	1.509 (5)	C16—C17	1.513 (4)
C1—C5	1.531 (5)	C16—C20	1.530 (4)
C1—H1	0.9800	C16—H16	0.9800
C3—C4	1.413 (17)	C18—C19	1.477 (16)
C3—H3A	0.9700	C18—H18A	0.9700
C3—H3B	0.9700	C18—H18B	0.9700
C4—H4A	0.9600	C19—H19A	0.9600
C4—H4B	0.9600	C19—H19B	0.9600
C4—H4C	0.9600	C19—H19C	0.9600
C4'—H4D	0.9600	C19'—H19D	0.9600
C4'—H4E	0.9600	C19'—H19E	0.9600
C4'—H4F	0.9600	C19'—H19F	0.9600
C5—C6	1.323 (5)	C20—C21	1.331 (4)
C5—C7	1.515 (5)	C20—C22	1.504 (4)
C6—C9	1.505 (5)	C21—C24	1.505 (5)
C6—C8	1.511 (5)	C21—C23	1.508 (5)
C7—H7A	0.9600	C22—H22A	0.9600
C7—H7B	0.9600	C22—H22B	0.9600
C7—H7C	0.9600	C22—H22C	0.9600
C8—H8A	0.9600	C23—H23A	0.9600
C8—H8B	0.9600	C23—H23B	0.9600
C8—H8C	0.9600	C23—H23C	0.9600
C9—H9A	0.9600	C24—H24A	0.9600
C9—H9B	0.9600	C24—H24B	0.9600
C9—H9C	0.9600	C24—H24C	0.9600
C10—C15	1.386 (4)	C25—C30	1.390 (4)
C10—C11	1.392 (4)	C25—C26	1.393 (4)
C11—C12	1.376 (5)	C26—C27	1.379 (4)
C11—H11	0.9300	C26—H26	0.9300
C12—C13	1.356 (5)	C27—C28	1.358 (4)
C12—H12	0.9300	C27—H27	0.9300
C13—C14	1.382 (5)	C28—C29	1.385 (4)
C14—C15	1.364 (5)	C29—C30	1.371 (4)
C14—H14	0.9300	C29—H29	0.9300
C15—H15	0.9300	C30—H30	0.9300
C2—O2—C3	117.8 (3)	C17—O4—C18	118.3 (3)
C10—N1—C1	123.0 (3)	C25—N2—C16	123.7 (2)
C10—N1—H1N	120 (3)	C25—N2—H2N	116 (2)
C1—N1—H1N	116 (3)	C16—N2—H2N	119 (2)
N1—C1—C2	108.2 (3)	N2—C16—C17	108.2 (2)
N1—C1—C5	114.0 (3)	N2—C16—C20	114.1 (3)
C2—C1—C5	107.8 (3)	C17—C16—C20	108.4 (2)
N1—C1—H1	108.9	N2—C16—H16	108.7
C2—C1—H1	108.9	C17—C16—H16	108.7
C5—C1—H1	108.9	C20—C16—H16	108.7
O1—C2—O2	124.1 (3)	O3—C17—O4	124.5 (3)
O1—C2—C1	125.4 (3)	O3—C17—C16	125.2 (3)
O2—C2—C1	110.5 (3)	O4—C17—C16	110.3 (3)
O2—C3—C4	108.7 (8)	O4—C18—C19	104.7 (6)
O2—C3—H3A	109.9	O4—C18—H18A	110.8
C4—C3—H3A	109.9	C19—C18—H18A	110.8
O2—C3—H3B	109.9	O4—C18—H18B	110.8
C4—C3—H3B	109.9	C19—C18—H18B	110.8
H3A—C3—H3B	108.3	H18A—C18—H18B	108.9
H4D—C4'—H4E	109.5	H19D—C19'—H19E	109.5
H4D—C4'—H4F	109.5	H19D—C19'—H19F	109.5
H4E—C4'—H4F	109.5	H19E—C19'—H19F	109.5
C6—C5—C7	123.1 (3)	C21—C20—C22	123.5 (3)
C6—C5—C1	122.9 (3)	C21—C20—C16	122.2 (3)
C7—C5—C1	114.0 (3)	C22—C20—C16	114.2 (3)
C5—C6—C9	124.2 (3)	C20—C21—C24	122.7 (3)
C5—C6—C8	122.6 (3)	C20—C21—C23	124.3 (3)
C9—C6—C8	113.1 (3)	C24—C21—C23	113.0 (3)
C5—C7—H7A	109.5	C20—C22—H22A	109.5
C5—C7—H7B	109.5	C20—C22—H22B	109.5
H7A—C7—H7B	109.5	H22A—C22—H22B	109.5
C5—C7—H7C	109.5	C20—C22—H22C	109.5
H7A—C7—H7C	109.5	H22A—C22—H22C	109.5
H7B—C7—H7C	109.5	H22B—C22—H22C	109.5
C6—C8—H8A	109.5	C21—C23—H23A	109.5
C6—C8—H8B	109.5	C21—C23—H23B	109.5
H8A—C8—H8B	109.5	H23A—C23—H23B	109.5
C6—C8—H8C	109.5	C21—C23—H23C	109.5
H8A—C8—H8C	109.5	H23A—C23—H23C	109.5
H8B—C8—H8C	109.5	H23B—C23—H23C	109.5
C6—C9—H9A	109.5	C21—C24—H24A	109.5
C6—C9—H9B	109.5	C21—C24—H24B	109.5
H9A—C9—H9B	109.5	H24A—C24—H24B	109.5
C6—C9—H9C	109.5	C21—C24—H24C	109.5
H9A—C9—H9C	109.5	H24A—C24—H24C	109.5
H9B—C9—H9C	109.5	H24B—C24—H24C	109.5
N1—C10—C15	120.0 (3)	N2—C25—C30	119.9 (3)
N1—C10—C11	122.3 (3)	N2—C25—C26	122.2 (3)
C15—C10—C11	117.7 (3)	C30—C25—C26	117.9 (3)
C12—C11—C10	120.8 (3)	C27—C26—C25	120.6 (3)
C12—C11—H11	119.6	C27—C26—H26	119.7
C10—C11—H11	119.6	C25—C26—H26	119.7
C13—C12—C11	119.8 (3)	C28—C27—C26	120.3 (3)
C13—C12—H12	120.1	C28—C27—H27	119.9
C11—C12—H12	120.1	C26—C27—H27	119.9
C12—C13—C14	120.8 (3)	C27—C28—C29	120.4 (3)
C12—C13—Br1	120.0 (3)	C27—C28—Br2	120.0 (2)
C14—C13—Br1	119.2 (3)	C29—C28—Br2	119.6 (2)
C15—C14—C13	119.2 (3)	C30—C29—C28	119.5 (3)
C15—C14—H14	120.4	C30—C29—H29	120.3
C13—C14—H14	120.4	C28—C29—H29	120.3
C14—C15—C10	121.6 (3)	C29—C30—C25	121.2 (3)
C14—C15—H15	119.2	C29—C30—H30	119.4
C10—C15—H15	119.2	C25—C30—H30	119.4
C10—N1—C1—C2	−178.9 (3)	C25—N2—C16—C17	178.2 (3)
C10—N1—C1—C5	61.1 (5)	C25—N2—C16—C20	57.4 (4)
C3—O2—C2—O1	−3.9 (6)	C18—O4—C17—O3	−4.1 (5)
C3—O2—C2—C1	173.9 (3)	C18—O4—C17—C16	175.2 (3)
N1—C1—C2—O1	−16.7 (5)	N2—C16—C17—O3	−10.7 (4)
C5—C1—C2—O1	107.1 (4)	C20—C16—C17—O3	113.5 (3)
N1—C1—C2—O2	165.4 (3)	N2—C16—C17—O4	170.0 (3)
C5—C1—C2—O2	−70.8 (4)	C20—C16—C17—O4	−65.7 (3)
C2—O2—C3—C4	174.9 (9)	C17—O4—C18—C19	−176.6 (7)
N1—C1—C5—C6	−144.0 (3)	N2—C16—C20—C21	−141.6 (3)
C2—C1—C5—C6	95.8 (4)	C17—C16—C20—C21	97.8 (3)
N1—C1—C5—C7	39.1 (4)	N2—C16—C20—C22	41.0 (4)
C2—C1—C5—C7	−81.2 (3)	C17—C16—C20—C22	−79.7 (3)
C7—C5—C6—C9	179.1 (3)	C22—C20—C21—C24	−1.0 (5)
C1—C5—C6—C9	2.5 (5)	C16—C20—C21—C24	−178.2 (3)
C7—C5—C6—C8	1.4 (5)	C22—C20—C21—C23	176.7 (3)
C1—C5—C6—C8	−175.2 (3)	C16—C20—C21—C23	−0.5 (5)
C1—N1—C10—C15	−164.7 (3)	C16—N2—C25—C30	−167.1 (3)
C1—N1—C10—C11	15.6 (6)	C16—N2—C25—C26	13.5 (5)
N1—C10—C11—C12	178.9 (3)	N2—C25—C26—C27	−178.9 (3)
C15—C10—C11—C12	−0.9 (5)	C30—C25—C26—C27	1.6 (5)
C10—C11—C12—C13	0.9 (6)	C25—C26—C27—C28	−0.6 (5)
C11—C12—C13—C14	0.0 (6)	C26—C27—C28—C29	−0.7 (5)
C11—C12—C13—Br1	179.9 (3)	C26—C27—C28—Br2	178.2 (2)
C12—C13—C14—C15	−0.9 (6)	C27—C28—C29—C30	1.0 (5)
Br1—C13—C14—C15	179.2 (3)	Br2—C28—C29—C30	−178.0 (2)
C13—C14—C15—C10	0.9 (6)	C28—C29—C30—C25	0.1 (5)
N1—C10—C15—C14	−179.9 (4)	N2—C25—C30—C29	179.2 (3)
C11—C10—C15—C14	−0.1 (5)	C26—C25—C30—C29	−1.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.86	2.44	3.235 (6)	154
N2—H2N···O1^i	0.86	2.37	3.153 (5)	153

Symmetry code: (i) −x+2, −y+1, −z+1.