Contrasting the supra­molecular structures in the isomeric pair 5-bromo-3-nitro­salicyl­aldehyde phenyl­hydrazone and 3-bromo-5-nitro­salicyl­aldehyde phenyl­hydrazone

Isomeric 5-bromo-3-nitro­salicyl­aldehyde phenyl­hydrazone and 3-bromo-5-nitro­salicyl­aldehyde phenyl­hydrazone, C₁₃H₁₀BrN₃O₃, both crystallize with two mol­ecules in the asymmetric unit. In both isomers, an intra­molecular O—H...N hydrogen bond links the hy­droxy group and the imine N atom. In the 5-bromo-3-nitro isomer, there are two independent N—H...O hydrogen-bonded chains, each mol­ecule in the asymmetric unit forming its own chain. These chains are then linked to form a three-dimensional framework by a combination of weak C—H...O, C—H...Br, C—H...π and π–π stacking inter­actions. In the 3-bromo-5-nitro isomer, N—H...O hydrogen bonds link the independent mol­ecules alternately into a zigzag chain, which is reinforced by a weak C—H...O inter­action. Individual chains are linked by a C—H...Br inter­action and a three-dimensional framework is generated by π–π stacking inter­actions.

S1. Comment

In the course of our continuing investigation of supramolecular arrangements in hydrazones, we have studied the supramolecular structures of hydrazones derived from 2-hydroxyacetophenone (Baddeley et al., 2009), bis(pyridin-2-yl) ketone (França et al., 2010), 2-aminoacetophenone (Howie et al., 2012) and iodo- and nitrobenzaldehydes with nitrophenylhydrazines (Glidewell et al., 2003, 2004; Wardell et al., 2005; Ferguson et al., 2005), as well as compounds obtained from 5-phenyl-2-hydrazinyl-1,3,4-thiadiazole (Carvalho et al., 2009), 2-(1,3-benzothiazolyl)hydrazine (Nogueira et al., 2011; Lindgren et al., 2012) and 7-chloro-4-hydrazinylquinoline (Howie et al., 2010; de Souza et al., 2012: Ferreira et al., 2012) with arenecarbaldehydes. We have now extended this study to the isomeric hydrazones obtained from the reaction of phenylhydrazine with 3-bromo-5-nitrosalicylaldehyde and 5-bromo-3-nitrosalicylaldehyde, and report here on their molecular and supramolecular structures.

Isomeric 5-bromo-3-nitrosalicylaldehyde phenylhydrazone, (I), and 3-bromo-5-nitrosalicylaldehyde phenylhydrazone, (II), have the potential for forming a wide variety of intermolecular interactions. These possibilities include N—H···O and C—H···O interactions with nitro O-atom acceptors, and O—H···X interactions with imide N and nitro O-atom acceptors. The presence of the two benzene rings also gives the possibility of the formation of C—H···π(arene) and π–π stacking interactions.

Both (I) and (II) crystallize with two molecules (A and B) in the asymmetric unit. Compound (I) is a three-component nonmerohedral twin.

Both (I) (Figs. 1 and 2) and (II) (Figs. 3 and 4) present an intramolecular O—H···N hydrogen bond between the hydroxy H atom and the imine group of the hydrazinyl unit. As a result, in both compounds the O—H bond plays no part in the building of the supramolecular structure. A search of the 2012 version of the Cambridge Structural Database (Allen, 2002) shows that the formation of this intramolecular O—H···N hydrogen bond is a very common occurrence. This search for molecules containing the salicylaldehyde group gave 457 hits for organic structures with R ≤ 0.10. Of these, ca 91% (417) were found to have (hydroxy)H···N distances in the range 1.5–2.5 Å and angles at the H atom in the range 135–160°. Within these ranges, the mean value for the distance was 1.864 (3) Å and the mean angle 145.80 (13)°. A scattergram of the H···N distance against the O—H···N angle shows a tight clustering of all values within the ranges given above. The values for (I) are 1.88 Å and 148°, respectively, for molecule A and 1.86 Å and 147°, respectively, for molecule B, while for (II), the respective values are 1.89 Å and 147° for molecule A, and 1.84 Å and 147° for molecule B, all of which lie well within the ranges given above.

Both molecules in (I) have a very similar geometry. The dihedral angles between the mean planes of the rings are 6.4 (2) and 6.0 (2)° for molecules A and B, respectively. A least-squares fit of the non-H atoms using PLATON MOLFIT with quaternion transformation (Mackay, 1984; Spek, 2009) shows that molecule A inverts onto molecule B (fit rotation angle of 179.70°), and gives r.m.s. values of 0.111 (unit weights) and 0.137 Å (weighted) for the fit of 14 atoms, excluding the nitro-group O atoms and atoms C12–C16 of the C11 ring. For all 20 non-H atoms, the r.m.s. values are 0.156 (unit weights) and 0.184 Å (weighted). In (II), the dihedral angles between the mean planes of the rings for molecules A and B are 9.1 (2) and 0.4 (2)°, respectively, which are markedly different, probably due to the participation of the ring of the phenylhydrazone group of molecule A in a C—H···O interaction. Molecule A inverts onto molecule B with a fit rotation angle of 179.03°, with r.m.s. values of 0.102 (unit weights) and 0.134 Å (weighted) for the fit of 14 atoms, excluding the nitro-group O atoms and atoms C12–C16 of the C11 ring. For all 20 non-H atoms, these values are 0.170 (unit weights) and 0.218 Å (weighted). These values reflect the fact that the intramolecular O—H···N hydrogen bond stabilizes the conformation of the 14 atoms which give the best fit between the independent molecules in each structure. The remaining six atoms, particularly the O atoms of the nitro groups, are involved in the intermolecular interactions which define the supramolecular structures, and as such have different conformations and thus give a poorer fit.

The participation of the hydroxy group of the salycilide residue in the intramolecular hydrogen bond leaves the N atom of the imide as the sole strong donor for the formation of the supramolecular structures of these two compounds. The natural acceptor is the nitro group attached to the benzene ring, since it allows for the formation of a strong N—H···O interaction. As the nitro group is positioned differently in both isomers, it is to be expected that they will have different supramolecular structures.

In (I), N—H···O hydrogen bonds link the molecules into two chains consisting of molecules of either type A or type B, so there are no molecule A···molecule B links involving the N—H···O interaction. Hydrogen-bonding details for (I) are given in Table 1. The N1A—H1A···O31A(x - 1/2, -y + 1/2, z + 1/2) and N1A—H1A···O32A(x - 1/2, -y + 1/2, z + 1/2) three-centred hydrogen bonds link molecules A into a C(9)C(9)R₁²(4) linear chain (for a description of graph-set motifs, see Bernstein et al., 1995) generated by the n-glide at y = 1/4, which runs parallel to [101] (Fig. 5). Likewise, molecules B are linked by the N1B—H1B···O32B(x + 1/2, -y + 1/2, z + 1/2) hydrogen bond into a linear C(9) chain generated by the n-glide at y = 1/4, which runs parallel to [101] (Fig. 6). These hydrogen-bonded chains are similar to those in the structures of (E)-2-nitrobenzaldeyde 4-nitropheylhydrazone and (E)-4-nitrobenzaldeyde 4-nitropheylhydrazone (Wardell et al., 2005). The chains interweave with each other, with molecules A and B lying almost parallel to each other, stacked head-to-tail, and almost parallel to (210). The interweaving and stacking are shown in Fig. 7. There is π–π stacking in the structure in which molecules A and B stack alternately head-to-tail above one another in the asymmetric unit and up the a axis (Fig. 8 and Table 3). The weak C36A—H36A···O31B(x + 1/2, -y + 1/2, z + 1/2) and C13B—H13B···Br5A(-x + 2, -y, -z + 1) interactions, as well as the C14A—H14A···Cg3(-x + 1/2, y + 1/2, -z + 1/2) C—H···π interaction (Fig. 9), link molecules A and B together in pairs (Cg3 is the centroid of the ring containing atom C11B). These D-type interactions (Bernstein et al., 1995) provide links between pairs of chains to create a very weakly bound three-dimensional network.

In (II), the molecules in the asymmetric unit are linked by an N—H···O hydrogen bond. Hydrogen-bonding details for (II) are given in Table 2. The N1A—H1A···O32B(x - 1, y + 1, z) and N1B—H13B···O32A interactions link molecules A and B in an alternating fashion into a zigzag C₂²(18) chain generated by unit translation. The weak C13A–H13A···O31A(x - 1, y + 1, z) hydrogen bond links molecules A together within this chain, forming an R₃³(18) ring involving two molecules A and one molecule B. The chain runs parallel to [110] (Fig. 10 and Table 2). The C14A—H14A···Br3B(x - 1, y + 1, z + 1) interaction, as in (I), links pairs of molecules together, providing links between the chains. As in (I), molecules A and B do not lie exactly parallel to each other. There is π–π stacking in the structure in which centrosymmetrically related molecules A and B stack in separate columns along the a axis (Fig. 11 and Table 4).

Related literature

For related literature, see: Allen (2002); Baddeley et al. (2009); Bernstein et al. (1995); Carvalho et al. (2009); Ferguson et al. (2005); Ferreira, de Souza, Wardell, Tiekink & Wardell (2012); França, de Lima, Wardell & Wardell (2010); Glidewell et al. (2003, 2004); Howie et al. (2010, 2012); Lindgren et al. (2012); Mackay (1984); Nogueira et al. (2011); Sheldrick (2008); Souza et al. (2012); Spek (2009); Wardell et al. (2005).

S2. Experimental

For the preparation of 5-bromo-3-nitrosalicylaldehyde phenylhydrazone, (I), a solution containing phenylhydrazine (PhNHNH₂) and 5-bromo-3-nitrosalicyldehyde in EtOH was refluxed for 1 h and rotary-evaporated to leave a solid residue. Purification was achieved via column chromatography on a silica column, using ethyl acetate–hexane [Solvent ratio?] as eluent, and recrystallization from EtOH (m.p. 455–457 K). 3-Bromo-5-nitrosalicylaldehyde phenylhydrazone, (II), was prepared in a similar manner from PhNHNH₂ and 3-bromo-5-nitrosalicyldehyde in EtOH (m.p. 517–519 K). Diffraction quality crystals for both compounds were obtained by slow evaporation from EtOH.

S3. Refinement

In both refinements, H atoms were treated as riding, with C—H(aromatic) = 0.95 Å and N—H = 0.88 Å, with U_iso = 1.2U_eq(C,N), or with O—H(hydroxy) = 0.84 Å, with U_iso = 1.5U_eq(O). The positions of the H atoms attached to the N and O atoms were calculated and checked on a difference map during and after the refinement was completed; these final positions were close to the H-atom positions derived from the difference maps, so justifying constrained refinement.

The crystal of (I) was a three-component non-merohedral twin. The twinned structure was refined using an HKLF 5 reflection file (Sheldrick, 2008) with BASF values of 0.119 (3) and 0.053 (3). Thus, the twin volume fractions are approximately 0.828:0.119:0.053. The twinning was discovered after an initial attempt at refinement gave a high R factor and the TwinRotMat option in PLATON (Spek, 2009) revealed the existence of three twin domains. The TwinRotMat option was used to generate the HKLF 5 reflection file from the original data, which had been integrated initially as a non-twinned data set.

In (II), the asymmetric unit was chosen so as to form a hydrogen-bonded unit composed of molecule A and molecule B. In both structures, the highest and lowest difference-map peaks were close to Br atoms.

Computing details

For both compounds, data collection: CrystalClear-SM (Rigaku, 2011); cell refinement: CrystalClear-SM (Rigaku, 2011); data reduction: CrystalClear-SM (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of molecule A of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular O—H···N interaction.
	Fig. 2. A view of molecule B of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular O—H···N interaction.
	Fig. 3. A view of molecule A of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular O—H···N interaction.
	Fig. 4. A view of molecule B of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular O—H···N interaction.
	Fig. 5. Part of the crystal structure of (I), showing the hydrogen-bonded chain consisting of molecule A which runs parallel to [101]. Atoms labelled with an asterisk (*), hash symbol (#) or dollar sign ($) are at the symmetry positions (x - 1/2, -y + 1/2, z + 1/2), (x + 1/2, -y + 1/2, z - 1/2) and (x - 1, y, z + 1), respectively. Hydrogen bonds are shown as dashed lines and uninvolved H atoms have been omitted.
	Fig. 6. Part of the crystal structure of (I), showing the hydrogen-bonded chain consisting of molecule B which runs parallel to [101]. Atoms labelled with an asterisk (*), hash symbol (#) or dollar sign ($) are at the symmetry positions (x + 1/2, -y + 1/2, z + 1/2), (x - 1/2, -y + 1/2, z - 1/2) and (x + 1, y, z + 1), respectively. Hydrogen bonds are shown as dashed lines and uninvolved H atoms have been omitted.
	Fig. 7. A stereoview of the packing of the molecules in the unit cell of (I), viewed along a, showing the interwoven chains. N—H···O hydrogen bonds are shown as dashed lines and uninvolved H atoms have been omitted.
	Fig. 8. A stereoview of the π–π stacking of the molecules of (I) running parallel to the a axis, with molecules A and B stacking head-to-tail alternately in the stack. H atoms have been omitted.
	Fig. 9. The discrete C—H···π interactions in the structure of (I), shown as dashed lines. Atoms labelled with an asterisk (*), hash symbol (#) or dollar sign ($) are at the symmetry positions (-x + 1/2, y + 1/2, -z + 1/2), (1 - x, 1 - y, 1 - z) and (x + 1/2, -y + 1/2, z + 1/2), respectively. H atoms not involved in the hydrogen bonding have been omitted.
	Fig. 10. Part of the crystal structure of (II), showing the zig-zag N—H···O hydrogen-bonded chain composed of molecules A and B, and the C—H···O hydrogen-bonded chain consisting of molecule A which runs parallel to [110]. Dashed lines indicate intermolecular interactions. Atoms labelled with an asterisk (*) or a hash symbol (#) are at the symmetry positions (x - 1, y + 1, z) and (x + 1, y - 1, z), respectively. H atoms not involved in the hydrogen bonding have been omitted.
	Fig. 11. A stereoview of the π–π stacking of the molecules of (II), running parallel to the a axis. Centrosymmetrically related molecules A and B stack in separate columns which are identified by the labelled Br atoms. H atoms have been omitted.

(I) 3-bromo-5-nitrosalicylaldehyde phenylhydrazone

Crystal data

C13H10BrN3O3	F(000) = 1344
Mr = 336.15	Dx = 1.690 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71075 Å
a = 8.517 (4) Å	Cell parameters from 7090 reflections
b = 21.699 (9) Å	θ = 2.4–31.3°
c = 14.301 (6) Å	µ = 3.12 mm^−1
β = 90.310 (9)°	T = 100 K
V = 2643 (2) Å^3	Needle, red
Z = 8	0.12 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn724+ diffractometer	6036 independent reflections
Radiation source: Rotating anode	5323 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.000
Detector resolution: 28.5714 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
profile data from ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear-SM; Rigaku, 2011)	k = −28→28
Tmin = 0.706, Tmax = 0.885	l = −18→18
6036 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.17	w = 1/[σ^2(Fo^2) + (0.0492P)^2 + 0.1403P] where P = (Fo^2 + 2Fc^2)/3
6036 reflections	(Δ/σ)max = 0.006
365 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.70 e Å^−3

Special details

Experimental. 5-Bromo-3-nitrosalicylaldehyde phenylhydrazone, (I): ¹H NMR (400MHz, DMSO-d₆, δ, p.p.m.): 6.83 (1H, t, m), 7.00 (2H, m), 7.28 (2H, m) [all phenyl],8.01 (1H, d, J = 2.5 Hz), 8.08 (1H, d, J = .5Hz) [C₆H₂], 8.13 (1H, s, CH═N), 10.89 (1H, s, NH), 11.84 (1H, br.s, OH).

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
Br5A	1.07411 (6)	0.08221 (2)	0.46106 (3)	0.02519 (13)
O2A	0.7481 (4)	0.24784 (14)	0.1806 (2)	0.0231 (7)
H2A	0.6913	0.2732	0.2091	0.035*
O31A	0.9469 (5)	0.19839 (18)	0.0615 (2)	0.0448 (10)
O32A	1.0161 (5)	0.10594 (17)	0.0929 (3)	0.0488 (11)
N1A	0.5424 (4)	0.35197 (17)	0.3660 (3)	0.0235 (9)
H1A	0.5478	0.3552	0.4272	0.028*
N2A	0.6255 (4)	0.30673 (16)	0.3237 (3)	0.0198 (8)
N3A	0.9627 (5)	0.15548 (18)	0.1165 (2)	0.0244 (9)
C3A	0.6970 (5)	0.2681 (2)	0.3776 (3)	0.0192 (9)
H3A	0.6837	0.2714	0.4433	0.023*
C11A	0.4489 (5)	0.3935 (2)	0.3171 (3)	0.0198 (9)
C12A	0.3645 (5)	0.4367 (2)	0.3695 (3)	0.0237 (10)
H12A	0.3736	0.4371	0.4357	0.028*
C13A	0.2682 (6)	0.4786 (2)	0.3248 (3)	0.0278 (11)
H13A	0.2111	0.5077	0.3606	0.033*
C14A	0.2536 (6)	0.4786 (2)	0.2275 (3)	0.0261 (10)
H14A	0.1860	0.5071	0.1969	0.031*
C15A	0.3399 (5)	0.4362 (2)	0.1759 (3)	0.0236 (10)
H15A	0.3322	0.4363	0.1096	0.028*
C16A	0.4362 (5)	0.3940 (2)	0.2197 (3)	0.0215 (9)
H16A	0.4941	0.3652	0.1836	0.026*
C31A	0.7972 (5)	0.2196 (2)	0.3408 (3)	0.0175 (9)
C32A	0.8227 (5)	0.2120 (2)	0.2423 (3)	0.0195 (9)
C33A	0.9265 (5)	0.16488 (19)	0.2154 (3)	0.0186 (9)
C34A	0.9988 (5)	0.1253 (2)	0.2781 (3)	0.0206 (9)
H34A	1.0655	0.0932	0.2568	0.025*
C35A	0.9718 (5)	0.1336 (2)	0.3722 (3)	0.0199 (9)
C36A	0.8737 (5)	0.1805 (2)	0.4035 (3)	0.0202 (9)
H36A	0.8586	0.1859	0.4687	0.024*
Br5B	−0.08804 (7)	0.39639 (2)	0.48495 (3)	0.03305 (15)
O2B	0.2748 (4)	0.23671 (14)	0.2149 (2)	0.0255 (7)
H2B	0.3351	0.2133	0.2449	0.038*
O31B	0.1628 (4)	0.31035 (18)	0.0878 (2)	0.0421 (10)
O32B	−0.0392 (4)	0.36555 (16)	0.1207 (2)	0.0317 (8)
N1B	0.4718 (4)	0.13263 (17)	0.3997 (3)	0.0237 (8)
H1B	0.4770	0.1302	0.4611	0.028*
N2B	0.3846 (4)	0.17778 (17)	0.3595 (3)	0.0202 (8)
N3B	0.0702 (5)	0.33190 (17)	0.1440 (2)	0.0226 (8)
C3B	0.3083 (5)	0.2146 (2)	0.4124 (3)	0.0213 (9)
H3B	0.3155	0.2100	0.4784	0.026*
C11B	0.5538 (5)	0.0897 (2)	0.3453 (3)	0.0223 (10)
C12B	0.6319 (5)	0.0422 (2)	0.3923 (3)	0.0278 (11)
H12B	0.6274	0.0396	0.4586	0.033*
C13B	0.7158 (6)	−0.0010 (2)	0.3418 (4)	0.0305 (11)
H13B	0.7689	−0.0333	0.3737	0.037*
C14B	0.7230 (5)	0.0025 (2)	0.2451 (4)	0.0282 (11)
H14B	0.7813	−0.0270	0.2106	0.034*
C15B	0.6439 (5)	0.0496 (2)	0.1993 (3)	0.0269 (11)
H15B	0.6479	0.0520	0.1330	0.032*
C16B	0.5593 (5)	0.0931 (2)	0.2482 (3)	0.0219 (10)
H16B	0.5054	0.1251	0.2160	0.026*
C31B	0.2108 (5)	0.2635 (2)	0.3734 (3)	0.0195 (9)
C32B	0.1947 (5)	0.2727 (2)	0.2751 (3)	0.0176 (9)
C33B	0.0936 (5)	0.3195 (2)	0.2435 (3)	0.0188 (9)
C34B	0.0097 (5)	0.3569 (2)	0.3055 (3)	0.0216 (10)
H34B	−0.0584	0.3884	0.2832	0.026*
C35B	0.0296 (5)	0.3466 (2)	0.4003 (3)	0.0212 (10)
C36B	0.1254 (5)	0.3009 (2)	0.4349 (3)	0.0218 (10)
H36B	0.1337	0.2946	0.5005	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br5A	0.0306 (3)	0.0251 (2)	0.0199 (2)	0.0062 (2)	0.0025 (2)	0.00746 (18)
O2A	0.0261 (18)	0.0235 (16)	0.0195 (15)	0.0067 (14)	−0.0036 (13)	0.0028 (13)
O31A	0.059 (3)	0.055 (2)	0.0205 (17)	0.026 (2)	0.0070 (18)	0.0117 (17)
O32A	0.076 (3)	0.045 (2)	0.0256 (19)	0.023 (2)	0.008 (2)	−0.0038 (18)
N1A	0.027 (2)	0.028 (2)	0.0166 (17)	0.0080 (18)	0.0031 (15)	0.0009 (16)
N2A	0.0188 (19)	0.0175 (18)	0.0232 (18)	−0.0005 (16)	0.0033 (15)	−0.0002 (15)
N3A	0.031 (2)	0.028 (2)	0.0148 (17)	0.0038 (18)	−0.0001 (15)	−0.0003 (16)
C3A	0.017 (2)	0.022 (2)	0.018 (2)	−0.0020 (19)	0.0029 (17)	0.0037 (18)
C11A	0.017 (2)	0.019 (2)	0.023 (2)	0.0002 (19)	0.0047 (18)	0.0037 (18)
C12A	0.029 (2)	0.024 (2)	0.018 (2)	−0.001 (2)	0.0050 (18)	0.0004 (19)
C13A	0.027 (3)	0.022 (2)	0.035 (3)	0.007 (2)	0.004 (2)	0.000 (2)
C14A	0.029 (3)	0.018 (2)	0.031 (2)	0.002 (2)	0.002 (2)	0.004 (2)
C15A	0.025 (2)	0.026 (2)	0.020 (2)	−0.001 (2)	0.0029 (18)	0.0041 (19)
C16A	0.022 (2)	0.021 (2)	0.022 (2)	0.001 (2)	0.0039 (19)	−0.0007 (18)
C31A	0.014 (2)	0.020 (2)	0.018 (2)	−0.0012 (18)	−0.0002 (16)	0.0027 (18)
C32A	0.020 (2)	0.019 (2)	0.020 (2)	−0.0048 (19)	−0.0045 (17)	0.0042 (18)
C33A	0.024 (2)	0.019 (2)	0.0125 (17)	−0.002 (2)	−0.0002 (17)	−0.0004 (16)
C34A	0.019 (2)	0.020 (2)	0.023 (2)	−0.0034 (19)	0.0014 (17)	0.0023 (19)
C35A	0.020 (2)	0.017 (2)	0.022 (2)	−0.0011 (19)	−0.0012 (17)	0.0052 (18)
C36A	0.021 (2)	0.026 (2)	0.0139 (18)	−0.0022 (19)	0.0018 (17)	0.0017 (18)
Br5B	0.0409 (3)	0.0364 (3)	0.0219 (2)	0.0094 (2)	0.0029 (2)	−0.0100 (2)
O2B	0.0295 (19)	0.0272 (18)	0.0198 (15)	0.0050 (15)	0.0042 (14)	−0.0019 (14)
O31B	0.051 (2)	0.060 (3)	0.0154 (16)	0.019 (2)	0.0065 (16)	−0.0003 (17)
O32B	0.040 (2)	0.0315 (18)	0.0231 (16)	0.0117 (17)	−0.0024 (15)	0.0021 (15)
N1B	0.023 (2)	0.027 (2)	0.0205 (18)	0.0012 (18)	−0.0061 (15)	0.0013 (17)
N2B	0.0192 (19)	0.0173 (18)	0.0242 (18)	−0.0008 (16)	−0.0021 (15)	0.0008 (16)
N3B	0.025 (2)	0.0230 (19)	0.0197 (17)	−0.0009 (18)	0.0008 (16)	−0.0020 (15)
C3B	0.018 (2)	0.024 (2)	0.022 (2)	−0.0067 (19)	0.0006 (17)	−0.0029 (19)
C11B	0.015 (2)	0.023 (2)	0.029 (2)	−0.0037 (19)	−0.0037 (19)	0.0007 (19)
C12B	0.030 (3)	0.023 (2)	0.030 (2)	−0.003 (2)	−0.011 (2)	0.001 (2)
C13B	0.030 (3)	0.019 (2)	0.043 (3)	0.003 (2)	−0.021 (2)	0.000 (2)
C14B	0.022 (2)	0.021 (2)	0.041 (3)	0.001 (2)	−0.002 (2)	−0.004 (2)
C15B	0.023 (2)	0.030 (3)	0.029 (2)	0.001 (2)	−0.0009 (19)	−0.002 (2)
C16B	0.021 (2)	0.020 (2)	0.025 (2)	0.002 (2)	−0.0009 (19)	0.0032 (18)
C31B	0.022 (2)	0.018 (2)	0.019 (2)	−0.0056 (19)	−0.0007 (17)	0.0008 (18)
C32B	0.017 (2)	0.019 (2)	0.017 (2)	−0.0048 (18)	0.0008 (16)	−0.0028 (18)
C33B	0.017 (2)	0.022 (2)	0.0174 (19)	−0.0065 (19)	0.0017 (17)	−0.0016 (17)
C34B	0.025 (2)	0.021 (2)	0.019 (2)	−0.001 (2)	0.0000 (17)	−0.0006 (19)
C35B	0.022 (2)	0.023 (2)	0.019 (2)	−0.0022 (19)	0.0023 (17)	−0.0025 (19)
C36B	0.025 (2)	0.026 (2)	0.0142 (19)	−0.007 (2)	−0.0006 (17)	0.0009 (18)

Geometric parameters (Å, º)

Br5A—C35A	1.899 (4)	Br5B—C35B	1.911 (4)
O2A—C32A	1.335 (5)	O2B—C32B	1.351 (5)
O2A—H2A	0.8400	O2B—H2B	0.8400
O31A—N3A	1.226 (5)	O31B—N3B	1.222 (5)
O32A—N3A	1.216 (5)	O32B—N3B	1.228 (5)
N1A—N2A	1.355 (5)	N1B—N2B	1.356 (5)
N1A—C11A	1.389 (6)	N1B—C11B	1.402 (6)
N1A—H1A	0.8800	N1B—H1B	0.8800
N2A—C3A	1.289 (5)	N2B—C3B	1.281 (5)
N3A—C33A	1.463 (5)	N3B—C33B	1.462 (5)
C3A—C31A	1.456 (6)	C3B—C31B	1.456 (6)
C3A—H3A	0.9500	C3B—H3B	0.9500
C11A—C16A	1.397 (6)	C11B—C16B	1.391 (6)
C11A—C12A	1.401 (6)	C11B—C12B	1.397 (6)
C12A—C13A	1.379 (6)	C12B—C13B	1.385 (7)
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.397 (7)	C13B—C14B	1.387 (7)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.392 (6)	C14B—C15B	1.387 (6)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—C16A	1.377 (6)	C15B—C16B	1.381 (6)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—H16A	0.9500	C16B—H16B	0.9500
C31A—C36A	1.393 (6)	C31B—C36B	1.403 (6)
C31A—C32A	1.436 (6)	C31B—C32B	1.426 (6)
C32A—C33A	1.406 (6)	C32B—C33B	1.404 (6)
C33A—C34A	1.383 (6)	C33B—C34B	1.401 (6)
C34A—C35A	1.378 (6)	C34B—C35B	1.383 (6)
C34A—H34A	0.9500	C34B—H34B	0.9500
C35A—C36A	1.392 (6)	C35B—C36B	1.375 (6)
C36A—H36A	0.9500	C36B—H36B	0.9500
C32A—O2A—H2A	109.5	C32B—O2B—H2B	109.5
N2A—N1A—C11A	123.1 (4)	N2B—N1B—C11B	121.2 (4)
N2A—N1A—H1A	118.5	N2B—N1B—H1B	119.4
C11A—N1A—H1A	118.5	C11B—N1B—H1B	119.4
C3A—N2A—N1A	116.8 (4)	C3B—N2B—N1B	118.6 (4)
O32A—N3A—O31A	122.2 (4)	O31B—N3B—O32B	122.7 (4)
O32A—N3A—C33A	118.2 (4)	O31B—N3B—C33B	119.0 (4)
O31A—N3A—C33A	119.4 (4)	O32B—N3B—C33B	118.2 (3)
N2A—C3A—C31A	122.0 (4)	N2B—C3B—C31B	121.2 (4)
N2A—C3A—H3A	119.0	N2B—C3B—H3B	119.4
C31A—C3A—H3A	119.0	C31B—C3B—H3B	119.4
N1A—C11A—C16A	123.2 (4)	C16B—C11B—C12B	120.1 (4)
N1A—C11A—C12A	117.4 (4)	C16B—C11B—N1B	122.5 (4)
C16A—C11A—C12A	119.4 (4)	C12B—C11B—N1B	117.4 (4)
C13A—C12A—C11A	119.9 (4)	C13B—C12B—C11B	119.6 (5)
C13A—C12A—H12A	120.0	C13B—C12B—H12B	120.2
C11A—C12A—H12A	120.0	C11B—C12B—H12B	120.2
C12A—C13A—C14A	120.8 (4)	C12B—C13B—C14B	120.6 (5)
C12A—C13A—H13A	119.6	C12B—C13B—H13B	119.7
C14A—C13A—H13A	119.6	C14B—C13B—H13B	119.7
C15A—C14A—C13A	118.9 (5)	C15B—C14B—C13B	119.2 (5)
C15A—C14A—H14A	120.6	C15B—C14B—H14B	120.4
C13A—C14A—H14A	120.6	C13B—C14B—H14B	120.4
C16A—C15A—C14A	120.9 (4)	C16B—C15B—C14B	121.2 (5)
C16A—C15A—H15A	119.5	C16B—C15B—H15B	119.4
C14A—C15A—H15A	119.5	C14B—C15B—H15B	119.4
C15A—C16A—C11A	120.1 (4)	C15B—C16B—C11B	119.3 (4)
C15A—C16A—H16A	120.0	C15B—C16B—H16B	120.3
C11A—C16A—H16A	120.0	C11B—C16B—H16B	120.3
C36A—C31A—C32A	119.2 (4)	C36B—C31B—C32B	119.3 (4)
C36A—C31A—C3A	118.8 (4)	C36B—C31B—C3B	118.5 (4)
C32A—C31A—C3A	122.0 (4)	C32B—C31B—C3B	122.1 (4)
O2A—C32A—C33A	122.7 (4)	O2B—C32B—C33B	121.6 (4)
O2A—C32A—C31A	120.5 (4)	O2B—C32B—C31B	120.1 (4)
C33A—C32A—C31A	116.8 (4)	C33B—C32B—C31B	118.3 (4)
C34A—C33A—C32A	123.5 (4)	C34B—C33B—C32B	122.0 (4)
C34A—C33A—N3A	116.4 (4)	C34B—C33B—N3B	116.2 (4)
C32A—C33A—N3A	120.1 (4)	C32B—C33B—N3B	121.8 (4)
C35A—C34A—C33A	118.4 (4)	C35B—C34B—C33B	117.7 (4)
C35A—C34A—H34A	120.8	C35B—C34B—H34B	121.1
C33A—C34A—H34A	120.8	C33B—C34B—H34B	121.1
C34A—C35A—C36A	120.8 (4)	C36B—C35B—C34B	122.7 (4)
C34A—C35A—Br5A	119.9 (3)	C36B—C35B—Br5B	119.4 (3)
C36A—C35A—Br5A	119.2 (3)	C34B—C35B—Br5B	117.9 (3)
C35A—C36A—C31A	121.2 (4)	C35B—C36B—C31B	120.0 (4)
C35A—C36A—H36A	119.4	C35B—C36B—H36B	120.0
C31A—C36A—H36A	119.4	C31B—C36B—H36B	120.0
C11A—N1A—N2A—C3A	−174.3 (4)	C11B—N1B—N2B—C3B	178.0 (4)
N1A—N2A—C3A—C31A	−176.5 (4)	N1B—N2B—C3B—C31B	−179.1 (4)
N2A—N1A—C11A—C16A	−2.3 (7)	N2B—N1B—C11B—C16B	4.3 (7)
N2A—N1A—C11A—C12A	177.7 (4)	N2B—N1B—C11B—C12B	−175.7 (4)
N1A—C11A—C12A—C13A	−179.1 (4)	C16B—C11B—C12B—C13B	0.6 (7)
C16A—C11A—C12A—C13A	0.9 (7)	N1B—C11B—C12B—C13B	−179.4 (4)
C11A—C12A—C13A—C14A	−0.1 (7)	C11B—C12B—C13B—C14B	0.0 (7)
C12A—C13A—C14A—C15A	−0.9 (7)	C12B—C13B—C14B—C15B	−0.5 (7)
C13A—C14A—C15A—C16A	1.1 (7)	C13B—C14B—C15B—C16B	0.4 (7)
C14A—C15A—C16A—C11A	−0.2 (7)	C14B—C15B—C16B—C11B	0.2 (7)
N1A—C11A—C16A—C15A	179.3 (4)	C12B—C11B—C16B—C15B	−0.7 (7)
C12A—C11A—C16A—C15A	−0.8 (7)	N1B—C11B—C16B—C15B	179.3 (4)
N2A—C3A—C31A—C36A	178.4 (4)	N2B—C3B—C31B—C36B	177.6 (4)
N2A—C3A—C31A—C32A	0.1 (7)	N2B—C3B—C31B—C32B	0.2 (7)
C36A—C31A—C32A—O2A	178.4 (4)	C36B—C31B—C32B—O2B	−179.3 (4)
C3A—C31A—C32A—O2A	−3.3 (7)	C3B—C31B—C32B—O2B	−2.0 (6)
C36A—C31A—C32A—C33A	−0.5 (6)	C36B—C31B—C32B—C33B	0.3 (6)
C3A—C31A—C32A—C33A	177.8 (4)	C3B—C31B—C32B—C33B	177.6 (4)
O2A—C32A—C33A—C34A	−176.7 (4)	O2B—C32B—C33B—C34B	179.8 (4)
C31A—C32A—C33A—C34A	2.2 (7)	C31B—C32B—C33B—C34B	0.3 (6)
O2A—C32A—C33A—N3A	3.1 (7)	O2B—C32B—C33B—N3B	−0.3 (6)
C31A—C32A—C33A—N3A	−178.0 (4)	C31B—C32B—C33B—N3B	−179.9 (4)
O32A—N3A—C33A—C34A	19.4 (6)	O31B—N3B—C33B—C34B	164.7 (4)
O31A—N3A—C33A—C34A	−156.5 (4)	O32B—N3B—C33B—C34B	−12.8 (6)
O32A—N3A—C33A—C32A	−160.4 (4)	O31B—N3B—C33B—C32B	−15.2 (6)
O31A—N3A—C33A—C32A	23.7 (6)	O32B—N3B—C33B—C32B	167.4 (4)
C32A—C33A—C34A—C35A	−2.1 (7)	C32B—C33B—C34B—C35B	0.1 (7)
N3A—C33A—C34A—C35A	178.1 (4)	N3B—C33B—C34B—C35B	−179.7 (4)
C33A—C34A—C35A—C36A	0.2 (7)	C33B—C34B—C35B—C36B	−1.1 (7)
C33A—C34A—C35A—Br5A	−177.9 (3)	C33B—C34B—C35B—Br5B	−178.7 (3)
C34A—C35A—C36A—C31A	1.4 (7)	C34B—C35B—C36B—C31B	1.6 (7)
Br5A—C35A—C36A—C31A	179.5 (3)	Br5B—C35B—C36B—C31B	179.2 (3)
C32A—C31A—C36A—C35A	−1.2 (7)	C32B—C31B—C36B—C35B	−1.2 (6)
C3A—C31A—C36A—C35A	−179.5 (4)	C3B—C31B—C36B—C35B	−178.6 (4)

Hydrogen-bond geometry (Å, º)

Cg3 is the centroid of the ring containing atom C11B.

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···N2A	0.84	1.88	2.634 (5)	148
O2B—H2B···N2B	0.84	1.86	2.601 (5)	147
N1A—H1A···O31A^i	0.88	2.41	3.115 (5)	138
N1A—H1A···O32A^i	0.88	2.53	3.380 (5)	162
N1B—H1B···O32B^ii	0.88	2.29	3.163 (5)	171
C36A—H36A···O31B^ii	0.95	2.39	3.204 (5)	143
C13B—H13B···Br5A^iii	0.95	2.91	3.768 (5)	151
C14A—H14A···Cg3^iv	0.95	2.89	3.655 (6)	139

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

(II) 5-Bromo-3-nitrosalicylaldehyde phenylhydrazone

Crystal data

C13H10BrN3O3	Z = 4
Mr = 336.15	F(000) = 672
Triclinic, P1	Dx = 1.737 Mg m^−3
a = 7.9022 (11) Å	Mo Kα radiation, λ = 0.71075 Å
b = 11.7662 (17) Å	Cell parameters from 8477 reflections
c = 14.917 (2) Å	θ = 3.1–27.6°
α = 68.971 (5)°	µ = 3.21 mm^−1
β = 83.143 (6)°	T = 100 K
γ = 88.375 (6)°	Lath, yellow
V = 1285.2 (3) Å^3	0.17 × 0.05 × 0.01 mm

Data collection

Rigaku AFC12 diffractometer	5866 independent reflections
Radiation source: Rotating anode	3699 reflections with I > 2σ(I)
Detector resolution: 28.5714 pixels mm^-1	Rint = 0.061
profile data from ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (CrystalClear-SM; Rigaku, 2011)	h = −6→10
Tmin = 0.611, Tmax = 0.969	k = −15→14
12426 measured reflections	l = −19→19

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0572P)^2] where P = (Fo^2 + 2Fc^2)/3
5866 reflections	(Δ/σ)max = 0.001
363 parameters	Δρmax = 0.77 e Å^−3
0 restraints	Δρmin = −1.58 e Å^−3

Special details

Experimental. 3-Bromo-5-nitrosalicylaldehyde phenyl hydrazone (II): (2H, m) [all phenyl], 8.21 (1H, s, CH═N), 8.30 (1H, d, J = 2.5 Hz), 8.46 (1H, d, J = 2.5Hz) [C₆H₂], 11.00 (1H, s, NH), 12.88(1H, br.s, OH).

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
Br3A	0.60081 (6)	0.62592 (4)	0.69434 (3)	0.02648 (15)
O2A	0.3833 (4)	0.8446 (3)	0.6176 (2)	0.0239 (7)
H2A	0.3207	0.9048	0.5958	0.036*
O31A	0.6921 (4)	0.5644 (3)	0.3535 (2)	0.0323 (8)
O32A	0.5570 (5)	0.7063 (3)	0.2529 (2)	0.0409 (9)
N1A	0.1408 (5)	1.1182 (3)	0.4514 (3)	0.0249 (9)
H1A	0.1253	1.1452	0.3899	0.030*
N2A	0.2352 (5)	1.0176 (3)	0.4853 (2)	0.0227 (9)
N3A	0.6041 (5)	0.6547 (4)	0.3335 (3)	0.0264 (9)
C3A	0.2978 (6)	0.9701 (4)	0.4239 (3)	0.0230 (10)
H3A	0.2780	1.0076	0.3582	0.028*
C11A	0.0673 (5)	1.1812 (4)	0.5082 (3)	0.0222 (10)
C12A	−0.0091 (5)	1.2918 (4)	0.4615 (3)	0.0250 (11)
H12A	−0.0083	1.3211	0.3932	0.030*
C13A	−0.0852 (6)	1.3580 (4)	0.5136 (3)	0.0265 (11)
H13A	−0.1347	1.4340	0.4810	0.032*
C14A	−0.0909 (6)	1.3158 (4)	0.6131 (3)	0.0304 (11)
H14A	−0.1439	1.3622	0.6489	0.036*
C15A	−0.0184 (6)	1.2045 (4)	0.6603 (3)	0.0292 (11)
H15A	−0.0239	1.1741	0.7288	0.035*
C16A	0.0622 (6)	1.1375 (4)	0.6080 (3)	0.0254 (11)
H16A	0.1135	1.0621	0.6405	0.030*
C31A	0.3981 (5)	0.8606 (4)	0.4524 (3)	0.0200 (10)
C32A	0.4379 (5)	0.8022 (4)	0.5475 (3)	0.0218 (10)
C33A	0.5376 (5)	0.6987 (4)	0.5682 (3)	0.0221 (10)
C34A	0.5929 (5)	0.6489 (4)	0.5000 (3)	0.0214 (10)
H34A	0.6585	0.5769	0.5157	0.026*
C35A	0.5497 (6)	0.7073 (4)	0.4077 (3)	0.0228 (10)
C36A	0.4563 (5)	0.8115 (4)	0.3823 (3)	0.0221 (10)
H36A	0.4314	0.8499	0.3176	0.026*
Br3B	0.93788 (6)	0.38619 (4)	−0.18163 (3)	0.02998 (15)
O2B	0.7248 (4)	0.5524 (3)	−0.1038 (2)	0.0227 (7)
H2B	0.6649	0.5983	−0.0814	0.034*
O31B	1.1211 (4)	0.1237 (3)	0.1628 (2)	0.0342 (8)
O32B	0.9895 (4)	0.1908 (3)	0.2691 (2)	0.0341 (8)
N1B	0.5140 (5)	0.7256 (3)	0.0530 (3)	0.0274 (9)
H1B	0.5104	0.7202	0.1136	0.033*
N2B	0.5986 (4)	0.6410 (3)	0.0248 (3)	0.0213 (8)
N3B	1.0220 (5)	0.1937 (4)	0.1854 (3)	0.0265 (9)
C3B	0.6674 (5)	0.5538 (4)	0.0895 (3)	0.0216 (10)
H3B	0.6552	0.5507	0.1545	0.026*
C11B	0.4322 (6)	0.8211 (4)	−0.0111 (3)	0.0251 (11)
C12B	0.3347 (6)	0.8981 (4)	0.0266 (4)	0.0300 (11)
H12B	0.3279	0.8848	0.0936	0.036*
C13B	0.2487 (7)	0.9928 (5)	−0.0330 (4)	0.0420 (14)
H13B	0.1804	1.0438	−0.0069	0.050*
C14B	0.2611 (6)	1.0143 (5)	−0.1309 (4)	0.0406 (14)
H14B	0.2028	1.0805	−0.1722	0.049*
C15B	0.3587 (6)	0.9391 (4)	−0.1685 (4)	0.0352 (13)
H15B	0.3666	0.9534	−0.2358	0.042*
C16B	0.4447 (6)	0.8433 (4)	−0.1090 (3)	0.0286 (11)
H16B	0.5127	0.7925	−0.1354	0.034*
C31B	0.7622 (5)	0.4611 (4)	0.0645 (3)	0.0189 (9)
C32B	0.7918 (5)	0.4655 (4)	−0.0317 (3)	0.0206 (10)
C33B	0.8928 (5)	0.3786 (4)	−0.0527 (3)	0.0228 (10)
C34B	0.9714 (5)	0.2876 (4)	0.0171 (3)	0.0213 (10)
H34B	1.0433	0.2297	0.0015	0.026*
C35B	0.9386 (5)	0.2863 (4)	0.1113 (3)	0.0205 (10)
C36B	0.8376 (5)	0.3698 (4)	0.1360 (3)	0.0191 (9)
H36B	0.8192	0.3653	0.2013	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br3A	0.0252 (3)	0.0322 (3)	0.0178 (2)	0.0031 (2)	−0.00421 (19)	−0.0036 (2)
O2A	0.0240 (18)	0.0296 (19)	0.0178 (16)	0.0052 (14)	−0.0026 (13)	−0.0084 (14)
O31A	0.033 (2)	0.0317 (19)	0.033 (2)	0.0069 (16)	−0.0059 (16)	−0.0127 (16)
O32A	0.068 (3)	0.037 (2)	0.0195 (18)	0.0099 (19)	−0.0121 (17)	−0.0098 (16)
N1A	0.026 (2)	0.029 (2)	0.019 (2)	0.0062 (18)	−0.0065 (16)	−0.0067 (17)
N2A	0.023 (2)	0.022 (2)	0.019 (2)	−0.0009 (17)	−0.0044 (16)	−0.0016 (17)
N3A	0.029 (2)	0.031 (2)	0.019 (2)	−0.0019 (19)	−0.0028 (17)	−0.0091 (18)
C3A	0.023 (2)	0.024 (2)	0.022 (2)	−0.001 (2)	−0.0065 (19)	−0.007 (2)
C11A	0.017 (2)	0.026 (2)	0.022 (2)	0.000 (2)	−0.0025 (18)	−0.008 (2)
C12A	0.019 (2)	0.029 (3)	0.025 (2)	−0.001 (2)	−0.007 (2)	−0.005 (2)
C13A	0.020 (2)	0.028 (3)	0.034 (3)	0.000 (2)	−0.005 (2)	−0.013 (2)
C14A	0.025 (3)	0.040 (3)	0.033 (3)	0.002 (2)	−0.007 (2)	−0.019 (2)
C15A	0.025 (3)	0.038 (3)	0.026 (3)	−0.002 (2)	−0.007 (2)	−0.012 (2)
C16A	0.024 (2)	0.026 (3)	0.023 (2)	−0.002 (2)	−0.005 (2)	−0.005 (2)
C31A	0.016 (2)	0.022 (2)	0.022 (2)	−0.0050 (19)	−0.0045 (18)	−0.0063 (19)
C32A	0.019 (2)	0.022 (2)	0.023 (2)	−0.0068 (19)	−0.0023 (19)	−0.006 (2)
C33A	0.017 (2)	0.026 (2)	0.019 (2)	−0.003 (2)	0.0008 (18)	−0.0044 (19)
C34A	0.016 (2)	0.022 (2)	0.020 (2)	−0.0050 (19)	−0.0021 (18)	−0.0011 (19)
C35A	0.023 (2)	0.023 (2)	0.021 (2)	−0.002 (2)	−0.0044 (19)	−0.006 (2)
C36A	0.020 (2)	0.024 (2)	0.017 (2)	−0.005 (2)	−0.0044 (18)	0.0001 (19)
Br3B	0.0350 (3)	0.0351 (3)	0.0215 (3)	0.0063 (2)	−0.0049 (2)	−0.0120 (2)
O2B	0.0227 (17)	0.0236 (17)	0.0204 (16)	0.0070 (14)	−0.0072 (13)	−0.0054 (14)
O31B	0.0323 (19)	0.034 (2)	0.0306 (19)	0.0157 (17)	−0.0082 (15)	−0.0048 (16)
O32B	0.037 (2)	0.039 (2)	0.0230 (18)	0.0114 (17)	−0.0102 (15)	−0.0058 (16)
N1B	0.024 (2)	0.034 (2)	0.024 (2)	0.0096 (19)	−0.0051 (17)	−0.0098 (19)
N2B	0.0167 (19)	0.023 (2)	0.026 (2)	0.0039 (17)	−0.0039 (16)	−0.0111 (17)
N3B	0.020 (2)	0.029 (2)	0.026 (2)	0.0004 (18)	−0.0069 (17)	−0.0019 (18)
C3B	0.018 (2)	0.026 (2)	0.017 (2)	0.0027 (19)	−0.0042 (18)	−0.0035 (19)
C11B	0.017 (2)	0.024 (2)	0.035 (3)	0.002 (2)	−0.011 (2)	−0.009 (2)
C12B	0.025 (3)	0.030 (3)	0.037 (3)	0.002 (2)	−0.003 (2)	−0.015 (2)
C13B	0.027 (3)	0.035 (3)	0.070 (4)	0.006 (2)	−0.018 (3)	−0.023 (3)
C14B	0.029 (3)	0.030 (3)	0.056 (4)	0.000 (2)	−0.018 (3)	−0.003 (3)
C15B	0.025 (3)	0.033 (3)	0.038 (3)	−0.007 (2)	−0.010 (2)	0.002 (2)
C16B	0.024 (3)	0.026 (3)	0.032 (3)	0.000 (2)	−0.007 (2)	−0.005 (2)
C31B	0.016 (2)	0.020 (2)	0.019 (2)	0.0007 (19)	−0.0062 (18)	−0.0034 (19)
C32B	0.016 (2)	0.022 (2)	0.020 (2)	−0.0061 (19)	−0.0044 (18)	−0.0026 (19)
C33B	0.016 (2)	0.027 (2)	0.022 (2)	−0.001 (2)	−0.0036 (18)	−0.006 (2)
C34B	0.020 (2)	0.023 (2)	0.019 (2)	0.003 (2)	−0.0016 (18)	−0.0054 (19)
C35B	0.013 (2)	0.023 (2)	0.022 (2)	0.0011 (19)	−0.0059 (18)	−0.0029 (19)
C36B	0.016 (2)	0.024 (2)	0.017 (2)	−0.0031 (19)	−0.0037 (17)	−0.0056 (19)

Geometric parameters (Å, º)

Br3A—C33A	1.888 (4)	Br3B—C33B	1.884 (4)
O2A—C32A	1.335 (5)	O2B—C32B	1.341 (5)
O2A—H2A	0.8400	O2B—H2B	0.8400
O31A—N3A	1.217 (5)	O31B—N3B	1.226 (5)
O32A—N3A	1.235 (4)	O32B—N3B	1.234 (5)
N1A—N2A	1.350 (5)	N1B—N2B	1.345 (5)
N1A—C11A	1.383 (6)	N1B—C11B	1.390 (5)
N1A—H1A	0.8800	N1B—H1B	0.8800
N2A—C3A	1.281 (5)	N2B—C3B	1.290 (5)
N3A—C35A	1.468 (6)	N3B—C35B	1.453 (5)
C3A—C31A	1.449 (6)	C3B—C31B	1.439 (6)
C3A—H3A	0.9500	C3B—H3B	0.9500
C11A—C16A	1.386 (6)	C11B—C16B	1.380 (6)
C11A—C12A	1.395 (6)	C11B—C12B	1.397 (6)
C12A—C13A	1.368 (6)	C12B—C13B	1.373 (7)
C12A—H12A	0.9500	C12B—H12B	0.9500
C13A—C14A	1.381 (6)	C13B—C14B	1.381 (7)
C13A—H13A	0.9500	C13B—H13B	0.9500
C14A—C15A	1.389 (6)	C14B—C15B	1.381 (7)
C14A—H14A	0.9500	C14B—H14B	0.9500
C15A—C16A	1.390 (6)	C15B—C16B	1.380 (6)
C15A—H15A	0.9500	C15B—H15B	0.9500
C16A—H16A	0.9500	C16B—H16B	0.9500
C31A—C36A	1.394 (6)	C31B—C36B	1.393 (5)
C31A—C32A	1.407 (5)	C31B—C32B	1.409 (6)
C32A—C33A	1.390 (6)	C32B—C33B	1.380 (6)
C33A—C34A	1.369 (6)	C33B—C34B	1.390 (6)
C34A—C35A	1.381 (5)	C34B—C35B	1.392 (6)
C34A—H34A	0.9500	C34B—H34B	0.9500
C35A—C36A	1.369 (6)	C35B—C36B	1.373 (6)
C36A—H36A	0.9500	C36B—H36B	0.9500
C32A—O2A—H2A	109.5	C32B—O2B—H2B	109.5
N2A—N1A—C11A	123.6 (3)	N2B—N1B—C11B	121.6 (4)
N2A—N1A—H1A	118.2	N2B—N1B—H1B	119.2
C11A—N1A—H1A	118.2	C11B—N1B—H1B	119.2
C3A—N2A—N1A	116.6 (4)	C3B—N2B—N1B	117.5 (4)
O31A—N3A—O32A	123.5 (4)	O31B—N3B—O32B	123.1 (4)
O31A—N3A—C35A	119.5 (4)	O31B—N3B—C35B	119.7 (4)
O32A—N3A—C35A	117.0 (4)	O32B—N3B—C35B	117.2 (4)
N2A—C3A—C31A	121.5 (4)	N2B—C3B—C31B	120.8 (4)
N2A—C3A—H3A	119.3	N2B—C3B—H3B	119.6
C31A—C3A—H3A	119.3	C31B—C3B—H3B	119.6
N1A—C11A—C16A	122.9 (4)	C16B—C11B—N1B	123.1 (4)
N1A—C11A—C12A	117.4 (4)	C16B—C11B—C12B	119.4 (4)
C16A—C11A—C12A	119.6 (4)	N1B—C11B—C12B	117.5 (4)
C13A—C12A—C11A	120.3 (4)	C13B—C12B—C11B	120.1 (5)
C13A—C12A—H12A	119.9	C13B—C12B—H12B	119.9
C11A—C12A—H12A	119.9	C11B—C12B—H12B	119.9
C12A—C13A—C14A	120.8 (4)	C12B—C13B—C14B	120.2 (5)
C12A—C13A—H13A	119.6	C12B—C13B—H13B	119.9
C14A—C13A—H13A	119.6	C14B—C13B—H13B	119.9
C13A—C14A—C15A	119.3 (4)	C15B—C14B—C13B	119.8 (5)
C13A—C14A—H14A	120.4	C15B—C14B—H14B	120.1
C15A—C14A—H14A	120.4	C13B—C14B—H14B	120.1
C14A—C15A—C16A	120.5 (4)	C16B—C15B—C14B	120.3 (5)
C14A—C15A—H15A	119.7	C16B—C15B—H15B	119.8
C16A—C15A—H15A	119.7	C14B—C15B—H15B	119.8
C11A—C16A—C15A	119.5 (4)	C11B—C16B—C15B	120.1 (5)
C11A—C16A—H16A	120.2	C11B—C16B—H16B	119.9
C15A—C16A—H16A	120.2	C15B—C16B—H16B	119.9
C36A—C31A—C32A	119.1 (4)	C36B—C31B—C32B	119.0 (4)
C36A—C31A—C3A	118.2 (4)	C36B—C31B—C3B	119.1 (4)
C32A—C31A—C3A	122.7 (4)	C32B—C31B—C3B	121.7 (4)
O2A—C32A—C33A	119.6 (4)	O2B—C32B—C33B	119.0 (4)
O2A—C32A—C31A	121.5 (4)	O2B—C32B—C31B	121.7 (4)
C33A—C32A—C31A	118.9 (4)	C33B—C32B—C31B	119.3 (4)
C34A—C33A—C32A	122.2 (4)	C32B—C33B—C34B	122.7 (4)
C34A—C33A—Br3A	119.1 (3)	C32B—C33B—Br3B	119.6 (3)
C32A—C33A—Br3A	118.6 (3)	C34B—C33B—Br3B	117.6 (3)
C33A—C34A—C35A	117.5 (4)	C33B—C34B—C35B	116.2 (4)
C33A—C34A—H34A	121.3	C33B—C34B—H34B	121.9
C35A—C34A—H34A	121.3	C35B—C34B—H34B	121.9
C36A—C35A—C34A	122.9 (4)	C36B—C35B—C34B	123.3 (4)
C36A—C35A—N3A	118.4 (4)	C36B—C35B—N3B	119.3 (4)
C34A—C35A—N3A	118.7 (4)	C34B—C35B—N3B	117.3 (4)
C35A—C36A—C31A	119.3 (4)	C35B—C36B—C31B	119.4 (4)
C35A—C36A—H36A	120.3	C35B—C36B—H36B	120.3
C31A—C36A—H36A	120.3	C31B—C36B—H36B	120.3
C11A—N1A—N2A—C3A	−178.8 (4)	C11B—N1B—N2B—C3B	−178.3 (4)
N1A—N2A—C3A—C31A	−178.7 (4)	N1B—N2B—C3B—C31B	−179.0 (4)
N2A—N1A—C11A—C16A	−9.7 (7)	N2B—N1B—C11B—C16B	−6.4 (7)
N2A—N1A—C11A—C12A	172.3 (4)	N2B—N1B—C11B—C12B	174.3 (4)
N1A—C11A—C12A—C13A	179.5 (4)	C16B—C11B—C12B—C13B	1.7 (7)
C16A—C11A—C12A—C13A	1.5 (7)	N1B—C11B—C12B—C13B	−178.9 (4)
C11A—C12A—C13A—C14A	−1.4 (7)	C11B—C12B—C13B—C14B	−1.5 (8)
C12A—C13A—C14A—C15A	0.0 (7)	C12B—C13B—C14B—C15B	0.8 (8)
C13A—C14A—C15A—C16A	1.3 (7)	C13B—C14B—C15B—C16B	−0.5 (7)
N1A—C11A—C16A—C15A	−178.2 (4)	N1B—C11B—C16B—C15B	179.3 (4)
C12A—C11A—C16A—C15A	−0.2 (7)	C12B—C11B—C16B—C15B	−1.4 (7)
C14A—C15A—C16A—C11A	−1.1 (7)	C14B—C15B—C16B—C11B	0.8 (7)
N2A—C3A—C31A—C36A	177.5 (4)	N2B—C3B—C31B—C36B	178.7 (4)
N2A—C3A—C31A—C32A	−2.2 (7)	N2B—C3B—C31B—C32B	3.6 (6)
C36A—C31A—C32A—O2A	−179.0 (4)	C36B—C31B—C32B—O2B	−178.9 (4)
C3A—C31A—C32A—O2A	0.6 (6)	C3B—C31B—C32B—O2B	−3.9 (6)
C36A—C31A—C32A—C33A	1.5 (6)	C36B—C31B—C32B—C33B	0.8 (6)
C3A—C31A—C32A—C33A	−178.8 (4)	C3B—C31B—C32B—C33B	175.9 (4)
O2A—C32A—C33A—C34A	177.9 (4)	O2B—C32B—C33B—C34B	178.0 (4)
C31A—C32A—C33A—C34A	−2.6 (6)	C31B—C32B—C33B—C34B	−1.8 (7)
O2A—C32A—C33A—Br3A	−2.9 (6)	O2B—C32B—C33B—Br3B	1.4 (6)
C31A—C32A—C33A—Br3A	176.6 (3)	C31B—C32B—C33B—Br3B	−178.4 (3)
C32A—C33A—C34A—C35A	1.6 (6)	C32B—C33B—C34B—C35B	1.9 (6)
Br3A—C33A—C34A—C35A	−177.5 (3)	Br3B—C33B—C34B—C35B	178.5 (3)
C33A—C34A—C35A—C36A	0.4 (6)	C33B—C34B—C35B—C36B	−1.1 (6)
C33A—C34A—C35A—N3A	−178.8 (4)	C33B—C34B—C35B—N3B	−178.8 (4)
O31A—N3A—C35A—C36A	177.5 (4)	O31B—N3B—C35B—C36B	−175.3 (4)
O32A—N3A—C35A—C36A	−2.2 (6)	O32B—N3B—C35B—C36B	4.0 (6)
O31A—N3A—C35A—C34A	−3.3 (6)	O31B—N3B—C35B—C34B	2.4 (6)
O32A—N3A—C35A—C34A	177.0 (4)	O32B—N3B—C35B—C34B	−178.3 (4)
C34A—C35A—C36A—C31A	−1.4 (7)	C34B—C35B—C36B—C31B	0.2 (6)
N3A—C35A—C36A—C31A	177.7 (4)	N3B—C35B—C36B—C31B	177.8 (4)
C32A—C31A—C36A—C35A	0.5 (6)	C32B—C31B—C36B—C35B	−0.1 (6)
C3A—C31A—C36A—C35A	−179.3 (4)	C3B—C31B—C36B—C35B	−175.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···N2A	0.84	1.89	2.635 (4)	147
O2B—H2B···N2B	0.84	1.84	2.585 (5)	147
N1B—H1B···O32A	0.88	2.10	2.967 (5)	168
N1A—H1A···O32B^i	0.88	2.10	2.933 (5)	157
C13A—H13A···O31A^i	0.95	2.50	3.361 (6)	151
C14A—H14A···Br3B^ii	0.95	2.79	3.480 (5)	130

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