Poly[[bis­{μ₂-N²,N⁶-bis­[(pyridin-3-yl)methyl]pyridine-2,6-dicarbox­amide}dichloridonickel(II)] N,N-dimethyl­formamide tetra­solvate]

In the title compound, {[NiCl₂(C₁₉H₁₇N₅O₂)₂]·4C₃H₇NO}_n, the Ni^II atom is located on an inversion centre and is in a six-coordinated octa­hedral geometry, formed by four pyridine N atoms from four N²,N⁶-bis­[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide (BPDA) ligands occupying the equatorial plane and two chloride anions at the axial sites. The bidentate bridging BPDA ligands link the Ni^II atoms into a two-dimensional corrugated grid-like flexible layer with a (4,4)-connected topology, which consists of left- and right-handed helical chains sharing the common Ni^II atoms. Investigation of the thermal stability shows that the network is stable up to 573 K.

S1. Comment

Owing to their intriguing architectures and potential applications in many areas, such as catalysis, sensing, magnetism, gas storage and separation, metal–organic frameworks have been widely investigated in the last decade (Bradshaw et al., 2005). U-Shaped symmetric bis(amidopyridine) ligands are frequently used, based on benzene-1,2-diamine, pyridine-2,6-diamine and pyridine-2,6-dicarboxylic acid, which combine a rigid aromatic group in the centre and flexible binding arms on each side. These compounds have flexible conformations and excellent self-assembly, through coordination bonds and hydrogen bonds occurring from the amide substitutes. These spacers can construct novel metal-containing structural motifs, such as isolated macrocycles, helicates and dynamic porous frameworks (Pan et al., 2010; Uemura et al., 2002; Burchell et al., 2006). For example, from reactions of a bis(pyridyl)-bis(amide) ligand, N²,N⁶-bis(pyridin-3-yl)pyridine-2,6-dicarboxamide, with nickel(II) and cobalt(II) salts, Li et al. (2012) produced a tetragonal molecular cage and a one-dimensional polymeric macrocyclic complex. Herein, we report the reaction of the multifunctional ligand N²,N⁶-bis[(pyridin-3-yl)methyl]pyridine-2,6-dicarboxamide (BPDA), in which each binding arm is elongated by one methylene unit compared with the analogous ligand N²,N⁶-bis(pyridin-3-yl)pyridine-2,6-dicarboxamide, and we report a novel nickel(II) coordination polymer of BPDA, the title compound, {[NiCl₂(BPDA)₂].4DMF}_n, (I) (DMF is N,N-dimethylformamide).

In (I), the Ni^II atom is located on an inversion centre in a six-coordinated octahedral geometry, with four pyridine N atoms of four BPDA ligands occupying the equatorial plane and two chloride anions at the axial sites (Fig. 1). The four coordinated pyridine N atoms are almost coplanar with the Ni^II atom. The four pyridine rings are arranged around the Ni^II atom in the well known paddlewheel pattern, with Ni—N bond lengths of 2.212 (2) (Ni1—N3) and 2.149 (2) Å [Ni1—N5ⁱ; symmetry code: (i) -x, y - 1/2, -z + 1/2]. The two chloride anions located at the axial sites are almost perpendicular to the equatorial plane. The Ni—Cl distance is 2.4450 (7) Å.

In (I), the U-shaped BPDA ligands lower the C_2v symmetry into pseudo-C₂ symmetry and adopt a helical conformation, with the pyridin-3-yl arms obviously twisted from the central pyridine ring [the dihedral angles between the pyridin-3-yl arms and the central pyridine are 78.3(s.u.?) and 84.1(s.u.?)°]. The helical conformation of BPDA is very similar to that of the isomer N,N'-bis[(pyridin-2-yl)methyl]pyridine-2,6-dicarboxamide found in Ag^I polymers (Wu et al., 2010). Bidentate bridging BPDA ligands link the Ni^II atoms into a two-dimensional corrugated sheet in the bc plane (Fig. 2), with a uniform (4,4)-connected topology. The layer structure of (I) is entwined along the b axis through left- and right-handed helical chains sharing the common Ni^II atoms, with a long pitch of 19.039 Å. Within this net, there are two types of helical chain which partially overlap with the adjacent central BPDA pyridine rings, resulting in two equal nano-squares which form one-dimensional channels as described below. The separation of adjacent Ni nodes bridged by BPDA is 13.508(s.u.?) Å.

In (I), the two-dimensional networks align through π–π stacking interactions between pyridine rings in adjacent layers, with the centroid-to-centroid distance being 3.72 (6) Å, and are thus extended into a three-dimensional supramolecular architecture with intriguing one-dimensional channels along the a axis (Fig. 3). The DMF molecules interact through N—H···O hydrogen-bonding interactions between the NH groups of the BPDA ligands and the DMF O atoms, or they occupy the channels. The percentage of effective free volume in (I) is 38.2% [total potential solvent volume of 1020.5(s.u.?) ų out of the unit-cell volume of 2674.8(s.u.?) ų] calculated using PLATON (Spek, 2003) with the DMF molecules removed from the model, indicating that the network structure of (I) could potentially provide a porous material for [ion?] absorption and exchange.

Thermogravimetric analysis (TGA) of (I) was carried out under an air atmosphere from 303 to 1023 K at a heating rate of 10 K min^-1 using a crystalline sample. As shown in Fig. 4, there are three weight-loss steps on heating. In the range 308–463 K, a weight loss of 22.52% occurs, corresponding to the loss of the four solvent DMF molecules. On heating above 573 K, a second weight-loss step is observed in the temperature range 573–688 K with a weight loss of 32.78%. This step indicates the decomposition of the framework in (I). A successive mass loss of 37.84% occurs in the temperature range 688–973 K, indicating the complete decomposition of the complex. The remaining 6.86% may be NiO, in good agreement with the theoretical value of 6.62%. These TGA results indicate that the two-dimensional network structure of (I) is stable up to 573 K.

Related literature

For related literature, see: Bradshaw et al. (2005); Burchell et al. (2006); Li et al. (2012); Pan et al. (2010); Spek (2003); Uemura et al. (2002); Wu et al. (2010); Yang et al. (2012).

S2. Experimental

BPDA was synthesised according to the method of Yang et al. (2012). For the preparation of the title compound, a solution of BPDA (69.4 mg, 0.2 mmol) in DMF (6 ml) was added dropwise to a solution of NiCl₂.6H₂O (23.8 mg, 0.1 mmol) in methanol (6 ml). The resulting mixture was stirred for 30 min and then filtered. The filtrate was allowed to evaporate at room temperature for a period of one month, producing green crystals of (I) in 56% yield. Selected IR data (KBr pellet, ν, cm^-1): 3268 (m), 3059 (w), 2930 (w), 1665 (vs), 1534 (vs), 1435 (s), 1382 (m), 1104 (m), 711 (m), 679 (m).

S3. Refinement

H atoms bonded to C atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) or 0.99 Å (methylene), and with U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise. The positions of the H atoms bonded to N atoms were refined with U_iso(H) = 1.2U_eq(C25).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment of the Ni^II atoms in (I). [Symmetry codes: (i) -x, y - 1/2, -z + 1/2; (ii) x, -y - 1/2, z + 1/2; (iii) -x, -y - 1, -z + 1.]
	Fig. 2. A view of the two-dimensional corrugated sheet of (I) (middle), formed by left- (left) and right-handed (right) helical chains sharing the common Ni^II atoms.
	Fig. 3. A view of the straight stacking of the layers in (I), with intriguing one-dimensional channels along the a axis being occupied by guest DMF molecules.
	Fig. 4. The TGA curve of (I).

Poly[[bis{µ₂-N²,N⁶-bis[(pyridin-3-yl)methyl]pyridine- 2,6-dicarboxamide}dichloridonickel(II)] N,N-dimethylformamide tetrasolvate]

Crystal data

[NiCl2(C19H17N5O2)2]·4C3H7NO	F(000) = 1172
Mr = 1116.75	Dx = 1.387 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ybc	Cell parameters from 2607 reflections
a = 7.6822 (8) Å	θ = 2.8–22.7°
b = 19.039 (2) Å	µ = 0.53 mm^−1
c = 19.1684 (18) Å	T = 293 K
β = 107.432 (4)°	Prism, green
V = 2674.8 (5) Å^3	0.31 × 0.24 × 0.11 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	3382 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 25.0°, θmin = 2.4°
ω scans	h = −9→9
18986 measured reflections	k = −22→22
4712 independent reflections	l = −22→22

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0518P)^2 + 0.0123P] where P = (Fo^2 + 2Fc^2)/3
4712 reflections	(Δ/σ)max < 0.001
350 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.24 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	0.0000	−0.5000	0.5000	0.03094 (16)
Cl1	0.29339 (9)	−0.44213 (4)	0.55473 (4)	0.0395 (2)
O1	−0.0909 (3)	−0.12612 (11)	0.58282 (11)	0.0605 (6)
O2	−0.4275 (3)	0.13157 (11)	0.31366 (11)	0.0555 (6)
O3	−0.1777 (4)	−0.11447 (13)	0.30310 (14)	0.0870 (9)
O4	−0.7336 (4)	−0.22197 (15)	0.36157 (15)	0.0881 (9)
N1	−0.2586 (3)	−0.01407 (11)	0.42927 (12)	0.0342 (5)
N2	−0.1097 (3)	−0.14252 (12)	0.46427 (13)	0.0415 (6)
N3	−0.1430 (3)	−0.39819 (11)	0.49317 (12)	0.0345 (5)
N4	−0.3411 (3)	0.02348 (13)	0.28741 (13)	0.0398 (6)
N5	−0.0180 (3)	0.02437 (11)	0.10711 (12)	0.0341 (5)
N6	−0.2511 (5)	−0.20905 (16)	0.22920 (16)	0.0683 (9)
N7	−0.7526 (4)	−0.19078 (16)	0.24524 (15)	0.0669 (8)
C1	−0.1336 (4)	−0.10497 (15)	0.51957 (15)	0.0389 (7)
C2	−0.2166 (4)	−0.03320 (14)	0.49941 (14)	0.0353 (7)
C3	−0.2428 (4)	0.01018 (16)	0.55336 (16)	0.0451 (8)
H3	−0.2101	−0.0050	0.6028	0.054*
C4	−0.3171 (4)	0.07555 (17)	0.53410 (16)	0.0504 (8)
H4	−0.3366	0.1064	0.5700	0.060*
C5	−0.3629 (4)	0.09585 (16)	0.46163 (16)	0.0435 (7)
H5	−0.4167	0.1404	0.4467	0.052*
C6	−0.3289 (3)	0.05000 (14)	0.41134 (14)	0.0323 (6)
C7	−0.3711 (4)	0.07215 (15)	0.33260 (15)	0.0368 (7)
C8	−0.0152 (4)	−0.20960 (15)	0.47661 (17)	0.0438 (7)
H8A	0.0832	−0.2073	0.5237	0.053*
H8B	0.0432	−0.2169	0.4376	0.053*
C9	−0.1338 (4)	−0.27255 (14)	0.47823 (14)	0.0355 (7)
C10	−0.3199 (4)	−0.26881 (15)	0.46779 (16)	0.0440 (7)
H10	−0.3816	−0.2250	0.4582	0.053*
C11	−0.4144 (4)	−0.32972 (16)	0.47151 (16)	0.0473 (8)
H11	−0.5417	−0.3281	0.4654	0.057*
C12	−0.3233 (4)	−0.39237 (15)	0.48413 (15)	0.0402 (7)
H12	−0.3902	−0.4338	0.4866	0.048*
C13	−0.0544 (4)	−0.33824 (14)	0.48939 (14)	0.0350 (7)
H13	0.0724	−0.3413	0.4948	0.042*
C14	−0.3636 (4)	0.03758 (17)	0.21066 (14)	0.0415 (7)
H14A	−0.4293	0.0826	0.1968	0.050*
H14B	−0.4389	0.0000	0.1805	0.050*
C15	−0.1824 (3)	0.04147 (14)	0.19447 (14)	0.0331 (6)
C16	−0.0250 (4)	0.06378 (15)	0.24615 (15)	0.0407 (7)
H16	−0.0267	0.0769	0.2938	0.049*
C17	0.1352 (4)	0.06667 (16)	0.22728 (15)	0.0450 (8)
H17	0.2450	0.0825	0.2616	0.054*
C18	0.1334 (4)	0.04617 (15)	0.15787 (15)	0.0407 (7)
H18	0.2444	0.0476	0.1457	0.049*
C19	−0.1722 (4)	0.02244 (14)	0.12611 (14)	0.0334 (6)
H19	−0.2808	0.0071	0.0906	0.040*
C20	−0.2059 (7)	−0.1441 (2)	0.2437 (2)	0.0897 (14)
H20	−0.1932	−0.1163	0.2044	0.108*
C21	−0.2747 (8)	−0.2423 (3)	0.1592 (2)	0.126 (2)
H21A	−0.2411	−0.2093	0.1262	0.189*
H21B	−0.4025	−0.2563	0.1382	0.189*
H21C	−0.1965	−0.2840	0.1658	0.189*
C22	−0.2702 (6)	−0.2536 (2)	0.2878 (2)	0.0913 (14)
H22A	−0.1527	−0.2758	0.3125	0.137*
H22B	−0.3616	−0.2900	0.2676	0.137*
H22C	−0.3092	−0.2251	0.3230	0.137*
C23	−0.7580 (5)	−0.2355 (2)	0.2968 (2)	0.0708 (11)
H23	−0.7834	−0.2831	0.2824	0.085*
C24	−0.7856 (8)	−0.2117 (3)	0.1698 (2)	0.1121 (18)
H24A	−0.8119	−0.2621	0.1649	0.168*
H24B	−0.6772	−0.2016	0.1546	0.168*
H24C	−0.8900	−0.1855	0.1387	0.168*
C25	−0.7108 (8)	−0.1183 (2)	0.2631 (3)	0.1151 (18)
H25A	−0.8120	−0.0963	0.2763	0.173*
H25B	−0.6929	−0.0940	0.2207	0.173*
H25C	−0.5991	−0.1150	0.3044	0.173*
H2	−0.143 (6)	−0.121 (3)	0.421 (3)	0.138*
H4A	−0.289 (7)	−0.015 (2)	0.306 (3)	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0304 (3)	0.0331 (3)	0.0307 (3)	−0.0005 (2)	0.0112 (2)	0.0028 (2)
Cl1	0.0349 (4)	0.0406 (4)	0.0421 (4)	−0.0019 (3)	0.0100 (3)	0.0015 (3)
O1	0.0940 (18)	0.0542 (14)	0.0314 (12)	0.0054 (13)	0.0158 (12)	0.0099 (10)
O2	0.0734 (16)	0.0477 (14)	0.0452 (13)	0.0194 (12)	0.0174 (11)	0.0081 (11)
O3	0.154 (3)	0.0560 (16)	0.0536 (16)	0.0120 (16)	0.0349 (17)	−0.0107 (13)
O4	0.108 (2)	0.100 (2)	0.0580 (18)	0.0199 (17)	0.0277 (16)	0.0097 (15)
N1	0.0360 (13)	0.0359 (14)	0.0315 (13)	−0.0054 (10)	0.0114 (10)	−0.0021 (10)
N2	0.0537 (16)	0.0319 (14)	0.0385 (14)	0.0033 (12)	0.0131 (13)	0.0038 (11)
N3	0.0377 (14)	0.0345 (14)	0.0326 (13)	0.0006 (11)	0.0125 (10)	0.0055 (10)
N4	0.0447 (15)	0.0458 (16)	0.0322 (13)	0.0026 (12)	0.0164 (12)	0.0021 (11)
N5	0.0327 (13)	0.0371 (13)	0.0325 (13)	0.0005 (10)	0.0097 (11)	−0.0016 (10)
N6	0.103 (3)	0.0512 (19)	0.0540 (19)	−0.0052 (17)	0.0288 (18)	−0.0085 (15)
N7	0.094 (2)	0.055 (2)	0.0505 (19)	0.0024 (17)	0.0198 (17)	0.0003 (15)
C1	0.0467 (18)	0.0355 (17)	0.0348 (18)	−0.0078 (14)	0.0128 (14)	0.0020 (14)
C2	0.0392 (16)	0.0370 (17)	0.0317 (16)	−0.0087 (13)	0.0140 (13)	−0.0026 (13)
C3	0.056 (2)	0.049 (2)	0.0295 (16)	−0.0043 (15)	0.0120 (14)	−0.0017 (14)
C4	0.066 (2)	0.051 (2)	0.0389 (18)	0.0011 (17)	0.0225 (16)	−0.0106 (15)
C5	0.0464 (18)	0.0411 (18)	0.0448 (19)	0.0004 (14)	0.0164 (15)	−0.0039 (14)
C6	0.0298 (15)	0.0345 (16)	0.0341 (15)	−0.0028 (12)	0.0118 (12)	−0.0020 (13)
C7	0.0346 (16)	0.0404 (18)	0.0365 (16)	0.0024 (13)	0.0122 (13)	0.0004 (14)
C8	0.0492 (19)	0.0349 (17)	0.0460 (18)	0.0002 (14)	0.0123 (15)	0.0054 (14)
C9	0.0409 (17)	0.0361 (16)	0.0297 (15)	0.0023 (13)	0.0108 (13)	0.0031 (12)
C10	0.0448 (19)	0.0353 (17)	0.0516 (19)	0.0082 (14)	0.0142 (15)	0.0053 (14)
C11	0.0347 (17)	0.047 (2)	0.061 (2)	0.0054 (15)	0.0159 (15)	0.0083 (16)
C12	0.0412 (18)	0.0394 (18)	0.0429 (18)	−0.0026 (14)	0.0171 (14)	0.0018 (14)
C13	0.0344 (16)	0.0378 (17)	0.0334 (16)	0.0008 (13)	0.0109 (13)	0.0035 (13)
C14	0.0398 (17)	0.058 (2)	0.0283 (15)	0.0038 (15)	0.0118 (13)	0.0015 (14)
C15	0.0344 (16)	0.0367 (16)	0.0269 (15)	0.0026 (13)	0.0071 (12)	0.0014 (12)
C16	0.0422 (18)	0.0498 (19)	0.0288 (15)	0.0024 (14)	0.0088 (13)	−0.0046 (13)
C17	0.0345 (17)	0.060 (2)	0.0349 (17)	−0.0067 (14)	0.0021 (13)	−0.0078 (14)
C18	0.0294 (16)	0.0516 (19)	0.0403 (17)	−0.0018 (14)	0.0090 (13)	−0.0051 (14)
C19	0.0297 (15)	0.0389 (16)	0.0301 (15)	−0.0018 (12)	0.0067 (12)	−0.0004 (12)
C20	0.143 (4)	0.064 (3)	0.068 (3)	0.011 (3)	0.042 (3)	0.003 (2)
C21	0.203 (6)	0.116 (4)	0.076 (3)	−0.047 (4)	0.068 (4)	−0.045 (3)
C22	0.123 (4)	0.069 (3)	0.075 (3)	−0.016 (3)	0.019 (3)	0.002 (2)
C23	0.081 (3)	0.059 (2)	0.068 (3)	0.009 (2)	0.017 (2)	0.002 (2)
C24	0.171 (5)	0.113 (4)	0.051 (3)	−0.001 (3)	0.031 (3)	−0.007 (2)
C25	0.191 (6)	0.064 (3)	0.098 (4)	−0.023 (3)	0.055 (4)	−0.005 (3)

Geometric parameters (Å, º)

Ni1—N3	2.212 (2)	C6—C7	1.506 (4)
Ni1—N5^i	2.149 (2)	C8—C9	1.512 (4)
Ni1—N5^ii	2.149 (2)	C8—H8A	0.9900
Ni1—N3^iii	2.212 (2)	C8—H8B	0.9900
Ni1—Cl1	2.4450 (7)	C9—C13	1.380 (4)
Ni1—Cl1^iii	2.4450 (7)	C9—C10	1.385 (4)
O1—C1	1.225 (3)	C10—C11	1.382 (4)
O2—C7	1.227 (3)	C10—H10	0.9500
O3—C20	1.230 (4)	C11—C12	1.367 (4)
O4—C23	1.226 (4)	C11—H11	0.9500
N1—C6	1.336 (3)	C12—H12	0.9500
N1—C2	1.336 (3)	C13—H13	0.9500
N2—C1	1.336 (3)	C14—C15	1.516 (4)
N2—C8	1.453 (4)	C14—H14A	0.9900
N2—H2	0.89 (5)	C14—H14B	0.9900
N3—C13	1.342 (3)	C15—C16	1.380 (4)
N3—C12	1.348 (3)	C15—C19	1.384 (3)
N4—C7	1.335 (3)	C16—C17	1.384 (4)
N4—C14	1.454 (3)	C16—H16	0.9500
N4—H4A	0.86 (5)	C17—C18	1.383 (4)
N5—C19	1.340 (3)	C17—H17	0.9500
N5—C18	1.340 (3)	C18—H18	0.9500
N5—Ni1^iv	2.149 (2)	C19—H19	0.9500
N6—C20	1.292 (5)	C20—H20	0.9500
N6—C21	1.445 (5)	C21—H21A	0.9800
N6—C22	1.450 (5)	C21—H21B	0.9800
N7—C23	1.314 (4)	C21—H21C	0.9800
N7—C25	1.436 (5)	C22—H22A	0.9800
N7—C24	1.448 (4)	C22—H22B	0.9800
C1—C2	1.509 (4)	C22—H22C	0.9800
C2—C3	1.384 (4)	C23—H23	0.9500
C3—C4	1.373 (4)	C24—H24A	0.9800
C3—H3	0.9500	C24—H24B	0.9800
C4—C5	1.382 (4)	C24—H24C	0.9800
C4—H4	0.9500	C25—H25A	0.9800
C5—C6	1.382 (4)	C25—H25B	0.9800
C5—H5	0.9500	C25—H25C	0.9800
N5^i—Ni1—N5^ii	180.00 (11)	C11—C10—C9	119.0 (3)
N5^i—Ni1—N3	85.83 (8)	C11—C10—H10	120.5
N5^ii—Ni1—N3	94.17 (8)	C9—C10—H10	120.5
N5^i—Ni1—N3^iii	94.17 (8)	C12—C11—C10	119.5 (3)
N5^ii—Ni1—N3^iii	85.83 (8)	C12—C11—H11	120.3
N3—Ni1—N3^iii	180.0	C10—C11—H11	120.3
N5^i—Ni1—Cl1	89.87 (6)	N3—C12—C11	123.1 (3)
N5^ii—Ni1—Cl1	90.13 (6)	N3—C12—H12	118.4
N3—Ni1—Cl1	90.46 (6)	C11—C12—H12	118.4
N3^iii—Ni1—Cl1	89.54 (6)	N3—C13—C9	124.9 (3)
N5^i—Ni1—Cl1^iii	90.13 (6)	N3—C13—H13	117.6
N5^ii—Ni1—Cl1^iii	89.87 (6)	C9—C13—H13	117.6
N3—Ni1—Cl1^iii	89.54 (6)	N4—C14—C15	112.2 (2)
N3^iii—Ni1—Cl1^iii	90.46 (6)	N4—C14—H14A	109.2
Cl1—Ni1—Cl1^iii	180.00 (3)	C15—C14—H14A	109.2
C6—N1—C2	117.7 (2)	N4—C14—H14B	109.2
C1—N2—C8	121.5 (2)	C15—C14—H14B	109.2
C1—N2—H2	115 (3)	H14A—C14—H14B	107.9
C8—N2—H2	123 (3)	C16—C15—C19	118.3 (2)
C13—N3—C12	116.2 (2)	C16—C15—C14	121.9 (2)
C13—N3—Ni1	119.85 (17)	C19—C15—C14	119.8 (2)
C12—N3—Ni1	123.54 (18)	C15—C16—C17	118.7 (3)
C7—N4—C14	122.5 (2)	C15—C16—H16	120.6
C7—N4—H4A	119 (3)	C17—C16—H16	120.6
C14—N4—H4A	118 (3)	C18—C17—C16	119.2 (3)
C19—N5—C18	117.2 (2)	C18—C17—H17	120.4
C19—N5—Ni1^iv	124.67 (18)	C16—C17—H17	120.4
C18—N5—Ni1^iv	118.05 (18)	N5—C18—C17	122.8 (3)
C20—N6—C21	124.8 (4)	N5—C18—H18	118.6
C20—N6—C22	118.4 (3)	C17—C18—H18	118.6
C21—N6—C22	116.7 (3)	N5—C19—C15	123.7 (2)
C23—N7—C25	120.0 (3)	N5—C19—H19	118.1
C23—N7—C24	122.5 (4)	C15—C19—H19	118.1
C25—N7—C24	117.5 (3)	O3—C20—N6	126.9 (4)
O1—C1—N2	123.3 (3)	O3—C20—H20	116.6
O1—C1—C2	121.2 (3)	N6—C20—H20	116.6
N2—C1—C2	115.4 (2)	N6—C21—H21A	109.5
N1—C2—C3	122.9 (3)	N6—C21—H21B	109.5
N1—C2—C1	117.4 (2)	H21A—C21—H21B	109.5
C3—C2—C1	119.6 (2)	N6—C21—H21C	109.5
C4—C3—C2	118.8 (3)	H21A—C21—H21C	109.5
C4—C3—H3	120.6	H21B—C21—H21C	109.5
C2—C3—H3	120.6	N6—C22—H22A	109.5
C3—C4—C5	118.9 (3)	N6—C22—H22B	109.5
C3—C4—H4	120.5	H22A—C22—H22B	109.5
C5—C4—H4	120.5	N6—C22—H22C	109.5
C6—C5—C4	118.7 (3)	H22A—C22—H22C	109.5
C6—C5—H5	120.7	H22B—C22—H22C	109.5
C4—C5—H5	120.7	O4—C23—N7	126.5 (4)
N1—C6—C5	122.9 (3)	O4—C23—H23	116.7
N1—C6—C7	117.5 (2)	N7—C23—H23	116.7
C5—C6—C7	119.5 (3)	N7—C24—H24A	109.5
O2—C7—N4	124.2 (3)	N7—C24—H24B	109.5
O2—C7—C6	120.4 (2)	H24A—C24—H24B	109.5
N4—C7—C6	115.4 (2)	N7—C24—H24C	109.5
N2—C8—C9	115.2 (2)	H24A—C24—H24C	109.5
N2—C8—H8A	108.5	H24B—C24—H24C	109.5
C9—C8—H8A	108.5	N7—C25—H25A	109.5
N2—C8—H8B	108.5	N7—C25—H25B	109.5
C9—C8—H8B	108.5	H25A—C25—H25B	109.5
H8A—C8—H8B	107.5	N7—C25—H25C	109.5
C13—C9—C10	117.3 (3)	H25A—C25—H25C	109.5
C13—C9—C8	118.7 (2)	H25B—C25—H25C	109.5
C10—C9—C8	124.0 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.89 (5)	2.20 (5)	3.023 (3)	154 (4)
N4—H4A···O3	0.86 (5)	2.08 (5)	2.887 (3)	156 (4)