4-Hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, cdaH
3) reacts with MnCl
2·2H
2O in the presence of 2-amino-4-methylpyrimidine in water to afford the tetranuclear title complex, [Mn
4(C
8H
3NO
5)
4(H
2O)
10]·3.34H
2O, built through carboxylate bridging. The tetranuclear complex sits on a centre of inversion at (
,
,
). In the crystal, discrete undecameric (H
2O)
10.34 water clusters (involving both coordinated and uncoordinated water molecules, with one site of an uncoordinated water molecule not fully occupied) assemble these tetranuclear Mn
II complex units
via an intricate array of hydrogen bonding into an overall three-dimensional network. The degree of structuring of the (H
2O)
10.34 supramolecular association of water molecules observed in the present compound, imposed by its environment and
vice versa, will be discussed in comparison to that observed for the (H
2O)
14 supramolecular clusters in the case of the dinuclear complex [Mn
2(cdaH)
2(H
2O)
4]·4H
2O [Ghosh
et al. (2005).
Inorg. Chem. 44, 3856-3862].
Supporting information
CCDC reference: 866740
The reaction of MnCl2.2H2O (12 mg, 0.075 mmol), 2-amino-4-methylpyrimidine
(30 mg, 0.30 mmol) and cdaH3 (33 mg, 0.15 mmol) in deionized water (10 ml)
afforded colourless prismatic crystals of the title compound (35% yield) upon
slow evaporation of solvent from the reaction mixture at room temperature.
Analysis found (calculated for C14H20Mn2N2O17): C 28.10 (28.11), H
3.35 (3.37), N 4.63% (4.68%).
The H atoms of the OH groups and water molecules were localized in the
difference Fourier syntheses and refined with a riding model with fixed
isotropic displacement parameters [Uiso(H) = 1.5Ueq(O)]. The
H(C) atoms were placed in calculated positions and included in the refinement
with a riding model with fixed isotropic displacement parameters
[Uiso(H) = 1.2Ueq(C)].
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and
publCIF (Westrip, 2010).
decaaquabis(µ
3-4-hydroxypyridine-2,6-dicarboxylato)bis(4-hydroxypyridine-
2,6-dicarboxylato)tetramanganese(II) 3.34-hydrate
top
Crystal data top
[Mn4(C8H3NO5)4(H2O)10]·3.34H2O | Z = 1 |
Mr = 1184.47 | F(000) = 601.1 |
Triclinic, P1 | Dx = 1.954 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6765 (3) Å | Cell parameters from 4750 reflections |
b = 10.9615 (5) Å | θ = 2.7–33.2° |
c = 14.1513 (7) Å | µ = 1.35 mm−1 |
α = 102.309 (1)° | T = 100 K |
β = 95.097 (1)° | Prism, colourless |
γ = 91.581 (1)° | 0.17 × 0.13 × 0.08 mm |
V = 1006.69 (8) Å3 | |
Data collection top
Bruker APEXII CCD diffractometer | 5282 independent reflections |
Radiation source: sealed tube | 4390 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 29.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −9→9 |
Tmin = 0.783, Tmax = 0.899 | k = −14→14 |
11968 measured reflections | l = −19→19 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0525P)2 + 0.6533P] where P = (Fo2 + 2Fc2)/3 |
5282 reflections | (Δ/σ)max = 0.002 |
317 parameters | Δρmax = 1.03 e Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
Crystal data top
[Mn4(C8H3NO5)4(H2O)10]·3.34H2O | γ = 91.581 (1)° |
Mr = 1184.47 | V = 1006.69 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.6765 (3) Å | Mo Kα radiation |
b = 10.9615 (5) Å | µ = 1.35 mm−1 |
c = 14.1513 (7) Å | T = 100 K |
α = 102.309 (1)° | 0.17 × 0.13 × 0.08 mm |
β = 95.097 (1)° | |
Data collection top
Bruker APEXII CCD diffractometer | 5282 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4390 reflections with I > 2σ(I) |
Tmin = 0.783, Tmax = 0.899 | Rint = 0.023 |
11968 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.03 e Å−3 |
5282 reflections | Δρmin = −0.73 e Å−3 |
317 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn1 | 0.75808 (4) | 0.33058 (3) | 0.04576 (2) | 0.00867 (8) | |
Mn2 | 0.55933 (6) | 0.45116 (3) | 0.36541 (3) | 0.02347 (10) | |
O1 | 0.8028 (2) | 0.39346 (13) | −0.09680 (10) | 0.0121 (3) | |
O2 | 0.8685 (2) | 0.33552 (14) | −0.25170 (10) | 0.0154 (3) | |
O3 | 0.7218 (2) | 0.15589 (13) | 0.10414 (10) | 0.0115 (3) | |
O4 | 0.6941 (2) | −0.05248 (13) | 0.07109 (10) | 0.0122 (3) | |
O5 | 0.8982 (2) | −0.14370 (14) | −0.27966 (11) | 0.0186 (3) | |
H5O | 0.9323 | −0.1249 | −0.3254 | 0.028* | |
O6 | 0.6879 (2) | 0.43900 (13) | 0.20899 (10) | 0.0143 (3) | |
O7 | 0.7149 (2) | 0.53798 (13) | 0.08997 (10) | 0.0121 (3) | |
O8 | 0.5035 (3) | 0.62213 (14) | 0.50331 (12) | 0.0243 (4) | |
O9 | 0.4441 (3) | 0.82619 (15) | 0.54829 (12) | 0.0290 (4) | |
O10 | 0.6426 (2) | 0.99140 (13) | 0.26106 (11) | 0.0147 (3) | |
H10O | 0.6654 | 0.9816 | 0.2035 | 0.022* | |
O1W | 1.0719 (2) | 0.37689 (13) | 0.10272 (10) | 0.0124 (3) | |
H1WA | 1.1652 | 0.3411 | 0.0857 | 0.019* | |
H1WB | 1.1077 | 0.4508 | 0.1030 | 0.019* | |
O2W | 0.4229 (2) | 0.30131 (13) | 0.01703 (10) | 0.0113 (3) | |
H2WA | 0.3964 | 0.2272 | −0.0122 | 0.017* | |
H2WB | 0.3787 | 0.3382 | −0.0216 | 0.017* | |
O3W | 0.8773 (4) | 0.4327 (3) | 0.41444 (15) | 0.0507 (6) | |
H3WA | 0.9296 | 0.3768 | 0.4459 | 0.076* | |
H3WB | 0.9769 | 0.4346 | 0.3786 | 0.076* | |
O4W | 0.2258 (3) | 0.44970 (16) | 0.30972 (12) | 0.0251 (4) | |
H4WA | 0.1903 | 0.4032 | 0.2655 | 0.038* | |
H4WB | 0.1809 | 0.5118 | 0.2901 | 0.038* | |
O5W | 0.5303 (3) | 0.25497 (15) | 0.28145 (12) | 0.0251 (4) | |
H5WA | 0.5384 | 0.1972 | 0.3087 | 0.038* | |
H5WB | 0.6023 | 0.2226 | 0.2374 | 0.038* | |
N1 | 0.7962 (2) | 0.16586 (15) | −0.07148 (12) | 0.0094 (3) | |
N2 | 0.5918 (3) | 0.64562 (16) | 0.33086 (12) | 0.0127 (3) | |
C1 | 0.8360 (3) | 0.17896 (18) | −0.15951 (14) | 0.0100 (3) | |
C2 | 0.8704 (3) | 0.07906 (19) | −0.23332 (14) | 0.0122 (4) | |
H2A | 0.9000 | 0.0916 | −0.2951 | 0.015* | |
C3 | 0.8604 (3) | −0.04129 (19) | −0.21447 (14) | 0.0125 (4) | |
C4 | 0.8092 (3) | −0.05534 (18) | −0.12308 (14) | 0.0116 (4) | |
H4A | 0.7950 | −0.1360 | −0.1091 | 0.014* | |
C5 | 0.7801 (3) | 0.05042 (18) | −0.05426 (14) | 0.0095 (3) | |
C6 | 0.8365 (3) | 0.31311 (18) | −0.17174 (14) | 0.0108 (4) | |
C7 | 0.7283 (3) | 0.05017 (18) | 0.04808 (14) | 0.0092 (3) | |
C8 | 0.5523 (3) | 0.75092 (19) | 0.39282 (14) | 0.0138 (4) | |
C9 | 0.5659 (3) | 0.86844 (18) | 0.37266 (14) | 0.0132 (4) | |
H9A | 0.5338 | 0.9402 | 0.4185 | 0.016* | |
C10 | 0.6283 (3) | 0.87912 (18) | 0.28279 (14) | 0.0116 (4) | |
C11 | 0.6739 (3) | 0.77039 (18) | 0.21894 (14) | 0.0108 (4) | |
H11A | 0.7214 | 0.7743 | 0.1583 | 0.013* | |
C12 | 0.6493 (3) | 0.65755 (18) | 0.24470 (14) | 0.0109 (4) | |
C13 | 0.4941 (4) | 0.7332 (2) | 0.48998 (16) | 0.0200 (5) | |
C14 | 0.6870 (3) | 0.53677 (18) | 0.17692 (14) | 0.0105 (4) | |
O6W | 1.0391 (3) | −0.0944 (2) | −0.44218 (15) | 0.0389 (5) | |
H6WA | 1.0177 | −0.1748 | −0.4675 | 0.058* | |
H6WB | 1.1590 | −0.0996 | −0.4389 | 0.058* | |
O7W | 0.9808 (5) | 0.3098 (3) | −0.4351 (2) | 0.0358 (11) | 0.669 (8) |
H7WA | 0.9490 | 0.3021 | −0.3716 | 0.054* | 0.669 (8) |
H7WB | 1.0976 | 0.3701 | −0.4222 | 0.054* | 0.669 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01178 (14) | 0.00594 (14) | 0.00872 (14) | 0.00037 (10) | 0.00382 (10) | 0.00137 (10) |
Mn2 | 0.0443 (2) | 0.01111 (17) | 0.01816 (18) | 0.00139 (15) | 0.01693 (15) | 0.00457 (13) |
O1 | 0.0182 (7) | 0.0078 (6) | 0.0113 (6) | 0.0007 (5) | 0.0056 (5) | 0.0023 (5) |
O2 | 0.0190 (7) | 0.0175 (7) | 0.0114 (7) | 0.0004 (6) | 0.0048 (5) | 0.0059 (6) |
O3 | 0.0158 (7) | 0.0087 (6) | 0.0105 (6) | 0.0015 (5) | 0.0031 (5) | 0.0022 (5) |
O4 | 0.0159 (7) | 0.0085 (6) | 0.0131 (7) | −0.0005 (5) | 0.0026 (5) | 0.0042 (5) |
O5 | 0.0263 (8) | 0.0132 (7) | 0.0149 (7) | 0.0021 (6) | 0.0081 (6) | −0.0027 (6) |
O6 | 0.0235 (7) | 0.0082 (6) | 0.0124 (7) | 0.0020 (5) | 0.0070 (6) | 0.0024 (5) |
O7 | 0.0167 (7) | 0.0104 (7) | 0.0096 (6) | 0.0021 (5) | 0.0048 (5) | 0.0017 (5) |
O8 | 0.0464 (10) | 0.0094 (7) | 0.0204 (8) | 0.0035 (7) | 0.0210 (7) | 0.0032 (6) |
O9 | 0.0598 (12) | 0.0102 (7) | 0.0211 (8) | 0.0064 (8) | 0.0263 (8) | 0.0024 (6) |
O10 | 0.0252 (8) | 0.0081 (6) | 0.0118 (7) | 0.0008 (6) | 0.0064 (6) | 0.0024 (5) |
O1W | 0.0141 (7) | 0.0084 (6) | 0.0154 (7) | 0.0009 (5) | 0.0050 (5) | 0.0025 (5) |
O2W | 0.0147 (7) | 0.0087 (6) | 0.0111 (6) | 0.0020 (5) | 0.0024 (5) | 0.0027 (5) |
O3W | 0.0595 (14) | 0.0756 (17) | 0.0199 (10) | −0.0188 (13) | 0.0042 (9) | 0.0198 (10) |
O4W | 0.0315 (9) | 0.0204 (8) | 0.0202 (8) | −0.0042 (7) | 0.0079 (7) | −0.0042 (7) |
O5W | 0.0441 (10) | 0.0149 (8) | 0.0199 (8) | −0.0018 (7) | 0.0159 (7) | 0.0070 (6) |
N1 | 0.0102 (7) | 0.0092 (7) | 0.0092 (7) | 0.0003 (6) | 0.0027 (6) | 0.0017 (6) |
N2 | 0.0172 (8) | 0.0108 (8) | 0.0107 (8) | 0.0015 (6) | 0.0066 (6) | 0.0015 (6) |
C1 | 0.0110 (8) | 0.0098 (9) | 0.0097 (8) | 0.0008 (7) | 0.0026 (7) | 0.0026 (7) |
C2 | 0.0126 (9) | 0.0134 (9) | 0.0103 (8) | 0.0009 (7) | 0.0042 (7) | 0.0006 (7) |
C3 | 0.0121 (9) | 0.0116 (9) | 0.0122 (9) | 0.0008 (7) | 0.0019 (7) | −0.0012 (7) |
C4 | 0.0130 (9) | 0.0090 (9) | 0.0127 (9) | 0.0004 (7) | 0.0019 (7) | 0.0020 (7) |
C5 | 0.0092 (8) | 0.0103 (9) | 0.0092 (8) | 0.0000 (7) | 0.0020 (6) | 0.0019 (7) |
C6 | 0.0101 (8) | 0.0110 (9) | 0.0118 (9) | −0.0005 (7) | 0.0016 (7) | 0.0032 (7) |
C7 | 0.0073 (8) | 0.0094 (8) | 0.0113 (8) | 0.0009 (6) | 0.0011 (6) | 0.0026 (7) |
C8 | 0.0205 (10) | 0.0102 (9) | 0.0113 (9) | 0.0010 (7) | 0.0073 (7) | 0.0010 (7) |
C9 | 0.0182 (10) | 0.0090 (9) | 0.0124 (9) | 0.0007 (7) | 0.0063 (7) | 0.0005 (7) |
C10 | 0.0134 (9) | 0.0093 (9) | 0.0123 (9) | 0.0004 (7) | 0.0032 (7) | 0.0021 (7) |
C11 | 0.0115 (9) | 0.0113 (9) | 0.0095 (8) | −0.0004 (7) | 0.0025 (7) | 0.0017 (7) |
C12 | 0.0122 (9) | 0.0104 (9) | 0.0100 (8) | 0.0004 (7) | 0.0035 (7) | 0.0008 (7) |
C13 | 0.0363 (13) | 0.0093 (9) | 0.0167 (10) | 0.0009 (9) | 0.0155 (9) | 0.0026 (8) |
C14 | 0.0108 (8) | 0.0097 (9) | 0.0110 (9) | 0.0004 (7) | 0.0034 (7) | 0.0015 (7) |
O6W | 0.0406 (11) | 0.0487 (13) | 0.0328 (11) | 0.0138 (10) | 0.0193 (9) | 0.0133 (9) |
O7W | 0.0378 (18) | 0.045 (2) | 0.0219 (15) | 0.0027 (14) | 0.0025 (12) | 0.0017 (12) |
Geometric parameters (Å, º) top
Mn1—O1W | 2.1825 (14) | O3W—H3WA | 0.8920 |
Mn1—N1 | 2.2138 (16) | O3W—H3WB | 0.8736 |
Mn1—O2W | 2.2403 (14) | O4W—H4WA | 0.7333 |
Mn1—O3 | 2.2566 (14) | O4W—H4WB | 0.8409 |
Mn1—O7 | 2.2594 (14) | O5W—H5WA | 0.8091 |
Mn1—O1 | 2.3070 (14) | O5W—H5WB | 0.8449 |
Mn1—O6 | 2.4538 (14) | N1—C1 | 1.333 (2) |
Mn2—O3W | 2.203 (3) | N1—C5 | 1.342 (2) |
Mn2—O5W | 2.2183 (17) | N2—C8 | 1.341 (3) |
Mn2—O8i | 2.2426 (16) | N2—C12 | 1.341 (2) |
Mn2—O4W | 2.2938 (18) | C1—C2 | 1.383 (3) |
Mn2—N2 | 2.2950 (17) | C1—C6 | 1.517 (3) |
Mn2—O6 | 2.4232 (15) | C2—C3 | 1.401 (3) |
Mn2—O8 | 2.4633 (16) | C2—H2A | 0.9500 |
O1—C6 | 1.267 (2) | C3—C4 | 1.405 (3) |
O2—C6 | 1.243 (2) | C4—C5 | 1.377 (3) |
O3—C7 | 1.261 (2) | C4—H4A | 0.9500 |
O4—C7 | 1.257 (2) | C5—C7 | 1.519 (3) |
O5—C3 | 1.338 (2) | C8—C9 | 1.380 (3) |
O5—H5O | 0.7711 | C8—C13 | 1.511 (3) |
O6—C14 | 1.250 (2) | C9—C10 | 1.400 (3) |
O7—C14 | 1.264 (2) | C9—H9A | 0.9500 |
O8—C13 | 1.273 (3) | C10—C11 | 1.393 (3) |
O8—Mn2i | 2.2426 (16) | C11—C12 | 1.372 (3) |
O9—C13 | 1.241 (3) | C11—H11A | 0.9500 |
O10—C10 | 1.334 (2) | C12—C14 | 1.502 (3) |
O10—H10O | 0.8270 | O6W—H6WA | 0.8800 |
O1W—H1WA | 0.7749 | O6W—H6WB | 0.8019 |
O1W—H1WB | 0.8379 | O7W—H7WA | 0.9618 |
O2W—H2WA | 0.8351 | O7W—H7WB | 0.9870 |
O2W—H2WB | 0.7885 | | |
| | | |
O1W—Mn1—N1 | 100.00 (6) | Mn2—O3W—H3WA | 128.2 |
O1W—Mn1—O2W | 168.64 (5) | Mn2—O3W—H3WB | 124.4 |
N1—Mn1—O2W | 90.19 (6) | H3WA—O3W—H3WB | 95.5 |
O1W—Mn1—O3 | 96.96 (5) | Mn2—O4W—H4WA | 117.2 |
N1—Mn1—O3 | 71.17 (6) | Mn2—O4W—H4WB | 119.6 |
O2W—Mn1—O3 | 81.50 (5) | H4WA—O4W—H4WB | 96.0 |
O1W—Mn1—O7 | 85.66 (5) | Mn2—O5W—H5WA | 120.9 |
N1—Mn1—O7 | 148.36 (6) | Mn2—O5W—H5WB | 126.0 |
O2W—Mn1—O7 | 88.27 (5) | H5WA—O5W—H5WB | 94.1 |
O3—Mn1—O7 | 139.50 (5) | C1—N1—C5 | 118.94 (17) |
O1W—Mn1—O1 | 92.74 (5) | C1—N1—Mn1 | 121.15 (13) |
N1—Mn1—O1 | 70.01 (5) | C5—N1—Mn1 | 119.91 (13) |
O2W—Mn1—O1 | 95.47 (5) | C8—N2—C12 | 116.90 (17) |
O3—Mn1—O1 | 141.05 (5) | C8—N2—Mn2 | 123.02 (13) |
O7—Mn1—O1 | 78.68 (5) | C12—N2—Mn2 | 120.07 (13) |
O1W—Mn1—O6 | 83.88 (5) | N1—C1—C2 | 122.99 (18) |
N1—Mn1—O6 | 155.46 (6) | N1—C1—C6 | 113.85 (16) |
O2W—Mn1—O6 | 84.77 (5) | C2—C1—C6 | 123.16 (17) |
O3—Mn1—O6 | 84.33 (5) | C1—C2—C3 | 118.13 (18) |
O7—Mn1—O6 | 55.65 (5) | C1—C2—H2A | 120.9 |
O1—Mn1—O6 | 134.32 (5) | C3—C2—H2A | 120.9 |
O3W—Mn2—O5W | 92.02 (9) | O5—C3—C2 | 122.88 (18) |
O3W—Mn2—O8i | 84.42 (7) | O5—C3—C4 | 118.39 (18) |
O5W—Mn2—O8i | 87.60 (6) | C2—C3—C4 | 118.74 (18) |
O3W—Mn2—O4W | 174.44 (8) | C5—C4—C3 | 118.46 (18) |
O5W—Mn2—O4W | 82.59 (7) | C5—C4—H4A | 120.8 |
O8i—Mn2—O4W | 93.97 (7) | C3—C4—H4A | 120.8 |
O3W—Mn2—N2 | 97.87 (8) | N1—C5—C4 | 122.63 (18) |
O5W—Mn2—N2 | 136.46 (6) | N1—C5—C7 | 112.91 (16) |
O8i—Mn2—N2 | 135.39 (6) | C4—C5—C7 | 124.46 (17) |
O4W—Mn2—N2 | 87.02 (6) | O2—C6—O1 | 125.79 (18) |
O3W—Mn2—O6 | 83.39 (6) | O2—C6—C1 | 119.09 (17) |
O5W—Mn2—O6 | 70.39 (5) | O1—C6—C1 | 115.13 (16) |
O8i—Mn2—O6 | 154.34 (6) | O4—C7—O3 | 124.70 (18) |
O4W—Mn2—O6 | 95.99 (6) | O4—C7—C5 | 119.14 (17) |
N2—Mn2—O6 | 68.85 (5) | O3—C7—C5 | 116.15 (16) |
O3W—Mn2—O8 | 94.93 (8) | N2—C8—C9 | 124.02 (18) |
O5W—Mn2—O8 | 154.34 (6) | N2—C8—C13 | 114.96 (18) |
O8i—Mn2—O8 | 68.60 (6) | C9—C8—C13 | 121.01 (18) |
O4W—Mn2—O8 | 89.41 (6) | C8—C9—C10 | 118.23 (18) |
N2—Mn2—O8 | 66.82 (6) | C8—C9—H9A | 120.9 |
O6—Mn2—O8 | 134.95 (5) | C10—C9—H9A | 120.9 |
C6—O1—Mn1 | 119.68 (12) | O10—C10—C11 | 122.30 (17) |
C7—O3—Mn1 | 119.63 (12) | O10—C10—C9 | 119.67 (17) |
C3—O5—H5O | 109.8 | C11—C10—C9 | 118.04 (18) |
C14—O6—Mn2 | 116.63 (12) | C12—C11—C10 | 119.18 (18) |
C14—O6—Mn1 | 86.48 (11) | C12—C11—H11A | 120.4 |
Mn2—O6—Mn1 | 154.03 (7) | C10—C11—H11A | 120.4 |
C14—O7—Mn1 | 95.07 (12) | N2—C12—C11 | 123.57 (18) |
C13—O8—Mn2i | 129.09 (14) | N2—C12—C14 | 114.91 (17) |
C13—O8—Mn2 | 119.11 (13) | C11—C12—C14 | 121.52 (17) |
Mn2i—O8—Mn2 | 111.40 (6) | O9—C13—O8 | 126.7 (2) |
C10—O10—H10O | 108.3 | O9—C13—C8 | 117.97 (19) |
Mn1—O1W—H1WA | 127.1 | O8—C13—C8 | 115.30 (18) |
Mn1—O1W—H1WB | 112.8 | O6—C14—O7 | 122.80 (18) |
H1WA—O1W—H1WB | 101.9 | O6—C14—C12 | 118.38 (17) |
Mn1—O2W—H2WA | 108.3 | O7—C14—C12 | 118.83 (17) |
Mn1—O2W—H2WB | 111.7 | H6WA—O6W—H6WB | 92.6 |
H2WA—O2W—H2WB | 101.7 | H7WA—O7W—H7WB | 104.2 |
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···O2Wii | 0.77 | 2.06 | 2.799 (2) | 159 |
O1W—H1WB···O1iii | 0.84 | 1.82 | 2.651 (2) | 176 |
O2W—H2WA···O4iv | 0.83 | 1.97 | 2.804 (2) | 173 |
O2W—H2WB···O7v | 0.79 | 1.98 | 2.687 (2) | 166 |
O3W—H3WA···O7Wvi | 0.89 | 1.95 | 2.800 (4) | 152 |
O5—H5O···O6W | 0.77 | 1.95 | 2.712 (3) | 173 |
O3W—H3WB···O4Wii | 0.87 | 2.02 | 2.890 (3) | 173 |
O4W—H4WA···O1Wvii | 0.73 | 2.32 | 2.949 (2) | 144 |
O4W—H4WB···O2v | 0.84 | 1.90 | 2.725 (3) | 169 |
O5W—H5WA···O10viii | 0.81 | 2.36 | 2.966 (3) | 133 |
O5W—H5WA···O9i | 0.81 | 2.09 | 2.734 (3) | 137 |
O5W—H5WB···O3 | 0.85 | 2.11 | 2.932 (2) | 165 |
O10—H10O···O4ix | 0.83 | 1.86 | 2.683 (2) | 174 |
O6W—H6WA···O7Wx | 0.88 | 1.80 | 2.608 (4) | 153 |
O6W—H6WB···O9xi | 0.80 | 2.10 | 2.869 (3) | 161 |
O7W—H7WA···O2 | 0.96 | 1.79 | 2.725 (3) | 163 |
O7W—H7WB···O3Wiii | 0.99 | 2.14 | 2.899 (5) | 132 |
O7W—H7WB···N2iii | 0.99 | 2.37 | 3.070 (4) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+2, −y+1, −z; (iv) −x+1, −y, −z; (v) −x+1, −y+1, −z; (vi) x, y, z+1; (vii) x−1, y, z; (viii) x, y−1, z; (ix) x, y+1, z; (x) −x+2, −y, −z−1; (xi) x+1, y−1, z−1. |
Experimental details
Crystal data |
Chemical formula | [Mn4(C8H3NO5)4(H2O)10]·3.34H2O |
Mr | 1184.47 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 6.6765 (3), 10.9615 (5), 14.1513 (7) |
α, β, γ (°) | 102.309 (1), 95.097 (1), 91.581 (1) |
V (Å3) | 1006.69 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.35 |
Crystal size (mm) | 0.17 × 0.13 × 0.08 |
|
Data collection |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.783, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11968, 5282, 4390 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.682 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.096, 1.02 |
No. of reflections | 5282 |
No. of parameters | 317 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.03, −0.73 |
Selected geometric parameters (Å, º) topMn1—O1W | 2.1825 (14) | Mn2—O3W | 2.203 (3) |
Mn1—N1 | 2.2138 (16) | Mn2—O5W | 2.2183 (17) |
Mn1—O2W | 2.2403 (14) | Mn2—O8i | 2.2426 (16) |
Mn1—O3 | 2.2566 (14) | Mn2—O4W | 2.2938 (18) |
Mn1—O7 | 2.2594 (14) | Mn2—N2 | 2.2950 (17) |
Mn1—O1 | 2.3070 (14) | Mn2—O6 | 2.4232 (15) |
Mn1—O6 | 2.4538 (14) | Mn2—O8 | 2.4633 (16) |
| | | |
O1W—Mn1—N1 | 100.00 (6) | O5W—Mn2—N2 | 136.46 (6) |
O1W—Mn1—O2W | 168.64 (5) | O8i—Mn2—N2 | 135.39 (6) |
N1—Mn1—O2W | 90.19 (6) | O4W—Mn2—N2 | 87.02 (6) |
O3—Mn1—O1 | 141.05 (5) | O8i—Mn2—O6 | 154.34 (6) |
O3W—Mn2—O5W | 92.02 (9) | O8i—Mn2—O8 | 68.60 (6) |
O3W—Mn2—O4W | 174.44 (8) | O6—Mn2—O8 | 134.95 (5) |
O5W—Mn2—O4W | 82.59 (7) | Mn2—O6—Mn1 | 154.03 (7) |
O3W—Mn2—N2 | 97.87 (8) | Mn2i—O8—Mn2 | 111.40 (6) |
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···O2Wii | 0.77 | 2.06 | 2.799 (2) | 159 |
O1W—H1WB···O1iii | 0.84 | 1.82 | 2.651 (2) | 176 |
O2W—H2WA···O4iv | 0.83 | 1.97 | 2.804 (2) | 173 |
O2W—H2WB···O7v | 0.79 | 1.98 | 2.687 (2) | 166 |
O3W—H3WA···O7Wvi | 0.89 | 1.95 | 2.800 (4) | 152 |
O5—H5O···O6W | 0.77 | 1.95 | 2.712 (3) | 173 |
O3W—H3WB···O4Wii | 0.87 | 2.02 | 2.890 (3) | 173 |
O4W—H4WA···O1Wvii | 0.73 | 2.32 | 2.949 (2) | 144 |
O4W—H4WB···O2v | 0.84 | 1.90 | 2.725 (3) | 169 |
O5W—H5WA···O10viii | 0.81 | 2.36 | 2.966 (3) | 133 |
O5W—H5WA···O9i | 0.81 | 2.09 | 2.734 (3) | 137 |
O5W—H5WB···O3 | 0.85 | 2.11 | 2.932 (2) | 165 |
O10—H10O···O4ix | 0.83 | 1.86 | 2.683 (2) | 174 |
O6W—H6WA···O7Wx | 0.88 | 1.80 | 2.608 (4) | 153 |
O6W—H6WB···O9xi | 0.80 | 2.10 | 2.869 (3) | 161 |
O7W—H7WA···O2 | 0.96 | 1.79 | 2.725 (3) | 163 |
O7W—H7WB···O3Wiii | 0.99 | 2.14 | 2.899 (5) | 132 |
O7W—H7WB···N2iii | 0.99 | 2.37 | 3.070 (4) | 127 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+2, −y+1, −z; (iv) −x+1, −y, −z; (v) −x+1, −y+1, −z; (vi) x, y, z+1; (vii) x−1, y, z; (viii) x, y−1, z; (ix) x, y+1, z; (x) −x+2, −y, −z−1; (xi) x+1, y−1, z−1. |
It is widely recognized that fluctuations and the rearrangement dynamics of hydrogen-bonding interactions among water molecules determine the fascinating properties of bulk water. In order to better understand the co-operative nature of hydrogen-bonding interactions among a collection of water molecules, in view of [with the aim of creating?] drawing models that could fully explain the properties of bulk water, water clustering within inorganic or organic crystal hosts has become an active research field within the realm of crystal engineering (Ludwig et al., 2001). In particular, metal–organic frameworks (MOFs) composed of mainly transition metal ions and bridging organic ligands may provide voids suitable to accommodate small water clusters of different shape and dimensionality whose binding properties and degree of structuring depend on their surroundings and vice versa (for some examples, see Duan et al., 2010; Ghosh et al., 2004; Kang et al., 2007; Ma et al. 2005; Song et al. 2007; Wei et al., 2006).
Recently, Ghosh et al. (2005) have reacted MnII acetate and 4-hydroxypyridine-2,6-dicarboxylic acid (chelidamic acid, cdaH3) (1:1 reaction molar ratio) in an aqueous/pyridine solvent mixture (1:1 v/v) to afford the dinuclear complex [Mn2(cdaH)2(H2O)4].4H2O; in this complex one-dimensional stair-like coordination polymers built through carboxylate- and aqua-bridging of metal centres are assembled by (H2O)14 supramolecular clusters of coordinated and uncoordinated water molecules into a three-dimensional MOF via hydrogen bonding. The stitching water cluster takes the shape of a central cyclic hexamer in a chair conformation and two acyclic tetramers protruding from opposite corners of the hexamer. Following our interest in the coordination chemistry of proton-transfer systems obtained from N-, S- and O-donor ligands and polycarboxylic acids (Aghabozorg et al. 2008; Mirzaei et al., 2011), we have reacted manganese(II) chloride dihydrate with cdaH3 and 2-amino-4-methylpyrimidine in a 1:2:4 molar ratio in aqueous solution. Colourless prismatic crystals were obtained upon slow evaporation of the reaction mixture and corresponding to the microanalytical formulation C14H20Mn2N2O17, which is very close to that reported by Ghosh et al. for the complex [Mn2(cdaH)2(H2O)4].4H2O (Ghosh et al., 2005); an X-ray diffraction analysis was undertaken to ascertain their nature.
The structure consists of a discrete linear tetranuclear MnII cluster sitting on an inversion centre in which each metal centre adopts a heptacoordinated pentagonal–bipyramidal geometry (Fig. 1). Each terminal MnII centre in the cluster is axially coordinated to two water molecules and to a tridentate cdaH2- dicarboxylate unit in the equatorial plane. An NO4 coordination in the pentagonal equatorial plane is completed by the O donors of a bidentate carboxylate group from the 2-position of another cdaH2- unit (Fig. 1). Each of the two MnII ions in the middle of the tetranuclear cluster still feature two axially coordinated water molecules. The equatorial plane is occupied by a third coordinated water molecule, by the pyridine N donor and two carboxylate O donors at the 2- and 6-positions of the previous cdaH2- unit connected to a terminal MnII centre in the cluster, and by one carboxylate O donor at the 6-position from the cdaH2- unit symmetry equivalent to the last one. In this way, the two MnII centres in the middle of the tetranuclear cluster feature an NO4 coordination in the equatorial plane as do the terminal ones, and result directly connected to each other by a carboxylate bridge (see Fig. 1 and Table 1 for selected geometric parameters). Interestingly, an identical tetranuclear CdII cluster has been described by Das et al. (2009) in the compound [Cd4(cdaH)4(H2O)10].4H2O obtained from pyridine-2,4,6-tricarboxylic acid (ptcH3) upon conversion of the carboxyl group in the 4-position to a hydroxy group.
In the title compound, [Mn4(cdaH)4(H2O)10].4H2O, (I), the water molecules equatorially coordinated to the middle MnII centres of the tetranuclear cluster and the hydroxy groups from the cdaH2- units bridging these metal ions generate via hydrogen bonds strips of interacting clusters which propagate along the b axis, and for each strip the composing clusters lie on the same plane (see Fig. 2 and Table 2 for the hydrogen-bond geometry). The above strips stack on top of each other along the a axis interacting via hydrogen bonds at the axially coordinated water molecules to give two-dimensional extended sheets whose thickness roughly corresponds to the length of the linear tetranuclear MnII cluster (see Fig. 3 and Table 2 for the hydrogen-bond geometry). Parallel offset two-dimensional extended sheets of hydrogen-bonded [Mn4(cdaH)4(H2O)10] linear clusters interact with each other via hydrogen bonds involving both axially metal coordinated and cocrystallized water molecules (see Fig. 4 and Table 2 for the hydrogen-bond geometry) to give a three-dimensional network. Undecameric (H2O)10.34 stitching clusters can be envisaged (Fig. 4) between each pair of interacting two-dimensional sheets. Analogously to what was observed for the stitching (H2O)14 supramolecular clusters in the compound [Mn2(cdaH)2(H2O)4].4H2O (Ghosh et al., 2005), also in the present case the (H2O)10.34 clusters can be described as a central cyclic assembly of water molecules (a smaller square tetramer in this case) buttressed by acyclic water assemblies (two trimers and a monomer in this case). The hydrogen-bonding stitching pattern determined by the (H2O)10.34 clusters features a linear sequence of seven fused R(8) cyclic motifs ending at each extremity with an R(11) cycle (Fig. 4) [for graph-set notation see ref?]. Interestingly, in the compound [Cd4(cdaH)4(H2O)10].4H2O (Das et al., 2009), which features the same stoichiometry as the title compound and a very similar tetranuclear CdII cluster in its structure, only acyclic branched (H2O)5 clusters determine the packing in the crystal lattice. This may be due to the fact that the [Cd4(cdaH)4(H2O)10] tetranuclear CdII cluster is not perfectly flat as [Mn4(cdaH)4(H2O)10], but a small twisting along the Cd—Cd—Cd—Cd axis brings the axially coordinated water molecules to assume a reciprocal disposition in which the H2O—Cd—H2O vectors are not parallel.