[mu]-{N,N'-Bis[2-(dimethyl­amino)ethyl]oxamidato(2-)}-1[kappa]²O,O':2[kappa]⁴N,N',N'',N'''-bis­(4,4'-dimethyl-2,2'-bipyridine-1[kappa]²N,N')dinickel(II) bis­(perchlorate)

In the crystal structure of the title complex, [Ni₂(C₁₀H₂₀N₄O₂)(C₁₂H₁₂N₂)₂](ClO₄)₂ or [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ {H₂dmaeoxd is N,N'-bis­[2-(dimethyl­amino)ethyl]oxamide and dmbp is 4,4'-dimethyl-2,2'-bipyridine}, the deprotonated dmaeoxd^2- ligand is in a cis conformation and bridges two Ni^II atoms, one of which is located in a slightly distorted square-planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd^2- ligands inter­act with each other via C-H...O hydrogen bonds and [pi]-[pi] inter­actions, which results in an extended chain along the c axis.

S1. Comment

There has been a great interest in the crystal engineering of self-assembled supramolecular architectures formed through relatively weak C—H···O and π–π stacking interactions (Blake et al., 1999; Lin et al., 2003). Considerable attention has been devoted to metal polypyridyl complexes (Kalyanasundaram & Grätzel 1998; Ye et al., 1998), in which the hydrophilic groups are linked via hydrogen bonds while the hydrophobic groups are stacked via π–π interactions. N,N'-Disubstituted oxamidates are well known as versatile bridging ligands, which can afford symmetric and asymmetric oxamidate bridges by the cis–trans conformational change (Ruiz et al., 1999). Four crystal structures of dinuclear oxamidate-bridged Ni^II complexes with the Ni atoms in different coordination geometries have been reported to date, namely [Ni(obbz)Ni(H₂O)₄]·2H₂O, (II) (Reference?), Ni(aeox)Ni(en)(SCN)₂, (III) (Chen et al., 1994), [Ni(aeox)Ni(phen)₂](ClO₄)₂·3H₂O, (IV) (Wei et al., 1995), and [Ni(apox)Ni(phen)₂](ClO₄)₂·CH₃OH·2H₂O, (V) (Jiu et al., 2000) [obbz is deprotonated N,N'-bis(2-aminobenzoato)oxamide, aeox is deprotonated N,N'-bis(2-aminoethyl)oxamide, en is ethylenediamine, phen is 1,10-phenanthroline and apox is deprotonated N,N'-bis(3-aminopropyl)oxamide]. In these complexes, however, the types of hydrogen-bond interactions were not discussed in detail and the π–π stacking was not studied at all. In order to study the supramolecular architecture of this kind of complex, we chose H₂dmaeoxd as a polydentate ligand to synthesize the title binuclear Ni^II complex, (I), formulated as [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂, and report its crystal structure here.

Compound (I) consists of an [Ni(dmaeoxd)Ni(dmbp)₂]²⁺ cation and two uncoordinated ClO₄^- anions. A view of the compound is depicted in Fig. 1, and selected bond lengths and angles are listed in Table 1. The deprotonated dmaeoxd^2- ligand exhibits a cisoid conformation and bridges two Ni^II atoms, with an Ni···Ni distance of 5.2955 (18) Å. A crystallographic twofold axis passes through this Ni···Ni vector and the middle of the C5—C5ⁱ bond [symmetry code: (i) 1 - x, y, 1/2 - z]. Within the bridging oxamide fragment, the C—O and C—N bonds have partial double-bond character [N2—C5 = 1.299 (4) Å and C5—O1 = 1.255 (4) Å], while the C5—C5ⁱ bond of 1.521 (6) Å is identical to the standard value of a single bond (Standard reference?). These bonds are similar to those in many other oxamidate complexes (Lloret et al., 1989; Real et al., 1993).

Atom Ni1 is coordinated by four N atoms of dmaeoxd, with the maximum deviation from the coordinated plane being 0.023 (3) Å for atom N2. The Ni1—N2 bond length of 1.853 (3) Å is comparable with the distances between the Ni and amide N atoms in compounds (II)–(V) (1.837–1.895 Å). The Ni1—N1 distance [1.976 (3) Å] is longer than the corresponding distance in compounds (III)–(V), which is perhaps due to the steric hindrance between the two pairs of methyl groups on atom N1. The bridging ligand coordinates atom Ni1 by forming three five-membered chelate rings. Those formed by the ethylene diamine fragment adopt a twist form, with puckering parameters (Cremer & Pople, 1975) of Q = 0.418 (4) Å and ϕ = 62.4 (5)°.

Atom Ni2 is coordinated by four N donors of two dmbp molecules and two O atoms of the dmaeoxd ligand. Due to the rigidity of the three bidentate ligands, the hexacoordinated atom Ni2 has a distorted octahedral geometry. Atom N4 and its symmetry-related atom N4ⁱ are axially coordinated, with an approximately linear N—Ni—N angle. The equatorial plane is defined by the other four atoms and the mean displacement from this plane is 0.173 Å. Atom Ni2 lies exactly in the plane. The terminal dmbp ligands are present in the usual chelating bidentate mode, except for the envelope form of the chelate ring on Ni2. The torsion angles Ni2—N3—C10—C11 and Ni2—N4—C11—C10 are -11.2 (4) and 15.5 (4)°, respectively.

As shown in Fig. 2, the binuclear cation complexes and perchlorate anions are connected through a non-classical hydrogen bond, C6—H6···O13 (Table 2), which gives rise to an ion triplet, [Ni(dmaeoxd)Ni(dmbp)₂]²⁺·2ClO₄^-. These triplets are linked into a one-dimensional ribbon along the c axis by a combination of a C12—H12···O1ⁱⁱ [symmetry code: (ii) x, 1 - y, 1/2 + z] interaction and a π–π stacking interaction between the dmbp ligand and that generated by the symmetry operation (1 - x, 1 - y, 1 - z), with separations of 3.505 (4) [atom C9 at (1 - x, 1 - y, 1 - z)] and 3.526 (4) Å [atom C13 at (1 - x, 1 - y, 1 - z)].

Related literature

For related literature, see: Blake et al. (1999); Chen et al. (1994); Cremer & Pople (1975); Jiu et al. (2000); Kalyanasundaram & Grätzel (1998); Lin et al. (2003); Lloret et al. (1989); Ojima & Yamada (1970); Real et al. (1993); Ruiz et al. (1999); Wei et al. (1995); Ye et al. (1998).

S2. Experimental

All reagents were of AR grade and were used without further purification. The H₂dmaeoxd ligand was synthesized according to the method of Ojima & Yamada (1970). [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ was obtained as follows. To a solution of H₂dmaeoxd (0.0230 g, 0.1 mmol) in methanol (10 ml) was added successively piperidine (0.2 mmol) and a solution of Ni(ClO₄)₂·6H₂O (0.0731 g, 0.2 mmol) in methanol (5 ml). After stirring for 20 min, dmbp (0.0368 g, 0.2 mmol) in methanol (5 ml) was added. The reaction mixture was stirred at 333 K for a further 2 h. Orange crystals of the title compound suitable for X-ray analysis were obtained from the solution by slow evaporation at room temperature on the second day (yield 67%). Spectroscopic analysis: IR (KBr pellet, γ, cm^-1): 1649 (vs), 1615 (vs), 1487 (m), 1471 (s), 1088 (vs), 833 (m), 623 (s).

S3. Refinement

All H atoms were placed in calculated positions, with C—H distances of 0.93 (aromatic), 0.96 (methyl) or 0.97 Å (methylene), and refined in riding mode, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C). The CH₃ groups bound to the pyridine rings were allowed to rotate freely around the C—C bond.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) 1 - x, y, 1/2 - z.]
	Fig. 2. A view showing the ribbon extending along [001], formed by C—H···O hydrogen bonds (dashed lines) and π-π stacking interactions. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (ii) x, 1 - y, 1/2 + z; (iii) x, 1 - y, z - 1/2.]

µ-{N,N'-Bis[2-(dimethylamino)ethyl]oxamidato(2-)}- 1κ²O,O':2κ⁴N,N',N'',N'''-bis(4,4'-dimethyl-2,2'-bipyridine- 1κ²N,N')dinickel(II) bis(perchlorate)

Crystal data

[Ni2(C10H20N4O2)(C12H12N2)2](ClO4)2	F(000) = 1896
Mr = 913.05	Dx = 1.538 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2683 reflections
a = 19.068 (6) Å	θ = 2.3–25.5°
b = 13.431 (4) Å	µ = 1.16 mm^−1
c = 15.920 (5) Å	T = 298 K
β = 104.744 (4)°	Block, orange
V = 3943 (2) Å^3	0.45 × 0.38 × 0.29 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	3470 independent reflections
Radiation source: fine-focus sealed tube	2338 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −22→22
Tmin = 0.612, Tmax = 0.716	k = −10→15
10149 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0464P)^2 + 5.2848P] where P = (Fo^2 + 2Fc^2)/3
3470 reflections	(Δ/σ)max < 0.001
256 parameters	Δρmax = 0.50 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.15403 (5)	0.2500	0.0409 (2)
O1	0.44689 (13)	0.42838 (18)	0.17369 (14)	0.0390 (6)
N1	0.43379 (19)	0.0663 (3)	0.1663 (2)	0.0578 (9)
N2	0.44962 (16)	0.2568 (2)	0.18333 (19)	0.0426 (8)
C1	0.4666 (3)	0.0381 (4)	0.0955 (3)	0.0979 (19)
H1A	0.5067	−0.0059	0.1175	0.147*
H1B	0.4833	0.0967	0.0721	0.147*
H1C	0.4310	0.0049	0.0505	0.147*
C2	0.4060 (3)	−0.0225 (4)	0.2016 (4)	0.0957 (19)
H2A	0.3673	−0.0514	0.1576	0.144*
H2B	0.3881	−0.0037	0.2505	0.144*
H2C	0.4443	−0.0702	0.2197	0.144*
C3	0.3676 (3)	0.1308 (4)	0.1305 (3)	0.0742 (15)
H3A	0.3374	0.1001	0.0786	0.089*
H3B	0.3394	0.1358	0.1731	0.089*
C4	0.3892 (2)	0.2315 (3)	0.1092 (3)	0.0574 (11)
H4A	0.4046	0.2310	0.0556	0.069*
H4B	0.3496	0.2784	0.1035	0.069*
C5	0.46976 (18)	0.3467 (3)	0.2083 (2)	0.0349 (8)
Ni2	0.5000	0.54830 (5)	0.2500	0.0371 (2)
N3	0.54611 (16)	0.6452 (2)	0.34900 (19)	0.0389 (7)
N4	0.42297 (16)	0.5480 (2)	0.31922 (18)	0.0400 (7)
C6	0.6064 (2)	0.6995 (3)	0.3574 (3)	0.0499 (10)
H6	0.6269	0.7042	0.3104	0.060*
C7	0.6392 (2)	0.7489 (3)	0.4333 (3)	0.0520 (10)
H7	0.6811	0.7857	0.4367	0.062*
C8	0.6101 (2)	0.7440 (3)	0.5045 (3)	0.0478 (10)
C9	0.5466 (2)	0.6893 (3)	0.4946 (2)	0.0417 (9)
H9	0.5248	0.6846	0.5405	0.050*
C10	0.51560 (18)	0.6418 (3)	0.4167 (2)	0.0360 (8)
C11	0.44678 (18)	0.5847 (3)	0.4008 (2)	0.0339 (8)
C12	0.40814 (18)	0.5704 (3)	0.4616 (2)	0.0384 (8)
H12	0.4268	0.5938	0.5179	0.046*
C13	0.34184 (19)	0.5219 (3)	0.4411 (2)	0.0393 (9)
C14	0.31761 (19)	0.4863 (3)	0.3566 (2)	0.0454 (10)
H14	0.2736	0.4527	0.3394	0.055*
C15	0.3592 (2)	0.5014 (3)	0.2988 (2)	0.0477 (10)
H15	0.3419	0.4778	0.2424	0.057*
C16	0.6453 (2)	0.7946 (4)	0.5892 (3)	0.0702 (14)
H16A	0.6911	0.7635	0.6148	0.105*
H16B	0.6144	0.7888	0.6281	0.105*
H16C	0.6528	0.8637	0.5788	0.105*
C17	0.2994 (2)	0.5077 (3)	0.5076 (2)	0.0550 (11)
H17A	0.3310	0.4839	0.5608	0.083*
H17B	0.2614	0.4601	0.4867	0.083*
H17C	0.2785	0.5702	0.5181	0.083*
Cl1	0.67672 (6)	0.83632 (9)	0.14899 (7)	0.0614 (3)
O11	0.7066 (2)	0.7814 (3)	0.0902 (2)	0.1060 (13)
O12	0.6018 (2)	0.8186 (3)	0.1303 (3)	0.1304 (18)
O13	0.7061 (3)	0.8090 (4)	0.2356 (3)	0.1341 (17)
O14	0.6898 (3)	0.9380 (3)	0.1419 (3)	0.1299 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0449 (4)	0.0382 (4)	0.0376 (4)	0.000	0.0069 (3)	0.000
O1	0.0501 (15)	0.0394 (15)	0.0239 (12)	0.0035 (12)	0.0029 (10)	−0.0019 (11)
N1	0.071 (2)	0.044 (2)	0.055 (2)	−0.0173 (18)	0.0083 (18)	−0.0053 (17)
N2	0.0452 (18)	0.0393 (19)	0.0366 (17)	−0.0020 (15)	−0.0019 (14)	−0.0016 (14)
C1	0.120 (5)	0.104 (5)	0.071 (4)	−0.015 (4)	0.026 (3)	−0.042 (3)
C2	0.102 (4)	0.064 (3)	0.113 (5)	−0.038 (3)	0.012 (4)	0.009 (3)
C3	0.062 (3)	0.073 (3)	0.074 (3)	−0.014 (3)	−0.008 (2)	−0.008 (3)
C4	0.058 (3)	0.052 (3)	0.051 (2)	−0.008 (2)	−0.009 (2)	−0.004 (2)
C5	0.0375 (19)	0.042 (2)	0.0243 (17)	0.0011 (18)	0.0064 (14)	−0.0003 (17)
Ni2	0.0450 (4)	0.0405 (4)	0.0256 (3)	0.000	0.0086 (3)	0.000
N3	0.0436 (17)	0.0373 (17)	0.0362 (17)	−0.0007 (15)	0.0108 (13)	0.0011 (14)
N4	0.0430 (17)	0.0465 (19)	0.0291 (16)	−0.0042 (15)	0.0065 (13)	−0.0066 (14)
C6	0.053 (2)	0.050 (2)	0.051 (2)	−0.010 (2)	0.021 (2)	−0.001 (2)
C7	0.044 (2)	0.045 (2)	0.065 (3)	−0.0109 (19)	0.010 (2)	−0.002 (2)
C8	0.047 (2)	0.041 (2)	0.049 (2)	0.0015 (19)	0.0024 (19)	−0.0075 (19)
C9	0.046 (2)	0.048 (2)	0.029 (2)	0.0001 (18)	0.0066 (16)	−0.0062 (17)
C10	0.0373 (19)	0.035 (2)	0.0339 (19)	0.0032 (16)	0.0061 (15)	−0.0002 (16)
C11	0.0371 (19)	0.036 (2)	0.0264 (18)	0.0014 (16)	0.0047 (15)	0.0000 (15)
C12	0.042 (2)	0.042 (2)	0.0283 (18)	0.0008 (17)	0.0021 (15)	−0.0036 (16)
C13	0.039 (2)	0.043 (2)	0.036 (2)	0.0062 (17)	0.0106 (16)	0.0033 (17)
C14	0.033 (2)	0.062 (3)	0.038 (2)	−0.0096 (18)	0.0046 (17)	−0.0061 (19)
C15	0.046 (2)	0.059 (3)	0.034 (2)	−0.005 (2)	0.0034 (17)	−0.0114 (19)
C16	0.062 (3)	0.076 (3)	0.067 (3)	−0.013 (3)	0.006 (2)	−0.028 (3)
C17	0.051 (2)	0.075 (3)	0.041 (2)	−0.005 (2)	0.0146 (19)	0.002 (2)
Cl1	0.0631 (7)	0.0709 (8)	0.0513 (6)	−0.0170 (6)	0.0161 (5)	−0.0119 (6)
O11	0.101 (3)	0.132 (4)	0.091 (3)	0.007 (3)	0.036 (2)	−0.036 (3)
O12	0.072 (3)	0.134 (4)	0.188 (5)	−0.029 (3)	0.039 (3)	−0.066 (3)
O13	0.166 (4)	0.159 (4)	0.064 (3)	−0.017 (4)	0.006 (3)	0.018 (3)
O14	0.181 (4)	0.073 (3)	0.160 (4)	−0.039 (3)	0.088 (4)	−0.007 (3)

Geometric parameters (Å, º)

Ni1—N1	1.976 (3)	C5—O1	1.255 (4)
Ni1—N1^i	1.976 (3)	C5—C5^i	1.521 (6)
Ni1—N2	1.853 (3)	C6—C7	1.381 (5)
Ni1—N2^i	1.853 (3)	C6—H6	0.9300
Ni2—N3	2.060 (3)	C7—C8	1.383 (5)
Ni2—N3^i	2.060 (3)	C7—H7	0.9300
Ni2—N4	2.048 (3)	C8—C9	1.390 (5)
Ni2—N4^i	2.048 (3)	C8—C16	1.508 (5)
Ni2—O1	2.114 (2)	C9—C10	1.385 (5)
Ni2—O1^i	2.114 (2)	C9—H9	0.9300
N1—C1	1.471 (6)	C10—C11	1.485 (5)
N1—C2	1.473 (5)	C11—C12	1.372 (5)
N1—C3	1.517 (6)	C12—C13	1.386 (5)
N2—C5	1.299 (4)	C12—H12	0.9300
N2—C4	1.464 (4)	C13—C14	1.391 (5)
N3—C6	1.339 (5)	C13—C17	1.500 (5)
N3—C10	1.350 (4)	C14—C15	1.373 (5)
N4—C15	1.333 (4)	C14—H14	0.9300
N4—C11	1.355 (4)	C15—H15	0.9300
C1—H1A	0.9600	C16—H16A	0.9600
C1—H1B	0.9600	C16—H16B	0.9600
C1—H1C	0.9600	C16—H16C	0.9600
C2—H2A	0.9600	C17—H17A	0.9600
C2—H2B	0.9600	C17—H17B	0.9600
C2—H2C	0.9600	C17—H17C	0.9600
C3—C4	1.478 (6)	Cl1—O13	1.398 (4)
C3—H3A	0.9700	Cl1—O14	1.398 (4)
C3—H3B	0.9700	Cl1—O12	1.404 (4)
C4—H4A	0.9700	Cl1—O11	1.420 (4)
C4—H4B	0.9700
N1—Ni1—N1^i	106.7 (2)	N2—C5—C5^i	111.51 (19)
N1—Ni1—N2	84.78 (14)	C5—O1—Ni2	110.6 (2)
N2^i—Ni1—N1	168.43 (14)	C6—N3—C10	118.2 (3)
N2^i—Ni1—N2	83.74 (18)	C6—N3—Ni2	127.5 (3)
N2^i—Ni1—N1^i	84.78 (14)	C10—N3—Ni2	113.8 (2)
N2—Ni1—N1^i	168.43 (14)	C15—N4—C11	117.8 (3)
O1—Ni2—O1^i	80.74 (13)	C15—N4—Ni2	127.2 (2)
N3—Ni2—O1	165.81 (10)	C11—N4—Ni2	113.8 (2)
N3—Ni2—O1^i	89.60 (10)	N3—C6—C7	122.3 (4)
N4—Ni2—O1	90.20 (10)	N3—C6—H6	118.8
N4—Ni2—O1^i	89.63 (11)	C7—C6—H6	118.8
N4—Ni2—N3	79.31 (11)	C6—C7—C8	120.5 (4)
N4—Ni2—N3^i	100.83 (12)	C6—C7—H7	119.8
N4^i—Ni2—N4	179.78 (17)	C8—C7—H7	119.8
N4^i—Ni2—N3	100.83 (12)	C7—C8—C9	116.8 (3)
N4^i—Ni2—N3^i	79.31 (11)	C7—C8—C16	122.1 (4)
N3—Ni2—N3^i	101.66 (16)	C9—C8—C16	121.1 (4)
N4^i—Ni2—O1	89.63 (11)	C10—C9—C8	120.4 (4)
N3^i—Ni2—O1	89.60 (10)	C10—C9—H9	119.8
N4^i—Ni2—O1^i	90.20 (10)	C8—C9—H9	119.8
N3^i—Ni2—O1^i	165.81 (10)	N3—C10—C9	121.8 (3)
C1—N1—C2	110.4 (4)	N3—C10—C11	115.0 (3)
C1—N1—C3	109.5 (4)	C9—C10—C11	123.2 (3)
C2—N1—C3	105.1 (4)	N4—C11—C12	121.1 (3)
C1—N1—Ni1	110.3 (3)	N4—C11—C10	114.7 (3)
C2—N1—Ni1	117.1 (3)	C12—C11—C10	124.2 (3)
C3—N1—Ni1	103.9 (3)	C11—C12—C13	121.4 (3)
C5—N2—C4	125.0 (3)	C11—C12—H12	119.3
C5—N2—Ni1	116.6 (2)	C13—C12—H12	119.3
C4—N2—Ni1	118.4 (2)	C12—C13—C14	116.6 (3)
N1—C1—H1A	109.5	C12—C13—C17	121.1 (3)
N1—C1—H1B	109.5	C14—C13—C17	122.2 (3)
H1A—C1—H1B	109.5	C15—C14—C13	119.4 (3)
N1—C1—H1C	109.5	C15—C14—H14	120.3
H1A—C1—H1C	109.5	C13—C14—H14	120.3
H1B—C1—H1C	109.5	N4—C15—C14	123.5 (3)
N1—C2—H2A	109.5	N4—C15—H15	118.2
N1—C2—H2B	109.5	C14—C15—H15	118.2
H2A—C2—H2B	109.5	C8—C16—H16A	109.5
N1—C2—H2C	109.5	C8—C16—H16B	109.5
H2A—C2—H2C	109.5	H16A—C16—H16B	109.5
H2B—C2—H2C	109.5	C8—C16—H16C	109.5
C4—C3—N1	110.8 (4)	H16A—C16—H16C	109.5
C4—C3—H3A	109.5	H16B—C16—H16C	109.5
N1—C3—H3A	109.5	C13—C17—H17A	109.5
C4—C3—H3B	109.5	C13—C17—H17B	109.5
N1—C3—H3B	109.5	H17A—C17—H17B	109.5
H3A—C3—H3B	108.1	C13—C17—H17C	109.5
N2—C4—C3	103.6 (3)	H17A—C17—H17C	109.5
N2—C4—H4A	111.0	H17B—C17—H17C	109.5
C3—C4—H4A	111.0	O13—Cl1—O14	107.5 (3)
N2—C4—H4B	111.0	O13—Cl1—O12	107.2 (3)
C3—C4—H4B	111.0	O14—Cl1—O12	110.0 (3)
H4A—C4—H4B	109.0	O13—Cl1—O11	112.7 (3)
O1—C5—N2	129.5 (3)	O14—Cl1—O11	110.2 (3)
O1—C5—C5^i	119.01 (18)	O12—Cl1—O11	109.3 (3)
N2^i—Ni1—N1—C1	99.4 (8)	O1—Ni2—N3—C10	−27.9 (6)
N2—Ni1—N1—C1	92.7 (3)	O1^i—Ni2—N3—C10	−74.7 (2)
N1^i—Ni1—N1—C1	−86.2 (3)	N3—Ni2—N4—C15	176.0 (3)
N2^i—Ni1—N1—C2	−133.1 (7)	N3^i—Ni2—N4—C15	76.0 (3)
N2—Ni1—N1—C2	−139.9 (4)	O1—Ni2—N4—C15	−13.6 (3)
N1^i—Ni1—N1—C2	41.2 (3)	O1^i—Ni2—N4—C15	−94.3 (3)
N2^i—Ni1—N1—C3	−17.8 (8)	N3—Ni2—N4—C11	−16.5 (2)
N2—Ni1—N1—C3	−24.6 (3)	N3^i—Ni2—N4—C11	−116.5 (2)
N1^i—Ni1—N1—C3	156.5 (3)	O1—Ni2—N4—C11	153.9 (2)
N2^i—Ni1—N2—C5	0.98 (19)	O1^i—Ni2—N4—C11	73.1 (2)
N1—Ni1—N2—C5	179.6 (3)	C10—N3—C6—C7	2.2 (6)
N1^i—Ni1—N2—C5	−5.8 (9)	Ni2—N3—C6—C7	−168.6 (3)
N2^i—Ni1—N2—C4	−176.9 (4)	N3—C6—C7—C8	−0.2 (6)
N1—Ni1—N2—C4	1.7 (3)	C6—C7—C8—C9	−1.2 (6)
N1^i—Ni1—N2—C4	176.3 (6)	C6—C7—C8—C16	178.4 (4)
C1—N1—C3—C4	−73.1 (5)	C7—C8—C9—C10	0.7 (5)
C2—N1—C3—C4	168.3 (4)	C16—C8—C9—C10	−178.9 (4)
Ni1—N1—C3—C4	44.8 (4)	C6—N3—C10—C9	−2.7 (5)
C5—N2—C4—C3	−155.4 (4)	Ni2—N3—C10—C9	169.4 (3)
Ni1—N2—C4—C3	22.4 (4)	C6—N3—C10—C11	176.8 (3)
N1—C3—C4—N2	−43.2 (5)	Ni2—N3—C10—C11	−11.2 (4)
C4—N2—C5—O1	−5.0 (6)	C8—C9—C10—N3	1.2 (5)
Ni1—N2—C5—O1	177.2 (3)	C8—C9—C10—C11	−178.2 (3)
C4—N2—C5—C5^i	175.4 (4)	C15—N4—C11—C12	2.9 (5)
Ni1—N2—C5—C5^i	−2.4 (5)	Ni2—N4—C11—C12	−165.8 (3)
N2—C5—O1—Ni2	177.8 (3)	C15—N4—C11—C10	−175.8 (3)
C5^i—C5—O1—Ni2	−2.6 (5)	Ni2—N4—C11—C10	15.5 (4)
C5—O1—Ni2—N4^i	91.2 (2)	N3—C10—C11—N4	−2.8 (4)
C5—O1—Ni2—N4	−88.6 (2)	C9—C10—C11—N4	176.6 (3)
C5—O1—Ni2—N3	−46.6 (5)	N3—C10—C11—C12	178.5 (3)
C5—O1—Ni2—N3^i	170.6 (2)	C9—C10—C11—C12	−2.1 (5)
C5—O1—Ni2—O1^i	0.98 (18)	N4—C11—C12—C13	−2.9 (5)
N4^i—Ni2—N3—C6	6.3 (3)	C10—C11—C12—C13	175.8 (3)
N4—Ni2—N3—C6	−173.9 (3)	C11—C12—C13—C14	1.6 (5)
N3^i—Ni2—N3—C6	−74.9 (3)	C11—C12—C13—C17	−179.1 (3)
O1—Ni2—N3—C6	143.2 (4)	C12—C13—C14—C15	−0.5 (5)
O1^i—Ni2—N3—C6	96.4 (3)	C17—C13—C14—C15	−179.8 (4)
N4^i—Ni2—N3—C10	−164.9 (2)	C11—N4—C15—C14	−1.9 (6)
N4—Ni2—N3—C10	15.0 (2)	Ni2—N4—C15—C14	165.1 (3)
N3^i—Ni2—N3—C10	114.0 (3)	C13—C14—C15—N4	0.7 (6)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O13	0.93	2.57	3.379 (6)	146
C12—H12···O1^ii	0.93	2.43	3.267 (4)	150

Symmetry code: (ii) x, −y+1, z+1/2.