A three-dimensional polycatenation framework: catena-poly[[di­aqua­bis­(4-{4-[4-(pyridin-4-yl)phen­oxy]phenyl}pyridine)­nickel(II)]-[mu]₂-naphthalene-2,6-di­carboxyl­ato]

In the title compound, [Ni(C₁₂H₆O₄)(C₂₂H₁₆N₂O)₂(H₂O)₂]_n, the Ni²⁺ cation resides on a centre of inversion in a slightly distorted octa­hedral [N₂O₄] environment. The two carboxyl­ate groups of each naphthalene-2,6-di­carboxyl­ate (NDC^2-) ligand, which reside on centres of inversion, link the Ni^II cations into a one-dimensional chain. Identical chains are linked by inter­molecular hydrogen bonds between coordinated water mol­ecules and the uncoordinated N atoms of 4-{4-[4-(pyridin-4-yl)phen­oxy]phen­yl}pyridine ligands to form (4,4)-topological sheets, and then the different sheets are inter­locked in an inclined fashion to give a three-dimensional polycatenation network. The stability of the structure is further enhanced by [pi]-[pi] stacking inter­actions between pyridine and benzene rings.

S1. Introduction

Recently, the design and synthesis of metal–organic coordination polymers have attracted muuch inter­est because of their inter­esting structural diversity and special properties, such as porosity, nonlinear optical activity, luminescence, magnetism and catalytic activity, as well as their intriguing variety of architectures and molecular topologies (Ni et al., 2005; Rowsell & Yaghi, 2005; Coronado et al., 2000; Guo et al., 2009). To construct novel coordination polymers, we usually choose carboxyl­ate-containing ligands which have varied coordination modes as the main connectors, and mixed ligands with N-donor groups as ancillary bridges (Deng et al., 2012; Dai et al., 2004; Sun et al., 2003). In the present case, we chose naphthalene-2,6-di­carb­oxy­lic acid (H₂NDC) as our main ligand and 4-{4-[4-(pyridin-4-yl)phen­oxy]­phenyl}­pyridine (BPDPE) as the N-donor assistant ligand to synthesize a nickel complex. Compared with the linear bis­(pyridine) ligand, BPDPE is a V-shaped pyridine ligand, which can be regarded as a half-flexible ligand to construct more inter­esting structures (Hu et al., 2012). We report here the synthesis and structure of the title compound, [Ni(NDC)(BPDPE)₂(H₂O)₂]_n, (I).

S2. Experimental

S2.1. Synthesis and crystallization

All starting chemicals and solvents used in this synthesis were of reagent quality and purchased from commercial sources without further purification. A mixture of NiCl₂.6H₂O (48 mg, 0.2 mmol), H₂NDC (22 mg, 0.1 mmol), BPDPE (32 mg, 0.1 mmol), DMF (7 ml) and water (7 ml) was placed in a Parr Teflon-lined stainless steel vessel (23 ml), heated to 393 K for 3 d, then cooled to room temperature slowly. Green diamond-like crystals of complex (I) (yield 34 mg, 70%) were collected at the bottom of the glass vessel.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bonded to C atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C). The aqua H atoms were placed so as to form a reasonable hydrogen-bond network, with O—H = 0.85 Å, and were refined as riding, with U_iso(H) = 1.2UU_eq(O).

S3. Results and discussion

Compound (I) crystallizes in the monoclinic space group P2₁/c, and the asymmetric unit contains half of a central Ni^II cation, half of a doubly deprotonated H₂NDC ligand, a BPDPE ligand and a coordinated water molecule. As shown in Fig. 1, the Ni^II centre is six-coordinated by two carboxyl­ate O atoms from two NDC^2- ligands, two N atoms from two BPDPE ligands and two O atoms from two water molecules to form a slightly distorted o­cta­hedron. The Ni^II cation resides on a centre of inversion, as does the NDC^2- ligand. The two carboxyl­ate groups of each NDC^2- ligand coordinate with the Ni^II cation in a monodentate manner and only one N atom of each BPDPE ligand coordinates with the Ni^II cation, so a one-dimensional chain structure is formed extending along the c axis, with an Ni···Ni distance within the chain of about 13.653 Å. There are two types of chain which are related by an ac glide and these are arranged alternately, which may reduce repulsion for a greater stabilization of the structure (Fig. 2).

There are inter­molecular O4—H4C···N2ⁱ (see Table 2 for details and symmetry code) and intra­molecular O4—H4B···O2ⁱⁱ hydrogen bonds (Table 2) in complex (I). The inter­molecular hydrogen bonds are formed between identical chains, so the same types of chain extend into a (4,4)-topological layered network via these inter­molecular hydrogen bonds (Fig. 3). Because of the spacious nature of the network, it allows the crossed layers to inter­penetrate with each other to form inclined polycatenation networks, which accomplishes the transition from a two-dimensional to a three-dimensional structure for (I) (Fig. 4) (Batten & Robson, 1998). This demonstrates that the uncoordinated N atom and coordinated water molecules can be well used in the synthesis of unusual coordination frameworks (Hu et al., 2012). Additionally, there are weak π–π stacking inter­actions between the nearest C6–C10/N2 pyridine and C11–C16 benzene rings, with an inter­planar distance of 3.68 Å. The dihedral angle α defined by the stacked rings is 12.12° and the slippage angles are β = 20.64 and γ = 17.78° (Fig. 5). This moderate stacking inter­action further enhances the stability of complex (I).

Related literature

For related literature, see: Batten & Robson (1998); Coronado et al. (2000); Dai et al. (2004); Deng et al. (2012); Guo et al. (2009); Hu et al. (2012); Ni et al. (2005); Rowsell & Yaghi (2005); Sun et al. (2003).

Computing details

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level. All H atoms have been omitted for clarity. [Symmetry codes: (i) -x + 3, -y + 1, -z + 2; (ii) x, y, z.]

Fig. 2. The two types of one-dimensional chain structure of (I), extending along the c axis.

Fig. 3. A view of the two-dimensional supramolecular layer stacked via intermolecular O—H···N hydrogen bonds (dashed lines). Different layers are shown in different colours and intramolecular hydrogen bonds have been omitted for clarity.

Fig. 4. (a) The three-dimensional network formed by the interlocking interaction in complex (I). (b) A space-filling model, showing the inclined interpenetration between the layers.

Fig. 5. The π–π stacking interactions in (I), shown as thin solid lines (light green in the electronic version of the journal). Dashed lines indicate intermolecular hydrogen bonds.

catena-Poly[[diaquabis(4-{4-[4-(pyridin-4-yl)phenoxy]phenyl}pyridine)nickel(II)]-µ₂-naphthalene-2,6-dicarboxylato]

Crystal data

[Ni(C12H6O4)(C22H16N2O)2(H2O)2]	F(000) = 996
Mr = 957.65	Dx = 1.418 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2556 reflections
a = 11.4739 (6) Å	θ = 3.0–28.6°
b = 15.9431 (7) Å	µ = 0.50 mm^−1
c = 13.4291 (8) Å	T = 290 K
β = 114.048 (7)°	Diamond-like, green
V = 2243.4 (2) Å^3	0.21 × 0.19 × 0.15 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	4407 independent reflections
Radiation source: fine-focus sealed tube	3337 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ and ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→14
Tmin = 0.890, Tmax = 0.916	k = −19→12
9294 measured reflections	l = −16→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 0.4401P] where P = (Fo^2 + 2Fc^2)/3
4407 reflections	(Δ/σ)max < 0.001
313 parameters	Δρmax = 0.47 e Å^−3
1 restraint	Δρmin = −0.36 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
C28	1.5548 (2)	0.39910 (19)	1.0747 (2)	0.0480 (7)
H28	1.5310	0.3429	1.0678	0.058*
C1	0.8999 (2)	0.63210 (17)	0.6008 (2)	0.0411 (7)
H1	0.9834	0.6509	0.6227	0.049*
C2	0.8213 (2)	0.67478 (17)	0.6381 (2)	0.0431 (7)
H2	0.8516	0.7217	0.6822	0.052*
C3	0.6972 (2)	0.64781 (17)	0.6097 (2)	0.0385 (6)
C4	0.6583 (2)	0.58020 (18)	0.5387 (2)	0.0443 (7)
H4	0.5749	0.5606	0.5146	0.053*
C5	0.7424 (2)	0.54190 (18)	0.5035 (2)	0.0425 (7)
H5	0.7130	0.4973	0.4550	0.051*
C6	0.0121 (4)	1.1782 (2)	0.4638 (3)	0.0695 (10)
H6	0.0204	1.2030	0.4044	0.083*
C7	0.0923 (3)	1.11316 (19)	0.5138 (3)	0.0617 (9)
H7	0.1542	1.0967	0.4897	0.074*
C8	0.0816 (2)	1.07171 (17)	0.6006 (2)	0.0424 (7)
C9	−0.0189 (3)	1.0983 (2)	0.6247 (3)	0.0547 (8)
H9	−0.0370	1.0706	0.6778	0.066*
C10	−0.0921 (3)	1.1658 (2)	0.5700 (3)	0.0655 (9)
H10	−0.1580	1.1822	0.5892	0.079*
C11	0.1694 (3)	1.00347 (17)	0.6605 (2)	0.0428 (7)
C12	0.1460 (3)	0.95092 (19)	0.7323 (3)	0.0509 (8)
H12	0.0751	0.9611	0.7476	0.061*
C13	0.2241 (3)	0.8842 (2)	0.7818 (3)	0.0534 (8)
H13	0.2066	0.8500	0.8301	0.064*
C14	0.3280 (3)	0.8685 (2)	0.7589 (3)	0.0542 (8)
C15	0.3585 (3)	0.9217 (2)	0.6946 (3)	0.0783 (12)
H15	0.4323	0.9128	0.6832	0.094*
C16	0.2804 (3)	0.9890 (2)	0.6458 (3)	0.0659 (10)
H16	0.3027	1.0253	0.6022	0.079*
C17	0.4718 (3)	0.7634 (2)	0.7554 (3)	0.0575 (9)
C18	0.4114 (3)	0.7278 (3)	0.6543 (3)	0.0680 (10)
H18	0.3229	0.7292	0.6186	0.082*
C19	0.4837 (3)	0.6898 (2)	0.6058 (3)	0.0584 (9)
H19	0.4433	0.6655	0.5373	0.070*
C20	0.6160 (2)	0.68767 (17)	0.6584 (2)	0.0419 (7)
C21	0.6722 (3)	0.7247 (2)	0.7604 (3)	0.0536 (8)
H21	0.7607	0.7244	0.7969	0.064*
C22	0.6007 (3)	0.7619 (2)	0.8091 (3)	0.0589 (9)
H22	0.6403	0.7857	0.8780	0.071*
C23	1.1790 (2)	0.46317 (19)	0.7315 (2)	0.0367 (6)
C24	1.3388 (3)	0.5745 (2)	0.8383 (2)	0.0490 (7)
H24	1.2918	0.6130	0.7851	0.059*
C25	1.2988 (2)	0.49020 (17)	0.8275 (2)	0.0370 (6)
C26	1.3672 (2)	0.43308 (19)	0.9036 (2)	0.0404 (7)
H26	1.3402	0.3775	0.8964	0.048*
C27	1.4817 (2)	0.45770 (17)	0.9958 (2)	0.0358 (6)
N1	0.86374 (18)	0.56559 (13)	0.53535 (17)	0.0336 (5)
N2	−0.0763 (3)	1.20860 (17)	0.4932 (3)	0.0668 (8)
Ni1	1.0000	0.5000	0.5000	0.02874 (15)
O1	1.13149 (16)	0.51694 (11)	0.65671 (14)	0.0400 (5)
O2	1.13494 (17)	0.39159 (13)	0.73173 (16)	0.0546 (6)
O3	0.4003 (2)	0.79838 (16)	0.8081 (2)	0.0760 (7)
O4	1.06571 (15)	0.61064 (11)	0.45375 (14)	0.0367 (4)
H4B	1.0046	0.6333	0.4007	0.055*
H4C	1.0928	0.6443	0.5075	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C28	0.0459 (16)	0.0455 (17)	0.0403 (16)	0.0010 (13)	0.0049 (14)	0.0079 (14)
C1	0.0352 (13)	0.0425 (16)	0.0482 (17)	−0.0030 (12)	0.0198 (13)	−0.0075 (14)
C2	0.0447 (15)	0.0416 (16)	0.0481 (17)	−0.0005 (13)	0.0240 (13)	−0.0116 (14)
C3	0.0376 (14)	0.0380 (15)	0.0436 (16)	0.0077 (12)	0.0204 (12)	0.0066 (13)
C4	0.0309 (13)	0.0478 (17)	0.0555 (18)	0.0000 (12)	0.0191 (13)	−0.0042 (15)
C5	0.0364 (14)	0.0403 (16)	0.0489 (17)	−0.0012 (12)	0.0154 (13)	−0.0092 (14)
C6	0.093 (3)	0.043 (2)	0.079 (3)	0.0029 (18)	0.043 (2)	0.0121 (19)
C7	0.074 (2)	0.0441 (18)	0.080 (2)	0.0038 (17)	0.044 (2)	0.0067 (17)
C8	0.0486 (15)	0.0336 (15)	0.0476 (16)	−0.0018 (13)	0.0223 (14)	−0.0058 (13)
C9	0.0561 (18)	0.0548 (19)	0.060 (2)	0.0116 (15)	0.0304 (16)	0.0089 (17)
C10	0.059 (2)	0.065 (2)	0.074 (2)	0.0168 (17)	0.0296 (18)	0.002 (2)
C11	0.0452 (15)	0.0447 (17)	0.0460 (16)	−0.0004 (13)	0.0262 (14)	−0.0047 (14)
C12	0.0531 (17)	0.0533 (19)	0.061 (2)	0.0113 (15)	0.0385 (16)	0.0069 (16)
C13	0.0626 (18)	0.0569 (19)	0.0592 (19)	0.0153 (16)	0.0436 (16)	0.0139 (16)
C14	0.0595 (18)	0.062 (2)	0.0543 (19)	0.0247 (16)	0.0367 (16)	0.0131 (16)
C15	0.069 (2)	0.096 (3)	0.100 (3)	0.037 (2)	0.065 (2)	0.042 (2)
C16	0.069 (2)	0.069 (2)	0.083 (3)	0.0189 (18)	0.055 (2)	0.032 (2)
C17	0.068 (2)	0.063 (2)	0.059 (2)	0.0332 (17)	0.0448 (18)	0.0241 (18)
C18	0.0458 (17)	0.104 (3)	0.060 (2)	0.0281 (18)	0.0269 (16)	0.019 (2)
C19	0.0460 (16)	0.083 (2)	0.0492 (18)	0.0143 (16)	0.0223 (15)	0.0039 (17)
C20	0.0420 (14)	0.0430 (16)	0.0468 (16)	0.0104 (12)	0.0243 (13)	0.0091 (14)
C21	0.0517 (17)	0.059 (2)	0.0564 (19)	0.0122 (15)	0.0281 (15)	−0.0023 (16)
C22	0.067 (2)	0.065 (2)	0.0545 (19)	0.0170 (17)	0.0347 (17)	−0.0015 (17)
C23	0.0268 (12)	0.0522 (17)	0.0283 (14)	0.0042 (12)	0.0083 (11)	−0.0057 (13)
C24	0.0413 (15)	0.0576 (19)	0.0366 (16)	0.0002 (14)	0.0040 (13)	0.0029 (15)
C25	0.0290 (12)	0.0524 (18)	0.0273 (13)	0.0067 (12)	0.0090 (11)	−0.0004 (13)
C26	0.0345 (14)	0.0527 (18)	0.0322 (14)	−0.0019 (13)	0.0119 (12)	−0.0013 (13)
C27	0.0335 (13)	0.0438 (15)	0.0317 (14)	0.0045 (12)	0.0148 (12)	0.0026 (13)
N1	0.0334 (11)	0.0330 (12)	0.0353 (12)	0.0023 (9)	0.0150 (9)	−0.0028 (10)
N2	0.083 (2)	0.0403 (15)	0.079 (2)	0.0101 (15)	0.0359 (17)	0.0057 (15)
Ni1	0.0261 (2)	0.0321 (3)	0.0248 (2)	0.00333 (18)	0.00703 (18)	−0.0026 (2)
O1	0.0354 (9)	0.0456 (11)	0.0282 (10)	0.0038 (8)	0.0019 (8)	−0.0036 (9)
O2	0.0451 (11)	0.0585 (14)	0.0413 (12)	−0.0046 (10)	−0.0017 (9)	0.0076 (11)
O3	0.0946 (16)	0.0898 (18)	0.0713 (16)	0.0552 (14)	0.0623 (14)	0.0368 (14)
O4	0.0338 (9)	0.0397 (10)	0.0320 (10)	0.0017 (8)	0.0088 (8)	−0.0001 (8)

Geometric parameters (Å, º)

C28—C24^i	1.368 (4)	C15—C16	1.381 (4)
C28—C27	1.405 (4)	C15—H15	0.9300
C28—H28	0.9300	C16—H16	0.9300
C1—N1	1.331 (3)	C17—C22	1.357 (4)
C1—C2	1.375 (4)	C17—C18	1.370 (5)
C1—H1	0.9300	C17—O3	1.400 (3)
C2—C3	1.385 (4)	C18—C19	1.385 (4)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.387 (4)	C19—C20	1.390 (4)
C3—C20	1.481 (4)	C19—H19	0.9300
C4—C5	1.378 (4)	C20—C21	1.386 (4)
C4—H4	0.9300	C21—C22	1.374 (4)
C5—N1	1.334 (3)	C21—H21	0.9300
C5—H5	0.9300	C22—H22	0.9300
C6—N2	1.321 (4)	C23—O2	1.249 (3)
C6—C7	1.367 (4)	C23—O1	1.263 (3)
C6—H6	0.9300	C23—C25	1.514 (4)
C7—C8	1.388 (4)	C24—C28^i	1.368 (4)
C7—H7	0.9300	C24—C25	1.408 (4)
C8—C9	1.386 (4)	C24—H24	0.9300
C8—C11	1.478 (4)	C25—C26	1.355 (4)
C9—C10	1.378 (4)	C26—C27	1.445 (3)
C9—H9	0.9300	C26—H26	0.9300
C10—N2	1.311 (4)	C27—C27^i	1.403 (5)
C10—H10	0.9300	N1—Ni1	2.0900 (19)
C11—C12	1.384 (4)	Ni1—O1	2.0470 (17)
C11—C16	1.385 (4)	Ni1—O1^ii	2.0470 (17)
C12—C13	1.376 (4)	Ni1—N1^ii	2.0900 (19)
C12—H12	0.9300	Ni1—O4^ii	2.1089 (17)
C13—C14	1.369 (4)	Ni1—O4	2.1089 (17)
C13—H13	0.9300	O4—H4B	0.8500
C14—C15	1.354 (4)	O4—H4C	0.8501
C14—O3	1.389 (4)
C24^i—C28—C27	119.3 (3)	C17—C18—C19	119.3 (3)
C24^i—C28—H28	120.3	C17—C18—H18	120.4
C27—C28—H28	120.3	C19—C18—H18	120.4
N1—C1—C2	124.1 (2)	C18—C19—C20	120.8 (3)
N1—C1—H1	118.0	C18—C19—H19	119.6
C2—C1—H1	118.0	C20—C19—H19	119.6
C1—C2—C3	120.0 (3)	C21—C20—C19	117.6 (3)
C1—C2—H2	120.0	C21—C20—C3	119.7 (2)
C3—C2—H2	120.0	C19—C20—C3	122.6 (3)
C2—C3—C4	115.9 (2)	C22—C21—C20	121.8 (3)
C2—C3—C20	120.4 (3)	C22—C21—H21	119.1
C4—C3—C20	123.6 (2)	C20—C21—H21	119.1
C5—C4—C3	120.4 (2)	C17—C22—C21	119.2 (3)
C5—C4—H4	119.8	C17—C22—H22	120.4
C3—C4—H4	119.8	C21—C22—H22	120.4
N1—C5—C4	123.4 (3)	O2—C23—O1	125.3 (2)
N1—C5—H5	118.3	O2—C23—C25	119.0 (2)
C4—C5—H5	118.3	O1—C23—C25	115.6 (3)
N2—C6—C7	125.3 (4)	C28^i—C24—C25	121.5 (3)
N2—C6—H6	117.4	C28^i—C24—H24	119.3
C7—C6—H6	117.4	C25—C24—H24	119.3
C6—C7—C8	120.0 (3)	C26—C25—C24	120.0 (2)
C6—C7—H7	120.0	C26—C25—C23	119.8 (3)
C8—C7—H7	120.0	C24—C25—C23	120.3 (2)
C9—C8—C7	114.7 (3)	C25—C26—C27	120.6 (3)
C9—C8—C11	123.1 (3)	C25—C26—H26	119.7
C7—C8—C11	122.2 (3)	C27—C26—H26	119.7
C10—C9—C8	119.9 (3)	C27^i—C27—C28	120.8 (3)
C10—C9—H9	120.0	C27^i—C27—C26	117.9 (3)
C8—C9—H9	120.0	C28—C27—C26	121.3 (3)
N2—C10—C9	125.2 (3)	C1—N1—C5	116.2 (2)
N2—C10—H10	117.4	C1—N1—Ni1	119.22 (16)
C9—C10—H10	117.4	C5—N1—Ni1	124.43 (18)
C12—C11—C16	116.7 (3)	C10—N2—C6	114.4 (3)
C12—C11—C8	122.8 (2)	O1—Ni1—O1^ii	180.0
C16—C11—C8	120.5 (3)	O1—Ni1—N1	90.38 (8)
C13—C12—C11	122.1 (3)	O1^ii—Ni1—N1	89.62 (8)
C13—C12—H12	119.0	O1—Ni1—N1^ii	89.62 (8)
C11—C12—H12	119.0	O1^ii—Ni1—N1^ii	90.38 (8)
C14—C13—C12	119.2 (3)	N1—Ni1—N1^ii	180.00 (6)
C14—C13—H13	120.4	O1—Ni1—O4^ii	90.56 (7)
C12—C13—H13	120.4	O1^ii—Ni1—O4^ii	89.44 (7)
C15—C14—C13	120.3 (3)	N1—Ni1—O4^ii	87.78 (7)
C15—C14—O3	123.2 (3)	N1^ii—Ni1—O4^ii	92.22 (7)
C13—C14—O3	116.5 (3)	O1—Ni1—O4	89.44 (7)
C14—C15—C16	120.2 (3)	O1^ii—Ni1—O4	90.56 (7)
C14—C15—H15	119.9	N1—Ni1—O4	92.22 (7)
C16—C15—H15	119.9	N1^ii—Ni1—O4	87.78 (7)
C15—C16—C11	121.2 (3)	O4^ii—Ni1—O4	180.0
C15—C16—H16	119.4	C23—O1—Ni1	128.79 (18)
C11—C16—H16	119.4	C14—O3—C17	116.1 (2)
C22—C17—C18	121.4 (3)	Ni1—O4—H4B	109.3
C22—C17—O3	118.4 (3)	Ni1—O4—H4C	109.2
C18—C17—O3	120.2 (3)	H4B—O4—H4C	109.5
N1—C1—C2—C3	1.6 (5)	O3—C17—C22—C21	177.4 (3)
C1—C2—C3—C4	−3.5 (4)	C20—C21—C22—C17	−0.8 (5)
C1—C2—C3—C20	173.6 (3)	C28^i—C24—C25—C26	−0.9 (4)
C2—C3—C4—C5	2.3 (4)	C28^i—C24—C25—C23	178.8 (3)
C20—C3—C4—C5	−174.6 (3)	O2—C23—C25—C26	10.2 (4)
C3—C4—C5—N1	0.9 (5)	O1—C23—C25—C26	−170.2 (2)
N2—C6—C7—C8	2.2 (6)	O2—C23—C25—C24	−169.5 (3)
C6—C7—C8—C9	3.9 (5)	O1—C23—C25—C24	10.2 (4)
C6—C7—C8—C11	−177.3 (3)	C24—C25—C26—C27	−0.4 (4)
C7—C8—C9—C10	−5.3 (4)	C23—C25—C26—C27	180.0 (2)
C11—C8—C9—C10	176.0 (3)	C24^i—C28—C27—C27^i	1.3 (5)
C8—C9—C10—N2	0.8 (5)	C24^i—C28—C27—C26	−178.8 (3)
C9—C8—C11—C12	11.6 (4)	C25—C26—C27—C27^i	0.8 (4)
C7—C8—C11—C12	−167.1 (3)	C25—C26—C27—C28	−179.1 (3)
C9—C8—C11—C16	−169.0 (3)	C2—C1—N1—C5	1.7 (4)
C7—C8—C11—C16	12.4 (5)	C2—C1—N1—Ni1	−173.3 (2)
C16—C11—C12—C13	−4.0 (5)	C4—C5—N1—C1	−2.9 (4)
C8—C11—C12—C13	175.5 (3)	C4—C5—N1—Ni1	171.8 (2)
C11—C12—C13—C14	−0.5 (5)	C9—C10—N2—C6	5.1 (5)
C12—C13—C14—C15	4.7 (5)	C7—C6—N2—C10	−6.7 (5)
C12—C13—C14—O3	−177.6 (3)	C1—N1—Ni1—O1	38.0 (2)
C13—C14—C15—C16	−4.2 (6)	C5—N1—Ni1—O1	−136.6 (2)
O3—C14—C15—C16	178.3 (4)	C1—N1—Ni1—O1^ii	−142.0 (2)
C14—C15—C16—C11	−0.5 (6)	C5—N1—Ni1—O1^ii	43.4 (2)
C12—C11—C16—C15	4.5 (5)	C1—N1—Ni1—O4^ii	128.5 (2)
C8—C11—C16—C15	−175.0 (3)	C5—N1—Ni1—O4^ii	−46.0 (2)
C22—C17—C18—C19	−0.2 (5)	C1—N1—Ni1—O4	−51.5 (2)
O3—C17—C18—C19	−176.8 (3)	C5—N1—Ni1—O4	134.0 (2)
C17—C18—C19—C20	−0.2 (5)	O2—C23—O1—Ni1	−16.5 (4)
C18—C19—C20—C21	0.0 (5)	C25—C23—O1—Ni1	163.91 (16)
C18—C19—C20—C3	−180.0 (3)	N1—Ni1—O1—C23	110.7 (2)
C2—C3—C20—C21	−26.9 (4)	N1^ii—Ni1—O1—C23	−69.3 (2)
C4—C3—C20—C21	149.9 (3)	O4^ii—Ni1—O1—C23	22.9 (2)
C2—C3—C20—C19	153.1 (3)	O4—Ni1—O1—C23	−157.1 (2)
C4—C3—C20—C19	−30.1 (4)	C15—C14—O3—C17	−26.7 (5)
C19—C20—C21—C22	0.5 (5)	C13—C14—O3—C17	155.7 (3)
C3—C20—C21—C22	−179.5 (3)	C22—C17—O3—C14	117.8 (3)
C18—C17—C22—C21	0.7 (5)	C18—C17—O3—C14	−65.4 (4)

Symmetry codes: (i) −x+3, −y+1, −z+2; (ii) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4C···N2^iii	0.85	2.35	2.959 (3)	129
O4—H4B···O2^ii	0.85	1.89	2.614 (2)	143

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