Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614020117/wq3073sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614020117/wq3073Isup2.hkl |
CCDC reference: 911157
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.
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).
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).
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—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.
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 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—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).
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).
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).
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).
[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) Å3 | 0.19 × 0.17 × 0.15 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-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 parameters | Δρmax = 0.62 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
[Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2O | V = 3221.6 (8) Å3 |
Mr = 804.40 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.429 (2) Å | µ = 1.21 mm−1 |
b = 11.5947 (17) Å | T = 293 K |
c = 18.360 (3) Å | 0.19 × 0.17 × 0.15 mm |
β = 101.230 (3)° |
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 = 0.834 | Rint = 0.015 |
8440 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.62 e Å−3 |
3160 reflections | Δρmin = −0.57 e Å−3 |
214 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—N3ii | 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—C3iii | 2.115 (5) |
C6—C7 | 1.356 (7) | Mo1—C1iii | 2.120 (4) |
C6—H6 | 0.9300 | Mo1—C4iii | 2.144 (5) |
C7—C8 | 1.388 (7) | Mo1—C2iii | 2.153 (4) |
C7—H7 | 0.9300 | N3—Mn1iv | 2.178 (4) |
C8—C9 | 1.357 (7) | N6—N7 | 1.292 (5) |
C8—H8 | 0.9300 | N7—C10i | 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—N7i | 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—C3iii | 104.6 (3) |
N3—C3—Mo1 | 179.4 (4) | C3—Mo1—C1iii | 145.91 (16) |
N4—C4—Mo1 | 176.9 (5) | C3iii—Mo1—C1iii | 86.07 (17) |
N5—C5—C6 | 123.7 (5) | C3—Mo1—C1 | 86.07 (17) |
N5—C5—H5 | 118.2 | C3iii—Mo1—C1 | 145.91 (16) |
C6—C5—H5 | 118.2 | C1iii—Mo1—C1 | 103.2 (2) |
C7—C6—C5 | 119.3 (5) | C3—Mo1—C4 | 70.36 (19) |
C7—C6—H6 | 120.4 | C3iii—Mo1—C4 | 76.79 (18) |
C5—C6—H6 | 120.4 | C1iii—Mo1—C4 | 143.52 (17) |
C6—C7—C8 | 117.9 (5) | C1—Mo1—C4 | 76.65 (17) |
C6—C7—H7 | 121.1 | C3—Mo1—C4iii | 76.79 (18) |
C8—C7—H7 | 121.1 | C3iii—Mo1—C4iii | 70.36 (18) |
C9—C8—C7 | 118.8 (5) | C1iii—Mo1—C4iii | 76.65 (17) |
C9—C8—H8 | 120.6 | C1—Mo1—C4iii | 143.52 (17) |
C7—C8—H8 | 120.6 | C4—Mo1—C4iii | 125.0 (3) |
N5—C9—C8 | 124.0 (4) | C3—Mo1—C2iii | 141.55 (16) |
N5—C9—C10 | 114.3 (4) | C3iii—Mo1—C2iii | 77.04 (17) |
C8—C9—C10 | 121.6 (4) | C1iii—Mo1—C2iii | 72.06 (15) |
N6—C10—N7i | 123.7 (4) | C1—Mo1—C2iii | 74.98 (16) |
N6—C10—C9 | 117.9 (4) | C4—Mo1—C2iii | 72.82 (18) |
N7i—C10—C9 | 118.4 (4) | C4iii—Mo1—C2iii | 135.81 (17) |
N8—C11—C12 | 167.9 (6) | C3—Mo1—C2 | 77.04 (17) |
C11—C12—H12A | 109.5 | C3iii—Mo1—C2 | 141.55 (16) |
C11—C12—H12B | 109.5 | C1iii—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 | C4iii—Mo1—C2 | 72.82 (18) |
H12B—C12—H12C | 109.5 | C2iii—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—Mn1iv | 154.1 (4) |
O1—Mn1—N8 | 90.61 (16) | C9—N5—C5 | 116.3 (4) |
N1—Mn1—N3ii | 104.93 (15) | C9—N5—Mn1 | 119.9 (3) |
O1—Mn1—N3ii | 163.73 (14) | C5—N5—Mn1 | 123.5 (3) |
N8—Mn1—N3ii | 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—C10i | 117.6 (4) |
N3ii—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 |
N3ii—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—Mn1iv | −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—N7i | 174.8 (4) | C6—C5—N5—C9 | 0.2 (8) |
C8—C9—C10—N7i | −2.0 (7) | C6—C5—N5—Mn1 | 173.8 (4) |
N3—C3—Mo1—C3iii | 112 (44) | N1—Mn1—N5—C9 | −176.4 (3) |
N3—C3—Mo1—C1iii | 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) | N3ii—Mn1—N5—C9 | 78.7 (4) |
N3—C3—Mo1—C4iii | 47 (44) | N6—Mn1—N5—C9 | −4.5 (3) |
N3—C3—Mo1—C2iii | −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—C3iii | 85 (13) | N3ii—Mn1—N5—C5 | −94.7 (4) |
N1—C1—Mo1—C1iii | −173 (100) | N6—Mn1—N5—C5 | −178.0 (4) |
N1—C1—Mo1—C4 | 45 (13) | N7i—C10—N6—N7 | −1.6 (8) |
N1—C1—Mo1—C4iii | −87 (13) | C9—C10—N6—N7 | −179.5 (4) |
N1—C1—Mo1—C2iii | 120 (13) | N7i—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—C3iii | −156 (9) | O1—Mn1—N6—N7 | −85.6 (4) |
N4—C4—Mo1—C1iii | −92 (9) | N8—Mn1—N6—N7 | 4.4 (4) |
N4—C4—Mo1—C1 | 2 (9) | N3ii—Mn1—N6—N7 | 92.8 (4) |
N4—C4—Mo1—C4iii | 150 (9) | N5—Mn1—N6—N7 | −176.6 (4) |
N4—C4—Mo1—C2iii | −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—C3iii | −101 (32) | N3ii—Mn1—N6—C10 | −90.3 (4) |
N2—C2—Mo1—C1iii | −164 (32) | N5—Mn1—N6—C10 | 0.3 (3) |
N2—C2—Mo1—C1 | 86 (32) | C10—N6—N7—C10i | 1.5 (7) |
N2—C2—Mo1—C4 | 39 (32) | Mn1—N6—N7—C10i | 178.3 (3) |
N2—C2—Mo1—C4iii | −84 (32) | C12—C11—N8—Mn1 | −146 (2) |
N2—C2—Mo1—C2iii | 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) | N3ii—Mn1—N8—C11 | 5.4 (7) |
N8—Mn1—N1—C1 | −123.8 (13) | N5—Mn1—N8—C11 | 84.9 (9) |
N3ii—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. |
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···N4v | 0.85 | 1.95 | 2.784 (5) | 166 |
O2—H2A···N2iii | 0.85 | 2.44 | 2.948 (5) | 119 |
O2—H2B···N2vi | 0.85 | 2.12 | 2.948 (5) | 166 |
C6—H6···N1iv | 0.93 | 2.60 | 3.527 (6) | 174 |
C8—H8···N7i | 0.93 | 2.54 | 2.847 (6) | 100 |
C12—H12A···N4vii | 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. |
Experimental details
Crystal data | |
Chemical formula | [Mn2Mo(CN)8(C12H8N6)(C2H3N)2(H2O)2]·2H2O |
Mr | 804.40 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 15.429 (2), 11.5947 (17), 18.360 (3) |
β (°) | 101.230 (3) |
V (Å3) | 3221.6 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.21 |
Crystal size (mm) | 0.19 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.794, 0.834 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8440, 3163, 2588 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.131, 1.11 |
No. of reflections | 3160 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.62, −0.57 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···O2 | 0.85 | 1.78 | 2.622 (5) | 173.9 |
O1—H1A···N4i | 0.85 | 1.95 | 2.784 (5) | 166.3 |
O2—H2A···N2ii | 0.85 | 2.44 | 2.948 (5) | 119.4 |
O2—H2B···N2iii | 0.85 | 2.12 | 2.948 (5) | 166.2 |
C6—H6···N1iv | 0.93 | 2.60 | 3.527 (6) | 173.9 |
C8—H8···N7v | 0.93 | 2.54 | 2.847 (6) | 99.6 |
C12—H12A···N4vi | 0.96 | 2.59 | 3.291 (6) | 129.8 |
Symmetry codes: (i) −x+3/2, −y+1/2, −z; (ii) −x+2, y, −z+1/2; (iii) x, −y+1, z−1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) x, y+1, z. |