Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tri­bromo­phen­yl)diazen­yl]naphthalen-2-ol

Chetioui, S.; Rouag, D.-A.; Djukic, J.-P.; Bochet, C.G.; Touzani, R.; Bailly, C.; Crochet, A.; Fromm, K.M.

doi:10.1107/S205698901601080X

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ISSN: 2056-9890

Volume 72| Part 8| August 2016| Pages 1093-1098

https://doi.org/10.1107/S205698901601080X

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Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol

Souheyla Chetioui,^a ^* Djamil-Azzeddine Rouag,^a Jean-Pierre Djukic,^b Christian G. Bochet,^c Rachid Touzani,^d,^e ^* Corinne Bailly,^f Aurélien Crochet ^g and Katharina M. Fromm ^c

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Faculté des Sciences Exactes, Département de Chimie, Université des Frères Mentouri Constantine, Constantine 25000, Algeria, ^bLaboratoire de Chimie et Systémique Organométallique (LCSOM), Institut de Chimie, Université de Strasbourg, UMR 7177., 4 rue Blaise Pascal, F-67070 Strasbourg Cedex, France, ^cChemistry Department, University of Fribourg, Chemin du Musee 9, CH-1700 Fribourg, Switzerland, ^dLaboratoire de Chimie Appliquée et Environnement, LCAE-URAC18, COSTE, Faculté des Sciences, Université Mohamed Premier, BP524, 60000 Oujda, Morocco, ^eFaculté Pluridisciplinaire Nador BP 300, Selouane 62702, Nador, Morocco, ^fService de Radiocristallographie, Institut de Chimie, Université de Strasbourg, UMR 7177, 67008 Strasbourg Cedex, France, and ^gFribourg Center for Nanomaterials, FriMat, University of Fribourg, Chemin du Musee 9, CH-1700 Fribourg, Switzerland
^*Correspondence e-mail: souheilachetioui@yahoo.fr, touzanir@yahoo.fr

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 7 May 2016; accepted 4 July 2016; online 12 July 2016)

In the copper(II) complex, bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}copper(II), [Cu(C₁₆H₈Br₃N₂O)₂], (I), the metal cation is coordinated by two N atoms and two O atoms from two bidentate (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olate ligands, forming a slightly distorted square-planar environment. In one of the ligands, the tribromobenzene ring is inclined to the naphthalene ring system by 37.4 (5)°, creating a weak intramolecular Cu⋯Br interaction [3.134 (2) Å], while in the other ligand, the tribromobenzene ring is inclined to the naphthalene ring system by 72.1 (6)°. In the isotypic nickel(II) and palladium(II) complexes, namely bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}nickel(II), [Ni(C₁₆H₈Br₃N₂O)₂], (II), and bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}palladium(II), [Pd(C₁₆H₈Br₃N₂O)₂], (III), respectively, the metal atoms are located on centres of inversion, hence the metal coordination spheres have perfect square-planar geometries. The tribromobenzene rings are inclined to the naphthalene ring systems by 80.79 (18)° in (II) and by 80.8 (3)° in (III). In the crystal of (I), molecules are linked by C—H⋯Br hydrogen bonds, forming chains along [010]. The chains are linked by C—H⋯π interactions, forming sheets parallel to (011). In the crystals of (II) and (III), molecules are linked by C—H⋯π interactions, forming slabs parallel to (10-1). For the copper(II) complex (I), a region of disordered electron density was corrected for using the SQUEEZE routine in PLATON [Spek (2015 ). Acta Cryst. C71, 9–18]. The formula mass and unit-cell characteristics of the disordered solvent molecules were not taken into account during refinement.

Keywords: crystal structures; copper(II); nickel(II); palladium(II); isotypic complexes; Cu⋯Br short contact; C—H⋯Br hydrogen bonds; C—H⋯π interactions.

CCDC references: 1490056; 1490055; 1490054

1. Chemical context

Recently, 1-phenylazo-2-naphthol derivatives have attracted attention because the phenylazo-naphtholate group can provide N,O-bidentate chelation to stabilize transition or main group metal complexes. Azo-metal chelates have also attracted increasing attention due to their interesting electronic and geometrical features in connection with their applications in molecular memory storage, non-linear optical elements and printing systems. Another advantage of complexes involving azo DNO's (dyes and pigments) and transition metal ions is the possibility to obtain new compounds with biological activity (Thomas et al., 2004 ; Reed et al., 2006 ). Transition metals have also been used in the treatment of several diseases, as metal complexes which are capable of cleaving DNA under physiological conditions are of interest in the development of metal-based anticancer agents. This is an impetus for chemists to develop innovative strategies for the preparation of more effective, target-specific and preferably non-covalently bound anticancer drugs (Chen et al., 2010 ; Cvek et al., 2008 ).

Being interested in the synthesis and preparation of metal complexes bearing such ligands, we have successfully synthesized and structurally characterized Cu^II complexes with N,O-bidentate phenylazo-naphtholate ligands (Chetioui et al., 2015a ,b ). In this work we are involved in the colour-generation mechanism of azo pigments typically characterized by the chromophore of the azo group (–N=N–) (Chetioui et al., 2013c ,d ) in order to synthesize new complexes with Cu(OAc)₂·H₂O, Ni(OAc)₂·H₂O, and Pd(OAc)₂·H₂O. We report herein on the synthesis and crystal structures of the title complexes, (I)–(III), of the ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol, whose crystal structure has been described previously (Chetioui et al., 2013c).

2. Structural commentary

In all three compounds the ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol (Chetioui et al., 2013c) coordinates in a N,O-bidentate manner. The metal atoms are coordinated by two oxygen atoms in a trans position of the C—O⁻ function and two nitrogen atoms in a trans position of the N=N function. In compound (I), Fig. 1, the values of the angles involving the copper and the two oxygen and two nitrogen atoms (Table 1) indicate that the geometry of the coordination polyhedron is distorted square-planar. It has a τ₄ value of 0.15 [Yang et al., 2007 ; extreme configurations: 0.00 for square-pyramidal (SQP) and 1.00 for tetrahedral (TET); 0.85 for trigonal–pyramidal (TRP)]. In one of the ligands, the tribromobenzene ring (C17–C22) is inclined to the naphthalene ring system (C23–C32) by 37.4 (5)°, creating a weak intramolecular Cu⋯Br interaction [Cu1⋯Br4 = 3.134 (2) Å]. In the other ligand, the tribromobenzene ring (C1–C6) is almost normal to the naphthalene ring system (C7-C16), making a dihedral angle of 72.1 (6)°. A similar short intramolecular metal–halogen contact has been observed in the centrosymmetric complex bis(1-[(E)-(2-chlorophenyl)diazenyl]naphthalen-2-olato)copper(II), viz. Cu⋯Cl = 3.153 (1) Å (Benaouida et al., 2013 ), and the chlorobenzene ring is inclined to the naphthalene ring system by 32.72 (12)°.

Table 1
Selected geometric parameters (Å, °) for (I)

Cu1—Br4	3.134 (2)	Cu1—O1	1.892 (9)
Cu1—N1	1.947 (12)	Cu1—O2	1.888 (8)
Cu1—N3	1.970 (11)

O2—Cu1—O1	169.4 (4)	O2—Cu1—N3	87.6 (4)
O2—Cu1—N1	91.3 (4)	O1—Cu1—N3	92.1 (4)
O1—Cu1—N1	90.9 (4)	N1—Cu1—N3	169.3 (5)

Figure 1
The molecular structure of compound (I)

, with atom labelling and 50% probability displacement ellipsoids. The intramolecular Cu⋯Br contact is shown as a dashed line (details are given in Table 1

Compounds (II) and (III), the nickel(II) (Fig. 2, Table 2) and palladium(II) (Fig. 3, Table 3) complexes, respectively, are isotypic. The metal atoms are each located on inversion centres, coordinating in a bidentate fashion to the N and O atoms of the ligand, hence the metal coordination spheres have perfect square-planar geometry. The tribromobenzene rings (C1–C6) are almost normal to the naphthalene ring systems (C7–C16) with a dihedral angle of 80.79 (18)° in (II) and 80.8 (3)° in (III).

Table 2
Selected geometric parameters (Å, °) for (II)

Ni—N1	1.876 (3)	Ni—O1	1.821 (3)

O1—Ni—O1ⁱ	180	O1ⁱ—Ni—N1	87.41 (14)
O1—Ni—N1	92.59 (14)	N1—Ni—N1ⁱ	180
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 3
Selected geometric parameters (Å, °) for (III)

Pd1—N1	2.004 (5)	Pd1—O1	1.972 (5)

O1—Pd1—O1ⁱ	180	O1ⁱ—Pd1—N1	88.7 (2)
O1—Pd1—N1	91.3 (2)	N1—Pd1—N1ⁱ	180
Symmetry code: (i) -x, -y, -z.

Figure 2
The molecular structure of compound (II)

, with atom labelling and 50% probability displacement ellipsoids. The unlabelled atoms are related to the labelled atoms by the symmetry operation (−x + 1, −y + 1, −z + 1).

Figure 3
The molecular structure of compound (III)

, with atom labelling and 50% probability displacement ellipsoids. The unlabelled atoms are related to the labelled atoms by the symmetry operation (−x, −y, −z).

3. Supramolecular features

As shown in Fig. 4, in the crystal of compound (I), molecules are linked by C—H⋯Br hydrogen bonds, forming chains along [001]. The chains are linked by C—H⋯π interactions, forming sheets lying parallel to (011). Details of these interactions are given in Table 4.

Table 4
Hydrogen-bond geometry (Å, °) for (I)

Cg1 is the centroid of the C27–C32 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯Br6ⁱ	0.95	2.75	3.546 (15)	142
C3—H3⋯Cg1ⁱⁱ	0.95	2.99	3.729 (15)	136
Symmetry codes: (i) x, y, z-1; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ .

Figure 4
The crystal packing of compound (I)

, viewed along the a axis. The intermolecular interactions are shown as dashed lines (see Table 4

for details), and for clarity only the H atoms involved in these interactions have been included.

The crystal packing in compound (II) [and isotypic compound (III)] is illustrated in Fig. 5. Molecules are linked by C—H⋯π interactions, forming slabs lying parallel to (10 $[\overline{1}]$ ). Details of the intermolecular interactions are given in Table 5 for (II) and Table 6 for (III).

Table 5
Hydrogen-bond geometry (Å, °) for (II)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg2ⁱⁱ	0.95	2.71	3.391 (5)	130
Symmetry code: (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Table 6
Hydrogen-bond geometry (Å, °) for (III)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯Cg2ⁱⁱ	0.93	2.70	3.371 (8)	129
Symmetry code: (ii) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 5
The crystal packing of compound (II)

, viewed along the normal to (10 $[\overline{1}]$ ). The intermolecular interactions are shown as dashed lines (see Table 5

for details), and for clarity only the H atoms involved in these interactions have been included.

4. Database survey

In the title ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol (CSD refcode AFOFIM; Chetioui et al., 2013c) the benzene ring is inclined to the naphthalene ring system by 33.80 (16)°. A search of the Cambridge Structural Database (Version 5.37, update February 2016; Groom et al., 2016 ) for square-planar metal complexes of (E)-1-(phenyldiazenyl)naphthalen-2-ol and its derivatives gave seven hits (Fig. 6). They include a zinc(II) complex of the ligand (E)-1-(phenyldiazenyl)naphthalen-2-ol (LUQQIZ; Gallegos et al., 2015 ), where the zinc atom has a distorted trigonal–pyramidal configuration with a τ₄ parameter of 0.77. In the two ligands, the phenyl rings are inclined to the naphthalene ring systems by 11.4 (2) and 9.2 (3)°. Among the other six complexes, in which the metal atoms are all located on inversion centres, there are three copper(II) complexes with the ligands (E)-1-(phenyldiazenyl)naphthalen-2-ol (refcode CBANAP; Jarvis, 1961 ), (E)-1-(2-chlorophenyl)diazenyl]naphthalen-2-ol (AFATIM; Benaouida et al., 2013) and (E)-1-(2,4-dimethylphenyl)diazenyl]naphthalen-2-ol (NOTNOB; Ferreira et al., 2015 ); two nickel complexes with the ligands (E)-1-(phenyldiazenyl)naphthalen-2-ol (NOTNUH; Ferreira et al., 2015) and (E)-1-(3-methylphenyl)diazenyl]naphthalen-2-ol (TOAZNI; Alcock et al., 1968 ); and one palladium complex with the ligand [(E)-1-(2-methylphenyl)diazenyl]naphthalen-2-ol (DURRIS; Lin et al., 2010 ). The orientation of the phenyl/benzene ring with respect to the naphthalene ring system varies quite considerably. In the palladium complex (DURRIS) and the copper complex (NOTNOB), where the benzene ring has a methyl group in the ortho position, the benzene ring is inclined to the naphthalene ring system by 74.41 (4) and 83.87 (6)°, respectively. In the other four complexes, the corresponding dihedral angles are 19.12 and 32.72 (12)° for the copper complexes CBANAP and AFATIM, respectively, and 24.06 (15) and ca 35.56° for the nickel complexes NOTNUH and TOAZNI, respectively.

Figure 6
The results of the database search (CSD; Groom et al., 2016

) for four-coordinate metal complexes of the ligand (E)-1-(phenyldiazenyl)naphthalen-2-ol and its derivatives.

5. Synthesis and crystallization

The title compounds were synthesized by the following procedure: (E)-1-[(2,4,6-tribromophenyl)diazenyl]-naphthalen-2-ol (2.0 mmol) and M(OAc)₂·H₂O (1.0 mmol; where M = Cu, Ni, Pd) was stirred at 298 K in a mixture of THF/MeOH (10/10 ml) for 24 h. The solvents were removed under vacuum and the residue was washed twice with hexane to give dark solids. The resulting solids were crystallized from CH₂Cl₂ to yield red block-like crystals for (I), black prismatic crystals for (II) and dark-red plate-like crystals for (III).

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 7. For all three compounds the C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.95 Å for (I) and (II) and 0.93 Å for (III), with U_iso(H) = 1.2U_eq(C). For the copper(II) complex (I), a region of disordered electron density was corrected for using the SQUEEZE routine in PLATON (Spek, 2015). The formula mass and unit-cell characteristics of the disordered solvent molecules were not taken into account during refinement. This complex crystallizes in the monoclinic space group P2₁, with the Flack parameter = −0.006 (14).

Table 7
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	[Cu(C₁₆H₈Br₃N₂O)₂]	[Ni(C₁₆H₈Br₃N₂O)₂]	[Pd(C₁₆H₈Br₃N₂O)₂]
M_r	1031.49	1026.66	1074.35
Crystal system, space group	Monoclinic, P2₁	Monoclinic, P2₁/n	Monoclinic, P2₁/n
Temperature (K)	173	173	200
a, b, c (Å)	11.9423 (7), 12.1314 (10), 12.8974 (10)	11.0909 (6), 12.4571 (6), 12.5382 (7)	11.1896 (8), 12.4540 (8), 12.5511 (9)
β (°)	107.032 (4)	107.820 (2)	107.749 (5)
V (Å³)	1786.6 (2)	1649.17 (15)	1665.8 (2)
Z	2	2	2
Radiation type	Mo Kα	Mo Kα	Cu Kα
μ (mm⁻¹)	7.36	7.89	13.23
Crystal size (mm)	0.20 × 0.15 × 0.06	0.30 × 0.22 × 0.06	0.12 × 0.09 × 0.03

Data collection
Diffractometer	Nonius KappaCCD	Nonius KappaCCD	STOE IPDS 2T
Absorption correction	Multi-scan (MULABS; Spek, 2009)	Multi-scan (MULABS; Spek, 2009)	Multi-scan (MULABS; Spek, 2009)
T_min, T_max	0.311, 0.386	0.151, 0.317	0.360, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14985, 7819, 4785	11360, 3745, 2214	13003, 2895, 2371
R_int	0.077	0.094	0.142
(sin θ/λ)_max (Å⁻¹)	0.650	0.649	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.140, 0.96	0.043, 0.096, 0.95	0.057, 0.170, 1.11
No. of reflections	7819	3745	2895
No. of parameters	388	205	206
No. of restraints	2	0	0
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.58	0.57, −0.66	0.88, −1.10
Absolute structure	Flack x determined using 1648 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )	–	–
Absolute structure parameter	−0.006 (14)	–	–
Computer programs: COLLECT (Nonius, 1998 ), X-AREA and X-RED32 (Stoe & Cie, 2002 ), DENZO (Otwinowski & Minor, 1997 ), SIR97 (Altomare et al., 1999 ), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC references: 1490056; 1490055; 1490054

Crystal structure: contains datablocks global, I, II, III. DOI: https://doi.org/10.1107/S205698901601080X/su5299sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901601080X/su5299Isup3.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698901601080X/su5299IIsup4.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S205698901601080X/su5299IIIsup2.hkl

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1998) for (I), (II); X-AREA (Stoe & Cie, 2002) for (III). Cell refinement: DENZO (Otwinowski & Minor, 1997) for (I), (II); X-AREA (Stoe & Cie, 2002) for (III). Data reduction: DENZO (Otwinowski & Minor, 1997) for (I), (II); X-RED32 (Stoe & Cie, 2002) for (III). Program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008) for (I), (II); SIR97 (Altomare et al., 1999) for (III). For all compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(I) Bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}copper(II) top

Crystal data top

[Cu(C₁₆H₈Br₃N₂O)₂]	F(000) = 982
M_r = 1031.49	D_x = 1.917 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 11.9423 (7) Å	Cell parameters from 19031 reflections
b = 12.1314 (10) Å	θ = 1.0–27.5°
c = 12.8974 (10) Å	µ = 7.36 mm⁻¹
β = 107.032 (4)°	T = 173 K
V = 1786.6 (2) Å³	Block, red
Z = 2	0.20 × 0.15 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	7819 independent reflections
Radiation source: sealed tube	4785 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
phi and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −15→15
T_min = 0.311, T_max = 0.386	k = −15→15
14985 measured reflections	l = −16→16

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.064	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0639P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
7819 reflections	Δρ_max = 0.59 e Å⁻³
388 parameters	Δρ_min = −0.58 e Å⁻³
2 restraints	Absolute structure: Flack x determined using 1648 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (14)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8599 (11)	1.0263 (11)	−0.0117 (12)	0.032 (3)
C2	0.7637 (10)	1.0951 (10)	−0.0438 (11)	0.029 (3)
C3	0.6867 (12)	1.0894 (11)	−0.1484 (12)	0.034 (3)
H3	0.6209	1.1370	−0.1709	0.041*
C4	0.7093 (12)	1.0134 (11)	−0.2171 (11)	0.036 (3)
C5	0.8009 (12)	0.9443 (13)	−0.1921 (12)	0.041 (4)
H5	0.8118	0.8927	−0.2438	0.049*
C6	0.8812 (11)	0.9500 (11)	−0.0865 (13)	0.038 (4)
C7	1.1218 (11)	1.0834 (10)	0.2004 (11)	0.037 (4)
C8	1.1126 (12)	1.0508 (12)	0.3013 (11)	0.038 (4)
C9	1.2090 (15)	1.0731 (12)	0.3969 (14)	0.050 (4)
H9	1.2028	1.0532	0.4662	0.060*
C10	1.3075 (13)	1.1215 (13)	0.3890 (14)	0.050 (3)
H10	1.3702	1.1346	0.4529	0.060*
C11	1.3195 (13)	1.1534 (13)	0.2865 (15)	0.050 (3)
C12	1.2277 (12)	1.1344 (11)	0.1930 (14)	0.042 (4)
C13	1.2435 (13)	1.1699 (12)	0.0916 (15)	0.051 (4)
H13	1.1810	1.1617	0.0267	0.061*
C14	1.3475 (13)	1.2156 (15)	0.0870 (17)	0.066 (5)
H14	1.3548	1.2383	0.0188	0.079*
C15	1.4404 (14)	1.2291 (16)	0.1775 (16)	0.060 (5)
H15	1.5122	1.2576	0.1713	0.072*
C16	1.4305 (13)	1.2026 (16)	0.274 (2)	0.075 (6)
H16	1.4947	1.2150	0.3369	0.090*
C17	0.9418 (11)	0.7896 (11)	0.3903 (12)	0.034 (3)
C18	1.0263 (12)	0.7317 (12)	0.3582 (12)	0.039 (4)
C19	1.1197 (13)	0.6785 (11)	0.4318 (13)	0.042 (4)
H19	1.1765	0.6396	0.4077	0.050*
C20	1.1273 (11)	0.6835 (12)	0.5348 (13)	0.039 (4)
C21	1.0499 (11)	0.7419 (11)	0.5769 (12)	0.038 (3)
H21	1.0600	0.7456	0.6526	0.046*
C22	0.9586 (11)	0.7938 (11)	0.5032 (12)	0.033 (3)
C23	0.6472 (5)	0.8679 (7)	0.2481 (6)	0.032 (3)
C24	0.6455 (5)	0.9058 (8)	0.1459 (7)	0.033 (3)
C25	0.5394 (7)	0.9308 (8)	0.0697 (6)	0.040 (4)
H25	0.5383	0.9567	−0.0001	0.047*
C26	0.4351 (5)	0.9179 (8)	0.0956 (6)	0.044 (4)
H26	0.3627	0.9350	0.0435	0.053*
C27	0.4369 (5)	0.8800 (8)	0.1978 (7)	0.035 (3)
C28	0.5429 (7)	0.8550 (7)	0.2740 (6)	0.035 (3)
C29	0.5396 (11)	0.8189 (12)	0.3776 (13)	0.042 (4)
H29	0.6110	0.7992	0.4299	0.050*
C30	0.4378 (14)	0.8113 (13)	0.4055 (14)	0.053 (4)
H30	0.4391	0.7902	0.4767	0.063*
C31	0.3284 (12)	0.8359 (12)	0.3248 (14)	0.048 (4)
H31	0.2568	0.8300	0.3424	0.057*
C32	0.3279 (12)	0.8675 (12)	0.2240 (12)	0.041 (4)
H32	0.2557	0.8815	0.1703	0.049*
N1	0.9383 (9)	1.0290 (9)	0.0989 (10)	0.035 (3)
N2	1.0368 (9)	1.0745 (9)	0.1038 (9)	0.032 (3)
N3	0.8497 (9)	0.8449 (9)	0.3100 (9)	0.031 (3)
N4	0.7460 (9)	0.8232 (8)	0.3214 (9)	0.031 (3)
O1	1.0249 (7)	0.9986 (8)	0.3181 (8)	0.040 (2)
O2	0.7408 (7)	0.9216 (8)	0.1119 (7)	0.038 (2)
Cu1	0.88988 (14)	0.94978 (13)	0.20990 (14)	0.0328 (4)
Br1	0.73408 (13)	1.19596 (12)	0.05505 (13)	0.0456 (4)
Br2	0.60688 (14)	1.00205 (14)	−0.36393 (13)	0.0535 (5)
Br3	1.01318 (13)	0.85864 (13)	−0.05111 (13)	0.0473 (4)
Br4	1.01312 (13)	0.72221 (13)	0.20691 (13)	0.0484 (4)
Br5	1.25913 (13)	0.61791 (13)	0.64036 (14)	0.0482 (4)
Br6	0.85805 (13)	0.88104 (13)	0.55982 (13)	0.0506 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.024 (7)	0.031 (7)	0.042 (9)	−0.010 (6)	0.014 (6)	−0.003 (7)
C2	0.023 (6)	0.020 (7)	0.045 (9)	−0.008 (6)	0.012 (6)	−0.003 (6)
C3	0.037 (8)	0.033 (8)	0.032 (9)	0.002 (6)	0.010 (7)	0.005 (7)
C4	0.041 (8)	0.031 (8)	0.023 (8)	−0.005 (7)	−0.008 (6)	0.008 (7)
C5	0.043 (8)	0.046 (9)	0.035 (9)	−0.006 (7)	0.014 (7)	−0.007 (7)
C6	0.033 (7)	0.027 (7)	0.057 (11)	0.006 (6)	0.019 (7)	0.000 (7)
C7	0.033 (8)	0.027 (8)	0.050 (10)	0.009 (6)	0.009 (7)	−0.002 (7)
C8	0.032 (8)	0.038 (8)	0.038 (10)	0.008 (7)	0.000 (7)	−0.004 (7)
C9	0.073 (11)	0.040 (9)	0.042 (11)	−0.007 (8)	0.025 (9)	−0.002 (8)
C10	0.040 (6)	0.048 (7)	0.060 (8)	0.002 (5)	0.012 (6)	−0.010 (6)
C11	0.040 (6)	0.048 (7)	0.060 (8)	0.002 (5)	0.012 (6)	−0.010 (6)
C12	0.032 (8)	0.034 (9)	0.061 (12)	−0.005 (7)	0.014 (8)	−0.007 (8)
C13	0.042 (9)	0.037 (9)	0.071 (14)	0.007 (7)	0.014 (9)	−0.001 (8)
C14	0.044 (10)	0.072 (13)	0.088 (15)	−0.007 (9)	0.028 (10)	0.018 (12)
C15	0.039 (9)	0.080 (13)	0.064 (13)	−0.003 (9)	0.020 (9)	−0.009 (11)
C16	0.035 (9)	0.066 (12)	0.12 (2)	−0.018 (9)	0.020 (10)	−0.031 (13)
C17	0.032 (7)	0.025 (7)	0.046 (10)	0.002 (6)	0.014 (7)	0.013 (7)
C18	0.047 (8)	0.036 (8)	0.039 (9)	−0.004 (7)	0.022 (7)	0.005 (7)
C19	0.045 (9)	0.031 (8)	0.053 (11)	0.006 (7)	0.019 (8)	0.019 (8)
C20	0.027 (7)	0.042 (9)	0.049 (10)	0.000 (7)	0.012 (7)	0.024 (8)
C21	0.033 (7)	0.039 (8)	0.037 (9)	0.010 (7)	0.003 (7)	0.008 (7)
C22	0.039 (8)	0.025 (7)	0.043 (9)	0.003 (6)	0.024 (7)	−0.004 (7)
C23	0.028 (7)	0.028 (7)	0.045 (9)	0.006 (6)	0.018 (6)	−0.007 (7)
C24	0.025 (7)	0.034 (8)	0.034 (9)	−0.004 (6)	0.001 (6)	−0.007 (6)
C25	0.034 (8)	0.043 (9)	0.038 (9)	−0.013 (7)	0.006 (7)	−0.007 (7)
C26	0.029 (8)	0.036 (8)	0.059 (11)	−0.007 (7)	−0.001 (7)	0.004 (7)
C27	0.040 (8)	0.029 (7)	0.034 (8)	0.002 (7)	0.007 (6)	0.009 (7)
C28	0.044 (8)	0.024 (7)	0.034 (9)	−0.002 (6)	0.009 (7)	−0.008 (6)
C29	0.025 (7)	0.048 (9)	0.050 (10)	0.002 (7)	0.008 (6)	0.011 (7)
C30	0.072 (11)	0.045 (9)	0.050 (11)	0.004 (9)	0.031 (9)	0.006 (8)
C31	0.029 (8)	0.046 (10)	0.064 (12)	0.009 (7)	0.006 (7)	0.007 (8)
C32	0.043 (8)	0.033 (8)	0.037 (9)	−0.004 (7)	−0.003 (7)	−0.001 (7)
N1	0.032 (6)	0.038 (7)	0.032 (7)	0.000 (5)	0.005 (5)	0.005 (5)
N2	0.027 (6)	0.043 (7)	0.025 (7)	−0.008 (5)	0.006 (5)	−0.003 (5)
N3	0.029 (6)	0.034 (6)	0.030 (7)	0.001 (5)	0.005 (5)	0.006 (5)
N4	0.038 (7)	0.022 (6)	0.032 (7)	−0.002 (5)	0.011 (5)	0.000 (5)
O1	0.030 (5)	0.052 (6)	0.035 (6)	−0.007 (5)	0.004 (4)	0.003 (5)
O2	0.031 (5)	0.048 (6)	0.027 (6)	−0.009 (4)	−0.002 (4)	0.007 (4)
Cu1	0.0300 (8)	0.0336 (9)	0.0334 (10)	−0.0028 (7)	0.0071 (7)	0.0030 (8)
Br1	0.0499 (9)	0.0385 (8)	0.0471 (10)	0.0081 (7)	0.0122 (7)	−0.0023 (7)
Br2	0.0559 (9)	0.0580 (10)	0.0374 (10)	−0.0012 (9)	−0.0006 (7)	0.0009 (8)
Br3	0.0452 (8)	0.0488 (9)	0.0470 (10)	0.0147 (8)	0.0118 (7)	−0.0006 (8)
Br4	0.0449 (8)	0.0618 (11)	0.0390 (10)	0.0137 (8)	0.0131 (7)	−0.0007 (8)
Br5	0.0397 (8)	0.0465 (9)	0.0494 (11)	0.0064 (7)	−0.0013 (7)	0.0111 (8)
Br6	0.0586 (10)	0.0565 (10)	0.0397 (10)	0.0181 (8)	0.0188 (8)	0.0027 (8)

Geometric parameters (Å, º) top

C1—C2	1.382 (17)	C18—Br4	1.914 (15)
C1—C6	1.413 (19)	C19—C20	1.31 (2)
C1—N1	1.460 (18)	C19—H19	0.9500
C2—C3	1.395 (19)	C20—C21	1.39 (2)
C2—Br1	1.874 (13)	C20—Br5	1.926 (13)
C3—C4	1.36 (2)	C21—C22	1.372 (18)
C3—H3	0.9500	C21—H21	0.9500
C4—C5	1.341 (19)	C22—Br6	1.900 (13)
C4—Br2	1.935 (13)	C23—N4	1.388 (12)
C5—C6	1.42 (2)	C23—C24	1.3900
C5—H5	0.9500	C23—C28	1.3900
C6—Br3	1.870 (13)	C24—O2	1.348 (10)
C7—N2	1.361 (16)	C24—C25	1.3900
C7—C8	1.394 (12)	C25—C26	1.3900
C7—C12	1.436 (19)	C25—H25	0.9500
C8—O1	1.296 (16)	C26—C27	1.3900
C8—C9	1.44 (2)	C26—H26	0.9500
C9—C10	1.34 (2)	C27—C28	1.3900
C9—H9	0.9500	C27—C32	1.445 (16)
C10—C11	1.42 (2)	C28—C29	1.418 (16)
C10—H10	0.9500	C29—C30	1.37 (2)
C11—C12	1.39 (2)	C29—H29	0.9500
C11—C16	1.50 (2)	C30—C31	1.44 (2)
C12—C13	1.44 (2)	C30—H30	0.9500
C13—C14	1.38 (2)	C31—C32	1.35 (2)
C13—H13	0.9500	C31—H31	0.9500
C14—C15	1.36 (2)	C32—H32	0.9500
C14—H14	0.9500	N1—N2	1.284 (14)
C15—C16	1.33 (3)	Cu1—Br4	3.134 (2)
C15—H15	0.9500	Cu1—N1	1.947 (12)
C16—H16	0.9500	N3—N4	1.315 (14)
C17—C18	1.389 (19)	Cu1—N3	1.970 (11)
C17—C22	1.411 (19)	Cu1—O1	1.892 (9)
C17—N3	1.437 (16)	Cu1—O2	1.888 (8)
C18—C19	1.39 (2)

C2—C1—C6	119.5 (13)	C18—C19—H19	120.8
C2—C1—N1	121.2 (12)	C19—C20—C21	124.2 (13)
C6—C1—N1	119.3 (12)	C19—C20—Br5	120.0 (11)
C1—C2—C3	121.0 (13)	C21—C20—Br5	115.6 (11)
C1—C2—Br1	119.8 (11)	C22—C21—C20	116.6 (14)
C3—C2—Br1	119.2 (10)	C22—C21—H21	121.7
C4—C3—C2	117.6 (12)	C20—C21—H21	121.7
C4—C3—H3	121.2	C21—C22—C17	122.8 (12)
C2—C3—H3	121.2	C21—C22—Br6	117.0 (11)
C5—C4—C3	124.9 (13)	C17—C22—Br6	120.1 (10)
C5—C4—Br2	115.3 (11)	N4—C23—C24	123.3 (7)
C3—C4—Br2	119.8 (10)	N4—C23—C28	115.8 (7)
C4—C5—C6	118.3 (13)	C24—C23—C28	120.0
C4—C5—H5	120.8	O2—C24—C25	114.8 (7)
C6—C5—H5	120.8	O2—C24—C23	125.2 (7)
C1—C6—C5	118.7 (12)	C25—C24—C23	120.0
C1—C6—Br3	121.9 (11)	C26—C25—C24	120.0
C5—C6—Br3	119.3 (11)	C26—C25—H25	120.0
N2—C7—C8	126.2 (12)	C24—C25—H25	120.0
N2—C7—C12	114.1 (12)	C25—C26—C27	120.0
C8—C7—C12	119.7 (13)	C25—C26—H26	120.0
O1—C8—C7	125.7 (12)	C27—C26—H26	120.0
O1—C8—C9	115.4 (12)	C28—C27—C26	120.0
C7—C8—C9	118.8 (13)	C28—C27—C32	120.5 (8)
C10—C9—C8	120.9 (15)	C26—C27—C32	119.5 (8)
C10—C9—H9	119.6	C27—C28—C23	120.0
C8—C9—H9	119.6	C27—C28—C29	117.6 (7)
C9—C10—C11	121.1 (15)	C23—C28—C29	122.4 (7)
C9—C10—H10	119.5	C30—C29—C28	122.7 (13)
C11—C10—H10	119.5	C30—C29—H29	118.6
C12—C11—C10	119.5 (15)	C28—C29—H29	118.6
C12—C11—C16	118.0 (17)	C29—C30—C31	118.9 (15)
C10—C11—C16	122.4 (16)	C29—C30—H30	120.6
C11—C12—C7	120.0 (15)	C31—C30—H30	120.6
C11—C12—C13	117.2 (14)	C32—C31—C30	119.9 (14)
C7—C12—C13	122.8 (14)	C32—C31—H31	120.0
C14—C13—C12	121.3 (16)	C30—C31—H31	120.0
C14—C13—H13	119.3	C31—C32—C27	120.2 (12)
C12—C13—H13	119.3	C31—C32—H32	119.9
C15—C14—C13	121.9 (18)	C27—C32—H32	119.9
C15—C14—H14	119.0	N2—N1—C1	111.9 (11)
C13—C14—H14	119.0	N2—N1—Cu1	129.9 (9)
C16—C15—C14	120.1 (17)	C1—N1—Cu1	117.7 (8)
C16—C15—H15	120.0	N1—N2—C7	120.3 (12)
C14—C15—H15	120.0	N4—N3—C17	111.9 (10)
C15—C16—C11	121.3 (18)	N4—N3—Cu1	128.3 (8)
C15—C16—H16	119.4	C17—N3—Cu1	119.4 (8)
C11—C16—H16	119.4	N3—N4—C23	119.1 (10)
C18—C17—C22	115.5 (12)	C8—O1—Cu1	125.8 (9)
C18—C17—N3	119.4 (13)	C24—O2—Cu1	121.9 (7)
C22—C17—N3	125.1 (12)	O2—Cu1—O1	169.4 (4)
C17—C18—C19	122.5 (14)	O2—Cu1—N1	91.3 (4)
C17—C18—Br4	119.0 (11)	O1—Cu1—N1	90.9 (4)
C19—C18—Br4	118.5 (11)	O2—Cu1—N3	87.6 (4)
C20—C19—C18	118.4 (14)	O1—Cu1—N3	92.1 (4)
C20—C19—H19	120.8	N1—Cu1—N3	169.3 (5)

C6—C1—C2—C3	0.6 (19)	N3—C17—C22—C21	−178.2 (12)
N1—C1—C2—C3	−177.6 (12)	C18—C17—C22—Br6	174.4 (10)
C6—C1—C2—Br1	179.6 (10)	N3—C17—C22—Br6	−2.0 (18)
N1—C1—C2—Br1	1.3 (16)	N4—C23—C24—O2	−11.8 (10)
C1—C2—C3—C4	0.6 (19)	C28—C23—C24—O2	179.9 (10)
Br1—C2—C3—C4	−178.4 (10)	N4—C23—C24—C25	168.3 (9)
C2—C3—C4—C5	−1 (2)	C28—C23—C24—C25	0.0
C2—C3—C4—Br2	−179.4 (9)	O2—C24—C25—C26	−179.9 (9)
C3—C4—C5—C6	0 (2)	C23—C24—C25—C26	0.0
Br2—C4—C5—C6	178.5 (10)	C24—C25—C26—C27	0.0
C2—C1—C6—C5	−1.6 (19)	C25—C26—C27—C28	0.0
N1—C1—C6—C5	176.7 (12)	C25—C26—C27—C32	179.7 (10)
C2—C1—C6—Br3	177.2 (10)	C26—C27—C28—C23	0.0
N1—C1—C6—Br3	−4.5 (17)	C32—C27—C28—C23	−179.7 (10)
C4—C5—C6—C1	1 (2)	C26—C27—C28—C29	178.7 (10)
C4—C5—C6—Br3	−177.5 (11)	C32—C27—C28—C29	−1.0 (12)
N2—C7—C8—O1	6 (2)	N4—C23—C28—C27	−169.2 (9)
C12—C7—C8—O1	−175.9 (13)	C24—C23—C28—C27	0.0
N2—C7—C8—C9	−175.9 (13)	N4—C23—C28—C29	12.2 (11)
C12—C7—C8—C9	2.2 (19)	C24—C23—C28—C29	−178.6 (11)
O1—C8—C9—C10	176.4 (14)	C27—C28—C29—C30	−2.0 (18)
C7—C8—C9—C10	−2 (2)	C23—C28—C29—C30	176.6 (11)
C8—C9—C10—C11	1 (2)	C28—C29—C30—C31	3 (2)
C9—C10—C11—C12	0 (2)	C29—C30—C31—C32	−1 (2)
C9—C10—C11—C16	−177.0 (15)	C30—C31—C32—C27	−2 (2)
C10—C11—C12—C7	0 (2)	C28—C27—C32—C31	2.9 (17)
C16—C11—C12—C7	177.5 (14)	C26—C27—C32—C31	−176.7 (11)
C10—C11—C12—C13	179.0 (14)	C2—C1—N1—N2	−107.0 (14)
C16—C11—C12—C13	−4 (2)	C6—C1—N1—N2	74.8 (15)
N2—C7—C12—C11	176.9 (12)	C2—C1—N1—Cu1	80.7 (14)
C8—C7—C12—C11	−1 (2)	C6—C1—N1—Cu1	−97.6 (12)
N2—C7—C12—C13	−1.8 (19)	C1—N1—N2—C7	−179.3 (11)
C8—C7—C12—C13	179.9 (13)	Cu1—N1—N2—C7	−8.1 (18)
C11—C12—C13—C14	3 (2)	C8—C7—N2—N1	−3 (2)
C7—C12—C13—C14	−178.0 (15)	C12—C7—N2—N1	179.0 (12)
C12—C13—C14—C15	0 (3)	C18—C17—N3—N4	131.8 (12)
C13—C14—C15—C16	−3 (3)	C22—C17—N3—N4	−52.0 (17)
C14—C15—C16—C11	2 (3)	C18—C17—N3—Cu1	−53.8 (15)
C12—C11—C16—C15	1 (3)	C22—C17—N3—Cu1	122.4 (12)
C10—C11—C16—C15	178.3 (17)	C17—N3—N4—C23	−178.2 (10)
C22—C17—C18—C19	1.8 (19)	Cu1—N3—N4—C23	8.0 (16)
N3—C17—C18—C19	178.4 (12)	C24—C23—N4—N3	20.3 (13)
C22—C17—C18—Br4	−179.3 (9)	C28—C23—N4—N3	−170.9 (8)
N3—C17—C18—Br4	−2.7 (17)	C7—C8—O1—Cu1	2 (2)
C17—C18—C19—C20	0 (2)	C9—C8—O1—Cu1	−176.2 (9)
Br4—C18—C19—C20	−178.8 (11)	C25—C24—O2—Cu1	154.8 (5)
C18—C19—C20—C21	−2 (2)	C23—C24—O2—Cu1	−25.1 (11)
C18—C19—C20—Br5	−176.8 (10)	C24—O2—Cu1—O1	−52 (3)
C19—C20—C21—C22	2 (2)	C24—O2—Cu1—N1	−153.4 (9)
Br5—C20—C21—C22	176.9 (10)	C24—O2—Cu1—N3	37.3 (9)
C20—C21—C22—C17	0 (2)	C8—O1—Cu1—O2	−110 (2)
C20—C21—C22—Br6	−176.3 (10)	C8—O1—Cu1—N1	−8.2 (11)
C18—C17—C22—C21	−1.8 (19)	C8—O1—Cu1—N3	161.5 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C27–C32 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···Br6ⁱ	0.95	2.75	3.546 (15)	142
C3—H3···Cg1ⁱⁱ	0.95	2.99	3.729 (15)	136

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

(II) Bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}nickel(II) top

Crystal data top

[Ni(C₁₆H₈Br₃N₂O)₂]	F(000) = 980
M_r = 1026.66	D_x = 2.067 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.0909 (6) Å	Cell parameters from 7253 reflections
b = 12.4571 (6) Å	θ = 1.0–27.5°
c = 12.5382 (7) Å	µ = 7.89 mm⁻¹
β = 107.820 (2)°	T = 173 K
V = 1649.17 (15) Å³	Prism, black
Z = 2	0.30 × 0.22 × 0.06 mm

Data collection top

Nonius KappaCCD diffractometer	3745 independent reflections
Radiation source: sealed tube	2214 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
phi and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (MULABS; Spek, 2009)	h = −13→14
T_min = 0.151, T_max = 0.317	k = −13→16
11360 measured reflections	l = −16→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.034P)²] where P = (F_o² + 2F_c²)/3
3745 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2389 (4)	0.4906 (3)	0.3565 (3)	0.0232 (10)
C2	0.2302 (4)	0.5055 (4)	0.2452 (4)	0.0287 (11)
C3	0.1396 (4)	0.4527 (4)	0.1602 (4)	0.0321 (12)
H3	0.1357	0.4619	0.0840	0.038*
C4	0.0551 (4)	0.3862 (3)	0.1896 (4)	0.0295 (12)
C5	0.0609 (4)	0.3679 (4)	0.3004 (4)	0.0318 (12)
H5	0.0028	0.3212	0.3192	0.038*
C6	0.1547 (4)	0.4204 (4)	0.3819 (3)	0.0277 (11)
C7	0.3408 (4)	0.6940 (3)	0.5623 (4)	0.0283 (11)
C8	0.4729 (4)	0.6805 (4)	0.6238 (4)	0.0293 (11)
C9	0.5307 (4)	0.7555 (4)	0.7110 (4)	0.0335 (12)
H9	0.6165	0.7462	0.7549	0.040*
C10	0.4637 (4)	0.8392 (4)	0.7310 (4)	0.0323 (12)
H10	0.5056	0.8894	0.7871	0.039*
C11	0.3320 (4)	0.8562 (4)	0.6717 (4)	0.0296 (11)
C12	0.2707 (4)	0.7808 (4)	0.5879 (3)	0.0272 (11)
C13	0.1395 (4)	0.7939 (4)	0.5345 (4)	0.0308 (12)
H13	0.0955	0.7435	0.4795	0.037*
C14	0.0748 (5)	0.8782 (4)	0.5608 (4)	0.0386 (13)
H14	−0.0135	0.8852	0.5240	0.046*
C15	0.1371 (5)	0.9547 (4)	0.6414 (4)	0.0416 (13)
H15	0.0916	1.0131	0.6591	0.050*
C16	0.2644 (5)	0.9436 (4)	0.6940 (4)	0.0342 (12)
H16	0.3075	0.9964	0.7466	0.041*
N1	0.3320 (3)	0.5483 (3)	0.4453 (3)	0.0251 (9)
N2	0.2773 (3)	0.6275 (3)	0.4773 (3)	0.0278 (9)
O1	0.5435 (3)	0.6061 (2)	0.6047 (2)	0.0328 (8)
Ni	0.5000	0.5000	0.5000	0.0271 (2)
Br1	0.16663 (5)	0.39355 (4)	0.53300 (4)	0.04164 (17)
Br2	0.34269 (5)	0.60009 (4)	0.20681 (4)	0.04697 (18)
Br3	−0.07417 (5)	0.31689 (4)	0.07466 (4)	0.05057 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.014 (2)	0.027 (2)	0.024 (2)	0.003 (2)	−0.0014 (19)	−0.004 (2)
C2	0.023 (2)	0.031 (3)	0.027 (2)	−0.007 (2)	0.000 (2)	−0.002 (2)
C3	0.029 (3)	0.037 (3)	0.025 (2)	0.004 (2)	0.001 (2)	0.000 (2)
C4	0.020 (2)	0.027 (3)	0.033 (3)	0.002 (2)	−0.005 (2)	−0.008 (2)
C5	0.028 (3)	0.030 (3)	0.034 (3)	−0.002 (2)	0.005 (2)	0.002 (2)
C6	0.025 (3)	0.031 (3)	0.022 (2)	0.006 (2)	0.000 (2)	0.001 (2)
C7	0.024 (3)	0.030 (3)	0.025 (2)	0.001 (2)	−0.002 (2)	−0.004 (2)
C8	0.025 (3)	0.034 (3)	0.025 (2)	−0.006 (2)	0.002 (2)	−0.004 (2)
C9	0.023 (3)	0.037 (3)	0.033 (3)	−0.003 (2)	−0.003 (2)	−0.009 (2)
C10	0.032 (3)	0.034 (3)	0.027 (2)	−0.009 (2)	0.002 (2)	−0.002 (2)
C11	0.033 (3)	0.028 (3)	0.026 (2)	−0.002 (2)	0.006 (2)	−0.001 (2)
C12	0.024 (3)	0.032 (3)	0.024 (2)	0.003 (2)	0.004 (2)	−0.002 (2)
C13	0.029 (3)	0.029 (3)	0.031 (2)	0.006 (2)	0.004 (2)	−0.003 (2)
C14	0.025 (3)	0.050 (3)	0.035 (3)	0.009 (3)	0.001 (2)	0.004 (3)
C15	0.043 (3)	0.040 (3)	0.042 (3)	0.017 (3)	0.011 (3)	0.001 (3)
C16	0.042 (3)	0.031 (3)	0.030 (3)	0.000 (2)	0.011 (2)	−0.003 (2)
N1	0.018 (2)	0.029 (2)	0.0214 (19)	−0.0025 (17)	−0.0034 (16)	−0.0038 (17)
N2	0.026 (2)	0.025 (2)	0.026 (2)	0.0012 (18)	−0.0019 (18)	−0.0021 (17)
O1	0.0247 (18)	0.0333 (19)	0.0316 (18)	0.0022 (15)	−0.0044 (15)	−0.0132 (14)
Ni	0.0197 (4)	0.0297 (5)	0.0255 (4)	0.0004 (4)	−0.0026 (4)	−0.0040 (4)
Br1	0.0424 (3)	0.0495 (4)	0.0289 (3)	−0.0039 (3)	0.0049 (2)	0.0067 (2)
Br2	0.0386 (3)	0.0609 (4)	0.0378 (3)	−0.0170 (3)	0.0063 (3)	0.0049 (3)
Br3	0.0419 (3)	0.0534 (4)	0.0427 (3)	−0.0125 (3)	−0.0073 (3)	−0.0172 (3)

Geometric parameters (Å, º) top

C1—C2	1.382 (6)	C9—H9	0.9500
C1—C6	1.385 (6)	C10—C11	1.437 (6)
C1—N1	1.455 (5)	C10—H10	0.9500
C2—C3	1.387 (6)	C11—C16	1.399 (7)
C2—Br2	1.883 (5)	C11—C12	1.419 (6)
C3—C4	1.382 (7)	C12—C13	1.413 (6)
C3—H3	0.9500	C13—C14	1.367 (6)
C4—C5	1.389 (6)	C13—H13	0.9500
C4—Br3	1.901 (4)	C14—C15	1.407 (7)
C5—C6	1.381 (6)	C14—H14	0.9500
C5—H5	0.9500	C15—C16	1.370 (7)
C6—Br1	1.888 (4)	C15—H15	0.9500
C7—N2	1.363 (5)	C16—H16	0.9500
C7—C12	1.425 (6)	N1—N2	1.285 (5)
C7—C8	1.441 (6)	Ni—N1	1.876 (3)
C8—O1	1.281 (5)	Ni—O1	1.821 (3)
C8—C9	1.431 (6)	Ni—O1ⁱ	1.821 (3)
C9—C10	1.348 (6)	Ni—N1ⁱ	1.877 (3)

C2—C1—C6	118.3 (4)	C16—C11—C12	119.9 (4)
C2—C1—N1	121.3 (4)	C16—C11—C10	122.2 (4)
C6—C1—N1	120.4 (4)	C12—C11—C10	117.8 (4)
C1—C2—C3	121.5 (4)	C13—C12—C11	117.7 (4)
C1—C2—Br2	119.7 (3)	C13—C12—C7	122.4 (4)
C3—C2—Br2	118.8 (4)	C11—C12—C7	119.9 (4)
C4—C3—C2	118.0 (4)	C14—C13—C12	121.0 (4)
C4—C3—H3	121.0	C14—C13—H13	119.5
C2—C3—H3	121.0	C12—C13—H13	119.5
C3—C4—C5	122.5 (4)	C13—C14—C15	121.0 (4)
C3—C4—Br3	119.0 (4)	C13—C14—H14	119.5
C5—C4—Br3	118.5 (4)	C15—C14—H14	119.5
C6—C5—C4	117.1 (4)	C16—C15—C14	119.0 (5)
C6—C5—H5	121.4	C16—C15—H15	120.5
C4—C5—H5	121.4	C14—C15—H15	120.5
C5—C6—C1	122.5 (4)	C15—C16—C11	121.3 (4)
C5—C6—Br1	117.7 (4)	C15—C16—H16	119.4
C1—C6—Br1	119.8 (3)	C11—C16—H16	119.4
N2—C7—C12	116.7 (4)	N2—N1—C1	109.0 (3)
N2—C7—C8	123.0 (4)	N2—N1—Ni	130.0 (3)
C12—C7—C8	120.2 (4)	C1—N1—Ni	120.9 (3)
O1—C8—C9	117.3 (4)	N1—N2—C7	122.0 (4)
O1—C8—C7	124.2 (4)	C8—O1—Ni	128.1 (3)
C9—C8—C7	118.5 (4)	O1—Ni—O1ⁱ	180
C10—C9—C8	120.3 (4)	O1—Ni—N1	92.59 (14)
C10—C9—H9	119.9	O1ⁱ—Ni—N1	87.41 (14)
C8—C9—H9	119.9	O1—Ni—N1ⁱ	87.41 (14)
C9—C10—C11	123.2 (4)	O1ⁱ—Ni—N1ⁱ	92.59 (14)
C9—C10—H10	118.4	N1—Ni—N1ⁱ	180
C11—C10—H10	118.4

C6—C1—C2—C3	0.3 (7)	C10—C11—C12—C7	−2.3 (7)
N1—C1—C2—C3	−178.4 (4)	N2—C7—C12—C13	4.6 (7)
C6—C1—C2—Br2	−180.0 (3)	C8—C7—C12—C13	−176.3 (4)
N1—C1—C2—Br2	1.3 (6)	N2—C7—C12—C11	−177.0 (4)
C1—C2—C3—C4	1.7 (7)	C8—C7—C12—C11	2.1 (7)
Br2—C2—C3—C4	−178.0 (3)	C11—C12—C13—C14	1.7 (7)
C2—C3—C4—C5	−2.3 (7)	C7—C12—C13—C14	−179.9 (5)
C2—C3—C4—Br3	177.6 (3)	C12—C13—C14—C15	0.3 (8)
C3—C4—C5—C6	0.8 (7)	C13—C14—C15—C16	−0.1 (8)
Br3—C4—C5—C6	−179.1 (3)	C14—C15—C16—C11	−2.2 (8)
C4—C5—C6—C1	1.4 (7)	C12—C11—C16—C15	4.2 (7)
C4—C5—C6—Br1	−178.4 (3)	C10—C11—C16—C15	−175.9 (4)
C2—C1—C6—C5	−1.9 (7)	C2—C1—N1—N2	100.7 (5)
N1—C1—C6—C5	176.8 (4)	C6—C1—N1—N2	−78.1 (5)
C2—C1—C6—Br1	177.8 (3)	C2—C1—N1—Ni	−82.2 (5)
N1—C1—C6—Br1	−3.4 (5)	C6—C1—N1—Ni	99.1 (4)
N2—C7—C8—O1	0.5 (7)	C1—N1—N2—C7	178.0 (4)
C12—C7—C8—O1	−178.6 (4)	Ni—N1—N2—C7	1.1 (6)
N2—C7—C8—C9	179.6 (4)	C12—C7—N2—N1	178.2 (4)
C12—C7—C8—C9	0.5 (7)	C8—C7—N2—N1	−0.9 (7)
O1—C8—C9—C10	176.2 (5)	C9—C8—O1—Ni	−179.4 (3)
C7—C8—C9—C10	−2.9 (7)	C7—C8—O1—Ni	−0.3 (7)
C8—C9—C10—C11	2.8 (7)	C8—O1—Ni—N1	0.4 (4)
C9—C10—C11—C16	179.9 (5)	C8—O1—Ni—N1ⁱ	−179.6 (4)
C9—C10—C11—C12	−0.2 (7)	N2—N1—Ni—O1	−0.8 (4)
C16—C11—C12—C13	−3.9 (7)	C1—N1—Ni—O1	−177.3 (3)
C10—C11—C12—C13	176.2 (4)	N2—N1—Ni—O1ⁱ	179.2 (4)
C16—C11—C12—C7	177.6 (4)	C1—N1—Ni—O1ⁱ	2.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg2ⁱⁱ	0.95	2.71	3.391 (5)	130

Symmetry code: (ii) x+1/2, −y+3/2, z+1/2.

(III) Bis{(E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-olato}palladium(II) top

Crystal data top

[Pd(C₁₆H₈Br₃N₂O)₂]	F(000) = 1016
M_r = 1074.35	D_x = 2.142 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54186 Å
a = 11.1896 (8) Å	Cell parameters from 3651 reflections
b = 12.4540 (8) Å	θ = 2.1–22.3°
c = 12.5511 (9) Å	µ = 13.23 mm⁻¹
β = 107.749 (5)°	T = 200 K
V = 1665.8 (2) Å³	Square plate, dark red
Z = 2	0.12 × 0.09 × 0.03 mm

Data collection top

STOE IPDS 2T diffractometer	2895 independent reflections
Radiation source: Genix-Cu,3D	2371 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.142
Detector resolution: 6.67 pixels mm^-1	θ_max = 67.7°, θ_min = 5.5°
rotation method scans	h = −13→12
Absorption correction: multi-scan (MULABS; Spek, 2009)	k = −14→14
T_min = 0.360, T_max = 1.000	l = −14→15
13003 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.170	w = 1/[σ²(F_o²) + (0.1019P)² + 0.8121P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max < 0.001
2895 reflections	Δρ_max = 0.88 e Å⁻³
206 parameters	Δρ_min = −1.10 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0040 (4)

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.16311 (8)	0.39498 (7)	0.53262 (6)	0.0659 (3)
Br2	0.33399 (8)	0.60480 (8)	0.20631 (7)	0.0737 (4)
Br3	−0.07036 (8)	0.31295 (7)	0.07577 (7)	0.0754 (4)
Pd1	0.5000	0.5000	0.5000	0.0456 (3)
O1	0.5428 (4)	0.6130 (4)	0.6155 (4)	0.0573 (12)
N1	0.3223 (5)	0.5521 (4)	0.4432 (4)	0.0468 (12)
N2	0.2730 (5)	0.6310 (4)	0.4798 (4)	0.0486 (12)
C1	0.2323 (6)	0.4941 (5)	0.3582 (5)	0.0471 (15)
C2	0.2246 (6)	0.5074 (5)	0.2447 (5)	0.0482 (15)
C3	0.1354 (7)	0.4532 (6)	0.1598 (5)	0.0563 (17)
H3	0.1311	0.4629	0.0836	0.068*
C4	0.0544 (7)	0.3855 (5)	0.1889 (6)	0.0532 (16)
C5	0.0597 (6)	0.3675 (5)	0.2996 (6)	0.0495 (15)
H5	0.0032	0.3195	0.3184	0.059*
C6	0.1513 (6)	0.4227 (5)	0.3817 (5)	0.0474 (14)
C7	0.3371 (6)	0.6961 (5)	0.5647 (5)	0.0464 (14)
C8	0.4672 (6)	0.6842 (6)	0.6279 (5)	0.0523 (15)
C9	0.5192 (7)	0.7634 (6)	0.7146 (6)	0.0570 (17)
H9	0.6039	0.7562	0.7601	0.068*
C10	0.4511 (7)	0.8468 (6)	0.7323 (6)	0.0604 (18)
H10	0.4904	0.8983	0.7877	0.072*
C11	0.3214 (7)	0.8605 (6)	0.6705 (6)	0.0536 (16)
C12	0.2640 (7)	0.7831 (5)	0.5895 (5)	0.0505 (15)
C13	0.1345 (7)	0.7932 (6)	0.5352 (6)	0.0583 (17)
H13	0.0933	0.7427	0.4793	0.070*
C14	0.0678 (8)	0.8748 (7)	0.5619 (7)	0.070 (2)
H14	−0.0202	0.8783	0.5263	0.084*
C15	0.1257 (8)	0.9538 (7)	0.6406 (6)	0.071 (2)
H15	0.0780	1.0109	0.6573	0.085*
C16	0.2509 (8)	0.9469 (7)	0.6922 (7)	0.0652 (19)
H16	0.2917	1.0010	0.7438	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0649 (6)	0.0817 (6)	0.0436 (5)	−0.0081 (4)	0.0055 (4)	0.0092 (3)
Br2	0.0614 (6)	0.0997 (7)	0.0531 (5)	−0.0261 (4)	0.0070 (4)	0.0073 (4)
Br3	0.0648 (6)	0.0834 (6)	0.0603 (6)	−0.0172 (4)	−0.0073 (4)	−0.0226 (4)
Pd1	0.0353 (4)	0.0550 (4)	0.0369 (4)	−0.0014 (3)	−0.0032 (3)	−0.0038 (3)
O1	0.042 (3)	0.065 (3)	0.052 (3)	0.003 (2)	−0.005 (2)	−0.009 (2)
N1	0.042 (3)	0.053 (3)	0.037 (3)	−0.007 (2)	−0.001 (2)	−0.004 (2)
N2	0.040 (3)	0.054 (3)	0.042 (3)	−0.004 (2)	−0.003 (2)	0.000 (2)
C1	0.038 (3)	0.054 (3)	0.037 (3)	0.007 (3)	−0.007 (3)	0.001 (3)
C2	0.036 (3)	0.061 (4)	0.037 (3)	0.000 (3)	−0.005 (3)	0.002 (3)
C3	0.049 (4)	0.073 (4)	0.038 (3)	0.004 (3)	−0.001 (3)	−0.001 (3)
C4	0.045 (4)	0.056 (4)	0.048 (4)	−0.005 (3)	−0.002 (3)	−0.005 (3)
C5	0.043 (4)	0.047 (3)	0.054 (4)	−0.002 (3)	0.008 (3)	0.002 (3)
C6	0.042 (3)	0.049 (3)	0.040 (3)	−0.002 (3)	−0.003 (3)	0.000 (3)
C7	0.035 (3)	0.057 (3)	0.042 (3)	−0.001 (3)	0.004 (3)	−0.005 (3)
C8	0.045 (4)	0.063 (4)	0.040 (3)	−0.007 (3)	0.001 (3)	0.001 (3)
C9	0.046 (4)	0.070 (4)	0.047 (4)	−0.004 (3)	0.002 (3)	−0.012 (3)
C10	0.059 (4)	0.070 (4)	0.043 (4)	−0.014 (4)	0.002 (3)	−0.010 (3)
C11	0.053 (4)	0.060 (4)	0.046 (4)	0.001 (3)	0.012 (3)	−0.002 (3)
C12	0.048 (4)	0.057 (4)	0.043 (3)	−0.007 (3)	0.008 (3)	−0.001 (3)
C13	0.046 (4)	0.070 (4)	0.052 (4)	0.000 (3)	0.004 (3)	−0.010 (3)
C14	0.056 (5)	0.080 (5)	0.064 (5)	0.002 (4)	0.004 (4)	−0.003 (4)
C15	0.074 (6)	0.072 (5)	0.060 (5)	0.019 (4)	0.009 (4)	0.001 (4)
C16	0.069 (5)	0.065 (4)	0.057 (4)	−0.002 (4)	0.013 (4)	0.002 (4)

Geometric parameters (Å, º) top

Br1—C6	1.889 (6)	C5—H5	0.9500
Br2—C2	1.887 (7)	C7—C8	1.437 (9)
Br3—C4	1.890 (7)	C7—C12	1.448 (9)
Pd1—O1	1.972 (5)	C8—C9	1.452 (10)
Pd1—O1ⁱ	1.972 (5)	C9—C10	1.346 (10)
Pd1—N1ⁱ	2.004 (5)	C9—H9	0.9500
Pd1—N1	2.004 (5)	C10—C11	1.432 (10)
O1—C8	1.268 (8)	C10—H10	0.9500
N1—N2	1.279 (8)	C11—C12	1.406 (10)
N1—C1	1.422 (8)	C11—C16	1.409 (11)
N2—C7	1.356 (8)	C12—C13	1.406 (10)
C1—C6	1.365 (9)	C13—C14	1.362 (11)
C1—C2	1.410 (9)	C13—H13	0.9500
C2—C3	1.393 (9)	C14—C15	1.405 (12)
C3—C4	1.367 (10)	C14—H14	0.9500
C3—H3	0.9500	C15—C16	1.355 (11)
C4—C5	1.390 (10)	C15—H15	0.9500
C5—C6	1.394 (9)	C16—H16	0.9500

O1—Pd1—O1ⁱ	180.0	N2—C7—C12	114.7 (6)
O1—Pd1—N1ⁱ	88.7 (2)	C8—C7—C12	120.1 (6)
O1ⁱ—Pd1—N1ⁱ	91.3 (2)	O1—C8—C7	127.3 (6)
O1—Pd1—N1	91.3 (2)	O1—C8—C9	115.9 (6)
O1ⁱ—Pd1—N1	88.7 (2)	C7—C8—C9	116.8 (6)
N1ⁱ—Pd1—N1	180.0	C10—C9—C8	122.0 (7)
C8—O1—Pd1	124.6 (4)	C10—C9—H9	119.0
N2—N1—C1	112.0 (5)	C8—C9—H9	119.0
N2—N1—Pd1	127.7 (4)	C9—C10—C11	122.3 (6)
C1—N1—Pd1	120.1 (4)	C9—C10—H10	118.9
N1—N2—C7	123.9 (5)	C11—C10—H10	118.9
C6—C1—C2	117.1 (6)	C12—C11—C16	120.3 (7)
C6—C1—N1	122.3 (6)	C12—C11—C10	118.3 (6)
C2—C1—N1	120.6 (6)	C16—C11—C10	121.4 (7)
C3—C2—C1	121.7 (6)	C13—C12—C11	117.7 (6)
C3—C2—Br2	119.0 (5)	C13—C12—C7	121.9 (6)
C1—C2—Br2	119.3 (5)	C11—C12—C7	120.4 (6)
C4—C3—C2	118.2 (6)	C14—C13—C12	120.6 (7)
C4—C3—H3	120.9	C14—C13—H13	119.7
C2—C3—H3	120.9	C12—C13—H13	119.7
C3—C4—C5	122.5 (6)	C13—C14—C15	121.7 (8)
C3—C4—Br3	119.5 (5)	C13—C14—H14	119.1
C5—C4—Br3	118.0 (5)	C15—C14—H14	119.1
C4—C5—C6	117.2 (6)	C16—C15—C14	118.7 (8)
C4—C5—H5	121.4	C16—C15—H15	120.7
C6—C5—H5	121.4	C14—C15—H15	120.7
C1—C6—C5	123.3 (6)	C15—C16—C11	120.9 (7)
C1—C6—Br1	119.2 (5)	C15—C16—H16	119.5
C5—C6—Br1	117.5 (5)	C11—C16—H16	119.5
N2—C7—C8	125.2 (6)

C1—N1—N2—C7	176.7 (6)	Pd1—O1—C8—C9	−177.0 (5)
Pd1—N1—N2—C7	1.8 (9)	N2—C7—C8—O1	0.2 (11)
N2—N1—C1—C6	−77.8 (7)	C12—C7—C8—O1	−179.5 (6)
Pd1—N1—C1—C6	97.6 (6)	N2—C7—C8—C9	179.0 (6)
N2—N1—C1—C2	103.1 (7)	C12—C7—C8—C9	−0.7 (9)
Pd1—N1—C1—C2	−81.6 (6)	O1—C8—C9—C10	176.2 (7)
C6—C1—C2—C3	2.2 (9)	C7—C8—C9—C10	−2.7 (10)
N1—C1—C2—C3	−178.6 (6)	C8—C9—C10—C11	2.8 (11)
C6—C1—C2—Br2	−180.0 (5)	C9—C10—C11—C12	0.7 (11)
N1—C1—C2—Br2	−0.8 (8)	C9—C10—C11—C16	178.4 (7)
C1—C2—C3—C4	−0.1 (10)	C16—C11—C12—C13	−2.3 (10)
Br2—C2—C3—C4	−178.0 (5)	C10—C11—C12—C13	175.4 (7)
C2—C3—C4—C5	−1.4 (11)	C16—C11—C12—C7	178.2 (6)
C2—C3—C4—Br3	178.6 (5)	C10—C11—C12—C7	−4.1 (10)
C3—C4—C5—C6	0.8 (10)	N2—C7—C12—C13	4.8 (9)
Br3—C4—C5—C6	−179.2 (5)	C8—C7—C12—C13	−175.4 (6)
C2—C1—C6—C5	−2.9 (10)	N2—C7—C12—C11	−175.7 (6)
N1—C1—C6—C5	177.9 (6)	C8—C7—C12—C11	4.1 (9)
C2—C1—C6—Br1	176.4 (5)	C11—C12—C13—C14	−0.8 (11)
N1—C1—C6—Br1	−2.8 (8)	C7—C12—C13—C14	178.7 (7)
C4—C5—C6—C1	1.5 (10)	C12—C13—C14—C15	2.6 (13)
C4—C5—C6—Br1	−177.8 (5)	C13—C14—C15—C16	−1.2 (13)
N1—N2—C7—C8	−2.2 (10)	C14—C15—C16—C11	−2.0 (12)
N1—N2—C7—C12	177.6 (6)	C12—C11—C16—C15	3.8 (11)
Pd1—O1—C8—C7	1.8 (10)	C10—C11—C16—C15	−173.9 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of ring C1-C6.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···Cg2ⁱⁱ	0.95	2.70	3.371 (8)	128

Symmetry code: (ii) x+1/2, −y+3/2, z+1/2.

Acknowledgements

The authors are grateful to the Algerian Ministry of Higher Education and Scientific Research, the Algerian Directorate General for Scientific Research and Technological Development, and the University of Constantine for financial support.

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Volume 72| Part 8| August 2016| Pages 1093-1098

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tri­bromo­phen­yl)diazen­yl]naphthalen-2-ol

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement details

Supporting information

Acknowledgements

References

research communications

Crystal structures of a copper(II) and the isotypic nickel(II) and palladium(II) complexes of the ligand (E)-1-[(2,4,6-tribromophenyl)diazenyl]naphthalen-2-ol

3. Supramolecular features