Bis[tris(propane-1,3-diamine-κ2N,N′)­nickel(II)] di­aqua­bis(propane-1,3-di­amine-κ2N,N′)nickel(II) hexa­bromide dihydrate

Yangui, A.; Rekik, W.; Elleuch, S.; Abid, Y.

doi:10.1107/S1600536814011052

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Pages m227-m228

doi:10.1107/S1600536814011052

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Bis[tris(propane-1,3-diamine-κ²N,N′)nickel(II)] diaquabis(propane-1,3-diamine-κ²N,N′)nickel(II) hexabromide dihydrate

Aymen Yangui,^a Walid Rekik,^b ^* Slim Elleuch ^a and Younes Abid ^a

^aLaboratoire de Physique Appliquée, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3018 Sfax, Tunisia, and ^bLaboratoire Physico-Chimie de l'Etat Solide, Département de Chimie, Faculté des Sciences de Sfax, Université de Sfax, BP 1171, 3018 Sfax, Tunisia
^*Correspondence e-mail: w_rekik@alinto.com

(Received 19 March 2014; accepted 13 May 2014; online 21 May 2014)

In the title compound, [Ni(C₃H₁₀N₂)₃]₂[Ni(C₃H₁₀N₂)₂(H₂O)₂]Br₆·2H₂O, one Ni²⁺ cation, located on an inversion centre, is coordinated by four N atoms from two ligands and by two water O atoms. The other Ni²⁺ cation, located in a general position, is coordinated by six N atoms from three ligands. In both cases, the Ni²⁺ cation has an octahedral coordination environment. The overall structural cohesion is ensured by three types of hydrogen bonds, N—H⋯Br, O—H⋯Br and O—H⋯O, which connect the two types of complex cations, the bromide counter-anions and the lattice water molecules into a three-dimensional network.

CCDC reference: 1002808

Related literature

For the multiple coordination modes of amine derivatives as ligands to metal ions, see: Manzur et al. (2007 ); Ismayilov et al. (2007 ); Austria et al. (2007 ). For control of the aggregation of molecules or ions in the solid state in crystal engineering, see: Burrows (2004 ). For hydrogen bonding in bifunctional ligands, see: Simard et al. (1991 ); Zerkowski & Whitesides (1994 ).

Experimental

Crystal data

[Ni(C₃H₁₀N₂)₃]₂[Ni(C₃H₁₀N₂)₂(H₂O)₂]Br₆·2H₂O
M_r = 1320.57
Triclinic, $[P \overline 1]$
a = 8.760 (5) Å
b = 13.327 (5) Å
c = 13.387 (5) Å
α = 107.774 (5)°
β = 109.045 (5)°
γ = 99.504 (5)°
V = 1344.6 (11) Å³
Z = 1
Mo Kα radiation
μ = 5.54 mm⁻¹
T = 296 K
0.36 × 0.30 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: analytical (de Meulenaer & Tompa, 1965 ) T_min = 0.215, T_max = 0.330
17594 measured reflections
8674 independent reflections
5022 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.084
S = 1.00
8674 reflections
257 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.84 (2)	1.98 (2)	2.805 (4)	169 (4)
O1—H2⋯Br3ⁱ	0.84 (2)	2.37 (2)	3.208 (3)	170 (3)
O2—H4⋯Br2	0.84 (2)	2.55 (2)	3.327 (3)	154 (4)
O2—H3⋯Br1	0.83 (2)	2.61 (2)	3.443 (3)	174 (3)
N1—H1A⋯Br2ⁱⁱ	0.97	2.58	3.541 (3)	170
N1—H1B⋯Br3ⁱ	0.97	2.90	3.699 (3)	141
N2—H2D⋯Br3ⁱⁱⁱ	0.97	2.77	3.630 (3)	149
N2—H2C⋯Br2	0.97	3.02	3.720 (3)	130
N3—H3A⋯Br3	0.97	2.73	3.467 (3)	133
N3—H3B⋯Br2ⁱⁱⁱ	0.97	2.70	3.544 (3)	146
N4—H4A⋯Br1^iv	0.97	2.70	3.644 (3)	163
N4—H4B⋯Br3^v	0.97	2.72	3.646 (3)	161
N5—H5A⋯Br1^vi	0.97	2.64	3.488 (2)	146
N5—H5B⋯Br2ⁱⁱⁱ	0.97	2.63	3.537 (3)	156
N6—H6A⋯Br1	0.97	2.49	3.445 (3)	170
N6—H6B⋯Br1^iv	0.97	2.55	3.504 (3)	169
N7—H7B⋯Br2ⁱⁱⁱ	0.97	2.75	3.615 (3)	149
N7—H7A⋯Br2	0.97	2.99	3.726 (3)	133
N8—H8A⋯Br3^v	0.97	2.59	3.558 (3)	175
N8—H8B⋯Br1	0.97	2.85	3.768 (3)	159
Symmetry codes: (i) x, y-1, z; (ii) -x, -y, -z; (iii) -x, -y+1, -z; (iv) -x+1, -y+1, -z+1; (v) -x+1, -y+2, -z+1; (vi) x-1, y, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ); data reduction: HKL DENZO (Otwinowski & Minor 1997) and HKL SCALEPACK; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1002808

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814011052/rk2424sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814011052/rk2424Isup2.hkl

checkCIF report

Comment top

Compounds having specific functional groups have received considerable attention due to their particular properties and applications. For example, derivatives of the amino acids have a biological activity and amine derivatives have potential ability to form metal–organic frameworks because of their multiple coordination modes as ligands to metal ions (Austria et al., 2007; Ismayilov et al., 2007; Manzur et al., 2007). The use of hydrogen bonds to control the aggregation of molecules or ions in the solid state is a key tool in crystal engineering (Burrows, 2004). Although such concepts were originally developed for organic systems, many studies have extended these ideas into the inorganic domain by using bifunctional ligands that are capable of simultaneously coordinating to a metal centre and presenting one or more hydrogen bonding (Simard et al., 1991; Zerkowski et al., 1994). In this context, we report here the chemical preparation and the crystal structure of a novel hybrid material using nickel as transition metal presenting the following formula [Ni(C₃N₂H₁₀)₂(H₂O)₂][Ni(C₃N₂H₁₀)₃]₂Br₆·2H₂O, (I). The asymmetric unit of I, represented in Fig. 1, contains two crystallographically independent nickel atoms. The first one occupies a general position and it is coordinated by three 1,3–diaminopropane molecules amine, which are bidentate ligands. The second type of nickel atom lies in a special position on inversion centre and it is coordinated by one molecule amine and one water molecule and their symmetric by the the inversion centre. Consequently, the nickel atoms, in this compound, adopt two different octahedral coordination. The asymmetric unit of I conatins also two free water molecules and three bromine ions. As it can be seen in Fig. 2, the cohesion of the crystal structure is ensured by three types of hydrogen bonds, N—H···Br, O—H···Br and O—H···O, established between the different entities ginving rise to a three dimensional H–bonds network.

Related literature top

For the multiple coordination modes of amine derivatives as ligands to metal ions, see: Manzur et al. (2007); Ismayilov et al. (2007); Austria et al. (2007). For control of the aggregation of molecules or ions in the solid state in crystal engineering, see: Burrows (2004). For hydrogen bonding in bifunctional ligands, see: Simard et al. (1991); Zerkowski & Whitesides (1994).

Experimental top

The title compound is resulting from a chemical reaction between three reagents: 1,3–diaminopropane (C₃H₁₀N₂), hydrobromic acid (HBr) and nickel bromide (NiBr₂). The 1 mmol of NiBr₂ and 1 mmol of the diamine with excess of HBr were mixed in the DMF solvent. The obtained solution is kept at room temperature. After 4 days, purple platelets were formed. The purity of the product was improved by a second recrystallization.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and HKL SCALEPACK (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Asymmetric unit of the structure of I extended by symmetry to give complete octahedron environment nickel atom. Displacement ellipsoids are presented at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) -x, -y, -z.
	Fig. 2. Projection of the structure of I along the a axis.

Bis[tris(propane-1,3-diamine-κ²N,N')nickel(II)] diaquabis(propane-1,3-diamine-κ²N,N')nickel(II) hexabromide dihydrate top

Crystal data top

[Ni(C₃H₁₀N₂)₃]₂[Ni(C₃H₁₀N₂)₂(H₂O)₂]Br₆·2H₂O	Z = 1
M_r = 1320.57	F(000) = 670
Triclinic, P1	D_x = 1.631 Mg m⁻³
a = 8.760 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.327 (5) Å	Cell parameters from 17594 reflections
c = 13.387 (5) Å	θ = 1.7–31.2°
α = 107.774 (5)°	µ = 5.54 mm⁻¹
β = 109.045 (5)°	T = 296 K
γ = 99.504 (5)°	Pellets, purple
V = 1344.6 (11) Å³	0.36 × 0.30 × 0.16 mm

Data collection top

Nonius KappaCCD diffractometer	8674 independent reflections
Radiation source: fine–focus sealed tube	5022 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.028
Detector resolution: 9 pixels mm^-1	θ_max = 31.2°, θ_min = 1.7°
rotation images, thick slices scans	h = −12→12
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	k = −19→18
T_min = 0.215, T_max = 0.330	l = −19→18
17594 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0337P)² + 0.1194P] where P = (F_o² + 2F_c²)/3
8674 reflections	(Δ/σ)_max = 0.001
257 parameters	Δρ_max = 0.90 e Å⁻³
6 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Ni(C₃H₁₀N₂)₃]₂[Ni(C₃H₁₀N₂)₂(H₂O)₂]Br₆·2H₂O	γ = 99.504 (5)°
M_r = 1320.57	V = 1344.6 (11) Å³
Triclinic, P1	Z = 1
a = 8.760 (5) Å	Mo Kα radiation
b = 13.327 (5) Å	µ = 5.54 mm⁻¹
c = 13.387 (5) Å	T = 296 K
α = 107.774 (5)°	0.36 × 0.30 × 0.16 mm
β = 109.045 (5)°

Data collection top

Nonius KappaCCD diffractometer	8674 independent reflections
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	5022 reflections with I > 2σ(I)
T_min = 0.215, T_max = 0.330	R_int = 0.028
17594 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	6 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.90 e Å⁻³
8674 reflections	Δρ_min = −0.74 e Å⁻³
257 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F², conventional R–factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.69831 (4)	0.50049 (3)	0.37689 (3)	0.05784 (10)
Br3	0.38496 (5)	1.04327 (3)	0.31879 (3)	0.07285 (12)
Ni1	0.0000	0.0000	0.0000	0.03393 (11)
Ni2	0.24711 (4)	0.65812 (2)	0.34338 (3)	0.03374 (9)
N3	0.1826 (3)	0.80148 (18)	0.3275 (2)	0.0479 (6)
H3A	0.2872	0.8609	0.3623	0.057*
H3B	0.1356	0.7875	0.2464	0.057*
N4	0.2454 (3)	0.71517 (19)	0.51262 (19)	0.0465 (6)
H4A	0.2339	0.6523	0.5346	0.056*
H4B	0.3555	0.7668	0.5650	0.056*
N5	−0.0146 (3)	0.56993 (17)	0.26203 (19)	0.0424 (5)
H5A	−0.0588	0.5801	0.3209	0.051*
H5B	−0.0703	0.6044	0.2122	0.051*
N6	0.3057 (3)	0.51614 (18)	0.3677 (2)	0.0491 (6)
H6A	0.4190	0.5213	0.3709	0.059*
H6B	0.3108	0.5223	0.4429	0.059*
N7	0.2549 (3)	0.6107 (2)	0.1765 (2)	0.0487 (6)
H7A	0.2807	0.5409	0.1602	0.058*
H7B	0.1415	0.5965	0.1215	0.058*
N8	0.5159 (3)	0.7397 (2)	0.4153 (2)	0.0527 (6)
H8A	0.5440	0.7955	0.4901	0.063*
H8B	0.5733	0.6855	0.4278	0.063*
C9	0.1995 (5)	0.4044 (2)	0.2877 (3)	0.0694 (10)
H9A	0.2356	0.3520	0.3198	0.083*
H9B	0.2153	0.3886	0.2167	0.083*
O2	0.4632 (4)	0.2799 (2)	0.1212 (3)	0.0724 (7)
C7	−0.0660 (4)	0.4506 (3)	0.1937 (3)	0.0608 (9)
H7C	−0.0349	0.4388	0.1287	0.073*
H7D	−0.1878	0.4215	0.1644	0.073*
C8	0.0148 (5)	0.3893 (3)	0.2623 (3)	0.0762 (11)
H8C	−0.0453	0.3114	0.2213	0.091*
H8D	0.0017	0.4128	0.3343	0.091*
C12	0.3715 (4)	0.6846 (3)	0.1526 (3)	0.0668 (10)
H12A	0.3364	0.7505	0.1559	0.080*
H12B	0.3629	0.6478	0.0754	0.080*
C10	0.5908 (4)	0.7931 (3)	0.3539 (3)	0.0670 (10)
H10A	0.7124	0.8206	0.3962	0.080*
H10B	0.5493	0.8558	0.3514	0.080*
C11	0.5517 (4)	0.7177 (3)	0.2342 (3)	0.0700 (10)
H11A	0.6220	0.7537	0.2047	0.084*
H11B	0.5825	0.6515	0.2365	0.084*
C6	0.1161 (4)	0.7689 (3)	0.5323 (3)	0.0581 (8)
H6C	0.1345	0.7911	0.6124	0.070*
H6D	0.0048	0.7160	0.4872	0.070*
C5	0.1219 (4)	0.8689 (2)	0.5008 (3)	0.0602 (9)
H5C	0.0513	0.9085	0.5289	0.072*
H5D	0.2369	0.9174	0.5397	0.072*
C4	0.0649 (4)	0.8433 (3)	0.3750 (3)	0.0561 (8)
H4C	−0.0453	0.7888	0.3348	0.067*
H4D	0.0530	0.9097	0.3614	0.067*
O1	0.2016 (3)	0.13735 (17)	0.13311 (19)	0.0517 (5)
N1	−0.0659 (3)	−0.03912 (19)	0.1248 (2)	0.0458 (6)
H1A	−0.0704	−0.1156	0.1105	0.055*
H1B	0.0263	0.0048	0.1986	0.055*
C2	−0.2457 (4)	0.0852 (2)	0.1389 (3)	0.0557 (8)
H2A	−0.1409	0.1416	0.1933	0.067*
H2B	−0.3326	0.0984	0.1668	0.067*
C1	−0.2248 (4)	−0.0249 (2)	0.1366 (3)	0.0566 (8)
H1C	−0.2239	−0.0320	0.2068	0.068*
H1D	−0.3203	−0.0828	0.0731	0.068*
C3	−0.2917 (4)	0.0979 (3)	0.0259 (3)	0.0570 (8)
H3C	−0.3864	0.0353	−0.0318	0.068*
H3D	−0.3278	0.1637	0.0321	0.068*
N2	−0.1514 (3)	0.10575 (18)	−0.0122 (2)	0.0446 (6)
H2C	−0.0768	0.1806	0.0304	0.053*
H2D	−0.1994	0.0965	−0.0919	0.053*
Br2	0.12791 (4)	0.32662 (3)	−0.04291 (3)	0.05752 (10)
H2	0.261 (4)	0.119 (3)	0.184 (2)	0.070 (12)*
H1	0.270 (4)	0.185 (3)	0.128 (3)	0.108 (17)*
H3	0.521 (4)	0.330 (2)	0.1855 (18)	0.084 (14)*
H4	0.405 (5)	0.307 (3)	0.079 (3)	0.111 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0568 (2)	0.0720 (2)	0.0668 (2)	0.02667 (17)	0.03530 (17)	0.04018 (18)
Br3	0.0733 (2)	0.04978 (19)	0.0567 (2)	−0.00541 (16)	−0.01077 (18)	0.02214 (16)
Ni1	0.0335 (2)	0.0323 (2)	0.0336 (3)	0.00772 (19)	0.0118 (2)	0.01223 (19)
Ni2	0.03470 (18)	0.03048 (17)	0.03582 (19)	0.00762 (13)	0.01576 (15)	0.01176 (14)
N3	0.0499 (14)	0.0408 (13)	0.0612 (16)	0.0171 (11)	0.0269 (13)	0.0235 (12)
N4	0.0570 (15)	0.0414 (13)	0.0385 (13)	0.0122 (11)	0.0188 (12)	0.0137 (10)
N5	0.0420 (13)	0.0409 (12)	0.0389 (13)	0.0028 (10)	0.0187 (11)	0.0106 (10)
N6	0.0630 (16)	0.0460 (14)	0.0553 (16)	0.0250 (12)	0.0345 (14)	0.0252 (12)
N7	0.0516 (15)	0.0519 (14)	0.0452 (14)	0.0109 (12)	0.0265 (12)	0.0169 (12)
N8	0.0403 (14)	0.0534 (15)	0.0570 (16)	0.0084 (12)	0.0165 (12)	0.0178 (12)
C9	0.108 (3)	0.0420 (18)	0.074 (2)	0.0338 (19)	0.049 (2)	0.0228 (17)
O2	0.0647 (17)	0.0603 (16)	0.081 (2)	0.0147 (14)	0.0234 (15)	0.0215 (16)
C7	0.059 (2)	0.0519 (18)	0.051 (2)	−0.0073 (16)	0.0266 (17)	0.0003 (15)
C8	0.099 (3)	0.0324 (16)	0.087 (3)	−0.0027 (18)	0.047 (2)	0.0101 (17)
C12	0.063 (2)	0.089 (3)	0.071 (2)	0.022 (2)	0.039 (2)	0.048 (2)
C10	0.0399 (17)	0.068 (2)	0.095 (3)	0.0065 (16)	0.0271 (19)	0.039 (2)
C11	0.059 (2)	0.093 (3)	0.091 (3)	0.028 (2)	0.049 (2)	0.055 (2)
C6	0.064 (2)	0.064 (2)	0.0399 (17)	0.0155 (17)	0.0264 (16)	0.0068 (15)
C5	0.060 (2)	0.0494 (18)	0.057 (2)	0.0242 (16)	0.0199 (17)	0.0008 (15)
C4	0.0552 (19)	0.0573 (19)	0.066 (2)	0.0295 (16)	0.0289 (17)	0.0248 (16)
O1	0.0493 (13)	0.0416 (12)	0.0456 (13)	0.0006 (10)	0.0058 (11)	0.0136 (10)
N1	0.0493 (14)	0.0446 (13)	0.0431 (14)	0.0090 (11)	0.0194 (12)	0.0181 (11)
C2	0.0550 (19)	0.0469 (17)	0.063 (2)	0.0095 (15)	0.0342 (17)	0.0097 (15)
C1	0.059 (2)	0.0500 (18)	0.061 (2)	0.0045 (15)	0.0353 (17)	0.0156 (15)
C3	0.0442 (17)	0.0560 (19)	0.068 (2)	0.0177 (15)	0.0221 (16)	0.0183 (16)
N2	0.0412 (13)	0.0419 (13)	0.0522 (15)	0.0136 (11)	0.0179 (12)	0.0204 (11)
Br2	0.0688 (2)	0.05470 (19)	0.04544 (18)	0.01940 (16)	0.01714 (16)	0.02018 (14)

Geometric parameters (Å, º) top

Ni1—N2ⁱ	2.095 (2)	C7—H7C	0.9700
Ni1—N2	2.095 (2)	C7—H7D	0.9700
Ni1—N1ⁱ	2.112 (2)	C8—H8C	0.9700
Ni1—N1	2.112 (2)	C8—H8D	0.9700
Ni1—O1ⁱ	2.129 (2)	C12—C11	1.493 (5)
Ni1—O1	2.129 (2)	C12—H12A	0.9700
Ni2—N5	2.127 (2)	C12—H12B	0.9700
Ni2—N6	2.130 (2)	C10—C11	1.497 (5)
Ni2—N3	2.131 (2)	C10—H10A	0.9700
Ni2—N7	2.155 (2)	C10—H10B	0.9700
Ni2—N4	2.165 (2)	C11—H11A	0.9700
Ni2—N8	2.166 (3)	C11—H11B	0.9700
N3—C4	1.476 (4)	C6—C5	1.513 (4)
N3—H3A	0.9700	C6—H6C	0.9700
N3—H3B	0.9700	C6—H6D	0.9700
N4—C6	1.487 (4)	C5—C4	1.499 (4)
N4—H4A	0.9700	C5—H5C	0.9700
N4—H4B	0.9700	C5—H5D	0.9700
N5—C7	1.475 (4)	C4—H4C	0.9700
N5—H5A	0.9700	C4—H4D	0.9700
N5—H5B	0.9700	O1—H2	0.843 (17)
N6—C9	1.465 (4)	O1—H1	0.839 (18)
N6—H6A	0.9700	N1—C1	1.486 (4)
N6—H6B	0.9700	N1—H1A	0.9700
N7—C12	1.481 (4)	N1—H1B	0.9700
N7—H7A	0.9700	C2—C1	1.501 (4)
N7—H7B	0.9700	C2—C3	1.504 (5)
N8—C10	1.472 (4)	C2—H2A	0.9700
N8—H8A	0.9700	C2—H2B	0.9700
N8—H8B	0.9700	C1—H1C	0.9700
C9—C8	1.505 (5)	C1—H1D	0.9700
C9—H9A	0.9700	C3—N2	1.476 (4)
C9—H9B	0.9700	C3—H3C	0.9700
O2—H3	0.834 (17)	C3—H3D	0.9700
O2—H4	0.841 (17)	N2—H2C	0.9700
C7—C8	1.495 (5)	N2—H2D	0.9700

N2ⁱ—Ni1—N2	180.0	C8—C7—H7D	109.2
N2ⁱ—Ni1—N1ⁱ	93.54 (9)	H7C—C7—H7D	107.9
N2—Ni1—N1ⁱ	86.46 (9)	C7—C8—C9	115.0 (3)
N2ⁱ—Ni1—N1	86.46 (9)	C7—C8—H8C	108.5
N2—Ni1—N1	93.54 (9)	C9—C8—H8C	108.5
N1ⁱ—Ni1—N1	180.0	C7—C8—H8D	108.5
N2ⁱ—Ni1—O1ⁱ	88.38 (10)	C9—C8—H8D	108.5
N2—Ni1—O1ⁱ	91.62 (10)	H8C—C8—H8D	107.5
N1ⁱ—Ni1—O1ⁱ	89.33 (10)	N7—C12—C11	113.5 (3)
N1—Ni1—O1ⁱ	90.67 (10)	N7—C12—H12A	108.9
N2ⁱ—Ni1—O1	91.62 (10)	C11—C12—H12A	108.9
N2—Ni1—O1	88.38 (10)	N7—C12—H12B	108.9
N1ⁱ—Ni1—O1	90.67 (10)	C11—C12—H12B	108.9
N1—Ni1—O1	89.33 (10)	H12A—C12—H12B	107.7
O1ⁱ—Ni1—O1	180.0	N8—C10—C11	113.4 (3)
N5—Ni2—N6	90.12 (10)	N8—C10—H10A	108.9
N5—Ni2—N3	88.80 (10)	C11—C10—H10A	108.9
N6—Ni2—N3	176.31 (9)	N8—C10—H10B	108.9
N5—Ni2—N7	88.31 (9)	C11—C10—H10B	108.9
N6—Ni2—N7	93.53 (9)	H10A—C10—H10B	107.7
N3—Ni2—N7	89.98 (10)	C12—C11—C10	115.1 (3)
N5—Ni2—N4	93.56 (9)	C12—C11—H11A	108.5
N6—Ni2—N4	89.02 (9)	C10—C11—H11A	108.5
N3—Ni2—N4	87.51 (9)	C12—C11—H11B	108.5
N7—Ni2—N4	176.84 (9)	C10—C11—H11B	108.5
N5—Ni2—N8	175.67 (9)	H11A—C11—H11B	107.5
N6—Ni2—N8	88.21 (10)	N4—C6—C5	112.3 (3)
N3—Ni2—N8	93.10 (10)	N4—C6—H6C	109.1
N7—Ni2—N8	87.80 (10)	C5—C6—H6C	109.1
N4—Ni2—N8	90.41 (10)	N4—C6—H6D	109.1
C4—N3—Ni2	120.60 (19)	C5—C6—H6D	109.1
C4—N3—H3A	107.2	H6C—C6—H6D	107.9
Ni2—N3—H3A	107.2	C4—C5—C6	114.6 (2)
C4—N3—H3B	107.2	C4—C5—H5C	108.6
Ni2—N3—H3B	107.2	C6—C5—H5C	108.6
H3A—N3—H3B	106.8	C4—C5—H5D	108.6
C6—N4—Ni2	119.51 (19)	C6—C5—H5D	108.6
C6—N4—H4A	107.4	H5C—C5—H5D	107.6
Ni2—N4—H4A	107.4	N3—C4—C5	113.1 (3)
C6—N4—H4B	107.4	N3—C4—H4C	109.0
Ni2—N4—H4B	107.4	C5—C4—H4C	109.0
H4A—N4—H4B	107.0	N3—C4—H4D	109.0
C7—N5—Ni2	118.69 (19)	C5—C4—H4D	109.0
C7—N5—H5A	107.6	H4C—C4—H4D	107.8
Ni2—N5—H5A	107.6	Ni1—O1—H2	112 (2)
C7—N5—H5B	107.6	Ni1—O1—H1	129 (3)
Ni2—N5—H5B	107.6	H2—O1—H1	105 (2)
H5A—N5—H5B	107.1	C1—N1—Ni1	120.33 (19)
C9—N6—Ni2	121.6 (2)	C1—N1—H1A	107.2
C9—N6—H6A	106.9	Ni1—N1—H1A	107.2
Ni2—N6—H6A	106.9	C1—N1—H1B	107.2
C9—N6—H6B	106.9	Ni1—N1—H1B	107.2
Ni2—N6—H6B	106.9	H1A—N1—H1B	106.9
H6A—N6—H6B	106.7	C1—C2—C3	115.4 (3)
C12—N7—Ni2	120.5 (2)	C1—C2—H2A	108.4
C12—N7—H7A	107.2	C3—C2—H2A	108.4
Ni2—N7—H7A	107.2	C1—C2—H2B	108.4
C12—N7—H7B	107.2	C3—C2—H2B	108.4
Ni2—N7—H7B	107.2	H2A—C2—H2B	107.5
H7A—N7—H7B	106.8	N1—C1—C2	111.9 (2)
C10—N8—Ni2	120.6 (2)	N1—C1—H1C	109.2
C10—N8—H8A	107.2	C2—C1—H1C	109.2
Ni2—N8—H8A	107.2	N1—C1—H1D	109.2
C10—N8—H8B	107.2	C2—C1—H1D	109.2
Ni2—N8—H8B	107.2	H1C—C1—H1D	107.9
H8A—N8—H8B	106.8	N2—C3—C2	113.4 (3)
N6—C9—C8	112.7 (3)	N2—C3—H3C	108.9
N6—C9—H9A	109.1	C2—C3—H3C	108.9
C8—C9—H9A	109.1	N2—C3—H3D	108.9
N6—C9—H9B	109.1	C2—C3—H3D	108.9
C8—C9—H9B	109.1	H3C—C3—H3D	107.7
H9A—C9—H9B	107.8	C3—N2—Ni1	120.99 (18)
H3—O2—H4	109 (3)	C3—N2—H2C	107.1
N5—C7—C8	112.1 (3)	Ni1—N2—H2C	107.1
N5—C7—H7C	109.2	C3—N2—H2D	107.1
C8—C7—H7C	109.2	Ni1—N2—H2D	107.1
N5—C7—H7D	109.2	H2C—N2—H2D	106.8

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.84 (2)	1.98 (2)	2.805 (4)	169 (4)
O1—H2···Br3ⁱⁱ	0.84 (2)	2.37 (2)	3.208 (3)	170 (3)
O2—H4···Br2	0.84 (2)	2.55 (2)	3.327 (3)	154 (4)
O2—H3···Br1	0.83 (2)	2.61 (2)	3.443 (3)	174 (3)
N1—H1A···Br2ⁱ	0.97	2.58	3.541 (3)	170
N1—H1B···Br3ⁱⁱ	0.97	2.90	3.699 (3)	141
N2—H2D···Br3ⁱⁱⁱ	0.97	2.77	3.630 (3)	149
N2—H2C···Br2	0.97	3.02	3.720 (3)	130
N3—H3A···Br3	0.97	2.73	3.467 (3)	133
N3—H3B···Br2ⁱⁱⁱ	0.97	2.70	3.544 (3)	146
N4—H4A···Br1^iv	0.97	2.70	3.644 (3)	163
N4—H4B···Br3^v	0.97	2.72	3.646 (3)	161
N5—H5A···Br1^vi	0.97	2.64	3.488 (2)	146
N5—H5B···Br2ⁱⁱⁱ	0.97	2.63	3.537 (3)	156
N6—H6A···Br1	0.97	2.49	3.445 (3)	170
N6—H6B···Br1^iv	0.97	2.55	3.504 (3)	169
N7—H7B···Br2ⁱⁱⁱ	0.97	2.75	3.615 (3)	149
N7—H7A···Br2	0.97	2.99	3.726 (3)	133
N8—H8A···Br3^v	0.97	2.59	3.558 (3)	175
N8—H8B···Br1	0.97	2.85	3.768 (3)	159

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.839 (18)	1.98 (2)	2.805 (4)	169 (4)
O1—H2···Br3ⁱ	0.843 (17)	2.374 (17)	3.208 (3)	170 (3)
O2—H4···Br2	0.841 (17)	2.55 (2)	3.327 (3)	154 (4)
O2—H3···Br1	0.834 (17)	2.613 (19)	3.443 (3)	174 (3)
N1—H1A···Br2ⁱⁱ	0.97	2.58	3.541 (3)	170.4
N1—H1B···Br3ⁱ	0.97	2.90	3.699 (3)	140.8
N2—H2D···Br3ⁱⁱⁱ	0.97	2.77	3.630 (3)	148.5
N2—H2C···Br2	0.97	3.02	3.720 (3)	130.0
N3—H3A···Br3	0.97	2.73	3.467 (3)	132.7
N3—H3B···Br2ⁱⁱⁱ	0.97	2.70	3.544 (3)	146.2
N4—H4A···Br1^iv	0.97	2.70	3.644 (3)	163.2
N4—H4B···Br3^v	0.97	2.72	3.646 (3)	160.6
N5—H5A···Br1^vi	0.97	2.64	3.488 (2)	145.6
N5—H5B···Br2ⁱⁱⁱ	0.97	2.63	3.537 (3)	155.7
N6—H6A···Br1	0.97	2.49	3.445 (3)	169.9
N6—H6B···Br1^iv	0.97	2.55	3.504 (3)	169.3
N7—H7B···Br2ⁱⁱⁱ	0.97	2.75	3.615 (3)	148.9
N7—H7A···Br2	0.97	2.99	3.726 (3)	133.2
N8—H8A···Br3^v	0.97	2.59	3.558 (3)	174.9
N8—H8B···Br1	0.97	2.85	3.768 (3)	159.2

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

Acknowledgements

Grateful thanks are expressed to Tarak Gargouri (Université de Sfax, Faculté des Sciences de Sfax) for his assistance with the single-crystal X-ray diffraction data collection.

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