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The title dinuclear manganese compound, [Mn2(C10H8N2)3(H2O)8](C7H6NO2)2(ClO4)2·2C10H8N2·4H2O, (I), has an inversion center located midway between the MnII ions. Each MnII ion has a distorted octa­hedral coordination environment, defined by two mutually cis N atoms from two different 4,4'-bipyridine (4,4'-bipy) ligands and four O atoms from four water mol­ecules. The asymmetric unit contains cationic [Mn(4,4'-bipy)1.5(H2O)4]2+, one isolated 4,4'-bipy mol­ecule, one 4-amino­benzoate ion, one disordered perchlorate ion and two uncoordinated water mol­ecules. In the dinuclear manganese cationic unit, one 4,4'-bipy acts as a bidentate bridging ligand between two MnII ions, while the other two act only as monodentate terminal ligands, giving rise to a `Z-type' [Mn2(4,4'-bipy)3(H2O)8] host unit. These host units are linked to each other via face-to-face [pi]-[pi] stacking inter­actions between monodentate terminal 4,4'-bipy ligands, generating a zigzag chain. The corners of these chains, defined by Mn(OH)4 units, are surrounded by the solvent water mol­ecules and the carboxyl­ate O atoms of the 4-amino­benzoate ions, and all of these are connected to each other via strong O-H...O hydrogen-bond inter­actions, leading to a three-dimensional grid network with a large cavity running along the b axis of the unit cell. The isolated 4,4'-bipy mol­ecules, the 4-amino­benzoate and perchlorate anions and the water mol­ecules are encapsulated in the cavities by numerous hydrogen-bond inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112033616/sk3444sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112033616/sk3444Isup2.hkl
Contains datablock I

mol

MDL mol file https://doi.org/10.1107/S0108270112033616/sk3444Isup3.mol
Supplementary material

CCDC reference: 908124

Comment top

Over the past two decades, the assembly, structures and potential applications of metal coordination polymers as functional materials have attracted much attention owing to their fascinating topologies and interesting properties in gas storage, optics, sensor, magnetism etc. (Li et al., 1999; Lehn, 1990; Yaghi et al., 2003; Eddaoudi et al., 2001). Considerable efforts have been invested in exploring open metal–organic polymers via covalent interactions (Phan et al., 2010; Yaghi et al., 1998; Moulton & Zaworotko, 2001). Aside from covalent interactions, ππ and hydrogen-bond contacts are also used to construct interesting coordination polymers with unique physical and chemical properties (Pan et al., 2001; Jenniefer & Muthiah, 2011; Lipstman & Goldberg, 2009; Xu & Xie, 2010).

The incorporation of transition metal ions into one-, two- and three-dimensional coordination frameworks is currently of great interest in supramolecular chemistry (Ma et al., 2004; Granifo et al., 2004; Cheng et al., 2011; Hazra et al., 2011). Noticeably, the selection of multifunctional organic ligands, such as carboxylates, bipyridine (bipy) or its derivatives, and mixtures of both carboxylate and bipy ligands, is a key point in the design and assembly of expected compounds (Tong & Chen, 2000; Liao et al., 2004; Prior et al., 2003; Ayyappan et al., 2002). In general, 4,4'-bipyridine (4,4'-bipy) ligands may act in bidentate bridging or monodentate terminal coordination modes to transition metal ions, giving rise to one-dimensional linear, zigzag, ladder, molecular antenna railroads and chains, two-dimensional square and rectangular grid networks, or three-dimensional non-interpenetrated and interpenetrated networks (Biradha et al., 2006).

In our continuing efforts in this field (Fang & Wang, 2010; Wang & Fang, 2010; Wang, Fan et al., 2010; Gao et al., 2011), we isolated the MnII supramolecular grid network structure µ2-4,4'-bipyridine-κN,N'-bis[tetraaqua(4,4'-bipyridine-κN)dimanganese(II)] bis(4-aminobenzoate) bis(perchlorate)–4,4'-bipyridine–water (1/2/4), (I), which is assembled from 4-aminobenzoate and 4,4'-bipy ligands. A search in the Cambridge Structural Database (CSD; Version 5.33; Allen, 2002) indicated only a few metal–organic compounds that are constructed from a mixture of 4-aminobenzoate and 4,4'-bipy ligands (Li et al., 2003; Qiu et al., 2008). The 4,4'-bipy ligands in (I) exhibit a `Z-type' coordination mode to MnII ions, resulting in the formation of a rectangular grid network hosting the organic ligands, anions and water molecules via weak noncovalent interactions.

Compound (I) is composed of a dinuclear manganese [Mn2(4,4'-bipy)3(H2O)8] unit that is located around an inversion center. The asymmetric unit contains contains cationic [Mn(4,4'-bipy)1.5(H2O)4]2+, one isolated 4,4'-bipy molecule, one 4-aminobenzoate ion, one disordered perchlorate ion and two uncoordinated water molecules (Fig. 1). The isolated perchlorate ion is independently disordered over two positions in an occupancy ratio of 58:42 (see Refinement). The MnII center is six-coordinated by two N atoms from two different 4,4'-bipyridine (4,4'-bipy) ligands and four O atoms from three [four?] water molecules, displaying a distorted octahedral coordination environment. The Mn—O and Mn—N bond lengths and their relevant angles (Table 1), all of which are within the ranges observed for other MnII complexes with oxygen or nitrogen donors (Zou et al., 2005), are 2.162 (3)–2.282 (3) Å and 85.18 (11)–178.11 (12)°, respectively. It is noted that only one 4,4'-bipy molecule in the structure acts as a bidentate bridging ligand between two Mn metal ions, while the other two act as monodentate terminal ligands, resulting in the formation of a `Z-type' host unit. There are numerous examples of metal coordination compounds derived from 4,4'-bipy ligands; however, few examples with a `Z-type' host unit are found (Qiu et al., 2008) in the CSD. The structure of (I) is isostructural with that of [Zn2(bipy)3(H2O)8](PF6)2(paba)2.2(bipy).4H2O (bipy = 4,4'-bipyridine and paba = 4-aminobenzoate; Qiu et al., 2008), the latter displaying significant changes in the metal-to-N/O bond lengths [2.097 (3)–2.168 (3) Å].

The most striking feature of the structure is that the `Z-type' host units are connected to each other via face-to-face ππ interactions among the pyridine rings of the 4,4'-bipy ligands to form an infinite zigzag chain, which is further supported by water–pyridine O—H···N hydrogen bonds (Table 2). The centroid–centroid distances between neighboring 4,4'-bipy ligands are ca 3.6–3.9 Å (Table 3), indicatve of normal ππ stacking interactions (Lee et al., 2007). The corners of these chains, built up by Mn(OH)4 units, are surrounded by the uncoordinated water molecules and the carboxylate O atoms of the 4-aminobenzoate ions, and all of these are connected to each other via strong water–water or water–carboxylate O—H··· O hydrogen-bond interactions, leading to a three-dimensional grid network with a large cavity of ca 19.2 × 12.8 Å2 [Å?] running along the b axis of the unit cell (the distance between two neighboring MnII ions) (Fig. 2). The arrangement is similar to that of [Cd2(4,4'-bipy)5(H2O)6](3-paba)2(ClO4)2.2(H2O) (3-paba = 3-aminobenzoate) reported by us (Gao et al., 2011), whose structure is constructed from stacking infinite `H-type' chains. Obviously, to form suitable ππ interactions and electrostatic forces of the short 2,2' H···H contacts, the pyridine ring of the monodentate terminal 4,4'-bipy ligand is nonplanar with a dihedral angle of 30.3 (3)°.

In the supramolecular structure of (I), four independent components (4,4'-bipy, 4-aminobenzoate, perchlorate anions and lattice water molecules) are encapsulated in the cavities by numerous hydrogen bonds (Table 2). Two molecules (O1W and O3W) of the Mn(OH2)4 unit are hydrogen bonded to the O5W water molecule in a cyclic R12(6) motif, O2W is hydrogen bonded to O6W and further hydrogen bonded to carboxylate atom O5 in an R34(10) ring (Etter et al., 1990; Bernstein et al., 1995). Meanwhile, two symmetry-related O6W water molecules are hydrogen bonded to carboxylate atoms O5 and O6 in an R44(12) ring, which are also linked to O1W and O5W, giving rise to an R35(11) ring. The isolated 4,4'-bipy ligands located in the middle of the cavity are supported by water–pyridine O—H···N hydrogen bonds. The remaining voids are occupied by numerous perchlorate anions that are linked by aminobenzoate–perchlorate N—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Allen (2002); Ayyappan et al. (2002); Bernstein et al. (1995); Biradha et al. (2006); Cheng et al. (2011); Eddaoudi et al. (2001); Etter et al. (1990); Fang & Wang (2010); Gao et al. (2011); Granifo et al. (2004); Hazra et al. (2011); Jenniefer & Muthiah (2011); Lee et al. (2007); Lehn (1990); Li et al. (1999, 2003); Liao et al. (2004); Lipstman & Goldberg (2009); Ma et al. (2004); Moulton & Zaworotko (2001); Pan et al. (2001); Phan et al. (2010); Prior et al. (2003); Qiu et al. (2008); Tong & Chen (2000); Wang & Fang (2010); Wang, Fan, Guo, Yin, Wang & Zhang (2010); Xu & Xie (2010); Yaghi et al. (1998, 2003); Zou et al. (2005).

Experimental top

A mixture of Mn(ClO4)2.6H2O (0.361 g, 1 mmol), 4,4'-bipy (0.234 g, 1.5 mmol) and 75% ethanol solution (20 ml) was stirred for 30 min at 353 K. 4-Aminobenzoic acid (0.137 g, 1 mmol) was added and the pH adjusted to 7.0 with an aqueous solution of sodium hydroxide (0.1 mol l-1). The mixture was stirred continuously for another 30 min and then filtered. Colorless single crystals were obtained at room temperature by slow evaporation of the filtrate over a period of several days (yield 67%, based on Mn).

Refinement top

The isolated perchlorate anion showed significantly elongated displacement ellipsoids indicating disorder over two positions. Thus it was refined as being disordered over two sites, with an occupancy ratio of 58:42. The occupancy factor was initially obtained from refinement with a free variable and then fixed to define the occupancy for each disordered group. Owing to the significant overlap of the disordered atoms, the following restraints were applied: the anisotropic displacement parameters of the disordered atoms were restrained to be close to isotropic and those of equivalent atoms were set to be identical. All water H atoms were tentatively located in difference density Fourier maps and were refined with O—H distance restraints of 0.84 (1) Å and with Uiso(H) = 1.5Ueq(O). In the final stage of refinement, they were treated as riding on their parent O atoms. All H atoms attached to C atoms were fixed geometrically and treated as riding, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The H atoms of the NH2 group were tentatively located in difference density Fourier maps and were refined with N—H distance restraints of 0.86 (1) Å and with Uiso(H) = 1.5Ueq(N).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and XP in SHELXTL (Sheldrick, 2008)'; software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major disorder component of the perchlorate anion is shown. Unlabeled atoms are related to labeled atoms by the symmetry transformation (-x + 1, -y + 1, -z + 1).
[Figure 2] Fig. 2. A ball-and-stick perspective view of the rectangular grid formed via the ππ overlap of adjacent 4,4'-bipy ligands of the `Z-type' host units and numerous hydrogen-bond interactions. (Hydrogen bonds and ππ interactions are shown as dashed lines.)
[Figure 3] Fig. 3. A ball-and-stick perspective view of the hydrogen-bond (dashed lines) assembly of Mn(OH2)4 units, 4-aminobenzoate anions and lattice water molecules. Other non-interacting H atoms have been omitted for clarity.
µ-4,4'-Bipyridine-κ2N:N'-bis[tetraaqua(4,4'-bipyridine- κN)dimanaganese(II)] bis(4-aminobenzoate) bis(perchlorate)–4,4'-bipyridine–water (1/2/4) top
Crystal data top
[Mn2(C10H8N2)3(H2O)8](C7H6NO2)2(ClO4)2·2C10H8N2·4H2OF(000) = 1640
Mr = 1578.15Dx = 1.432 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3600 reflections
a = 19.4565 (6) Åθ = 1.3–28.0°
b = 7.0010 (2) ŵ = 0.50 mm1
c = 31.1252 (9) ÅT = 296 K
β = 120.322 (2)°Block, colourless
V = 3659.73 (19) Å30.25 × 0.23 × 0.19 mm
Z = 2
Data collection top
Bruker APEXII area-detector
diffractometer
6638 independent reflections
Radiation source: fine-focus sealed tube3566 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.106
ϕ and ω scanθmax = 25.2°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2323
Tmin = 0.885, Tmax = 0.911k = 88
43254 measured reflectionsl = 3737
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) = 0.137H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0384P)2 + 3.6414P]
where P = (Fo2 + 2Fc2)/3
6638 reflections(Δ/σ)max < 0.001
514 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
[Mn2(C10H8N2)3(H2O)8](C7H6NO2)2(ClO4)2·2C10H8N2·4H2OV = 3659.73 (19) Å3
Mr = 1578.15Z = 2
Monoclinic, P21/cMo Kα radiation
a = 19.4565 (6) ŵ = 0.50 mm1
b = 7.0010 (2) ÅT = 296 K
c = 31.1252 (9) Å0.25 × 0.23 × 0.19 mm
β = 120.322 (2)°
Data collection top
Bruker APEXII area-detector
diffractometer
6638 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
3566 reflections with I > 2σ(I)
Tmin = 0.885, Tmax = 0.911Rint = 0.106
43254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.137H-atom parameters constrained
S = 1.01Δρmax = 0.32 e Å3
6638 reflectionsΔρmin = 0.38 e Å3
514 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*/UeqOcc. (<1)
C10.1592 (2)0.5519 (6)0.37135 (14)0.0523 (11)
H10.21200.59100.38600.063*
C20.1150 (2)0.5379 (5)0.31996 (14)0.0460 (10)
H20.13850.56390.30100.055*
C30.0356 (2)0.4849 (5)0.29700 (14)0.0439 (10)
C40.0060 (2)0.4375 (6)0.32767 (15)0.0531 (11)
H40.04640.39630.31400.064*
C50.0542 (3)0.4512 (6)0.37857 (15)0.0566 (12)
H50.03310.41630.39840.068*
C60.0152 (2)0.4866 (5)0.24212 (14)0.0445 (10)
C70.0143 (2)0.4519 (6)0.21074 (14)0.0492 (10)
H70.06800.42490.22380.059*
C80.0365 (3)0.4577 (6)0.15995 (15)0.0569 (12)
H80.01530.43410.13960.068*
C90.1427 (3)0.5289 (6)0.16819 (16)0.0601 (12)
H90.19670.55590.15400.072*
C100.0964 (2)0.5262 (6)0.21951 (15)0.0531 (11)
H100.11940.55060.23890.064*
C110.3685 (3)0.6891 (7)0.51128 (18)0.0703 (14)
H110.35720.80070.52270.084*
C120.4416 (3)0.6732 (7)0.51514 (18)0.0707 (14)
H120.47810.77270.52880.085*
C130.4612 (2)0.5105 (6)0.49887 (14)0.0482 (10)
C140.4044 (2)0.3688 (6)0.48012 (16)0.0576 (12)
H140.41480.25440.46930.069*
C150.3323 (2)0.3966 (7)0.47738 (15)0.0582 (11)
H150.29490.29880.46440.070*
C160.6348 (3)0.3216 (7)0.31685 (17)0.0693 (14)
H160.68830.33480.32680.083*
C170.5802 (2)0.3238 (7)0.26629 (16)0.0612 (12)
H170.59720.33840.24340.073*
C180.5004 (2)0.3040 (6)0.25033 (15)0.0501 (10)
C190.4804 (3)0.2842 (7)0.28697 (15)0.0664 (13)
H190.42730.27120.27820.080*
C200.5392 (3)0.2837 (7)0.33653 (17)0.0725 (14)
H200.52410.26970.36030.087*
C210.4388 (2)0.3028 (6)0.19664 (15)0.0511 (10)
C220.4586 (3)0.2737 (7)0.16031 (15)0.0641 (13)
H220.51160.25810.16920.077*
C230.4001 (3)0.2677 (7)0.11121 (16)0.0713 (14)
H230.41530.24670.08770.086*
C240.3044 (3)0.3209 (7)0.12989 (17)0.0699 (14)
H240.25100.33850.11990.084*
C250.3591 (2)0.3286 (7)0.17978 (15)0.0635 (13)
H250.34220.35140.20240.076*
C260.0924 (2)0.4170 (9)0.11106 (16)0.0599 (12)
C270.1527 (2)0.4093 (7)0.16539 (14)0.0479 (10)
C280.1816 (2)0.5742 (7)0.19315 (16)0.0573 (11)
H280.16420.69180.17740.069*
C290.2357 (3)0.5694 (7)0.24368 (16)0.0641 (12)
H290.25380.68320.26130.077*
C300.2632 (3)0.3955 (8)0.26841 (15)0.0625 (12)
C310.2351 (3)0.2286 (7)0.24063 (16)0.0617 (12)
H310.25290.11070.25610.074*
C320.1808 (2)0.2369 (7)0.19021 (16)0.0556 (11)
H320.16260.12360.17240.067*
Mn10.19251 (4)0.59722 (10)0.48287 (2)0.0544 (2)
N10.1296 (2)0.5120 (5)0.40095 (12)0.0522 (9)
N20.1144 (2)0.4949 (5)0.13803 (12)0.0577 (9)
N30.31295 (19)0.5551 (5)0.49225 (12)0.0537 (9)
N40.3167 (3)0.3877 (7)0.31860 (14)0.0979 (15)
H4A0.33010.49840.33240.147*
H4B0.33380.27650.33140.147*
N50.6163 (2)0.3022 (6)0.35213 (13)0.0674 (11)
N60.3234 (2)0.2898 (5)0.09510 (13)0.0627 (10)
O50.07010 (18)0.2620 (5)0.08745 (11)0.0810 (10)
O60.06471 (18)0.5767 (5)0.09159 (11)0.0810 (10)
Cl10.6161 (8)0.3909 (18)0.1182 (3)0.113 (5)0.42
O1A0.5626 (13)0.512 (3)0.0954 (9)0.257 (13)0.42
O2A0.6646 (14)0.421 (4)0.1665 (9)0.171 (11)0.42
O3A0.6632 (12)0.390 (5)0.0944 (9)0.220 (11)0.42
O4A0.5811 (9)0.2006 (15)0.1106 (5)0.105 (4)0.42
Cl20.6212 (4)0.3877 (9)0.1187 (2)0.071 (2)0.58
O1B0.6483 (7)0.5559 (16)0.1066 (4)0.145 (4)0.58
O2B0.6276 (8)0.423 (4)0.1666 (7)0.119 (5)0.58
O3B0.6734 (8)0.2434 (17)0.1238 (5)0.163 (6)0.58
O4B0.5425 (6)0.360 (3)0.0849 (5)0.182 (7)0.58
O1W0.07715 (16)0.6169 (5)0.47872 (10)0.0867 (11)
H1W0.04590.70500.46460.130*
H2W0.07900.60710.50540.130*
O2W0.19660 (16)0.2964 (4)0.50386 (10)0.0673 (9)
H3W0.15650.25400.50260.101*
H4W0.23300.26010.53100.101*
O3W0.24120 (17)0.6961 (5)0.55858 (9)0.0757 (10)
H5W0.21830.64830.57190.113*
H6W0.28790.70330.58100.113*
O4W0.19026 (19)0.8932 (4)0.46060 (10)0.0839 (11)
H7W0.16850.92130.43100.126*
H8W0.18440.98930.47350.126*
O5W0.1333 (2)0.9056 (5)0.08642 (13)0.0972 (12)
H9W0.11551.00960.09120.146*
H10W0.11080.81160.09160.146*
O6W0.0710 (2)0.1244 (7)0.49565 (12)0.143 (2)
H11W0.05270.20730.50720.215*
H12W0.03330.04810.47790.215*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.048 (2)0.065 (3)0.041 (2)0.002 (2)0.019 (2)0.000 (2)
C20.052 (3)0.053 (3)0.037 (2)0.000 (2)0.026 (2)0.0008 (19)
C30.046 (2)0.044 (2)0.037 (2)0.0032 (19)0.018 (2)0.0046 (19)
C40.047 (2)0.065 (3)0.048 (3)0.010 (2)0.025 (2)0.005 (2)
C50.058 (3)0.076 (3)0.041 (2)0.005 (2)0.028 (2)0.003 (2)
C60.047 (2)0.044 (2)0.038 (2)0.0020 (19)0.019 (2)0.0042 (19)
C70.048 (2)0.059 (3)0.037 (2)0.004 (2)0.019 (2)0.003 (2)
C80.065 (3)0.067 (3)0.041 (3)0.005 (2)0.028 (2)0.001 (2)
C90.046 (3)0.067 (3)0.054 (3)0.001 (2)0.015 (2)0.006 (2)
C100.046 (2)0.063 (3)0.044 (3)0.003 (2)0.018 (2)0.010 (2)
C110.054 (3)0.073 (3)0.089 (4)0.004 (3)0.040 (3)0.027 (3)
C120.053 (3)0.074 (3)0.087 (4)0.011 (2)0.037 (3)0.028 (3)
C130.042 (2)0.059 (3)0.038 (2)0.000 (2)0.016 (2)0.005 (2)
C140.045 (2)0.058 (3)0.067 (3)0.000 (2)0.027 (2)0.010 (2)
C150.042 (2)0.065 (3)0.061 (3)0.005 (2)0.022 (2)0.010 (2)
C160.051 (3)0.081 (4)0.055 (3)0.000 (2)0.011 (3)0.004 (3)
C170.045 (3)0.080 (3)0.048 (3)0.003 (2)0.015 (2)0.000 (2)
C180.047 (2)0.051 (3)0.041 (2)0.002 (2)0.014 (2)0.005 (2)
C190.050 (3)0.091 (4)0.043 (3)0.004 (3)0.012 (2)0.007 (3)
C200.067 (3)0.094 (4)0.049 (3)0.004 (3)0.024 (3)0.010 (3)
C210.043 (2)0.054 (3)0.042 (2)0.006 (2)0.011 (2)0.003 (2)
C220.042 (2)0.093 (4)0.046 (3)0.005 (2)0.014 (2)0.007 (3)
C230.053 (3)0.106 (4)0.046 (3)0.008 (3)0.018 (2)0.012 (3)
C240.042 (3)0.100 (4)0.052 (3)0.003 (3)0.013 (2)0.004 (3)
C250.048 (3)0.091 (4)0.041 (3)0.001 (2)0.015 (2)0.007 (2)
C260.038 (2)0.090 (4)0.049 (3)0.004 (3)0.020 (2)0.002 (3)
C270.038 (2)0.061 (3)0.043 (2)0.006 (2)0.0194 (19)0.004 (2)
C280.054 (3)0.060 (3)0.054 (3)0.001 (2)0.025 (2)0.006 (2)
C290.063 (3)0.067 (3)0.051 (3)0.016 (3)0.020 (2)0.015 (3)
C300.057 (3)0.079 (4)0.041 (3)0.008 (3)0.017 (2)0.002 (3)
C310.060 (3)0.064 (3)0.048 (3)0.006 (2)0.018 (2)0.007 (2)
C320.050 (3)0.060 (3)0.052 (3)0.010 (2)0.023 (2)0.008 (2)
Mn10.0389 (3)0.0848 (5)0.0319 (3)0.0111 (3)0.0124 (3)0.0017 (3)
N10.047 (2)0.063 (2)0.042 (2)0.0024 (17)0.0196 (18)0.0014 (17)
N20.057 (2)0.063 (2)0.042 (2)0.0091 (19)0.0166 (19)0.0017 (18)
N30.0403 (19)0.070 (3)0.047 (2)0.0014 (18)0.0192 (17)0.0034 (18)
N40.103 (3)0.099 (3)0.048 (2)0.002 (3)0.005 (2)0.004 (2)
N50.061 (3)0.077 (3)0.044 (2)0.005 (2)0.011 (2)0.006 (2)
N60.050 (2)0.078 (3)0.043 (2)0.005 (2)0.0104 (19)0.004 (2)
O50.061 (2)0.097 (3)0.054 (2)0.0003 (19)0.0063 (17)0.0204 (19)
O60.061 (2)0.094 (3)0.060 (2)0.008 (2)0.0109 (17)0.024 (2)
Cl10.103 (8)0.148 (10)0.057 (6)0.010 (7)0.017 (5)0.044 (5)
O1A0.144 (18)0.21 (2)0.30 (3)0.080 (16)0.027 (16)0.19 (2)
O2A0.20 (2)0.135 (14)0.061 (10)0.06 (2)0.019 (14)0.004 (10)
O3A0.151 (15)0.34 (3)0.21 (2)0.10 (2)0.115 (15)0.12 (2)
O4A0.121 (10)0.068 (7)0.112 (9)0.016 (6)0.049 (8)0.011 (6)
Cl20.056 (3)0.068 (3)0.083 (5)0.006 (2)0.030 (3)0.020 (3)
O1B0.149 (10)0.127 (8)0.143 (9)0.011 (8)0.062 (8)0.069 (7)
O2B0.097 (8)0.178 (11)0.084 (8)0.048 (8)0.049 (8)0.038 (7)
O3B0.184 (12)0.155 (10)0.207 (12)0.100 (9)0.141 (10)0.088 (9)
O4B0.073 (7)0.34 (2)0.101 (8)0.070 (11)0.020 (6)0.096 (12)
O1W0.0513 (18)0.156 (3)0.0456 (18)0.035 (2)0.0194 (15)0.008 (2)
O2W0.0409 (16)0.107 (3)0.0432 (16)0.0036 (16)0.0136 (14)0.0110 (17)
O3W0.0512 (18)0.128 (3)0.0355 (16)0.0049 (18)0.0125 (14)0.0042 (17)
O4W0.106 (3)0.076 (2)0.0424 (17)0.030 (2)0.0175 (17)0.0025 (17)
O5W0.115 (3)0.085 (3)0.132 (3)0.007 (2)0.093 (3)0.006 (2)
O6W0.090 (3)0.258 (6)0.064 (2)0.092 (3)0.026 (2)0.007 (3)
Geometric parameters (Å, º) top
C1—N11.340 (5)C25—H250.9300
C1—C21.385 (5)C26—O61.256 (5)
C1—H10.9300C26—O51.259 (5)
C2—C31.385 (5)C26—C271.495 (6)
C2—H20.9300C27—C281.380 (6)
C3—C41.382 (5)C27—C321.388 (6)
C3—C61.480 (5)C28—C291.382 (6)
C4—C51.378 (5)C28—H280.9300
C4—H40.9300C29—C301.395 (6)
C5—N11.337 (5)C29—H290.9300
C5—H50.9300C30—N41.373 (5)
C6—C71.381 (5)C30—C311.391 (6)
C6—C101.396 (5)C31—C321.381 (5)
C7—C81.378 (5)C31—H310.9300
C7—H70.9300C32—H320.9300
C8—N21.337 (5)Mn1—O3W2.162 (3)
C8—H80.9300Mn1—O4W2.179 (3)
C9—N21.327 (5)Mn1—O1W2.187 (3)
C9—C101.382 (5)Mn1—O2W2.195 (3)
C9—H90.9300Mn1—N32.230 (3)
C10—H100.9300Mn1—N12.282 (3)
C11—N31.324 (5)N4—H4A0.8606
C11—C121.370 (6)N4—H4B0.8611
C11—H110.9300Cl1—O1A1.249 (19)
C12—C131.376 (6)Cl1—O4B1.294 (14)
C12—H120.9300Cl1—O2A1.33 (3)
C13—C141.376 (5)Cl1—O2B1.42 (2)
C13—C13i1.483 (8)Cl1—O3A1.44 (2)
C14—C151.376 (5)Cl1—O1B1.444 (16)
C14—H140.9300Cl1—O4A1.460 (15)
C15—N31.327 (5)Cl1—O3B1.464 (15)
C15—H150.9300O1A—Cl21.322 (16)
C16—N51.324 (6)O2A—Cl21.31 (2)
C16—C171.385 (6)O3A—Cl21.37 (2)
C16—H160.9300O4A—Cl21.479 (14)
C17—C181.377 (5)Cl2—O4B1.364 (12)
C17—H170.9300Cl2—O3B1.384 (13)
C18—C191.386 (6)Cl2—O1B1.417 (11)
C18—C211.485 (5)Cl2—O2B1.45 (2)
C19—C201.381 (6)O1W—H1W0.8200
C19—H190.9300O1W—H2W0.8170
C20—N51.328 (6)O2W—H3W0.8173
C20—H200.9300O2W—H4W0.8212
C21—C251.375 (5)O3W—H5W0.8164
C21—C221.381 (6)O3W—H6W0.8219
C22—C231.370 (5)O4W—H7W0.8214
C22—H220.9300O4W—H8W0.8201
C23—N61.322 (5)O5W—H9W0.8499
C23—H230.9300O5W—H10W0.8497
C24—N61.326 (5)O6W—H11W0.8498
C24—C251.370 (5)O6W—H12W0.8485
C24—H240.9300
N1—C1—C2123.2 (4)O6—C26—O5123.3 (4)
N1—C1—H1118.4O6—C26—C27118.6 (5)
C2—C1—H1118.4O5—C26—C27118.1 (5)
C1—C2—C3119.7 (4)C28—C27—C32117.2 (4)
C1—C2—H2120.2C28—C27—C26121.1 (4)
C3—C2—H2120.2C32—C27—C26121.7 (4)
C4—C3—C2117.0 (4)C27—C28—C29121.8 (4)
C4—C3—C6122.1 (4)C27—C28—H28119.1
C2—C3—C6121.0 (4)C29—C28—H28119.1
C5—C4—C3119.9 (4)C28—C29—C30120.6 (4)
C5—C4—H4120.0C28—C29—H29119.7
C3—C4—H4120.0C30—C29—H29119.7
N1—C5—C4123.5 (4)N4—C30—C31120.5 (5)
N1—C5—H5118.3N4—C30—C29121.5 (5)
C4—C5—H5118.3C31—C30—C29118.0 (4)
C7—C6—C10116.6 (4)C32—C31—C30120.4 (4)
C7—C6—C3122.8 (4)C32—C31—H31119.8
C10—C6—C3120.7 (4)C30—C31—H31119.8
C8—C7—C6119.5 (4)C31—C32—C27122.0 (4)
C8—C7—H7120.3C31—C32—H32119.0
C6—C7—H7120.3C27—C32—H32119.0
N2—C8—C7124.3 (4)O3W—Mn1—O4W88.25 (12)
N2—C8—H8117.9O3W—Mn1—O1W85.18 (11)
C7—C8—H8117.9O4W—Mn1—O1W93.79 (13)
N2—C9—C10123.6 (4)O3W—Mn1—O2W93.03 (12)
N2—C9—H9118.2O4W—Mn1—O2W178.11 (12)
C10—C9—H9118.2O1W—Mn1—O2W87.71 (12)
C9—C10—C6119.8 (4)O3W—Mn1—N392.66 (12)
C9—C10—H10120.1O4W—Mn1—N391.05 (13)
C6—C10—H10120.1O1W—Mn1—N3174.64 (13)
N3—C11—C12124.0 (4)O2W—Mn1—N387.50 (12)
N3—C11—H11118.0O3W—Mn1—N1173.95 (12)
C12—C11—H11118.0O4W—Mn1—N188.85 (11)
C11—C12—C13120.2 (4)O1W—Mn1—N189.71 (12)
C11—C12—H12119.9O2W—Mn1—N190.00 (12)
C13—C12—H12119.9N3—Mn1—N192.70 (12)
C12—C13—C14116.1 (4)C5—N1—C1116.6 (3)
C12—C13—C13i122.0 (5)C5—N1—Mn1119.6 (3)
C14—C13—C13i121.9 (5)C1—N1—Mn1122.6 (3)
C15—C14—C13120.0 (4)C9—N2—C8116.3 (4)
C15—C14—H14120.0C11—N3—C15115.9 (4)
C13—C14—H14120.0C11—N3—Mn1122.1 (3)
N3—C15—C14123.8 (4)C15—N3—Mn1121.9 (3)
N3—C15—H15118.1C30—N4—H4A113.4
C14—C15—H15118.1C30—N4—H4B117.1
N5—C16—C17124.8 (5)H4A—N4—H4B129.4
N5—C16—H16117.6C16—N5—C20115.9 (4)
C17—C16—H16117.6C23—N6—C24115.8 (4)
C18—C17—C16119.1 (4)O1A—Cl1—O2A117 (2)
C18—C17—H17120.4O1A—Cl1—O3A106.1 (19)
C16—C17—H17120.4O2A—Cl1—O3A108.0 (17)
C17—C18—C19116.5 (4)O1A—Cl1—O4A109.9 (16)
C17—C18—C21121.9 (4)O2A—Cl1—O4A109.5 (14)
C19—C18—C21121.5 (4)O3A—Cl1—O4A106.2 (16)
C20—C19—C18120.1 (4)O2A—Cl2—O1A112.9 (19)
C20—C19—H19120.0O4B—Cl2—O1B109.7 (11)
C18—C19—H19120.0O3B—Cl2—O1B106.6 (8)
N5—C20—C19123.6 (5)O4B—Cl2—O2B107.3 (8)
N5—C20—H20118.2O3B—Cl2—O2B109.2 (11)
C19—C20—H20118.2O1B—Cl2—O2B106.3 (11)
C25—C21—C22115.7 (4)Mn1—O1W—H1W122.7
C25—C21—C18122.9 (4)Mn1—O1W—H2W114.7
C22—C21—C18121.4 (4)H1W—O1W—H2W104.4
C23—C22—C21120.0 (4)Mn1—O2W—H3W116.3
C23—C22—H22120.0Mn1—O2W—H4W119.0
C21—C22—H22120.0H3W—O2W—H4W104.2
N6—C23—C22124.2 (4)Mn1—O3W—H5W111.7
N6—C23—H23117.9Mn1—O3W—H6W129.4
C22—C23—H23117.9H5W—O3W—H6W104.2
N6—C24—C25123.7 (4)Mn1—O4W—H7W120.1
N6—C24—H24118.1Mn1—O4W—H8W127.6
C25—C24—H24118.1H7W—O4W—H8W103.5
C24—C25—C21120.5 (4)H9W—O5W—H10W109.7
C24—C25—H25119.7H11W—O6W—H12W107.2
C21—C25—H25119.7
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O5ii0.822.052.743 (4)143
O1W—H2W···O5Wiii0.822.192.959 (4)157
O2W—H3W···O6W0.821.812.618 (4)170
O2W—H4W···N6iv0.821.912.727 (4)172
O3W—H5W···O5Wiii0.821.962.739 (4)159
O3W—H6W···N5i0.821.972.763 (4)161
O4W—H7W···N2ii0.821.922.745 (4)177
O4W—H8W···O2Wv0.822.313.103 (4)162
O5W—H9W···O5v0.851.952.789 (5)168
O5W—H10W···O60.851.872.706 (5)167
O6W—H11W···O5iv0.852.362.975 (5)130
O6W—H12W···O6vi0.852.052.687 (4)132
N4—H4A···O3Bvii0.862.213.018 (12)156
N4—H4A···O4Avii0.862.243.030 (13)152
N4—H4B···O1Bviii0.862.363.112 (15)146
N4—H4B···O2Aviii0.862.493.30 (3)156
N4—H4B···O2Bviii0.862.583.39 (2)157
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1/2, z+1/2; (iii) x, y+3/2, z+1/2; (iv) x, y+1/2, z+1/2; (v) x, y+1, z; (vi) x, y1/2, z+1/2; (vii) x+1, y+1/2, z+1/2; (viii) x+1, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Mn2(C10H8N2)3(H2O)8](C7H6NO2)2(ClO4)2·2C10H8N2·4H2O
Mr1578.15
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)19.4565 (6), 7.0010 (2), 31.1252 (9)
β (°) 120.322 (2)
V3)3659.73 (19)
Z2
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.25 × 0.23 × 0.19
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.885, 0.911
No. of measured, independent and
observed [I > 2σ(I)] reflections
43254, 6638, 3566
Rint0.106
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.137, 1.01
No. of reflections6638
No. of parameters514
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.38

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and XP in SHELXTL (Sheldrick, 2008)', SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Mn1—O3W2.162 (3)Mn1—O2W2.195 (3)
Mn1—O4W2.179 (3)Mn1—N32.230 (3)
Mn1—O1W2.187 (3)Mn1—N12.282 (3)
O3W—Mn1—O4W88.25 (12)O1W—Mn1—N3174.64 (13)
O3W—Mn1—O1W85.18 (11)O2W—Mn1—N387.50 (12)
O4W—Mn1—O1W93.79 (13)O3W—Mn1—N1173.95 (12)
O3W—Mn1—O2W93.03 (12)O4W—Mn1—N188.85 (11)
O4W—Mn1—O2W178.11 (12)O1W—Mn1—N189.71 (12)
O1W—Mn1—O2W87.71 (12)O2W—Mn1—N190.00 (12)
O3W—Mn1—N392.66 (12)N3—Mn1—N192.70 (12)
O4W—Mn1—N391.05 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O5i0.822.052.743 (4)143
O1W—H2W···O5Wii0.822.192.959 (4)157
O2W—H3W···O6W0.821.812.618 (4)170
O2W—H4W···N6iii0.821.912.727 (4)172
O3W—H5W···O5Wii0.821.962.739 (4)159
O3W—H6W···N5iv0.821.972.763 (4)161
O4W—H7W···N2i0.821.922.745 (4)177
O4W—H8W···O2Wv0.822.313.103 (4)162
O5W—H9W···O5v0.851.952.789 (5)168
O5W—H10W···O60.851.872.706 (5)167
O6W—H11W···O5iii0.852.362.975 (5)130
O6W—H12W···O6vi0.852.052.687 (4)132
N4—H4A···O3Bvii0.862.213.018 (12)156
N4—H4A···O4Avii0.862.243.030 (13)152
N4—H4B···O1Bviii0.862.363.112 (15)146
N4—H4B···O2Aviii0.862.493.30 (3)156
N4—H4B···O2Bviii0.862.583.39 (2)157
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+3/2, z+1/2; (iii) x, y+1/2, z+1/2; (iv) x+1, y+1, z+1; (v) x, y+1, z; (vi) x, y1/2, z+1/2; (vii) x+1, y+1/2, z+1/2; (viii) x+1, y1/2, z+1/2.
Table 3. ππ stacking interactions (Å, °) top
Cg1 is the centroid of the N1/C1–C5 ring, Cg2 is the centroid of the N2/C6–C10 ring, Cg3 is the centroid of the N5/C16–C20 ring and Cg4 is the centroid of the N6/C21–C25 ring.
CgICgJCgI···CgJaCgI···P(J)bCgJ···P(I)cSlippage
Cg1Cg2i3.696 (2)3.5073.3941.312
Cg1Cg2iv3.631 (2)3.3203.2601.144
Cg3Cg4vii3.834 (3)3.4453.5111.610
Cg3Cg4viii3.757 (3)3.4563.4411.468
Symmetry codes: (i) -x, y - 1/2, -z + 1/2; (iv) -x, y + 1/2, -z + 1/2; (vii) -x + 1, y - 1/2, -z + 1/2; (viii) -x + 1, y + 1/2, -z + 1/2. Notes: (a) the distance between centroids; (b) the perpendicular distance of CgI on ring plane J; (c) the perpendicular distance of CgJ on ring plane I; slippage is the vertical displacement between ring centroids.
 

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