A new one-dimensional nickel metal–organic framework: catena-poly[[[di­aqua­bis­(4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfan­yl]meth­yl}benzoato-κO)nickel(II)]-μ-4,4′-bi­pyridine-κ²N:N′] monohydrate]

The title complex, {[Ni(C₁₅H₁₁N₄O₂S)₂(C₁₀H₈N₂)(H₂O)₂]·H₂O}_n, was synthesized by the reaction of nickel chloride, 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfan­yl]meth­yl}benzoic acid (HL) and 4,4′-bi­pyridine (bpy) under hydro­thermal conditions. The asymmetric unit contains two half Ni^II ions, each located on an inversion centre, two L⁻ ligands, one bpy ligand, two coordinated water mol­ecules and one unligated water mol­ecule. Each Ni^II centre is six-coordinated by two monodentate carboxyl­ate O atoms from two different L⁻ ligands, two pyridine N atoms from two different bpy ligands and two terminal water mol­ecules, displaying a nearly ideal octa­hedral geometry. The Ni^II ions are bridged by 4,4′-bi­pyridine ligands to afford a linear array, with an Ni...Ni separation of 11.361 (1) Å, which is further decorated by two monodentate L⁻ ligands trans to each other, resulting in a one-dimensional fishbone-like chain structure. These one-dimensional fishbone-like chains are further linked by O—H...O, O—H...N and C—H...O hydrogen bonds and π–π stacking inter­actions to form a three-dimensional supra­molecular architecture. The thermal stability of the title complex was investigated via thermogravimetric analysis.

S1. Introduction

In the fields of supra­molecular chemistry and crystal engineering, the design and assembly of metal–organic frameworks (MOFs) has attracted great inter­est in recent years, not only because of their potential applications in gas adsorption/separation (Li et al., 2009, 2012; Gutiérrez-Sevillano et al., 2013), catalysis (Corma et al., 2010; Yoon et al., 2012; Gascon et al., 2014), luminescence (Allendorf et al., 2009; Heine & Müller-Buschbaum, 2013) and magnetism (Kurmoo et al., 2009), but also because of the variety of their architectures and topologies (O'Keeffe & Yaghi, 2012; Li et al., 2014). In essence, the structural and functional diversity of such crystalline materials rests with the choice of building units (metal ions and organic ligands) and synthetic pathways. In particular, the organic ligands have a direct influence on the MOFs obtained because of their different spacer lengths, flexibility, steric hindrance effects, conformational preferences, and so on (Hoskins & Robson, 1989; Ji et al., 2011; Cook et al., 2013). Thus, selecting a suitable organic ligand with versatile binding modes to coordinate to a metal ion is crucial in the construction of metal–organic systems.

Up to now, rigid pyridine-based ligands and carboxyl­ate ligands were employed extensively for the preparation of functional MOFs (Eddaoudi et al., 2001; Ghosh et al., 2009; Inokuma et al., 2010; Kim et al., 2010; Lim et al., 2010; Cook et al., 2013). However, investigations of the use of flexible carboxyl­ate ligands in the construction of metal–organic systems is rare (Liu et al., 2008; Dai et al., 2009; Cui et al., 2012). The conformational freedom of flexible carboxyl­ate ligands may provide more possibilities for the construction of metal–organic systems and structures with unusual topologies. On the other hand, ancillary ligands containing donor N atoms, such as 4,4'-bi­pyridine, have been used widely together with carboxyl­ate ligands to meet the coordination geometry requirements of metal ions and construct the desired frameworks (Liu et al., 2008; Ji et al., 2011). In order to understand the structural aspects of MOFs containing flexible carboxyl­ate building blocks, we chose 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoic acid (HL) as a flexible carboxyl­ate ligand and introduced rigid bidentate linear 4,4'-bi­pyridine (bpy) as coligand, to react with the Ni^II ion, and successfully obtained a new complex, {[Ni(L)₂(bpy)(H₂O)₂].H₂O}_n, (I), under hydro­thermal conditions. The synthesis, crystal structure and thermal properties of (I) are reported here.

S2. Experimental

S2.1. Synthesis and crystallization

4-{[(1-Phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoic acid (HL) was prepared according to our previously reported method (Zhang et al., 2012). For the synthesis of (I), a mixture of NiCl₂.6H₂O (23.8 mg, 0.1 mmol), HL (62.4 mg, 0.2 mmol) and 4,4'-bi­pyridine (15.6 mg, 0.1 mmol) in H₂O (10 ml) was placed in a Teflon-lined stainless steel vessel, heated at 393 K for 3 d and then cooled to room temperature. Green block-shaped crystals of (I) were obtained (yield 54.6%, based on HL). Elemental analysis for C₄₀H₃₆N₁₀NiO₇S₂: C 53.88, H 4.07, N 15.71%; found: C 53.79, H 4.12, N 15.85%. IR (KBr, cm^-1): 3392, 3071, 1602, 1540, 1386, 1318, 1233, 1218, 1173, 1090, 1067, 1015, 866, 844, 816, 785, 760, 730, 694, 631.

The powder X-ray diffraction (PXRD) pattern was recorded on a Bruker D8 Advance diffractometer with Cu Kα radiation (λ = 1.5406 Å) at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to anisotropically refined atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.93 (aromatic and pyridine) or 0.97 Å (methyl­ene) and U_iso(H) = 1.2U_eq(C). Water H atoms were located in difference Fourier syntheses and refined with an O—H distance restraint of 0.85 Å and U_iso(H) = 1.2U_eq(O). Examination of the refined structure using PLATON (Spek, 2009) revealed the presence of a void, having a total volume of 83 ų per unit cell, centred at approximately (1/2, 1/2, 0). Although this empty space is suitable for the inclusion of a small solvent molecule, such as water, the total electron density found within the cavity is only 0.2 electrons.

S3. Results and discussion

The asymmetric unit of the title compound, (I), contains two half Ni^II ions, two 4-{[(1-phenyl-1H-tetra­zol-5-yl)sulfanyl]methyl}­benzoate (L^-) ligands, one bpy ligand, two coordinated water molecules and one isolated water molecule (Fig. 1). Each Ni^II ion is six-coordinated by two monodentate carboxyl­ate O atoms [O1 and O1ⁱ for Ni1; O3 and O3ⁱⁱ for Ni2; symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y+1, -z-1) from two different L^- ligands, two pyridine N atoms (N9 and N9ⁱ for Ni1; N10 and N10ⁱⁱ for Ni2) from two different bpy ligands, and two terminal water molecules (O5 and O5ⁱ for Ni1; N6, N6ⁱ for Ni2), displaying a nearly ideal o­cta­hedral geometry. The Ni—O/N bond lengths (Table 2) range from 2.027 (2) to 2.141 (3) Å, which are within the normal range (Wang et al., 2005). The dihedral angles between planes of the tetra­zole rings and the adjacent terminal benzene rings are 40.4 (2) and 45.8 (2)° in the two L^- ligands. The planes of the pyridine rings of each 4,4'-bi­pyridine molecule are twisted, with a dihedral angle of 19.8 (1)°.

As shown in Fig. 2, two monodentate L^- ligands link to one Ni^II ion to form an [Ni(L)₂(H₂O)₂] chair-like SBU (secondary building unit). One inter­esting feature of (I) is the presence of two different conformations of chair-like SBUs, viz. [Ni1(L)₂(H₂O)₂] and [Ni2(L)₂(H₂O)₂]. The Ni1 and Ni2 ions are bridged by an 4,4'-bi­pyridine ligand to afford a linear array with an Ni1···Ni2 separation of 11.361 (1) Å, which is further decorated with the monodentate L^- ligands on both sides, resulting in a fishbone-like chain structure. Only a few examples containing a one-dimensional fishbone-like structural motif have been reported to date (Dai et al., 2009; Wang et al., 2009; Li et al., 2010; Li & Du, 2011; Chen et al., 2012; Wang et al., 2012; Çolak et al., 2013). Intra­chain O5—H5A···O2 and O6—H6A···O4 hydrogen bonds are observed between the coordinated water molecules and adjacent uncoordinated carboxyl­ate O atoms (Table 3), which may play an important role in stabilizing the fishbone-like chain structure. In addition, inter­chain hydrogen bonds [O5—H5B···O7ⁱⁱⁱ, C3—H3···N3^iv, C37—H37···N6ⁱⁱⁱ and C12—H12···S2^iv; symmetry codes: (iii) x, y-1, z-1; (iv) -x+2, -y+1, -z+1] and C—H···π inter­actions [H28···Cg1^iv = 2.89 Å, C28···Cg1^iv = 3.797 (6) Å and C28—H28···Cg1^iv = 166°; Cg1 is the centroid of the C2—C7 ring] involving the isolated water molecules and L^- ligands inter­link such one-dimensional arrays to afford a two-dimensional layer (Fig. 3), which are further extended via O—H···O, O—H···N and C—H···O hydrogen bonds [O7—H7A···O6^v, O6—H6B···N4^v, O7—H7B···N7^vi, C19—H19···O2^vii and C27—H27···O4^v; symmetry codes: (v) -x+1, -y+1, -z; (vi) -x+1, -y+2, -z+1; (vii) x, y+1, z] and π–π stacking inter­actions, with a Cg1···Cg2^v separation of 3.719 (3) Å (Cg2 is the centroid of the C17–C22 ring) between benzoate rings to form a three-dimensional supra­molecular architecture (Fig. 4).

To investigate the thermal stability of (I), thermogravimetric analysis (TGA) was carried out under a nitro­gen atmosphere (Fig. 5). The TGA curve for (I) shows weight losses of 2.15 and 4.07% in the temperature range 298–418 K, corresponding to the loss of one isolated water molecule (calculated 2.02%) and two coordinated water molecules (calculated 4.04%). The framework is then stable up to 583 K, but collapses on further heating. The phase purity of the bulk as-synthesized samples for (I) was examined by PXRD (powder X-ray diffraction) experiment. All major peaks of the experimental PXRD analysis match quite well with those of the simulated PXRD analysis, indicating reasonable crystalline phase purity (Fig. 6).

Related literature

For related literature, see: Allendorf et al. (2009); Chen et al. (2012); Cook et al. (2013); Corma et al. (2010); Cui et al. (2012); Dai et al. (2009); Eddaoudi et al. (2001); Gascon et al. (2014); Ghosh et al. (2009); Gutiérrez-Sevillano, Martín-Calvo, Dubbeldam, Calero & Hamad (2013); Heine & Müller-Buschbaum (2013); Hoskins & Robson (1989); Inokuma et al. (2010); Ji et al. (2011); Kim et al. (2010); Kurmoo (2009); Li & Du (2011); Li et al. (2009, 2010, 2012, 2014); Lim et al. (2010); Liu et al. (2008); O'Keeffe & Yaghi (2012); Wang et al. (2005, 2009, 2012); Yoon et al. (2012); Zhang et al. (2012); Çolak et al. (2013).

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SMART (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The coordination environment around the Ni^II centres in (I), showing the atom-numbering scheme. The nonbonded water molecule is not shown. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y+1, -z-1.]
	Fig. 2. (a) Ball-stick and (b) space-filling representation of the one-dimensional fishbone-like chain structure formed by 4,4'-bipyridine, Ni^IIions and L^- ligands.
	Fig. 3. (a) Ball-stick and (b) space-filling representation of the two-dimensional layer constructed via interchain hydrogen bonds (red dotted lines) and C—H···π interactions (turquoise dotted lines). Different chains are shown in different colours.
	Fig. 4. The three-dimensional supramolecular architecture constructed via interlayer hydrogen bonds (red dotted lines) and π–π stacking interactions (turquoise dotted lines). Different layers are shown in different colours.
	Fig. 5. The TGA curve measured for complex (I).
	Fig. 6. Powder X-ray diffraction patterns of complex (I).

catena-Poly[[[diaquabis(4-{[(1-phenyl-1H-tetrazol-5-yl)sulfanyl]methyl}benzoato-κO)nickel(II)]-µ-4,4'-bipyridine-κ²N:N'] monohydrate]

Crystal data

[Ni(C15H11N4O2S)2(C10H8N2)(H2O)2]·H2O	Z = 2
Mr = 891.62	F(000) = 924
Triclinic, P1	Dx = 1.428 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.6931 (11) Å	Cell parameters from 2364 reflections
b = 13.0160 (12) Å	θ = 2.4–23.7°
c = 14.3559 (14) Å	µ = 0.63 mm^−1
α = 103.065 (1)°	T = 298 K
β = 112.942 (2)°	Block, green
γ = 96.471 (1)°	0.38 × 0.28 × 0.19 mm
V = 2073.6 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	7207 independent reflections
Radiation source: fine-focus sealed tube	4118 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→15
Tmin = 0.796, Tmax = 0.890	k = −15→15
10523 measured reflections	l = −17→10

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.035P)^2] where P = (Fo^2 + 2Fc^2)/3
7207 reflections	(Δ/σ)max = 0.001
544 parameters	Δρmax = 0.61 e Å^−3
0 restraints	Δρmin = −0.51 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	1.0000	0.0000	0.0000	0.02966 (19)
Ni2	0.5000	0.5000	−0.5000	0.0314 (2)
N1	1.0035 (3)	0.4626 (3)	0.7871 (3)	0.0452 (9)
N2	0.9822 (3)	0.5515 (3)	0.8418 (3)	0.0528 (10)
N3	0.9048 (3)	0.5845 (3)	0.7734 (3)	0.0550 (10)
N4	0.8707 (3)	0.5189 (3)	0.6732 (3)	0.0480 (9)
N5	0.5812 (3)	0.9532 (3)	0.3546 (3)	0.0449 (9)
N6	0.5468 (4)	1.0343 (3)	0.4051 (3)	0.0581 (11)
N7	0.4586 (3)	1.0527 (3)	0.3331 (3)	0.0594 (11)
N8	0.4318 (3)	0.9858 (3)	0.2353 (3)	0.0552 (10)
N9	0.9118 (3)	0.1025 (2)	−0.0867 (2)	0.0314 (8)
N10	0.5783 (3)	0.4056 (2)	−0.4004 (2)	0.0315 (8)
O1	0.9540 (2)	0.06388 (19)	0.11728 (18)	0.0349 (6)
O2	0.7651 (3)	−0.0167 (2)	0.0539 (2)	0.0614 (9)
O3	0.4732 (2)	0.59216 (19)	−0.38011 (18)	0.0369 (7)
O4	0.3494 (3)	0.4673 (2)	−0.3669 (2)	0.0604 (9)
O5	0.8487 (2)	−0.12178 (19)	−0.07653 (19)	0.0414 (7)
H5A	0.8035	−0.0992	−0.0497	0.050*
H5B	0.8133	−0.1431	−0.1437	0.050*
O6	0.3335 (2)	0.39434 (18)	−0.55708 (18)	0.0401 (7)
H6A	0.3389	0.4027	−0.4946	0.048*
H6B	0.2881	0.4310	−0.5887	0.048*
O7	0.7261 (3)	0.8207 (2)	0.7035 (2)	0.0705 (10)
H7A	0.7165	0.7626	0.6573	0.085*
H7B	0.6712	0.8543	0.6816	0.085*
S1	0.93028 (11)	0.33692 (10)	0.58547 (9)	0.0619 (4)
S2	0.52089 (11)	0.82483 (9)	0.15464 (9)	0.0560 (3)
C1	0.8560 (4)	0.0525 (3)	0.1206 (3)	0.0370 (10)
C2	0.8477 (3)	0.1306 (3)	0.2111 (3)	0.0337 (9)
C3	0.9319 (3)	0.2257 (3)	0.2680 (3)	0.0417 (10)
H3	0.9948	0.2400	0.2515	0.050*
C4	0.9238 (4)	0.2996 (3)	0.3490 (3)	0.0455 (11)
H4	0.9809	0.3636	0.3860	0.055*
C5	0.8316 (4)	0.2797 (3)	0.3760 (3)	0.0417 (10)
C6	0.7483 (4)	0.1847 (3)	0.3197 (3)	0.0450 (11)
H6	0.6862	0.1697	0.3372	0.054*
C7	0.7552 (4)	0.1113 (3)	0.2377 (3)	0.0436 (11)
H7	0.6971	0.0481	0.1998	0.052*
C8	0.8266 (4)	0.3598 (3)	0.4671 (3)	0.0510 (12)
H8A	0.7481	0.3478	0.4635	0.061*
H8B	0.8485	0.4332	0.4661	0.061*
C9	0.9328 (4)	0.4439 (3)	0.6837 (3)	0.0409 (10)
C10	1.0840 (4)	0.4056 (4)	0.8408 (3)	0.0491 (11)
C11	1.1563 (5)	0.3654 (4)	0.7993 (4)	0.0762 (16)
H11	1.1567	0.3785	0.7384	0.091*
C12	1.2290 (5)	0.3043 (5)	0.8507 (5)	0.104 (2)
H12	1.2762	0.2734	0.8218	0.125*
C13	1.2327 (5)	0.2886 (5)	0.9418 (5)	0.098 (2)
H13	1.2829	0.2485	0.9757	0.118*
C14	1.1624 (5)	0.3322 (4)	0.9834 (4)	0.0831 (17)
H14	1.1649	0.3221	1.0462	0.100*
C15	1.0880 (4)	0.3908 (4)	0.9333 (4)	0.0633 (14)
H15	1.0402	0.4204	0.9621	0.076*
C16	0.4153 (4)	0.5591 (3)	−0.3344 (3)	0.0385 (10)
C17	0.4270 (4)	0.6364 (3)	−0.2346 (3)	0.0376 (10)
C18	0.5070 (3)	0.7346 (3)	−0.1885 (3)	0.0401 (10)
H18	0.5577	0.7519	−0.2179	0.048*
C19	0.5126 (4)	0.8077 (3)	−0.0989 (3)	0.0454 (11)
H19	0.5682	0.8728	−0.0678	0.054*
C20	0.4360 (4)	0.7841 (3)	−0.0555 (3)	0.0465 (11)
C21	0.3566 (4)	0.6861 (4)	−0.1017 (3)	0.0616 (14)
H21	0.3053	0.6689	−0.0729	0.074*
C22	0.3519 (4)	0.6128 (4)	−0.1899 (3)	0.0606 (14)
H22	0.2976	0.5468	−0.2198	0.073*
C23	0.4392 (4)	0.8648 (3)	0.0392 (3)	0.0554 (12)
H23A	0.3601	0.8657	0.0319	0.066*
H23B	0.4770	0.9368	0.0456	0.066*
C24	0.5098 (4)	0.9254 (3)	0.2503 (3)	0.0440 (11)
C25	0.6863 (4)	0.9209 (4)	0.4107 (3)	0.0477 (11)
C26	0.6913 (5)	0.8143 (4)	0.3957 (4)	0.0622 (14)
H26	0.6248	0.7604	0.3494	0.075*
C27	0.7952 (5)	0.7872 (4)	0.4494 (4)	0.0766 (16)
H27	0.7994	0.7148	0.4380	0.092*
C28	0.8914 (5)	0.8657 (5)	0.5190 (4)	0.0790 (16)
H28	0.9615	0.8469	0.5549	0.095*
C29	0.8858 (5)	0.9723 (5)	0.5365 (4)	0.0764 (16)
H29	0.9514	1.0255	0.5861	0.092*
C30	0.7829 (4)	1.0014 (4)	0.4807 (3)	0.0597 (13)
H30	0.7795	1.0738	0.4904	0.072*
C31	0.8729 (4)	0.0762 (3)	−0.1916 (3)	0.0419 (11)
H31	0.8913	0.0157	−0.2253	0.050*
C32	0.8076 (4)	0.1331 (3)	−0.2523 (3)	0.0444 (11)
H32	0.7831	0.1105	−0.3252	0.053*
C33	0.7773 (3)	0.2236 (3)	−0.2073 (3)	0.0319 (9)
C34	0.8193 (3)	0.2523 (3)	−0.0987 (3)	0.0383 (10)
H34	0.8031	0.3131	−0.0633	0.046*
C35	0.8848 (3)	0.1917 (3)	−0.0425 (3)	0.0408 (10)
H35	0.9122	0.2138	0.0308	0.049*
C36	0.7050 (3)	0.2856 (3)	−0.2727 (3)	0.0281 (9)
C37	0.6358 (3)	0.2410 (3)	−0.3803 (3)	0.0386 (10)
H37	0.6298	0.1686	−0.4124	0.046*
C38	0.5763 (3)	0.3015 (3)	−0.4399 (3)	0.0374 (10)
H38	0.5317	0.2686	−0.5121	0.045*
C39	0.6405 (3)	0.4470 (3)	−0.2962 (3)	0.0388 (10)
H39	0.6419	0.5185	−0.2654	0.047*
C40	0.7024 (3)	0.3917 (3)	−0.2318 (3)	0.0370 (10)
H40	0.7433	0.4256	−0.1594	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0342 (4)	0.0312 (4)	0.0227 (4)	0.0143 (3)	0.0081 (3)	0.0103 (3)
Ni2	0.0456 (5)	0.0291 (4)	0.0197 (4)	0.0176 (3)	0.0102 (4)	0.0099 (3)
N1	0.056 (2)	0.048 (2)	0.035 (2)	0.0180 (19)	0.021 (2)	0.0125 (18)
N2	0.069 (3)	0.045 (2)	0.039 (2)	0.017 (2)	0.021 (2)	0.0055 (19)
N3	0.072 (3)	0.049 (2)	0.044 (2)	0.018 (2)	0.027 (2)	0.010 (2)
N4	0.059 (2)	0.052 (2)	0.040 (2)	0.021 (2)	0.025 (2)	0.0149 (19)
N5	0.053 (2)	0.047 (2)	0.030 (2)	0.0104 (19)	0.020 (2)	0.0002 (18)
N6	0.067 (3)	0.059 (3)	0.043 (2)	0.017 (2)	0.027 (2)	−0.004 (2)
N7	0.060 (3)	0.060 (3)	0.049 (3)	0.017 (2)	0.027 (2)	−0.009 (2)
N8	0.052 (3)	0.062 (3)	0.044 (2)	0.016 (2)	0.022 (2)	−0.001 (2)
N9	0.038 (2)	0.0304 (18)	0.0233 (18)	0.0144 (15)	0.0073 (16)	0.0116 (15)
N10	0.040 (2)	0.0307 (18)	0.0215 (17)	0.0122 (15)	0.0092 (16)	0.0092 (15)
O1	0.0358 (16)	0.0436 (16)	0.0281 (15)	0.0176 (13)	0.0135 (13)	0.0119 (13)
O2	0.047 (2)	0.066 (2)	0.052 (2)	−0.0025 (16)	0.0225 (17)	−0.0127 (17)
O3	0.0519 (18)	0.0350 (15)	0.0241 (14)	0.0190 (13)	0.0139 (14)	0.0090 (12)
O4	0.090 (2)	0.0442 (18)	0.0424 (18)	−0.0026 (17)	0.0362 (19)	−0.0007 (15)
O5	0.0406 (17)	0.0454 (16)	0.0303 (15)	0.0089 (13)	0.0104 (14)	0.0055 (13)
O6	0.0524 (18)	0.0360 (15)	0.0273 (15)	0.0140 (13)	0.0100 (14)	0.0117 (13)
O7	0.072 (2)	0.060 (2)	0.0475 (19)	0.0275 (17)	0.0036 (18)	−0.0080 (16)
S1	0.0761 (9)	0.0716 (9)	0.0367 (7)	0.0399 (7)	0.0209 (7)	0.0081 (6)
S2	0.0704 (9)	0.0605 (8)	0.0324 (6)	0.0284 (6)	0.0202 (6)	0.0014 (6)
C1	0.050 (3)	0.036 (2)	0.028 (2)	0.016 (2)	0.017 (2)	0.012 (2)
C2	0.034 (2)	0.042 (2)	0.027 (2)	0.0135 (19)	0.013 (2)	0.0122 (19)
C3	0.041 (3)	0.050 (3)	0.037 (2)	0.007 (2)	0.021 (2)	0.011 (2)
C4	0.047 (3)	0.045 (3)	0.041 (3)	0.009 (2)	0.020 (2)	0.005 (2)
C5	0.047 (3)	0.052 (3)	0.032 (2)	0.018 (2)	0.019 (2)	0.015 (2)
C6	0.040 (3)	0.062 (3)	0.040 (3)	0.012 (2)	0.024 (2)	0.016 (2)
C7	0.040 (3)	0.048 (3)	0.038 (2)	0.005 (2)	0.017 (2)	0.007 (2)
C8	0.056 (3)	0.064 (3)	0.035 (2)	0.025 (2)	0.022 (2)	0.011 (2)
C9	0.045 (3)	0.052 (3)	0.034 (2)	0.014 (2)	0.022 (2)	0.015 (2)
C10	0.054 (3)	0.060 (3)	0.042 (3)	0.019 (2)	0.023 (3)	0.023 (2)
C11	0.075 (4)	0.108 (4)	0.061 (4)	0.041 (3)	0.032 (3)	0.035 (3)
C12	0.092 (5)	0.143 (6)	0.092 (5)	0.071 (4)	0.040 (4)	0.042 (5)
C13	0.103 (5)	0.133 (6)	0.083 (5)	0.071 (4)	0.036 (4)	0.063 (4)
C14	0.094 (5)	0.094 (4)	0.070 (4)	0.034 (4)	0.029 (4)	0.047 (4)
C15	0.068 (4)	0.065 (3)	0.059 (3)	0.023 (3)	0.023 (3)	0.024 (3)
C16	0.053 (3)	0.038 (3)	0.028 (2)	0.018 (2)	0.018 (2)	0.010 (2)
C17	0.048 (3)	0.039 (2)	0.025 (2)	0.012 (2)	0.016 (2)	0.0061 (19)
C18	0.045 (3)	0.043 (3)	0.035 (2)	0.013 (2)	0.020 (2)	0.011 (2)
C19	0.044 (3)	0.045 (3)	0.036 (2)	0.010 (2)	0.012 (2)	−0.002 (2)
C20	0.057 (3)	0.049 (3)	0.027 (2)	0.018 (2)	0.015 (2)	0.002 (2)
C21	0.077 (4)	0.067 (3)	0.043 (3)	0.001 (3)	0.039 (3)	0.003 (3)
C22	0.078 (4)	0.053 (3)	0.043 (3)	−0.007 (3)	0.031 (3)	0.001 (2)
C23	0.069 (3)	0.056 (3)	0.039 (3)	0.023 (2)	0.022 (3)	0.008 (2)
C24	0.052 (3)	0.044 (3)	0.033 (3)	0.007 (2)	0.021 (2)	0.001 (2)
C25	0.056 (3)	0.052 (3)	0.035 (3)	0.010 (2)	0.021 (2)	0.010 (2)
C26	0.070 (4)	0.060 (3)	0.054 (3)	0.010 (3)	0.024 (3)	0.016 (3)
C27	0.092 (5)	0.072 (4)	0.071 (4)	0.027 (4)	0.034 (4)	0.028 (3)
C28	0.081 (4)	0.082 (4)	0.066 (4)	0.030 (4)	0.015 (3)	0.031 (3)
C29	0.075 (4)	0.089 (4)	0.051 (3)	0.014 (3)	0.017 (3)	0.014 (3)
C30	0.067 (4)	0.062 (3)	0.045 (3)	0.015 (3)	0.020 (3)	0.012 (3)
C31	0.055 (3)	0.043 (3)	0.031 (2)	0.028 (2)	0.015 (2)	0.013 (2)
C32	0.063 (3)	0.047 (3)	0.023 (2)	0.029 (2)	0.013 (2)	0.012 (2)
C33	0.039 (2)	0.029 (2)	0.027 (2)	0.0090 (18)	0.012 (2)	0.0098 (18)
C34	0.055 (3)	0.031 (2)	0.028 (2)	0.019 (2)	0.014 (2)	0.0095 (19)
C35	0.056 (3)	0.036 (2)	0.024 (2)	0.018 (2)	0.008 (2)	0.0118 (19)
C36	0.036 (2)	0.024 (2)	0.026 (2)	0.0109 (18)	0.0121 (19)	0.0099 (18)
C37	0.053 (3)	0.028 (2)	0.023 (2)	0.012 (2)	0.006 (2)	0.0031 (18)
C38	0.049 (3)	0.032 (2)	0.021 (2)	0.013 (2)	0.004 (2)	0.0061 (19)
C39	0.055 (3)	0.029 (2)	0.027 (2)	0.021 (2)	0.010 (2)	0.0070 (19)
C40	0.053 (3)	0.036 (2)	0.018 (2)	0.014 (2)	0.010 (2)	0.0084 (19)

Geometric parameters (Å, º)

Ni1—O1^i	2.027 (2)	C8—H8B	0.9700
Ni1—O1	2.027 (2)	C10—C11	1.365 (6)
Ni1—O5	2.071 (2)	C10—C15	1.367 (6)
Ni1—O5^i	2.071 (2)	C11—C12	1.389 (7)
Ni1—N9	2.141 (3)	C11—H11	0.9300
Ni1—N9^i	2.141 (3)	C12—C13	1.352 (7)
Ni2—O3^ii	2.033 (2)	C12—H12	0.9300
Ni2—O3	2.033 (2)	C13—C14	1.361 (7)
Ni2—O6	2.125 (2)	C13—H13	0.9300
Ni2—O6^ii	2.125 (2)	C14—C15	1.367 (7)
Ni2—N10^ii	2.122 (3)	C14—H14	0.9300
Ni2—N10	2.122 (3)	C15—H15	0.9300
N1—C9	1.348 (5)	C16—C17	1.496 (5)
N1—N2	1.363 (4)	C17—C18	1.379 (5)
N1—C10	1.416 (5)	C17—C22	1.384 (5)
N2—N3	1.284 (5)	C18—C19	1.388 (5)
N3—N4	1.365 (4)	C18—H18	0.9300
N4—C9	1.321 (5)	C19—C20	1.386 (5)
N5—C24	1.347 (5)	C19—H19	0.9300
N5—N6	1.355 (4)	C20—C21	1.375 (5)
N5—C25	1.431 (5)	C20—C23	1.501 (5)
N6—N7	1.284 (5)	C21—C22	1.379 (5)
N7—N8	1.361 (4)	C21—H21	0.9300
N8—C24	1.316 (5)	C22—H22	0.9300
N9—C31	1.334 (4)	C23—H23A	0.9700
N9—C35	1.340 (4)	C23—H23B	0.9700
N10—C39	1.330 (4)	C25—C26	1.367 (6)
N10—C38	1.339 (4)	C25—C30	1.373 (6)
O1—C1	1.257 (4)	C26—C27	1.376 (6)
O2—C1	1.254 (4)	C26—H26	0.9300
O3—C16	1.260 (4)	C27—C28	1.356 (6)
O4—C16	1.250 (4)	C27—H27	0.9300
O5—H5A	0.8505	C28—C29	1.368 (6)
O5—H5B	0.8497	C28—H28	0.9300
O6—H6A	0.8520	C29—C30	1.387 (6)
O6—H6B	0.8499	C29—H29	0.9300
O7—H7A	0.8460	C30—H30	0.9300
O7—H7B	0.8580	C31—C32	1.364 (5)
S1—C9	1.730 (4)	C31—H31	0.9300
S1—C8	1.812 (4)	C32—C33	1.379 (5)
S2—C24	1.732 (4)	C32—H32	0.9300
S2—C23	1.807 (4)	C33—C34	1.379 (5)
C1—C2	1.506 (5)	C33—C36	1.487 (5)
C2—C3	1.380 (5)	C34—C35	1.370 (5)
C2—C7	1.382 (5)	C34—H34	0.9300
C3—C4	1.378 (5)	C35—H35	0.9300
C3—H3	0.9300	C36—C40	1.383 (4)
C4—C5	1.386 (5)	C36—C37	1.384 (5)
C4—H4	0.9300	C37—C38	1.364 (5)
C5—C6	1.373 (5)	C37—H37	0.9300
C5—C8	1.504 (5)	C38—H38	0.9300
C6—C7	1.378 (5)	C39—C40	1.362 (5)
C6—H6	0.9300	C39—H39	0.9300
C7—H7	0.9300	C40—H40	0.9300
C8—H8A	0.9700
O1^i—Ni1—O1	180.00 (11)	C10—C11—H11	121.0
O1^i—Ni1—O5	87.94 (10)	C12—C11—H11	121.0
O1—Ni1—O5	92.06 (10)	C13—C12—C11	121.5 (6)
O1^i—Ni1—O5^i	92.06 (10)	C13—C12—H12	119.3
O1—Ni1—O5^i	87.94 (10)	C11—C12—H12	119.3
O5—Ni1—O5^i	180.00 (17)	C12—C13—C14	119.4 (6)
O1^i—Ni1—N9	90.50 (10)	C12—C13—H13	120.3
O1—Ni1—N9	89.50 (10)	C14—C13—H13	120.3
O5—Ni1—N9	90.43 (10)	C13—C14—C15	120.4 (5)
O5^i—Ni1—N9	89.57 (10)	C13—C14—H14	119.8
O1^i—Ni1—N9^i	89.50 (10)	C15—C14—H14	119.8
O1—Ni1—N9^i	90.50 (10)	C10—C15—C14	119.9 (5)
O5—Ni1—N9^i	89.57 (10)	C10—C15—H15	120.0
O5^i—Ni1—N9^i	90.43 (10)	C14—C15—H15	120.0
N9—Ni1—N9^i	180.0 (2)	O4—C16—O3	124.6 (4)
O3^ii—Ni2—O3	180.000 (1)	O4—C16—C17	118.5 (4)
O3^ii—Ni2—N10^ii	88.90 (10)	O3—C16—C17	116.8 (4)
O3—Ni2—N10^ii	91.10 (10)	C18—C17—C22	118.5 (3)
O3^ii—Ni2—N10	91.10 (10)	C18—C17—C16	121.5 (4)
O3—Ni2—N10	88.90 (10)	C22—C17—C16	119.8 (4)
O3^ii—Ni2—O6	89.45 (10)	C17—C18—C19	120.7 (4)
O3—Ni2—O6	90.55 (9)	C17—C18—H18	119.6
N10^ii—Ni2—O6	89.89 (10)	C19—C18—H18	119.6
N10—Ni2—O6	90.11 (10)	C20—C19—C18	120.4 (4)
O3^ii—Ni2—O6^ii	90.55 (9)	C20—C19—H19	119.8
O3—Ni2—O6^ii	89.45 (10)	C18—C19—H19	119.8
N10—Ni2—N10^ii	180.0 (1)	C21—C20—C19	118.5 (4)
N10^ii—Ni2—O6^ii	90.11 (10)	C21—C20—C23	121.0 (4)
N10—Ni2—O6^ii	89.89 (10)	C19—C20—C23	120.4 (4)
O6—Ni2—O6^ii	180.000 (1)	C20—C21—C22	121.1 (4)
C9—N1—N2	107.3 (4)	C20—C21—H21	119.4
C9—N1—C10	131.9 (4)	C22—C21—H21	119.4
N2—N1—C10	120.7 (3)	C21—C22—C17	120.6 (4)
N3—N2—N1	107.0 (3)	C21—C22—H22	119.7
N2—N3—N4	111.1 (3)	C17—C22—H22	119.7
C9—N4—N3	105.5 (3)	C20—C23—S2	107.6 (3)
C24—N5—N6	107.9 (4)	C20—C23—H23A	110.2
C24—N5—C25	131.0 (4)	S2—C23—H23A	110.2
N6—N5—C25	120.5 (3)	C20—C23—H23B	110.2
N7—N6—N5	106.2 (3)	S2—C23—H23B	110.2
N6—N7—N8	111.7 (3)	H23A—C23—H23B	108.5
C24—N8—N7	105.4 (4)	N8—C24—N5	108.8 (4)
C31—N9—C35	115.5 (3)	N8—C24—S2	126.9 (3)
C31—N9—Ni1	120.8 (2)	N5—C24—S2	124.3 (4)
C35—N9—Ni1	123.6 (2)	C26—C25—C30	120.9 (5)
C39—N10—C38	115.3 (3)	C26—C25—N5	121.8 (4)
C39—N10—Ni2	122.9 (2)	C30—C25—N5	117.3 (4)
C38—N10—Ni2	121.6 (2)	C25—C26—C27	119.7 (5)
C1—O1—Ni1	130.8 (2)	C25—C26—H26	120.1
C16—O3—Ni2	126.3 (2)	C27—C26—H26	120.1
Ni1—O5—H5A	104.0	C28—C27—C26	120.2 (5)
Ni1—O5—H5B	120.5	C28—C27—H27	119.9
H5A—O5—H5B	111.0	C26—C27—H27	119.9
Ni2—O6—H6A	92.1	C27—C28—C29	120.3 (6)
Ni2—O6—H6B	101.1	C27—C28—H28	119.9
H6A—O6—H6B	111.4	C29—C28—H28	119.9
H7A—O7—H7B	112.1	C28—C29—C30	120.4 (5)
C9—S1—C8	101.7 (2)	C28—C29—H29	119.8
C24—S2—C23	99.1 (2)	C30—C29—H29	119.8
O2—C1—O1	125.4 (3)	C25—C30—C29	118.5 (5)
O2—C1—C2	118.0 (4)	C25—C30—H30	120.7
O1—C1—C2	116.6 (4)	C29—C30—H30	120.7
C3—C2—C7	118.3 (3)	N9—C31—C32	123.6 (4)
C3—C2—C1	120.0 (3)	N9—C31—H31	118.2
C7—C2—C1	121.6 (4)	C32—C31—H31	118.2
C4—C3—C2	120.9 (4)	C31—C32—C33	121.2 (4)
C4—C3—H3	119.6	C31—C32—H32	119.4
C2—C3—H3	119.6	C33—C32—H32	119.4
C3—C4—C5	120.7 (4)	C34—C33—C32	115.4 (4)
C3—C4—H4	119.7	C34—C33—C36	122.9 (3)
C5—C4—H4	119.7	C32—C33—C36	121.7 (3)
C6—C5—C4	118.3 (4)	C35—C34—C33	120.4 (3)
C6—C5—C8	121.8 (4)	C35—C34—H34	119.8
C4—C5—C8	119.8 (4)	C33—C34—H34	119.8
C5—C6—C7	121.1 (4)	N9—C35—C34	123.9 (3)
C5—C6—H6	119.4	N9—C35—H35	118.0
C7—C6—H6	119.4	C34—C35—H35	118.0
C6—C7—C2	120.7 (4)	C40—C36—C37	114.9 (3)
C6—C7—H7	119.7	C40—C36—C33	123.1 (3)
C2—C7—H7	119.7	C37—C36—C33	122.0 (3)
C5—C8—S1	105.5 (3)	C38—C37—C36	121.0 (3)
C5—C8—H8A	110.6	C38—C37—H37	119.5
S1—C8—H8A	110.6	C36—C37—H37	119.5
C5—C8—H8B	110.6	N10—C38—C37	123.7 (3)
S1—C8—H8B	110.6	N10—C38—H38	118.2
H8A—C8—H8B	108.8	C37—C38—H38	118.2
N4—C9—N1	109.1 (4)	N10—C39—C40	124.3 (3)
N4—C9—S1	128.2 (3)	N10—C39—H39	117.9
N1—C9—S1	122.8 (3)	C40—C39—H39	117.9
C11—C10—C15	120.7 (5)	C39—C40—C36	120.8 (3)
C11—C10—N1	119.6 (4)	C39—C40—H40	119.6
C15—C10—N1	119.7 (4)	C36—C40—H40	119.6
C10—C11—C12	118.0 (5)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.85	1.89	2.687 (3)	156
O6—H6A···O4	0.85	1.78	2.598 (3)	160
O5—H5B···O7^iii	0.85	1.94	2.791 (4)	174
C3—H3···N3^iv	0.93	2.65	3.351 (5)	132
C37—H37···N6^iii	0.93	2.53	3.296 (5)	140
C12—H12···S2^iv	0.93	2.94	3.774 (6)	150
O7—H7A···O6^v	0.85	2.08	2.906 (3)	167
O6—H6B···N4^v	0.85	2.17	2.985 (4)	161
O7—H7B···N7^vi	0.86	2.13	2.966 (5)	166
C19—H19···O2^vii	0.93	2.45	3.303 (5)	152
C27—H27···O4^v	0.93	2.57	3.303 (6)	136

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