Crystal structure of bis-{N-[2-(di-methyl-amino)-eth-yl]quinolin-8-amine-κ(3) N,N',N''}nickel(II) dichloride 3.5-hydrate.

In the title compound, [Ni(C13H17N3)2]Cl2·3.5H2O, the geom-etry of the NiN6 complex cation is slightly distorted octa-hedral, with a facial arrangement of the two tridentate N-[2-(di--methyl-amino)-eth-yl]quinolin-8-amine ligands around the metal ion. The asymmetric unit consists of two independent complex half-mol-ecules located on centres of inversion, together with two chloride counter-anions and 3.5 water mol-ecules 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 inter-actions form a three-dimensional network structure.

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 ▶).

Experimental

Crystal data

[Ni(C13H17N3)2]Cl2·3.5H2O

M = 623.26

Triclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.090

S = 1.03

6714 reflections

383 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.59 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019035/zs2312sup1.cif

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

Click here for additional data file.

. DOI: 10.1107/S1600536814019035/zs2312fig1.tif

The asymmetric of the title complex showing atom labels and 50% probability displacement ellipsoids. Hydrogen atoms have been omitted.

Click here for additional data file.

. DOI: 10.1107/S1600536814019035/zs2312fig2.tif

Packing in the crystal structure showing the O—H⋯O, O—H⋯Cl and N—H⋯Cl inter­actions as dotted lines.

CCDC reference: 1020674

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Ni(C13H17N3)2]Cl2·3.5H2O	Z = 2
Mr = 623.26	F(000) = 658
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0261P)2 + 1.4643P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
6714 reflections	Δρmax = 0.46 e Å−3
383 parameters	Δρmin = −0.59 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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···O2iv	0.84 (1)	2.05 (2)	2.863 (5)	165 (6)
O2—H1O2···Cl2v	0.84 (1)	2.33 (1)	3.162 (3)	172 (4)
O2—H2O2···Cl1vi	0.83 (1)	2.37 (2)	3.179 (2)	163 (4)
O3—H1O3···Cl2vii	0.85 (1)	2.38 (1)	3.222 (2)	174 (3)
O3—H2O3···Cl1vii	0.85 (1)	2.36 (1)	3.2008 (19)	170 (3)
O4—H1O4···O1viii	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)

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⋯Cl1iv	0.83 (1)	2.37 (2)	3.179 (2)	163 (4)
O3—H1O3⋯Cl2v	0.85 (1)	2.38 (1)	3.222 (2)	174 (3)
O3—H2O3⋯Cl1v	0.85 (1)	2.36 (1)	3.2008 (19)	170 (3)
O4—H1O4⋯O1vi	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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .