A novel nickel(II) coordination polymer incorporating 1,4-phenylene­diacetic acid and 1,10-phenanthroline

The title nickel(II) coordination polymer, viz. poly[[bis­(1,10-phenanthroline)tris­(μ₃-1,4-phenyl­enediacetato)trinickel(II)] dihydrate], {[Ni₃(C₁₀H₈O₄)₃(C₁₂H₈N₂)₂]·2H₂O}_n, consists of linear trinuclear building blocks with two crystallographically unique Ni atoms. One Ni^II atom and the geometric centre of one 1,4-phenyl­enediacetate ligand in the trinuclear unit both lie on inversion centres, while the other unique Ni^II atom lies near the inversion centre, together with another 1,4-phenyl­enediacetate ligand. Each pair of adjacent trinuclear units is bridged by 1,4-phenyl­enediacetate ligands, forming two kinds of infinite chains along the a and b axes, respectively. These two kinds of chains crosslink to yield a two-dimensional network in the ab plane. The two-dimensional sheets further stack along the c axis via π–π stacking inter­actions and hydrogen bonds, forming a three-dimensional supramolecular structure.

S1. Comment

The rational design of high-dimensional metal–organic frameworks has attracted much attention, owing to their fascinating framework structures and their potential applications as functional solid materials, such as gas storage, heterogeneous catalysis and magnetic materials (Kitaura et al., 2002; Seo et al., 2000; Pavlishchuk et al., 2001; Swiegers et al., 2000; Hagrman et al., 1999). Among the linker molecules, carboxylic acids with aromatic rings have been extensively studied because of their versatile properties. Such work has usually concentrated on rigid aromatic carboxylic acids, such as 1,4-dicarboxylic benzoic acid and 1,2,4-tricarboxylic benzoic acid (Stepanow et al., 2004; Rosi et al., 2003). The use of much more flexible aromatic carboxylic acids, such as 1,4-phenylenediacetic acids (H₂PDA) (Lin et al., 2005; Babb et al., 2003), is rare. Metal–organic frameworks assembled with 1,4-phenylenediacetic acids may show much more interesting properties. It is also interesting to investigate the structural changes while such compounds are functioning as solid materials. In this work, we introduce an ancillary ligand of 1,10-phenanthroline (phen) to tune the structure. Therefore, we report here the synthesis and X-ray structure of the title complex, {[Ni₃(phen)₂(PDA)₃]·2H₂O}_n, (I), which exhibits a two-dimensional network structure assembled from Ni^II cations and 1,4-phenylenediacetate anions via two kinds of cross-linked one-dimensional chains.

Single-crystal X-ray diffraction analysis reveals that compound (I) consists of trinuclear nickel building blocks, [Ni₃(phen)₂(PDA)₃] (Fig. 1), in which atom Ni1 and the geometric centre of one PDA²⁻ ligand both lie on inversion centres. Another crystallographically unique Ni^II atom (Ni2) and another PDA²⁻ ligand are located near the inversion centre. Both crystallographically unique Ni^II atoms (Ni1 and Ni2) have distorted octahedral coordination environments. Atom Ni1 is coordinated to six carboxylate O atoms from six PDA²⁻ ligands, with Ni—O bond lengths in the range 2.031 (2)–2.104 (2) Å and the O—Ni1—O bond angles varying from 85.27 (9) to 180.0° (Table 1). Atom Ni2 is coordinated to two N atoms from one phen molecule and four carboxylate O atoms from three carboxylate groups of PDA²⁻ ligands, with the Ni—N and Ni—O bond lengths in the ranges 2.071 (3)–2.089 (3) and 1.990 (2)–2.268 (2) Å, respectively. The O—Ni2—O bond angles range from 60.31 (8) to 159.39 (9)°. These carboxylate groups of the 1,4-phenylenediacetate ligands show two types of coordination mode. One type of carboxylate group chelates to one Ni^II atom and, at the same time, affords one of the carboxylate O atoms to bridge another Ni^II atom. The other type of carboxylate group acts simply as a bidentate bridge connecting two Ni^II atoms. Therefore, two Ni2 atoms are bridged to one Ni1 atom via six bridging carboxylate groups, resulting in the formation of a linear trinuclear nickel unit with an Ni1···Ni2 separation of 3.4714 (7) Å.

Each pair of neighbouring trinuclear [Ni₃(phen)₂(PDA)₃] units is connected by two PDA²⁻ ligands to form an infinite coordination chain along the a axis. The shortest Ni1···Ni1 or Ni2···Ni2 separation in this chain is 10.708 (3) Å. Alternatively, another kind of one-dimensional coordination chain is constructed via the bridging of each pair of adjacent trinuclear [Ni₃(phen)₂(PDA)₃] units by one PDA²⁻ ligand along the b axis. The shortest Ni1···Ni1 or Ni2···Ni2 separation in this chain is 11.172 (3) Å. The two types of infinite chains cross-link in the ab plane to yield a two-dimensional network, as shown in Fig. 2. This differs from the reported structures of 1,4-phenylenediacetate complexes, which exhibit only one-dimensional infinite chains (Lin et al., 2005; Babb et al., 2003).

As shown in Fig. 3, 1,10-phenanthroline molecules from adjacent two-dimensional sheets are parallel to each other and partly overlap in a head-to-tail mode with a separation of 3.4296 Å, indicating significant π–π stacking effects. These π–π stacking interactions between 1,10-phenanthroline molecules lead to the formation of a three-dimensional supramolecular network by the stacking of two-dimensional sheets along the c axis. Free water molecules in the structure interact with adjacent two-dimensional sheets by formation of hydrogen bonds (Table 2), further stabilizing the three-dimensional supramolecular structure.

S2. Experimental

To a mixture of NiCl₂·6H₂O (0.0951 g, 0.4 mmol), 1,4-phenylenediacetic acid (0.1572 g, 0.8 mmol), NaOH (0.064 g, 1.6 mmol) and phen (0.0793 g, 0.4 mmol), placed in a 23 ml Teflon-lined autoclave, were added distilled water (8 ml) and ethanol (2 ml). The mixture was then heated at 433 K for 200 h. The autoclave was then cooled over a period of 48 h and the resulting green crystals of (I) were separated from the solution and dried. Elemental analysis for C₅₄H₄₄N₄Ni₃O₁₄, calculated: C 56.45, H 3.86, N 4.88%; found: C 56.47, H 3.65, N 4.24%.

S3. Refinement

H atoms of water molecules were located in a difference Fourier map. During refinement, O—H and H···H distances were restrained to ensure a reasonable geometry for the water molecules. H atoms on C atoms were placed in calculated positions, with C—H = 0.93 Å in aromatic rings and 0.97 Å for others, and refined in riding mode with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids. For clarity, H atoms have been omitted. Atoms labelled with the suffixes A–C are at the symmetry positions (−x + 1, −y + 1, −z + 2), (x − 1, y, z) and (−x + 2, −y + 1, −z + 2), respectively.
	Fig. 2. The two-dimensional network in the structure of (I). For clarity, H atoms and 1,10-phenanthroline molecules have been omitted.
	Fig. 3. A packing diagram of the two-dimensional sheets along the c axis. Dashed lines indicate O—H···O hydrogen bonds.

poly[[bis(1,10-phenanthroline)tris(µ₃-1,4-phenylenediacetato)trinickel(II)] dihydrate]

Crystal data

[Ni3(C10H8O4)3(C12H8N2)2]·2H2O	Z = 1
Mr = 1149.06	F(000) = 592
Triclinic, P1	Dx = 1.604 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.708 (3) Å	Cell parameters from 2429 reflections
b = 11.172 (3) Å	θ = 2.2–27.8°
c = 12.448 (3) Å	µ = 1.25 mm^−1
α = 107.126 (4)°	T = 298 K
β = 101.059 (4)°	Block, green
γ = 115.803 (3)°	0.29 × 0.17 × 0.14 mm
V = 1189.3 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4148 independent reflections
Radiation source: fine-focus sealed tube	3102 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→12
Tmin = 0.713, Tmax = 0.844	k = −13→13
6299 measured reflections	l = −14→8

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0296P)^2 + 0.6844P] where P = (Fo^2 + 2Fc^2)/3
4148 reflections	(Δ/σ)max = 0.004
346 parameters	Δρmax = 0.60 e Å^−3
3 restraints	Δρmin = −0.33 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	0.5000	1.0000	0.02372 (15)
Ni2	0.26388 (4)	0.42348 (4)	0.72300 (3)	0.02559 (13)
N1	0.1354 (3)	0.5204 (3)	0.7334 (2)	0.0286 (6)
N2	0.0885 (3)	0.2830 (3)	0.5572 (2)	0.0297 (6)
O1	0.4903 (2)	0.3409 (2)	0.85126 (19)	0.0305 (5)
O2	0.3798 (2)	0.3326 (2)	0.67459 (19)	0.0340 (5)
O3	1.2841 (2)	0.3732 (2)	0.97944 (19)	0.0328 (5)
O4	1.1469 (2)	0.2806 (2)	0.7831 (2)	0.0352 (6)
O5	0.4366 (2)	0.5854 (2)	0.88518 (18)	0.0258 (5)
O6	0.4473 (2)	0.6300 (2)	0.7267 (2)	0.0379 (6)
O7	0.3489 (4)	0.3213 (6)	0.4110 (4)	0.1086 (14)
H28	0.421 (5)	0.398 (4)	0.417 (6)	0.130*
H29	0.391 (6)	0.309 (7)	0.468 (4)	0.130*
C1	0.6585 (3)	0.2249 (4)	0.7380 (3)	0.0315 (8)
C2	0.7634 (4)	0.3260 (4)	0.8531 (3)	0.0357 (8)
H2	0.7567	0.4053	0.8958	0.043*
C3	0.8782 (3)	0.3099 (4)	0.9051 (3)	0.0352 (8)
H3	0.9474	0.3789	0.9826	0.042*
C4	0.8928 (3)	0.1943 (4)	0.8450 (3)	0.0312 (8)
C5	0.7887 (4)	0.0938 (4)	0.7308 (3)	0.0393 (9)
H5	0.7957	0.0146	0.6883	0.047*
C6	0.6738 (4)	0.1090 (4)	0.6784 (3)	0.0405 (9)
H6	0.6048	0.0395	0.6010	0.049*
C7	0.4650 (3)	0.3118 (3)	0.7418 (3)	0.0270 (7)
C8	0.5361 (4)	0.2406 (5)	0.6732 (3)	0.0476 (10)
H8A	0.4560	0.1427	0.6141	0.057*
H8B	0.5755	0.2956	0.6279	0.057*
C9	1.1657 (3)	0.2905 (3)	0.8883 (3)	0.0261 (7)
C10	1.0257 (3)	0.1877 (4)	0.9033 (3)	0.0329 (8)
H10A	1.0036	0.0877	0.8666	0.039*
H10B	1.0442	0.2152	0.9888	0.039*
C11	0.5667 (3)	0.9196 (3)	0.9634 (3)	0.0320 (8)
C12	0.5504 (4)	1.0050 (3)	0.9066 (3)	0.0345 (8)
H12	0.5845	1.0091	0.8436	0.041*
C13	0.4844 (3)	1.0839 (3)	0.9425 (3)	0.0352 (8)
H13	0.4741	1.1401	0.9031	0.042*
C14	0.5005 (3)	0.6704 (3)	0.8378 (3)	0.0286 (7)
C15	0.6301 (4)	0.8256 (4)	0.9188 (3)	0.0393 (9)
H15A	0.6900	0.8634	0.8740	0.047*
H15B	0.6932	0.8267	0.9869	0.047*
C16	0.1648 (4)	0.6443 (4)	0.8179 (3)	0.0403 (9)
H16	0.2527	0.6975	0.8856	0.048*
C17	0.0699 (4)	0.6986 (4)	0.8098 (3)	0.0451 (10)
H17	0.0961	0.7872	0.8703	0.054*
C18	−0.0607 (4)	0.6216 (4)	0.7132 (3)	0.0444 (10)
H18	−0.1254	0.6562	0.7077	0.053*
C19	−0.0970 (4)	0.4901 (4)	0.6223 (3)	0.0350 (8)
C20	0.0062 (3)	0.4446 (3)	0.6356 (3)	0.0287 (7)
C21	−0.0216 (3)	0.3136 (3)	0.5427 (3)	0.0298 (8)
C22	−0.1574 (4)	0.2247 (4)	0.4439 (3)	0.0400 (9)
C23	−0.1807 (4)	0.0941 (4)	0.3606 (3)	0.0518 (11)
H23	−0.2700	0.0303	0.2939	0.062*
C24	−0.0727 (4)	0.0602 (4)	0.3772 (3)	0.0493 (10)
H24	−0.0887	−0.0278	0.3236	0.059*
C25	0.0622 (4)	0.1596 (4)	0.4758 (3)	0.0405 (9)
H25	0.1370	0.1377	0.4844	0.049*
C26	−0.2317 (4)	0.4003 (4)	0.5159 (3)	0.0454 (10)
H26	−0.2995	0.4306	0.5046	0.054*
C27	−0.2613 (4)	0.2733 (4)	0.4327 (4)	0.0478 (10)
H27	−0.3512	0.2156	0.3664	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0218 (3)	0.0302 (3)	0.0206 (3)	0.0159 (3)	0.0060 (2)	0.0104 (3)
Ni2	0.0243 (2)	0.0313 (2)	0.0223 (2)	0.01678 (19)	0.00614 (18)	0.01103 (19)
N1	0.0251 (14)	0.0355 (16)	0.0248 (15)	0.0175 (13)	0.0065 (12)	0.0116 (13)
N2	0.0324 (15)	0.0308 (15)	0.0259 (15)	0.0171 (13)	0.0091 (12)	0.0124 (13)
O1	0.0380 (13)	0.0394 (13)	0.0251 (13)	0.0278 (11)	0.0135 (10)	0.0142 (11)
O2	0.0390 (13)	0.0479 (14)	0.0263 (12)	0.0323 (12)	0.0113 (11)	0.0152 (11)
O3	0.0239 (12)	0.0430 (14)	0.0298 (13)	0.0172 (11)	0.0076 (11)	0.0158 (11)
O4	0.0287 (12)	0.0420 (14)	0.0275 (13)	0.0124 (11)	0.0095 (11)	0.0161 (11)
O5	0.0256 (11)	0.0298 (12)	0.0245 (12)	0.0166 (10)	0.0062 (10)	0.0133 (10)
O6	0.0402 (14)	0.0470 (15)	0.0352 (14)	0.0256 (12)	0.0139 (12)	0.0240 (12)
O7	0.076 (3)	0.170 (4)	0.109 (3)	0.070 (3)	0.045 (3)	0.082 (3)
C1	0.0310 (18)	0.046 (2)	0.0283 (18)	0.0265 (17)	0.0146 (15)	0.0162 (16)
C2	0.0344 (19)	0.038 (2)	0.038 (2)	0.0234 (17)	0.0144 (17)	0.0120 (17)
C3	0.0267 (18)	0.0323 (19)	0.034 (2)	0.0126 (16)	0.0042 (15)	0.0078 (16)
C4	0.0239 (17)	0.038 (2)	0.038 (2)	0.0164 (16)	0.0150 (16)	0.0204 (17)
C5	0.039 (2)	0.046 (2)	0.038 (2)	0.0300 (18)	0.0139 (18)	0.0117 (18)
C6	0.038 (2)	0.055 (2)	0.0263 (19)	0.0301 (19)	0.0091 (16)	0.0082 (17)
C7	0.0261 (17)	0.0268 (17)	0.0278 (19)	0.0146 (15)	0.0099 (15)	0.0105 (15)
C8	0.055 (2)	0.082 (3)	0.031 (2)	0.055 (2)	0.0195 (19)	0.023 (2)
C9	0.0251 (17)	0.0289 (18)	0.034 (2)	0.0202 (15)	0.0126 (16)	0.0151 (15)
C10	0.0259 (17)	0.039 (2)	0.040 (2)	0.0170 (16)	0.0139 (16)	0.0230 (17)
C11	0.0258 (17)	0.0221 (17)	0.0333 (19)	0.0082 (15)	0.0005 (15)	0.0073 (15)
C12	0.0356 (19)	0.0293 (19)	0.0319 (19)	0.0123 (16)	0.0094 (16)	0.0142 (16)
C13	0.0346 (19)	0.0290 (19)	0.032 (2)	0.0117 (16)	0.0014 (16)	0.0160 (16)
C14	0.0281 (18)	0.0329 (18)	0.032 (2)	0.0224 (16)	0.0075 (15)	0.0150 (16)
C15	0.0241 (17)	0.034 (2)	0.051 (2)	0.0108 (16)	0.0070 (17)	0.0183 (18)
C16	0.036 (2)	0.047 (2)	0.036 (2)	0.0246 (18)	0.0110 (17)	0.0127 (18)
C17	0.054 (2)	0.051 (2)	0.042 (2)	0.036 (2)	0.024 (2)	0.0164 (19)
C18	0.045 (2)	0.061 (3)	0.054 (3)	0.040 (2)	0.025 (2)	0.033 (2)
C19	0.0311 (19)	0.048 (2)	0.042 (2)	0.0240 (17)	0.0172 (17)	0.0307 (18)
C20	0.0256 (17)	0.0360 (19)	0.0285 (18)	0.0162 (15)	0.0094 (15)	0.0191 (16)
C21	0.0253 (17)	0.0365 (19)	0.0260 (18)	0.0139 (15)	0.0060 (14)	0.0174 (16)
C22	0.034 (2)	0.044 (2)	0.031 (2)	0.0124 (17)	0.0035 (16)	0.0192 (18)
C23	0.046 (2)	0.047 (2)	0.030 (2)	0.010 (2)	−0.0059 (18)	0.0112 (19)
C24	0.057 (3)	0.038 (2)	0.030 (2)	0.018 (2)	0.0043 (19)	0.0065 (18)
C25	0.050 (2)	0.041 (2)	0.034 (2)	0.0264 (19)	0.0149 (18)	0.0163 (18)
C26	0.031 (2)	0.066 (3)	0.051 (2)	0.028 (2)	0.0133 (18)	0.037 (2)
C27	0.028 (2)	0.061 (3)	0.042 (2)	0.0156 (19)	−0.0010 (17)	0.029 (2)

Geometric parameters (Å, º)

Ni1—O3^i	2.031 (2)	C6—H6	0.9300
Ni1—O3^ii	2.031 (2)	C7—C8	1.523 (4)
Ni1—O5	2.099 (2)	C8—H8A	0.9700
Ni1—O5^iii	2.099 (2)	C8—H8B	0.9700
Ni1—O1	2.104 (2)	C9—C10	1.528 (4)
Ni1—O1^iii	2.104 (2)	C10—H10A	0.9700
Ni2—O2	1.990 (2)	C10—H10B	0.9700
Ni2—O4^i	1.999 (2)	C11—C13^v	1.389 (5)
Ni2—O5	2.067 (2)	C11—C12	1.392 (4)
Ni2—N2	2.071 (3)	C11—C15	1.515 (5)
Ni2—N1	2.089 (3)	C12—C13	1.381 (5)
Ni2—O6	2.268 (2)	C12—H12	0.9300
N1—C16	1.326 (4)	C13—C11^v	1.389 (5)
N1—C20	1.357 (4)	C13—H13	0.9300
N2—C25	1.319 (4)	C14—C15	1.513 (4)
N2—C21	1.357 (4)	C15—H15A	0.9700
O1—C7	1.248 (4)	C15—H15B	0.9700
O2—C7	1.262 (4)	C16—C17	1.393 (5)
O3—C9	1.248 (4)	C16—H16	0.9300
O3—Ni1^iv	2.031 (2)	C17—C18	1.357 (5)
O4—C9	1.250 (4)	C17—H17	0.9300
O4—Ni2^iv	1.999 (2)	C18—C19	1.395 (5)
O5—C14	1.279 (4)	C18—H18	0.9300
O6—C14	1.244 (4)	C19—C20	1.406 (4)
O7—H28	0.84 (5)	C19—C26	1.437 (5)
O7—H29	0.85 (6)	C20—C21	1.435 (4)
C1—C2	1.384 (4)	C21—C22	1.397 (4)
C1—C6	1.385 (4)	C22—C23	1.399 (5)
C1—C8	1.509 (4)	C22—C27	1.437 (5)
C2—C3	1.386 (4)	C23—C24	1.364 (5)
C2—H2	0.9300	C23—H23	0.9300
C3—C4	1.379 (4)	C24—C25	1.395 (5)
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.373 (5)	C25—H25	0.9300
C4—C10	1.511 (4)	C26—C27	1.342 (5)
C5—C6	1.381 (5)	C26—H26	0.9300
C5—H5	0.9300	C27—H27	0.9300
O3^i—Ni1—O3^ii	180	C7—C8—H8A	106.9
O3^i—Ni1—O5	90.90 (8)	C1—C8—H8B	106.9
O3^ii—Ni1—O5	89.10 (8)	C7—C8—H8B	106.9
O3^i—Ni1—O5^iii	89.10 (8)	H8A—C8—H8B	106.7
O3^ii—Ni1—O5^iii	90.90 (8)	O3—C9—O4	127.3 (3)
O5—Ni1—O5^iii	180	O3—C9—C10	118.1 (3)
O3^i—Ni1—O1	94.73 (9)	O4—C9—C10	114.6 (3)
O3^ii—Ni1—O1	85.27 (8)	C4—C10—C9	111.4 (3)
O5—Ni1—O1	89.45 (8)	C4—C10—H10A	109.3
O5^iii—Ni1—O1	90.55 (8)	C9—C10—H10A	109.3
O3^i—Ni1—O1^iii	85.27 (9)	C4—C10—H10B	109.3
O3^ii—Ni1—O1^iii	94.73 (9)	C9—C10—H10B	109.3
O5—Ni1—O1^iii	90.55 (8)	H10A—C10—H10B	108.0
O5^iii—Ni1—O1^iii	89.45 (8)	C13^v—C11—C12	118.4 (3)
O1—Ni1—O1^iii	180	C13^v—C11—C15	120.7 (3)
O2—Ni2—O4^i	96.62 (10)	C12—C11—C15	120.8 (3)
O2—Ni2—O5	93.60 (9)	C13—C12—C11	120.9 (3)
O4^i—Ni2—O5	99.08 (9)	C13—C12—H12	119.6
O2—Ni2—N2	91.37 (10)	C11—C12—H12	119.6
O4^i—Ni2—N2	85.83 (10)	C12—C13—C11^v	120.7 (3)
O5—Ni2—N2	172.56 (9)	C12—C13—H13	119.6
O2—Ni2—N1	166.22 (9)	C11^v—C13—H13	119.6
O4^i—Ni2—N1	93.07 (10)	O6—C14—O5	119.9 (3)
O5—Ni2—N1	94.51 (9)	O6—C14—C15	120.2 (3)
N2—Ni2—N1	79.57 (10)	O5—C14—C15	119.6 (3)
O2—Ni2—O6	85.80 (9)	C14—C15—C11	107.9 (3)
O4^i—Ni2—O6	159.39 (9)	C14—C15—H15A	110.1
O5—Ni2—O6	60.31 (8)	C11—C15—H15A	110.1
N2—Ni2—O6	114.64 (10)	C14—C15—H15B	110.1
N1—Ni2—O6	88.57 (10)	C11—C15—H15B	110.1
C16—N1—C20	117.4 (3)	H15A—C15—H15B	108.4
C16—N1—Ni2	129.6 (2)	N1—C16—C17	123.1 (3)
C20—N1—Ni2	113.0 (2)	N1—C16—H16	118.5
C25—N2—C21	117.7 (3)	C17—C16—H16	118.5
C25—N2—Ni2	128.0 (2)	C18—C17—C16	119.7 (3)
C21—N2—Ni2	113.4 (2)	C18—C17—H17	120.1
C7—O1—Ni1	136.1 (2)	C16—C17—H17	120.1
C7—O2—Ni2	126.9 (2)	C17—C18—C19	119.4 (3)
C9—O3—Ni1^iv	132.4 (2)	C17—C18—H18	120.3
C9—O4—Ni2^iv	130.7 (2)	C19—C18—H18	120.3
C14—O5—Ni2	93.97 (18)	C18—C19—C20	117.5 (3)
C14—O5—Ni1	136.82 (19)	C18—C19—C26	124.0 (3)
Ni2—O5—Ni1	112.86 (10)	C20—C19—C26	118.5 (3)
C14—O6—Ni2	85.8 (2)	N1—C20—C19	123.0 (3)
H28—O7—H29	100 (5)	N1—C20—C21	116.8 (3)
C2—C1—C6	117.3 (3)	C19—C20—C21	120.2 (3)
C2—C1—C8	123.2 (3)	N2—C21—C22	123.5 (3)
C6—C1—C8	119.4 (3)	N2—C21—C20	116.8 (3)
C1—C2—C3	120.5 (3)	C22—C21—C20	119.7 (3)
C1—C2—H2	119.8	C21—C22—C23	116.6 (3)
C3—C2—H2	119.8	C21—C22—C27	118.8 (3)
C4—C3—C2	121.8 (3)	C23—C22—C27	124.5 (3)
C4—C3—H3	119.1	C24—C23—C22	120.0 (3)
C2—C3—H3	119.1	C24—C23—H23	120.0
C5—C4—C3	117.8 (3)	C22—C23—H23	120.0
C5—C4—C10	122.7 (3)	C23—C24—C25	119.0 (3)
C3—C4—C10	119.4 (3)	C23—C24—H24	120.5
C4—C5—C6	120.7 (3)	C25—C24—H24	120.5
C4—C5—H5	119.6	N2—C25—C24	123.0 (3)
C6—C5—H5	119.6	N2—C25—H25	118.5
C5—C6—C1	121.9 (3)	C24—C25—H25	118.5
C5—C6—H6	119.1	C27—C26—C19	121.1 (3)
C1—C6—H6	119.1	C27—C26—H26	119.4
O1—C7—O2	126.7 (3)	C19—C26—H26	119.4
O1—C7—C8	121.2 (3)	C26—C27—C22	121.5 (3)
O2—C7—C8	112.1 (3)	C26—C27—H27	119.3
C1—C8—C7	121.5 (3)	C22—C27—H27	119.3
C1—C8—H8A	106.9

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H28···O6^vi	0.84 (5)	2.51 (6)	2.990 (5)	117 (5)
O7—H29···O2	0.85 (6)	2.54 (5)	3.193 (5)	135 (6)

Symmetry code: (vi) −x+1, −y+1, −z+1.