A three-dimensional cyanide-bridged heterometallic coordination polymer: poly[[diaceto­nitrile­di­aqua­[[mu]₂-3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine-[kappa]⁴N¹,N⁶:N³,N⁴]tetra-[mu]-cyanido-tetracyanidodi­manganese(II)­molybdate(IV)] dihydrate]

A metal coordination polymer, {[Mn₂Mo(CN)₈(C₁₂H₈N₆)(CH₃CN)₂(H₂O)₂]·2H₂O}_n, has been synthesized by the reaction of Mn(ClO₄)₂·6H₂O with 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine (bptz) and (Bu₃N)₃[Mo(CN)₈] at room temperature. The polymer was characterized by IR spectroscopy, elemental analysis and X-ray diffraction, and the magnetic properties were also investigated. The X-ray diffraction analysis reveals that the compound is a new three-dimensional coordination polymer with a PtS-type network. Magnetic investigation shows anti­ferromagnetic coupling between adjacent Mn²⁺ cations.

S1. Introduction

The study of molecular magnets is a hot topic in the field of materials science because of their promising future applications. Cyanide is often employed as a bridging ligand between spin carriers, due to the fact that it can mediate a foreseeable magnetic coupling inter­action. Recently, cyanide-bridged bimetallic systems based on o­cta­cyano­metallates [M^IV(V)(CN)₈]^4-(3-) (M = Mo, W and Nb) have attracted great attention in the area of molecular magnetism because of their inter­esting and special properties (Dechambenoit & Long, 2011; Nowicka et al., 2012; Przychodzeń et al., 2006; Sieklucka et al., 2005, 2009, 2011). Compared with the widely investigated hexa­cyano­metallate, the o­cta­cyano­metallate building block is more versatile due to the greater number of spatial configurations which are possible [e.g. square anti­prism (D_4d), dodecahedron (D_2d) and bicapped trigonal prism (C_2v)], so that o­cta­cyano­metallate-based compounds show rich magnetic properties which range from low-dimensional magnets (SMMs and SCMs) to long-range ordered magnets (Freedman et al., 2006; Herrera et al., 2003; Kashiwagi et al., 2004; Lim et al., 2006; Podgajny et al., 2012; Song et al., 2003, 2005; Zhong et al., 2000). A variety of structures based on [M(CN)₈]^3-/4-, including zero-dimensional clusters, one-dimensional chains, two-dimensional networks and three-dimenisonal frameworks, have been successfully prepared (Liu et al., 2009; Nowicka et al., 2012). To the best of our knowledge, there are only a few examples based on [Mo(CN)₈]^3-/4- and Mn²⁺ cations which have been structurally and magnetically characterised so far (Kosaka et al., 2008; Larionova et al., 2004; Le Goff et al., 2004; Ma et al., 2008; Ma & Ren, 2009; Milon et al., 2007; Przychodzeń et al., 2004; Wang et al., 2010, 2014). To further understand the magnetic inter­action between Mo–Mn couples, it is necessary to investigate the magnetic properties of new Mo–Mn compounds. Herein, we describe the synthesis, crystal structure and magnetic properties of a new cyanide-bridged coordination polymer, {[Mn₂(bptz)(CH₃CN)₂(H₂O)₂{Mo(CN)₈}]·2H₂O}_n, (I), where bptz is 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine.

S2. Experimental

The reagent 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine (bptz) was purchased from Aldrich and used without further purification. (Bu₃N)₃[Mo(CN)₈] was prepared according to the literature (Bok et al., 1975). All other reagents were commercially available and used as received. The IR spectrum was obtained from a KBr disc on a VECTOR 22 spectrometer. Elemental analysis was 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.

S2.1. Synthesis and crystallization

To an aqueous solution (12 ml) of Mn(ClO₄)₂·6H₂O (0.0112 g, 0.0300 mmol) was added an aceto­nitrile solution (2 ml) of bptz (0.00350 g, 0.0150 mmol), followed by the addition of a CH₃CN solution (2 ml) of (Bu₃N)₃[Mo(CN)₈] (0.0187 g, 0.0200 mmol). The resulting orange solution was filtered and the orange filtrate was allowed to evaporate slowly in the dark at room temperature. Yellow crystals of (I) suitable for X-ray structure determination were obtained after one week (yield 23.1%, based on Mn). Analysis, calculated for C₂₄H₂₂Mn₂MoN₁₆O₄: C 35.84, N 27.86, H 2.76%; found: C 35.91, N 27.93, H 2.77%. Selected IR datum (KBr): 2112 cm^-1 (ν_CN).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were placed in geometrically idealized positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, or C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms. Water H atoms were located in a difference Fourier map. Their positions were geometrically optimized and they were constrained to ride on their parent atom, with U_iso(H) = 1.2U_eq(O).

S3. Results and discussion

Compound (I) crystallizes in the space group C2/c with an asymmetric unit consisting of half an [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ cation, half an [Mo(CN)₈]^4- anion and one solvent water molecule (Fig. 1). The geometry around the [Mo(CN)₈]^4- anion is a slightly distorted dodecahedron. Four cyanide ligands of each [Mo(CN)₈]^4- anion are connected by a nitro­gen bridge to four Mn atoms, while the other four cyanide ligands are terminal. The Mo—C bond lengths range between 2.116 (5) and 2.153 (5) Å and the C≡N bond lengths are within the range 1.146 (6)–1.168 (6) Å. The Mo–C≡N bonds are almost linear, with the Mo–C≡N angles varying from 176.9 (5) to 179.5 (4)°. These distances and angles are normal for [Mo(CN)₈]^4- anions. In the [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ cation, two Mn²⁺ cations are each chelated by two N atoms of the bridging bptz ligand in an anti orientation, and the two Mn²⁺ cations bridged by the tetra­zine ring are separated by 7.3110 (14) Å. Each Mn²⁺ cation lies in a distorted MnN₅O o­cta­hedral environment, which is provided by two N atoms from the bptz chelating ligand, two N atoms from two different [Mo(CN)₈]^4- anions, one N atom from a coordinated aceto­nitrile molecule and one O atom from a coordinated aqua molecule. The Mn—N_bptz distances are distributed in the range 2.284 (4)–2.315 (4) Å, the Mn—N_cyanide distances are in the range 2.135 (4)–2.177 (4)Å, and the Mn—N—C angles [154.1 (4)–162.0 (4)°] deviate somewhat from linearity. As displayed in Fig. 2, the [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ units are linked via cyanides to adjacent four-connected [Mo^IV(CN)₄(µ-CN)₄]^4- centres to form a three-dimensional structure.

From a topological viewpoint, if each Mn₂(bptz) unit is viewed as a simplified Mn₂ secondary building unit, then it connects to four [Mo(CN)₈]^4- anions, giving 4-connectivity, while each [Mo(CN)₈] unit links to four Mn₂ secondary building units (SBUs), also affording 4-connectivity, thus resulting in the overall 4,4-connected net. A calculation with the TOPOS software (Blatov et al., 2000) reveals a three-dimensional 4,4-connected net with 2-nodal 4²·8⁴ topology, which is classified as a PtS net (Fig. 3). To the best of our knowledge, this topology has never been reported before for an o­cta­cyano­metallate-based bimetallic compound. The unligated water molecules occupy a solvent-accessible incipient space comprising 2.8% of the unit-cell volume, according to PLATON (Spek, 2009). In addition, there are inter­molecular hydrogen bonds between the water molecules and cyanide ligands (Table 2) which further stabilize the three-dimensional architecture of (I).

Variable-temperature magnetic susceptibility measurements were performed on crystalline samples of (I) in the range 1.8–300 K, as shown in Fig. 4. The χ_MT products are almost constant (8.94–8.89 emu K mol^-1) from room temperature down to 65 K, close to the spin-only value of 8.75 emu K mol^-1 based on an Mn₂ unit with S_Mn = 5/2 and assuming g_Mn = 2, implying basic paramagnetic properties for (I). Below 10 K, χ_MT decreases sharply, reaching 7.14 emu K mol^-1 at 1.8 K, indicating weak anti­ferromagnetic coupling between Mn²⁺ cations mediated by [Mo^IV(CN)₈]^4- groups, while the shortest Mn^II···Mn^II distance across the [Mo^IV(CN)₈]^4- group is 7.3654 (15) Å. In the temperature range of 1.8–300 K, the magnetic susceptibility data of (I) are fitted with the Curie–Weiss law, affording a Curie constant of 9.01 emu K mol^-1 with a Weiss constant (θ) of -0.47 K. This small and negative Weiss constant confirms a weak anti­ferromagnetic exchange inter­action between adjacent Mn^II cations. Given this magnetic inter­action between Mn^II cations arising only from inter­molecular inter­actions [Rephrasing OK? Original text not clear], the molecular field approximation gives fitting results of g = 2.02 (3), zj' = -0.02 (6) cm^-1 and R = 7.3 × 10^-4, which further confirms a weak anti­ferromagnetic exchange inter­action between adjacent Mn²⁺ cations.

In summary, we have reported the synthesis, structure and magnetic characterization of a new three-dimensional cyano-bridged coordination polymer, {[Mn₂(bptz)(CH₃CN)₂(H₂O)₂{Mo(CN)₈}]·2H₂O}_n [bptz = 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine], which has a PtS-type network. Magnetic investigation shows anti­ferromagnetic coupling between adjacent Mn²⁺ cations.

Related literature

For related literature, see: Blatov et al. (2000); Bok et al. (1975); Dechambenoit & Long (2011); Freedman et al. (2006); Herrera et al. (2003); Kashiwagi et al. (2004); Kosaka et al. (2008); Larionova et al. (2004); Le Goff, Willemin, Coulon, Larionova, Donnadieu & Clérac (2004); Lim et al. (2006); Liu et al. (2009); Ma & Ren (2009); Ma et al. (2008); Milon et al. (2007); Nowicka et al. (2012); Podgajny et al. (2012); Przychodzeń et al. (2004, 2006); Sieklucka et al. (2005, 2009, 2011); Song et al. (2003, 2005); Spek (2009); Wang et al. (2010, 2014); Zhong et al. (2000).

Structure description

The study of molecular magnets is a hot topic in the field of materials science because of their promising future applications. Cyanide is often employed as a bridging ligand between spin carriers, due to the fact that it can mediate a foreseeable magnetic coupling inter­action. Recently, cyanide-bridged bimetallic systems based on o­cta­cyano­metallates [M^IV(V)(CN)₈]^4-(3-) (M = Mo, W and Nb) have attracted great attention in the area of molecular magnetism because of their inter­esting and special properties (Dechambenoit & Long, 2011; Nowicka et al., 2012; Przychodzeń et al., 2006; Sieklucka et al., 2005, 2009, 2011). Compared with the widely investigated hexa­cyano­metallate, the o­cta­cyano­metallate building block is more versatile due to the greater number of spatial configurations which are possible [e.g. square anti­prism (D_4d), dodecahedron (D_2d) and bicapped trigonal prism (C_2v)], so that o­cta­cyano­metallate-based compounds show rich magnetic properties which range from low-dimensional magnets (SMMs and SCMs) to long-range ordered magnets (Freedman et al., 2006; Herrera et al., 2003; Kashiwagi et al., 2004; Lim et al., 2006; Podgajny et al., 2012; Song et al., 2003, 2005; Zhong et al., 2000). A variety of structures based on [M(CN)₈]^3-/4-, including zero-dimensional clusters, one-dimensional chains, two-dimensional networks and three-dimenisonal frameworks, have been successfully prepared (Liu et al., 2009; Nowicka et al., 2012). To the best of our knowledge, there are only a few examples based on [Mo(CN)₈]^3-/4- and Mn²⁺ cations which have been structurally and magnetically characterised so far (Kosaka et al., 2008; Larionova et al., 2004; Le Goff et al., 2004; Ma et al., 2008; Ma & Ren, 2009; Milon et al., 2007; Przychodzeń et al., 2004; Wang et al., 2010, 2014). To further understand the magnetic inter­action between Mo–Mn couples, it is necessary to investigate the magnetic properties of new Mo–Mn compounds. Herein, we describe the synthesis, crystal structure and magnetic properties of a new cyanide-bridged coordination polymer, {[Mn₂(bptz)(CH₃CN)₂(H₂O)₂{Mo(CN)₈}]·2H₂O}_n, (I), where bptz is 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine.

The reagent 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine (bptz) was purchased from Aldrich and used without further purification. (Bu₃N)₃[Mo(CN)₈] was prepared according to the literature (Bok et al., 1975). All other reagents were commercially available and used as received. The IR spectrum was obtained from a KBr disc on a VECTOR 22 spectrometer. Elemental analysis was 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 space group C2/c with an asymmetric unit consisting of half an [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ cation, half an [Mo(CN)₈]^4- anion and one solvent water molecule (Fig. 1). The geometry around the [Mo(CN)₈]^4- anion is a slightly distorted dodecahedron. Four cyanide ligands of each [Mo(CN)₈]^4- anion are connected by a nitro­gen bridge to four Mn atoms, while the other four cyanide ligands are terminal. The Mo—C bond lengths range between 2.116 (5) and 2.153 (5) Å and the C≡N bond lengths are within the range 1.146 (6)–1.168 (6) Å. The Mo–C≡N bonds are almost linear, with the Mo–C≡N angles varying from 176.9 (5) to 179.5 (4)°. These distances and angles are normal for [Mo(CN)₈]^4- anions. In the [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ cation, two Mn²⁺ cations are each chelated by two N atoms of the bridging bptz ligand in an anti orientation, and the two Mn²⁺ cations bridged by the tetra­zine ring are separated by 7.3110 (14) Å. Each Mn²⁺ cation lies in a distorted MnN₅O o­cta­hedral environment, which is provided by two N atoms from the bptz chelating ligand, two N atoms from two different [Mo(CN)₈]^4- anions, one N atom from a coordinated aceto­nitrile molecule and one O atom from a coordinated aqua molecule. The Mn—N_bptz distances are distributed in the range 2.284 (4)–2.315 (4) Å, the Mn—N_cyanide distances are in the range 2.135 (4)–2.177 (4)Å, and the Mn—N—C angles [154.1 (4)–162.0 (4)°] deviate somewhat from linearity. As displayed in Fig. 2, the [Mn₂(bptz)(CH₃CN)₂(H₂O)₂]⁴⁺ units are linked via cyanides to adjacent four-connected [Mo^IV(CN)₄(µ-CN)₄]^4- centres to form a three-dimensional structure.

From a topological viewpoint, if each Mn₂(bptz) unit is viewed as a simplified Mn₂ secondary building unit, then it connects to four [Mo(CN)₈]^4- anions, giving 4-connectivity, while each [Mo(CN)₈] unit links to four Mn₂ secondary building units (SBUs), also affording 4-connectivity, thus resulting in the overall 4,4-connected net. A calculation with the TOPOS software (Blatov et al., 2000) reveals a three-dimensional 4,4-connected net with 2-nodal 4²·8⁴ topology, which is classified as a PtS net (Fig. 3). To the best of our knowledge, this topology has never been reported before for an o­cta­cyano­metallate-based bimetallic compound. The unligated water molecules occupy a solvent-accessible incipient space comprising 2.8% of the unit-cell volume, according to PLATON (Spek, 2009). In addition, there are inter­molecular hydrogen bonds between the water molecules and cyanide ligands (Table 2) which further stabilize the three-dimensional architecture of (I).

Variable-temperature magnetic susceptibility measurements were performed on crystalline samples of (I) in the range 1.8–300 K, as shown in Fig. 4. The χ_MT products are almost constant (8.94–8.89 emu K mol^-1) from room temperature down to 65 K, close to the spin-only value of 8.75 emu K mol^-1 based on an Mn₂ unit with S_Mn = 5/2 and assuming g_Mn = 2, implying basic paramagnetic properties for (I). Below 10 K, χ_MT decreases sharply, reaching 7.14 emu K mol^-1 at 1.8 K, indicating weak anti­ferromagnetic coupling between Mn²⁺ cations mediated by [Mo^IV(CN)₈]^4- groups, while the shortest Mn^II···Mn^II distance across the [Mo^IV(CN)₈]^4- group is 7.3654 (15) Å. In the temperature range of 1.8–300 K, the magnetic susceptibility data of (I) are fitted with the Curie–Weiss law, affording a Curie constant of 9.01 emu K mol^-1 with a Weiss constant (θ) of -0.47 K. This small and negative Weiss constant confirms a weak anti­ferromagnetic exchange inter­action between adjacent Mn^II cations. Given this magnetic inter­action between Mn^II cations arising only from inter­molecular inter­actions [Rephrasing OK? Original text not clear], the molecular field approximation gives fitting results of g = 2.02 (3), zj' = -0.02 (6) cm^-1 and R = 7.3 × 10^-4, which further confirms a weak anti­ferromagnetic exchange inter­action between adjacent Mn²⁺ cations.

In summary, we have reported the synthesis, structure and magnetic characterization of a new three-dimensional cyano-bridged coordination polymer, {[Mn₂(bptz)(CH₃CN)₂(H₂O)₂{Mo(CN)₈}]·2H₂O}_n [bptz = 3,6-bis­(pyridin-2-yl)-1,2,4,5-tetra­zine], which has a PtS-type network. Magnetic investigation shows anti­ferromagnetic coupling between adjacent Mn²⁺ cations.

For related literature, see: Blatov et al. (2000); Bok et al. (1975); Dechambenoit & Long (2011); Freedman et al. (2006); Herrera et al. (2003); Kashiwagi et al. (2004); Kosaka et al. (2008); Larionova et al. (2004); Le Goff, Willemin, Coulon, Larionova, Donnadieu & Clérac (2004); Lim et al. (2006); Liu et al. (2009); Ma & Ren (2009); Ma et al. (2008); Milon et al. (2007); Nowicka et al. (2012); Podgajny et al. (2012); Przychodzeń et al. (2004, 2006); Sieklucka et al. (2005, 2009, 2011); Song et al. (2003, 2005); Spek (2009); Wang et al. (2010, 2014); Zhong et al. (2000).

Synthesis and crystallization

To an aqueous solution (12 ml) of Mn(ClO₄)₂·6H₂O (0.0112 g, 0.0300 mmol) was added an aceto­nitrile solution (2 ml) of bptz (0.00350 g, 0.0150 mmol), followed by the addition of a CH₃CN solution (2 ml) of (Bu₃N)₃[Mo(CN)₈] (0.0187 g, 0.0200 mmol). The resulting orange solution was filtered and the orange filtrate was allowed to evaporate slowly in the dark at room temperature. Yellow crystals of (I) suitable for X-ray structure determination were obtained after one week (yield 23.1%, based on Mn). Analysis, calculated for C₂₄H₂₂Mn₂MoN₁₆O₄: C 35.84, N 27.86, H 2.76%; found: C 35.91, N 27.93, H 2.77%. Selected IR datum (KBr): 2112 cm^-1 (ν_CN).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were placed in geometrically idealized positions and treated using a riding-model approximation, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, or C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms. Water H atoms were located in a difference Fourier map. Their positions were geometrically optimized and they were constrained to ride on their parent atom, with U_iso(H) = 1.2U_eq(O).

Computing details

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

Figures

	Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the three-dimensional structure of (I).
	Fig. 3. A network perspective view of the 4,4-connected 2-nodal 4^2·8^4 topology in (I). Blue and red spheres represent the Mn2 SUB and the [Mo(CN)8]^4- anion, respectively.
	Fig. 4. A plot of χMT versus T for (I). The red solid line corresponds to the best fit to the data.

Poly[[diacetonitrilediaqua[µ₂-3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine-κ⁴N¹,N⁶:N³,N⁴]tetra-µ-cyanido-tetracyanidodimanganese(II)molybdate(IV)] dihydrate]

Crystal data

[Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2O	F(000) = 1608
Mr = 804.40	Dx = 1.658 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2729 reflections
a = 15.429 (2) Å	θ = 2.1–25.1°
b = 11.5947 (17) Å	µ = 1.21 mm^−1
c = 18.360 (3) Å	T = 293 K
β = 101.230 (3)°	Block, yellow
V = 3221.6 (8) Å^3	0.19 × 0.17 × 0.15 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3163 independent reflections
Radiation source: fine-focus sealed tube	2588 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −18→17
Tmin = 0.794, Tmax = 0.834	k = −14→8
8440 measured reflections	l = −19→22

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.131	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0779P)^2] where P = (Fo^2 + 2Fc^2)/3
3160 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.62 e Å^−3
0 restraints	Δρmin = −0.57 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
C1	0.8934 (3)	0.3483 (4)	0.2109 (2)	0.0282 (9)
C2	0.9654 (3)	0.3196 (4)	0.3447 (2)	0.0324 (10)
C3	0.9041 (3)	0.1232 (4)	0.2797 (2)	0.0351 (10)
C4	0.9293 (3)	0.1494 (4)	0.1528 (3)	0.0418 (12)
C5	0.6564 (4)	0.2297 (4)	0.1771 (3)	0.0463 (13)
H5	0.7142	0.2296	0.2037	0.056*
C6	0.6028 (3)	0.1392 (4)	0.1868 (3)	0.0456 (13)
H6	0.6240	0.0799	0.2195	0.055*
C7	0.5184 (3)	0.1370 (4)	0.1482 (3)	0.0470 (13)
H7	0.4804	0.0769	0.1541	0.056*
C8	0.4904 (4)	0.2274 (4)	0.0998 (3)	0.0467 (13)
H8	0.4336	0.2281	0.0712	0.056*
C9	0.5475 (3)	0.3149 (4)	0.0949 (3)	0.0349 (10)
C10	0.5221 (3)	0.4139 (4)	0.0432 (2)	0.0350 (10)
C11	0.7674 (4)	0.7462 (5)	0.1147 (3)	0.0499 (14)
C12	0.7702 (4)	0.8778 (4)	0.1190 (3)	0.0499 (13)
H12A	0.8298	0.9039	0.1218	0.075*
H12B	0.7493	0.9028	0.1624	0.075*
H12C	0.7331	0.9096	0.0755	0.075*
Mn1	0.71550 (4)	0.47689 (6)	0.12395 (4)	0.0323 (2)
Mo1	1.0000	0.23475 (4)	0.2500	0.01949 (16)
N1	0.8339 (3)	0.4082 (3)	0.1893 (2)	0.0376 (9)
N2	0.9463 (3)	0.3637 (4)	0.3951 (2)	0.0456 (10)
N3	0.8514 (3)	0.0618 (4)	0.2967 (2)	0.0457 (11)
N4	0.8888 (3)	0.1078 (4)	0.1002 (2)	0.0501 (11)
N5	0.6304 (2)	0.3178 (3)	0.1317 (2)	0.0359 (9)
N6	0.5801 (3)	0.4998 (3)	0.0449 (2)	0.0346 (9)
N7	0.5589 (2)	0.5866 (3)	0.0009 (2)	0.0368 (9)
N8	0.7644 (3)	0.6434 (4)	0.0971 (2)	0.0494 (11)
O1	0.7471 (2)	0.4036 (3)	0.02394 (18)	0.0453 (9)
H1B	0.7987	0.4175	0.0163	0.054*
H1A	0.7046	0.4121	−0.0128	0.054*
O2	0.9031 (2)	0.4621 (3)	−0.0005 (2)	0.0497 (9)
H2A	0.9339	0.4848	0.0405	0.060*
H2B	0.9060	0.5136	−0.0329	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.025 (2)	0.035 (2)	0.024 (2)	0.0045 (18)	0.0030 (17)	−0.0095 (18)
C2	0.028 (2)	0.040 (3)	0.028 (2)	0.0001 (19)	0.0016 (18)	−0.002 (2)
C3	0.033 (2)	0.032 (2)	0.034 (2)	−0.007 (2)	−0.0087 (19)	0.0007 (19)
C4	0.033 (3)	0.046 (3)	0.040 (3)	−0.001 (2)	−0.006 (2)	−0.006 (2)
C5	0.040 (3)	0.045 (3)	0.045 (3)	0.007 (2)	−0.013 (2)	0.017 (2)
C6	0.045 (3)	0.037 (3)	0.047 (3)	−0.004 (2)	−0.010 (2)	0.013 (2)
C7	0.049 (3)	0.041 (3)	0.047 (3)	−0.011 (2)	0.000 (2)	0.016 (2)
C8	0.045 (3)	0.042 (3)	0.048 (3)	−0.012 (2)	−0.003 (2)	0.014 (2)
C9	0.037 (3)	0.031 (2)	0.036 (2)	0.005 (2)	0.005 (2)	0.001 (2)
C10	0.030 (2)	0.037 (3)	0.032 (2)	0.0065 (19)	−0.0060 (18)	−0.004 (2)
C11	0.054 (3)	0.047 (3)	0.051 (3)	−0.009 (3)	0.015 (3)	0.012 (3)
C12	0.057 (3)	0.041 (3)	0.058 (3)	0.001 (3)	0.026 (3)	0.011 (3)
Mn1	0.0270 (4)	0.0323 (4)	0.0327 (4)	0.0045 (3)	−0.0059 (3)	−0.0004 (3)
Mo1	0.0194 (3)	0.0182 (3)	0.0180 (3)	0.000	−0.00332 (17)	0.000
N1	0.037 (2)	0.043 (2)	0.029 (2)	0.0104 (19)	−0.0028 (16)	−0.0071 (17)
N2	0.044 (2)	0.050 (3)	0.045 (2)	−0.004 (2)	0.014 (2)	−0.013 (2)
N3	0.040 (2)	0.045 (2)	0.050 (3)	−0.013 (2)	0.0055 (19)	0.016 (2)
N4	0.043 (3)	0.048 (3)	0.050 (3)	−0.007 (2)	−0.012 (2)	−0.015 (2)
N5	0.036 (2)	0.033 (2)	0.032 (2)	0.0047 (17)	−0.0102 (16)	0.0070 (17)
N6	0.035 (2)	0.0243 (18)	0.039 (2)	0.0017 (16)	−0.0055 (17)	0.0039 (17)
N7	0.035 (2)	0.040 (2)	0.032 (2)	−0.0055 (17)	−0.0031 (16)	0.0004 (17)
N8	0.044 (2)	0.047 (3)	0.051 (3)	−0.005 (2)	−0.005 (2)	0.019 (2)
O1	0.0395 (19)	0.059 (2)	0.0346 (17)	0.0047 (17)	0.0014 (14)	−0.0001 (17)
O2	0.048 (2)	0.052 (2)	0.050 (2)	−0.0064 (17)	0.0119 (17)	0.0185 (18)

Geometric parameters (Å, º)

C1—N1	1.158 (5)	C11—C12	1.528 (7)
C1—Mo1	2.120 (4)	C12—H12A	0.9600
C2—N2	1.146 (6)	C12—H12B	0.9600
C2—Mo1	2.153 (4)	C12—H12C	0.9600
C3—N3	1.168 (6)	Mn1—N1	2.135 (4)
C3—Mo1	2.115 (5)	Mn1—O1	2.163 (3)
C4—N4	1.148 (6)	Mn1—N8	2.165 (4)
C4—Mo1	2.144 (5)	Mn1—N3^ii	2.178 (4)
C5—N5	1.329 (6)	Mn1—N5	2.284 (4)
C5—C6	1.370 (7)	Mn1—N6	2.315 (4)
C5—H5	0.9300	Mo1—C3^iii	2.115 (5)
C6—C7	1.356 (7)	Mo1—C1^iii	2.120 (4)
C6—H6	0.9300	Mo1—C4^iii	2.144 (5)
C7—C8	1.388 (7)	Mo1—C2^iii	2.153 (4)
C7—H7	0.9300	N3—Mn1^iv	2.178 (4)
C8—C9	1.357 (7)	N6—N7	1.292 (5)
C8—H8	0.9300	N7—C10^i	1.351 (5)
C9—N5	1.326 (6)	O1—H1B	0.8499
C9—C10	1.493 (6)	O1—H1A	0.8500
C10—N6	1.335 (6)	O2—H2A	0.8501
C10—N7^i	1.351 (5)	O2—H2B	0.8501
C11—N8	1.233 (7)
N1—C1—Mo1	178.5 (4)	N5—Mn1—N6	70.88 (13)
N2—C2—Mo1	179.2 (4)	C3—Mo1—C3^iii	104.6 (3)
N3—C3—Mo1	179.4 (4)	C3—Mo1—C1^iii	145.91 (16)
N4—C4—Mo1	176.9 (5)	C3^iii—Mo1—C1^iii	86.07 (17)
N5—C5—C6	123.7 (5)	C3—Mo1—C1	86.07 (17)
N5—C5—H5	118.2	C3^iii—Mo1—C1	145.91 (16)
C6—C5—H5	118.2	C1^iii—Mo1—C1	103.2 (2)
C7—C6—C5	119.3 (5)	C3—Mo1—C4	70.36 (19)
C7—C6—H6	120.4	C3^iii—Mo1—C4	76.79 (18)
C5—C6—H6	120.4	C1^iii—Mo1—C4	143.52 (17)
C6—C7—C8	117.9 (5)	C1—Mo1—C4	76.65 (17)
C6—C7—H7	121.1	C3—Mo1—C4^iii	76.79 (18)
C8—C7—H7	121.1	C3^iii—Mo1—C4^iii	70.36 (18)
C9—C8—C7	118.8 (5)	C1^iii—Mo1—C4^iii	76.65 (17)
C9—C8—H8	120.6	C1—Mo1—C4^iii	143.52 (17)
C7—C8—H8	120.6	C4—Mo1—C4^iii	125.0 (3)
N5—C9—C8	124.0 (4)	C3—Mo1—C2^iii	141.55 (16)
N5—C9—C10	114.3 (4)	C3^iii—Mo1—C2^iii	77.04 (17)
C8—C9—C10	121.6 (4)	C1^iii—Mo1—C2^iii	72.06 (15)
N6—C10—N7^i	123.7 (4)	C1—Mo1—C2^iii	74.98 (16)
N6—C10—C9	117.9 (4)	C4—Mo1—C2^iii	72.82 (18)
N7^i—C10—C9	118.4 (4)	C4^iii—Mo1—C2^iii	135.81 (17)
N8—C11—C12	167.9 (6)	C3—Mo1—C2	77.04 (17)
C11—C12—H12A	109.5	C3^iii—Mo1—C2	141.55 (16)
C11—C12—H12B	109.5	C1^iii—Mo1—C2	74.98 (16)
H12A—C12—H12B	109.5	C1—Mo1—C2	72.06 (15)
C11—C12—H12C	109.5	C4—Mo1—C2	135.81 (17)
H12A—C12—H12C	109.5	C4^iii—Mo1—C2	72.82 (18)
H12B—C12—H12C	109.5	C2^iii—Mo1—C2	125.6 (2)
N1—Mn1—O1	91.20 (13)	C1—N1—Mn1	162.0 (3)
N1—Mn1—N8	99.39 (16)	C3—N3—Mn1^iv	154.1 (4)
O1—Mn1—N8	90.61 (16)	C9—N5—C5	116.3 (4)
N1—Mn1—N3^ii	104.93 (15)	C9—N5—Mn1	119.9 (3)
O1—Mn1—N3^ii	163.73 (14)	C5—N5—Mn1	123.5 (3)
N8—Mn1—N3^ii	88.88 (18)	N7—N6—C10	118.7 (4)
N1—Mn1—N5	95.89 (14)	N7—N6—Mn1	124.7 (3)
O1—Mn1—N5	87.89 (14)	C10—N6—Mn1	116.6 (3)
N8—Mn1—N5	164.67 (14)	N6—N7—C10^i	117.6 (4)
N3^ii—Mn1—N5	88.31 (16)	C11—N8—Mn1	143.1 (4)
N1—Mn1—N6	164.60 (15)	Mn1—O1—H1B	116.1
O1—Mn1—N6	80.72 (13)	Mn1—O1—H1A	111.2
N8—Mn1—N6	93.82 (15)	H1B—O1—H1A	116.7
N3^ii—Mn1—N6	83.09 (15)	H2A—O2—H2B	107.7
N5—C5—C6—C7	0.5 (9)	N5—Mn1—N1—C1	55.0 (13)
C5—C6—C7—C8	0.4 (8)	N6—Mn1—N1—C1	24.9 (16)
C6—C7—C8—C9	−1.9 (8)	Mo1—C3—N3—Mn1^iv	−6 (45)
C7—C8—C9—N5	2.7 (8)	C8—C9—N5—C5	−1.8 (7)
C7—C8—C9—C10	179.2 (5)	C10—C9—N5—C5	−178.5 (4)
N5—C9—C10—N6	−7.2 (6)	C8—C9—N5—Mn1	−175.7 (4)
C8—C9—C10—N6	176.0 (5)	C10—C9—N5—Mn1	7.6 (5)
N5—C9—C10—N7^i	174.8 (4)	C6—C5—N5—C9	0.2 (8)
C8—C9—C10—N7^i	−2.0 (7)	C6—C5—N5—Mn1	173.8 (4)
N3—C3—Mo1—C3^iii	112 (44)	N1—Mn1—N5—C9	−176.4 (3)
N3—C3—Mo1—C1^iii	7 (45)	O1—Mn1—N5—C9	−85.4 (4)
N3—C3—Mo1—C1	−101 (44)	N8—Mn1—N5—C9	−0.8 (8)
N3—C3—Mo1—C4	−178 (100)	N3^ii—Mn1—N5—C9	78.7 (4)
N3—C3—Mo1—C4^iii	47 (44)	N6—Mn1—N5—C9	−4.5 (3)
N3—C3—Mo1—C2^iii	−161 (44)	N1—Mn1—N5—C5	10.1 (4)
N3—C3—Mo1—C2	−28 (44)	O1—Mn1—N5—C5	101.1 (4)
N1—C1—Mo1—C3	−26 (13)	N8—Mn1—N5—C5	−174.3 (6)
N1—C1—Mo1—C3^iii	85 (13)	N3^ii—Mn1—N5—C5	−94.7 (4)
N1—C1—Mo1—C1^iii	−173 (100)	N6—Mn1—N5—C5	−178.0 (4)
N1—C1—Mo1—C4	45 (13)	N7^i—C10—N6—N7	−1.6 (8)
N1—C1—Mo1—C4^iii	−87 (13)	C9—C10—N6—N7	−179.5 (4)
N1—C1—Mo1—C2^iii	120 (13)	N7^i—C10—N6—Mn1	−178.7 (3)
N1—C1—Mo1—C2	−103 (13)	C9—C10—N6—Mn1	3.4 (5)
N4—C4—Mo1—C3	93 (9)	N1—Mn1—N6—N7	−144.7 (5)
N4—C4—Mo1—C3^iii	−156 (9)	O1—Mn1—N6—N7	−85.6 (4)
N4—C4—Mo1—C1^iii	−92 (9)	N8—Mn1—N6—N7	4.4 (4)
N4—C4—Mo1—C1	2 (9)	N3^ii—Mn1—N6—N7	92.8 (4)
N4—C4—Mo1—C4^iii	150 (9)	N5—Mn1—N6—N7	−176.6 (4)
N4—C4—Mo1—C2^iii	−76 (9)	N1—Mn1—N6—C10	32.2 (7)
N4—C4—Mo1—C2	48 (9)	O1—Mn1—N6—C10	91.3 (3)
N2—C2—Mo1—C3	−4 (32)	N8—Mn1—N6—C10	−178.7 (3)
N2—C2—Mo1—C3^iii	−101 (32)	N3^ii—Mn1—N6—C10	−90.3 (4)
N2—C2—Mo1—C1^iii	−164 (32)	N5—Mn1—N6—C10	0.3 (3)
N2—C2—Mo1—C1	86 (32)	C10—N6—N7—C10^i	1.5 (7)
N2—C2—Mo1—C4	39 (32)	Mn1—N6—N7—C10^i	178.3 (3)
N2—C2—Mo1—C4^iii	−84 (32)	C12—C11—N8—Mn1	−146 (2)
N2—C2—Mo1—C2^iii	142 (32)	N1—Mn1—N8—C11	−99.5 (7)
Mo1—C1—N1—Mn1	−45 (14)	O1—Mn1—N8—C11	169.1 (7)
O1—Mn1—N1—C1	−33.0 (13)	N3^ii—Mn1—N8—C11	5.4 (7)
N8—Mn1—N1—C1	−123.8 (13)	N5—Mn1—N8—C11	84.9 (9)
N3^ii—Mn1—N1—C1	144.8 (12)	N6—Mn1—N8—C11	88.4 (7)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O2	0.85	1.78	2.622 (5)	174
O1—H1A···N4^v	0.85	1.95	2.784 (5)	166
O2—H2A···N2^iii	0.85	2.44	2.948 (5)	119
O2—H2B···N2^vi	0.85	2.12	2.948 (5)	166
C6—H6···N1^iv	0.93	2.60	3.527 (6)	174
C8—H8···N7^i	0.93	2.54	2.847 (6)	100
C12—H12A···N4^vii	0.96	2.59	3.291 (6)	130

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