The synthesis, crystal structure and magnetic properties of a one-dimensional terbium(III)-octa­cyanido­molybdate(V) assembly

A one-dimensional cyanide-bridged coordination polymer, poly[[aqua­di-[mu]-cyanido-[kappa]⁴C:N-hexacyanido-[kappa]⁶C-(di­methyl­formamide-[kappa]O)bis­(3,4,7,8-tetra­methyl-1,10-phenanthroline-[kappa]²N,N')terbium(III)molybdate(V)] 4.5-hydrate], [MoTb(CN)₈(C₁₆H₁₆N₂)₂(C₃H₇NO)(H₂O)]·4.5H₂O}_n, has been prepared and characterized through IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The compound consists of one-dimensional chains in which cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ (tmphen is 3,4,7,8-tetra­methyl-1,10-phenanthroline) and anionic [Mo^V(CN)₈]^3- units are linked in an alternating fashion through bridging cyanide ligands. Neighbouring chains are connected by three types of hydrogen bonds (O-H...O, O-H...N and C-H...O) and by [pi]-[pi] inter­actions to form a three-dimensional supra­molecular structure. In addition, magnetic investigations show that ferromagnetic inter­actions exist in the compound.

S1. Introduction

There has been growing inter­est in the study of molecular magnets because of their promising applications. Recently, o­cta­cyanidometallate-based magnets have drawn much attention in molecular magnetism due to their variety of spatial configurations, e.g. square anti­prism (D_4d), dodecahedron (D_2d) and bicapped trigonal prism (C_2v) (Nowicka et al., 2012; Przychodzeń et al., 2006; Sieklucka et al., 2005, 2009, 2011). In fact, the investigation of o­cta­cyanidometallate-based bimetallic systems has mainly focused on first-row transition metal ions (Freedman et al., 2006; Lim et al., 2006; Song et al., 2003, 2005; Wang et al., 2010; Zhong et al., 2000). The synthesis of compounds containing o­cta­cyanidometallate(V) and lanthanide ions is still relatively challenging. Among these compounds, there are only a few based on anionic o­cta­cyanidomolybdate(V) with rare earth ions, viz. [Tb^III(pzam)₃(H₂O)Mo^V(CN)₈]·H₂O (pzam is pyrazine-2-carboxamide; Prins et al., 2007), {[Yb^III(bpy)₂(DMF)(H₂O)][Mo^V(CN)₈]·0.5bpy·4.5H₂O}_n (bpy is 2,2'-bipyridinyl and DMF is di­methyl­formamide; Ma et al., 2010), [Ln(CH₃CN)₂(H₂O)₄][Mo(CN)₈]·CH₃CN (Qian et al., 2010), [Pr(tmphen)(DMF)₅][M(CN)₈]·DMF·2H₂O (tmphen is 3,4,7,8-tetra­methyl-1,10-phenanthroline; Qian et al., 2011), Nd(phen)_n(DMF)_m[Mo(CN)₈] (phen is 1,10-phenanthroline; Long et al., 2011) and [Ln^III(DMF)₆Mo^V(CN)₈]_n (Tong et al., 2013).

In the search for new materials of 4d–4f cyanide-bridged assemblies of the [Mo(CN)₈]^3- building block, we report here the synthesis, crystal structure and magnetic properties of an o­cta­cyanidomolybdate-based compound with a one-dimensional chain structure, namely {[Tb(tmphen)₂(DMF)(H₂O){Mo(CN)₈}]4.5H₂O}_n, (I).

S1.1. Experimental

Cs₃[Mo(CN)₈]·4H₂O was prepared according to a previously reported procedure (Bok et al., 1975). All other reagents and solvents used in the experiment were purchased from commercial sources and used without further purification. IR spectra were obtained within the range 4000–400 cm^-1 as KBr discs on a VECTOR 22 spectrometer. Elemental analyses were performed on a Perkin–Elmer 240C elemental analyser. Magnetic measurements on a microcrystalline sample were carried out on a Quantum Design MPMP-XL7 superconducting quantum inter­ference device (SQUID) magnetometer.

S1.2. Synthesis and crystallization

To a solution of Tb(NO₃)₃·6H₂O (45.1 mg, 0.1 mmol) and Cs₃[Mo(CN)₈]·4H₂O (15.7 mg, 0.02 mmol) in H₂O (8 ml), a solution of tmphen (4.8 mg, 0.02 mmol) in CH₃CN (4 ml) was added dropwise with gentle stirring. The yellow precipitate which formed was dissolved using DMF (ca 2 ml). The resulting mixture was allowed to stand in the dark without disturbance for several weeks and red prismatic [Block given in CIF tables - please clarify] single crystals of (I) suitable for X-ray analysis were obtained (yield 31.2%, based on Tb). Compound (I) is insoluble in all common solvents. Elemental analysis for C₈₆H₁₀₀Mo₂N₂₆O₁₃Tb₂: C 46.62, H 4.55, N 16.44%; found: C 46.71, H 4.56, N 16.49%. IR stretching cyanide (KBr, ν, cm^-1): 2113, 2165.

S1.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms attached to aromatic C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. Methyl H atoms were positioned geometrically and refined using a riding model [C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C)]. The H atoms of the solvent water molecules were located in difference Fourier maps; their positions were geometrically optimized and they were constrained to ride on their parent atoms, with O—H = 0.85 Å and U_iso(H) = 1.2U_eq(O). The H atoms of the coordinated aqua molecules were refined isotropically, with O—H distance restraints of 0.96 Å, and they were constrained to ride on their parent atoms with U_iso(H) = 1.5U_eq(O).

S2. Results and discussion

Compound (I) crystallizes in the monoclinic space group P2₁/c with an asymmetric unit consisting of a cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ unit, an anionic [Mo(CN)₈]^3- unit and four and a half solvent water molecules, as shown in Fig. 1. Atom Tb1 is coordinated by four pyridine N-donor atoms from two chelating tmphen ligands, two cyanide N atoms from different [Mo(CN)₈]^3- units and two O atoms from a coordinated DMF molecule and a coordinated water molecule, to form a distorted eight-coordinate tetra­gonal anti­prismatic {TbN₆O₂} coordination environment. The Tb—N bond lengths are in the range 2.470 (6)–2.556 (6) Å and the Tb—O bond lengths are in the range 2.304 (5)–2.358 (6) Å (Table 2). The Tb—N≡C linkages are poorly linear, with angles of 170.9 (6) and 173.9 (6)°. The [Mo^V(CN)₈]^3- unit adopts a slightly distorted square-anti­prism configuration, with N1/N3/N7/N8 and N2/N4/N5/N6 as the two basic planes, in which the mean deviations from each plane are 0.2901 (1) and 0.0910 (2) Å, respectively. The two basic planes are almost parallel to each other, with a dihedral angle of 1.5 (1)°. The Mo—C bond lengths range from 2.123 (7) to 2.175 (8) Å, while the C≡N bond lengths range from 1.123 (9) to 1.198 (8) Å. All the Mo—C≡N linkages are almost linear, with angles ranging from 176.0 (7) to 179.6 (7)° (Table 2).

As shown in Fig. 2, the cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ units are linked alternately by anionic [Mo(CN)₈]^3- units through two trans-cyanide groups [C1—Mo1—C2 = 145.8 (3)°] to form a one-dimensional cyanide-bridged chain. The Mo1···Tb1···Mo1' angle is 152.2 (2)°, which is an indication of the zigzag chain structure. The intra­chain Mo···Tb distances across the cyanide bridge are 5.7733 (8) (Tb—C1≡N1—Mo) and 5.7751 (8) Å (Tb—C2≡N2—Mo). The two equivalent chains are separated from each other, with a minimum inter­metallic distance between the Tb and Mo atoms of 11.748 (2) Å in the unit cell.

In the solid state, neighbouring chains inter­act weakly through π–π inter­actions, leading to a two-dimensional supra­molecular folded layer. First of all, there are π–π inter­actions between the benzene and pyridine rings, with Cg1···Cg2, Cg1···Cg3 and Cg2···Cg4 (Cg1, Cg2, Cg3 and Cg4 are the centroids of the N9/C9/C10/C12/C14/C15, N12/C35/C34/C36/C38/C40, C30–C35 and C14–C19 rings, respectively) centroid-to-centroid separations of 3.493 (4), 3.682 (4) and 3.614 (4) Å, respectively, in the chains. Secondly, neighbouring chains are inter­connected by π–π inter­actions between the benzene and pyridine rings, with Cg1···Cg5^ix, Cg5···Cg4^ix, Cg6···Cg6^x and Cg4···Cg4^ix centroid-to-centroid separations of 3.792 (4), 3.733 (3), 3.692 (4) and 3.676 (4) Å, respectively, to form a two-dimensional layer [Cg5 and Cg6 are the centroids of the N10/C16/C17/C20/C22/C24 and N11/C25/C26/C28/C30/C31 rings, respectively; symmetry codes: (ix) -x + 1, -y + 2, -z + 1; (x) -x + 2, -y + 2, -z + 1; see Fig. 3 and Table 3 for details].

There are also extensive inter- and intra­molecular O—H···O, O—H···N and C—H···O hydrogen bonds connecting the one-dimensional chains into a three-dimensional supra­molecular framework (see Fig. 4 and Table 4 for details). The coordinated water molecule, O2, forms a hydrogen bond to the inter­stitial water molecule O6. Water molecule O6 also accepts two hydrogen bonds from O7 and in turn donates hydrogen bonds to atoms O4 and O5ⁱⁱ [symmetry code: (ii) -x + 1, -y + 1, -z + 1]. Water molecule O5 also forms a hydrogen bond to cyanide atoms N5ⁱⁱ and N4^vi of an adjacent chain [symmetry code: (vi) x, -y + 3/2, z + 1/2]. Water molecule O4 acts a hydrogen-bond acceptor from water molecule O6, and serves as a hydrogen-bond donor to water molecule O3 and cyanide atom N3^v [symmetry code: (v) -x + 1, y - 1/2, -z + 1/2]. The final water molecule, O3, forms hydrogen bonds to cyanide atoms N6ⁱⁱⁱ and N8^iv of two additional chains adjacent to that formed by the identity molecule [symmetry codes: (iii) -x + 1, y + 1/2, -z + 1/2; (iv) x - 1, y, z].

Approximately 7.7% of the crystal volume is occupied by the solvent molecules, with a volume of 219.0 ų in each unit cell (2854.0 ų) based on a PLATON calculation (Spek, 2009). Inter­estingly, four solvent water molecules [O3, O4, O5ⁱⁱ and O6; symmetry code: (ii) -x + 1, -y + 1, -z + 1] form a water tetra­mer via hydrogen bonds in (I).

Variable-temperature magnetic measurements were performed on polycrystalline samples of (I) in the range 1.8–300 K in a field of 100 Oe, plotted in the form of χ_MT versus T (Fig. 5). At 300 K, the χ_MT value of (I) is 12.22 cm³ K mol^-1, which is larger than the spin-only value of 12.19 cm³ K mol^-1 for isolated Tb^III (J = 6, g = 3/2) and Mo^V (S = 1/2, g = 2). As the temperature decreases, the χ_MT value gradually decreases and reaches a minimum of 9.34 cm³ K mol^-1 at 5.0 K, after which point it increases to a maximum of 10.00 cm³ K mol^-1 at 1.8 K. The initial decrease is mainly ascribed to the thermal depopulation of the Stark levels of the Tb^{III 7}F₆ ground state. The abrupt increase in χ_MT at low temperature indicates that the coupling inter­action between metal ions overcomes the depopulation of the ground state, leading to a net spin along the field, but a conclusion cannot be drawn about the magnetic coupling nature (Wang, 2013; Zhou et al., 2010).

As shown in Fig. 6, the field dependence of the magnetization performed at 1.8 K shows a rapid increase in magnetization with field, with a magnetization value of 6.06 N µ_B mol^-1 at 70 kOe, corresponding well with the ferromagnetic ground-state spin of 6 µ_B (Prins et al., 2007; Wang, 2013). Thus, ferromagnetic inter­actions between Mo^V and Tb^III ions exist in (I).

In conclusion, the one-dimensional cyanide-bridged coordination polymer {[Tb(tmphen)₂(DMF)(H₂O){Mo(CN)₈}].4.5H₂O}_n, (I), has been prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. Compound (I) consists of one-dimensional chains, in which cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ and anionic [Mo^V(CN)₈]^3- units link in an alternating fashion through bridging cyanide ligands. In addition, magnetic investigations show that ferromagnetic inter­actions exist in (I).

Related literature

For related literature, see: Bok et al. (1975); Freedman et al. (2006); Lim et al. (2006); Long et al. (2011); Ma et al. (2010); Nowicka et al. (2012); Prins et al. (2007); Przychodzeń et al. (2006); Qian et al. (2010, 2011); Sieklucka et al. (2005, 2009, 2011); Song et al. (2003, 2005); Spek (2009); Tong et al. (2013); Wang (2013); Wang et al. (2010); Zhong et al. (2000); Zhou et al. (2010).

Structure description

There has been growing inter­est in the study of molecular magnets because of their promising applications. Recently, o­cta­cyanidometallate-based magnets have drawn much attention in molecular magnetism due to their variety of spatial configurations, e.g. square anti­prism (D_4d), dodecahedron (D_2d) and bicapped trigonal prism (C_2v) (Nowicka et al., 2012; Przychodzeń et al., 2006; Sieklucka et al., 2005, 2009, 2011). In fact, the investigation of o­cta­cyanidometallate-based bimetallic systems has mainly focused on first-row transition metal ions (Freedman et al., 2006; Lim et al., 2006; Song et al., 2003, 2005; Wang et al., 2010; Zhong et al., 2000). The synthesis of compounds containing o­cta­cyanidometallate(V) and lanthanide ions is still relatively challenging. Among these compounds, there are only a few based on anionic o­cta­cyanidomolybdate(V) with rare earth ions, viz. [Tb^III(pzam)₃(H₂O)Mo^V(CN)₈]·H₂O (pzam is pyrazine-2-carboxamide; Prins et al., 2007), {[Yb^III(bpy)₂(DMF)(H₂O)][Mo^V(CN)₈]·0.5bpy·4.5H₂O}_n (bpy is 2,2'-bipyridinyl and DMF is di­methyl­formamide; Ma et al., 2010), [Ln(CH₃CN)₂(H₂O)₄][Mo(CN)₈]·CH₃CN (Qian et al., 2010), [Pr(tmphen)(DMF)₅][M(CN)₈]·DMF·2H₂O (tmphen is 3,4,7,8-tetra­methyl-1,10-phenanthroline; Qian et al., 2011), Nd(phen)_n(DMF)_m[Mo(CN)₈] (phen is 1,10-phenanthroline; Long et al., 2011) and [Ln^III(DMF)₆Mo^V(CN)₈]_n (Tong et al., 2013).

In the search for new materials of 4d–4f cyanide-bridged assemblies of the [Mo(CN)₈]^3- building block, we report here the synthesis, crystal structure and magnetic properties of an o­cta­cyanidomolybdate-based compound with a one-dimensional chain structure, namely {[Tb(tmphen)₂(DMF)(H₂O){Mo(CN)₈}]4.5H₂O}_n, (I).

Cs₃[Mo(CN)₈]·4H₂O was prepared according to a previously reported procedure (Bok et al., 1975). All other reagents and solvents used in the experiment were purchased from commercial sources and used without further purification. IR spectra were obtained within the range 4000–400 cm^-1 as KBr discs on a VECTOR 22 spectrometer. Elemental analyses were performed on a Perkin–Elmer 240C elemental analyser. Magnetic measurements on a microcrystalline sample were carried out on a Quantum Design MPMP-XL7 superconducting quantum inter­ference device (SQUID) magnetometer.

Compound (I) crystallizes in the monoclinic space group P2₁/c with an asymmetric unit consisting of a cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ unit, an anionic [Mo(CN)₈]^3- unit and four and a half solvent water molecules, as shown in Fig. 1. Atom Tb1 is coordinated by four pyridine N-donor atoms from two chelating tmphen ligands, two cyanide N atoms from different [Mo(CN)₈]^3- units and two O atoms from a coordinated DMF molecule and a coordinated water molecule, to form a distorted eight-coordinate tetra­gonal anti­prismatic {TbN₆O₂} coordination environment. The Tb—N bond lengths are in the range 2.470 (6)–2.556 (6) Å and the Tb—O bond lengths are in the range 2.304 (5)–2.358 (6) Å (Table 2). The Tb—N≡C linkages are poorly linear, with angles of 170.9 (6) and 173.9 (6)°. The [Mo^V(CN)₈]^3- unit adopts a slightly distorted square-anti­prism configuration, with N1/N3/N7/N8 and N2/N4/N5/N6 as the two basic planes, in which the mean deviations from each plane are 0.2901 (1) and 0.0910 (2) Å, respectively. The two basic planes are almost parallel to each other, with a dihedral angle of 1.5 (1)°. The Mo—C bond lengths range from 2.123 (7) to 2.175 (8) Å, while the C≡N bond lengths range from 1.123 (9) to 1.198 (8) Å. All the Mo—C≡N linkages are almost linear, with angles ranging from 176.0 (7) to 179.6 (7)° (Table 2).

As shown in Fig. 2, the cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ units are linked alternately by anionic [Mo(CN)₈]^3- units through two trans-cyanide groups [C1—Mo1—C2 = 145.8 (3)°] to form a one-dimensional cyanide-bridged chain. The Mo1···Tb1···Mo1' angle is 152.2 (2)°, which is an indication of the zigzag chain structure. The intra­chain Mo···Tb distances across the cyanide bridge are 5.7733 (8) (Tb—C1≡N1—Mo) and 5.7751 (8) Å (Tb—C2≡N2—Mo). The two equivalent chains are separated from each other, with a minimum inter­metallic distance between the Tb and Mo atoms of 11.748 (2) Å in the unit cell.

In the solid state, neighbouring chains inter­act weakly through π–π inter­actions, leading to a two-dimensional supra­molecular folded layer. First of all, there are π–π inter­actions between the benzene and pyridine rings, with Cg1···Cg2, Cg1···Cg3 and Cg2···Cg4 (Cg1, Cg2, Cg3 and Cg4 are the centroids of the N9/C9/C10/C12/C14/C15, N12/C35/C34/C36/C38/C40, C30–C35 and C14–C19 rings, respectively) centroid-to-centroid separations of 3.493 (4), 3.682 (4) and 3.614 (4) Å, respectively, in the chains. Secondly, neighbouring chains are inter­connected by π–π inter­actions between the benzene and pyridine rings, with Cg1···Cg5^ix, Cg5···Cg4^ix, Cg6···Cg6^x and Cg4···Cg4^ix centroid-to-centroid separations of 3.792 (4), 3.733 (3), 3.692 (4) and 3.676 (4) Å, respectively, to form a two-dimensional layer [Cg5 and Cg6 are the centroids of the N10/C16/C17/C20/C22/C24 and N11/C25/C26/C28/C30/C31 rings, respectively; symmetry codes: (ix) -x + 1, -y + 2, -z + 1; (x) -x + 2, -y + 2, -z + 1; see Fig. 3 and Table 3 for details].

There are also extensive inter- and intra­molecular O—H···O, O—H···N and C—H···O hydrogen bonds connecting the one-dimensional chains into a three-dimensional supra­molecular framework (see Fig. 4 and Table 4 for details). The coordinated water molecule, O2, forms a hydrogen bond to the inter­stitial water molecule O6. Water molecule O6 also accepts two hydrogen bonds from O7 and in turn donates hydrogen bonds to atoms O4 and O5ⁱⁱ [symmetry code: (ii) -x + 1, -y + 1, -z + 1]. Water molecule O5 also forms a hydrogen bond to cyanide atoms N5ⁱⁱ and N4^vi of an adjacent chain [symmetry code: (vi) x, -y + 3/2, z + 1/2]. Water molecule O4 acts a hydrogen-bond acceptor from water molecule O6, and serves as a hydrogen-bond donor to water molecule O3 and cyanide atom N3^v [symmetry code: (v) -x + 1, y - 1/2, -z + 1/2]. The final water molecule, O3, forms hydrogen bonds to cyanide atoms N6ⁱⁱⁱ and N8^iv of two additional chains adjacent to that formed by the identity molecule [symmetry codes: (iii) -x + 1, y + 1/2, -z + 1/2; (iv) x - 1, y, z].

Approximately 7.7% of the crystal volume is occupied by the solvent molecules, with a volume of 219.0 ų in each unit cell (2854.0 ų) based on a PLATON calculation (Spek, 2009). Inter­estingly, four solvent water molecules [O3, O4, O5ⁱⁱ and O6; symmetry code: (ii) -x + 1, -y + 1, -z + 1] form a water tetra­mer via hydrogen bonds in (I).

Variable-temperature magnetic measurements were performed on polycrystalline samples of (I) in the range 1.8–300 K in a field of 100 Oe, plotted in the form of χ_MT versus T (Fig. 5). At 300 K, the χ_MT value of (I) is 12.22 cm³ K mol^-1, which is larger than the spin-only value of 12.19 cm³ K mol^-1 for isolated Tb^III (J = 6, g = 3/2) and Mo^V (S = 1/2, g = 2). As the temperature decreases, the χ_MT value gradually decreases and reaches a minimum of 9.34 cm³ K mol^-1 at 5.0 K, after which point it increases to a maximum of 10.00 cm³ K mol^-1 at 1.8 K. The initial decrease is mainly ascribed to the thermal depopulation of the Stark levels of the Tb^{III 7}F₆ ground state. The abrupt increase in χ_MT at low temperature indicates that the coupling inter­action between metal ions overcomes the depopulation of the ground state, leading to a net spin along the field, but a conclusion cannot be drawn about the magnetic coupling nature (Wang, 2013; Zhou et al., 2010).

As shown in Fig. 6, the field dependence of the magnetization performed at 1.8 K shows a rapid increase in magnetization with field, with a magnetization value of 6.06 N µ_B mol^-1 at 70 kOe, corresponding well with the ferromagnetic ground-state spin of 6 µ_B (Prins et al., 2007; Wang, 2013). Thus, ferromagnetic inter­actions between Mo^V and Tb^III ions exist in (I).

In conclusion, the one-dimensional cyanide-bridged coordination polymer {[Tb(tmphen)₂(DMF)(H₂O){Mo(CN)₈}].4.5H₂O}_n, (I), has been prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. Compound (I) consists of one-dimensional chains, in which cationic [Tb(tmphen)₂(DMF)(H₂O)]³⁺ and anionic [Mo^V(CN)₈]^3- units link in an alternating fashion through bridging cyanide ligands. In addition, magnetic investigations show that ferromagnetic inter­actions exist in (I).

For related literature, see: Bok et al. (1975); Freedman et al. (2006); Lim et al. (2006); Long et al. (2011); Ma et al. (2010); Nowicka et al. (2012); Prins et al. (2007); Przychodzeń et al. (2006); Qian et al. (2010, 2011); Sieklucka et al. (2005, 2009, 2011); Song et al. (2003, 2005); Spek (2009); Tong et al. (2013); Wang (2013); Wang et al. (2010); Zhong et al. (2000); Zhou et al. (2010).

Synthesis and crystallization

To a solution of Tb(NO₃)₃·6H₂O (45.1 mg, 0.1 mmol) and Cs₃[Mo(CN)₈]·4H₂O (15.7 mg, 0.02 mmol) in H₂O (8 ml), a solution of tmphen (4.8 mg, 0.02 mmol) in CH₃CN (4 ml) was added dropwise with gentle stirring. The yellow precipitate which formed was dissolved using DMF (ca 2 ml). The resulting mixture was allowed to stand in the dark without disturbance for several weeks and red prismatic [Block given in CIF tables - please clarify] single crystals of (I) suitable for X-ray analysis were obtained (yield 31.2%, based on Tb). Compound (I) is insoluble in all common solvents. Elemental analysis for C₈₆H₁₀₀Mo₂N₂₆O₁₃Tb₂: C 46.62, H 4.55, N 16.44%; found: C 46.71, H 4.56, N 16.49%. IR stretching cyanide (KBr, ν, cm^-1): 2113, 2165.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms attached to aromatic C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C)]. Methyl H atoms were positioned geometrically and refined using a riding model [C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C)]. The H atoms of the solvent water molecules were located in difference Fourier maps; their positions were geometrically optimized and they were constrained to ride on their parent atoms, with O—H = 0.85 Å and U_iso(H) = 1.2U_eq(O). The H atoms of the coordinated aqua molecules were refined isotropically, with O—H distance restraints of 0.96 Å, and they were constrained to ride on their parent atoms with U_iso(H) = 1.5U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the one-dimensional infinite structure of (I). H atoms have been omitted for clarity. [Symmetry codes: (vii) x, -y + 1/2, z + 1/2; (xi) x, -y + 1/2, z - 1/2.]
	Fig. 3. A perspective view of the two-dimensional supramolecular structure of (I), incorporating π–π interactions (dashed lines?).
	Fig. 4. A perspective view of the three-dimensional supramolecular structure of (I), incorporating hydrogen bonds (dashed lines?).
	Fig. 5. The temperature dependence of the χMT product for (I) at 100 Oe.
	Fig. 6. A plot of magnetization versus applied magnetic field for (I) at 1.8 K.

Poly[[aquadi-µ-cyanido-κ⁴C:N-hexacyanido-κ⁶C-(dimethylformamide-κO)bis(3,4,7,8-tetramethyl-1,10-phenanthroline-κ²N,N')terbium(III)molybdate(V)] 4.5-hydrate]

Crystal data

[MoTb(CN)8(C16H16N2)2(C3H7NO)(H2O)]·4.5H2O	F(000) = 2232
Mr = 2215.63	Dx = 1.554 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.7649 (14) Å	Cell parameters from 4723 reflections
b = 13.474 (2) Å	θ = 2.2–23.1°
c = 21.0984 (12) Å	µ = 1.81 mm^−1
β = 96.671 (3)°	T = 291 K
V = 4733.7 (9) Å^3	Block, red
Z = 2	0.20 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	6573 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.031
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θmax = 26.0°, θmin = 2.1°
Tmin = 0.70, Tmax = 0.77	h = −20→12
25037 measured reflections	k = −16→16
9290 independent reflections	l = −26→25

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.062	H-atom parameters constrained
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.07P)^2 + 1.22P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
9290 reflections	Δρmax = 1.11 e Å^−3
569 parameters	Δρmin = −0.88 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7597 (4)	0.6872 (5)	0.3781 (3)	0.0376 (17)
C2	0.7616 (4)	0.6188 (5)	0.1895 (3)	0.0341 (16)
C3	0.7923 (5)	0.7613 (6)	0.2703 (3)	0.045 (2)
C4	0.6578 (5)	0.6779 (5)	0.2650 (3)	0.0395 (17)
C5	0.6779 (5)	0.5179 (6)	0.3258 (4)	0.052 (2)
C6	0.7985 (5)	0.4675 (6)	0.2541 (3)	0.0420 (18)
C7	0.8296 (5)	0.5272 (6)	0.3715 (4)	0.049 (2)
C8	0.8962 (5)	0.6255 (6)	0.2848 (4)	0.049 (2)
C9	0.7185 (5)	1.0845 (5)	0.5637 (3)	0.0415 (18)
H9	0.7586	1.0687	0.5964	0.050*
C10	0.7031 (6)	1.1845 (6)	0.5518 (4)	0.055 (2)
C11	0.7548 (6)	1.2625 (6)	0.5894 (4)	0.065 (3)
H11A	0.7214	1.3161	0.6006	0.098*
H11B	0.7941	1.2875	0.5638	0.098*
H11C	0.7816	1.2331	0.6276	0.098*
C12	0.6429 (6)	1.2089 (6)	0.5041 (4)	0.059 (2)
C13	0.6247 (6)	1.3213 (6)	0.4880 (5)	0.074 (3)
H13D	0.6729	1.3595	0.4977	0.111*
H13E	0.5843	1.3451	0.5131	0.111*
H13F	0.6057	1.3279	0.4435	0.111*
C14	0.5958 (3)	1.1301 (3)	0.4709 (2)	0.054 (2)
C15	0.6184 (3)	1.0327 (4)	0.4853 (2)	0.0423 (19)
C16	0.5784 (3)	0.9548 (3)	0.4522 (2)	0.0465 (19)
C17	0.5158 (3)	0.9743 (4)	0.4046 (2)	0.048 (2)
C18	0.4932 (3)	1.0717 (4)	0.3902 (2)	0.060 (2)
H17	0.4514	1.0848	0.3584	0.072*
C19	0.5332 (3)	1.1496 (3)	0.4234 (3)	0.062 (3)
H16	0.5181	1.2148	0.4137	0.074*
C20	0.4777 (5)	0.8926 (6)	0.3709 (3)	0.0445 (19)
C21	0.4096 (5)	0.9081 (7)	0.3170 (4)	0.062 (2)
H21A	0.3676	0.8609	0.3213	0.093*
H21B	0.4297	0.8988	0.2766	0.093*
H21C	0.3887	0.9741	0.3194	0.093*
C22	0.5061 (5)	0.7972 (7)	0.3863 (4)	0.055 (2)
C23	0.4685 (5)	0.7037 (7)	0.3551 (4)	0.063 (3)
H23A	0.4630	0.7111	0.3096	0.094*
H23B	0.4166	0.6934	0.3689	0.094*
H23C	0.5023	0.6477	0.3672	0.094*
C24	0.5680 (4)	0.7902 (7)	0.4324 (4)	0.050 (2)
H24	0.5852	0.7260	0.4429	0.060*
C25	0.9239 (5)	0.9612 (7)	0.5823 (4)	0.051 (2)
H25	0.9298	0.9036	0.6068	0.061*
C26	0.9741 (5)	1.0422 (7)	0.6013 (4)	0.055 (2)
C27	1.0302 (5)	1.0268 (7)	0.6627 (4)	0.071 (3)
H27A	1.0208	1.0777	0.6928	0.107*
H27B	1.0849	1.0301	0.6536	0.107*
H27C	1.0202	0.9630	0.6804	0.107*
C28	0.9700 (5)	1.1246 (7)	0.5622 (4)	0.060 (3)
C29	1.0257 (6)	1.2144 (7)	0.5801 (5)	0.079 (3)
H29A	1.0675	1.1951	0.6128	0.119*
H29B	0.9950	1.2675	0.5955	0.119*
H29C	1.0491	1.2362	0.5431	0.119*
C30	0.8663 (3)	1.0416 (3)	0.4909 (2)	0.0446 (19)
C31	0.9120 (3)	1.1263 (4)	0.5058 (2)	0.053 (2)
C32	0.8999 (3)	1.2106 (3)	0.4680 (3)	0.064 (3)
H32	0.9305	1.2672	0.4779	0.077*
C33	0.8420 (4)	1.2102 (3)	0.4152 (3)	0.064 (3)
H33	0.8338	1.2666	0.3898	0.077*
C34	0.7962 (3)	1.1256 (4)	0.4002 (2)	0.049 (2)
C35	0.8084 (3)	1.0413 (3)	0.4381 (2)	0.0420 (18)
C36	0.7351 (6)	1.1207 (7)	0.3469 (4)	0.057 (2)
C37	0.7117 (6)	1.2154 (8)	0.3067 (5)	0.082 (3)
H37A	0.6560	1.2301	0.3085	0.123*
H37B	0.7208	1.2042	0.2632	0.123*
H37C	0.7439	1.2703	0.3237	0.123*
C38	0.6956 (5)	1.0353 (7)	0.3310 (4)	0.054 (2)
C39	0.6314 (6)	1.0211 (7)	0.2751 (4)	0.062 (2)
H39A	0.6466	1.0558	0.2386	0.093*
H39B	0.5813	1.0469	0.2859	0.093*
H39C	0.6257	0.9517	0.2655	0.093*
C40	0.7172 (5)	0.9544 (6)	0.3704 (3)	0.049 (2)
H40	0.6948	0.8935	0.3575	0.059*
C41	0.8720 (6)	0.6491 (7)	0.5475 (5)	0.069 (3)
H41	0.8484	0.6151	0.5118	0.082*
C42	0.9583 (6)	0.6448 (7)	0.6483 (4)	0.073 (3)
H42A	0.9431	0.7134	0.6490	0.110*
H42B	1.0157	0.6398	0.6501	0.110*
H42C	0.9407	0.6112	0.6843	0.110*
C43	0.9293 (6)	0.4919 (6)	0.5768 (5)	0.074 (3)
H43A	0.8850	0.4717	0.5465	0.112*
H43B	0.9288	0.4544	0.6154	0.112*
H43C	0.9788	0.4800	0.5592	0.112*
Mo1	0.77105 (4)	0.60957 (4)	0.29208 (3)	0.02978 (16)
N1	0.7530 (4)	0.7315 (4)	0.4265 (3)	0.0429 (16)
N2	0.7589 (4)	0.6243 (5)	0.1350 (3)	0.0436 (16)
N3	0.8053 (5)	0.8455 (5)	0.2599 (4)	0.064 (2)
N4	0.5963 (5)	0.7187 (6)	0.2467 (4)	0.071 (2)
N5	0.6272 (5)	0.4722 (6)	0.3436 (4)	0.077 (2)
N6	0.8143 (5)	0.3910 (5)	0.2339 (3)	0.0556 (19)
N7	0.8610 (5)	0.4816 (6)	0.4114 (3)	0.068 (2)
N8	0.9633 (4)	0.6366 (6)	0.2774 (4)	0.062 (2)
N9	0.6815 (4)	1.0106 (4)	0.5327 (3)	0.0394 (15)
N10	0.6078 (4)	0.8610 (5)	0.4649 (3)	0.0464 (16)
N11	0.8680 (4)	0.9616 (5)	0.5311 (3)	0.0423 (15)
N12	0.7665 (4)	0.9552 (4)	0.4245 (3)	0.0393 (14)
N13	0.9220 (5)	0.6001 (6)	0.5909 (4)	0.068 (2)
O1	0.8558 (4)	0.7406 (4)	0.5537 (2)	0.0524 (15)
O2	0.6790 (4)	0.7108 (4)	0.5567 (3)	0.0645 (17)
H2X	0.7077	0.7048	0.5925	0.077*
H2Y	0.6712	0.6554	0.5378	0.077*
O3	0.1219 (4)	0.6876 (5)	0.2650 (3)	0.079 (2)
H3X	0.1336	0.7479	0.2663	0.095*
H3Y	0.0727	0.6797	0.2694	0.095*
O4	0.2075 (4)	0.5282 (5)	0.3129 (3)	0.078 (2)
H4X	0.1983	0.4709	0.2968	0.093*
H4Y	0.1811	0.5770	0.2957	0.093*
O5	0.5351 (4)	0.6232 (5)	0.6495 (3)	0.084 (2)
H5X	0.5478	0.6672	0.6777	0.100*
H5Y	0.4888	0.6009	0.6544	0.100*
O6	0.3524 (5)	0.4536 (5)	0.4079 (3)	0.091 (2)
H6X	0.3144	0.4714	0.3801	0.109*
H6Y	0.3891	0.4272	0.3889	0.109*
O7	0.5000	0.0000	1.0000	0.092 (3)
H7X	0.4900	0.0462	0.9728	0.111*	0.5
H7Y	0.5501	−0.0119	1.0048	0.111*	0.5
Tb1	0.75075 (2)	0.84437 (2)	0.51854 (2)	0.03251 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.040 (4)	0.028 (3)	0.044 (4)	0.007 (3)	0.003 (3)	−0.007 (3)
C2	0.043 (4)	0.036 (4)	0.024 (3)	0.005 (3)	0.008 (3)	−0.014 (3)
C3	0.063 (5)	0.053 (5)	0.022 (3)	0.009 (4)	0.013 (4)	−0.016 (3)
C4	0.041 (4)	0.044 (4)	0.034 (4)	0.009 (4)	0.006 (3)	−0.009 (3)
C5	0.058 (5)	0.051 (5)	0.055 (5)	−0.016 (4)	0.033 (4)	−0.020 (4)
C6	0.047 (5)	0.042 (4)	0.039 (4)	0.002 (4)	0.013 (4)	−0.002 (3)
C7	0.052 (5)	0.055 (5)	0.039 (4)	0.039 (4)	0.003 (4)	0.005 (4)
C8	0.044 (5)	0.052 (5)	0.050 (5)	0.005 (4)	−0.002 (4)	−0.012 (4)
C9	0.058 (5)	0.038 (4)	0.030 (4)	0.008 (4)	0.012 (4)	0.001 (3)
C10	0.068 (6)	0.041 (5)	0.058 (5)	0.012 (4)	0.017 (5)	0.010 (4)
C11	0.093 (8)	0.040 (5)	0.065 (6)	−0.004 (5)	0.021 (6)	−0.012 (4)
C12	0.085 (7)	0.047 (5)	0.044 (5)	0.017 (5)	0.005 (5)	0.006 (4)
C13	0.083 (7)	0.048 (5)	0.084 (7)	0.029 (5)	−0.024 (6)	0.014 (5)
C14	0.060 (6)	0.057 (5)	0.042 (4)	0.024 (4)	−0.004 (4)	−0.007 (4)
C15	0.052 (5)	0.057 (5)	0.020 (3)	0.019 (4)	0.014 (3)	0.005 (3)
C16	0.036 (4)	0.065 (5)	0.037 (4)	0.002 (4)	−0.001 (3)	−0.003 (4)
C17	0.035 (4)	0.079 (6)	0.027 (4)	0.007 (4)	−0.005 (3)	0.006 (4)
C18	0.054 (5)	0.084 (7)	0.040 (5)	0.012 (5)	−0.006 (4)	0.024 (5)
C19	0.074 (7)	0.063 (6)	0.049 (5)	0.031 (5)	0.012 (5)	0.015 (4)
C20	0.038 (4)	0.069 (6)	0.029 (4)	0.014 (4)	0.012 (3)	−0.011 (4)
C21	0.049 (5)	0.078 (6)	0.053 (5)	−0.001 (5)	−0.021 (4)	−0.002 (5)
C22	0.040 (5)	0.083 (7)	0.042 (5)	−0.013 (5)	0.003 (4)	−0.018 (5)
C23	0.054 (5)	0.084 (6)	0.047 (5)	−0.003 (5)	−0.011 (4)	−0.034 (5)
C24	0.031 (4)	0.068 (6)	0.048 (5)	−0.011 (4)	−0.001 (4)	−0.022 (4)
C25	0.041 (5)	0.066 (5)	0.044 (5)	−0.013 (4)	0.003 (4)	−0.009 (4)
C26	0.035 (4)	0.087 (7)	0.048 (5)	−0.020 (5)	0.017 (4)	−0.021 (5)
C27	0.043 (5)	0.092 (7)	0.075 (6)	−0.026 (5)	−0.005 (5)	0.006 (6)
C28	0.052 (5)	0.078 (6)	0.057 (5)	−0.034 (5)	0.033 (5)	−0.040 (5)
C29	0.074 (7)	0.077 (7)	0.088 (7)	−0.039 (6)	0.018 (6)	−0.040 (6)
C30	0.038 (4)	0.056 (5)	0.042 (4)	0.004 (4)	0.014 (4)	−0.015 (4)
C31	0.049 (5)	0.057 (5)	0.057 (5)	−0.012 (4)	0.024 (4)	−0.016 (4)
C32	0.066 (6)	0.058 (6)	0.073 (6)	−0.034 (5)	0.026 (5)	−0.002 (5)
C33	0.073 (7)	0.051 (5)	0.077 (6)	−0.007 (5)	0.042 (6)	0.016 (5)
C34	0.063 (6)	0.053 (5)	0.031 (4)	−0.009 (4)	0.015 (4)	−0.003 (4)
C35	0.061 (5)	0.039 (4)	0.029 (4)	0.009 (4)	0.018 (4)	0.007 (3)
C36	0.068 (6)	0.064 (6)	0.045 (5)	0.026 (5)	0.025 (5)	0.016 (4)
C37	0.080 (8)	0.082 (7)	0.086 (7)	0.020 (6)	0.014 (6)	0.028 (6)
C38	0.059 (6)	0.063 (6)	0.039 (4)	0.006 (5)	−0.001 (4)	0.013 (4)
C39	0.068 (6)	0.073 (6)	0.042 (5)	0.007 (5)	−0.003 (4)	0.016 (4)
C40	0.076 (6)	0.051 (5)	0.022 (3)	0.000 (4)	0.012 (4)	−0.001 (3)
C41	0.072 (7)	0.070 (7)	0.059 (6)	0.000 (6)	−0.013 (5)	−0.009 (5)
C42	0.074 (7)	0.080 (7)	0.061 (6)	−0.014 (6)	−0.012 (5)	0.003 (5)
C43	0.079 (7)	0.059 (6)	0.084 (7)	0.028 (6)	0.001 (6)	0.024 (5)
Mo1	0.0352 (3)	0.0324 (3)	0.0211 (3)	0.0016 (3)	0.0008 (2)	−0.0021 (2)
N1	0.057 (4)	0.030 (3)	0.038 (3)	0.009 (3)	−0.014 (3)	−0.011 (3)
N2	0.048 (4)	0.048 (4)	0.032 (3)	0.001 (3)	−0.007 (3)	0.004 (3)
N3	0.081 (6)	0.041 (4)	0.073 (5)	−0.016 (4)	0.025 (5)	−0.002 (4)
N4	0.059 (5)	0.082 (6)	0.074 (5)	0.026 (5)	0.013 (4)	0.010 (4)
N5	0.078 (6)	0.080 (6)	0.079 (6)	−0.021 (5)	0.033 (5)	0.019 (5)
N6	0.068 (5)	0.048 (4)	0.054 (4)	0.011 (4)	0.019 (4)	−0.015 (3)
N7	0.073 (5)	0.070 (5)	0.057 (4)	0.035 (4)	−0.013 (4)	0.010 (4)
N8	0.039 (4)	0.071 (5)	0.079 (5)	−0.018 (4)	0.019 (4)	−0.016 (4)
N9	0.047 (4)	0.037 (3)	0.034 (3)	0.015 (3)	0.005 (3)	−0.002 (3)
N10	0.041 (4)	0.053 (4)	0.043 (4)	−0.011 (3)	−0.002 (3)	−0.004 (3)
N11	0.038 (4)	0.052 (4)	0.036 (3)	−0.008 (3)	−0.001 (3)	−0.007 (3)
N12	0.038 (4)	0.034 (3)	0.044 (4)	0.009 (3)	−0.001 (3)	0.000 (3)
N13	0.068 (5)	0.066 (5)	0.068 (5)	−0.001 (4)	−0.004 (4)	0.002 (4)
O1	0.075 (4)	0.049 (3)	0.031 (3)	0.018 (3)	−0.007 (3)	0.002 (2)
O2	0.095 (5)	0.053 (4)	0.044 (3)	−0.014 (4)	0.003 (3)	0.002 (3)
O3	0.062 (4)	0.086 (5)	0.094 (5)	−0.021 (4)	0.026 (4)	−0.014 (4)
O4	0.074 (5)	0.077 (5)	0.085 (5)	−0.008 (4)	0.018 (4)	0.012 (4)
O5	0.075 (5)	0.092 (5)	0.074 (5)	−0.017 (4)	−0.032 (4)	0.018 (4)
O6	0.095 (6)	0.086 (5)	0.096 (5)	−0.025 (4)	0.032 (5)	0.014 (4)
O7	0.083 (7)	0.103 (8)	0.094 (7)	−0.015 (6)	0.028 (6)	−0.025 (6)
Tb1	0.0405 (2)	0.03430 (19)	0.02140 (17)	0.00310 (16)	−0.00188 (13)	−0.00136 (14)

Geometric parameters (Å, º)

C1—N1	1.198 (8)	C28—C31	1.447 (10)
C1—Mo1	2.123 (7)	C28—C29	1.547 (11)
C2—N2	1.147 (8)	C29—H29A	0.9600
C2—Mo1	2.156 (7)	C29—H29B	0.9600
C3—N3	1.181 (9)	C29—H29C	0.9600
C3—Mo1	2.134 (9)	C30—N11	1.370 (7)
C4—N4	1.194 (10)	C30—C31	1.3900
C4—Mo1	2.127 (8)	C30—C35	1.3900
C5—N5	1.147 (10)	C31—C32	1.3900
C5—Mo1	2.175 (8)	C32—C33	1.3900
C6—N6	1.157 (9)	C32—H32	0.9300
C6—Mo1	2.146 (8)	C33—C34	1.3900
C7—N7	1.123 (9)	C33—H33	0.9300
C7—Mo1	2.149 (7)	C34—C35	1.3900
C8—N8	1.163 (10)	C34—C36	1.432 (10)
C8—Mo1	2.133 (9)	C35—N12	1.369 (7)
C9—N9	1.307 (9)	C36—C38	1.350 (12)
C9—C10	1.390 (10)	C36—C37	1.557 (12)
C9—H9	0.9300	C37—H37A	0.9600
C10—C12	1.380 (11)	C37—H37B	0.9600
C10—C11	1.526 (12)	C37—H37C	0.9600
C11—H11A	0.9600	C38—C40	1.393 (11)
C11—H11B	0.9600	C38—C39	1.513 (11)
C11—H11C	0.9600	C39—H39A	0.9600
C12—C14	1.453 (10)	C39—H39B	0.9600
C12—C13	1.574 (11)	C39—H39C	0.9600
C13—H13D	0.9600	C40—N12	1.329 (9)
C13—H13E	0.9600	C40—H40	0.9300
C13—H13F	0.9600	C41—O1	1.272 (10)
C14—C15	1.3900	C41—N13	1.341 (11)
C14—C19	1.3900	C41—H41	0.9300
C15—C16	1.3900	C42—N13	1.423 (11)
C15—N9	1.400 (7)	C42—H42A	0.9600
C16—N10	1.371 (7)	C42—H42B	0.9600
C16—C17	1.3900	C42—H42C	0.9600
C17—C18	1.3900	C43—N13	1.497 (11)
C17—C20	1.422 (9)	C43—H43A	0.9600
C18—C19	1.3900	C43—H43B	0.9600
C18—H17	0.9300	C43—H43C	0.9600
C19—H16	0.9300	N1—Tb1	2.470 (6)
C20—C22	1.396 (12)	N2—Tb1^i	2.481 (6)
C20—C21	1.529 (10)	N9—Tb1	2.556 (6)
C21—H21A	0.9600	N10—Tb1	2.539 (6)
C21—H21B	0.9600	N11—Tb1	2.512 (6)
C21—H21C	0.9600	N12—Tb1	2.522 (6)
C22—C24	1.341 (10)	O1—Tb1	2.304 (5)
C22—C23	1.523 (11)	O2—Tb1	2.358 (6)
C23—H23A	0.9600	O2—H2X	0.8507
C23—H23B	0.9600	O2—H2Y	0.8502
C23—H23C	0.9600	O3—H3X	0.8360
C24—N10	1.311 (9)	O3—H3Y	0.8468
C24—H24	0.9300	O4—H4X	0.8498
C25—N11	1.346 (9)	O4—H4Y	0.8503
C25—C26	1.407 (11)	O5—H5X	0.8499
C25—H25	0.9300	O5—H5Y	0.8500
C26—C28	1.381 (13)	O6—H6X	0.8498
C26—C27	1.524 (12)	O6—H6Y	0.8499
C27—H27A	0.9600	O7—H7X	0.8500
C27—H27B	0.9600	O7—H7Y	0.8501
C27—H27C	0.9600	Tb1—N2^ii	2.481 (6)
N1—C1—Mo1	179.6 (7)	C36—C37—H37C	109.5
N2—C2—Mo1	178.0 (7)	H37A—C37—H37C	109.5
N3—C3—Mo1	178.1 (7)	H37B—C37—H37C	109.5
N4—C4—Mo1	176.0 (7)	C36—C38—C40	115.6 (8)
N5—C5—Mo1	177.8 (8)	C36—C38—C39	125.8 (8)
N6—C6—Mo1	179.1 (8)	C40—C38—C39	118.5 (8)
N7—C7—Mo1	177.4 (7)	C38—C39—H39A	109.5
N8—C8—Mo1	176.1 (8)	C38—C39—H39B	109.5
N9—C9—C10	125.5 (8)	H39A—C39—H39B	109.5
N9—C9—H9	117.3	C38—C39—H39C	109.5
C10—C9—H9	117.3	H39A—C39—H39C	109.5
C12—C10—C9	117.9 (8)	H39B—C39—H39C	109.5
C12—C10—C11	122.6 (8)	N12—C40—C38	126.8 (8)
C9—C10—C11	119.4 (8)	N12—C40—H40	116.6
C10—C11—H11A	109.5	C38—C40—H40	116.6
C10—C11—H11B	109.5	O1—C41—N13	122.0 (8)
H11A—C11—H11B	109.5	O1—C41—H41	119.0
C10—C11—H11C	109.5	N13—C41—H41	119.0
H11A—C11—H11C	109.5	N13—C42—H42A	109.5
H11B—C11—H11C	109.5	N13—C42—H42B	109.5
C10—C12—C14	119.2 (7)	H42A—C42—H42B	109.5
C10—C12—C13	119.6 (8)	N13—C42—H42C	109.5
C14—C12—C13	121.2 (7)	H42A—C42—H42C	109.5
C12—C13—H13D	109.5	H42B—C42—H42C	109.5
C12—C13—H13E	109.5	N13—C43—H43A	109.5
H13D—C13—H13E	109.5	N13—C43—H43B	109.5
C12—C13—H13F	109.5	H43A—C43—H43B	109.5
H13D—C13—H13F	109.5	N13—C43—H43C	109.5
H13E—C13—H13F	109.5	H43A—C43—H43C	109.5
C15—C14—C19	120.0	H43B—C43—H43C	109.5
C15—C14—C12	117.8 (5)	C1—Mo1—C4	81.4 (3)
C19—C14—C12	122.1 (5)	C1—Mo1—C8	101.5 (3)
C14—C15—C16	120.0	C4—Mo1—C8	142.3 (3)
C14—C15—N9	121.4 (4)	C1—Mo1—C3	75.3 (3)
C16—C15—N9	118.6 (4)	C4—Mo1—C3	72.2 (3)
N10—C16—C17	122.6 (4)	C8—Mo1—C3	72.4 (3)
N10—C16—C15	117.1 (4)	C1—Mo1—C6	143.5 (3)
C17—C16—C15	120.0	C4—Mo1—C6	120.6 (3)
C16—C17—C18	120.0	C8—Mo1—C6	78.9 (3)
C16—C17—C20	118.2 (5)	C3—Mo1—C6	136.5 (3)
C18—C17—C20	121.8 (5)	C1—Mo1—C7	70.5 (3)
C19—C18—C17	120.0	C4—Mo1—C7	138.2 (3)
C19—C18—H17	120.0	C8—Mo1—C7	75.2 (3)
C17—C18—H17	120.0	C3—Mo1—C7	126.2 (3)
C18—C19—C14	120.0	C6—Mo1—C7	74.5 (3)
C18—C19—H16	120.0	C1—Mo1—C2	145.8 (3)
C14—C19—H16	120.0	C4—Mo1—C2	75.3 (3)
C22—C20—C17	118.3 (7)	C8—Mo1—C2	83.1 (3)
C22—C20—C21	120.3 (7)	C3—Mo1—C2	73.9 (3)
C17—C20—C21	121.3 (7)	C6—Mo1—C2	70.8 (3)
C20—C21—H21A	109.5	C7—Mo1—C2	141.8 (3)
C20—C21—H21B	109.5	C1—Mo1—C5	82.0 (3)
H21A—C21—H21B	109.5	C4—Mo1—C5	71.4 (3)
C20—C21—H21C	109.5	C8—Mo1—C5	146.2 (3)
H21A—C21—H21C	109.5	C3—Mo1—C5	139.4 (3)
H21B—C21—H21C	109.5	C6—Mo1—C5	79.0 (3)
C24—C22—C20	116.6 (8)	C7—Mo1—C5	74.5 (3)
C24—C22—C23	120.1 (9)	C2—Mo1—C5	112.9 (3)
C20—C22—C23	123.2 (7)	C1—N1—Tb1	170.9 (6)
C22—C23—H23A	109.5	C2—N2—Tb1^i	173.9 (6)
C22—C23—H23B	109.5	C9—N9—C15	118.1 (6)
H23A—C23—H23B	109.5	C9—N9—Tb1	122.0 (5)
C22—C23—H23C	109.5	C15—N9—Tb1	114.8 (4)
H23A—C23—H23C	109.5	C24—N10—C16	114.8 (6)
H23B—C23—H23C	109.5	C24—N10—Tb1	124.4 (6)
N10—C24—C22	129.1 (9)	C16—N10—Tb1	117.9 (4)
N10—C24—H24	115.4	C25—N11—C30	117.6 (6)
C22—C24—H24	115.4	C25—N11—Tb1	123.1 (5)
N11—C25—C26	124.3 (8)	C30—N11—Tb1	118.0 (4)
N11—C25—H25	117.9	C40—N12—C35	116.1 (6)
C26—C25—H25	117.9	C40—N12—Tb1	124.1 (5)
C28—C26—C25	117.9 (8)	C35—N12—Tb1	115.7 (4)
C28—C26—C27	126.8 (8)	C41—N13—C42	123.0 (8)
C25—C26—C27	115.3 (9)	C41—N13—C43	113.7 (8)
C26—C27—H27A	109.5	C42—N13—C43	123.0 (8)
C26—C27—H27B	109.5	C41—O1—Tb1	136.0 (6)
H27A—C27—H27B	109.5	Tb1—O2—H2X	96.7
C26—C27—H27C	109.5	Tb1—O2—H2Y	124.4
H27A—C27—H27C	109.5	H2X—O2—H2Y	112.0
H27B—C27—H27C	109.5	H3X—O3—H3Y	110.3
C26—C28—C31	119.1 (7)	H4X—O4—H4Y	118.1
C26—C28—C29	119.8 (9)	H5X—O5—H5Y	108.6
C31—C28—C29	121.1 (9)	H6X—O6—H6Y	108.6
C28—C29—H29A	109.5	H7X—O7—H7Y	109.5
C28—C29—H29B	109.5	O1—Tb1—O2	80.1 (2)
H29A—C29—H29B	109.5	O1—Tb1—N1	78.37 (18)
C28—C29—H29C	109.5	O2—Tb1—N1	81.6 (2)
H29A—C29—H29C	109.5	O1—Tb1—N2^ii	80.33 (19)
H29B—C29—H29C	109.5	O2—Tb1—N2^ii	76.3 (2)
N11—C30—C31	122.3 (4)	N1—Tb1—N2^ii	151.5 (2)
N11—C30—C35	117.1 (4)	O1—Tb1—N11	77.8 (2)
C31—C30—C35	120.0	O2—Tb1—N11	150.2 (2)
C30—C31—C32	120.0	N1—Tb1—N11	112.7 (2)
C30—C31—C28	118.3 (5)	N2^ii—Tb1—N11	80.6 (2)
C32—C31—C28	121.7 (5)	O1—Tb1—N12	117.8 (2)
C33—C32—C31	120.0	O2—Tb1—N12	145.59 (19)
C33—C32—H32	120.0	N1—Tb1—N12	74.5 (2)
C31—C32—H32	120.0	N2^ii—Tb1—N12	132.85 (19)
C34—C33—C32	120.0	N11—Tb1—N12	63.81 (19)
C34—C33—H33	120.0	O1—Tb1—N10	147.6 (2)
C32—C33—H33	120.0	O2—Tb1—N10	74.2 (2)
C33—C34—C35	120.0	N1—Tb1—N10	78.7 (2)
C33—C34—C36	122.7 (5)	N2^ii—Tb1—N10	111.6 (2)
C35—C34—C36	117.3 (5)	N11—Tb1—N10	132.7 (2)
N12—C35—C34	122.3 (4)	N12—Tb1—N10	77.1 (2)
N12—C35—C30	117.7 (4)	O1—Tb1—N9	146.63 (19)
C34—C35—C30	120.0	O2—Tb1—N9	111.9 (2)
C38—C36—C34	121.3 (7)	N1—Tb1—N9	132.82 (18)
C38—C36—C37	118.5 (8)	N2^ii—Tb1—N9	73.10 (19)
C34—C36—C37	120.1 (9)	N11—Tb1—N9	78.3 (2)
C36—C37—H37A	109.5	N12—Tb1—N9	70.32 (19)
C36—C37—H37B	109.5	N10—Tb1—N9	63.7 (2)
H37A—C37—H37B	109.5
N9—C9—C10—C12	1.2 (12)	C30—C31—C32—C33	0.0
N9—C9—C10—C11	−176.3 (7)	C28—C31—C32—C33	−178.2 (6)
C9—C10—C12—C14	3.2 (12)	C31—C32—C33—C34	0.0
C11—C10—C12—C14	−179.4 (8)	C32—C33—C34—C35	0.0
C9—C10—C12—C13	−178.6 (8)	C32—C33—C34—C36	179.4 (6)
C11—C10—C12—C13	−1.3 (13)	C33—C34—C35—N12	−178.1 (5)
C10—C12—C14—C15	−5.3 (10)	C36—C34—C35—N12	2.4 (6)
C13—C12—C14—C15	176.5 (7)	C33—C34—C35—C30	0.0
C10—C12—C14—C19	178.7 (6)	C36—C34—C35—C30	−179.5 (6)
C13—C12—C14—C19	0.5 (11)	N11—C30—C35—N12	−10.4 (6)
C19—C14—C15—C16	0.0	C31—C30—C35—N12	178.2 (5)
C12—C14—C15—C16	−176.1 (6)	N11—C30—C35—C34	171.4 (5)
C19—C14—C15—N9	179.5 (5)	C31—C30—C35—C34	0.0
C12—C14—C15—N9	3.4 (6)	C33—C34—C36—C38	175.3 (6)
C14—C15—C16—N10	174.6 (5)	C35—C34—C36—C38	−5.2 (10)
N9—C15—C16—N10	−4.9 (6)	C33—C34—C36—C37	−6.1 (9)
C14—C15—C16—C17	0.0	C35—C34—C36—C37	173.4 (6)
N9—C15—C16—C17	−179.5 (5)	C34—C36—C38—C40	1.1 (12)
N10—C16—C17—C18	−174.3 (6)	C37—C36—C38—C40	−177.5 (8)
C15—C16—C17—C18	0.0	C34—C36—C38—C39	−178.7 (8)
N10—C16—C17—C20	4.2 (6)	C37—C36—C38—C39	2.6 (14)
C15—C16—C17—C20	178.6 (6)	C36—C38—C40—N12	6.8 (13)
C16—C17—C18—C19	0.0	C39—C38—C40—N12	−173.4 (8)
C20—C17—C18—C19	−178.5 (6)	C10—C9—N9—C15	−3.2 (11)
C17—C18—C19—C14	0.0	C10—C9—N9—Tb1	150.2 (6)
C15—C14—C19—C18	0.0	C14—C15—N9—C9	0.7 (8)
C12—C14—C19—C18	175.9 (6)	C16—C15—N9—C9	−179.8 (5)
C16—C17—C20—C22	−1.3 (8)	C14—C15—N9—Tb1	−154.5 (3)
C18—C17—C20—C22	177.3 (5)	C16—C15—N9—Tb1	25.0 (5)
C16—C17—C20—C21	−178.8 (6)	C22—C24—N10—C16	4.4 (12)
C18—C17—C20—C21	−0.2 (9)	C22—C24—N10—Tb1	−155.9 (7)
C17—C20—C22—C24	0.0 (11)	C17—C16—N10—C24	−5.5 (8)
C21—C20—C22—C24	177.5 (7)	C15—C16—N10—C24	180.0 (5)
C17—C20—C22—C23	177.9 (7)	C17—C16—N10—Tb1	156.1 (3)
C21—C20—C22—C23	−4.6 (12)	C15—C16—N10—Tb1	−18.4 (6)
C20—C22—C24—N10	−1.7 (13)	C26—C25—N11—C30	7.9 (11)
C23—C22—C24—N10	−179.7 (8)	C26—C25—N11—Tb1	−158.6 (6)
N11—C25—C26—C28	−5.2 (12)	C31—C30—N11—C25	−8.9 (8)
N11—C25—C26—C27	177.1 (8)	C35—C30—N11—C25	179.9 (5)
C25—C26—C28—C31	3.3 (12)	C31—C30—N11—Tb1	158.3 (3)
C27—C26—C28—C31	−179.4 (8)	C35—C30—N11—Tb1	−12.9 (6)
C25—C26—C28—C29	−178.3 (8)	C38—C40—N12—C35	−9.5 (12)
C27—C26—C28—C29	−1.0 (14)	C38—C40—N12—Tb1	146.6 (7)
N11—C30—C31—C32	−171.0 (6)	C34—C35—N12—C40	4.4 (8)
C35—C30—C31—C32	0.0	C30—C35—N12—C40	−173.8 (5)
N11—C30—C31—C28	7.3 (7)	C34—C35—N12—Tb1	−153.7 (3)
C35—C30—C31—C28	178.2 (6)	C30—C35—N12—Tb1	28.2 (5)
C26—C28—C31—C30	−4.3 (9)	O1—C41—N13—C42	2.6 (16)
C29—C28—C31—C30	177.2 (6)	O1—C41—N13—C43	176.7 (9)
C26—C28—C31—C32	173.8 (6)	N13—C41—O1—Tb1	−154.4 (7)
C29—C28—C31—C32	−4.6 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2Y···O6^iii	0.85	1.93	2.415 (8)	115
O3—H3X···N6^iv	0.84	2.12	2.942 (9)	169
O3—H3Y···N8^v	0.85	1.95	2.787 (9)	170
O4—H4X···N3^vi	0.85	2.07	2.897 (10)	165
O4—H4Y···O3	0.85	1.86	2.712 (10)	175
O5—H5X···N4^ii	0.85	2.21	3.050 (10)	173
O5—H5Y···N5^iii	0.85	2.18	3.028 (11)	172
O6—H6X···O4	0.85	2.28	3.131 (10)	174
O6—H6Y···O5^iii	0.85	1.72	2.573 (11)	179
O7—H7X···O6^vii	0.85	2.54	3.028 (8)	117
O7—H7Y···O6^viii	0.85	2.36	3.028 (8)	136

Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2; (v) x−1, y, z; (vi) −x+1, y−1/2, −z+1/2; (vii) x, −y+1/2, z+1/2; (viii) −x+1, y−1/2, −z+3/2.