metal-organic compounds
trans-Tetraaquabis[bis(pyridin-3-yl)methanone-κN]manganese(II) bis(perchlorate)
aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
*Correspondence e-mail: binliu92@yahoo.cn
In the title complex, [Mn(C11H8N2O)2(H2O)4](ClO4)2, the Mn2+ ion is located on an inversion center with the slightly distorted N2O4 octahedral coordination sphere comprising N-atom donors from two monodentate trans-related bis(pyridin-3-yl)methanone ligands and four water ligands. The two perchlorate anions are linked to the mononuclear complex molecule through water O—H⋯O hydrogen bonds while inter-complex water O—H⋯N(pyridine) interactions form an infinite chain structure extending along the b axis. The perchlorate anions also function as inter-unit links through water O—H⋯O hydrogen bonds which, together with water O—H⋯O(carbonyl) interactions, give a three-dimensional framework structure.
Related literature
For background to coordination chemistry based on pyridylmethanone derivatives, see: Huang et al. (2003); Chen et al. (2005); For transition metal complexes of bis(pyridin-3-yl)methanone, see: Zhang (2011); Chen & Mak (2005).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536811052184/zs2167sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811052184/zs2167Isup2.hkl
Bis(pyridin-3-yl)methanone was prepared according to the previously reported procedure (Chen & Mak 2005). The title complex was synthesized by reacting the ligand (19 mg, 0.1 mmol) with Mn(ClO4)2 . 6H2O (36 mg, 0.1 mmol) in 5 ml of methanol followed by the addition of 1 ml of deionized water. The clear solution obtained was stirred at room temperature for three hours, filtered and the filtrate left to slowly evaporate at room temperature. The block-like crystals were deposited after about three weeks (22.9 mg, 66% yield based on the ligand).
All H atoms were located in the difference electron density maps but were placed in idealized positions and allowed to ride on the carrier atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C or O).
Data collection: APEX2 (Bruker 2007); cell
SAINT (Bruker 2007); data reduction: SAINT (Bruker 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009).[Mn(C11H8N2O)2(H2O)4](ClO4)2 | F(000) = 710 |
Mr = 694.29 | Dx = 1.601 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 261 reflections |
a = 8.410 (2) Å | θ = 2.2–27.2° |
b = 11.962 (3) Å | µ = 0.72 mm−1 |
c = 14.386 (4) Å | T = 296 K |
β = 95.476 (5)° | Block, colorless |
V = 1440.6 (6) Å3 | 0.45 × 0.32 × 0.25 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 2529 independent reflections |
Radiation source: fine-focus sealed tube | 1853 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −10→9 |
Tmin = 0.572, Tmax = 1.000 | k = −13→14 |
7576 measured reflections | l = −8→17 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0816P)2] P = (Fo2 + 2Fc2)/3 |
2529 reflections | (Δ/σ)max < 0.001 |
196 parameters | Δρmax = 0.48 e Å−3 |
4 restraints | Δρmin = −0.51 e Å−3 |
[Mn(C11H8N2O)2(H2O)4](ClO4)2 | V = 1440.6 (6) Å3 |
Mr = 694.29 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.410 (2) Å | µ = 0.72 mm−1 |
b = 11.962 (3) Å | T = 296 K |
c = 14.386 (4) Å | 0.45 × 0.32 × 0.25 mm |
β = 95.476 (5)° |
Bruker APEXII CCD area-detector diffractometer | 2529 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 1853 reflections with I > 2σ(I) |
Tmin = 0.572, Tmax = 1.000 | Rint = 0.076 |
7576 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 4 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.48 e Å−3 |
2529 reflections | Δρmin = −0.51 e Å−3 |
196 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.0230 (3) | |
O1 | 0.1206 (3) | 0.9254 (2) | 0.26771 (19) | 0.0445 (8) | |
N1 | 0.3187 (5) | 1.1514 (3) | 0.4615 (3) | 0.0486 (10) | |
N2 | 0.2861 (3) | 0.6001 (2) | 0.4305 (2) | 0.0298 (7) | |
C1 | 0.3036 (6) | 1.1271 (4) | 0.5509 (3) | 0.0560 (13) | |
H1A | 0.3305 | 1.1816 | 0.5958 | 0.067* | |
C2 | 0.2504 (6) | 1.0259 (4) | 0.5794 (3) | 0.0587 (14) | |
H2A | 0.2426 | 1.0122 | 0.6425 | 0.070* | |
C3 | 0.2084 (5) | 0.9447 (3) | 0.5142 (3) | 0.0443 (11) | |
H3A | 0.1721 | 0.8753 | 0.5322 | 0.053* | |
C4 | 0.2211 (4) | 0.9681 (3) | 0.4213 (3) | 0.0296 (9) | |
C5 | 0.2765 (5) | 1.0732 (3) | 0.3991 (3) | 0.0428 (11) | |
H5A | 0.2843 | 1.0895 | 0.3365 | 0.051* | |
C6 | 0.1683 (4) | 0.8891 (3) | 0.3445 (3) | 0.0304 (9) | |
C7 | 0.1633 (4) | 0.7661 (3) | 0.3635 (2) | 0.0272 (8) | |
C8 | 0.2842 (4) | 0.7106 (3) | 0.4172 (3) | 0.0300 (9) | |
H8A | 0.3684 | 0.7526 | 0.4455 | 0.036* | |
C9 | 0.1591 (4) | 0.5423 (3) | 0.3913 (3) | 0.0391 (10) | |
H9A | 0.1553 | 0.4656 | 0.4015 | 0.047* | |
C10 | 0.0360 (5) | 0.5911 (3) | 0.3373 (3) | 0.0500 (13) | |
H10A | −0.0487 | 0.5478 | 0.3113 | 0.060* | |
C11 | 0.0373 (5) | 0.7041 (3) | 0.3213 (3) | 0.0403 (11) | |
H11A | −0.0442 | 0.7382 | 0.2831 | 0.048* | |
Cl1 | 0.58846 (12) | 0.78266 (8) | 0.19059 (7) | 0.0363 (3) | |
O2 | 0.4655 (4) | 0.8174 (4) | 0.2446 (3) | 0.0884 (13) | |
O3 | 0.5324 (4) | 0.7861 (3) | 0.0946 (2) | 0.0706 (11) | |
O4 | 0.6421 (5) | 0.6736 (3) | 0.2170 (2) | 0.0752 (12) | |
O5 | 0.7196 (4) | 0.8584 (3) | 0.2095 (3) | 0.0671 (10) | |
O1W | 0.5725 (3) | 0.6446 (2) | 0.58278 (18) | 0.0372 (7) | |
O2W | 0.6431 (3) | 0.5430 (2) | 0.38484 (19) | 0.0429 (7) | |
H1WA | 0.6090 | 0.7146 | 0.5761 | 0.064* | |
H2WA | 0.6821 | 0.4815 | 0.3606 | 0.064* | |
H2WB | 0.6215 | 0.5865 | 0.3351 | 0.064* | |
H1WB | 0.5147 | 0.6440 | 0.6352 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0316 (5) | 0.0164 (4) | 0.0206 (4) | −0.0026 (3) | 0.0008 (3) | 0.0006 (3) |
O1 | 0.069 (2) | 0.0323 (15) | 0.0293 (16) | 0.0054 (14) | −0.0088 (14) | 0.0023 (13) |
N1 | 0.075 (3) | 0.0299 (19) | 0.041 (2) | −0.0167 (18) | 0.0046 (19) | 0.0002 (16) |
N2 | 0.0303 (17) | 0.0231 (17) | 0.0355 (19) | −0.0009 (13) | 0.0006 (14) | −0.0005 (14) |
C1 | 0.087 (4) | 0.037 (3) | 0.043 (3) | −0.017 (2) | 0.001 (3) | −0.010 (2) |
C2 | 0.107 (4) | 0.043 (3) | 0.027 (2) | −0.024 (3) | 0.008 (3) | −0.001 (2) |
C3 | 0.071 (3) | 0.029 (2) | 0.033 (2) | −0.011 (2) | 0.004 (2) | 0.0025 (18) |
C4 | 0.037 (2) | 0.0231 (18) | 0.029 (2) | −0.0018 (16) | 0.0037 (17) | −0.0006 (16) |
C5 | 0.066 (3) | 0.033 (2) | 0.029 (2) | −0.007 (2) | 0.004 (2) | 0.0059 (18) |
C6 | 0.035 (2) | 0.025 (2) | 0.031 (2) | 0.0033 (16) | −0.0004 (17) | 0.0002 (16) |
C7 | 0.029 (2) | 0.027 (2) | 0.026 (2) | 0.0007 (15) | 0.0037 (16) | −0.0037 (16) |
C8 | 0.030 (2) | 0.025 (2) | 0.034 (2) | −0.0047 (15) | −0.0026 (17) | −0.0045 (16) |
C9 | 0.037 (2) | 0.025 (2) | 0.055 (3) | −0.0073 (18) | 0.004 (2) | −0.0016 (19) |
C10 | 0.030 (2) | 0.033 (2) | 0.083 (4) | −0.0073 (18) | −0.013 (2) | −0.009 (2) |
C11 | 0.032 (2) | 0.034 (2) | 0.053 (3) | 0.0036 (18) | −0.008 (2) | −0.005 (2) |
Cl1 | 0.0444 (6) | 0.0336 (6) | 0.0316 (6) | 0.0038 (4) | 0.0070 (4) | 0.0028 (4) |
O2 | 0.067 (3) | 0.130 (4) | 0.075 (3) | 0.023 (2) | 0.040 (2) | 0.003 (3) |
O3 | 0.097 (3) | 0.073 (2) | 0.039 (2) | 0.025 (2) | −0.0151 (19) | −0.0047 (17) |
O4 | 0.123 (3) | 0.0360 (18) | 0.064 (3) | 0.012 (2) | −0.003 (2) | 0.0135 (17) |
O5 | 0.061 (2) | 0.058 (2) | 0.082 (3) | −0.0116 (17) | −0.0004 (19) | 0.0085 (19) |
O1W | 0.0595 (18) | 0.0210 (13) | 0.0305 (15) | −0.0106 (12) | 0.0009 (13) | −0.0003 (11) |
O2W | 0.0547 (18) | 0.0373 (16) | 0.0393 (17) | −0.0002 (14) | 0.0173 (14) | 0.0067 (13) |
Mn1—O1Wi | 2.155 (2) | C5—H5A | 0.9300 |
Mn1—O1W | 2.155 (2) | C6—C7 | 1.499 (5) |
Mn1—O2W | 2.199 (3) | C7—C11 | 1.386 (5) |
Mn1—O2Wi | 2.199 (3) | C7—C8 | 1.386 (5) |
Mn1—N2i | 2.307 (3) | C8—H8A | 0.9300 |
Mn1—N2 | 2.307 (3) | C9—C10 | 1.365 (6) |
O1—C6 | 1.218 (4) | C9—H9A | 0.9300 |
N1—C5 | 1.321 (5) | C10—C11 | 1.371 (6) |
N1—C1 | 1.337 (6) | C10—H10A | 0.9300 |
N2—C8 | 1.336 (4) | C11—H11A | 0.9300 |
N2—C9 | 1.350 (4) | Cl1—O2 | 1.414 (4) |
C1—C2 | 1.367 (6) | Cl1—O3 | 1.416 (3) |
C1—H1A | 0.9300 | Cl1—O4 | 1.420 (3) |
C2—C3 | 1.374 (6) | Cl1—O5 | 1.434 (3) |
C2—H2A | 0.9300 | O1W—H1WA | 0.9000 |
C3—C4 | 1.379 (5) | O1W—H1WB | 0.9400 |
C3—H3A | 0.9300 | O2W—H2WA | 0.8900 |
C4—C5 | 1.389 (5) | O2W—H2WB | 0.8900 |
C4—C6 | 1.489 (5) | ||
O1Wi—Mn1—O1W | 180.00 (7) | N1—C5—H5A | 118.0 |
O1Wi—Mn1—O2W | 85.27 (10) | C4—C5—H5A | 118.0 |
O1W—Mn1—O2W | 94.73 (10) | O1—C6—C4 | 119.8 (3) |
O1Wi—Mn1—O2Wi | 94.73 (10) | O1—C6—C7 | 120.1 (3) |
O1W—Mn1—O2Wi | 85.27 (10) | C4—C6—C7 | 119.9 (3) |
O2W—Mn1—O2Wi | 180.0 | C11—C7—C8 | 118.6 (3) |
O1Wi—Mn1—N2i | 89.47 (10) | C11—C7—C6 | 118.6 (3) |
O1W—Mn1—N2i | 90.53 (10) | C8—C7—C6 | 122.7 (3) |
O2W—Mn1—N2i | 89.29 (11) | N2—C8—C7 | 123.5 (3) |
O2Wi—Mn1—N2i | 90.71 (11) | N2—C8—H8A | 118.2 |
O1Wi—Mn1—N2 | 90.53 (10) | C7—C8—H8A | 118.2 |
O1W—Mn1—N2 | 89.47 (10) | N2—C9—C10 | 123.1 (4) |
O2W—Mn1—N2 | 90.71 (11) | N2—C9—H9A | 118.5 |
O2Wi—Mn1—N2 | 89.29 (11) | C10—C9—H9A | 118.5 |
N2i—Mn1—N2 | 180.000 (1) | C9—C10—C11 | 120.0 (4) |
C5—N1—C1 | 117.2 (4) | C9—C10—H10A | 120.0 |
C8—N2—C9 | 116.6 (3) | C11—C10—H10A | 120.0 |
C8—N2—Mn1 | 125.0 (2) | C10—C11—C7 | 118.2 (4) |
C9—N2—Mn1 | 117.9 (2) | C10—C11—H11A | 120.9 |
N1—C1—C2 | 123.0 (4) | C7—C11—H11A | 120.9 |
N1—C1—H1A | 118.5 | O2—Cl1—O3 | 109.5 (2) |
C2—C1—H1A | 118.5 | O2—Cl1—O4 | 110.7 (3) |
C1—C2—C3 | 119.4 (4) | O3—Cl1—O4 | 110.8 (2) |
C1—C2—H2A | 120.3 | O2—Cl1—O5 | 107.5 (2) |
C3—C2—H2A | 120.3 | O3—Cl1—O5 | 110.2 (2) |
C2—C3—C4 | 118.7 (4) | O4—Cl1—O5 | 108.1 (2) |
C2—C3—H3A | 120.6 | Mn1—O1W—H1WA | 140.3 |
C4—C3—H3A | 120.6 | Mn1—O1W—H1WB | 107.0 |
C3—C4—C5 | 117.7 (4) | H1WA—O1W—H1WB | 108 |
C3—C4—C6 | 123.1 (3) | Mn1—O2W—H2WA | 110.5 |
C5—C4—C6 | 119.1 (3) | Mn1—O2W—H2WB | 131.2 |
N1—C5—C4 | 124.0 (4) | H2WA—O2W—H2WB | 102.9 |
O1Wi—Mn1—N2—C8 | −150.3 (3) | C5—C4—C6—O1 | −25.7 (6) |
O1W—Mn1—N2—C8 | 29.7 (3) | C3—C4—C6—C7 | −25.7 (6) |
O2W—Mn1—N2—C8 | −65.0 (3) | C5—C4—C6—C7 | 158.5 (4) |
O2Wi—Mn1—N2—C8 | 115.0 (3) | O1—C6—C7—C11 | −35.3 (5) |
O1Wi—Mn1—N2—C9 | 22.3 (3) | C4—C6—C7—C11 | 140.5 (4) |
O1W—Mn1—N2—C9 | −157.7 (3) | O1—C6—C7—C8 | 141.0 (4) |
O2W—Mn1—N2—C9 | 107.5 (3) | C4—C6—C7—C8 | −43.3 (5) |
O2Wi—Mn1—N2—C9 | −72.5 (3) | C9—N2—C8—C7 | −2.4 (6) |
C5—N1—C1—C2 | 1.4 (8) | Mn1—N2—C8—C7 | 170.3 (3) |
N1—C1—C2—C3 | −0.7 (9) | C11—C7—C8—N2 | 0.1 (6) |
C1—C2—C3—C4 | −0.1 (8) | C6—C7—C8—N2 | −176.1 (4) |
C2—C3—C4—C5 | 0.2 (7) | C8—N2—C9—C10 | 2.5 (6) |
C2—C3—C4—C6 | −175.6 (4) | Mn1—N2—C9—C10 | −170.6 (4) |
C1—N1—C5—C4 | −1.3 (7) | N2—C9—C10—C11 | −0.4 (7) |
C3—C4—C5—N1 | 0.5 (7) | C9—C10—C11—C7 | −1.9 (7) |
C6—C4—C5—N1 | 176.5 (4) | C8—C7—C11—C10 | 2.0 (6) |
C3—C4—C6—O1 | 150.1 (4) | C6—C7—C11—C10 | 178.4 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···N1ii | 0.90 | 1.82 | 2.704 (4) | 169 |
O2W—H2WA···O5iii | 0.89 | 2.01 | 2.889 (5) | 171 |
O2W—H2WB···O4 | 0.89 | 2.01 | 2.876 (4) | 162 |
O1W—H1WB···O1iv | 0.94 | 2.19 | 2.782 (3) | 120 |
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+3/2, y−1/2, −z+1/2; (iv) x+1/2, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C11H8N2O)2(H2O)4](ClO4)2 |
Mr | 694.29 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 8.410 (2), 11.962 (3), 14.386 (4) |
β (°) | 95.476 (5) |
V (Å3) | 1440.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.45 × 0.32 × 0.25 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.572, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7576, 2529, 1853 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.143, 1.04 |
No. of reflections | 2529 |
No. of parameters | 196 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.51 |
Computer programs: APEX2 (Bruker 2007), SAINT (Bruker 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···N1i | 0.90 | 1.82 | 2.704 (4) | 169 |
O2W—H2WA···O5ii | 0.89 | 2.01 | 2.889 (5) | 171 |
O2W—H2WB···O4 | 0.89 | 2.01 | 2.876 (4) | 162 |
O1W—H1WB···O1iii | 0.94 | 2.19 | 2.782 (3) | 120 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+3/2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2. |
Acknowledgements
The authors are grateful for financial support from the Beijing Municipal Education Commission.
References
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The coordination chemistry of the pyridyl ketone derivatives has attracted much attention due to the angular-shaped C(sp2)—CO—C(sp2) moiety and the rotatable C—C σ bonds to the pyridyl groups (Huang et al., 2003; Chen et al., 2005). Recently, we reported the zigzag chain structure of the zinc(II) complex with bis(pyridin-3-yl)methanone (Zhang, 2011). Herein, we report the structure of a new mononuclear complex of this ligand with manganese(II), the title complex [Mn(C11H12N2O)2(H2O)4](ClO4)2.
In this complex, the Mn2+ ion is located on an inversion center with the slightly distorted N2O4 octahedral coordination sphere comprising N-atom donors from two monodentate trans-related bis(pyridine-3-yl)methanone ligands and four water ligands (Fig. 1). This is significantly different from that found in the polymeric complex [(CuL2)(ClO4)2]n [L = bis(pyridin-3-yl)methanone], in which the N4O2 distorted octahedral Cu2+ center is surrounded by four equatorial pyridyl N-atom donors and two axially related perchlorate O-atoms (Chen et al., 2005). In the present structure, the two perchlorate anions are linked to the mononuclear complex moiety through water O2W—H···O4 hydrogen bonds (Table 1) while inter-complex water O1W—H···N1(pyridyl) interactions form an infinite chain structure extending along the b axis (Fig. 2). The perchlorate anions also function as inter-unit links through water O2W—H···O4/O5 hydrogen bonds which with water O1W—H··· O1(carbonyl) interactions give a three-dimensional framework structure.