Crystal structure of bis­{N-[2-(di­methyl­amino)­eth­yl]quinolin-8-amine-κ3N,N′,N′′}nickel(II) dichloride 3.5-hydrate

Kariuki, B.M.; Al-Sudani, A.-R.H.

doi:10.1107/S1600536814019035

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages m339-m340

doi:10.1107/S1600536814019035

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Crystal structure of bis{N-[2-(dimethylamino)ethyl]quinolin-8-amine-κ³N,N′,N′′}nickel(II) dichloride 3.5-hydrate

Benson M. Kariuki ^a and Abdul-Razak H. Al-Sudani ^b ^*

^aSchool of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, and ^bDepartment of Chemistry, College of Science, Baghdad University for Women, Baghdad, Iraq
^*Correspondence e-mail: alsudani@uobaghdad.edu.iq

Edited by G. Smith, Queensland University of Technology, Australia (Received 10 August 2014; accepted 22 August 2014; online 30 August 2014)

In the title compound, [Ni(C₁₃H₁₇N₃)₂]Cl₂·3.5H₂O, the geometry of the NiN₆ complex cation is slightly distorted octahedral, with a facial arrangement of the two tridentate N-[2-(dimethylamino)ethyl]quinolin-8-amine ligands around the metal ion. The asymmetric unit consists of two independent complex half-molecules located on centres of inversion, together with two chloride counter-anions and 3.5 water molecules of solvation, one of which is disordered across an inversion centre. In the crystal, O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen-bonding interactions form a three-dimensional network structure.

Keywords: crystal structure; N-[2-(dimethylamino)ethyl]quinolin-8-amine; nickel(II) complex; hydrogen bonding.

CCDC reference: 1020674

1. Related literature

For background to N-containing ligands, including quinoline derivatives, see: Kizirian (2008 ); Miodragovic et al. (2008 ); Puviarasan et al. (2004 ); Singh et al. (2008 ); Zhang et al. (2009 ). For complexes incorporating N-[2-(dimethylamino)ethyl]quinolin-8-amine, see: Al-Sudani & Kariuki (2013 ); Al-Sudani (2014 ).

2. Experimental

2.1. Crystal data

[Ni(C₁₃H₁₇N₃)₂]Cl₂·3.5H₂O
M_r = 623.26
Triclinic, $[P \overline 1]$
a = 10.6940 (2) Å
b = 11.8612 (4) Å
c = 12.1088 (3) Å
α = 90.520 (1)°
β = 101.181 (2)°
γ = 102.259 (2)°
V = 1470.39 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 150 K
0.18 × 0.16 × 0.08 mm

2.1.2. Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.857, T_max = 0.933
10258 measured reflections
6714 independent reflections
5592 reflections with I > 2σ(I)
R_int = 0.023

2.1.3. Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.090
S = 1.03
6714 reflections
383 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl2	1.00	2.27	3.2038 (18)	155
N5—H5⋯Cl1	1.00	2.33	3.2715 (19)	156
O1—H1O1⋯O2ⁱ	0.83 (1)	1.71 (1)	2.541 (5)	173 (6)
O1—H2O1⋯O2ⁱⁱ	0.84 (1)	2.05 (2)	2.863 (5)	165 (6)
O2—H1O2⋯Cl2ⁱⁱⁱ	0.84 (1)	2.33 (1)	3.162 (3)	172 (4)
O2—H2O2⋯Cl1^iv	0.83 (1)	2.37 (2)	3.179 (2)	163 (4)
O3—H1O3⋯Cl2^v	0.85 (1)	2.38 (1)	3.222 (2)	174 (3)
O3—H2O3⋯Cl1^v	0.85 (1)	2.36 (1)	3.2008 (19)	170 (3)
O4—H1O4⋯O1^vi	0.85 (1)	1.91 (1)	2.755 (5)	177 (4)
O4—H2O4⋯Cl1	0.85 (1)	2.33 (1)	3.180 (3)	173 (3)
Symmetry codes: (i) x, y-1, z; (ii) -x, -y+1, -z+2; (iii) -x, -y+1, -z+1; (iv) x, y, z+1; (v) -x+1, -y+1, -z+1; (vi) x, y+1, z-1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2008 ), ORTEP-3 for Windows (Farrugia, 2012 ) and CHEMDRAW Ultra (Cambridge Soft, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1020674

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019035/zs2312sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814019035/zs2312Isup2.hkl

checkCIF report

Comment top

As stated previously, (Al-Sudani & Kariuki, 2013), metal complexes of N-containing ligands occupy an important position in coordination chemistry (Singh et al., 2008; Miodragovic et al., 2008; Zhang et al., 2009). Some quinoline-containing ligands show interesting biological activities (Puviarasan et al., 2004). 8-[2-(dimethylamino)ethylamino]quinoline (NN'N"), is an asymmetric and potentially tridentate chelating ligand with the same donor atoms. With zinc (Al-Sudani, 2014) and cadmium ions (Al-Sudani & Kariuki, 2013), it forms neutral 1:1 metal to ligand mole ratio complexes with monomeric distorted square-pyrimidal and dimeric distorted octahedral geometries, respectively.

In the nickel(II) complex with the ligand 8-[2-(dimethylamino)ethylamino] quinoline, the title compound, C₂₆H₃₄N₆Ni · 2Cl · 3.5(H₂O), is ionic with a 1:2 metal to ligand mole ratio and has a slightly distorted bis-tridentate NiN₆ octahedral coordination [Ni—N bond length range, 2.0777 (16)–2.2397 (17) Å] (Fig. 1). The asymmetric unit consists of two independent half molecules with the Ni²⁺ ions (Ni1 and Ni2) located on centres of inversion, as well as two chloride anions and 3.5 water molecules, one of which (O1) is disordered across an inversion centre. A network of O—H···O, O—H···Cl and N—H···Cl hydtrogen-bonding interactions are present in the crystal structure (Table 1) giving a three-dimensional network (Fig. 2). In the three complexes with this ligand (Zn, Cd and Ni), the unequivelant nitrogen donor atoms of the ligands are arranged facially around the metal ion.

Related literature top

For background to N-containing ligands, including quinoline derivatives, see: Kizirian (2008); Miodragovic et al. (2008); Puviarasan et al. (2004); Singh et al. (2008); Zhang et al.(2009). For complexes incorporating N-[2-(dimethylamino)ethyl]quinolin-8-amine, see: Al-Sudani & Kariuki (2013); Al-Sudani (2014).

Experimental top

To a stirred methanoic solution (30 ml) containing a slight excess of the ligand (NN'N") (0.9 g; 0.0042 mol) kept under a positive nitrogen pressure, a methanoic solution (20 ml) of NiCl₂ . 6H₂O (0.47 g; 0.002 mol) was slowly added. The resulting brownish violet solution was stirred at room temperature overnight. A small amount of anhydrous MgSO₄ was added and the reaction solution was stirred for a further one hour. After the removal of the drying agent by filtration, the solvent was removed by vacuum. The solid was washed twice with a small amount of diethyl ether (15 ml) to remove any of the unreacted ligand and was then dried under vacuum at 50 °C. The mass of the collected solid was 0.5 g which, based on the molecular formula of [Ni(NN'N")2] Cl₂ represented a yield of ca. 45%. A suitable light brown–violet block shaped crystal of the title complex was obtained via slow diffusion of diethyl ether into a small amount of an acetonitrile solution of the compound kept under an atmosphere of nitrogen gas. Single crystal X-ray structure determination has identified the complex as [Ni(NN'N")2] Cl₂·3.5H₂O. In the process of measuring the melting point, the colour of the crystalline brown–violet solid changed to pale green and finally to very dark green. The dark green material was identified as a bimetallic complex of the formula [Ni(NN'N")Cl₂]₂ which decomposed at ca. 240 °C.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008), ORTEP-3 for Windows (Farrugia, 2012) and CHEMDRAW Ultra (Cambridge Soft, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric of the title complex showing atom labels and 50% probability displacement ellipsoids. Hydrogen atoms have been omitted.
	Fig. 2. Packing in the crystal structure showing the O—H···O, O—H···Cl and N—H···Cl interactions as dotted lines.

Bis{N-[2-(dimethylamino)ethyl]quinolin-8-amine-κ³N,N',N''}nickel(II) dichloride 3.5-hydrate top

Crystal data top

[Ni(C₁₃H₁₇N₃)₂]Cl₂·3.5H2O	Z = 2
M_r = 623.26	F(000) = 658
Triclinic, P1	D_x = 1.408 Mg m⁻³
a = 10.6940 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8612 (4) Å	Cell parameters from 5592 reflections
c = 12.1088 (3) Å	θ = 2.0–25.2°
α = 90.520 (1)°	µ = 0.88 mm⁻¹
β = 101.181 (2)°	T = 150 K
γ = 102.259 (2)°	Block, violet
V = 1470.39 (7) Å³	0.18 × 0.16 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	6714 independent reflections
Radiation source: fine-focus sealed tube	5592 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
CCD slices, ω and ϕ scans	θ_max = 27.7°, θ_min = 2.0°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −13→13
T_min = 0.857, T_max = 0.933	k = −14→15
10258 measured reflections	l = −15→15

Refinement top

Refinement on F²	12 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0261P)² + 1.4643P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
6714 reflections	Δρ_max = 0.46 e Å⁻³
383 parameters	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Ni(C₁₃H₁₇N₃)₂]Cl₂·3.5H2O	γ = 102.259 (2)°
M_r = 623.26	V = 1470.39 (7) Å³
Triclinic, P1	Z = 2
a = 10.6940 (2) Å	Mo Kα radiation
b = 11.8612 (4) Å	µ = 0.88 mm⁻¹
c = 12.1088 (3) Å	T = 150 K
α = 90.520 (1)°	0.18 × 0.16 × 0.08 mm
β = 101.181 (2)°

Data collection top

Nonius KappaCCD diffractometer	6714 independent reflections
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	5592 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.933	R_int = 0.023
10258 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	12 restraints
wR(F²) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.46 e Å⁻³
6714 reflections	Δρ_min = −0.59 e Å⁻³
383 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.1605 (2)	−0.0934 (2)	0.70598 (18)	0.0262 (5)
H1	0.0799	−0.1382	0.7180	0.031*
C2	0.2745 (2)	−0.0947 (2)	0.78635 (19)	0.0335 (5)
H2	0.2703	−0.1398	0.8505	0.040*
C3	0.3911 (2)	−0.0301 (2)	0.7709 (2)	0.0336 (5)
H3	0.4685	−0.0283	0.8255	0.040*
C4	0.3964 (2)	0.0340 (2)	0.67356 (19)	0.0277 (5)
C5	0.27726 (19)	0.02971 (18)	0.59635 (17)	0.0212 (4)
C6	0.27629 (19)	0.09175 (18)	0.49678 (18)	0.0224 (4)
C7	0.3910 (2)	0.1567 (2)	0.4765 (2)	0.0302 (5)
H7	0.3908	0.1983	0.4098	0.036*
C8	0.5094 (2)	0.1622 (2)	0.5540 (2)	0.0358 (6)
H8	0.5881	0.2080	0.5391	0.043*
C9	0.5123 (2)	0.1027 (2)	0.6499 (2)	0.0340 (5)
H9	0.5928	0.1075	0.7012	0.041*
C10	0.1447 (2)	0.00486 (19)	0.31787 (17)	0.0254 (4)
H10A	0.2263	0.0272	0.2886	0.030*
H10B	0.0709	0.0142	0.2578	0.030*
C11	0.1257 (2)	−0.11934 (19)	0.34988 (18)	0.0248 (4)
H11A	0.1214	−0.1698	0.2831	0.030*
H11B	0.2010	−0.1288	0.4083	0.030*
C12	−0.1075 (2)	−0.1898 (2)	0.29630 (19)	0.0314 (5)
H12A	−0.0959	−0.2577	0.2559	0.047*
H12B	−0.1096	−0.1262	0.2454	0.047*
H12C	−0.1897	−0.2090	0.3233	0.047*
C13	0.0092 (2)	−0.25829 (19)	0.45980 (19)	0.0298 (5)
H13A	0.0202	−0.3208	0.4115	0.045*
H13B	−0.0719	−0.2827	0.4879	0.045*
H13C	0.0834	−0.2401	0.5237	0.045*
C14	0.4792 (2)	0.57059 (19)	0.24055 (17)	0.0241 (4)
H14	0.4000	0.5922	0.2081	0.029*
C15	0.5159 (2)	0.5735 (2)	0.35907 (18)	0.0279 (5)
H15	0.4634	0.5988	0.4049	0.034*
C16	0.6272 (2)	0.5397 (2)	0.40723 (18)	0.0285 (5)
H16	0.6525	0.5411	0.4870	0.034*
C17	0.7048 (2)	0.50270 (19)	0.33842 (17)	0.0239 (4)
C18	0.66485 (19)	0.50777 (17)	0.21999 (16)	0.0204 (4)
C19	0.7417 (2)	0.47741 (18)	0.14687 (17)	0.0215 (4)
C20	0.8527 (2)	0.43944 (19)	0.18998 (18)	0.0262 (5)
H20	0.9051	0.4199	0.1409	0.031*
C21	0.8896 (2)	0.4292 (2)	0.30789 (19)	0.0285 (5)
H21	0.9649	0.4001	0.3369	0.034*
C22	0.8183 (2)	0.4607 (2)	0.37999 (18)	0.0268 (5)
H22	0.8451	0.4544	0.4588	0.032*
C23	0.2283 (2)	0.4009 (2)	0.01160 (18)	0.0269 (5)
H23A	0.1344	0.3883	−0.0234	0.032*
H23B	0.2369	0.4071	0.0944	0.032*
C24	0.2821 (2)	0.2997 (2)	−0.02055 (19)	0.0278 (5)
H24A	0.2325	0.2276	0.0047	0.033*
H24B	0.2705	0.2922	−0.1036	0.033*
C25	0.4344 (2)	0.2817 (2)	0.15013 (18)	0.0282 (5)
H25A	0.3904	0.2006	0.1522	0.042*
H25B	0.3936	0.3307	0.1910	0.042*
H25C	0.5269	0.2920	0.1856	0.042*
C26	0.4790 (2)	0.2333 (2)	−0.0273 (2)	0.0321 (5)
H26A	0.5716	0.2419	0.0070	0.048*
H26B	0.4702	0.2500	−0.1072	0.048*
H26C	0.4323	0.1539	−0.0203	0.048*
Cl1	0.17945 (7)	0.69447 (6)	0.09796 (5)	0.04344 (16)
Cl2	0.17828 (6)	0.32313 (5)	0.30115 (5)	0.03642 (14)
N1	0.15965 (16)	−0.03312 (15)	0.61464 (14)	0.0205 (3)
N2	0.15207 (16)	0.08100 (15)	0.41938 (14)	0.0203 (3)
H2A	0.1392	0.1590	0.3958	0.024*
N3	0.00298 (16)	−0.15441 (15)	0.39384 (14)	0.0216 (4)
N4	0.54994 (16)	0.53923 (15)	0.17267 (14)	0.0211 (4)
N5	0.30146 (16)	0.51031 (16)	−0.02755 (14)	0.0220 (4)
H5	0.2917	0.5784	0.0167	0.026*
N6	0.42293 (17)	0.31473 (15)	0.03107 (14)	0.0235 (4)
Ni1	0.0000	0.0000	0.5000	0.01664 (9)
Ni2	0.5000	0.5000	0.0000	0.01794 (9)
O1	0.0938 (4)	0.0324 (3)	0.9528 (3)	0.0467 (9)	0.5
H1O1	0.059 (6)	−0.0378 (15)	0.943 (6)	0.070*	0.5
H2O1	0.055 (6)	0.065 (4)	0.992 (5)	0.070*	0.5
O2	0.0033 (3)	0.8165 (2)	0.91596 (19)	0.0614 (6)
H1O2	−0.038 (4)	0.778 (3)	0.8572 (18)	0.092*
H2O2	0.034 (4)	0.776 (3)	0.966 (2)	0.092*
O3	0.78812 (19)	0.40276 (17)	0.65477 (15)	0.0400 (4)
H1O3	0.794 (3)	0.4737 (10)	0.670 (2)	0.060*
H2O3	0.804 (3)	0.374 (2)	0.7181 (14)	0.060*
O4	0.2998 (2)	0.9624 (2)	0.0870 (2)	0.0639 (6)
H1O4	0.238 (3)	0.987 (3)	0.046 (3)	0.096*
H2O4	0.274 (4)	0.8898 (11)	0.093 (4)	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0267 (11)	0.0283 (12)	0.0244 (10)	0.0095 (9)	0.0033 (9)	0.0018 (9)
C2	0.0372 (13)	0.0379 (14)	0.0260 (11)	0.0161 (11)	−0.0010 (10)	0.0061 (10)
C3	0.0295 (12)	0.0382 (14)	0.0310 (12)	0.0154 (10)	−0.0074 (10)	−0.0024 (10)
C4	0.0236 (10)	0.0261 (12)	0.0328 (11)	0.0112 (9)	−0.0018 (9)	−0.0048 (9)
C5	0.0179 (9)	0.0204 (10)	0.0250 (10)	0.0067 (8)	0.0009 (8)	−0.0034 (8)
C6	0.0195 (10)	0.0204 (10)	0.0281 (10)	0.0074 (8)	0.0033 (8)	−0.0003 (8)
C7	0.0246 (11)	0.0251 (12)	0.0426 (13)	0.0062 (9)	0.0097 (10)	0.0040 (10)
C8	0.0190 (10)	0.0296 (13)	0.0577 (16)	0.0031 (9)	0.0074 (10)	−0.0013 (11)
C9	0.0198 (10)	0.0329 (13)	0.0470 (14)	0.0097 (9)	−0.0028 (10)	−0.0054 (11)
C10	0.0273 (11)	0.0286 (12)	0.0221 (10)	0.0071 (9)	0.0085 (8)	0.0006 (9)
C11	0.0247 (10)	0.0276 (12)	0.0245 (10)	0.0089 (9)	0.0073 (8)	−0.0033 (9)
C12	0.0305 (12)	0.0312 (13)	0.0302 (12)	0.0068 (10)	0.0007 (9)	−0.0094 (10)
C13	0.0395 (13)	0.0204 (11)	0.0320 (12)	0.0101 (9)	0.0095 (10)	−0.0006 (9)
C14	0.0229 (10)	0.0261 (11)	0.0249 (10)	0.0083 (9)	0.0058 (8)	0.0012 (9)
C15	0.0315 (12)	0.0333 (13)	0.0224 (10)	0.0100 (10)	0.0104 (9)	0.0000 (9)
C16	0.0331 (12)	0.0327 (13)	0.0198 (10)	0.0073 (10)	0.0053 (9)	0.0009 (9)
C17	0.0251 (10)	0.0234 (11)	0.0220 (10)	0.0046 (8)	0.0024 (8)	0.0027 (8)
C18	0.0199 (9)	0.0187 (10)	0.0203 (9)	0.0025 (8)	0.0003 (8)	0.0015 (8)
C19	0.0225 (10)	0.0205 (10)	0.0210 (10)	0.0045 (8)	0.0032 (8)	0.0025 (8)
C20	0.0250 (11)	0.0266 (11)	0.0278 (11)	0.0075 (9)	0.0049 (9)	0.0039 (9)
C21	0.0234 (11)	0.0312 (12)	0.0311 (11)	0.0105 (9)	0.0003 (9)	0.0074 (9)
C22	0.0273 (11)	0.0297 (12)	0.0207 (10)	0.0057 (9)	−0.0012 (8)	0.0062 (9)
C23	0.0221 (10)	0.0345 (13)	0.0253 (10)	0.0069 (9)	0.0065 (8)	0.0096 (9)
C24	0.0245 (11)	0.0268 (12)	0.0287 (11)	0.0002 (9)	0.0027 (9)	0.0039 (9)
C25	0.0331 (12)	0.0265 (12)	0.0268 (11)	0.0087 (9)	0.0074 (9)	0.0078 (9)
C26	0.0436 (14)	0.0224 (12)	0.0353 (12)	0.0120 (10)	0.0143 (11)	0.0018 (9)
Cl1	0.0589 (4)	0.0479 (4)	0.0332 (3)	0.0311 (3)	0.0112 (3)	0.0026 (3)
Cl2	0.0428 (3)	0.0371 (3)	0.0393 (3)	0.0192 (3)	0.0201 (3)	0.0156 (3)
N1	0.0195 (8)	0.0222 (9)	0.0202 (8)	0.0077 (7)	0.0013 (7)	−0.0009 (7)
N2	0.0191 (8)	0.0208 (9)	0.0216 (8)	0.0067 (7)	0.0029 (7)	0.0015 (7)
N3	0.0221 (8)	0.0204 (9)	0.0223 (8)	0.0060 (7)	0.0031 (7)	−0.0016 (7)
N4	0.0222 (8)	0.0229 (9)	0.0183 (8)	0.0057 (7)	0.0032 (7)	0.0013 (7)
N5	0.0224 (8)	0.0249 (9)	0.0196 (8)	0.0075 (7)	0.0037 (7)	0.0026 (7)
N6	0.0257 (9)	0.0212 (9)	0.0235 (9)	0.0062 (7)	0.0039 (7)	0.0035 (7)
Ni1	0.01521 (17)	0.01787 (19)	0.01697 (17)	0.00518 (13)	0.00185 (13)	0.00047 (13)
Ni2	0.01852 (18)	0.02006 (19)	0.01495 (17)	0.00518 (14)	0.00156 (13)	0.00111 (14)
O1	0.056 (2)	0.028 (2)	0.051 (2)	0.0087 (18)	0.0000 (19)	−0.0011 (17)
O2	0.0768 (16)	0.0634 (15)	0.0489 (12)	0.0309 (13)	0.0067 (11)	0.0157 (11)
O3	0.0440 (10)	0.0422 (11)	0.0364 (9)	0.0131 (9)	0.0102 (8)	0.0017 (8)
O4	0.0583 (14)	0.0596 (15)	0.0636 (15)	0.0000 (12)	0.0018 (11)	−0.0004 (12)

Geometric parameters (Å, º) top

C1—N1	1.322 (3)	C19—N5ⁱ	1.448 (3)
C1—C2	1.407 (3)	C20—C21	1.419 (3)
C1—H1	0.9500	C20—H20	0.9500
C2—C3	1.365 (3)	C21—C22	1.362 (3)
C2—H2	0.9500	C21—H21	0.9500
C3—C4	1.412 (3)	C22—H22	0.9500
C3—H3	0.9500	C23—N5	1.499 (3)
C4—C9	1.412 (3)	C23—C24	1.515 (3)
C4—C5	1.418 (3)	C23—H23A	0.9900
C5—N1	1.378 (3)	C23—H23B	0.9900
C5—C6	1.418 (3)	C24—N6	1.486 (3)
C6—C7	1.370 (3)	C24—H24A	0.9900
C6—N2	1.450 (3)	C24—H24B	0.9900
C7—C8	1.411 (3)	C25—N6	1.486 (3)
C7—H7	0.9500	C25—H25A	0.9800
C8—C9	1.364 (4)	C25—H25B	0.9800
C8—H8	0.9500	C25—H25C	0.9800
C9—H9	0.9500	C26—N6	1.480 (3)
C10—N2	1.498 (3)	C26—H26A	0.9800
C10—C11	1.508 (3)	C26—H26B	0.9800
C10—H10A	0.9900	C26—H26C	0.9800
C10—H10B	0.9900	N1—Ni1	2.0909 (17)
C11—N3	1.491 (3)	N2—Ni1	2.1189 (16)
C11—H11A	0.9900	N2—H2A	1.0000
C11—H11B	0.9900	N3—Ni1	2.2374 (17)
C12—N3	1.485 (3)	N4—Ni2	2.0778 (16)
C12—H12A	0.9800	N5—C19ⁱ	1.448 (3)
C12—H12B	0.9800	N5—Ni2	2.1143 (17)
C12—H12C	0.9800	N5—H5	1.0000
C13—N3	1.481 (3)	N6—Ni2	2.2397 (17)
C13—H13A	0.9800	Ni1—N1ⁱⁱ	2.0909 (17)
C13—H13B	0.9800	Ni1—N2ⁱⁱ	2.1189 (16)
C13—H13C	0.9800	Ni1—N3ⁱⁱ	2.2373 (17)
C14—N4	1.319 (3)	Ni2—N4ⁱ	2.0777 (16)
C14—C15	1.411 (3)	Ni2—N5ⁱ	2.1144 (17)
C14—H14	0.9500	Ni2—N6ⁱ	2.2397 (17)
C15—C16	1.361 (3)	O1—H1O1	0.833 (10)
C15—H15	0.9500	O1—H2O1	0.836 (10)
C16—C17	1.411 (3)	O2—H1O2	0.835 (10)
C16—H16	0.9500	O2—H2O2	0.833 (10)
C17—C22	1.414 (3)	O3—H1O3	0.846 (10)
C17—C18	1.420 (3)	O3—H2O3	0.846 (10)
C18—N4	1.380 (3)	O4—H1O4	0.848 (10)
C18—C19	1.411 (3)	O4—H2O4	0.854 (10)
C19—C20	1.370 (3)

N1—C1—C2	123.5 (2)	H23A—C23—H23B	108.2
N1—C1—H1	118.2	N6—C24—C23	111.42 (18)
C2—C1—H1	118.2	N6—C24—H24A	109.3
C3—C2—C1	119.1 (2)	C23—C24—H24A	109.3
C3—C2—H2	120.5	N6—C24—H24B	109.3
C1—C2—H2	120.5	C23—C24—H24B	109.3
C2—C3—C4	119.9 (2)	H24A—C24—H24B	108.0
C2—C3—H3	120.1	N6—C25—H25A	109.5
C4—C3—H3	120.1	N6—C25—H25B	109.5
C9—C4—C3	124.0 (2)	H25A—C25—H25B	109.5
C9—C4—C5	118.6 (2)	N6—C25—H25C	109.5
C3—C4—C5	117.4 (2)	H25A—C25—H25C	109.5
N1—C5—C6	117.79 (18)	H25B—C25—H25C	109.5
N1—C5—C4	122.12 (19)	N6—C26—H26A	109.5
C6—C5—C4	120.09 (19)	N6—C26—H26B	109.5
C7—C6—C5	119.51 (19)	H26A—C26—H26B	109.5
C7—C6—N2	123.0 (2)	N6—C26—H26C	109.5
C5—C6—N2	117.51 (17)	H26A—C26—H26C	109.5
C6—C7—C8	120.5 (2)	H26B—C26—H26C	109.5
C6—C7—H7	119.8	C1—N1—C5	117.98 (18)
C8—C7—H7	119.8	C1—N1—Ni1	128.92 (14)
C9—C8—C7	120.8 (2)	C5—N1—Ni1	112.58 (13)
C9—C8—H8	119.6	C6—N2—C10	110.88 (16)
C7—C8—H8	119.6	C6—N2—Ni1	109.03 (12)
C8—C9—C4	120.5 (2)	C10—N2—Ni1	106.62 (12)
C8—C9—H9	119.7	C6—N2—H2A	110.1
C4—C9—H9	119.7	C10—N2—H2A	110.1
N2—C10—C11	109.39 (17)	Ni1—N2—H2A	110.1
N2—C10—H10A	109.8	C13—N3—C12	106.35 (17)
C11—C10—H10A	109.8	C13—N3—C11	108.99 (16)
N2—C10—H10B	109.8	C12—N3—C11	108.26 (16)
C11—C10—H10B	109.8	C13—N3—Ni1	112.67 (13)
H10A—C10—H10B	108.2	C12—N3—Ni1	116.48 (13)
N3—C11—C10	110.47 (17)	C11—N3—Ni1	103.85 (12)
N3—C11—H11A	109.6	C14—N4—C18	118.37 (17)
C10—C11—H11A	109.6	C14—N4—Ni2	129.17 (14)
N3—C11—H11B	109.6	C18—N4—Ni2	111.46 (13)
C10—C11—H11B	109.6	C19ⁱ—N5—C23	111.93 (16)
H11A—C11—H11B	108.1	C19ⁱ—N5—Ni2	107.77 (12)
N3—C12—H12A	109.5	C23—N5—Ni2	106.88 (12)
N3—C12—H12B	109.5	C19ⁱ—N5—H5	110.1
H12A—C12—H12B	109.5	C23—N5—H5	110.1
N3—C12—H12C	109.5	Ni2—N5—H5	110.1
H12A—C12—H12C	109.5	C26—N6—C25	106.69 (17)
H12B—C12—H12C	109.5	C26—N6—C24	108.98 (17)
N3—C13—H13A	109.5	C25—N6—C24	108.49 (16)
N3—C13—H13B	109.5	C26—N6—Ni2	113.21 (13)
H13A—C13—H13B	109.5	C25—N6—Ni2	117.61 (13)
N3—C13—H13C	109.5	C24—N6—Ni2	101.49 (13)
H13A—C13—H13C	109.5	N1ⁱⁱ—Ni1—N1	180.00 (9)
H13B—C13—H13C	109.5	N1ⁱⁱ—Ni1—N2	99.10 (6)
N4—C14—C15	123.0 (2)	N1—Ni1—N2	80.90 (6)
N4—C14—H14	118.5	N1ⁱⁱ—Ni1—N2ⁱⁱ	80.90 (6)
C15—C14—H14	118.5	N1—Ni1—N2ⁱⁱ	99.11 (6)
C16—C15—C14	119.5 (2)	N2—Ni1—N2ⁱⁱ	180.00 (7)
C16—C15—H15	120.3	N1ⁱⁱ—Ni1—N3ⁱⁱ	88.88 (6)
C14—C15—H15	120.3	N1—Ni1—N3ⁱⁱ	91.12 (6)
C15—C16—C17	119.85 (19)	N2—Ni1—N3ⁱⁱ	97.02 (6)
C15—C16—H16	120.1	N2ⁱⁱ—Ni1—N3ⁱⁱ	82.98 (6)
C17—C16—H16	120.1	N1ⁱⁱ—Ni1—N3	91.12 (6)
C16—C17—C22	124.18 (19)	N1—Ni1—N3	88.88 (6)
C16—C17—C18	117.32 (19)	N2—Ni1—N3	82.98 (6)
C22—C17—C18	118.50 (19)	N2ⁱⁱ—Ni1—N3	97.02 (6)
N4—C18—C19	118.02 (17)	N3ⁱⁱ—Ni1—N3	180.0
N4—C18—C17	121.87 (18)	N4ⁱ—Ni2—N4	180.0
C19—C18—C17	120.10 (19)	N4ⁱ—Ni2—N5	81.04 (6)
C20—C19—C18	119.92 (19)	N4—Ni2—N5	98.96 (6)
C20—C19—N5ⁱ	122.84 (18)	N4ⁱ—Ni2—N5ⁱ	98.96 (6)
C18—C19—N5ⁱ	117.24 (18)	N4—Ni2—N5ⁱ	81.04 (6)
C19—C20—C21	120.1 (2)	N5—Ni2—N5ⁱ	180.0
C19—C20—H20	120.0	N4ⁱ—Ni2—N6	89.87 (6)
C21—C20—H20	120.0	N4—Ni2—N6	90.13 (6)
C22—C21—C20	120.8 (2)	N5—Ni2—N6	84.17 (7)
C22—C21—H21	119.6	N5ⁱ—Ni2—N6	95.83 (7)
C20—C21—H21	119.6	N4ⁱ—Ni2—N6ⁱ	90.13 (6)
C21—C22—C17	120.5 (2)	N4—Ni2—N6ⁱ	89.87 (6)
C21—C22—H22	119.7	N5—Ni2—N6ⁱ	95.83 (7)
C17—C22—H22	119.7	N5ⁱ—Ni2—N6ⁱ	84.17 (7)
N5—C23—C24	109.85 (17)	N6—Ni2—N6ⁱ	180.00 (4)
N5—C23—H23A	109.7	H1O1—O1—H2O1	110 (3)
C24—C23—H23A	109.7	H1O2—O2—H2O2	113 (2)
N5—C23—H23B	109.7	H1O3—O3—H2O3	105 (2)
C24—C23—H23B	109.7	H1O4—O4—H2O4	108 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl2	1.00	2.27	3.2038 (18)	155
N5—H5···Cl1	1.00	2.33	3.2715 (19)	156
O1—H1O1···O2ⁱⁱⁱ	0.83 (1)	1.71 (1)	2.541 (5)	173 (6)
O1—H2O1···O2^iv	0.84 (1)	2.05 (2)	2.863 (5)	165 (6)
O2—H1O2···Cl2^v	0.84 (1)	2.33 (1)	3.162 (3)	172 (4)
O2—H2O2···Cl1^vi	0.83 (1)	2.37 (2)	3.179 (2)	163 (4)
O3—H1O3···Cl2^vii	0.85 (1)	2.38 (1)	3.222 (2)	174 (3)
O3—H2O3···Cl1^vii	0.85 (1)	2.36 (1)	3.2008 (19)	170 (3)
O4—H1O4···O1^viii	0.85 (1)	1.91 (1)	2.755 (5)	177 (4)
O4—H2O4···Cl1	0.85 (1)	2.33 (1)	3.180 (3)	173 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl2	1.00	2.27	3.2038 (18)	155
N5—H5···Cl1	1.00	2.33	3.2715 (19)	156
O1—H1O1···O2ⁱ	0.833 (10)	1.711 (12)	2.541 (5)	173 (6)
O1—H2O1···O2ⁱⁱ	0.836 (10)	2.048 (17)	2.863 (5)	165 (6)
O2—H1O2···Cl2ⁱⁱⁱ	0.835 (10)	2.333 (11)	3.162 (3)	172 (4)
O2—H2O2···Cl1^iv	0.833 (10)	2.373 (15)	3.179 (2)	163 (4)
O3—H1O3···Cl2^v	0.846 (10)	2.379 (10)	3.222 (2)	174 (3)
O3—H2O3···Cl1^v	0.846 (10)	2.363 (11)	3.2008 (19)	170 (3)
O4—H1O4···O1^vi	0.848 (10)	1.908 (11)	2.755 (5)	177 (4)
O4—H2O4···Cl1	0.854 (10)	2.331 (12)	3.180 (3)	173 (3)

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

Acknowledgements

Gratitude is expressed to Professor P. G. Edwards of the School of Chemistry, Cardiff University, for the opportunity for ARHAS to work in his laboratory as an academic visitor for many years, without which this work would not have been accomplished, as well as for his invaluable advice and financial support.

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