An unusual three-dimensional chiral threefold polycatenating network self-assembled from inclined two-dimensional (4,4) layer motifs

In the coordination compound poly[diaqua­([mu]₂-4,4'-bipyri­dine)([mu]₂-4-carboxyl­atocinnamato)nickel(II)], [Ni(C₁₀H₆O₄)(C₁₀H₈N₂)(H₂O)₂]_n, both the 4-carboxylato­cinnamate and 4,4'-bipyridine (4,4'-bpy) ligands act as bidentate bridges, connecting the Ni^II centres in an octa­hedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates two other identical layers, thus giving a rare 2D [rightwards arrow] 3D polycatenating network (2D and 3D are two- and three-dimensional, respectively), with a mutually parallel arrangement of the layers. The chiral 4,4'-bpy ligands link the Ni^II centres into chiral chains, thus introducing chirality into the layer and the resulting 3D network.

S1. Comment

The construction of metal–organic assemblies has attracted increasing attention in recent years, not only for their potential applications but also due to their fascinating architectures and topologies (Ferey et al., 2005; Murray et al., 2009). Examples of some of the interesting networks of entanglement systems include polycatenation, polythreading, polyknotting and Borromean links (Batten & Robson, 1998; Batten, 2001; Carlucci, Ciani & Proserpio, 2003). Of particular interest to us is the fact that the entanglement of lower-dimensional polymeric structures can generate a structure of overall higher dimensionality, which has been classified as polycatenation. That is, the whole catenated array has a higher dimensionality than the component motifs, such as one-dimensional → two-dimensional, one-dimensional → three-dimensional and two-dimensional → three-dimensional (one-dimensional, two-dimensional and three-dimensional are one-, two- and three-dimensional, respectively). A dimensionality increase from two-dimensional layers to an overall three-dimensional entanglement can occur for systems interpenetrating in parallel or inclined fashion. Although the first two-dimensional → three-dimensional parallel interpenetration was reported over ten years ago (Liu & Tilley, 1997), such compounds are still relatively rare (Blatov et al., 2004; Baburin et al., 2005; Guo et al., 2009).

The (4,4) and (6,3) nets are the most common two-dimensional topologies, which are inclined to interpenetrate when large four- or six-membered rings are formed, or when the network shows undulating features, or both. For the former case, three possible arrangements of interpenetrating sheets have been observed in the examples reported to date: parallel–parallel (p-p), parallel–diagonal (p-d) and diagonal–diagonal (d-d), depending on how the networks orient and penetrate through each other (Zaworotko, 2001; Herbstein, 2001; Biradha et al., 2000). The majority of them, however, consist of two identical sets of two-dimensional parallel layers, spanning two different stacking directions. Only a limited number of networks have been found that contain more than two sets of differently oriented layers (Kondo et al., 2000; Carlucci, Ciani, Proserpio & Rizzato, 2003; Chen et al., 2006; Zhuang et al., 2007) since this possibility was first predicted (Batten & Robson, 1998).

Meanwhile, chiral units and homochiral interactions between them would be crucial to the synthesis of chiral interpenetrating structures through spontaneous resolution upon crystallization without any chiral auxiliary (Gao et al., 2004; Bai et al., 2005). 4,4'-Bipyridine (4,4'-bpy), which only possesses the ideal achiral geometry of D_2h symmetry without any twist between the two pyridyl rings, would easily become chiral once if there were any twist in the molecule. This kind of ligand is a potential source of chiral units which may be induced into a chiral configuration by coordination bonds or hydrogen bonds (Cotton et al., 2003; Mukherjee et al., 2004). Here, we report the title coordination compound, [Ni(acc)₂(4,4'-bpy)(H₂O)₂]_n, (I) (H₂acc is 4-carboxycinnamic acid), which features an unusual chiral three-dimensional threefold polycatenating network self-assembled from inclined interpenetration of two-dimensional (4,4) layer motifs.

Compound (I) crystallizes in the noncentrosymmetric hexagonal space group P3₂, and the asymmetric unit is composed of one Ni^II centre, one acc²⁻ anion, one 4,4'-bpy molecule and two coordinated water molecules (Fig. 1). The Ni^II centre adopts an octahedral coordination geometry, with two carboxylate O atoms from different acc²⁻ anions and two N atoms from two 4,4'-bpy ligands in the equatorial plane, and two aqua O atoms occupying the axial positions. The acc²⁻ anion is significantly disordered (see below) and adopts a bis(monodentate) bridging mode, linking two Ni^II centres. The Ni^II centres are linked by acc²⁻ anions and 4,4'-bpy ligands into a two-dimensional grid in the ac plane (Fig. 2), with dimensions of 13.49 (6) × 11.26 (2) Å based on the separation of the metal ions.

As expected, the large dimensions of these two-dimensional grids allow them to interpenetrate in an extensive and unusual fashion (Fig. 3a). Each two-dimensional grid interpenetrates two adjacent ones, and these three different sets are parallel to the crystallographic c axis, displaying relative rotations about this axis of 120° as required by the symmetry. This network is highly unusual in that the three stacking sheets occur along three coplanar directions, and the interlocking mode can be described as parallel–parallel–parallel (p-p-p) with the same `density of catenation' (2/2/2) (Carlucci, Ciani, Proserpio & Rizzato, 2003). Each grid is surrounded by four other grids to form triangular interspaces (Fig. 3b), in which the coordinated water molecules O5 and O6 form O—H···O hydrogen bonds with the uncoordinated carboxylate O atoms O4 and O2, respectively, resulting a right-handed helical chain (Fig. 4 and Table 2). These interactions, to some extent, stabilize the whole special interpenetration mode.

To the best of our knowledge, only a few compounds are known to contain three sets of (4,4) nets. The first two, [Pt(HL)₂L₂]·2H₂O (HL is isonicotinic acid) and [Fe(bpb)₂(NCS)₂]·0.5MeOH [bpb is 1,4-bis(4-pyridyl)butadiyne], are both three-dimensional networks containing three sets of (4,4) layers stacked in three `perpendicular' directions (Aakeroy et al., 1999; Moliner et al., 2000). Structures with three sets in coplanar directions, however, were only reported very recently, namely [Ni(cpoa)(4,4'-bpy)(H₂O)₂] (H₂cpoa is 4-carboxyphenoxy acetic acid; Chen et al., 2006), [Ni(L)(4,4'-bpy)(H₂O)₂] (H₂L is trans,trans-muconic acid; Zhuang et al., 2007) and [Ni₆(bpe)₁₀(H₂O)₁₆](SO₄)₆.xH₂O] [bpe is bis(4-pyridyl)ethane] (Carlucci, Ciani, Proserpio & Rizzato, 2003). The first two examples are very similar to (I), with the same three sets interpenetrating each other, while the third is different in that one rectangular net and two sets of square nets interpenetrate in inclined mode with the density of catenation of (2/4/4). The compound we report thus represents one of the very limited examples of a two-dimensional → three-dimensional polycatenating framework generated by inclined (4,4) nets.

Another fascinating feature of the title compound is the introduction of chirality into the structure by spontaneous resolution upon crystallization. The two pyridine rings of 4,4'-bpy are twisted out of the plane with a dihedral angle of 44.6 (5)°, nearly twice the twist seen in similar structures (Chen et al., 2006). The 4,4'-bpy ligand thus adopts a large twisted chiral configuration and introduces chirality into the Ni^II–4,4'-bpy chains, the two-dimensional homochiral sheets and finally the three-dimensional framework. Interactions between the 4,4'-bpy molecules of the different nets contribute to reinforcement of the three-dimensional framework. Two C—H groups (C14—H14 and C16—H16) in one pyridyl ring of the 4,4'-bpy in a given sheet have C—H···π interactions with the centroid Cg of the other pyridyl ring of a neighbouring sheet containing atom N2 (Fig. 5). The C···Cg distances and the C—H···Cg angle are in the ranges 3.76 (1)–3.77 (1) Å and 164.2 (7)–166.2 (7)°, respectively.

S2. Experimental

A mixture of NiCl₂·6H₂O (0.025 g, 0.1 mmol), H₂acc (0.020 g, 0.1 mmol), 4,4'-bpy (0.017 g, 0.1 mmol), dimethylformamide (5 ml) and H₂O (5 ml) was placed in a Teflon reactor and heated at 393 K for 24 h. After cooling to room temperature, blue [Green in CIF data - please clarify] crystals of (I) were obtained in 45% yield based on H₂acc. Elemental analysis for C₂₀H₁₈N₂O₆Ni (M_r 684.0): C 35.09, H 2.63, N 4.09%; found: C 35.18, H 2.70, N 4.02%. FT–IR (KBr pellet, cm⁻¹): 3407 (s), 1630 (s), 1577 (s), 1386 (w), 1298 (w), 1218 (w), 1113 (w), 1050 (w), 1004 (w), 931 (w), 898 (w), 704 (w), 638 (w), 544 (w), 516 (w).

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms, with C—H = 0.93 (pyridine, arene) or 0.97 Å (methylene) [U_iso(H) = 1.2U_eq(C)] and O—H = 0.82 Å (water) [U_iso(H) = 1.5U_eq(O)].

The acc²⁻ anion ligand is disordered both rotationally about the axis that includes the carboxylate C—C bonds and lengthwise, having the arene ring connected to either atom C1 or C12. That is, when the arene ring is connected to atom C1, the bond between atoms C8 and C9 represents the vinyl group, while when the arene ring is connected to atom C12, the vinyl group should be assigned to the bond between atoms C4 and C5. The disordered arene rings and C ═C bonds were refined using a rigid group model, where the atoms were fitted to two orientations of an ideal naphthalene moiety which were allowed to translate and rotate (the AFIX 116 instruction in SHELXL97; Sheldrick, 2008). The first group including atoms C4–C9 possesses the same occupancy factors, which all were distributed over two positions (unprimed and primed) with refined site occupation factors of 0.56 (1)/0.44 (1) related to the rotational disorder about the carboxylate C—C bonds. Atoms C2, C3, C10 and C11 assigned to the second group were also distributed over two positions, and they were refined with site occupation factors of 0.279 (6)/0.221 (6) due to the lengthwise disorder that flips the entire ligand. H atoms were assigned site occupation factors consistent with the parent C atoms. The disordered model still leaves several residual electron-density peaks in this region of the structure, but further modelling of the disorder was unfruitful.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 local coordination environment for the Ni^II centres in (I). Displacement ellipsoids are drawn at the 20% probability level and H atoms have been omitted for clarity. The disordered orientations of the acc^2− ligand are shown as primed and unprimed atoms with open and filled bonds, respectively. [Symmetry codes: (i) x, y, 1 + z; (ii) 1 + x, y, z.]
	Fig. 2. The two-dimensional grid of (I) along the ac plane, constructed from acc^2− anions and 4,4'-bpy ligands, connecting the Ni^II ions.
	Fig. 3. (a) A view of the three-dimensional structure of (I) along the c axis. (b) A schematic representation of the modes of inclined interpenetration by complementary (4,4) networks.
	Fig. 4. The left-handed hydrogen-bonded helical chains formed between the coordinated water molecules and the uncoordinated carboxylate O atoms within the triangular interspaces. The helical axes are represented by the long bars. [Symmtry codes: (i) x, y, 1 + z; (ii) 1 − y, x − y, 2/3 + z; (iii) 1 − x + y, 2 − x, 1/3 + z.]
	Fig. 5. Weak C—H···π interactions between adjacent two-dimensional layers, viewed along the a axis. For clarity, the acc^2− anions are simplified into long rods connecting the metal centres. The centroids (Cg) of the pyridyl rings of 4,4'-bpy are represented by black dots. [Symmtry codes: (i) −x + y, 1 − x, 1/3 + z; (ii) 1 − y, 1 + x − y, −1/3 + z.]

poly[diaqua(µ₂-4,4'-bipyridine)(µ₂-4-carboxylatocinnamato)nickel(II)]

Crystal data

[Ni(C10H6O4)(C10H8N2)(H2O)2]	Dx = 1.483 Mg m^−3
Mr = 441.07	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P32	Cell parameters from 1991 reflections
Hall symbol: P 32	θ = 5.6–22.6°
a = 11.261 (2) Å	µ = 1.02 mm^−1
c = 13.495 (6) Å	T = 298 K
V = 1482.0 (8) Å^3	Block, green
Z = 3	0.32 × 0.30 × 0.26 mm
F(000) = 684

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3429 independent reflections
Radiation source: fine-focus sealed tube	2458 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→12
Tmin = 0.736, Tmax = 0.777	k = −13→13
7628 measured reflections	l = −15→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.211	w = 1/[σ^2(Fo^2) + (0.1135P)^2 + 3.2806P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3429 reflections	Δρmax = 1.02 e Å^−3
324 parameters	Δρmin = −0.65 e Å^−3
937 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

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	Occ. (<1)
Ni1	0.89237 (9)	0.66653 (11)	1.16739 (12)	0.0337 (3)
O1	0.8978 (6)	0.6717 (7)	1.0184 (6)	0.042 (2)
O2	0.9894 (9)	0.8922 (8)	0.9802 (6)	0.067 (2)
O3	0.8932 (6)	0.6610 (6)	0.3162 (7)	0.043 (2)
O4	0.7634 (9)	0.4409 (8)	0.3545 (6)	0.069 (2)
O5	0.7857 (6)	0.4526 (6)	1.1565 (5)	0.0402 (16)
H5C	0.7666	0.4421	1.2180	0.048*
H5D	0.7115	0.4104	1.1238	0.048*
O6	0.9994 (6)	0.8809 (6)	1.1782 (5)	0.0402 (17)
H6C	0.9909	0.8916	1.1167	0.048*
H6D	0.9681	0.9238	1.2109	0.048*
N1	0.7053 (8)	0.6665 (10)	1.1674 (6)	0.0390 (17)
N2	0.0794 (8)	0.6671 (10)	1.1671 (6)	0.0414 (19)
C1	0.9366 (10)	0.7676 (12)	0.9569 (7)	0.052 (3)
C2	0.904 (3)	0.564 (2)	0.7371 (16)	0.091 (4)	0.221 (6)
H2	0.9102	0.4854	0.7249	0.109*	0.221 (6)
C3	0.918 (3)	0.614 (3)	0.8332 (14)	0.082 (5)	0.221 (6)
H3	0.9335	0.5687	0.8853	0.098*	0.221 (6)
C4	0.910 (2)	0.731 (3)	0.8513 (12)	0.086 (4)	0.442 (13)
H4	0.9067	0.6477	0.8338	0.103*	0.221 (6)
C5	0.887 (2)	0.798 (2)	0.7734 (14)	0.094 (4)	0.442 (13)
H5	0.8816	0.8760	0.7856	0.113*	0.442 (13)
C6	0.8734 (18)	0.7478 (18)	0.6774 (13)	0.099 (4)	0.442 (13)
H6	0.8529	0.7910	0.6268	0.119*	0.221 (6)
C7	0.882 (2)	0.6308 (19)	0.6592 (13)	0.102 (4)	0.442 (13)
H7	0.8986	0.5913	0.7125	0.123*	0.221 (6)
C8	0.868 (3)	0.581 (2)	0.5632 (14)	0.099 (4)	0.442 (13)
H8	0.8737	0.5027	0.5510	0.119*	0.442 (13)
C9	0.845 (3)	0.648 (3)	0.4853 (12)	0.100 (5)	0.442 (13)
H9	0.8436	0.7245	0.4969	0.120*	0.221 (6)
C10	0.837 (3)	0.765 (3)	0.5034 (14)	0.101 (5)	0.221 (6)
H10	0.8218	0.8100	0.4513	0.121*	0.221 (6)
C11	0.851 (3)	0.815 (2)	0.5995 (16)	0.100 (4)	0.221 (6)
H11	0.8451	0.8932	0.6116	0.120*	0.221 (6)
C2'	0.7300 (18)	0.5251 (19)	0.7451 (12)	0.102 (4)	0.279 (6)
H2'	0.6482	0.4429	0.7373	0.122*	0.279 (6)
C3'	0.773 (2)	0.581 (2)	0.8391 (11)	0.097 (5)	0.279 (6)
H3'	0.7195	0.5359	0.8942	0.117*	0.279 (6)
C4'	0.895 (2)	0.704 (2)	0.8508 (10)	0.087 (4)	0.558 (13)
H4'	0.8208	0.6288	0.8431	0.105*	0.279 (6)
C5'	0.9746 (18)	0.7711 (18)	0.7684 (12)	0.104 (4)	0.558 (13)
H5'	1.0564	0.8534	0.7763	0.125*	0.558 (13)
C6'	0.9319 (14)	0.7154 (15)	0.6745 (10)	0.098 (4)	0.558 (13)
H6'	0.9795	0.7546	0.6189	0.118*	0.279 (6)
C7'	0.8096 (14)	0.5924 (14)	0.6628 (10)	0.094 (4)	0.558 (13)
H7'	0.7471	0.5422	0.7140	0.113*	0.279 (6)
C8'	0.7669 (16)	0.5367 (16)	0.5688 (11)	0.099 (4)	0.558 (13)
H8'	0.6851	0.4544	0.5610	0.119*	0.558 (13)
C9'	0.8465 (19)	0.6039 (19)	0.4865 (10)	0.072 (4)	0.558 (13)
H9'	0.9282	0.6897	0.5013	0.087*	0.279 (6)
C10'	0.969 (2)	0.727 (2)	0.4981 (11)	0.086 (5)	0.279 (6)
H10'	1.0220	0.7719	0.4431	0.103*	0.279 (6)
C11'	1.0114 (17)	0.7827 (18)	0.5921 (12)	0.089 (4)	0.279 (6)
H11'	1.0933	0.8650	0.5999	0.107*	0.279 (6)
C12	0.8357 (9)	0.5672 (11)	0.3786 (7)	0.045 (2)
C13	0.6664 (9)	0.7090 (10)	1.2460 (7)	0.046 (2)
H13	0.7223	0.7370	1.3018	0.055*
C14	0.5459 (10)	0.7132 (11)	1.2481 (7)	0.050 (2)
H14	0.5240	0.7480	1.3033	0.060*
C15	0.4574 (9)	0.6653 (11)	1.1673 (7)	0.043 (2)
C16	0.4987 (10)	0.6192 (11)	1.0861 (8)	0.051 (2)
H16	0.4427	0.5852	1.0306	0.062*
C17	0.6224 (9)	0.6244 (10)	1.0887 (7)	0.048 (2)
H17	0.6504	0.5971	1.0326	0.057*
C18	0.0889 (9)	0.5597 (10)	1.1353 (8)	0.048 (2)
H18	0.0090	0.4824	1.1142	0.058*
C19	0.2053 (9)	0.5561 (11)	1.1316 (7)	0.046 (2)
H19	0.2056	0.4799	1.1053	0.055*
C20	0.3265 (9)	0.6666 (10)	1.1671 (8)	0.043 (2)
C21	0.3180 (9)	0.7769 (10)	1.2033 (7)	0.048 (2)
H21	0.3951	0.8522	1.2299	0.058*
C22	0.1940 (10)	0.7748 (11)	1.1996 (7)	0.047 (2)
H22	0.1909	0.8518	1.2208	0.057*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0311 (6)	0.0444 (7)	0.0308 (5)	0.0228 (5)	−0.0016 (5)	−0.0025 (4)
O1	0.052 (5)	0.056 (5)	0.020 (5)	0.030 (3)	0.003 (3)	0.001 (3)
O2	0.102 (6)	0.060 (5)	0.031 (4)	0.034 (5)	0.009 (4)	0.008 (3)
O3	0.045 (5)	0.047 (4)	0.040 (6)	0.025 (3)	−0.006 (3)	0.000 (3)
O4	0.088 (6)	0.066 (5)	0.032 (4)	0.024 (4)	−0.001 (4)	0.006 (3)
O5	0.036 (3)	0.054 (4)	0.029 (4)	0.022 (3)	−0.001 (2)	−0.004 (3)
O6	0.041 (4)	0.055 (4)	0.031 (4)	0.029 (3)	−0.002 (3)	−0.005 (3)
N1	0.035 (4)	0.054 (4)	0.034 (4)	0.026 (4)	−0.012 (3)	−0.017 (3)
N2	0.043 (5)	0.052 (4)	0.034 (4)	0.026 (4)	−0.005 (3)	−0.006 (3)
C1	0.050 (6)	0.075 (8)	0.037 (6)	0.035 (6)	−0.003 (4)	−0.010 (5)
C2	0.106 (7)	0.102 (7)	0.078 (6)	0.063 (7)	−0.005 (6)	−0.007 (6)
C3	0.101 (8)	0.097 (8)	0.074 (6)	0.069 (7)	0.001 (7)	−0.015 (6)
C4	0.102 (8)	0.100 (8)	0.072 (6)	0.063 (7)	−0.003 (6)	−0.009 (6)
C5	0.107 (8)	0.104 (8)	0.078 (6)	0.057 (7)	−0.003 (6)	−0.008 (6)
C6	0.107 (7)	0.110 (7)	0.078 (5)	0.052 (7)	−0.011 (6)	−0.001 (5)
C7	0.111 (7)	0.108 (7)	0.082 (5)	0.050 (7)	−0.007 (6)	−0.014 (5)
C8	0.110 (8)	0.110 (8)	0.081 (6)	0.057 (7)	−0.004 (6)	−0.008 (6)
C9	0.109 (8)	0.109 (8)	0.083 (6)	0.054 (7)	−0.005 (7)	−0.002 (6)
C10	0.113 (8)	0.108 (8)	0.081 (6)	0.055 (8)	−0.007 (7)	−0.008 (7)
C11	0.112 (8)	0.107 (8)	0.082 (6)	0.057 (7)	−0.005 (6)	−0.007 (6)
C2'	0.112 (8)	0.109 (8)	0.082 (6)	0.054 (7)	−0.005 (6)	−0.008 (6)
C3'	0.109 (8)	0.106 (8)	0.081 (6)	0.057 (7)	−0.008 (7)	−0.009 (6)
C4'	0.103 (8)	0.102 (8)	0.075 (6)	0.065 (7)	−0.003 (6)	−0.003 (6)
C5'	0.115 (7)	0.109 (7)	0.083 (6)	0.053 (7)	−0.007 (6)	−0.008 (6)
C6'	0.114 (7)	0.103 (7)	0.085 (5)	0.060 (7)	−0.007 (6)	−0.012 (5)
C7'	0.110 (7)	0.106 (7)	0.080 (5)	0.064 (6)	0.007 (6)	−0.008 (5)
C8'	0.110 (7)	0.105 (7)	0.087 (6)	0.056 (7)	−0.010 (6)	−0.005 (6)
C9'	0.096 (7)	0.089 (7)	0.068 (6)	0.074 (6)	−0.011 (6)	−0.004 (6)
C10'	0.102 (8)	0.099 (8)	0.076 (6)	0.064 (7)	−0.012 (7)	−0.008 (6)
C11'	0.104 (7)	0.102 (7)	0.078 (6)	0.063 (7)	−0.006 (6)	−0.007 (6)
C12	0.041 (5)	0.068 (7)	0.031 (5)	0.030 (5)	−0.001 (4)	−0.006 (5)
C13	0.044 (5)	0.071 (6)	0.034 (5)	0.037 (5)	−0.011 (4)	−0.013 (4)
C14	0.043 (5)	0.075 (7)	0.039 (5)	0.035 (5)	−0.003 (4)	−0.019 (5)
C15	0.034 (5)	0.065 (6)	0.039 (5)	0.031 (5)	0.008 (4)	0.024 (4)
C16	0.051 (6)	0.071 (7)	0.047 (6)	0.042 (6)	−0.014 (5)	−0.012 (5)
C17	0.046 (5)	0.068 (6)	0.037 (5)	0.034 (5)	−0.006 (4)	−0.017 (5)
C18	0.029 (5)	0.048 (6)	0.065 (7)	0.016 (4)	−0.004 (4)	−0.011 (5)
C19	0.040 (5)	0.057 (6)	0.048 (5)	0.030 (5)	−0.009 (4)	−0.013 (5)
C20	0.028 (5)	0.041 (5)	0.062 (6)	0.019 (4)	0.004 (4)	0.003 (4)
C21	0.034 (5)	0.055 (6)	0.062 (6)	0.026 (5)	−0.009 (4)	−0.022 (5)
C22	0.045 (6)	0.065 (7)	0.044 (6)	0.037 (5)	−0.012 (4)	−0.011 (5)

Geometric parameters (Å, º)

Ni1—O3^i	2.009 (10)	C11—H6	0.4644
Ni1—O1	2.011 (9)	C11—H11	0.9300
Ni1—O5	2.091 (6)	C2'—C3'	1.3900
Ni1—O6	2.096 (6)	C2'—C7'	1.3900
Ni1—N2^ii	2.103 (7)	C2'—H2'	0.9300
Ni1—N1	2.107 (7)	C2'—H7'	0.4617
O1—C1	1.255 (13)	C3'—C4'	1.3900
O2—C1	1.260 (13)	C3'—H3'	0.9300
O3—C12	1.249 (12)	C3'—H4'	0.5435
O3—Ni1^iii	2.009 (10)	C4'—C5'	1.3900
O4—C12	1.278 (12)	C4'—H4	0.7441
O5—H5C	0.8500	C4'—H4'	0.8466
O5—H5D	0.8500	C5'—C6'	1.3900
O6—H6C	0.8501	C5'—H5'	0.9300
O6—H6D	0.8499	C6'—C7'	1.3900
N1—C13	1.324 (12)	C6'—C11'	1.3900
N1—C17	1.335 (12)	C6'—H6'	0.8993
N2—C22	1.328 (14)	C7'—C8'	1.3900
N2—C18	1.337 (14)	C7'—H7	1.2113
N2—Ni1^iv	2.103 (7)	C7'—H7'	0.9457
C1—C4	1.472 (19)	C8'—C9'	1.3900
C1—C4'	1.565 (16)	C8'—H8'	0.9300
C2—C3	1.3900	C9'—C10'	1.3900
C2—C7	1.3900	C9'—C12	1.502 (15)
C2—H2	0.9300	C9'—H9'	0.9650
C2—H7	0.4816	C10'—C11'	1.3900
C3—C4	1.3900	C10'—H9'	0.4409
C3—H3	0.9300	C10'—H10'	0.9300
C3—H4	0.4641	C11'—H6'	0.4957
C4—C5	1.3900	C11'—H11'	0.9300
C4—H4	0.9462	C13—C14	1.383 (12)
C4—H4'	1.0871	C13—H13	0.9300
C5—C6	1.3900	C14—C15	1.391 (14)
C5—H5	0.9300	C14—H14	0.9300
C6—C7	1.3900	C15—C16	1.389 (14)
C6—C11	1.3900	C15—C20	1.481 (10)
C6—H6	0.9311	C16—C17	1.365 (13)
C7—C8	1.3900	C16—H16	0.9300
C7—H7	0.9129	C17—H17	0.9300
C8—C9	1.3900	C18—C19	1.332 (13)
C8—H8	0.9300	C18—H18	0.9300
C9—C10	1.3900	C19—C20	1.394 (14)
C9—C12	1.68 (2)	C19—H19	0.9300
C9—H9	0.8847	C20—C21	1.382 (14)
C9—H9'	0.8356	C21—C22	1.386 (12)
C10—C11	1.3900	C21—H21	0.9300
C10—H9	0.5072	C22—H22	0.9300
C10—H10	0.9300
O3^i—Ni1—O1	177.9 (2)	C3'—C2'—H2'	120.0
O3^i—Ni1—O5	92.5 (3)	C7'—C2'—H2'	120.0
O1—Ni1—O5	87.4 (3)	C3'—C2'—H7'	131.5
O3^i—Ni1—O6	87.6 (2)	H2'—C2'—H7'	108.1
O1—Ni1—O6	92.5 (3)	C4'—C3'—C2'	120.0
O5—Ni1—O6	179.9 (4)	C2'—C3'—H4	104.4
O3^i—Ni1—N2^ii	88.9 (3)	C4'—C3'—H3'	120.0
O1—Ni1—N2^ii	89.0 (3)	C2'—C3'—H3'	120.0
O5—Ni1—N2^ii	90.1 (3)	H4—C3'—H3'	126.9
O6—Ni1—N2^ii	89.9 (3)	C2'—C3'—H4'	119.1
O3^i—Ni1—N1	91.1 (3)	H3'—C3'—H4'	120.9
O1—Ni1—N1	90.9 (3)	C3'—C4'—C5'	120.0
O5—Ni1—N1	90.1 (3)	C3'—C4'—C1	118.8 (12)
O6—Ni1—N1	90.0 (3)	C5'—C4'—C1	121.2 (12)
N2^ii—Ni1—N1	179.8 (5)	C3'—C4'—H4	68.1
C1—O1—Ni1	132.8 (7)	C5'—C4'—H4	83.0
C12—O3—Ni1^iii	133.7 (7)	C1—C4'—H4	122.1
Ni1—O5—H5C	93.0	C5'—C4'—H4'	119.4
Ni1—O5—H5D	121.3	C1—C4'—H4'	119.3
H5C—O5—H5D	108.7	H4—C4'—H4'	67.6
Ni1—O6—H6C	93.1	C4'—C5'—C6'	120.0
Ni1—O6—H6D	121.8	C6'—C5'—H4	102.6
H6C—O6—H6D	108.7	C4'—C5'—H5'	120.0
C13—N1—C17	117.8 (7)	C6'—C5'—H5'	120.0
C13—N1—Ni1	120.7 (6)	H4—C5'—H5'	130.6
C17—N1—Ni1	121.4 (6)	C5'—C6'—C7'	120.0
C22—N2—C18	116.9 (8)	C5'—C6'—C11'	120.0
C22—N2—Ni1^iv	121.1 (7)	C7'—C6'—C11'	120.0
C18—N2—Ni1^iv	122.0 (7)	C5'—C6'—H7	88.6
O1—C1—O2	124.0 (9)	C7'—C6'—H7	52.4
O1—C1—C4	117.6 (13)	C11'—C6'—H7	129.4
O2—C1—C4	118.3 (14)	C5'—C6'—H6'	123.6
O1—C1—C4'	108.4 (11)	C7'—C6'—H6'	116.4
O2—C1—C4'	127.3 (12)	H7—C6'—H6'	127.7
C3—C2—C7	120.0	C8'—C7'—C6'	120.0
C3—C2—H2	120.0	C8'—C7'—C2'	120.0
C7—C2—H2	120.0	C6'—C7'—C2'	120.0
C3—C2—H7	114.0	C8'—C7'—H7	127.0
H2—C2—H7	125.9	C6'—C7'—H7	62.3
C2—C3—C4	120.0	C2'—C7'—H7	82.2
C2—C3—H3	120.0	C8'—C7'—H7'	114.3
C4—C3—H3	120.0	C6'—C7'—H7'	125.7
C2—C3—H4	109.4	H7—C7'—H7'	87.8
H3—C3—H4	129.7	C9'—C8'—C7'	120.0
C2—C3—H4'	103.6	C9'—C8'—H8'	120.0
C4—C3—H4'	48.9	C7'—C8'—H8'	120.0
H3—C3—H4'	115.0	C8'—C9'—C10'	120.0
C3—C4—C5	120.0	C8'—C9'—C12	133.1 (11)
C3—C4—C1	109.7 (14)	C10'—C9'—C12	106.7 (11)
C5—C4—C1	130.1 (14)	C8'—C9'—H9	97.4
C5—C4—H4	114.9	C10'—C9'—H9	60.5
C1—C4—H4	115.0	C12—C9'—H9	109.4
C3—C4—H4'	56.5	C8'—C9'—H9'	114.4
C5—C4—H4'	100.0	C12—C9'—H9'	112.4
C1—C4—H4'	110.4	H9—C9'—H9'	58.3
H4—C4—H4'	51.3	C11'—C10'—C9'	120.0
C6—C5—C4	120.0	C11'—C10'—H9	97.9
C6—C5—H5	120.0	C9'—C10'—H9	59.4
C4—C5—H5	120.0	C11'—C10'—H9'	107.6
C5—C6—C7	120.0	H9—C10'—H9'	55.1
C5—C6—C11	120.0	C11'—C10'—H10'	120.0
C7—C6—C11	120.0	C9'—C10'—H10'	120.0
C5—C6—H6	118.7	H9—C10'—H10'	111.8
C7—C6—H6	121.2	H9'—C10'—H10'	132.3
C5—C6—H6'	125.6	C10'—C11'—C6'	120.0
C7—C6—H6'	59.4	C10'—C11'—H6'	113.5
C11—C6—H6'	85.8	C6'—C11'—H9'	104.6
H6—C6—H6'	89.2	H6'—C11'—H9'	98.1
C8—C7—C6	120.0	C10'—C11'—H11'	120.0
C8—C7—C2	120.0	C6'—C11'—H11'	120.0
C6—C7—C2	120.0	H6'—C11'—H11'	126.5
C8—C7—H7	123.1	H9'—C11'—H11'	135.4
C6—C7—H7	116.9	O3—C12—O4	122.9 (9)
C8—C7—H6'	85.0	O3—C12—C9'	119.0 (12)
C6—C7—H6'	60.8	O4—C12—C9'	118.1 (11)
C2—C7—H6'	125.2	O3—C12—C9	104.7 (12)
H7—C7—H6'	123.1	O4—C12—C9	130.9 (12)
C8—C7—H7'	108.2	N1—C13—C14	122.4 (8)
C6—C7—H7'	91.0	N1—C13—H13	118.8
C2—C7—H7'	70.7	C14—C13—H13	118.8
H7—C7—H7'	71.3	C13—C14—C15	119.7 (8)
H6'—C7—H7'	151.4	C13—C14—H14	120.1
C7—C8—C9	120.0	C15—C14—H14	120.1
C7—C8—H8	120.0	C16—C15—C14	117.0 (7)
C9—C8—H8	120.0	C16—C15—C20	121.5 (8)
C7—C8—H9'	107.8	C14—C15—C20	121.4 (9)
H8—C8—H9'	120.6	C17—C16—C15	119.3 (9)
C10—C9—C8	120.0	C17—C16—H16	120.4
C10—C9—C12	130.5 (14)	C15—C16—H16	120.4
C8—C9—C12	109.5 (14)	N1—C17—C16	123.6 (9)
C8—C9—H9	119.6	N1—C17—H17	118.2
C12—C9—H9	130.8	C16—C17—H17	118.2
C10—C9—H9'	90.5	C19—C18—N2	124.4 (9)
C8—C9—H9'	69.7	C19—C18—H18	117.8
C12—C9—H9'	106.2	N2—C18—H18	117.8
H9—C9—H9'	88.3	C18—C19—C20	120.0 (9)
C11—C10—C9	120.0	C18—C19—H19	120.0
C11—C10—H9	119.2	C20—C19—H19	120.0
C11—C10—H10	120.0	C21—C20—C19	116.5 (8)
C9—C10—H10	120.0	C21—C20—C15	121.6 (8)
H9—C10—H10	120.6	C19—C20—C15	121.9 (8)
C10—C11—C6	120.0	C20—C21—C22	119.6 (9)
C10—C11—H6	122.3	C20—C21—H21	120.2
C10—C11—H11	120.0	C22—C21—H21	120.2
C6—C11—H11	120.0	N2—C22—C21	122.5 (10)
H6—C11—H11	117.3	N2—C22—H22	118.7
C3'—C2'—C7'	120.0	C21—C22—H22	118.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5C···O4^i	0.85	1.84	2.681 (10)	168
O5—H5D···O4^v	0.85	2.04	2.873 (9)	169
O6—H6D···O2^vi	0.85	2.03	2.871 (9)	168
O6—H6C···O2	0.85	1.84	2.679 (10)	168

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