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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614020117/wq3073sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229614020117/wq3073Isup2.hkl
Contains datablock I

CCDC reference: 911157

Introduction top

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 [MIV(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 (D4d), dodecahedron (D2d) and bicapped trigonal prism (C2v)], 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.

Experimental top

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.

Synthesis and crystallization top

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 (νCN).

Refinement top

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 Uiso(H) = 1.2Ueq(C) for aromatic H atoms, or C—H = 0.96 Å and Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(O).

Results and discussion top

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 CN bond lengths are within the range 1.146 (6)–1.168 (6) Å. The Mo–CN bonds are almost linear, with the Mo–CN 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—Nbptz distances are distributed in the range 2.284 (4)–2.315 (4) Å, the Mn—Ncyanide 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 [MoIV(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 χMT 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 SMn = 5/2 and assuming gMn = 2, implying basic paramagnetic properties for (I). Below 10 K, χMT decreases sharply, reaching 7.14 emu K mol-1 at 1.8 K, indicating weak anti­ferromagnetic coupling between Mn2+ cations mediated by [MoIV(CN)8]4- groups, while the shortest MnII···MnII distance across the [MoIV(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 MnII cations. Given this magnetic inter­action between MnII 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 top

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 top

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 [MIV(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 (D4d), dodecahedron (D2d) and bicapped trigonal prism (C2v)], 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 CN bond lengths are within the range 1.146 (6)–1.168 (6) Å. The Mo–CN bonds are almost linear, with the Mo–CN 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—Nbptz distances are distributed in the range 2.284 (4)–2.315 (4) Å, the Mn—Ncyanide 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 [MoIV(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 χMT 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 SMn = 5/2 and assuming gMn = 2, implying basic paramagnetic properties for (I). Below 10 K, χMT decreases sharply, reaching 7.14 emu K mol-1 at 1.8 K, indicating weak anti­ferromagnetic coupling between Mn2+ cations mediated by [MoIV(CN)8]4- groups, while the shortest MnII···MnII distance across the [MoIV(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 MnII cations. Given this magnetic inter­action between MnII 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 top

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 (νCN).

Refinement details top

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 Uiso(H) = 1.2Ueq(C) for aromatic H atoms, or C—H = 0.96 Å and Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(O).

Computing details top

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 top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A view of the three-dimensional structure of (I).
[Figure 3] Fig. 3. A network perspective view of the 4,4-connected 2-nodal 42·84 topology in (I). Blue and red spheres represent the Mn2 SUB and the [Mo(CN)8]4- anion, respectively.
[Figure 4] 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] top
Crystal data top
[Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2OF(000) = 1608
Mr = 804.40Dx = 1.658 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2729 reflections
a = 15.429 (2) Åθ = 2.1–25.1°
b = 11.5947 (17) ŵ = 1.21 mm1
c = 18.360 (3) ÅT = 293 K
β = 101.230 (3)°Block, yellow
V = 3221.6 (8) Å30.19 × 0.17 × 0.15 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3163 independent reflections
Radiation source: fine-focus sealed tube2588 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
φ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 1817
Tmin = 0.794, Tmax = 0.834k = 148
8440 measured reflectionsl = 1922
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0779P)2]
where P = (Fo2 + 2Fc2)/3
3160 reflections(Δ/σ)max < 0.001
214 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
[Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2OV = 3221.6 (8) Å3
Mr = 804.40Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.429 (2) ŵ = 1.21 mm1
b = 11.5947 (17) ÅT = 293 K
c = 18.360 (3) Å0.19 × 0.17 × 0.15 mm
β = 101.230 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
3163 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
2588 reflections with I > 2σ(I)
Tmin = 0.794, Tmax = 0.834Rint = 0.015
8440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.131H-atom parameters constrained
S = 1.11Δρmax = 0.62 e Å3
3160 reflectionsΔρmin = 0.57 e Å3
214 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
C10.8934 (3)0.3483 (4)0.2109 (2)0.0282 (9)
C20.9654 (3)0.3196 (4)0.3447 (2)0.0324 (10)
C30.9041 (3)0.1232 (4)0.2797 (2)0.0351 (10)
C40.9293 (3)0.1494 (4)0.1528 (3)0.0418 (12)
C50.6564 (4)0.2297 (4)0.1771 (3)0.0463 (13)
H50.71420.22960.20370.056*
C60.6028 (3)0.1392 (4)0.1868 (3)0.0456 (13)
H60.62400.07990.21950.055*
C70.5184 (3)0.1370 (4)0.1482 (3)0.0470 (13)
H70.48040.07690.15410.056*
C80.4904 (4)0.2274 (4)0.0998 (3)0.0467 (13)
H80.43360.22810.07120.056*
C90.5475 (3)0.3149 (4)0.0949 (3)0.0349 (10)
C100.5221 (3)0.4139 (4)0.0432 (2)0.0350 (10)
C110.7674 (4)0.7462 (5)0.1147 (3)0.0499 (14)
C120.7702 (4)0.8778 (4)0.1190 (3)0.0499 (13)
H12A0.82980.90390.12180.075*
H12B0.74930.90280.16240.075*
H12C0.73310.90960.07550.075*
Mn10.71550 (4)0.47689 (6)0.12395 (4)0.0323 (2)
Mo11.00000.23475 (4)0.25000.01949 (16)
N10.8339 (3)0.4082 (3)0.1893 (2)0.0376 (9)
N20.9463 (3)0.3637 (4)0.3951 (2)0.0456 (10)
N30.8514 (3)0.0618 (4)0.2967 (2)0.0457 (11)
N40.8888 (3)0.1078 (4)0.1002 (2)0.0501 (11)
N50.6304 (2)0.3178 (3)0.1317 (2)0.0359 (9)
N60.5801 (3)0.4998 (3)0.0449 (2)0.0346 (9)
N70.5589 (2)0.5866 (3)0.0009 (2)0.0368 (9)
N80.7644 (3)0.6434 (4)0.0971 (2)0.0494 (11)
O10.7471 (2)0.4036 (3)0.02394 (18)0.0453 (9)
H1B0.79870.41750.01630.054*
H1A0.70460.41210.01280.054*
O20.9031 (2)0.4621 (3)0.0005 (2)0.0497 (9)
H2A0.93390.48480.04050.060*
H2B0.90600.51360.03290.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.025 (2)0.035 (2)0.024 (2)0.0045 (18)0.0030 (17)0.0095 (18)
C20.028 (2)0.040 (3)0.028 (2)0.0001 (19)0.0016 (18)0.002 (2)
C30.033 (2)0.032 (2)0.034 (2)0.007 (2)0.0087 (19)0.0007 (19)
C40.033 (3)0.046 (3)0.040 (3)0.001 (2)0.006 (2)0.006 (2)
C50.040 (3)0.045 (3)0.045 (3)0.007 (2)0.013 (2)0.017 (2)
C60.045 (3)0.037 (3)0.047 (3)0.004 (2)0.010 (2)0.013 (2)
C70.049 (3)0.041 (3)0.047 (3)0.011 (2)0.000 (2)0.016 (2)
C80.045 (3)0.042 (3)0.048 (3)0.012 (2)0.003 (2)0.014 (2)
C90.037 (3)0.031 (2)0.036 (2)0.005 (2)0.005 (2)0.001 (2)
C100.030 (2)0.037 (3)0.032 (2)0.0065 (19)0.0060 (18)0.004 (2)
C110.054 (3)0.047 (3)0.051 (3)0.009 (3)0.015 (3)0.012 (3)
C120.057 (3)0.041 (3)0.058 (3)0.001 (3)0.026 (3)0.011 (3)
Mn10.0270 (4)0.0323 (4)0.0327 (4)0.0045 (3)0.0059 (3)0.0004 (3)
Mo10.0194 (3)0.0182 (3)0.0180 (3)0.0000.00332 (17)0.000
N10.037 (2)0.043 (2)0.029 (2)0.0104 (19)0.0028 (16)0.0071 (17)
N20.044 (2)0.050 (3)0.045 (2)0.004 (2)0.014 (2)0.013 (2)
N30.040 (2)0.045 (2)0.050 (3)0.013 (2)0.0055 (19)0.016 (2)
N40.043 (3)0.048 (3)0.050 (3)0.007 (2)0.012 (2)0.015 (2)
N50.036 (2)0.033 (2)0.032 (2)0.0047 (17)0.0102 (16)0.0070 (17)
N60.035 (2)0.0243 (18)0.039 (2)0.0017 (16)0.0055 (17)0.0039 (17)
N70.035 (2)0.040 (2)0.032 (2)0.0055 (17)0.0031 (16)0.0004 (17)
N80.044 (2)0.047 (3)0.051 (3)0.005 (2)0.005 (2)0.019 (2)
O10.0395 (19)0.059 (2)0.0346 (17)0.0047 (17)0.0014 (14)0.0001 (17)
O20.048 (2)0.052 (2)0.050 (2)0.0064 (17)0.0119 (17)0.0185 (18)
Geometric parameters (Å, º) top
C1—N11.158 (5)C11—C121.528 (7)
C1—Mo12.120 (4)C12—H12A0.9600
C2—N21.146 (6)C12—H12B0.9600
C2—Mo12.153 (4)C12—H12C0.9600
C3—N31.168 (6)Mn1—N12.135 (4)
C3—Mo12.115 (5)Mn1—O12.163 (3)
C4—N41.148 (6)Mn1—N82.165 (4)
C4—Mo12.144 (5)Mn1—N3ii2.178 (4)
C5—N51.329 (6)Mn1—N52.284 (4)
C5—C61.370 (7)Mn1—N62.315 (4)
C5—H50.9300Mo1—C3iii2.115 (5)
C6—C71.356 (7)Mo1—C1iii2.120 (4)
C6—H60.9300Mo1—C4iii2.144 (5)
C7—C81.388 (7)Mo1—C2iii2.153 (4)
C7—H70.9300N3—Mn1iv2.178 (4)
C8—C91.357 (7)N6—N71.292 (5)
C8—H80.9300N7—C10i1.351 (5)
C9—N51.326 (6)O1—H1B0.8499
C9—C101.493 (6)O1—H1A0.8500
C10—N61.335 (6)O2—H2A0.8501
C10—N7i1.351 (5)O2—H2B0.8501
C11—N81.233 (7)
N1—C1—Mo1178.5 (4)N5—Mn1—N670.88 (13)
N2—C2—Mo1179.2 (4)C3—Mo1—C3iii104.6 (3)
N3—C3—Mo1179.4 (4)C3—Mo1—C1iii145.91 (16)
N4—C4—Mo1176.9 (5)C3iii—Mo1—C1iii86.07 (17)
N5—C5—C6123.7 (5)C3—Mo1—C186.07 (17)
N5—C5—H5118.2C3iii—Mo1—C1145.91 (16)
C6—C5—H5118.2C1iii—Mo1—C1103.2 (2)
C7—C6—C5119.3 (5)C3—Mo1—C470.36 (19)
C7—C6—H6120.4C3iii—Mo1—C476.79 (18)
C5—C6—H6120.4C1iii—Mo1—C4143.52 (17)
C6—C7—C8117.9 (5)C1—Mo1—C476.65 (17)
C6—C7—H7121.1C3—Mo1—C4iii76.79 (18)
C8—C7—H7121.1C3iii—Mo1—C4iii70.36 (18)
C9—C8—C7118.8 (5)C1iii—Mo1—C4iii76.65 (17)
C9—C8—H8120.6C1—Mo1—C4iii143.52 (17)
C7—C8—H8120.6C4—Mo1—C4iii125.0 (3)
N5—C9—C8124.0 (4)C3—Mo1—C2iii141.55 (16)
N5—C9—C10114.3 (4)C3iii—Mo1—C2iii77.04 (17)
C8—C9—C10121.6 (4)C1iii—Mo1—C2iii72.06 (15)
N6—C10—N7i123.7 (4)C1—Mo1—C2iii74.98 (16)
N6—C10—C9117.9 (4)C4—Mo1—C2iii72.82 (18)
N7i—C10—C9118.4 (4)C4iii—Mo1—C2iii135.81 (17)
N8—C11—C12167.9 (6)C3—Mo1—C277.04 (17)
C11—C12—H12A109.5C3iii—Mo1—C2141.55 (16)
C11—C12—H12B109.5C1iii—Mo1—C274.98 (16)
H12A—C12—H12B109.5C1—Mo1—C272.06 (15)
C11—C12—H12C109.5C4—Mo1—C2135.81 (17)
H12A—C12—H12C109.5C4iii—Mo1—C272.82 (18)
H12B—C12—H12C109.5C2iii—Mo1—C2125.6 (2)
N1—Mn1—O191.20 (13)C1—N1—Mn1162.0 (3)
N1—Mn1—N899.39 (16)C3—N3—Mn1iv154.1 (4)
O1—Mn1—N890.61 (16)C9—N5—C5116.3 (4)
N1—Mn1—N3ii104.93 (15)C9—N5—Mn1119.9 (3)
O1—Mn1—N3ii163.73 (14)C5—N5—Mn1123.5 (3)
N8—Mn1—N3ii88.88 (18)N7—N6—C10118.7 (4)
N1—Mn1—N595.89 (14)N7—N6—Mn1124.7 (3)
O1—Mn1—N587.89 (14)C10—N6—Mn1116.6 (3)
N8—Mn1—N5164.67 (14)N6—N7—C10i117.6 (4)
N3ii—Mn1—N588.31 (16)C11—N8—Mn1143.1 (4)
N1—Mn1—N6164.60 (15)Mn1—O1—H1B116.1
O1—Mn1—N680.72 (13)Mn1—O1—H1A111.2
N8—Mn1—N693.82 (15)H1B—O1—H1A116.7
N3ii—Mn1—N683.09 (15)H2A—O2—H2B107.7
N5—C5—C6—C70.5 (9)N5—Mn1—N1—C155.0 (13)
C5—C6—C7—C80.4 (8)N6—Mn1—N1—C124.9 (16)
C6—C7—C8—C91.9 (8)Mo1—C3—N3—Mn1iv6 (45)
C7—C8—C9—N52.7 (8)C8—C9—N5—C51.8 (7)
C7—C8—C9—C10179.2 (5)C10—C9—N5—C5178.5 (4)
N5—C9—C10—N67.2 (6)C8—C9—N5—Mn1175.7 (4)
C8—C9—C10—N6176.0 (5)C10—C9—N5—Mn17.6 (5)
N5—C9—C10—N7i174.8 (4)C6—C5—N5—C90.2 (8)
C8—C9—C10—N7i2.0 (7)C6—C5—N5—Mn1173.8 (4)
N3—C3—Mo1—C3iii112 (44)N1—Mn1—N5—C9176.4 (3)
N3—C3—Mo1—C1iii7 (45)O1—Mn1—N5—C985.4 (4)
N3—C3—Mo1—C1101 (44)N8—Mn1—N5—C90.8 (8)
N3—C3—Mo1—C4178 (100)N3ii—Mn1—N5—C978.7 (4)
N3—C3—Mo1—C4iii47 (44)N6—Mn1—N5—C94.5 (3)
N3—C3—Mo1—C2iii161 (44)N1—Mn1—N5—C510.1 (4)
N3—C3—Mo1—C228 (44)O1—Mn1—N5—C5101.1 (4)
N1—C1—Mo1—C326 (13)N8—Mn1—N5—C5174.3 (6)
N1—C1—Mo1—C3iii85 (13)N3ii—Mn1—N5—C594.7 (4)
N1—C1—Mo1—C1iii173 (100)N6—Mn1—N5—C5178.0 (4)
N1—C1—Mo1—C445 (13)N7i—C10—N6—N71.6 (8)
N1—C1—Mo1—C4iii87 (13)C9—C10—N6—N7179.5 (4)
N1—C1—Mo1—C2iii120 (13)N7i—C10—N6—Mn1178.7 (3)
N1—C1—Mo1—C2103 (13)C9—C10—N6—Mn13.4 (5)
N4—C4—Mo1—C393 (9)N1—Mn1—N6—N7144.7 (5)
N4—C4—Mo1—C3iii156 (9)O1—Mn1—N6—N785.6 (4)
N4—C4—Mo1—C1iii92 (9)N8—Mn1—N6—N74.4 (4)
N4—C4—Mo1—C12 (9)N3ii—Mn1—N6—N792.8 (4)
N4—C4—Mo1—C4iii150 (9)N5—Mn1—N6—N7176.6 (4)
N4—C4—Mo1—C2iii76 (9)N1—Mn1—N6—C1032.2 (7)
N4—C4—Mo1—C248 (9)O1—Mn1—N6—C1091.3 (3)
N2—C2—Mo1—C34 (32)N8—Mn1—N6—C10178.7 (3)
N2—C2—Mo1—C3iii101 (32)N3ii—Mn1—N6—C1090.3 (4)
N2—C2—Mo1—C1iii164 (32)N5—Mn1—N6—C100.3 (3)
N2—C2—Mo1—C186 (32)C10—N6—N7—C10i1.5 (7)
N2—C2—Mo1—C439 (32)Mn1—N6—N7—C10i178.3 (3)
N2—C2—Mo1—C4iii84 (32)C12—C11—N8—Mn1146 (2)
N2—C2—Mo1—C2iii142 (32)N1—Mn1—N8—C1199.5 (7)
Mo1—C1—N1—Mn145 (14)O1—Mn1—N8—C11169.1 (7)
O1—Mn1—N1—C133.0 (13)N3ii—Mn1—N8—C115.4 (7)
N8—Mn1—N1—C1123.8 (13)N5—Mn1—N8—C1184.9 (9)
N3ii—Mn1—N1—C1144.8 (12)N6—Mn1—N8—C1188.4 (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, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.851.782.622 (5)174
O1—H1A···N4v0.851.952.784 (5)166
O2—H2A···N2iii0.852.442.948 (5)119
O2—H2B···N2vi0.852.122.948 (5)166
C6—H6···N1iv0.932.603.527 (6)174
C8—H8···N7i0.932.542.847 (6)100
C12—H12A···N4vii0.962.593.291 (6)130
Symmetry codes: (i) x+1, y+1, z; (iii) x+2, y, z+1/2; (iv) x+3/2, y1/2, z+1/2; (v) x+3/2, y+1/2, z; (vi) x, y+1, z1/2; (vii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2O
Mr804.40
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)15.429 (2), 11.5947 (17), 18.360 (3)
β (°) 101.230 (3)
V3)3221.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.21
Crystal size (mm)0.19 × 0.17 × 0.15
Data collection
DiffractometerBruker SMART APEX CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.794, 0.834
No. of measured, independent and
observed [I > 2σ(I)] reflections
8440, 3163, 2588
Rint0.015
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.131, 1.11
No. of reflections3160
No. of parameters214
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.57

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O20.851.782.622 (5)173.9
O1—H1A···N4i0.851.952.784 (5)166.3
O2—H2A···N2ii0.852.442.948 (5)119.4
O2—H2B···N2iii0.852.122.948 (5)166.2
C6—H6···N1iv0.932.603.527 (6)173.9
C8—H8···N7v0.932.542.847 (6)99.6
C12—H12A···N4vi0.962.593.291 (6)129.8
Symmetry codes: (i) x+3/2, y+1/2, z; (ii) x+2, y, z+1/2; (iii) x, y+1, z1/2; (iv) x+3/2, y1/2, z+1/2; (v) x+1, y+1, z; (vi) x, y+1, z.
 

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