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metal-organic compounds
Tetraaquabis[3-(pyridin-4-yl)benzoato-κN]manganese(II)
aDepartment of Environmental and Municipal Engineering, North China University of Water Conservancy and Electric Power, Zhengzhou 450011, People's Republic of China
*Correspondence e-mail: gaoruqin@ncwu.edu.cn
In the title compound, [Mn(C12H8NO2)2(H2O)4], the Mn2+ ion lies on a twofold rotation axis and has a distorted N2O4 octahedral coordination geometry formed by four water O atoms in the equatorial plane and two apical pyridyl N atoms. A three-dimensional network is formed in the by multiple O—H⋯O hydrogen bonds between the coordinating water molecules and the free carboxylate groups.
Related literature
For pyridyl–multicarboxylate–metal frameworks, see: Huang et al. (2007). For 3-pyridin-4-ylbenzoate compounds, see: Wu et al. (2011
) For the isotypic Co complex, see: Wang & Li (2011
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1994
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: XP in SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812014602/bt5868sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812014602/bt5868Isup2.hkl
The title compound, (1), was prepared according to the following process. A mixture of MnCO3 (0.012 g, 0.1 mmol), PBC (0.040 g, 0.2 mmol) and deionized water (10 ml) was sealed into a 25 ml Teflon-lined stainless autoclave. The autoclave was heated at 160 °C for four days. As cooled to room temperature gradually, pale yellow needle crystals of (1) suitable for X-ray analysis were obtained in 64% yield (based on Mn).
All H atoms were located in a difference map. The coordinates of the water H atoms were refined with U(H) set to 1.2Ueq(O). H atoms bonded to C were refined as riding with C-H = 0.95Å and 1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell
SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).[Mn(C12H8NO2)2(H2O)4] | F(000) = 1084 |
Mr = 523.39 | Dx = 1.503 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1769 reflections |
a = 24.935 (3) Å | θ = 3.0–27.6° |
b = 7.1911 (6) Å | µ = 0.63 mm−1 |
c = 13.9283 (16) Å | T = 293 K |
β = 112.199 (13)° | Needle, yellow |
V = 2312.4 (4) Å3 | 0.24 × 0.20 × 0.16 mm |
Z = 4 |
Siemens SMART CCD diffractometer | 2035 independent reflections |
Radiation source: fine-focus sealed tube | 1673 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω scan | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −29→29 |
Tmin = 0.875, Tmax = 0.913 | k = −5→8 |
4456 measured reflections | l = −16→16 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0389P)2] where P = (Fo2 + 2Fc2)/3 |
2035 reflections | (Δ/σ)max < 0.001 |
171 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
[Mn(C12H8NO2)2(H2O)4] | V = 2312.4 (4) Å3 |
Mr = 523.39 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.935 (3) Å | µ = 0.63 mm−1 |
b = 7.1911 (6) Å | T = 293 K |
c = 13.9283 (16) Å | 0.24 × 0.20 × 0.16 mm |
β = 112.199 (13)° |
Siemens SMART CCD diffractometer | 2035 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1673 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 0.913 | Rint = 0.028 |
4456 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.19 e Å−3 |
2035 reflections | Δρmin = −0.20 e Å−3 |
171 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 | ||
Mn1 | 0.0000 | 0.30640 (6) | 0.7500 | 0.03055 (16) | |
O1 | 0.46120 (6) | 0.2912 (2) | 0.87784 (13) | 0.0494 (4) | |
O2 | 0.40494 (7) | 0.2263 (2) | 0.96408 (12) | 0.0557 (5) | |
O3 | 0.03234 (7) | 0.5054 (2) | 0.87792 (12) | 0.0434 (4) | |
O4 | −0.02832 (7) | 0.0811 (2) | 0.63641 (12) | 0.0414 (4) | |
N1 | 0.08789 (7) | 0.3200 (2) | 0.73735 (13) | 0.0343 (4) | |
C1 | 0.41251 (9) | 0.2746 (3) | 0.88379 (18) | 0.0373 (5) | |
C2 | 0.35888 (8) | 0.3161 (3) | 0.78874 (16) | 0.0307 (5) | |
C3 | 0.30485 (8) | 0.3071 (3) | 0.79533 (16) | 0.0304 (4) | |
H3 | 0.3024 | 0.2747 | 0.8597 | 0.036* | |
C4 | 0.25382 (8) | 0.3442 (3) | 0.71007 (15) | 0.0296 (5) | |
C5 | 0.25909 (9) | 0.3921 (3) | 0.61674 (16) | 0.0372 (5) | |
H5 | 0.2253 | 0.4182 | 0.5574 | 0.045* | |
C6 | 0.31246 (9) | 0.4019 (3) | 0.60960 (16) | 0.0422 (6) | |
H6 | 0.3151 | 0.4351 | 0.5455 | 0.051* | |
C7 | 0.36272 (9) | 0.3639 (3) | 0.69523 (17) | 0.0372 (5) | |
H7 | 0.3995 | 0.3707 | 0.6895 | 0.045* | |
C8 | 0.19674 (8) | 0.3344 (3) | 0.71925 (15) | 0.0294 (5) | |
C9 | 0.19034 (9) | 0.3677 (3) | 0.81302 (16) | 0.0368 (5) | |
H9 | 0.2233 | 0.3967 | 0.8732 | 0.044* | |
C10 | 0.13683 (9) | 0.3587 (3) | 0.81876 (17) | 0.0384 (5) | |
H10 | 0.1341 | 0.3812 | 0.8840 | 0.046* | |
C11 | 0.09364 (9) | 0.2880 (3) | 0.64725 (17) | 0.0362 (5) | |
H11 | 0.0598 | 0.2597 | 0.5884 | 0.043* | |
C12 | 0.14589 (9) | 0.2939 (3) | 0.63492 (16) | 0.0364 (5) | |
H12 | 0.1473 | 0.2703 | 0.5688 | 0.044* | |
H3A | 0.0499 (10) | 0.451 (3) | 0.9365 (18) | 0.055* | |
H4A | −0.0072 (10) | −0.013 (3) | 0.6343 (18) | 0.055* | |
H3B | 0.0120 (11) | 0.588 (3) | 0.8818 (18) | 0.055* | |
H4B | −0.0448 (10) | 0.126 (3) | 0.5770 (19) | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0213 (3) | 0.0359 (3) | 0.0354 (3) | 0.000 | 0.0119 (2) | 0.000 |
O1 | 0.0229 (8) | 0.0438 (9) | 0.0791 (12) | −0.0003 (7) | 0.0165 (8) | 0.0015 (8) |
O2 | 0.0358 (9) | 0.0824 (12) | 0.0427 (9) | −0.0011 (8) | 0.0076 (8) | 0.0058 (9) |
O3 | 0.0351 (10) | 0.0453 (10) | 0.0458 (10) | 0.0083 (7) | 0.0107 (8) | −0.0068 (8) |
O4 | 0.0409 (10) | 0.0388 (9) | 0.0435 (9) | 0.0052 (7) | 0.0147 (8) | −0.0010 (7) |
N1 | 0.0263 (9) | 0.0370 (10) | 0.0409 (10) | 0.0025 (8) | 0.0139 (8) | 0.0045 (8) |
C1 | 0.0272 (12) | 0.0313 (11) | 0.0493 (13) | −0.0015 (10) | 0.0098 (10) | −0.0065 (10) |
C2 | 0.0238 (11) | 0.0273 (10) | 0.0420 (12) | −0.0025 (9) | 0.0136 (9) | −0.0063 (9) |
C3 | 0.0271 (11) | 0.0300 (10) | 0.0365 (11) | −0.0015 (9) | 0.0149 (9) | −0.0028 (9) |
C4 | 0.0254 (11) | 0.0277 (11) | 0.0388 (11) | −0.0013 (9) | 0.0157 (9) | −0.0013 (9) |
C5 | 0.0293 (12) | 0.0440 (12) | 0.0368 (12) | −0.0019 (10) | 0.0110 (10) | 0.0020 (10) |
C6 | 0.0404 (14) | 0.0547 (14) | 0.0383 (12) | −0.0023 (12) | 0.0227 (11) | 0.0028 (11) |
C7 | 0.0294 (12) | 0.0384 (12) | 0.0508 (13) | −0.0050 (10) | 0.0229 (11) | −0.0056 (10) |
C8 | 0.0248 (11) | 0.0276 (11) | 0.0373 (11) | 0.0021 (9) | 0.0134 (9) | 0.0050 (9) |
C9 | 0.0255 (11) | 0.0453 (12) | 0.0387 (12) | −0.0006 (10) | 0.0110 (10) | −0.0005 (10) |
C10 | 0.0287 (12) | 0.0524 (13) | 0.0366 (11) | 0.0023 (10) | 0.0152 (10) | 0.0000 (10) |
C11 | 0.0241 (11) | 0.0423 (12) | 0.0398 (12) | 0.0009 (10) | 0.0094 (9) | 0.0006 (10) |
C12 | 0.0295 (12) | 0.0443 (12) | 0.0377 (11) | 0.0001 (10) | 0.0154 (10) | −0.0011 (10) |
Mn1—O4 | 2.1867 (16) | C3—C4 | 1.400 (3) |
Mn1—O4i | 2.1867 (16) | C3—H3 | 0.9500 |
Mn1—O3 | 2.1878 (16) | C4—C5 | 1.398 (3) |
Mn1—O3i | 2.1878 (16) | C4—C8 | 1.478 (3) |
Mn1—N1 | 2.2661 (16) | C5—C6 | 1.373 (3) |
Mn1—N1i | 2.2661 (16) | C5—H5 | 0.9500 |
O1—C1 | 1.253 (2) | C6—C7 | 1.392 (3) |
O2—C1 | 1.252 (3) | C6—H6 | 0.9500 |
O3—H3A | 0.86 (2) | C7—H7 | 0.9500 |
O3—H3B | 0.80 (2) | C8—C9 | 1.395 (3) |
O4—H4A | 0.86 (3) | C8—C12 | 1.395 (3) |
O4—H4B | 0.84 (2) | C9—C10 | 1.368 (3) |
N1—C11 | 1.336 (3) | C9—H9 | 0.9500 |
N1—C10 | 1.344 (3) | C10—H10 | 0.9500 |
C1—C2 | 1.514 (3) | C11—C12 | 1.378 (3) |
C2—C7 | 1.385 (3) | C11—H11 | 0.9500 |
C2—C3 | 1.386 (3) | C12—H12 | 0.9500 |
O4—Mn1—O4i | 84.40 (9) | C2—C3—C4 | 121.98 (18) |
O4—Mn1—O3 | 173.04 (6) | C2—C3—H3 | 119.0 |
O4i—Mn1—O3 | 88.64 (6) | C4—C3—H3 | 119.0 |
O4—Mn1—O3i | 88.64 (6) | C5—C4—C3 | 117.47 (18) |
O4i—Mn1—O3i | 173.04 (6) | C5—C4—C8 | 121.60 (18) |
O3—Mn1—O3i | 98.31 (10) | C3—C4—C8 | 120.92 (18) |
O4—Mn1—N1 | 91.89 (6) | C6—C5—C4 | 120.93 (19) |
O4i—Mn1—N1 | 91.76 (6) | C6—C5—H5 | 119.5 |
O3—Mn1—N1 | 88.02 (6) | C4—C5—H5 | 119.5 |
O3i—Mn1—N1 | 88.75 (6) | C5—C6—C7 | 120.74 (19) |
O4—Mn1—N1i | 91.76 (6) | C5—C6—H6 | 119.6 |
O4i—Mn1—N1i | 91.89 (6) | C7—C6—H6 | 119.6 |
O3—Mn1—N1i | 88.75 (6) | C2—C7—C6 | 119.66 (19) |
O3i—Mn1—N1i | 88.02 (6) | C2—C7—H7 | 120.2 |
N1—Mn1—N1i | 175.06 (8) | C6—C7—H7 | 120.2 |
Mn1—O3—H3A | 112.0 (16) | C9—C8—C12 | 115.78 (18) |
Mn1—O3—H3B | 119.7 (18) | C9—C8—C4 | 121.83 (18) |
H3A—O3—H3B | 113 (2) | C12—C8—C4 | 122.39 (18) |
Mn1—O4—H4A | 124.7 (16) | C10—C9—C8 | 120.39 (19) |
Mn1—O4—H4B | 109.7 (17) | C10—C9—H9 | 119.8 |
H4A—O4—H4B | 110 (2) | C8—C9—H9 | 119.8 |
C11—N1—C10 | 116.28 (18) | N1—C10—C9 | 123.71 (19) |
C11—N1—Mn1 | 121.06 (14) | N1—C10—H10 | 118.1 |
C10—N1—Mn1 | 122.66 (14) | C9—C10—H10 | 118.1 |
O2—C1—O1 | 124.2 (2) | N1—C11—C12 | 123.65 (19) |
O2—C1—C2 | 117.03 (19) | N1—C11—H11 | 118.2 |
O1—C1—C2 | 118.8 (2) | C12—C11—H11 | 118.2 |
C7—C2—C3 | 119.22 (19) | C11—C12—C8 | 120.20 (19) |
C7—C2—C1 | 121.28 (19) | C11—C12—H12 | 119.9 |
C3—C2—C1 | 119.50 (18) | C8—C12—H12 | 119.9 |
Symmetry code: (i) −x, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2ii | 0.86 (2) | 1.91 (2) | 2.732 (2) | 160 (2) |
O3—H3B···O1iii | 0.80 (2) | 1.92 (3) | 2.715 (2) | 175 (2) |
O4—H4A···O1iv | 0.86 (3) | 1.86 (3) | 2.728 (2) | 176 (2) |
O4—H4B···O2v | 0.84 (2) | 1.92 (2) | 2.726 (2) | 161 (2) |
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+2; (iii) x−1/2, y+1/2, z; (iv) −x+1/2, y−1/2, −z+3/2; (v) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C12H8NO2)2(H2O)4] |
Mr | 523.39 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.935 (3), 7.1911 (6), 13.9283 (16) |
β (°) | 112.199 (13) |
V (Å3) | 2312.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.63 |
Crystal size (mm) | 0.24 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.875, 0.913 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4456, 2035, 1673 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.079, 1.05 |
No. of reflections | 2035 |
No. of parameters | 171 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.20 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2i | 0.86 (2) | 1.91 (2) | 2.732 (2) | 160 (2) |
O3—H3B···O1ii | 0.80 (2) | 1.92 (3) | 2.715 (2) | 175 (2) |
O4—H4A···O1iii | 0.86 (3) | 1.86 (3) | 2.728 (2) | 176 (2) |
O4—H4B···O2iv | 0.84 (2) | 1.92 (2) | 2.726 (2) | 161 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+2; (ii) x−1/2, y+1/2, z; (iii) −x+1/2, y−1/2, −z+3/2; (iv) x−1/2, −y+1/2, z−1/2. |
Acknowledgements
This work was supported by the Natural Science Foundation of China.
References
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Pyridyl-containing multi-carboxylic acids have been extensively investigated on the construction of various metal-organic frameworks (Huang et al., 2007). Pyridylbenzoate ligands which possess a pyridyl group and a benzoic acid group are typical unsymmetrical spacers. Very recently, a serial of coordination polymers of 3-pyridin-4-ylbenzoic acid (PBC) was synthesized and characterized (Wu, et al., 2011). Herein we report a new Mn(II) complex with (PBC), namely, [Mn(PBC)2(H2O)4] (1) which is isostructural with the complex [Co(PBC)2(H2O)4] (Wang & Li, 2011).
As showed in Fig. 1, (1) is a mononuclear complex with a twofold axis passing through the Mn(II) center along b axis and equally splitting the whole molecule. In (1) the Mn(II) center is ligated by four O of coordinated water molecules in the equatorial plane, and two PBC acting as monodentate ligands occupy the axial positions through their pyridyl nitrogen atoms coordinating to Mn(II). Thus the Mn(II) ion is in a six-coordinated octahedral geometry. The bond distances of Mn—O and Mn—N range from 2.1867 (16) to 2.2661 (16) Å, while the in-plane and axis-transition angles are 173.04 (6) and 175.06 (8) °, respectively, indicating a slight distortion of the octahedral coordination sphere around the Mn(II) center.
Further aggregation of the monomers (1) is formed by the multiple hydrogen-bonding between the coordinated water molecules (as donors) and the uncoordinated carboxylate groups (as acceptors) (Table 1). Hydrogen-bonding system among monomers (1) is rather complicated: each water molecule forms two O—H···O hydrogen bonds with carboxylate groups of neighbouring complex molecules, while every carboxylate group of PBC forms three hydrogen bonds. Consequently, every monomer acts as a novel six-connected supramolecular synthon to connect with six adjacent monomers. Notably, the hydrogen-bonding models of the carboxyl group of PBC play an important role in the formation of crystal structure of (1). For example, as shown in Fig. 2, the O1 atom of the carboxylate group of PBC in a hydrogen-bonding bridging mode ligates to two water molecules from two neighboring monomers, and as a result, monomers (1) are regularly arrayed in ab plane and linked into two-dimensional layers by strong hydrogen bonding (O3···O1, 2.715 (2) Å; O4···O1, 2.728 (2) Å). The layer structure is stabilized by forceful face-to-face π···π stacking interactions between adjacent benzoicate groups and pyridyl groups of PBC with a centroid to centroid distance of 3.62 (1) Å. Intriguingly, the benzoicate group and pyridyl group of PBC distort to 27.6 (0) ° to meet the formation of hydrogen bonding. The layers are further bound together to create the three-dimensional supramolecular architecture by hydrogen bonds between the O2 atom of the carboxylate group of PBC and two water molecules in the adjacent complex molecue. monomer.