Ethyl 4-[1-(4-bromo­phenyl)-3-methyl-5-oxo-4,5-di­hydro-1H-1,2,4-triazol-4-yl­imino­methyl]­phenoxy­acetate

In the crystal structure of the title compound, C₂₀H₁₉BrN₄O₄, the asymmetric unit consists of two crystallographically independent mol­ecules, which differ in the relative orient­ations of the triazole and phenyl rings. In the crystal structure, both mol­ecules form approximately centrosymmetric dimers through weak C—H...O intermolecular interactions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.046
• wR factor = 0.126
• Data-to-parameter ratio = 19.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .....       0.91

Alert level C
CRYSC01_ALERT_1_C There is an ordering error in _exptl_crystal_colour.
            It should be (QUALIFIER) (INTENSITY) (BASE_COLOUR).
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           29.48
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total              10124
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns        11111
           Completeness (_total/calc)             91.12%

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

The triazole moiety possesses many pharmacological properties, such as acting as an antimicrobial (Habib et al., 1997), antiviral (Ergen et al., 1996), anti-HIV-1 (Invidiata et al., 1996), antifungal, antimycobacterial and anticonvulsant agent (Gu¨lerman et al., 1997). It is also a highly potent eosinophilia inhibitor (Naito et al., 1996) and is used as fungicide (Crofton, 1996) and herbicide (Tada et al., 1995). Some triazole derivatives have been evaluated for their antibacterial activity against both Gram-positive and Gram-negative bacteria (Bs et al., 1996). In view of these importance, the structure determination of the title compound, (I), was carried out.

A perspective view of (I), including the atomic numbering scheme, is shown in Fig. 1. The asymmetric unit consists of two crystallographically independent molecules. The overall r.m.s fit of these molecules is 0.233 Å. The corresponding bond distances and angles in the independent molecules agree with each other, but the two molecules differ in the relative orientations of the mean planes of the A/B and B/C rings, with dihedral angles of 3.83 (11) [10.24 (11)°] and 3.70 (9) [14.14 (11)°], respectively. The dihedral angle between the mean planes of the A and C rings is 5.32 (11)° [3.91 (10)°], the values in brackets correspond to values for molecule B. The bond lengths and angles of the triazole moiety in (I) are unexceptional and comparable with those reported for related structures (Chen et al., 1998; Wang et al., 1998; Thamotharan, Parthasarathi, Sunagar et al., 2003; Thamotharan, Parthasarathi, Hunnur et al., 2003; Thamotharan, Parthasarathi, Kavali et al., 2003). In (I), the N4A—N12A—C13A—C14A torsion angle of −178.3 (2)° [−177.3 (2)° for molecule B] indicates that the imine group has an E configuration. The ethoxycarbonylmethoxy group is oriented at an angle of 29.42 (15)° [31.33 (17)°] with respect to the mean plane of the ring C.

The phenyl ring substituted at N2 of the triazole ring is oriented almost coplanar [3.83 (11)°; 10.24 (10)° for molecule B] with respect to the plane of the triazole ring, while the corresponding angles in the chloro (Thamotharan, Parthasarathi, Sunagar et al., 2003; Thamotharan, Parthasarathi, Kavali et al., 2003) and bromo (Thamotharan, Parthasarathi, Hunnur et al., 2003) derivatives of triazole are 30.63 (9), 4.86 (5) and 8.93 (14)°, respectively.

The exocyclic angles C16A—C17A—O29A, O22A—C22A—O23A and O22A—C22A—C21A deviate significantly from the normal value of 120° (Table 1) and may be due to the steric repulsion [H16A···H21A = 2.16 Å (H16B···H21D = 2.13 Å in molecule B) and H24B···O22A = 2.41 Å (H24D···O22B = 2.37 Å in molecule B)].

In the crystal structure, the atom C8B of molecule B acts as donor for a weak intermolecular C—H···O interaction with the carbonyl atom O22B of centrosymmetrically related molecule at (-x, 2 − y, −z), which leads to an R²₂(34) motif. Atoms C10A and C10B are involved in a weak intermolecular C—H···O interaction with the atoms O3B and O3A of centrosymmetrically related molecule at (-x, 2 − y, 1 − z) and each interaction has a graph-set motif of R²₂(14) (Fig. 2) (Bernstein et al., 1995).

S2. Experimental

The title compound prepared by heating 4-amino-2-(p-bromophenyl)-5-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one with p-hydroxybenzaldehyde to give the corresponding hydrazone, and then further reaction with ethylbromoacetate in the presence of dry K₂CO₃ and KI. The solid obtained, (I), was crystallized from acetone (m.p. 428–431 K). The crystal was bounded by the {010}, {011} and the {610} pinacoids.

S3. Refinement

The structure was solved with DIRDIF99 (Beurskens et al., 1999) using the TRACOR option, with the input Br atom at the origin. The methyl H atoms were constrained to an ideal geometry (C—H = 0.96 Å), with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the parent C—C bond. All remaining H atoms were placed in geometrically idealized position (C—H = 0.93–0.97 Å) and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: IPDS (Stoe & Cie, 1997); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: DIRDIF99 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).

Figures

	Fig. 1. View of two independent molecules of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii.
	Fig. 2. The C—H···O contacts in two centrosymmetric dimers of (I) [symmetry code: (#) −x, 2 − y, 1 − z].

Ethyl 4-[1-(4-bromophenyl)-3-methyl-5-oxo-4,5-dihydro- 1H-1,2,4-triazol-4-yliminomethyl]phenoxyacetate

Crystal data

C20H19BrN4O4	Z = 4
Mr = 459.30	F(000) = 936
Triclinic, P1	Dx = 1.526 Mg m^−3
Hall symbol: -P 1	Melting point: 428 K
a = 8.5176 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.5566 (12) Å	Cell parameters from 15908 reflections
c = 17.2643 (15) Å	θ = 2.4–29.5°
α = 113.407 (6)°	µ = 2.09 mm^−1
β = 94.601 (7)°	T = 293 K
γ = 103.763 (6)°	Obelisk, translucent colourless
V = 1999.5 (3) Å^3	0.46 × 0.11 × 0.08 mm

Data collection

Stoe IPDS diffractometer	10124 independent reflections
Radiation source: sealed LFF X-ray tube, 12 x 0.4 mm	6462 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.026
Detector resolution: 9 pixels mm^-1	θmax = 29.5°, θmin = 2.4°
rotation method scans	h = −11→10
Absorption correction: integration (X-RED in IPDS; Stoe & Cie, 1997)	k = −20→21
Tmin = 0.537, Tmax = 0.861	l = −23→23
19783 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: constr
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0552P)^2 + 0.6771P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.002
10124 reflections	Δρmax = 0.52 e Å^−3
528 parameters	Δρmin = −0.42 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: 0.0045 (6)

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
Br1A	−0.07665 (5)	1.04785 (3)	0.66958 (2)	0.07535 (13)
O3A	0.1951 (3)	0.63426 (14)	0.60607 (11)	0.0592 (5)
O20A	0.5662 (3)	0.15699 (16)	0.50014 (13)	0.0664 (6)
O22A	0.3592 (3)	0.0727 (2)	0.58373 (18)	0.0847 (7)
O23A	0.5634 (3)	0.13732 (18)	0.69870 (15)	0.0736 (6)
N1A	0.0682 (3)	0.62379 (16)	0.40479 (13)	0.0525 (5)
N2A	0.0964 (3)	0.66883 (15)	0.49445 (12)	0.0462 (5)
N4A	0.1736 (3)	0.53837 (15)	0.45866 (13)	0.0472 (5)
N12A	0.2362 (3)	0.46170 (16)	0.45262 (14)	0.0509 (5)
C3A	0.1599 (3)	0.61725 (18)	0.53058 (16)	0.0456 (6)
C5A	0.1154 (4)	0.54634 (19)	0.38626 (16)	0.0504 (6)
C6A	0.0568 (3)	0.75770 (18)	0.53669 (15)	0.0430 (5)
C7A	−0.0169 (3)	0.7947 (2)	0.48736 (16)	0.0489 (6)
H7A	−0.0396	0.7612	0.4276	0.059*
C8A	−0.0566 (3)	0.8808 (2)	0.52657 (17)	0.0508 (6)
H8A	−0.1067	0.9056	0.4938	0.061*
C9A	−0.0210 (3)	0.92937 (19)	0.61458 (16)	0.0484 (6)
C10A	0.0525 (4)	0.8946 (2)	0.66494 (16)	0.0538 (7)
H10A	0.0759	0.9288	0.7246	0.065*
C11A	0.0913 (4)	0.8075 (2)	0.62533 (16)	0.0536 (7)
H11A	0.1406	0.7828	0.6585	0.064*
C13A	0.2956 (3)	0.45912 (19)	0.52105 (17)	0.0491 (6)
H13A	0.2945	0.5071	0.5745	0.059*
C14A	0.3658 (3)	0.38040 (18)	0.51554 (16)	0.0466 (6)
C15A	0.4250 (4)	0.37611 (19)	0.59072 (17)	0.0517 (6)
H15A	0.4192	0.4235	0.6434	0.062*
C16A	0.4928 (3)	0.3026 (2)	0.58910 (17)	0.0508 (6)
H16A	0.5312	0.3003	0.6400	0.061*
C17A	0.5022 (3)	0.2331 (2)	0.51089 (17)	0.0511 (6)
C18A	0.4442 (4)	0.2369 (2)	0.43505 (18)	0.0591 (7)
H18A	0.4509	0.1898	0.3824	0.071*
C19A	0.3772 (4)	0.3098 (2)	0.43750 (17)	0.0546 (7)
H19A	0.3391	0.3119	0.3864	0.066*
C21A	0.6315 (4)	0.1504 (2)	0.5746 (2)	0.0618 (8)
H21A	0.7022	0.2145	0.6154	0.074*
H21B	0.6987	0.1061	0.5592	0.074*
C22A	0.4991 (4)	0.1144 (2)	0.6174 (2)	0.0594 (7)
C24A	0.4581 (5)	0.0983 (3)	0.7490 (3)	0.0803 (10)
H24A	0.4828	0.1462	0.8086	0.096*
H24B	0.3427	0.0849	0.7260	0.096*
C25A	0.4900 (5)	0.0087 (3)	0.7436 (3)	0.0835 (10)
H25A	0.4652	−0.0384	0.6845	0.125*
H25B	0.4220	−0.0173	0.7756	0.125*
H25C	0.6040	0.0226	0.7672	0.125*
C51A	0.1082 (5)	0.4729 (2)	0.29759 (18)	0.0723 (9)
H51A	0.0675	0.4937	0.2566	0.108*
H51B	0.0359	0.4105	0.2880	0.108*
H51C	0.2167	0.4673	0.2910	0.108*
Br1B	−0.47366 (6)	1.39562 (3)	0.18860 (3)	0.09018 (16)
O3B	−0.1704 (3)	0.99101 (15)	0.11899 (11)	0.0613 (5)
O20B	0.2541 (3)	0.53525 (15)	0.00873 (13)	0.0716 (6)
O22B	0.5755 (3)	0.6577 (2)	0.07419 (18)	0.0863 (7)
O23B	0.5702 (3)	0.63849 (18)	0.19614 (15)	0.0763 (6)
N1B	−0.2845 (3)	0.99034 (17)	−0.07971 (13)	0.0538 (5)
N2B	−0.2655 (3)	1.03058 (15)	0.00983 (12)	0.0470 (5)
N4B	−0.1759 (3)	0.90365 (16)	−0.02855 (13)	0.0484 (5)
N12B	−0.1129 (3)	0.82677 (16)	−0.03591 (14)	0.0523 (5)
C3B	−0.1996 (3)	0.97747 (19)	0.04392 (16)	0.0475 (6)
C5B	−0.2303 (4)	0.9149 (2)	−0.09999 (16)	0.0513 (6)
C6B	−0.3145 (3)	1.11490 (18)	0.05337 (15)	0.0448 (5)
C7B	−0.4037 (3)	1.1475 (2)	0.00535 (16)	0.0506 (6)
H7B	−0.4314	1.1129	−0.0542	0.061*
C8B	−0.4512 (4)	1.2304 (2)	0.04512 (18)	0.0560 (7)
H8B	−0.5101	1.2525	0.0130	0.067*
C9B	−0.4100 (4)	1.2801 (2)	0.13318 (19)	0.0560 (7)
C10B	−0.3234 (4)	1.2490 (2)	0.18235 (18)	0.0587 (7)
H10B	−0.2984	1.2832	0.2420	0.070*
C11B	−0.2743 (4)	1.1661 (2)	0.14178 (17)	0.0556 (7)
H11B	−0.2141	1.1449	0.1742	0.067*
C13B	−0.0544 (4)	0.8231 (2)	0.03228 (17)	0.0531 (6)
H13B	−0.0584	0.8697	0.0858	0.064*
C14B	0.0191 (3)	0.74554 (19)	0.02632 (17)	0.0498 (6)
C15B	0.1070 (4)	0.7516 (2)	0.10018 (17)	0.0561 (7)
H15B	0.1121	0.8029	0.1528	0.067*
C16B	0.1876 (4)	0.6831 (2)	0.09766 (18)	0.0574 (7)
H16B	0.2465	0.6887	0.1480	0.069*
C17B	0.1796 (4)	0.6072 (2)	0.02035 (18)	0.0546 (7)
C18B	0.0914 (4)	0.5994 (2)	−0.05518 (18)	0.0624 (8)
H18B	0.0865	0.5480	−0.1077	0.075*
C19B	0.0118 (4)	0.6677 (2)	−0.05183 (18)	0.0576 (7)
H19B	−0.0475	0.6619	−0.1022	0.069*
C21B	0.3468 (4)	0.5392 (2)	0.0827 (2)	0.0665 (8)
H21C	0.3664	0.4763	0.0689	0.080*
H21D	0.2832	0.5510	0.1280	0.080*
C22B	0.5098 (4)	0.6183 (2)	0.1148 (2)	0.0627 (8)
C24B	0.7354 (5)	0.7077 (3)	0.2362 (3)	0.0825 (10)
H24C	0.7390	0.7470	0.2966	0.099*
H24D	0.7603	0.7514	0.2086	0.099*
C25B	0.8588 (5)	0.6544 (3)	0.2281 (3)	0.0825 (10)
H25D	0.8305	0.6085	0.2526	0.124*
H25E	0.9654	0.7001	0.2579	0.124*
H25F	0.8611	0.6197	0.1683	0.124*
C51B	−0.2261 (4)	0.8484 (2)	−0.18875 (17)	0.0671 (8)
H51D	−0.2939	0.7834	−0.2026	0.101*
H51E	−0.1148	0.8476	−0.1931	0.101*
H51F	−0.2669	0.8711	−0.2283	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1A	0.0967 (3)	0.0683 (2)	0.0693 (2)	0.0519 (2)	0.01909 (17)	0.02160 (15)
O3A	0.0831 (14)	0.0615 (11)	0.0434 (9)	0.0366 (11)	0.0088 (9)	0.0249 (8)
O20A	0.0878 (16)	0.0677 (12)	0.0635 (12)	0.0500 (12)	0.0186 (10)	0.0320 (10)
O22A	0.0612 (16)	0.0843 (17)	0.1089 (19)	0.0129 (14)	−0.0012 (13)	0.0500 (15)
O23A	0.0677 (15)	0.0868 (16)	0.0835 (15)	0.0198 (13)	0.0113 (11)	0.0560 (13)
N1A	0.0672 (15)	0.0526 (12)	0.0390 (10)	0.0266 (12)	0.0047 (9)	0.0171 (9)
N2A	0.0554 (13)	0.0470 (11)	0.0393 (10)	0.0226 (10)	0.0051 (9)	0.0180 (8)
N4A	0.0575 (14)	0.0436 (10)	0.0437 (10)	0.0210 (10)	0.0057 (9)	0.0193 (9)
N12A	0.0594 (14)	0.0443 (11)	0.0546 (12)	0.0235 (11)	0.0101 (10)	0.0223 (9)
C3A	0.0503 (15)	0.0463 (13)	0.0454 (13)	0.0191 (12)	0.0074 (10)	0.0225 (10)
C5A	0.0603 (17)	0.0486 (13)	0.0422 (12)	0.0215 (13)	0.0059 (11)	0.0170 (10)
C6A	0.0418 (14)	0.0452 (12)	0.0445 (12)	0.0160 (11)	0.0066 (10)	0.0203 (10)
C7A	0.0555 (16)	0.0539 (14)	0.0407 (12)	0.0237 (13)	0.0068 (10)	0.0199 (11)
C8A	0.0531 (16)	0.0560 (15)	0.0516 (14)	0.0251 (13)	0.0082 (11)	0.0268 (12)
C9A	0.0475 (15)	0.0490 (13)	0.0528 (14)	0.0225 (13)	0.0135 (11)	0.0206 (11)
C10A	0.0675 (18)	0.0532 (14)	0.0408 (12)	0.0263 (14)	0.0077 (11)	0.0161 (11)
C11A	0.0671 (18)	0.0552 (14)	0.0422 (13)	0.0271 (14)	0.0027 (11)	0.0208 (11)
C13A	0.0528 (16)	0.0443 (13)	0.0526 (14)	0.0177 (13)	0.0101 (11)	0.0215 (11)
C14A	0.0475 (15)	0.0424 (12)	0.0509 (13)	0.0140 (12)	0.0069 (11)	0.0213 (11)
C15A	0.0614 (18)	0.0451 (13)	0.0478 (13)	0.0197 (13)	0.0068 (12)	0.0174 (11)
C16A	0.0584 (17)	0.0515 (14)	0.0486 (13)	0.0215 (13)	0.0063 (11)	0.0253 (11)
C17A	0.0530 (16)	0.0523 (14)	0.0580 (15)	0.0251 (13)	0.0113 (12)	0.0283 (12)
C18A	0.076 (2)	0.0594 (16)	0.0478 (14)	0.0361 (16)	0.0133 (13)	0.0195 (12)
C19A	0.0683 (19)	0.0580 (15)	0.0463 (13)	0.0305 (15)	0.0084 (12)	0.0250 (12)
C21A	0.0632 (19)	0.0644 (17)	0.0740 (19)	0.0337 (16)	0.0111 (14)	0.0378 (15)
C22A	0.0545 (19)	0.0507 (15)	0.082 (2)	0.0220 (15)	0.0085 (15)	0.0346 (14)
C24A	0.086 (3)	0.084 (2)	0.083 (2)	0.029 (2)	0.0230 (19)	0.044 (2)
C25A	0.090 (3)	0.088 (3)	0.093 (3)	0.034 (2)	0.025 (2)	0.054 (2)
C51A	0.107 (3)	0.0668 (18)	0.0426 (14)	0.0440 (19)	0.0063 (15)	0.0142 (13)
Br1B	0.1253 (4)	0.0611 (2)	0.0856 (3)	0.0507 (2)	0.0141 (2)	0.02098 (18)
O3B	0.0808 (15)	0.0668 (12)	0.0413 (9)	0.0378 (11)	0.0057 (9)	0.0203 (9)
O20B	0.0909 (16)	0.0613 (12)	0.0622 (12)	0.0390 (12)	−0.0006 (11)	0.0196 (10)
O22B	0.0851 (19)	0.104 (2)	0.1018 (19)	0.0390 (16)	0.0292 (15)	0.0672 (17)
O23B	0.0705 (16)	0.0815 (15)	0.0803 (15)	0.0197 (13)	−0.0004 (11)	0.0424 (12)
N1B	0.0650 (15)	0.0587 (13)	0.0390 (10)	0.0219 (12)	0.0086 (10)	0.0204 (9)
N2B	0.0553 (13)	0.0485 (11)	0.0382 (10)	0.0187 (11)	0.0064 (9)	0.0185 (9)
N4B	0.0500 (13)	0.0517 (12)	0.0435 (11)	0.0189 (11)	0.0083 (9)	0.0183 (9)
N12B	0.0504 (14)	0.0496 (12)	0.0548 (12)	0.0204 (11)	0.0101 (10)	0.0170 (10)
C3B	0.0468 (15)	0.0494 (13)	0.0440 (13)	0.0157 (12)	0.0057 (10)	0.0178 (10)
C5B	0.0555 (17)	0.0539 (14)	0.0428 (13)	0.0162 (13)	0.0099 (11)	0.0190 (11)
C6B	0.0450 (15)	0.0439 (12)	0.0465 (13)	0.0124 (12)	0.0086 (10)	0.0208 (10)
C7B	0.0558 (17)	0.0544 (14)	0.0433 (13)	0.0159 (13)	0.0044 (11)	0.0240 (11)
C8B	0.0597 (18)	0.0551 (15)	0.0601 (16)	0.0183 (14)	0.0075 (13)	0.0315 (13)
C9B	0.0641 (19)	0.0438 (13)	0.0604 (16)	0.0191 (14)	0.0132 (13)	0.0208 (12)
C10B	0.075 (2)	0.0526 (15)	0.0452 (14)	0.0229 (15)	0.0055 (13)	0.0160 (11)
C11B	0.0662 (19)	0.0569 (15)	0.0446 (13)	0.0236 (15)	0.0025 (12)	0.0212 (12)
C13B	0.0537 (17)	0.0560 (15)	0.0512 (14)	0.0222 (14)	0.0118 (12)	0.0210 (12)
C14B	0.0476 (15)	0.0500 (14)	0.0518 (14)	0.0166 (13)	0.0108 (11)	0.0205 (11)
C15B	0.0637 (18)	0.0610 (16)	0.0457 (13)	0.0274 (15)	0.0130 (12)	0.0194 (12)
C16B	0.0614 (18)	0.0658 (17)	0.0480 (14)	0.0251 (15)	0.0082 (12)	0.0245 (13)
C17B	0.0566 (17)	0.0490 (14)	0.0585 (15)	0.0203 (14)	0.0088 (12)	0.0212 (12)
C18B	0.076 (2)	0.0515 (15)	0.0479 (14)	0.0254 (15)	−0.0017 (13)	0.0084 (12)
C19B	0.0626 (18)	0.0551 (15)	0.0501 (14)	0.0215 (14)	−0.0004 (12)	0.0175 (12)
C21B	0.077 (2)	0.0609 (17)	0.0698 (19)	0.0315 (17)	0.0062 (15)	0.0317 (15)
C22B	0.067 (2)	0.0667 (18)	0.0734 (19)	0.0353 (17)	0.0180 (15)	0.0390 (16)
C24B	0.083 (3)	0.076 (2)	0.083 (2)	0.030 (2)	0.0053 (19)	0.0260 (19)
C25B	0.078 (3)	0.089 (3)	0.090 (2)	0.037 (2)	0.0171 (19)	0.041 (2)
C51B	0.087 (2)	0.0704 (19)	0.0436 (14)	0.0308 (18)	0.0164 (14)	0.0191 (13)

Geometric parameters (Å, º)

Br1A—C9A	1.903 (2)	Br1B—C9B	1.903 (3)
O3A—C3A	1.218 (3)	O3B—C3B	1.222 (3)
O20A—C17A	1.372 (3)	O20B—C17B	1.370 (3)
O20A—C21A	1.411 (3)	O20B—C21B	1.418 (4)
O22A—C22A	1.183 (4)	O22B—C22B	1.193 (4)
O23A—C22A	1.336 (4)	O23B—C22B	1.339 (4)
O23A—C24A	1.488 (4)	O23B—C24B	1.466 (4)
N1A—C5A	1.289 (3)	N1B—C5B	1.293 (3)
N1A—N2A	1.394 (3)	N1B—N2B	1.397 (3)
N2A—C3A	1.370 (3)	N2B—C3B	1.378 (3)
N2A—C6A	1.420 (3)	N2B—C6B	1.410 (3)
N4A—C5A	1.370 (3)	N4B—C5B	1.373 (3)
N4A—N12A	1.389 (3)	N4B—N12B	1.389 (3)
N4A—C3A	1.394 (3)	N4B—C3B	1.391 (3)
N12A—C13A	1.267 (3)	N12B—C13B	1.269 (3)
C5A—C51A	1.488 (4)	C5B—C51B	1.479 (4)
C6A—C11A	1.381 (3)	C6B—C11B	1.379 (4)
C6A—C7A	1.388 (3)	C6B—C7B	1.392 (3)
C7A—C8A	1.378 (3)	C7B—C8B	1.374 (4)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—C9A	1.370 (4)	C8B—C9B	1.372 (4)
C8A—H8A	0.9300	C8B—H8B	0.9300
C9A—C10A	1.374 (4)	C9B—C10B	1.376 (4)
C10A—C11A	1.387 (3)	C10B—C11B	1.384 (4)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—H11A	0.9300	C11B—H11B	0.9300
C13A—C14A	1.460 (3)	C13B—C14B	1.460 (4)
C13A—H13A	0.9300	C13B—H13B	0.9300
C14A—C15A	1.387 (4)	C14B—C15B	1.383 (4)
C14A—C19A	1.388 (4)	C14B—C19B	1.394 (4)
C15A—C16A	1.391 (3)	C15B—C16B	1.388 (4)
C15A—H15A	0.9300	C15B—H15B	0.9300
C16A—C17A	1.377 (4)	C16B—C17B	1.369 (4)
C16A—H16A	0.9300	C16B—H16B	0.9300
C17A—C18A	1.390 (4)	C17B—C18B	1.398 (4)
C18A—C19A	1.374 (4)	C18B—C19B	1.376 (4)
C18A—H18A	0.9300	C18B—H18B	0.9300
C19A—H19A	0.9300	C19B—H19B	0.9300
C21A—C22A	1.514 (4)	C21B—C22B	1.507 (5)
C21A—H21A	0.9700	C21B—H21C	0.9700
C21A—H21B	0.9700	C21B—H21D	0.9700
C24A—C25A	1.451 (5)	C24B—C25B	1.469 (5)
C24A—H24A	0.9700	C24B—H24C	0.9700
C24A—H24B	0.9700	C24B—H24D	0.9700
C25A—H25A	0.9600	C25B—H25D	0.9600
C25A—H25B	0.9600	C25B—H25E	0.9600
C25A—H25C	0.9600	C25B—H25F	0.9600
C51A—H51A	0.9600	C51B—H51D	0.9600
C51A—H51B	0.9600	C51B—H51E	0.9600
C51A—H51C	0.9600	C51B—H51F	0.9600
C17A—O20A—C21A	117.9 (2)	C17B—O20B—C21B	117.5 (2)
C22A—O23A—C24A	118.4 (3)	C22B—O23B—C24B	118.1 (3)
C5A—N1A—N2A	104.67 (19)	C5B—N1B—N2B	105.1 (2)
C3A—N2A—N1A	112.46 (19)	C3B—N2B—N1B	111.83 (19)
C3A—N2A—C6A	128.2 (2)	C3B—N2B—C6B	128.4 (2)
N1A—N2A—C6A	119.30 (18)	N1B—N2B—C6B	119.7 (2)
C5A—N4A—N12A	120.9 (2)	C5B—N4B—N12B	121.1 (2)
C5A—N4A—C3A	108.56 (19)	C5B—N4B—C3B	108.7 (2)
N12A—N4A—C3A	130.6 (2)	N12B—N4B—C3B	130.3 (2)
C13A—N12A—N4A	119.1 (2)	C13B—N12B—N4B	118.7 (2)
O3A—C3A—N2A	129.6 (2)	O3B—C3B—N2B	128.8 (2)
O3A—C3A—N4A	128.0 (2)	O3B—C3B—N4B	128.4 (2)
N2A—C3A—N4A	102.40 (19)	N2B—C3B—N4B	102.8 (2)
N1A—C5A—N4A	111.9 (2)	N1B—C5B—N4B	111.6 (2)
N1A—C5A—C51A	125.1 (2)	N1B—C5B—C51B	124.8 (2)
N4A—C5A—C51A	123.0 (2)	N4B—C5B—C51B	123.6 (2)
C11A—C6A—C7A	120.0 (2)	C11B—C6B—C7B	119.6 (2)
C11A—C6A—N2A	121.1 (2)	C11B—C6B—N2B	121.6 (2)
C7A—C6A—N2A	118.9 (2)	C7B—C6B—N2B	118.8 (2)
C8A—C7A—C6A	120.2 (2)	C8B—C7B—C6B	120.7 (2)
C8A—C7A—H7A	119.9	C8B—C7B—H7B	119.7
C6A—C7A—H7A	119.9	C6B—C7B—H7B	119.7
C9A—C8A—C7A	119.0 (2)	C9B—C8B—C7B	118.7 (2)
C9A—C8A—H8A	120.5	C9B—C8B—H8B	120.7
C7A—C8A—H8A	120.5	C7B—C8B—H8B	120.7
C8A—C9A—C10A	122.0 (2)	C8B—C9B—C10B	121.9 (2)
C8A—C9A—Br1A	119.44 (19)	C8B—C9B—Br1B	118.9 (2)
C10A—C9A—Br1A	118.60 (19)	C10B—C9B—Br1B	119.2 (2)
C9A—C10A—C11A	118.9 (2)	C9B—C10B—C11B	119.1 (2)
C9A—C10A—H10A	120.5	C9B—C10B—H10B	120.5
C11A—C10A—H10A	120.5	C11B—C10B—H10B	120.5
C6A—C11A—C10A	120.0 (2)	C6B—C11B—C10B	120.0 (2)
C6A—C11A—H11A	120.0	C6B—C11B—H11B	120.0
C10A—C11A—H11A	120.0	C10B—C11B—H11B	120.0
N12A—C13A—C14A	119.6 (2)	N12B—C13B—C14B	119.7 (2)
N12A—C13A—H13A	120.2	N12B—C13B—H13B	120.1
C14A—C13A—H13A	120.2	C14B—C13B—H13B	120.1
C15A—C14A—C19A	118.5 (2)	C15B—C14B—C19B	118.3 (2)
C15A—C14A—C13A	119.2 (2)	C15B—C14B—C13B	119.1 (2)
C19A—C14A—C13A	122.3 (2)	C19B—C14B—C13B	122.5 (2)
C14A—C15A—C16A	121.5 (2)	C14B—C15B—C16B	121.6 (2)
C14A—C15A—H15A	119.3	C14B—C15B—H15B	119.2
C16A—C15A—H15A	119.3	C16B—C15B—H15B	119.2
C17A—C16A—C15A	119.0 (2)	C17B—C16B—C15B	119.4 (3)
C17A—C16A—H16A	120.5	C17B—C16B—H16B	120.3
C15A—C16A—H16A	120.5	C15B—C16B—H16B	120.3
O20A—C17A—C16A	124.9 (2)	C16B—C17B—O20B	125.4 (3)
O20A—C17A—C18A	114.9 (2)	C16B—C17B—C18B	120.1 (2)
C16A—C17A—C18A	120.1 (2)	O20B—C17B—C18B	114.6 (2)
C19A—C18A—C17A	120.4 (2)	C19B—C18B—C17B	120.0 (2)
C19A—C18A—H18A	119.8	C19B—C18B—H18B	120.0
C17A—C18A—H18A	119.8	C17B—C18B—H18B	120.0
C18A—C19A—C14A	120.5 (2)	C18B—C19B—C14B	120.6 (3)
C18A—C19A—H19A	119.7	C18B—C19B—H19B	119.7
C14A—C19A—H19A	119.7	C14B—C19B—H19B	119.7
O20A—C21A—C22A	112.8 (2)	O20B—C21B—C22B	112.4 (3)
O20A—C21A—H21A	109.0	O20B—C21B—H21C	109.1
C22A—C21A—H21A	109.0	C22B—C21B—H21C	109.1
O20A—C21A—H21B	109.0	O20B—C21B—H21D	109.1
C22A—C21A—H21B	109.0	C22B—C21B—H21D	109.1
H21A—C21A—H21B	107.8	H21C—C21B—H21D	107.9
O22A—C22A—O23A	125.2 (3)	O22B—C22B—O23B	124.7 (3)
O22A—C22A—C21A	124.9 (3)	O22B—C22B—C21B	125.3 (3)
O23A—C22A—C21A	109.9 (3)	O23B—C22B—C21B	110.0 (3)
C25A—C24A—O23A	108.8 (3)	O23B—C24B—C25B	110.2 (3)
C25A—C24A—H24A	109.9	O23B—C24B—H24C	109.6
O23A—C24A—H24A	109.9	C25B—C24B—H24C	109.6
C25A—C24A—H24B	109.9	O23B—C24B—H24D	109.6
O23A—C24A—H24B	109.9	C25B—C24B—H24D	109.6
H24A—C24A—H24B	108.3	H24C—C24B—H24D	108.1
C24A—C25A—H25A	109.5	C24B—C25B—H25D	109.5
C24A—C25A—H25B	109.5	C24B—C25B—H25E	109.5
H25A—C25A—H25B	109.5	H25D—C25B—H25E	109.5
C24A—C25A—H25C	109.5	C24B—C25B—H25F	109.5
H25A—C25A—H25C	109.5	H25D—C25B—H25F	109.5
H25B—C25A—H25C	109.5	H25E—C25B—H25F	109.5
C5A—C51A—H51A	109.5	C5B—C51B—H51D	109.5
C5A—C51A—H51B	109.5	C5B—C51B—H51E	109.5
H51A—C51A—H51B	109.5	H51D—C51B—H51E	109.5
C5A—C51A—H51C	109.5	C5B—C51B—H51F	109.5
H51A—C51A—H51C	109.5	H51D—C51B—H51F	109.5
H51B—C51A—H51C	109.5	H51E—C51B—H51F	109.5
C5A—N1A—N2A—C3A	−0.6 (3)	C5B—N1B—N2B—C6B	−179.6 (2)
C5A—N1A—N2A—C6A	−179.9 (2)	C5B—N4B—N12B—C13B	175.5 (3)
C5A—N4A—N12A—C13A	176.9 (3)	C3B—N4B—N12B—C13B	−6.0 (4)
C3A—N4A—N12A—C13A	−1.6 (4)	N1B—N2B—C3B—O3B	−178.4 (3)
N1A—N2A—C3A—O3A	−178.2 (3)	C6B—N2B—C3B—O3B	0.7 (5)
C6A—N2A—C3A—O3A	1.0 (5)	N1B—N2B—C3B—N4B	1.1 (3)
N1A—N2A—C3A—N4A	1.3 (3)	C6B—N2B—C3B—N4B	−179.9 (2)
C6A—N2A—C3A—N4A	−179.5 (2)	C5B—N4B—C3B—O3B	178.2 (3)
C5A—N4A—C3A—O3A	178.0 (3)	N12B—N4B—C3B—O3B	−0.4 (5)
N12A—N4A—C3A—O3A	−3.3 (5)	C5B—N4B—C3B—N2B	−1.2 (3)
C5A—N4A—C3A—N2A	−1.4 (3)	N12B—N4B—C3B—N2B	−179.9 (2)
N12A—N4A—C3A—N2A	177.2 (3)	N2B—N1B—C5B—N4B	−0.3 (3)
N2A—N1A—C5A—N4A	−0.3 (3)	N2B—N1B—C5B—C51B	179.9 (3)
N2A—N1A—C5A—C51A	179.4 (3)	N12B—N4B—C5B—N1B	179.8 (2)
N12A—N4A—C5A—N1A	−177.6 (2)	C3B—N4B—C5B—N1B	1.0 (3)
C3A—N4A—C5A—N1A	1.2 (3)	N12B—N4B—C5B—C51B	−0.4 (4)
N12A—N4A—C5A—C51A	2.6 (4)	C3B—N4B—C5B—C51B	−179.2 (3)
C3A—N4A—C5A—C51A	−178.6 (3)	C3B—N2B—C6B—C11B	11.6 (4)
C3A—N2A—C6A—C11A	4.5 (4)	N1B—N2B—C6B—C11B	−169.4 (3)
N1A—N2A—C6A—C11A	−176.3 (3)	C3B—N2B—C6B—C7B	−169.3 (3)
C3A—N2A—C6A—C7A	−175.8 (3)	N1B—N2B—C6B—C7B	9.7 (4)
N1A—N2A—C6A—C7A	3.3 (4)	C11B—C6B—C7B—C8B	0.4 (4)
C11A—C6A—C7A—C8A	−0.3 (4)	N2B—C6B—C7B—C8B	−178.8 (3)
N2A—C6A—C7A—C8A	−179.9 (3)	C6B—C7B—C8B—C9B	−0.5 (4)
C6A—C7A—C8A—C9A	0.5 (4)	C7B—C8B—C9B—C10B	−0.2 (5)
C7A—C8A—C9A—C10A	−0.2 (4)	C7B—C8B—C9B—Br1B	179.5 (2)
C7A—C8A—C9A—Br1A	−179.5 (2)	C8B—C9B—C10B—C11B	1.0 (5)
C8A—C9A—C10A—C11A	−0.2 (4)	Br1B—C9B—C10B—C11B	−178.7 (2)
Br1A—C9A—C10A—C11A	179.1 (2)	C7B—C6B—C11B—C10B	0.4 (4)
C7A—C6A—C11A—C10A	−0.1 (4)	N2B—C6B—C11B—C10B	179.5 (3)
N2A—C6A—C11A—C10A	179.5 (3)	C9B—C10B—C11B—C6B	−1.1 (5)
C9A—C10A—C11A—C6A	0.3 (5)	N4B—N12B—C13B—C14B	−177.3 (2)
N4A—N12A—C13A—C14A	−178.3 (2)	N12B—C13B—C14B—C15B	169.1 (3)
N12A—C13A—C14A—C15A	−177.6 (3)	N12B—C13B—C14B—C19B	−7.5 (4)
N12A—C13A—C14A—C19A	3.0 (4)	C19B—C14B—C15B—C16B	0.5 (5)
C19A—C14A—C15A—C16A	−0.7 (4)	C13B—C14B—C15B—C16B	−176.2 (3)
C13A—C14A—C15A—C16A	179.9 (3)	C14B—C15B—C16B—C17B	−0.3 (5)
C14A—C15A—C16A—C17A	0.5 (4)	C15B—C16B—C17B—O20B	179.6 (3)
C21A—O20A—C17A—C16A	−1.7 (4)	C15B—C16B—C17B—C18B	0.2 (5)
C21A—O20A—C17A—C18A	178.3 (3)	C21B—O20B—C17B—C16B	0.2 (5)
C15A—C16A—C17A—O20A	179.9 (3)	C21B—O20B—C17B—C18B	179.5 (3)
C15A—C16A—C17A—C18A	−0.1 (4)	C16B—C17B—C18B—C19B	−0.3 (5)
O20A—C17A—C18A—C19A	180.0 (3)	O20B—C17B—C18B—C19B	−179.7 (3)
C16A—C17A—C18A—C19A	0.0 (5)	C17B—C18B—C19B—C14B	0.5 (5)
C17A—C18A—C19A—C14A	−0.2 (5)	C15B—C14B—C19B—C18B	−0.6 (5)
C15A—C14A—C19A—C18A	0.6 (4)	C13B—C14B—C19B—C18B	176.0 (3)
C13A—C14A—C19A—C18A	180.0 (3)	C17B—O20B—C21B—C22B	−74.6 (3)
C17A—O20A—C21A—C22A	74.5 (3)	C24B—O23B—C22B—O22B	−5.6 (4)
C24A—O23A—C22A—O22A	7.5 (4)	C24B—O23B—C22B—C21B	174.7 (3)
C24A—O23A—C22A—C21A	−173.0 (2)	O20B—C21B—C22B—O22B	−17.6 (4)
O20A—C21A—C22A—O22A	18.3 (4)	O20B—C21B—C22B—O23B	162.1 (2)
O20A—C21A—C22A—O23A	−161.3 (2)	C22B—O23B—C24B—C25B	−95.4 (4)
C22A—O23A—C24A—C25A	95.2 (4)	N4A—N12A—C13A—H13A	1.7
C5B—N1B—N2B—C3B	−0.5 (3)	N4B—N12B—C13B—H13B	2.7

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8B—H8B···O22B^i	0.93	2.54	3.430 (4)	161
C10A—H10A···O3B^ii	0.93	2.45	3.371 (3)	172
C10B—H10B···O3A^ii	0.93	2.39	3.314 (3)	171

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