A novel octa­nuclear nickel(II)-molybdenum(VI) heterometallic cluster based on the salicyl­hydroxamate ligand

Salicyl­hydroxamic acid (H₃shi) is known for its strong coordination ability and multiple coordination modes, and can easily coordinate to metal cations to form compounds with five- or six-membered rings, as well as mono-, di- and multinuclear compounds with inter­esting structures having potential applications in organic chemistry, coordination chemistry, and the materials and biological sciences. A novel octa­nuclear nickel(II)-molybdenum(VI) heterometallic cluster based on the salicyl­hydroxamate ligand, namely di-[mu]₃-acetato-di-[mu]₂-acetato-di-[mu]₃-hydroxido-di-[mu]₃-oxido-tetra­oxido­octa­kis­(pyridine-[kappa]N)bis­([mu]₅-salicyl­hy­droxamato)hexa­nickel(II)dimolybdenum(VI) monohydrate, [Mo₂Ni₆(C₇H₄NO₃)₂(C₂H₃O₂)₄O₅(OH)₂(C₅H₅N)₈]·H₂O, (I), was synthesized by the reaction of sodium molybdate, nickel acetate and salicyl­hydroxamic acid in a di­methyl­formamide/pyridine/methanol solution at room temperature. The salicyl­hydroxamate(3-) (shi^3-), acetate and oxide ligands adopt complicated coordination modes and link six Ni^II and two Mo^VI cations into the octa­nuclear heterometallic cluster. All of the metal cations exhibit octa­hedral coordination geometries and are connected to each other through the sharing of corners, edges or planes. The heterometallic clusters are further connected to form two-dimensional supra­molecular layers through weak C-H...O hydrogen bonds. Studies of the magnetic properties of the title compound reveal anti­ferromagnetic inter­actions between the Ni^II cations.

S1. Introduction

Salicyl­hydroxamic acid (H₃shi) is one of the old and evergreen ligands because of its strong coordination ability and multiple coordination modes (Pecoraro, 1989; Lah et al., 1989). The shi^3- ligand can easily coordinate to metal cations to form compounds with five- or six-membered rings, as well as mono-, di- and multinuclear compounds with inter­esting structures. These complexes have potential applications in organic chemistry, coordination chemistry, and the materials and biological sciences, due to their unique chemical properties, biological activities and magnetic properties (Alexiou et al., 2003; Lah & Pecoraro, 1991; Zaleski, Cutland-Van Noord et al., 2007). Therefore, studies of coordination complexes based on shi^3- ligand are important. Given these considerations, many compounds generated by salicyl­hydroxamate (shi^3-) ligands have been synthesized and characterized. Among which, most of them contain 3d metal cations, such as Mn^II, Fe^II, Cu^II, Ni^II etc. (Lah et al., 1989; Kessissoglou et al.,1994; Psomas et al., 2001; Gibney et al., 1994), with fascinating structures and unusual magnetic properties, and exhibit high-spin (S) ground values and single-molecule magnetic (SMM) behaviour. Some involve the main group atoms Sn or Ga (Lah et al., 1993; Zhao et al., 2010), while other heterometallic clusters utilize the hydroximic acid ligand, 3d and 4f metal cations (Boron et al., 2010; Cutland et al., 2001; Zaleski, Kampf et al., 2007; Govor et al., 2008), or alkaline or alkaline earth metals (Gibney et al., 1996; Kessissoglou et al., 2002). No 3d–4d heterometallic clusters involving shi^3- ligands have been reported. Among all of the metal clusters involving the shi^3- ligand, most of them exhibit the metallacrown structure, such as 9-MC-4, 12-MC4, 15-MC-5 etc. Only a few examples do not adopt the metallacrown structure (Alexiou et al., 2002; Psomas et al., 1998). In this work, a novel 3d–4d o­cta­nuclear heterometallic cluster [Ni₆Mo₂(µ₅-shi)₂(µ₃-OAc)₂(µ₂-OAc)₂(µ₃-OH)₂(µ₃-O)₂O₄(py)₈]·2H₂O, (I), was synthesized, in which, six Ni^II and two Mo^VI cations are linked together by shi^3-, acetate and oxide ligands. The magnetic properties of (I) were also investigated.

S2. Experimental

S2.1. Synthesis and crystallization

All analytical grade chemicals were obtained commercially and used without further purification. Complex (I) was prepared by the solvent evaporation method. A solution (10 ml) of Ni(OAc)₂·2H₂O (0.021 g, 0.1 mmol) in methanol and a solution (5 ml) of Na₂MoO₄·2H₂O (0.145 g, 0.6 mmol) in di­methyl­formamide were added to a stirred colourless solution of salicyl­hydroxamic acid (H₃shi) (0.015 g, 0.1 mmol) in pyridine (10 ml). The resulting green suspension was maintained under magnetic stirring at room temperature for 4 h. The solution was filtered and the filtrate was left undisturbed, producing black crystals of (I) (yield 15.9 mg, 49.8%, based on Ni). Analysis calculated for C₆₂H₆₆Mo₂N₁₀Ni₆O₂₄: H 3.51, C 39.59, N 7.45%; found: H 3.42, C 38.37, N 7.98%. IR (KBr, cm^-1): 3384 (br, s), 1611 (s), 1584 (s), 1445 (m), 1072 (m), 929 (m), 882 (w), 756 (s), 698 (s), 629 (s), 545 (m).

S2.2. Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 1. All H atoms were positioned wth geometrical restraints and treated as riding on their parent atoms, with alkyl C—H = 0.96 Å , aryl C—H = 0.93 Å and O—H = 0.85 Å, and with U_iso(H) = 1.5U_eq(C, alkyl) and 1.2U_eq(O, C aryl). The occupancy ratio of the lattice water molecule O12 was defined as 0.5 for the suitable thermal vibration parameters [not clear].

S3. Results and discussion

X-ray single-crystal diffraction studies reveal that compound (I) crystallizes in the triclinic system in the space group P1 (No. 2). The asymmetric unit contains three nickel and one molybdenum cations, one shi^3- ligand, two acetate anions, four oxide anions, four coordinated pyridine molecules and one lattice water molecule. As shown in Fig. 1a, atom Ni1 sits at the centre of a distorted o­cta­hedron and is coordinated by two oxime O atoms (O2 and O2ⁱ), two µ₃-oxide atoms (O8 and O9ⁱ), one carboxyl­ate O atom from an acetate anion (O5) and one pyridine N atom (N2). Atom Ni2 also sits in the centre of a distorted o­cta­hedron and is coordinated by a phenolate O atom (O3) of a shi^3- ligand, one µ₃-oxide atom (O8), two carboxyl­ate O atoms (O4 and O7) from two different acetate anions, and two pyridine N atoms (N3 and N4). Atom Ni3 is chelated by the shi^3- ligand through its oxime N1 and phenolate O3 atoms, and forms a six-membered ring, and is coordinated by two µ₃-oxide atoms (O8 and O9), one carboxyl­ate O atom (O6) from an acetate anion, and a pyridine N atom (N5). Atom Mo1 is chelated by the shi^3- ligand through its alkoxide O1 and oxime O2 atoms, and forms a five-membered ring, and is coordinated by one µ₃-oxide atom (O9), one carboxyl­ate O atom (O5), and two terminal oxide atoms (O10 and O11). Thus, the shi^3- ligand chelates Ni3 and Mo1 cations, and bridges three Ni cations (Ni1, Ni1ⁱ and Ni2), thus adopting a µ₅-η⁷-coordination mode. The two acetate anions display different coordination modes, i.e. one bridges two Ni^II cations (Ni2 and Ni3), adopting a syn–syn-µ₂-η¹:η¹ coordination mode and the other bridges two Ni^II cations (Ni1 and Ni2) and an Mo1 cation, adopting a µ₃-η¹:η² coordination mode. The µ₃-oxide atoms also exhibit different linkages, i.e. µ₃-O8 bridges three Ni^II cations (Ni1, Ni2 and Ni3), while µ₃-O8 bridges two Nii^II cations (Ni3 and Ni1ⁱ) and an Mo1ⁱ cation. Thus, three Ni^II and one Mo cation are linked together by the shi^3-, acetate, and µ₃-O8 ligands to form a Ni₃Mo cluster. The Ni₃Mo cluster is connected by symmetry (-x+2, -y+1,-z) to a second cluster, through the µ₃-O9/O9ⁱ pair and the oxime O2/O2ⁱ pair of atoms to generate an Ni₆Mo₂ o­cta­nuclear heterometallic cluster. In the cluster, atoms Ni1, Ni2 and Ni3ⁱ are very nearly linear, with an Ni2—Ni1—Ni3ⁱ angle of 174.92 (3)°, and bond lengths Ni1—Ni2 = 3.6586 (11)Å and Ni1—Ni3ⁱ = 3.4661 (11)Å. As shown in Fig. 1(b), the linear arrangement of three Ni—O/N o­cta­hedra are corner-shared, which is connected with the other Ni₃ cluster (Ni1ⁱ—Ni2²—Ni3) through edge-sharing. The Ni2—Ni3 and Ni1—Ni1ⁱ bond lengths between the two Ni₃ clusters are similar, with values of 3.0058 (14) and 3.1879 (14) Å, respectively. These two linear Ni₃ clusters are nearly parallel, and the six Ni^II cations are nearly coplanar, forming an Ni₆ sheet, with an average deviation of 0.0080 Å from the least-squares plane. The two MoO₆ o­cta­hedra sit on either side of the Ni₆ sheet, sharing a plane with the Ni1O₅N o­cta­hedron.

Bond-valence sum (BVS) analysis on compound I using the parameters of Brese & O'Keeffe (1991), revealed minor deviations from the expected values of 2 valence units (v.u.) for all Ni atoms, 6 v.u. for the Mo atom, 2 v.u. for the three oxide atoms (O9, O10 and O11) and 1 v.u. for the O8 atom (the µ₃-O8 is an hy­droxy group). The formula of compound (I) can be defined as [Ni₆Mo₂(µ₅-shi)₂(µ₃-OAc)₂(µ₂-OAc)₂(µ₃-OH)₂(µ₃-O)₂O₄(py)₈]·2H₂O.

As shown in Fig. 2(a), there is intra­molecular O—H···O hydrogen bonding. The lattice water molecule (O12) acts as a hydrogen-bond donor to the terminal O atom (O10ⁱ) and a carboxyl­ate O atom (O6). The µ₃-OH group also hydrogen bonds with the other terminal O atoms (O11ⁱ), and acts as a hydrogen-bond donor. These intra­molecular hydrogen bonds presumably stabilize the heterometallic cluster, while inter­molecular C—H···O hydrogen bonds link the heterometallic clusters and form two-dimensional supra­molecular layer. As shown in Fig. 2(b), the two terminal O atoms (O10 and O11) and the lattice water molecule (O12) bond with the H atoms of pyridine ligands from two adjacent clusters. Thus, each molecule hydrogen bonds with four adjacent molecules. The two-dimensional supra­molecular layer is formed through a complicated C—H···O hydrogen-bond structure. The parameters of the hydrogen bonds are listed in Table 3.

One the basis of the structure of (I), the two Mo^VI cations do not contribute to the magnetism with S = 0. The magnetic properties of (I) is di­cta­ted by the Ni₆ cluster. Direct-current magnetic susceptibility measurements were performed on polycrystalline samples of (I) in the temperature range 2–300 K in an applied field of 1000 Oe. As shown in Fig. 3, the χ_MT value decreases with decreasing temperature from 6.27 cm³ mol^-1 K at 300 K to 0.78 cm³ K mol^-1 K at 2 K, indicating the presence of an anti­ferromagnetic exchange inter­action. The χ_MT value at 300 K is consistent with the spin-only value of 6.00 cm³ mol^-1 K of six Ni^II cations with S = 1 and g = 2. Compound (I) obeys the Curie–Weiss law [1/χ_M = C/(T-θ)] in the high-temperature region (100–300 K) with the Curie constant C = 7.69 cm³ mol^-1 K and a Weiss constant θ = -61.84 K. The negative θ value also suggests the anti­ferromagnetic coupling between the Ni^II cations incompound (I).

In summary, a novel o­cta­nuclear heterometallic cluster has been synthesized and characterized. In the compound, six Ni^II and two Mo^VI cations are linked together by µ₅-shi^3-, µ₃/µ₂-a­ctate and µ₃-O/OH ligands to form the first 3d–4d heterometallic cluster based on the shi^3- ligand. All of the metal cations exhibit o­cta­hedral coordination geometries and are connected to each other through corner-, edge- and plane-sharing. The heterometallic clusters are further connected to form two-dimensional supra­molecular layers through weak C—H···O hydrogen bonds. Studies of the magnetic properties of the title compound reveal anti­ferromagnetic inter­actions between the Ni^II cations.

Structure description

Salicyl­hydroxamic acid (H₃shi) is one of the old and evergreen ligands because of its strong coordination ability and multiple coordination modes (Pecoraro, 1989; Lah et al., 1989). The shi^3- ligand can easily coordinate to metal cations to form compounds with five- or six-membered rings, as well as mono-, di- and multinuclear compounds with inter­esting structures. These complexes have potential applications in organic chemistry, coordination chemistry, and the materials and biological sciences, due to their unique chemical properties, biological activities and magnetic properties (Alexiou et al., 2003; Lah & Pecoraro, 1991; Zaleski, Cutland-Van Noord et al., 2007). Therefore, studies of coordination complexes based on shi^3- ligand are important. Given these considerations, many compounds generated by salicyl­hydroxamate (shi^3-) ligands have been synthesized and characterized. Among which, most of them contain 3d metal cations, such as Mn^II, Fe^II, Cu^II, Ni^II etc. (Lah et al., 1989; Kessissoglou et al.,1994; Psomas et al., 2001; Gibney et al., 1994), with fascinating structures and unusual magnetic properties, and exhibit high-spin (S) ground values and single-molecule magnetic (SMM) behaviour. Some involve the main group atoms Sn or Ga (Lah et al., 1993; Zhao et al., 2010), while other heterometallic clusters utilize the hydroximic acid ligand, 3d and 4f metal cations (Boron et al., 2010; Cutland et al., 2001; Zaleski, Kampf et al., 2007; Govor et al., 2008), or alkaline or alkaline earth metals (Gibney et al., 1996; Kessissoglou et al., 2002). No 3d–4d heterometallic clusters involving shi^3- ligands have been reported. Among all of the metal clusters involving the shi^3- ligand, most of them exhibit the metallacrown structure, such as 9-MC-4, 12-MC4, 15-MC-5 etc. Only a few examples do not adopt the metallacrown structure (Alexiou et al., 2002; Psomas et al., 1998). In this work, a novel 3d–4d o­cta­nuclear heterometallic cluster [Ni₆Mo₂(µ₅-shi)₂(µ₃-OAc)₂(µ₂-OAc)₂(µ₃-OH)₂(µ₃-O)₂O₄(py)₈]·2H₂O, (I), was synthesized, in which, six Ni^II and two Mo^VI cations are linked together by shi^3-, acetate and oxide ligands. The magnetic properties of (I) were also investigated.

X-ray single-crystal diffraction studies reveal that compound (I) crystallizes in the triclinic system in the space group P1 (No. 2). The asymmetric unit contains three nickel and one molybdenum cations, one shi^3- ligand, two acetate anions, four oxide anions, four coordinated pyridine molecules and one lattice water molecule. As shown in Fig. 1a, atom Ni1 sits at the centre of a distorted o­cta­hedron and is coordinated by two oxime O atoms (O2 and O2ⁱ), two µ₃-oxide atoms (O8 and O9ⁱ), one carboxyl­ate O atom from an acetate anion (O5) and one pyridine N atom (N2). Atom Ni2 also sits in the centre of a distorted o­cta­hedron and is coordinated by a phenolate O atom (O3) of a shi^3- ligand, one µ₃-oxide atom (O8), two carboxyl­ate O atoms (O4 and O7) from two different acetate anions, and two pyridine N atoms (N3 and N4). Atom Ni3 is chelated by the shi^3- ligand through its oxime N1 and phenolate O3 atoms, and forms a six-membered ring, and is coordinated by two µ₃-oxide atoms (O8 and O9), one carboxyl­ate O atom (O6) from an acetate anion, and a pyridine N atom (N5). Atom Mo1 is chelated by the shi^3- ligand through its alkoxide O1 and oxime O2 atoms, and forms a five-membered ring, and is coordinated by one µ₃-oxide atom (O9), one carboxyl­ate O atom (O5), and two terminal oxide atoms (O10 and O11). Thus, the shi^3- ligand chelates Ni3 and Mo1 cations, and bridges three Ni cations (Ni1, Ni1ⁱ and Ni2), thus adopting a µ₅-η⁷-coordination mode. The two acetate anions display different coordination modes, i.e. one bridges two Ni^II cations (Ni2 and Ni3), adopting a syn–syn-µ₂-η¹:η¹ coordination mode and the other bridges two Ni^II cations (Ni1 and Ni2) and an Mo1 cation, adopting a µ₃-η¹:η² coordination mode. The µ₃-oxide atoms also exhibit different linkages, i.e. µ₃-O8 bridges three Ni^II cations (Ni1, Ni2 and Ni3), while µ₃-O8 bridges two Nii^II cations (Ni3 and Ni1ⁱ) and an Mo1ⁱ cation. Thus, three Ni^II and one Mo cation are linked together by the shi^3-, acetate, and µ₃-O8 ligands to form a Ni₃Mo cluster. The Ni₃Mo cluster is connected by symmetry (-x+2, -y+1,-z) to a second cluster, through the µ₃-O9/O9ⁱ pair and the oxime O2/O2ⁱ pair of atoms to generate an Ni₆Mo₂ o­cta­nuclear heterometallic cluster. In the cluster, atoms Ni1, Ni2 and Ni3ⁱ are very nearly linear, with an Ni2—Ni1—Ni3ⁱ angle of 174.92 (3)°, and bond lengths Ni1—Ni2 = 3.6586 (11)Å and Ni1—Ni3ⁱ = 3.4661 (11)Å. As shown in Fig. 1(b), the linear arrangement of three Ni—O/N o­cta­hedra are corner-shared, which is connected with the other Ni₃ cluster (Ni1ⁱ—Ni2²—Ni3) through edge-sharing. The Ni2—Ni3 and Ni1—Ni1ⁱ bond lengths between the two Ni₃ clusters are similar, with values of 3.0058 (14) and 3.1879 (14) Å, respectively. These two linear Ni₃ clusters are nearly parallel, and the six Ni^II cations are nearly coplanar, forming an Ni₆ sheet, with an average deviation of 0.0080 Å from the least-squares plane. The two MoO₆ o­cta­hedra sit on either side of the Ni₆ sheet, sharing a plane with the Ni1O₅N o­cta­hedron.

Bond-valence sum (BVS) analysis on compound I using the parameters of Brese & O'Keeffe (1991), revealed minor deviations from the expected values of 2 valence units (v.u.) for all Ni atoms, 6 v.u. for the Mo atom, 2 v.u. for the three oxide atoms (O9, O10 and O11) and 1 v.u. for the O8 atom (the µ₃-O8 is an hy­droxy group). The formula of compound (I) can be defined as [Ni₆Mo₂(µ₅-shi)₂(µ₃-OAc)₂(µ₂-OAc)₂(µ₃-OH)₂(µ₃-O)₂O₄(py)₈]·2H₂O.

As shown in Fig. 2(a), there is intra­molecular O—H···O hydrogen bonding. The lattice water molecule (O12) acts as a hydrogen-bond donor to the terminal O atom (O10ⁱ) and a carboxyl­ate O atom (O6). The µ₃-OH group also hydrogen bonds with the other terminal O atoms (O11ⁱ), and acts as a hydrogen-bond donor. These intra­molecular hydrogen bonds presumably stabilize the heterometallic cluster, while inter­molecular C—H···O hydrogen bonds link the heterometallic clusters and form two-dimensional supra­molecular layer. As shown in Fig. 2(b), the two terminal O atoms (O10 and O11) and the lattice water molecule (O12) bond with the H atoms of pyridine ligands from two adjacent clusters. Thus, each molecule hydrogen bonds with four adjacent molecules. The two-dimensional supra­molecular layer is formed through a complicated C—H···O hydrogen-bond structure. The parameters of the hydrogen bonds are listed in Table 3.

One the basis of the structure of (I), the two Mo^VI cations do not contribute to the magnetism with S = 0. The magnetic properties of (I) is di­cta­ted by the Ni₆ cluster. Direct-current magnetic susceptibility measurements were performed on polycrystalline samples of (I) in the temperature range 2–300 K in an applied field of 1000 Oe. As shown in Fig. 3, the χ_MT value decreases with decreasing temperature from 6.27 cm³ mol^-1 K at 300 K to 0.78 cm³ K mol^-1 K at 2 K, indicating the presence of an anti­ferromagnetic exchange inter­action. The χ_MT value at 300 K is consistent with the spin-only value of 6.00 cm³ mol^-1 K of six Ni^II cations with S = 1 and g = 2. Compound (I) obeys the Curie–Weiss law [1/χ_M = C/(T-θ)] in the high-temperature region (100–300 K) with the Curie constant C = 7.69 cm³ mol^-1 K and a Weiss constant θ = -61.84 K. The negative θ value also suggests the anti­ferromagnetic coupling between the Ni^II cations incompound (I).

In summary, a novel o­cta­nuclear heterometallic cluster has been synthesized and characterized. In the compound, six Ni^II and two Mo^VI cations are linked together by µ₅-shi^3-, µ₃/µ₂-a­ctate and µ₃-O/OH ligands to form the first 3d–4d heterometallic cluster based on the shi^3- ligand. All of the metal cations exhibit o­cta­hedral coordination geometries and are connected to each other through corner-, edge- and plane-sharing. The heterometallic clusters are further connected to form two-dimensional supra­molecular layers through weak C—H···O hydrogen bonds. Studies of the magnetic properties of the title compound reveal anti­ferromagnetic inter­actions between the Ni^II cations.

Synthesis and crystallization

All analytical grade chemicals were obtained commercially and used without further purification. Complex (I) was prepared by the solvent evaporation method. A solution (10 ml) of Ni(OAc)₂·2H₂O (0.021 g, 0.1 mmol) in methanol and a solution (5 ml) of Na₂MoO₄·2H₂O (0.145 g, 0.6 mmol) in di­methyl­formamide were added to a stirred colourless solution of salicyl­hydroxamic acid (H₃shi) (0.015 g, 0.1 mmol) in pyridine (10 ml). The resulting green suspension was maintained under magnetic stirring at room temperature for 4 h. The solution was filtered and the filtrate was left undisturbed, producing black crystals of (I) (yield 15.9 mg, 49.8%, based on Ni). Analysis calculated for C₆₂H₆₆Mo₂N₁₀Ni₆O₂₄: H 3.51, C 39.59, N 7.45%; found: H 3.42, C 38.37, N 7.98%. IR (KBr, cm^-1): 3384 (br, s), 1611 (s), 1584 (s), 1445 (m), 1072 (m), 929 (m), 882 (w), 756 (s), 698 (s), 629 (s), 545 (m).

Refinement details

Crystal data, data collection, and structure refinement details are summarized in Table 1. All H atoms were positioned wth geometrical restraints and treated as riding on their parent atoms, with alkyl C—H = 0.96 Å , aryl C—H = 0.93 Å and O—H = 0.85 Å, and with U_iso(H) = 1.5U_eq(C, alkyl) and 1.2U_eq(O, C aryl). The occupancy ratio of the lattice water molecule O12 was defined as 0.5 for the suitable thermal vibration parameters [not clear].

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: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. (a) The structure of compound (I) showing the atom-labelling scheme and 50% probability displacement ellipsoids for non-H atoms [symmetry code: (i) -x + 2, -y + 1, -z]. (b) A polyhedral presentation of the heterometallic Ni6Mo2 cluster (the closed blue polyhedra represent the Ni—N/O octahedra and the open purple polyhedra represent MoO6 octahedra).
	Fig. 2. (a) The intramolecular O—H···O hydrogen bonds and (b) the intermolecular C—H···O hydrogen bonds linking the clusters to form the two-dimensional supramolecular layer. [Symmetry codes: (ii) x-1, y, z; (iii) x, y+1, z; (iv) x, y-1, z.]
	Fig. 3. The temperature dependence of χMT and 1/χM (inset) for complex (I). Colour code: measured values in black and calculated curve in red.

Di-µ₃-acetato-di-µ₂-acetato-di-µ₃-hydroxido-di-µ₃-oxido-tetraoxidooctakis(pyridine-κN)bis(µ₅-salicylhydroxamato)hexanickel(II)dimolybdenum(VI) dihydrate

Crystal data

[Mo2Ni6(C7H4NO3)2(C2H3O2)4O6(OH)2(C5H5N)8]·H2O	Z = 1
Mr = 1861.38	F(000) = 942
Triclinic, P1	Dx = 1.749 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5079 (8) Å	Cell parameters from 6238 reflections
b = 12.7461 (9) Å	θ = 2.7–25.0°
c = 14.5850 (13) Å	µ = 1.99 mm^−1
α = 111.551 (7)°	T = 293 K
β = 95.979 (7)°	Block, black
γ = 98.854 (6)°	0.50 × 0.30 × 0.30 mm
V = 1767.6 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	6238 independent reflections
Radiation source: fine-focus sealed tube	4334 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
phi and ω scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −12→12
Tmin = 0.437, Tmax = 0.587	k = −15→13
11408 measured reflections	l = −17→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) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0298P)^2] where P = (Fo^2 + 2Fc^2)/3
6238 reflections	(Δ/σ)max = 0.005
472 parameters	Δρmax = 0.89 e Å^−3
0 restraints	Δρmin = −0.51 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	Occ. (<1)
Ni1	0.94587 (6)	0.44119 (5)	0.07153 (5)	0.02408 (18)
Ni2	0.92605 (7)	0.64918 (6)	0.31885 (5)	0.0319 (2)
Ni3	1.02780 (7)	0.73525 (6)	0.16868 (5)	0.02695 (19)
Mo1	1.21127 (5)	0.38549 (4)	0.05418 (4)	0.02680 (15)
O1	1.3068 (3)	0.5309 (3)	0.1757 (3)	0.0318 (9)
O2	1.1240 (3)	0.5341 (3)	0.0556 (3)	0.0236 (8)
O3	1.0886 (4)	0.7702 (3)	0.3156 (3)	0.0341 (10)
O4	1.0424 (4)	0.5366 (3)	0.3334 (3)	0.0367 (10)
O5	1.0618 (3)	0.4169 (3)	0.1809 (3)	0.0296 (9)
O6	0.8786 (4)	0.8259 (3)	0.2012 (3)	0.0381 (10)
O7	0.7991 (4)	0.7537 (3)	0.3071 (3)	0.0423 (11)
O8	0.9046 (3)	0.5865 (3)	0.1661 (3)	0.0264 (9)
H5A	0.8271	0.5882	0.1442	0.032*
O9	0.9536 (3)	0.6842 (3)	0.0160 (3)	0.0260 (9)
O10	1.2661 (4)	0.2909 (3)	0.0996 (3)	0.0367 (10)
O11	1.3063 (3)	0.3906 (3)	−0.0337 (3)	0.0340 (10)
O12	0.7689 (9)	0.9221 (7)	0.0782 (8)	0.075 (4)	0.489 (10)
H12C	0.8036	0.9014	0.1223	0.090*	0.489 (10)
H12D	0.7544	0.8653	0.0220	0.090*	0.489 (10)
N1	1.1651 (4)	0.6359 (3)	0.1432 (3)	0.0252 (11)
N2	0.7823 (4)	0.3257 (4)	0.0615 (3)	0.0317 (12)
N3	0.7641 (5)	0.5313 (4)	0.3251 (4)	0.0369 (12)
N4	0.9642 (5)	0.7399 (4)	0.4773 (4)	0.0413 (13)
N5	1.1476 (5)	0.8830 (4)	0.1649 (4)	0.0344 (12)
C1	1.2557 (5)	0.6227 (4)	0.2037 (4)	0.0256 (13)
C2	1.2977 (5)	0.7109 (4)	0.3059 (4)	0.0298 (14)
C3	1.4221 (6)	0.7250 (5)	0.3566 (5)	0.0397 (16)
H3	1.4770	0.6786	0.3240	0.048*
C4	1.4681 (6)	0.8031 (5)	0.4516 (5)	0.0539 (19)
H4	1.5526	0.8106	0.4831	0.065*
C5	1.3866 (6)	0.8704 (6)	0.4998 (5)	0.055 (2)
H5	1.4164	0.9243	0.5650	0.066*
C6	1.2617 (6)	0.8601 (5)	0.4540 (5)	0.0456 (17)
H6	1.2091	0.9079	0.4884	0.055*
C7	1.2119 (5)	0.7792 (4)	0.3568 (4)	0.0307 (14)
C8	0.7915 (6)	0.2359 (5)	0.0860 (5)	0.0463 (17)
H8	0.8738	0.2282	0.1096	0.056*
C9	0.6841 (7)	0.1540 (6)	0.0778 (6)	0.064 (2)
H9	0.6934	0.0931	0.0968	0.077*
C10	0.5615 (7)	0.1642 (6)	0.0406 (6)	0.069 (2)
H10	0.4877	0.1089	0.0327	0.082*
C11	0.5498 (6)	0.2562 (6)	0.0154 (5)	0.054 (2)
H11	0.4686	0.2656	−0.0086	0.065*
C12	0.6624 (6)	0.3342 (5)	0.0269 (5)	0.0420 (16)
H12	0.6551	0.3967	0.0097	0.050*
C13	0.7714 (7)	0.4784 (6)	0.3882 (5)	0.0567 (19)
H13	0.8520	0.4920	0.4282	0.068*
C14	0.6689 (7)	0.4052 (6)	0.3988 (6)	0.067 (2)
H14	0.6794	0.3718	0.4453	0.080*
C15	0.5552 (7)	0.3837 (6)	0.3410 (6)	0.067 (2)
H15	0.4839	0.3347	0.3466	0.081*
C16	0.5416 (7)	0.4328 (6)	0.2729 (6)	0.064 (2)
H16	0.4622	0.4161	0.2304	0.077*
C17	0.6487 (6)	0.5084 (6)	0.2682 (5)	0.0497 (18)
H17	0.6389	0.5442	0.2235	0.060*
C18	0.9185 (8)	0.8347 (6)	0.5184 (6)	0.078 (3)
H18	0.8592	0.8536	0.4781	0.094*
C19	0.9545 (9)	0.9056 (7)	0.6168 (7)	0.095 (3)
H19	0.9211	0.9720	0.6424	0.114*
C20	1.0398 (8)	0.8788 (7)	0.6780 (6)	0.079 (3)
H20	1.0644	0.9254	0.7458	0.095*
C21	1.0869 (8)	0.7835 (7)	0.6374 (5)	0.070 (2)
H21	1.1460	0.7630	0.6765	0.084*
C22	1.0468 (7)	0.7161 (6)	0.5369 (5)	0.0522 (19)
H22	1.0803	0.6500	0.5099	0.063*
C23	1.0936 (6)	0.9447 (5)	0.1219 (5)	0.0421 (16)
H23	1.0072	0.9175	0.0889	0.051*
C24	1.1617 (7)	1.0485 (5)	0.1243 (5)	0.056 (2)
H24	1.1204	1.0902	0.0942	0.067*
C25	1.2874 (7)	1.0887 (6)	0.1704 (6)	0.069 (2)
H25	1.3341	1.1587	0.1740	0.083*
C26	1.3439 (7)	1.0227 (6)	0.2117 (6)	0.074 (2)
H26	1.4311	1.0470	0.2429	0.089*
C27	1.2727 (6)	0.9216 (6)	0.2071 (5)	0.0541 (19)
H27	1.3136	0.8777	0.2348	0.065*
C28	1.0902 (5)	0.4596 (5)	0.2759 (5)	0.0321 (14)
C29	1.1857 (6)	0.4101 (6)	0.3223 (5)	0.0488 (18)
H29A	1.2675	0.4648	0.3490	0.073*
H29B	1.1990	0.3404	0.2725	0.073*
H29C	1.1521	0.3933	0.3753	0.073*
C30	0.7968 (6)	0.8139 (5)	0.2548 (5)	0.0387 (16)
C31	0.6862 (6)	0.8750 (6)	0.2571 (6)	0.071 (2)
H31A	0.7101	0.9383	0.2373	0.107*
H31B	0.6669	0.9036	0.3237	0.107*
H31C	0.6103	0.8224	0.2118	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0246 (4)	0.0222 (4)	0.0239 (4)	0.0049 (3)	0.0030 (3)	0.0077 (3)
Ni2	0.0344 (4)	0.0333 (4)	0.0249 (4)	0.0074 (3)	0.0056 (4)	0.0077 (3)
Ni3	0.0297 (4)	0.0215 (4)	0.0274 (4)	0.0062 (3)	0.0039 (3)	0.0070 (3)
Mo1	0.0274 (3)	0.0227 (3)	0.0298 (3)	0.0075 (2)	0.0022 (2)	0.0094 (2)
O1	0.030 (2)	0.029 (2)	0.035 (2)	0.0095 (18)	−0.0009 (19)	0.0113 (18)
O2	0.025 (2)	0.0201 (19)	0.022 (2)	0.0036 (16)	0.0018 (17)	0.0061 (16)
O3	0.037 (2)	0.031 (2)	0.028 (2)	0.0067 (18)	0.001 (2)	0.0052 (18)
O4	0.039 (2)	0.040 (2)	0.030 (2)	0.011 (2)	0.003 (2)	0.011 (2)
O5	0.032 (2)	0.033 (2)	0.025 (2)	0.0103 (18)	0.0017 (19)	0.0116 (18)
O6	0.042 (3)	0.032 (2)	0.038 (3)	0.014 (2)	0.010 (2)	0.008 (2)
O7	0.046 (3)	0.043 (3)	0.042 (3)	0.019 (2)	0.016 (2)	0.015 (2)
O8	0.027 (2)	0.025 (2)	0.025 (2)	0.0053 (16)	0.0020 (17)	0.0082 (17)
O9	0.027 (2)	0.0223 (19)	0.026 (2)	0.0027 (16)	0.0038 (18)	0.0071 (17)
O10	0.036 (2)	0.030 (2)	0.044 (3)	0.0108 (18)	0.000 (2)	0.0142 (19)
O11	0.032 (2)	0.034 (2)	0.036 (2)	0.0108 (18)	0.008 (2)	0.0116 (19)
O12	0.093 (9)	0.050 (7)	0.074 (8)	0.023 (6)	−0.001 (6)	0.015 (6)
N1	0.029 (3)	0.019 (2)	0.022 (3)	0.002 (2)	0.001 (2)	0.002 (2)
N2	0.034 (3)	0.029 (3)	0.031 (3)	0.004 (2)	0.011 (2)	0.010 (2)
N3	0.032 (3)	0.045 (3)	0.030 (3)	0.003 (2)	0.006 (3)	0.013 (3)
N4	0.042 (3)	0.044 (3)	0.031 (3)	0.005 (3)	0.009 (3)	0.008 (3)
N5	0.042 (3)	0.023 (3)	0.039 (3)	0.008 (2)	0.011 (3)	0.011 (2)
C1	0.021 (3)	0.021 (3)	0.036 (4)	0.001 (2)	0.008 (3)	0.013 (3)
C2	0.033 (3)	0.023 (3)	0.030 (3)	0.004 (3)	−0.002 (3)	0.009 (3)
C3	0.034 (4)	0.039 (4)	0.038 (4)	0.005 (3)	−0.001 (3)	0.009 (3)
C4	0.037 (4)	0.060 (5)	0.045 (5)	0.003 (3)	−0.006 (4)	0.004 (4)
C5	0.046 (4)	0.061 (5)	0.029 (4)	−0.007 (4)	−0.010 (3)	−0.004 (3)
C6	0.048 (4)	0.038 (4)	0.035 (4)	0.002 (3)	0.006 (3)	−0.001 (3)
C7	0.038 (4)	0.023 (3)	0.025 (3)	0.000 (3)	0.000 (3)	0.007 (3)
C8	0.046 (4)	0.035 (4)	0.060 (5)	0.001 (3)	0.008 (4)	0.025 (3)
C9	0.063 (5)	0.047 (4)	0.091 (6)	0.003 (4)	0.013 (5)	0.040 (4)
C10	0.051 (5)	0.046 (5)	0.094 (7)	−0.011 (4)	0.018 (5)	0.018 (5)
C11	0.027 (4)	0.049 (4)	0.080 (6)	0.007 (3)	0.008 (4)	0.018 (4)
C12	0.036 (4)	0.035 (4)	0.047 (4)	0.003 (3)	0.008 (3)	0.009 (3)
C13	0.049 (5)	0.076 (5)	0.045 (5)	−0.004 (4)	−0.004 (4)	0.033 (4)
C14	0.055 (5)	0.088 (6)	0.069 (6)	−0.008 (4)	0.008 (5)	0.055 (5)
C15	0.052 (5)	0.076 (6)	0.076 (6)	−0.006 (4)	−0.001 (5)	0.043 (5)
C16	0.032 (4)	0.087 (6)	0.073 (6)	0.002 (4)	−0.004 (4)	0.038 (5)
C17	0.037 (4)	0.065 (5)	0.048 (5)	0.012 (4)	0.004 (4)	0.023 (4)
C18	0.098 (7)	0.078 (6)	0.042 (5)	0.046 (5)	0.008 (5)	−0.006 (4)
C19	0.108 (8)	0.093 (7)	0.057 (6)	0.050 (6)	0.010 (6)	−0.012 (5)
C20	0.100 (7)	0.070 (6)	0.035 (5)	0.014 (5)	0.006 (5)	−0.014 (4)
C21	0.089 (6)	0.074 (6)	0.037 (5)	0.015 (5)	0.004 (4)	0.014 (4)
C22	0.065 (5)	0.042 (4)	0.042 (5)	0.011 (4)	0.010 (4)	0.008 (3)
C23	0.044 (4)	0.038 (4)	0.045 (4)	0.004 (3)	0.005 (3)	0.019 (3)
C24	0.074 (5)	0.043 (4)	0.068 (5)	0.017 (4)	0.020 (5)	0.038 (4)
C25	0.063 (5)	0.053 (5)	0.094 (7)	−0.011 (4)	0.011 (5)	0.041 (5)
C26	0.052 (5)	0.067 (5)	0.111 (7)	−0.015 (4)	−0.003 (5)	0.059 (5)
C27	0.039 (4)	0.055 (4)	0.074 (6)	0.002 (3)	−0.002 (4)	0.037 (4)
C28	0.034 (3)	0.032 (3)	0.036 (4)	0.003 (3)	0.006 (3)	0.021 (3)
C29	0.047 (4)	0.075 (5)	0.037 (4)	0.025 (4)	0.006 (3)	0.031 (4)
C30	0.035 (4)	0.024 (3)	0.046 (4)	0.010 (3)	0.012 (3)	−0.002 (3)
C31	0.057 (5)	0.067 (5)	0.113 (7)	0.030 (4)	0.036 (5)	0.048 (5)

Geometric parameters (Å, º)

Ni1—O8	2.004 (3)	C4—C5	1.368 (8)
Ni1—N2	2.038 (5)	C4—H4	0.9300
Ni1—O5	2.049 (4)	C5—C6	1.374 (8)
Ni1—O2^i	2.072 (4)	C5—H5	0.9300
Ni1—O2	2.138 (3)	C6—C7	1.397 (7)
Ni1—O9^i	2.146 (3)	C6—H6	0.9300
Ni2—O8	2.045 (3)	C8—C9	1.377 (8)
Ni2—O7	2.062 (4)	C8—H8	0.9300
Ni2—O4	2.076 (4)	C9—C10	1.389 (9)
Ni2—N3	2.123 (5)	C9—H9	0.9300
Ni2—N4	2.131 (5)	C10—C11	1.369 (9)
Ni2—O3	2.135 (4)	C10—H10	0.9300
Ni3—O3	2.031 (4)	C11—C12	1.375 (8)
Ni3—N1	2.038 (4)	C11—H11	0.9300
Ni3—O6	2.080 (3)	C12—H12	0.9300
Ni3—O9	2.099 (4)	C13—C14	1.374 (9)
Ni3—O8	2.111 (3)	C13—H13	0.9300
Ni3—N5	2.120 (5)	C14—C15	1.316 (9)
Mo1—O10	1.716 (4)	C14—H14	0.9300
Mo1—O11	1.718 (4)	C15—C16	1.362 (10)
Mo1—O9^i	1.824 (3)	C15—H15	0.9300
Mo1—O1	2.056 (4)	C16—C17	1.389 (9)
Mo1—O2	2.222 (3)	C16—H16	0.9300
Mo1—O5	2.510 (4)	C17—H17	0.9300
O1—C1	1.308 (5)	C18—C19	1.359 (10)
O2—N1	1.413 (5)	C18—H18	0.9300
O2—Ni1^i	2.072 (4)	C19—C20	1.368 (10)
O3—C7	1.339 (6)	C19—H19	0.9300
O4—C28	1.246 (6)	C20—C21	1.337 (9)
O5—C28	1.271 (6)	C20—H20	0.9300
O6—C30	1.249 (7)	C21—C22	1.378 (9)
O7—C30	1.266 (7)	C21—H21	0.9300
O8—H5A	0.8500	C22—H22	0.9300
O9—Mo1^i	1.824 (3)	C23—C24	1.390 (8)
O9—Ni1^i	2.146 (3)	C23—H23	0.9300
O12—H12C	0.8500	C24—C25	1.347 (9)
O12—H12D	0.8500	C24—H24	0.9300
N1—C1	1.303 (6)	C25—C26	1.369 (9)
N2—C8	1.331 (7)	C25—H25	0.9300
N2—C12	1.343 (7)	C26—C27	1.363 (9)
N3—C17	1.322 (7)	C26—H26	0.9300
N3—C13	1.328 (8)	C27—H27	0.9300
N4—C22	1.311 (8)	C28—C29	1.494 (7)
N4—C18	1.325 (7)	C29—H29A	0.9600
N5—C27	1.326 (7)	C29—H29B	0.9600
N5—C23	1.328 (7)	C29—H29C	0.9600
C1—C2	1.469 (7)	C30—C31	1.493 (7)
C2—C3	1.385 (7)	C31—H31A	0.9600
C2—C7	1.425 (7)	C31—H31B	0.9600
C3—C4	1.357 (8)	C31—H31C	0.9600
C3—H3	0.9300
O8—Ni1—N2	99.94 (15)	C23—N5—Ni3	118.5 (4)
O8—Ni1—O5	94.19 (14)	N1—C1—O1	121.0 (5)
N2—Ni1—O5	97.24 (17)	N1—C1—C2	119.2 (4)
O8—Ni1—O2^i	94.19 (13)	O1—C1—C2	119.8 (5)
N2—Ni1—O2^i	94.66 (17)	C3—C2—C7	118.5 (5)
O5—Ni1—O2^i	164.04 (14)	C3—C2—C1	119.5 (5)
O8—Ni1—O2	91.54 (13)	C7—C2—C1	121.9 (5)
N2—Ni1—O2	168.18 (14)	C4—C3—C2	123.4 (5)
O5—Ni1—O2	84.64 (14)	C4—C3—H3	118.3
O2^i—Ni1—O2	81.58 (14)	C2—C3—H3	118.3
O8—Ni1—O9^i	163.33 (14)	C3—C4—C5	118.1 (6)
N2—Ni1—O9^i	95.88 (15)	C3—C4—H4	120.9
O5—Ni1—O9^i	78.55 (13)	C5—C4—H4	120.9
O2^i—Ni1—O9^i	89.71 (13)	C4—C5—C6	121.4 (6)
O2—Ni1—O9^i	72.99 (12)	C4—C5—H5	119.3
O8—Ni2—O7	86.92 (15)	C6—C5—H5	119.3
O8—Ni2—O4	94.40 (14)	C5—C6—C7	121.4 (6)
O7—Ni2—O4	175.63 (17)	C5—C6—H6	119.3
O8—Ni2—N3	96.28 (17)	C7—C6—H6	119.3
O7—Ni2—N3	88.23 (18)	O3—C7—C6	119.5 (5)
O4—Ni2—N3	87.49 (17)	O3—C7—C2	123.3 (5)
O8—Ni2—N4	170.72 (18)	C6—C7—C2	117.2 (5)
O7—Ni2—N4	89.55 (18)	N2—C8—C9	122.7 (6)
O4—Ni2—N4	89.76 (18)	N2—C8—H8	118.7
N3—Ni2—N4	92.18 (19)	C9—C8—H8	118.7
O8—Ni2—O3	84.81 (14)	C8—C9—C10	118.6 (7)
O7—Ni2—O3	91.35 (15)	C8—C9—H9	120.7
O4—Ni2—O3	92.91 (14)	C10—C9—H9	120.7
N3—Ni2—O3	178.81 (16)	C11—C10—C9	119.6 (7)
N4—Ni2—O3	86.71 (17)	C11—C10—H10	120.2
O3—Ni3—N1	85.18 (16)	C9—C10—H10	120.2
O3—Ni3—O6	91.96 (15)	C10—C11—C12	117.6 (6)
N1—Ni3—O6	174.19 (17)	C10—C11—H11	121.2
O3—Ni3—O9	174.44 (15)	C12—C11—H11	121.2
N1—Ni3—O9	94.05 (15)	N2—C12—C11	124.0 (6)
O6—Ni3—O9	88.31 (14)	N2—C12—H12	118.0
O3—Ni3—O8	85.80 (15)	C11—C12—H12	118.0
N1—Ni3—O8	84.72 (15)	N3—C13—C14	124.9 (7)
O6—Ni3—O8	90.03 (14)	N3—C13—H13	117.6
O9—Ni3—O8	88.64 (13)	C14—C13—H13	117.6
O3—Ni3—N5	96.61 (17)	C15—C14—C13	117.9 (7)
N1—Ni3—N5	95.75 (17)	C15—C14—H14	121.0
O6—Ni3—N5	89.60 (16)	C13—C14—H14	121.0
O9—Ni3—N5	88.95 (17)	C14—C15—C16	120.3 (8)
O8—Ni3—N5	177.58 (17)	C14—C15—H15	119.9
O10—Mo1—O11	104.67 (17)	C16—C15—H15	119.9
O10—Mo1—O9^i	106.80 (17)	C15—C16—C17	118.6 (7)
O11—Mo1—O9^i	105.57 (16)	C15—C16—H16	120.7
O10—Mo1—O1	94.89 (16)	C17—C16—H16	120.7
O11—Mo1—O1	100.82 (16)	N3—C17—C16	122.4 (7)
O9^i—Mo1—O1	139.85 (13)	N3—C17—H17	118.8
O10—Mo1—O2	157.59 (15)	C16—C17—H17	118.8
O11—Mo1—O2	95.03 (14)	N4—C18—C19	123.0 (8)
O9^i—Mo1—O2	77.34 (13)	N4—C18—H18	118.5
O1—Mo1—O2	70.62 (12)	C19—C18—H18	118.5
O10—Mo1—O5	86.98 (15)	C18—C19—C20	119.7 (7)
O11—Mo1—O5	167.82 (14)	C18—C19—H19	120.2
O9^i—Mo1—O5	73.71 (13)	C20—C19—H19	120.2
O1—Mo1—O5	74.18 (13)	C21—C20—C19	117.9 (7)
O2—Mo1—O5	72.87 (12)	C21—C20—H20	121.0
C1—O1—Mo1	119.9 (3)	C19—C20—H20	121.0
N1—O2—Ni1^i	114.9 (3)	C20—C21—C22	119.2 (7)
N1—O2—Ni1	107.6 (2)	C20—C21—H21	120.4
Ni1^i—O2—Ni1	98.42 (14)	C22—C21—H21	120.4
N1—O2—Mo1	115.8 (3)	N4—C22—C21	123.7 (6)
Ni1^i—O2—Mo1	124.39 (15)	N4—C22—H22	118.1
Ni1—O2—Mo1	86.75 (12)	C21—C22—H22	118.1
C7—O3—Ni3	124.7 (3)	N5—C23—C24	122.3 (6)
C7—O3—Ni2	123.7 (3)	N5—C23—H23	118.9
Ni3—O3—Ni2	92.33 (15)	C24—C23—H23	118.9
C28—O4—Ni2	136.3 (4)	C25—C24—C23	119.9 (7)
C28—O5—Ni1	137.8 (3)	C25—C24—H24	120.1
C28—O5—Mo1	129.3 (3)	C23—C24—H24	120.1
Ni1—O5—Mo1	81.45 (13)	C24—C25—C26	117.6 (7)
C30—O6—Ni3	125.9 (4)	C24—C25—H25	121.2
C30—O7—Ni2	129.6 (4)	C26—C25—H25	121.2
Ni1—O8—Ni2	129.22 (17)	C27—C26—C25	120.1 (7)
Ni1—O8—Ni3	112.05 (15)	C27—C26—H26	119.9
Ni2—O8—Ni3	92.65 (13)	C25—C26—H26	119.9
Ni1—O8—H5A	106.9	N5—C27—C26	122.9 (6)
Ni2—O8—H5A	106.9	N5—C27—H27	118.6
Ni3—O8—H5A	107.0	C26—C27—H27	118.6
Mo1^i—O9—Ni3	130.21 (18)	O4—C28—O5	125.7 (5)
Mo1^i—O9—Ni1^i	97.63 (14)	O4—C28—C29	117.4 (5)
Ni3—O9—Ni1^i	109.47 (14)	O5—C28—C29	116.9 (5)
H12C—O12—H12D	108.1	C28—C29—H29A	109.5
C1—N1—O2	110.1 (4)	C28—C29—H29B	109.5
C1—N1—Ni3	131.9 (4)	H29A—C29—H29B	109.5
O2—N1—Ni3	112.5 (3)	C28—C29—H29C	109.5
C8—N2—C12	117.5 (5)	H29A—C29—H29C	109.5
C8—N2—Ni1	120.6 (4)	H29B—C29—H29C	109.5
C12—N2—Ni1	121.9 (4)	O6—C30—O7	125.6 (5)
C17—N3—C13	115.9 (6)	O6—C30—C31	117.4 (6)
C17—N3—Ni2	122.0 (5)	O7—C30—C31	117.0 (6)
C13—N3—Ni2	122.1 (5)	C30—C31—H31A	109.5
C22—N4—C18	116.5 (6)	C30—C31—H31B	109.5
C22—N4—Ni2	122.8 (4)	H31A—C31—H31B	109.5
C18—N4—Ni2	120.0 (5)	C30—C31—H31C	109.5
C27—N5—C23	117.2 (6)	H31A—C31—H31C	109.5
C27—N5—Ni3	124.3 (4)	H31B—C31—H31C	109.5

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C31—H31A···O12	0.96	2.41	3.064 (13)	125
C29—H29B···O10	0.96	2.57	3.304 (7)	134
C23—H23···O12	0.93	2.50	3.353 (11)	152
C22—H22···O4	0.93	2.40	2.999 (7)	122
C18—H18···O7	0.93	2.31	2.932 (9)	124
C16—H16···O10^ii	0.93	2.52	3.397 (8)	157
C16—H16···O1^ii	0.93	2.60	3.343 (8)	137
C12—H12···O11^i	0.93	2.56	3.436 (7)	156
C11—H11···O11^ii	0.93	2.59	3.444 (7)	153
C9—H9···O12^iii	0.93	2.37	3.218 (11)	152
C8—H8···O5	0.93	2.65	3.182 (7)	117
O12—H12D···O10^i	0.85	2.09	2.924 (10)	169
O12—H12C···O6	0.85	1.93	2.770 (11)	169
O8—H5A···O11^i	0.85	2.15	2.907 (5)	149
C9—H9···O12^iii	0.93	2.37	3.218 (11)	152
C25—H25···O10^iv	0.93	2.47	3.138 (9)	129
C16—H16···O10^ii	0.93	2.52	3.397 (8)	157
C11—H11···O11^ii	0.93	2.59	3.444 (7)	153
O8—H5A···O11^i	0.85	2.15	2.907 (5)	149
O12—H12D···O10^i	0.85	2.09	2.924 (10)	169
O12—H12C···O6	0.85	1.93	2.770 (11)	169

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