In the centrosymmetric title complex, [Mn(C7H8N2O2)4(H2O)2](ClO4)2, the MnII ion is in an octahedral environment, with the equatorial plane being defined by the O atoms of four monodentate carboxylate groups, and the octahedron being completed by two trans-coordinated water molecules. There are intramolecular hydrogen bonds between the coordinated water molecules and the non-coordinated O atoms of the carboxylate groups. Hydrogen bonds between the amino groups and the carboxylate groups of neighbouring molecules generate a layered hydrogen-bonded network.
Supporting information
CCDC reference: 182985
Mn(ClO4)2·6H2O (1.00 mmol) was mixed with 4-amino-N-pyridine
acetate (4.00 mmol) in a thick Pyrex tube, and pyridine (0.10 ml) and
n-butanol (2.50 ml) were then added. The solution was heated at 363 K for 2 d,
and was then kept at ambient temperature for one week for crystallization.
Colourless prismatic crystals of (I) formed.
All H atoms were placed in geometrically calculated positions, with C—H =
0.93–0.97 Å and N—H = 0.86 Å, and refined as riding atoms, with
Uiso = 1.2Ueq(parent atom). The occupancy factor for a
second orientation of the perchlorate ion refined to close to 1/2, therefore
the occupancies of the perchlorate O atoms were set to 0.5 for the final
refinement.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Tetrakis[(4-aminopyridinio)acetato-
κO]diaquamanganese(II) diperchlorate
top
Crystal data top
[Mn(C7H8N2O2)4(H2O)2](ClO4)2 | Z = 1 |
Mr = 898.49 | F(000) = 463 |
Triclinic, P1 | Dx = 1.583 Mg m−3 |
a = 9.049 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.507 (3) Å | Cell parameters from 2867 reflections |
c = 10.779 (3) Å | θ = 1.4–27.8° |
α = 71.79 (4)° | µ = 0.58 mm−1 |
β = 89.52 (4)° | T = 293 K |
γ = 76.13 (4)° | Prism, colourless |
V = 942.7 (4) Å3 | 0.3 × 0.2 × 0.2 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3275 independent reflections |
Radiation source: fine-focus sealed tube | 2834 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1997) | h = −8→10 |
Tmin = 0.870, Tmax = 0.901 | k = −11→12 |
4859 measured reflections | l = −10→12 |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0923P)2 + 0.2644P] where P = (Fo2 + 2Fc2)/3 |
3275 reflections | (Δ/σ)max < 0.001 |
295 parameters | Δρmax = 0.48 e Å−3 |
160 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
[Mn(C7H8N2O2)4(H2O)2](ClO4)2 | γ = 76.13 (4)° |
Mr = 898.49 | V = 942.7 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 9.049 (2) Å | Mo Kα radiation |
b = 10.507 (3) Å | µ = 0.58 mm−1 |
c = 10.779 (3) Å | T = 293 K |
α = 71.79 (4)° | 0.3 × 0.2 × 0.2 mm |
β = 89.52 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3275 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1997) | 2834 reflections with I > 2σ(I) |
Tmin = 0.870, Tmax = 0.901 | Rint = 0.043 |
4859 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 160 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.48 e Å−3 |
3275 reflections | Δρmin = −0.45 e Å−3 |
295 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn | 0.5000 | 0.5000 | 0.5000 | 0.0412 (2) | |
O1W | 0.3803 (3) | 0.5874 (3) | 0.6475 (2) | 0.0598 (6) | |
H1WA | 0.3754 | 0.5083 | 0.7096 | 0.072* | |
H1WB | 0.2876 | 0.6282 | 0.6049 | 0.072* | |
O1 | 0.1171 (3) | 0.6735 (3) | 0.4687 (3) | 0.0687 (7) | |
O2 | 0.2827 (3) | 0.5108 (3) | 0.4126 (3) | 0.0620 (7) | |
O3 | 0.4198 (4) | 0.3141 (3) | 0.8073 (3) | 0.0907 (10) | |
O4 | 0.5123 (3) | 0.2935 (2) | 0.6218 (2) | 0.0597 (6) | |
N1 | 0.2135 (4) | 0.2511 (3) | 0.0093 (3) | 0.0714 (9) | |
H1A | 0.2863 | 0.2524 | −0.0426 | 0.086* | |
H1B | 0.1615 | 0.1903 | 0.0197 | 0.086* | |
N2 | 0.7765 (4) | −0.2212 (4) | 0.4847 (4) | 0.0727 (9) | |
H2A | 0.7329 | −0.2831 | 0.4777 | 0.087* | |
H2B | 0.8570 | −0.2099 | 0.4441 | 0.087* | |
C1 | 0.1638 (3) | 0.6040 (4) | 0.3959 (4) | 0.0533 (8) | |
C2 | 0.0659 (5) | 0.6423 (5) | 0.2688 (4) | 0.0766 (12) | |
H2C | −0.0404 | 0.6533 | 0.2883 | 0.092* | |
H2D | 0.0769 | 0.7306 | 0.2109 | 0.092* | |
C3 | 0.2240 (4) | 0.5378 (4) | 0.1233 (4) | 0.0653 (9) | |
H3A | 0.2801 | 0.6034 | 0.1134 | 0.078* | |
N3 | 0.1065 (3) | 0.5386 (3) | 0.2009 (3) | 0.0614 (8) | |
C4 | 0.2618 (4) | 0.4441 (4) | 0.0600 (3) | 0.0626 (9) | |
H4A | 0.3429 | 0.4466 | 0.0065 | 0.075* | |
N4 | 0.6079 (3) | 0.0138 (3) | 0.7186 (3) | 0.0554 (7) | |
C5 | 0.1812 (4) | 0.3429 (4) | 0.0731 (3) | 0.0565 (8) | |
C6 | 0.0625 (4) | 0.3438 (4) | 0.1588 (4) | 0.0629 (9) | |
H6A | 0.0064 | 0.2777 | 0.1735 | 0.075* | |
C7 | 0.0306 (4) | 0.4403 (5) | 0.2192 (4) | 0.0685 (10) | |
H7A | −0.0473 | 0.4387 | 0.2760 | 0.082* | |
C8 | 0.4889 (4) | 0.2472 (3) | 0.7390 (3) | 0.0556 (8) | |
C9 | 0.5523 (6) | 0.0927 (4) | 0.8068 (4) | 0.0725 (11) | |
H9A | 0.6354 | 0.0795 | 0.8695 | 0.087* | |
H9B | 0.4730 | 0.0556 | 0.8554 | 0.087* | |
C10 | 0.5385 (4) | −0.0810 (3) | 0.7033 (3) | 0.0552 (8) | |
H10A | 0.4522 | −0.0935 | 0.7483 | 0.066* | |
C11 | 0.5887 (4) | −0.1583 (3) | 0.6257 (3) | 0.0507 (7) | |
H11A | 0.5366 | −0.2216 | 0.6169 | 0.061* | |
C12 | 0.7198 (4) | −0.1434 (3) | 0.5578 (3) | 0.0516 (8) | |
C13 | 0.7874 (4) | −0.0408 (4) | 0.5720 (4) | 0.0671 (10) | |
H13A | 0.8717 | −0.0238 | 0.5258 | 0.081* | |
C14 | 0.7316 (4) | 0.0328 (4) | 0.6515 (4) | 0.0646 (10) | |
H14A | 0.7796 | 0.0988 | 0.6604 | 0.078* | |
Cl1 | −0.14846 (13) | 0.06845 (12) | 0.13633 (11) | 0.0775 (4) | |
O11 | 0.0057 (6) | 0.0542 (11) | 0.1141 (9) | 0.115 (3) | 0.50 |
O12 | −0.1681 (10) | 0.0976 (11) | 0.2535 (6) | 0.111 (3) | 0.50 |
O13 | −0.1814 (10) | −0.0588 (6) | 0.1530 (9) | 0.107 (3) | 0.50 |
O14 | −0.2431 (12) | 0.1661 (8) | 0.0364 (9) | 0.178 (4) | 0.50 |
O11' | −0.2394 (11) | 0.1683 (8) | 0.1829 (11) | 0.137 (3) | 0.50 |
O12' | −0.0392 (11) | −0.0201 (9) | 0.2325 (9) | 0.181 (4) | 0.50 |
O13' | −0.2372 (10) | −0.0073 (9) | 0.1018 (9) | 0.116 (3) | 0.50 |
O14' | −0.0830 (12) | 0.1400 (7) | 0.0290 (8) | 0.130 (3) | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0416 (4) | 0.0427 (4) | 0.0447 (4) | −0.0139 (3) | 0.0052 (3) | −0.0190 (3) |
O1W | 0.0635 (14) | 0.0626 (14) | 0.0642 (15) | −0.0184 (11) | 0.0153 (11) | −0.0338 (12) |
O1 | 0.0516 (13) | 0.0903 (19) | 0.0774 (17) | −0.0095 (12) | 0.0060 (12) | −0.0513 (15) |
O2 | 0.0474 (13) | 0.0650 (15) | 0.0821 (17) | −0.0062 (11) | −0.0113 (11) | −0.0409 (13) |
O3 | 0.151 (3) | 0.0582 (16) | 0.0636 (17) | −0.0189 (17) | 0.0401 (18) | −0.0266 (13) |
O4 | 0.0833 (16) | 0.0448 (13) | 0.0518 (14) | −0.0169 (11) | 0.0145 (12) | −0.0162 (10) |
N1 | 0.095 (2) | 0.0628 (19) | 0.0570 (18) | −0.0136 (17) | 0.0041 (16) | −0.0252 (15) |
N2 | 0.0645 (19) | 0.081 (2) | 0.099 (3) | −0.0339 (17) | 0.0286 (18) | −0.054 (2) |
C1 | 0.0429 (17) | 0.060 (2) | 0.069 (2) | −0.0177 (15) | 0.0054 (15) | −0.0324 (17) |
C2 | 0.068 (2) | 0.084 (3) | 0.081 (3) | 0.006 (2) | −0.013 (2) | −0.050 (2) |
C3 | 0.071 (2) | 0.063 (2) | 0.064 (2) | −0.0197 (18) | −0.0004 (18) | −0.0215 (18) |
N3 | 0.0565 (17) | 0.0682 (19) | 0.0621 (18) | −0.0040 (14) | −0.0070 (14) | −0.0330 (15) |
C4 | 0.072 (2) | 0.065 (2) | 0.0524 (19) | −0.0186 (18) | 0.0130 (17) | −0.0210 (17) |
N4 | 0.0691 (18) | 0.0438 (15) | 0.0511 (16) | −0.0110 (13) | 0.0022 (13) | −0.0143 (12) |
C5 | 0.068 (2) | 0.0540 (19) | 0.0410 (17) | −0.0038 (16) | −0.0059 (15) | −0.0143 (14) |
C6 | 0.066 (2) | 0.072 (2) | 0.058 (2) | −0.0240 (18) | 0.0016 (17) | −0.0258 (18) |
C7 | 0.054 (2) | 0.095 (3) | 0.064 (2) | −0.018 (2) | 0.0057 (17) | −0.036 (2) |
C8 | 0.072 (2) | 0.0477 (18) | 0.0519 (19) | −0.0184 (16) | 0.0094 (16) | −0.0206 (15) |
C9 | 0.114 (3) | 0.050 (2) | 0.051 (2) | −0.014 (2) | 0.008 (2) | −0.0184 (16) |
C10 | 0.0573 (19) | 0.0491 (18) | 0.0568 (19) | −0.0167 (15) | 0.0108 (15) | −0.0113 (15) |
C11 | 0.0472 (16) | 0.0478 (17) | 0.0613 (19) | −0.0182 (14) | 0.0040 (14) | −0.0184 (15) |
C12 | 0.0447 (16) | 0.0513 (18) | 0.063 (2) | −0.0154 (14) | 0.0044 (14) | −0.0219 (16) |
C13 | 0.0510 (19) | 0.066 (2) | 0.101 (3) | −0.0287 (17) | 0.0200 (19) | −0.040 (2) |
C14 | 0.057 (2) | 0.058 (2) | 0.090 (3) | −0.0242 (17) | 0.0010 (19) | −0.033 (2) |
Cl1 | 0.12867 (7) | 0.1431 (7) | 0.1156 (7) | −0.0481 (6) | 0.0266 (6) | −0.0394 (6) |
O11 | 0.091 (4) | 0.184 (8) | 0.132 (6) | −0.077 (5) | 0.044 (4) | −0.105 (6) |
O12 | 0.116 (6) | 0.171 (8) | 0.084 (5) | −0.067 (5) | 0.029 (4) | −0.071 (5) |
O13 | 0.134 (7) | 0.065 (4) | 0.126 (7) | −0.045 (4) | 0.040 (5) | −0.026 (4) |
O14 | 0.214 (9) | 0.129 (7) | 0.158 (8) | −0.034 (7) | −0.040 (8) | −0.006 (7) |
O11' | 0.144 (7) | 0.105 (6) | 0.187 (9) | −0.047 (5) | 0.065 (7) | −0.070 (6) |
O12' | 0.170 (8) | 0.174 (8) | 0.166 (8) | −0.014 (7) | −0.071 (7) | −0.026 (7) |
O13' | 0.123 (6) | 0.151 (8) | 0.116 (7) | −0.078 (6) | 0.004 (5) | −0.069 (6) |
O14' | 0.191 (8) | 0.079 (5) | 0.117 (6) | −0.053 (5) | 0.080 (6) | −0.014 (4) |
Geometric parameters (Å, º) top
Mn—O4i | 2.133 (2) | C4—H4A | 0.9300 |
Mn—O4 | 2.133 (2) | N4—C10 | 1.349 (5) |
Mn—O2i | 2.151 (2) | N4—C14 | 1.349 (5) |
Mn—O2 | 2.151 (2) | N4—C9 | 1.459 (5) |
Mn—O1Wi | 2.225 (2) | C5—C6 | 1.411 (5) |
Mn—O1W | 2.225 (2) | C6—C7 | 1.344 (5) |
O1W—H1WA | 0.9001 | C6—H6A | 0.9300 |
O1W—H1WB | 0.9000 | C7—H7A | 0.9300 |
O1—C1 | 1.238 (4) | C8—C9 | 1.523 (5) |
O2—C1 | 1.240 (4) | C9—H9A | 0.9700 |
O3—C8 | 1.238 (4) | C9—H9B | 0.9700 |
O4—C8 | 1.240 (4) | C10—C11 | 1.344 (5) |
N1—C5 | 1.330 (5) | C10—H10A | 0.9300 |
N1—H1A | 0.8600 | C11—C12 | 1.404 (5) |
N1—H1B | 0.8600 | C11—H11A | 0.9300 |
N2—C12 | 1.322 (4) | C12—C13 | 1.406 (5) |
N2—H2A | 0.8600 | C13—C14 | 1.345 (5) |
N2—H2B | 0.8600 | C13—H13A | 0.9300 |
C1—C2 | 1.526 (5) | C14—H14A | 0.9300 |
C2—N3 | 1.469 (5) | Cl1—O14 | 1.360 (5) |
C2—H2C | 0.9700 | Cl1—O12' | 1.375 (5) |
C2—H2D | 0.9700 | Cl1—O14' | 1.383 (4) |
C3—C4 | 1.344 (5) | Cl1—O13' | 1.383 (4) |
C3—N3 | 1.347 (5) | Cl1—O12 | 1.390 (4) |
C3—H3A | 0.9300 | Cl1—O11' | 1.392 (4) |
N3—C7 | 1.337 (5) | Cl1—O11 | 1.394 (4) |
C4—C5 | 1.400 (5) | Cl1—O13 | 1.396 (4) |
| | | |
O4i—Mn—O4 | 180.00 | N3—C7—C6 | 122.6 (4) |
O4i—Mn—O2i | 90.15 (11) | N3—C7—H7A | 118.7 |
O4—Mn—O2i | 89.85 (11) | C6—C7—H7A | 118.7 |
O4i—Mn—O2 | 89.85 (11) | O3—C8—O4 | 126.6 (3) |
O4—Mn—O2 | 90.15 (11) | O3—C8—C9 | 116.3 (3) |
O2i—Mn—O2 | 180.0 | O4—C8—C9 | 117.1 (3) |
O4i—Mn—O1Wi | 91.80 (10) | N4—C9—C8 | 114.5 (3) |
O4—Mn—O1Wi | 88.20 (10) | N4—C9—H9A | 108.6 |
O2i—Mn—O1Wi | 89.49 (9) | C8—C9—H9A | 108.6 |
O2—Mn—O1Wi | 90.51 (9) | N4—C9—H9B | 108.6 |
O4i—Mn—O1W | 88.20 (10) | C8—C9—H9B | 108.6 |
O4—Mn—O1W | 91.80 (10) | H9A—C9—H9B | 107.6 |
O2i—Mn—O1W | 90.51 (9) | C11—C10—N4 | 122.8 (3) |
O2—Mn—O1W | 89.49 (9) | C11—C10—H10A | 118.6 |
O1Wi—Mn—O1W | 180.0 | N4—C10—H10A | 118.6 |
Mn—O1W—H1WA | 99.4 | C10—C11—C12 | 120.0 (3) |
Mn—O1W—H1WB | 100.1 | C10—C11—H11A | 120.0 |
H1WA—O1W—H1WB | 108.7 | C12—C11—H11A | 120.0 |
C1—O2—Mn | 127.5 (2) | N2—C12—C11 | 121.9 (3) |
C8—O4—Mn | 130.8 (2) | N2—C12—C13 | 121.9 (3) |
C5—N1—H1A | 120.0 | C11—C12—C13 | 116.2 (3) |
C5—N1—H1B | 120.0 | C14—C13—C12 | 120.8 (3) |
H1A—N1—H1B | 120.0 | C14—C13—H13A | 119.6 |
C12—N2—H2A | 120.0 | C12—C13—H13A | 119.6 |
C12—N2—H2B | 120.0 | C13—C14—N4 | 121.9 (3) |
H2A—N2—H2B | 120.0 | C13—C14—H14A | 119.1 |
O1—C1—O2 | 127.5 (3) | N4—C14—H14A | 119.1 |
O1—C1—C2 | 115.6 (3) | O14—Cl1—O12' | 172.6 (6) |
O1—O1W—O3 | 111.15 (13) | O14—Cl1—O14' | 62.1 (5) |
O2—C1—C2 | 116.9 (3) | O12'—Cl1—O14' | 111.3 (5) |
N3—C2—C1 | 113.1 (3) | O14—Cl1—O13' | 77.8 (5) |
N3—C2—H2C | 109.0 | O12'—Cl1—O13' | 108.6 (5) |
C1—C2—H2C | 109.0 | O14'—Cl1—O13' | 111.3 (5) |
N3—C2—H2D | 109.0 | O14—Cl1—O12 | 111.9 (5) |
C1—C2—H2D | 109.0 | O12'—Cl1—O12 | 68.5 (5) |
H2C—C2—H2D | 107.8 | O14'—Cl1—O12 | 126.0 (5) |
C4—C3—N3 | 121.4 (4) | O13'—Cl1—O12 | 119.8 (6) |
C4—C3—H3A | 119.3 | O14—Cl1—O11' | 70.4 (5) |
N3—C3—H3A | 119.3 | O12'—Cl1—O11' | 109.7 (5) |
C7—N3—C3 | 118.9 (3) | O14'—Cl1—O11' | 106.0 (4) |
C7—N3—C2 | 120.3 (3) | O13'—Cl1—O11' | 109.9 (5) |
C3—N3—C2 | 120.7 (4) | O14—Cl1—O11 | 113.5 (5) |
C3—C4—C5 | 121.1 (3) | O12'—Cl1—O11 | 60.1 (5) |
C3—C4—H4A | 119.4 | O14'—Cl1—O11 | 51.3 (4) |
C5—C4—H4A | 119.4 | O13'—Cl1—O11 | 123.9 (6) |
C10—N4—C14 | 118.3 (3) | O12—Cl1—O11 | 106.6 (4) |
C10—N4—C9 | 121.0 (3) | O11'—Cl1—O11 | 126.0 (5) |
C14—N4—C9 | 120.6 (3) | O14—Cl1—O13 | 108.4 (5) |
N1—C5—C4 | 122.5 (3) | O12'—Cl1—O13 | 78.0 (5) |
N1—C5—C6 | 121.5 (4) | O14'—Cl1—O13 | 124.9 (6) |
C4—C5—C6 | 115.9 (3) | O12—Cl1—O13 | 108.3 (4) |
C7—C6—C5 | 119.9 (4) | O11'—Cl1—O13 | 122.1 (6) |
C7—C6—H6A | 120.0 | O11—Cl1—O13 | 108.0 (4) |
C5—C6—H6A | 120.0 | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3 | 0.90 | 1.93 | 2.787 (4) | 160 |
N1—H1A···O3ii | 0.86 | 2.05 | 2.879 (5) | 163 |
O1W—H1WB···O1 | 0.90 | 2.00 | 2.856 (4) | 158 |
N2—H2A···O2iii | 0.86 | 2.35 | 3.072 (5) | 142 |
N2—H2A···O4iii | 0.86 | 2.51 | 3.205 (5) | 138 |
N2—H2B···O1iv | 0.86 | 2.35 | 3.038 (5) | 137 |
Symmetry codes: (ii) x, y, z−1; (iii) −x+1, −y, −z+1; (iv) x+1, y−1, z. |
Experimental details
Crystal data |
Chemical formula | [Mn(C7H8N2O2)4(H2O)2](ClO4)2 |
Mr | 898.49 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.049 (2), 10.507 (3), 10.779 (3) |
α, β, γ (°) | 71.79 (4), 89.52 (4), 76.13 (4) |
V (Å3) | 942.7 (4) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.58 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.870, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4859, 3275, 2834 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.148, 1.05 |
No. of reflections | 3275 |
No. of parameters | 295 |
No. of restraints | 160 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.45 |
Selected geometric parameters (Å, º) topMn—O4 | 2.133 (2) | N2—C12 | 1.322 (4) |
Mn—O2 | 2.151 (2) | C2—N3 | 1.469 (5) |
Mn—O1W | 2.225 (2) | C3—C4 | 1.344 (5) |
O1—C1 | 1.238 (4) | N3—C7 | 1.337 (5) |
O2—C1 | 1.240 (4) | N4—C10 | 1.349 (5) |
O3—C8 | 1.238 (4) | N4—C14 | 1.349 (5) |
O4—C8 | 1.240 (4) | N4—C9 | 1.459 (5) |
N1—C5 | 1.330 (5) | C5—C6 | 1.411 (5) |
| | | |
O4—Mn—O2 | 90.15 (11) | O1—O1W—O3 | 111.15 (13) |
O4—Mn—O1W | 91.80 (10) | N3—C2—C1 | 113.1 (3) |
O2—Mn—O1W | 89.49 (9) | C7—N3—C2 | 120.3 (3) |
C1—O2—Mn | 127.5 (2) | N1—C5—C4 | 122.5 (3) |
C8—O4—Mn | 130.8 (2) | O3—C8—O4 | 126.6 (3) |
O1—C1—O2 | 127.5 (3) | O3—C8—C9 | 116.3 (3) |
O1—C1—C2 | 115.6 (3) | N2—C12—C11 | 121.9 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O3 | 0.90 | 1.925 | 2.787 (4) | 160 |
N1—H1A···O3i | 0.86 | 2.046 | 2.879 (5) | 163 |
O1W—H1WB···O1 | 0.90 | 2.003 | 2.856 (4) | 158 |
N2—H2A···O2ii | 0.86 | 2.352 | 3.072 (5) | 142 |
N2—H2A···O4ii | 0.86 | 2.513 | 3.205 (5) | 138 |
N2—H2B···O1iii | 0.86 | 2.353 | 3.038 (5) | 137 |
Symmetry codes: (i) x, y, z−1; (ii) −x+1, −y, −z+1; (iii) x+1, y−1, z. |
Manganese complexes containing coordinated carboxylate have been extensively studied for their structural chemistry and biological function. Much research has focused on the preparation of model compounds to mimic various manganese enzymes, such as manganese catalase (Christou, 1989) and the water-oxidizing oxygen-evolving complex (OEC) of photosystem II (Linburg et al., 1999). A rich structural diversity of carboxylate-containing Mn complexes has been revealed. The carboxylate ligand can coordinate to Mn, in different oxidation states, in different coordination fashions, such as syn and anti, and monodentate and bidentate (Iikura & Nagata, 1998). Here, we present the structure of a further such complex, the title compound, (I). \sch
The structure described here shows (I) to be a centrosymmetric mononuclear species, with Mn at a crystallographic centre of symmetry. The MnII is in an octahedral environment, with the equatorial plane being defined by the O atoms of four unidentate carboxylate groups of the (4-aminopyridinio)acetate ligands, and the octahedron being completed by two trans-coordinated water molecules (Fig. 1). The perchlorate ions are not coordinated to Mn.
Bond lengths and angles in (I) are normal and the unique angles in the octahedron are close to ideal (Table 1). In particular, the Mn—O1W distance (Mn-water) is 2.225 (2) Å, which is similar to the value of 2.218 (2) Å found in [Mn(H2O)6(HC4O3NH2)2] by Hosein et al. (1998). The C—O distances in (I) are normal, indicating that the coordination of MnII to acetate does not affect the geometry of the acetate.
The dihedral angles of the basal plane through atoms O2, O2A, O4 and O4A with the O2- and O4-containing acetate plane are 37.5 (2) and 56.5 (1)°, respectively. The dihedral angles between the N3- and N4-containing pyridyl rings, and the C2- and C9-containing acetate planes, are 77.8 (2) and 61.7 (2)°, respectively. The orientation of the pyridyl ring is defined by the torsion angles of 179.6 (3)° for C2—N3—C3—C4 and 178.4 (4)° for C9—N4—C14—C13.
The non-coordinated carboxylate O atoms (O1 and O3) and the water molecule, O1W, are cis with respect to the equatorial plane (Fig. 1), and each of O1 and O3 is the receptor in an intramolecular hydrogen bond from O1W (Table 2). In the crystal, intermolecular hydrogen bonds between the amino group of the ligand and the O atoms of the carboxylate groups from neighbouring molecules, together with weak hydrogen bonds formed between the amino groups and a disordered perchlorate ion, form a layered hydrogen-bonded network.