In the title one-dimensional coordination polymer, {[Mn(C
5O
5)(C
10H
8N
2)(H
2O)]·H
2O}
n, each Mn
II ion is seven-coordinated by four O atoms from two croconate ligands, two N atoms from a 2,2′-bipyridine (2,2′-bipy) ligand and one O atom from an aqua ligand. The croconate ligand bridges the Mn
II ions in a bis-bidentate chelation mode, forming an extended [Mn(C
5O
5)]
n chain running parallel to the [001] direction, with the lipophilic 2,2′-bipy ligands lying along one side and the hydrophilic water molecules along the opposite side. Coordinated water and solvent water molecules are arranged in the hydrophilic layer, which is characterized by O—H
O hydrogen bonds between croconate ligands. Meanwhile, 2,2′-bipy ligands from adjacent chains partially overlap and exhibit π–π interactions to form a lipophilic layer. The hydrophilic and lipophilic layers are arranged alternately to build a layer structure.
Supporting information
CCDC references: 774878; 774879
[K2(C5O5)] (0.032 g, 0.15 mmol) and MnCl2.4H2O (0.044 g, 0.22 mmol)
were separately dissolved in water (10 ml), and 2,2'-bipy (0.036 g, 0.23 mmol)
was dissolved in ethanol (10 ml). These three solutions were then mixed. The
mixture was filtered, giving a greenish-yellow solution. Pale-green prismatic
crystals of (I) were obtained by slow evaporation of this solution at room
temperature over several weeks. Analysis, found: C 45.97, N 7.45, H 3.05%;
calculated for [Mn(C5O5)(C10H8N2)(H2O)].H2O: C 46.53, N 7.23, H
3.12%.
All H atoms were located in difference Fourier maps, and their positions and
isotropic displacement parameters were refined freely. The C—H distances are
in the range 0.941 (16)–0.984 (15) Å. There are relatively large differences
between the anisotropic displacements along the Mn—O bonds [diff(Mn—O)]
involving the two chelating rings. These may be due to the nature of the
structure itself. The dominant ionic Mn—O coordination bonds are not as
strong as a typical covalent bond. The MnII ion has seven Mn—X bonds and
the MnO5N2 coordination polyhedron is totally asymmetric. The weak and
multiple bonding in the coordination polyhedron may bring about some
deviations from the Hirshfeld rigid-bond postulate (Hirshfeld, 1976).
Lutz &
Spek (2009) reported that certain Zn—O(carboxylate) coordination
bonds fail
the Hirshfeld rigid-bond postulate, which was attributed to steric strain in
the chelate ring. Similar steric strain may also be present in (I). The five
atoms in the equatorial position of the distorted MnO5N2 pentagonal
bipyramid may be a little crowded. We note that diff(Mn1—N2) (8.7 s.u.)
involving the equatorial atom N2 is larger than diff(Mn1—N1) (5.7 s.u.)
involving the axial atom N1.
For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008) and DIAMOND (Brandenburg, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).
(I) Poly[[[aqua(2,2'-bipyridine-
κ2N,
N')manganese(II)]-µ-
croconato-
κ4O,
O':
O'',
O'''] monohydrate]
top
Crystal data top
[Mn(C5O5)(C10H8N2)(H2O)]·H2O | F(000) = 788 |
Mr = 387.21 | Dx = 1.740 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9577 reflections |
a = 11.3363 (2) Å | θ = 2.6–33.1° |
b = 9.3622 (1) Å | µ = 0.94 mm−1 |
c = 14.4053 (2) Å | T = 135 K |
β = 104.8460 (6)° | Prism, pale-green |
V = 1477.84 (4) Å3 | 0.26 × 0.20 × 0.11 mm |
Z = 4 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 5570 independent reflections |
Radiation source: fine-focus sealed tube | 5142 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 10 pixels mm-1 | θmax = 33.0°, θmin = 1.9° |
ϕ and ω scans | h = −17→17 |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | k = −14→14 |
Tmin = 0.790, Tmax = 0.904 | l = −20→22 |
33771 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | All H-atom parameters refined |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0316P)2 + 0.6657P] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max = 0.002 |
5570 reflections | Δρmax = 0.50 e Å−3 |
275 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0020 (4) |
Crystal data top
[Mn(C5O5)(C10H8N2)(H2O)]·H2O | V = 1477.84 (4) Å3 |
Mr = 387.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3363 (2) Å | µ = 0.94 mm−1 |
b = 9.3622 (1) Å | T = 135 K |
c = 14.4053 (2) Å | 0.26 × 0.20 × 0.11 mm |
β = 104.8460 (6)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 5570 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | 5142 reflections with I > 2σ(I) |
Tmin = 0.790, Tmax = 0.904 | Rint = 0.018 |
33771 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.064 | All H-atom parameters refined |
S = 0.99 | Δρmax = 0.50 e Å−3 |
5570 reflections | Δρmin = −0.31 e Å−3 |
275 parameters | |
Special details top
Experimental. Scan width 0.3° ω, Crystal to detector distance 5.96 cm |
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 >
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 | |
Mn1 | 0.684601 (11) | 0.136951 (13) | 0.798151 (9) | 0.01353 (4) | |
O1 | 0.64305 (6) | 0.36233 (7) | 0.84470 (5) | 0.01713 (12) | |
O2 | 0.69659 (6) | 0.12198 (7) | 0.96469 (5) | 0.01690 (12) | |
O3 | 0.68641 (7) | 0.28465 (8) | 0.66655 (5) | 0.02153 (13) | |
O4 | 0.64686 (6) | −0.01037 (7) | 0.66163 (5) | 0.01967 (12) | |
O5 | 0.60917 (6) | 0.61730 (7) | 0.96076 (5) | 0.01930 (12) | |
O6 | 0.50163 (7) | 0.06724 (10) | 0.78987 (6) | 0.02909 (17) | |
H6A | 0.4708 (15) | 0.0771 (18) | 0.8352 (12) | 0.035 (4)* | |
H6B | 0.4651 (16) | 0.012 (2) | 0.7534 (14) | 0.043 (5)* | |
O7 | 0.40443 (8) | 0.11709 (9) | 0.94229 (7) | 0.02875 (17) | |
H7A | 0.3853 (17) | 0.055 (2) | 0.9735 (14) | 0.053 (5)* | |
H7B | 0.4032 (17) | 0.191 (2) | 0.9712 (14) | 0.048 (5)* | |
N1 | 0.88715 (7) | 0.20062 (8) | 0.83436 (6) | 0.01642 (13) | |
N2 | 0.80304 (7) | −0.06249 (8) | 0.84553 (5) | 0.01566 (13) | |
C1 | 0.92428 (9) | 0.33343 (10) | 0.82123 (7) | 0.01973 (16) | |
H1 | 0.8590 (13) | 0.4009 (15) | 0.7978 (10) | 0.024 (3)* | |
C2 | 1.04630 (9) | 0.36918 (10) | 0.83453 (7) | 0.02126 (17) | |
H2 | 1.0695 (13) | 0.4666 (16) | 0.8253 (10) | 0.024 (3)* | |
C3 | 1.13363 (9) | 0.26271 (11) | 0.86028 (7) | 0.02256 (17) | |
H3 | 1.2189 (14) | 0.2795 (17) | 0.8680 (11) | 0.033 (4)* | |
C4 | 1.09650 (8) | 0.12501 (10) | 0.87448 (7) | 0.02093 (17) | |
H4 | 1.1554 (14) | 0.0518 (17) | 0.8943 (11) | 0.032 (4)* | |
C5 | 0.97229 (8) | 0.09781 (9) | 0.86212 (6) | 0.01548 (14) | |
C6 | 0.92508 (8) | −0.04680 (9) | 0.87424 (6) | 0.01500 (14) | |
C7 | 1.00256 (9) | −0.16065 (10) | 0.91059 (7) | 0.02089 (16) | |
H7 | 1.0909 (13) | −0.1435 (14) | 0.9336 (11) | 0.023 (3)* | |
C8 | 0.95203 (10) | −0.29509 (10) | 0.91378 (8) | 0.02414 (18) | |
H8 | 1.0020 (15) | −0.3742 (16) | 0.9369 (12) | 0.032 (4)* | |
C9 | 0.82694 (10) | −0.31224 (10) | 0.88098 (8) | 0.02464 (19) | |
H9 | 0.7906 (14) | −0.4040 (17) | 0.8810 (11) | 0.030 (4)* | |
C10 | 0.75550 (9) | −0.19272 (10) | 0.84857 (7) | 0.02112 (17) | |
H10 | 0.6684 (14) | −0.2011 (17) | 0.8260 (11) | 0.030 (4)* | |
C11 | 0.64960 (7) | 0.36809 (9) | 0.93330 (6) | 0.01355 (13) | |
C12 | 0.67600 (7) | 0.24299 (9) | 0.99502 (6) | 0.01342 (13) | |
C13 | 0.67313 (7) | 0.28685 (9) | 1.09142 (6) | 0.01509 (14) | |
C14 | 0.65074 (7) | 0.44100 (9) | 1.08891 (6) | 0.01466 (14) | |
C15 | 0.63350 (7) | 0.49386 (9) | 0.98982 (6) | 0.01401 (13) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01516 (6) | 0.01414 (6) | 0.01166 (6) | 0.00095 (4) | 0.00411 (4) | −0.00048 (4) |
O1 | 0.0235 (3) | 0.0180 (3) | 0.0108 (3) | 0.0034 (2) | 0.0059 (2) | 0.0003 (2) |
O2 | 0.0205 (3) | 0.0154 (3) | 0.0152 (3) | 0.0020 (2) | 0.0054 (2) | −0.0009 (2) |
O3 | 0.0306 (3) | 0.0219 (3) | 0.0121 (3) | 0.0001 (3) | 0.0055 (2) | −0.0023 (2) |
O4 | 0.0257 (3) | 0.0211 (3) | 0.0136 (3) | 0.0037 (2) | 0.0077 (2) | 0.0049 (2) |
O5 | 0.0238 (3) | 0.0151 (3) | 0.0200 (3) | 0.0014 (2) | 0.0075 (2) | 0.0006 (2) |
O6 | 0.0223 (3) | 0.0439 (5) | 0.0237 (4) | −0.0131 (3) | 0.0109 (3) | −0.0170 (3) |
O7 | 0.0358 (4) | 0.0219 (3) | 0.0351 (4) | −0.0014 (3) | 0.0210 (3) | −0.0039 (3) |
N1 | 0.0173 (3) | 0.0149 (3) | 0.0172 (3) | 0.0003 (2) | 0.0047 (2) | 0.0007 (2) |
N2 | 0.0167 (3) | 0.0151 (3) | 0.0161 (3) | −0.0004 (2) | 0.0059 (2) | −0.0005 (2) |
C1 | 0.0231 (4) | 0.0157 (3) | 0.0211 (4) | −0.0008 (3) | 0.0068 (3) | 0.0013 (3) |
C2 | 0.0256 (4) | 0.0196 (4) | 0.0193 (4) | −0.0059 (3) | 0.0070 (3) | −0.0005 (3) |
C3 | 0.0192 (4) | 0.0254 (4) | 0.0230 (4) | −0.0058 (3) | 0.0053 (3) | −0.0015 (3) |
C4 | 0.0160 (3) | 0.0219 (4) | 0.0241 (4) | −0.0008 (3) | 0.0037 (3) | −0.0005 (3) |
C5 | 0.0158 (3) | 0.0162 (3) | 0.0143 (3) | −0.0002 (3) | 0.0036 (3) | −0.0005 (3) |
C6 | 0.0169 (3) | 0.0149 (3) | 0.0134 (3) | 0.0012 (3) | 0.0042 (3) | 0.0002 (3) |
C7 | 0.0214 (4) | 0.0193 (4) | 0.0214 (4) | 0.0047 (3) | 0.0044 (3) | 0.0024 (3) |
C8 | 0.0312 (5) | 0.0174 (4) | 0.0260 (5) | 0.0064 (3) | 0.0115 (4) | 0.0047 (3) |
C9 | 0.0319 (5) | 0.0152 (4) | 0.0318 (5) | 0.0001 (3) | 0.0172 (4) | 0.0020 (3) |
C10 | 0.0221 (4) | 0.0172 (4) | 0.0266 (5) | −0.0025 (3) | 0.0108 (3) | −0.0008 (3) |
C11 | 0.0142 (3) | 0.0153 (3) | 0.0116 (3) | 0.0003 (2) | 0.0042 (2) | −0.0005 (2) |
C12 | 0.0135 (3) | 0.0156 (3) | 0.0113 (3) | 0.0000 (2) | 0.0033 (2) | 0.0001 (3) |
C13 | 0.0160 (3) | 0.0179 (3) | 0.0114 (3) | −0.0011 (3) | 0.0034 (3) | −0.0006 (3) |
C14 | 0.0149 (3) | 0.0176 (3) | 0.0121 (3) | −0.0024 (3) | 0.0046 (3) | −0.0018 (3) |
C15 | 0.0142 (3) | 0.0156 (3) | 0.0131 (3) | −0.0007 (2) | 0.0050 (3) | −0.0013 (3) |
Geometric parameters (Å, º) top
Mn1—N1 | 2.2991 (8) | C1—C2 | 1.3880 (14) |
Mn1—N2 | 2.2990 (7) | C1—H1 | 0.966 (14) |
Mn1—O1 | 2.2990 (6) | C2—C3 | 1.3867 (14) |
Mn1—O2 | 2.3719 (7) | C2—H2 | 0.968 (15) |
Mn1—O3 | 2.3508 (7) | C3—C4 | 1.3875 (14) |
Mn1—O4 | 2.3499 (7) | C3—H3 | 0.957 (16) |
Mn1—O6 | 2.1484 (8) | C4—C5 | 1.3967 (12) |
O1—C11 | 1.2605 (10) | C4—H4 | 0.948 (16) |
O2—C12 | 1.2574 (10) | C5—C6 | 1.4824 (12) |
C13—O3i | 1.2484 (11) | C6—C7 | 1.3950 (12) |
C14—O4i | 1.2428 (10) | C7—C8 | 1.3885 (14) |
O3—C13ii | 1.2484 (11) | C7—H7 | 0.984 (15) |
O4—C14ii | 1.2428 (10) | C8—C9 | 1.3844 (15) |
O5—C15 | 1.2360 (10) | C8—H8 | 0.941 (16) |
O6—H6A | 0.820 (17) | C9—C10 | 1.3900 (14) |
O6—H6B | 0.779 (19) | C9—H9 | 0.953 (16) |
O7—H7A | 0.80 (2) | C10—H10 | 0.960 (15) |
O7—H7B | 0.81 (2) | C11—C12 | 1.4544 (11) |
N1—C1 | 1.3416 (11) | C12—C13 | 1.4566 (12) |
N1—C5 | 1.3491 (11) | C13—C14 | 1.4641 (12) |
N2—C6 | 1.3467 (11) | C14—C15 | 1.4757 (12) |
N2—C10 | 1.3382 (11) | C11—C15 | 1.4693 (11) |
| | | |
O6—Mn1—O1 | 91.60 (3) | C1—C2—H2 | 120.3 (8) |
O6—Mn1—N2 | 104.59 (3) | C2—C3—C4 | 118.98 (9) |
O1—Mn1—N2 | 143.76 (3) | C2—C3—H3 | 122.9 (10) |
O6—Mn1—N1 | 170.14 (3) | C4—C3—H3 | 118.1 (10) |
O1—Mn1—N1 | 87.89 (3) | C3—C4—C5 | 118.99 (9) |
N2—Mn1—N1 | 70.72 (3) | C3—C4—H4 | 119.9 (10) |
O6—Mn1—O4 | 78.99 (3) | C5—C4—H4 | 121.1 (10) |
O1—Mn1—O4 | 140.88 (2) | N1—C5—C4 | 121.94 (8) |
N2—Mn1—O4 | 74.87 (2) | N1—C5—C6 | 115.72 (7) |
N1—Mn1—O4 | 107.41 (3) | C4—C5—C6 | 122.28 (8) |
O6—Mn1—O3 | 109.98 (3) | N2—C6—C7 | 122.03 (8) |
O1—Mn1—O3 | 74.94 (2) | N2—C6—C5 | 115.91 (7) |
N2—Mn1—O3 | 126.30 (3) | C7—C6—C5 | 122.03 (8) |
N1—Mn1—O3 | 79.39 (3) | C8—C7—C6 | 118.66 (9) |
O4—Mn1—O3 | 73.00 (2) | C8—C7—H7 | 122.0 (8) |
O6—Mn1—O2 | 80.94 (3) | C6—C7—H7 | 119.4 (8) |
O1—Mn1—O2 | 73.87 (2) | C9—C8—C7 | 119.28 (9) |
N2—Mn1—O2 | 76.94 (2) | C9—C8—H8 | 120.1 (10) |
N1—Mn1—O2 | 89.47 (3) | C7—C8—H8 | 120.6 (10) |
O4—Mn1—O2 | 139.71 (2) | C8—C9—C10 | 118.61 (9) |
O3—Mn1—O2 | 147.17 (2) | C8—C9—H9 | 120.6 (9) |
C11—O1—Mn1 | 111.79 (5) | C10—C9—H9 | 120.7 (9) |
C12—O2—Mn1 | 109.30 (5) | N2—C10—C9 | 122.66 (9) |
C13ii—O3—Mn1 | 111.08 (6) | N2—C10—H10 | 116.8 (10) |
C14ii—O4—Mn1 | 111.13 (6) | C9—C10—H10 | 120.5 (10) |
Mn1—O6—H6A | 121.5 (11) | O1—C11—C12 | 122.28 (7) |
Mn1—O6—H6B | 125.4 (13) | O1—C11—C15 | 127.73 (8) |
H6A—O6—H6B | 110.5 (17) | C12—C11—C15 | 110.00 (7) |
H7A—O7—H7B | 107.0 (19) | O2—C12—C11 | 122.72 (7) |
C1—N1—C5 | 118.46 (8) | O2—C12—C13 | 129.56 (8) |
C1—N1—Mn1 | 122.65 (6) | C11—C12—C13 | 107.72 (7) |
C5—N1—Mn1 | 118.64 (6) | O3i—C13—C12 | 130.40 (8) |
C10—N2—C6 | 118.68 (8) | O3i—C13—C14 | 122.12 (8) |
C10—N2—Mn1 | 122.70 (6) | C12—C13—C14 | 107.48 (7) |
C6—N2—Mn1 | 118.58 (6) | O4i—C14—C13 | 122.52 (8) |
N1—C1—C2 | 122.80 (9) | O4i—C14—C15 | 127.99 (8) |
N1—C1—H1 | 114.5 (9) | C13—C14—C15 | 109.49 (7) |
C2—C1—H1 | 122.6 (9) | O5—C15—C11 | 127.61 (8) |
C3—C2—C1 | 118.78 (9) | O5—C15—C14 | 127.15 (8) |
C3—C2—H2 | 120.9 (8) | C11—C15—C14 | 105.23 (7) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7 | 0.820 (17) | 1.919 (18) | 2.7373 (12) | 175.0 (17) |
O6—H6B···O1iii | 0.779 (19) | 2.137 (19) | 2.9153 (10) | 177.2 (18) |
O7—H7A···O2iv | 0.80 (2) | 2.20 (2) | 2.9838 (11) | 169.1 (19) |
O7—H7B···O5v | 0.81 (2) | 2.06 (2) | 2.8755 (11) | 176.8 (19) |
C7—H7···O2vi | 0.984 (15) | 2.487 (15) | 3.4425 (12) | 163.8 (12) |
Symmetry codes: (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, −y, −z+2; (v) −x+1, −y+1, −z+2; (vi) −x+2, −y, −z+2. |
(II) Poly[[[aqua(2,2'-bipyridine-
κ2N,
N')manganese(II)]-µ-
croconato-
κ4O,
O':
O'',
O'''] monohydrate]
top
Crystal data top
[Mn(C5O5)(C10H8N2)(H2O)]·H2O | F(000) = 788 |
Mr = 387.21 | Dx = 1.720 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6113 reflections |
a = 11.3911 (2) Å | θ = 2.9–27.5° |
b = 9.4023 (1) Å | µ = 0.93 mm−1 |
c = 14.4361 (2) Å | T = 291 K |
β = 104.740 (1)° | Prism, pale-green |
V = 1495.26 (3) Å3 | 0.50 × 0.17 × 0.13 mm |
Z = 4 | |
Data collection top
Bruker APEX2 CCD area-detector diffractometer | 3251 independent reflections |
Radiation source: fine-focus sealed tube | 2966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
Detector resolution: 10 pixels mm-1 | θmax = 27.0°, θmin = 1.9° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | k = −12→8 |
Tmin = 0.654, Tmax = 0.889 | l = −17→18 |
10311 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | All H-atom parameters refined |
wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.654P] where P = (Fo2 + 2Fc2)/3 |
S = 0.96 | (Δ/σ)max = 0.001 |
3251 reflections | Δρmax = 0.27 e Å−3 |
275 parameters | Δρmin = −0.26 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0062 (6) |
Crystal data top
[Mn(C5O5)(C10H8N2)(H2O)]·H2O | V = 1495.26 (3) Å3 |
Mr = 387.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.3911 (2) Å | µ = 0.93 mm−1 |
b = 9.4023 (1) Å | T = 291 K |
c = 14.4361 (2) Å | 0.50 × 0.17 × 0.13 mm |
β = 104.740 (1)° | |
Data collection top
Bruker APEX2 CCD area-detector diffractometer | 3251 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | 2966 reflections with I > 2σ(I) |
Tmin = 0.654, Tmax = 0.889 | Rint = 0.016 |
10311 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.062 | All H-atom parameters refined |
S = 0.96 | Δρmax = 0.27 e Å−3 |
3251 reflections | Δρmin = −0.26 e Å−3 |
275 parameters | |
Special details top
Experimental. Scan width 0.5° ω, Crystal to detector distance 6.02 cm |
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 >
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 | |
Mn1 | 0.685703 (18) | 0.13748 (2) | 0.798547 (13) | 0.02386 (8) | |
O1 | 0.64361 (9) | 0.36163 (10) | 0.84543 (7) | 0.0293 (2) | |
O2 | 0.69761 (9) | 0.12284 (10) | 0.96504 (7) | 0.0291 (2) | |
O3 | 0.68758 (10) | 0.28426 (12) | 0.66611 (7) | 0.0373 (2) | |
O4 | 0.64784 (9) | −0.00889 (11) | 0.66128 (7) | 0.0342 (2) | |
O5 | 0.60963 (10) | 0.61501 (10) | 0.96111 (7) | 0.0331 (2) | |
O6 | 0.50393 (11) | 0.06671 (16) | 0.79010 (10) | 0.0490 (3) | |
H6A | 0.4694 (18) | 0.079 (2) | 0.8351 (15) | 0.053 (6)* | |
H6B | 0.469 (2) | 0.015 (2) | 0.7544 (17) | 0.058 (7)* | |
O7 | 0.40479 (13) | 0.11779 (17) | 0.94164 (11) | 0.0502 (3) | |
H7A | 0.385 (2) | 0.057 (3) | 0.9714 (19) | 0.084 (9)* | |
H7B | 0.402 (2) | 0.191 (3) | 0.9678 (18) | 0.075 (8)* | |
N1 | 0.88745 (10) | 0.20027 (12) | 0.83449 (8) | 0.0279 (2) | |
N2 | 0.80325 (10) | −0.06149 (12) | 0.84535 (8) | 0.0269 (2) | |
C1 | 0.92501 (15) | 0.33227 (16) | 0.82211 (11) | 0.0336 (3) | |
H1 | 0.8623 (15) | 0.4000 (19) | 0.7992 (12) | 0.036 (4)* | |
C2 | 1.04557 (15) | 0.36752 (17) | 0.83568 (11) | 0.0362 (3) | |
H2 | 1.0690 (16) | 0.461 (2) | 0.8277 (12) | 0.041 (5)* | |
C3 | 1.13186 (14) | 0.26196 (18) | 0.86124 (11) | 0.0384 (3) | |
H3 | 1.2137 (18) | 0.279 (2) | 0.8684 (13) | 0.048 (5)* | |
C4 | 1.09496 (14) | 0.12544 (18) | 0.87456 (12) | 0.0360 (3) | |
H4 | 1.1522 (17) | 0.051 (2) | 0.8943 (13) | 0.043 (5)* | |
C5 | 0.97164 (12) | 0.09809 (15) | 0.86180 (9) | 0.0261 (3) | |
C6 | 0.92461 (12) | −0.04632 (15) | 0.87346 (9) | 0.0259 (3) | |
C7 | 1.00084 (15) | −0.15974 (17) | 0.90884 (11) | 0.0351 (3) | |
H7 | 1.0874 (18) | −0.1466 (19) | 0.9314 (13) | 0.042 (5)* | |
C8 | 0.95076 (17) | −0.29293 (17) | 0.91223 (12) | 0.0414 (4) | |
H8 | 1.0004 (17) | −0.372 (2) | 0.9341 (13) | 0.045 (5)* | |
C9 | 0.82694 (17) | −0.30929 (17) | 0.88033 (13) | 0.0413 (4) | |
H9 | 0.7890 (17) | −0.401 (2) | 0.8795 (13) | 0.046 (5)* | |
C10 | 0.75643 (15) | −0.19115 (16) | 0.84863 (11) | 0.0354 (3) | |
H10 | 0.6698 (17) | −0.198 (2) | 0.8269 (13) | 0.044 (5)* | |
C11 | 0.65021 (11) | 0.36720 (14) | 0.93363 (9) | 0.0231 (3) | |
C12 | 0.67681 (11) | 0.24317 (14) | 0.99503 (9) | 0.0231 (3) | |
C13 | 0.67400 (12) | 0.28695 (15) | 1.09142 (9) | 0.0261 (3) | |
C14 | 0.65142 (11) | 0.43985 (15) | 1.08892 (9) | 0.0253 (3) | |
C15 | 0.63387 (11) | 0.49253 (14) | 0.98997 (9) | 0.0243 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.02616 (12) | 0.02487 (12) | 0.02091 (11) | 0.00186 (8) | 0.00666 (8) | −0.00096 (7) |
O1 | 0.0394 (5) | 0.0314 (5) | 0.0185 (4) | 0.0059 (4) | 0.0098 (4) | 0.0007 (4) |
O2 | 0.0344 (5) | 0.0275 (5) | 0.0256 (5) | 0.0040 (4) | 0.0080 (4) | −0.0012 (4) |
O3 | 0.0518 (6) | 0.0387 (6) | 0.0205 (5) | 0.0001 (5) | 0.0079 (4) | −0.0042 (4) |
O4 | 0.0437 (6) | 0.0371 (6) | 0.0243 (5) | 0.0064 (5) | 0.0133 (4) | 0.0092 (4) |
O5 | 0.0398 (6) | 0.0262 (5) | 0.0350 (5) | 0.0018 (4) | 0.0127 (4) | 0.0001 (4) |
O6 | 0.0378 (6) | 0.0727 (9) | 0.0404 (7) | −0.0202 (6) | 0.0171 (5) | −0.0274 (6) |
O7 | 0.0584 (8) | 0.0396 (7) | 0.0632 (9) | −0.0016 (6) | 0.0348 (7) | −0.0066 (7) |
N1 | 0.0292 (6) | 0.0263 (6) | 0.0285 (6) | 0.0000 (5) | 0.0080 (5) | 0.0004 (4) |
N2 | 0.0286 (6) | 0.0268 (6) | 0.0268 (5) | 0.0006 (5) | 0.0097 (4) | −0.0008 (4) |
C1 | 0.0393 (8) | 0.0279 (7) | 0.0345 (7) | −0.0003 (6) | 0.0112 (6) | 0.0020 (6) |
C2 | 0.0451 (9) | 0.0323 (8) | 0.0324 (8) | −0.0117 (7) | 0.0120 (6) | −0.0015 (6) |
C3 | 0.0318 (8) | 0.0442 (9) | 0.0388 (8) | −0.0103 (7) | 0.0082 (6) | −0.0033 (7) |
C4 | 0.0276 (7) | 0.0385 (8) | 0.0404 (8) | 0.0006 (6) | 0.0060 (6) | −0.0010 (6) |
C5 | 0.0271 (6) | 0.0290 (7) | 0.0218 (6) | 0.0002 (5) | 0.0054 (5) | −0.0012 (5) |
C6 | 0.0286 (6) | 0.0281 (7) | 0.0216 (6) | 0.0024 (5) | 0.0073 (5) | −0.0014 (5) |
C7 | 0.0344 (8) | 0.0342 (8) | 0.0357 (8) | 0.0073 (6) | 0.0071 (6) | 0.0034 (6) |
C8 | 0.0544 (10) | 0.0301 (8) | 0.0431 (9) | 0.0129 (7) | 0.0187 (7) | 0.0084 (7) |
C9 | 0.0541 (10) | 0.0249 (8) | 0.0530 (10) | −0.0019 (7) | 0.0285 (8) | 0.0018 (7) |
C10 | 0.0366 (8) | 0.0297 (8) | 0.0440 (8) | −0.0044 (6) | 0.0178 (7) | −0.0017 (6) |
C11 | 0.0208 (6) | 0.0283 (7) | 0.0202 (6) | −0.0003 (5) | 0.0053 (5) | −0.0014 (5) |
C12 | 0.0201 (6) | 0.0281 (7) | 0.0206 (6) | 0.0003 (5) | 0.0042 (5) | −0.0015 (5) |
C13 | 0.0245 (6) | 0.0334 (7) | 0.0200 (6) | −0.0025 (5) | 0.0049 (5) | −0.0006 (5) |
C14 | 0.0229 (6) | 0.0317 (7) | 0.0222 (6) | −0.0053 (5) | 0.0070 (5) | −0.0049 (5) |
C15 | 0.0219 (6) | 0.0276 (7) | 0.0241 (6) | −0.0018 (5) | 0.0074 (5) | −0.0029 (5) |
Geometric parameters (Å, º) top
Mn1—N1 | 2.3006 (12) | C1—C2 | 1.377 (2) |
Mn1—N2 | 2.2998 (12) | C1—H1 | 0.951 (18) |
Mn1—O1 | 2.3010 (10) | C2—C3 | 1.379 (2) |
Mn1—O2 | 2.3766 (10) | C2—H2 | 0.930 (19) |
Mn1—O3 | 2.3623 (10) | C3—C4 | 1.379 (2) |
Mn1—O4 | 2.3605 (11) | C3—H3 | 0.925 (19) |
Mn1—O6 | 2.1486 (12) | C4—C5 | 1.393 (2) |
O1—C11 | 1.2573 (16) | C4—H4 | 0.946 (19) |
O2—C12 | 1.2554 (16) | C5—C6 | 1.4849 (19) |
C13—O3i | 1.2450 (17) | C6—C7 | 1.388 (2) |
C14—O4i | 1.2394 (16) | C7—C8 | 1.382 (2) |
O3—C13ii | 1.2450 (17) | C7—H7 | 0.964 (19) |
O4—C14ii | 1.2394 (16) | C8—C9 | 1.376 (3) |
O5—C15 | 1.2319 (17) | C8—H8 | 0.94 (2) |
O6—H6A | 0.85 (2) | C9—C10 | 1.379 (2) |
O6—H6B | 0.75 (2) | C9—H9 | 0.96 (2) |
O7—H7A | 0.78 (3) | C10—H10 | 0.959 (19) |
O7—H7B | 0.79 (3) | C11—C12 | 1.4494 (18) |
N1—C1 | 1.3395 (19) | C12—C13 | 1.4592 (17) |
N1—C5 | 1.3438 (18) | C13—C14 | 1.459 (2) |
N2—C6 | 1.3456 (17) | C14—C15 | 1.4765 (18) |
N2—C10 | 1.3363 (19) | C11—C15 | 1.4704 (18) |
| | | |
O6—Mn1—N2 | 104.20 (5) | C3—C2—H2 | 120.2 (11) |
O6—Mn1—N1 | 170.14 (5) | C2—C3—C4 | 119.03 (14) |
N2—Mn1—N1 | 70.67 (4) | C2—C3—H3 | 122.5 (13) |
O6—Mn1—O1 | 91.74 (5) | C4—C3—H3 | 118.5 (12) |
N2—Mn1—O1 | 143.90 (4) | C3—C4—C5 | 119.08 (15) |
N1—Mn1—O1 | 88.26 (4) | C3—C4—H4 | 121.0 (11) |
O6—Mn1—O4 | 78.71 (4) | C5—C4—H4 | 119.9 (11) |
N2—Mn1—O4 | 74.97 (4) | N1—C5—C4 | 121.81 (13) |
N1—Mn1—O4 | 107.32 (4) | N1—C5—C6 | 115.84 (12) |
O1—Mn1—O4 | 140.69 (3) | C4—C5—C6 | 122.30 (13) |
O6—Mn1—O3 | 110.00 (5) | N2—C6—C7 | 121.88 (13) |
N2—Mn1—O3 | 126.05 (4) | N2—C6—C5 | 115.81 (12) |
N1—Mn1—O3 | 79.54 (4) | C7—C6—C5 | 122.29 (13) |
O1—Mn1—O3 | 75.43 (3) | C8—C7—C6 | 118.94 (15) |
O4—Mn1—O3 | 72.46 (4) | C8—C7—H7 | 120.0 (11) |
O6—Mn1—O2 | 81.12 (4) | C6—C7—H7 | 121.1 (11) |
N2—Mn1—O2 | 77.09 (4) | C9—C8—C7 | 119.11 (15) |
N1—Mn1—O2 | 89.43 (4) | C9—C8—H8 | 120.2 (12) |
O1—Mn1—O2 | 73.63 (3) | C7—C8—H8 | 120.6 (12) |
O4—Mn1—O2 | 140.03 (3) | C8—C9—C10 | 118.80 (15) |
O3—Mn1—O2 | 147.39 (4) | C8—C9—H9 | 121.5 (11) |
C11—O1—Mn1 | 111.89 (8) | C10—C9—H9 | 119.7 (11) |
C12—O2—Mn1 | 109.23 (8) | N2—C10—C9 | 122.86 (15) |
C13ii—O3—Mn1 | 111.23 (9) | N2—C10—H10 | 116.1 (12) |
C14ii—O4—Mn1 | 111.35 (9) | C9—C10—H10 | 121.0 (12) |
Mn1—O6—H6A | 122.7 (14) | O1—C11—C12 | 122.36 (12) |
Mn1—O6—H6B | 125.1 (17) | O1—C11—C15 | 127.61 (12) |
H6A—O6—H6B | 111 (2) | C12—C11—C15 | 110.04 (11) |
H7A—O7—H7B | 109 (3) | O2—C12—C11 | 122.86 (11) |
C1—N1—C5 | 118.24 (12) | O2—C12—C13 | 129.42 (12) |
C1—N1—Mn1 | 122.84 (10) | C11—C12—C13 | 107.72 (11) |
C5—N1—Mn1 | 118.69 (9) | O3i—C13—C14 | 122.24 (12) |
C10—N2—C6 | 118.34 (12) | O3i—C13—C12 | 130.25 (14) |
C10—N2—Mn1 | 123.01 (10) | C14—C13—C12 | 107.51 (11) |
C6—N2—Mn1 | 118.62 (9) | O4i—C14—C13 | 122.58 (12) |
N1—C1—C2 | 123.01 (15) | O4i—C14—C15 | 127.90 (13) |
N1—C1—H1 | 115.4 (11) | C13—C14—C15 | 109.51 (11) |
C2—C1—H1 | 121.4 (11) | O5—C15—C11 | 127.67 (12) |
C1—C2—C3 | 118.80 (15) | O5—C15—C14 | 127.18 (12) |
C1—C2—H2 | 121.0 (11) | C11—C15—C14 | 105.15 (11) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7 | 0.85 (2) | 1.90 (2) | 2.7474 (18) | 175 (2) |
O6—H6B···O1iii | 0.75 (2) | 2.21 (2) | 2.9492 (16) | 176 (2) |
O7—H7A···O2iv | 0.78 (3) | 2.24 (3) | 3.0156 (18) | 171 (3) |
O7—H7B···O5v | 0.79 (3) | 2.12 (3) | 2.9030 (18) | 178 (3) |
C7—H7···O2vi | 0.964 (19) | 2.534 (19) | 3.4715 (19) | 164.2 (15) |
Symmetry codes: (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, −y, −z+2; (v) −x+1, −y+1, −z+2; (vi) −x+2, −y, −z+2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Mn(C5O5)(C10H8N2)(H2O)]·H2O | [Mn(C5O5)(C10H8N2)(H2O)]·H2O |
Mr | 387.21 | 387.21 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 135 | 291 |
a, b, c (Å) | 11.3363 (2), 9.3622 (1), 14.4053 (2) | 11.3911 (2), 9.4023 (1), 14.4361 (2) |
β (°) | 104.8460 (6) | 104.740 (1) |
V (Å3) | 1477.84 (4) | 1495.26 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.94 | 0.93 |
Crystal size (mm) | 0.26 × 0.20 × 0.11 | 0.50 × 0.17 × 0.13 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (APEX2; Bruker, 2005) | Multi-scan (APEX2; Bruker, 2005) |
Tmin, Tmax | 0.790, 0.904 | 0.654, 0.889 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33771, 5570, 5142 | 10311, 3251, 2966 |
Rint | 0.018 | 0.016 |
(sin θ/λ)max (Å−1) | 0.766 | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.064, 0.99 | 0.024, 0.062, 0.96 |
No. of reflections | 5570 | 3251 |
No. of parameters | 275 | 275 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.50, −0.31 | 0.27, −0.26 |
Selected bond lengths (Å) for (I) topMn1—N1 | 2.2991 (8) | Mn1—O6 | 2.1484 (8) |
Mn1—N2 | 2.2990 (7) | O1—C11 | 1.2605 (10) |
Mn1—O1 | 2.2990 (6) | O2—C12 | 1.2574 (10) |
Mn1—O2 | 2.3719 (7) | C13—O3i | 1.2484 (11) |
Mn1—O3 | 2.3508 (7) | C14—O4i | 1.2428 (10) |
Mn1—O4 | 2.3499 (7) | O5—C15 | 1.2360 (10) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7 | 0.820 (17) | 1.919 (18) | 2.7373 (12) | 175.0 (17) |
O6—H6B···O1ii | 0.779 (19) | 2.137 (19) | 2.9153 (10) | 177.2 (18) |
O7—H7A···O2iii | 0.80 (2) | 2.20 (2) | 2.9838 (11) | 169.1 (19) |
O7—H7B···O5iv | 0.81 (2) | 2.06 (2) | 2.8755 (11) | 176.8 (19) |
C7—H7···O2v | 0.984 (15) | 2.487 (15) | 3.4425 (12) | 163.8 (12) |
Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y, −z+2; (iv) −x+1, −y+1, −z+2; (v) −x+2, −y, −z+2. |
Selected bond lengths (Å) for (II) topMn1—N1 | 2.3006 (12) | Mn1—O6 | 2.1486 (12) |
Mn1—N2 | 2.2998 (12) | O1—C11 | 1.2573 (16) |
Mn1—O1 | 2.3010 (10) | O2—C12 | 1.2554 (16) |
Mn1—O2 | 2.3766 (10) | C13—O3i | 1.2450 (17) |
Mn1—O3 | 2.3623 (10) | C14—O4i | 1.2394 (16) |
Mn1—O4 | 2.3605 (11) | O5—C15 | 1.2319 (17) |
Symmetry code: (i) x, −y+1/2, z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6A···O7 | 0.85 (2) | 1.90 (2) | 2.7474 (18) | 175 (2) |
O6—H6B···O1ii | 0.75 (2) | 2.21 (2) | 2.9492 (16) | 176 (2) |
O7—H7A···O2iii | 0.78 (3) | 2.24 (3) | 3.0156 (18) | 171 (3) |
O7—H7B···O5iv | 0.79 (3) | 2.12 (3) | 2.9030 (18) | 178 (3) |
C7—H7···O2v | 0.964 (19) | 2.534 (19) | 3.4715 (19) | 164.2 (15) |
Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) −x+1, −y, −z+2; (iv) −x+1, −y+1, −z+2; (v) −x+2, −y, −z+2. |
The chemistry of the croconate dianion (C5O52-) dates from 1825 (Gmelin, 1825). In recent years, the coordination chemistry of the croconate ligand has attracted much attention because of its capability of constructing various one- to three-dimensional frameworks. One or two croconate ligands can bidentately chelate a metal ion to form [M(C5O5)] (Brouca-Cabarrecq & Trombe, 1992a,b) or [M(C5O5)2] complexes (Chen et al., 2005). Various croconato–metal frameworks with three to five O atoms involved in coordination and bridging have also been formed (Glick & Dahl, 1966; Brouca-Cabarrecq & Trombe, 1992a,b; Cornia et al., 1993; Maji et al., 2003). We have previously reported several mixed-ligand complexes formulated as [M(C5O5)(phen)2] (phen = 1,10-phenanthroline; Chen et al., 2007; Chen, Chen et al., 2008). Within this series, [Mn(C5O5)(phen)2] (Reference?) and [Cu(C5O5)(phen)2] (Reference?) crystallize in space group C2/c, while [Co(C5O5)(phen)2] (Reference?) and [Ni(C5O5)(phen)2] (Reference?) crystallize in space group Pbcn. These complexes do not show polymeric network structures.
2,2'-Bipyridine (2,2'-bipy) also has excellent chelating and π-conjugation ability. However, in comparison with phen, it has greater structural flexibility and has accordingly been used to build supramolecular architectures (Sun et al., 2005). We therefore chose 2,2'-bipy in place of phen to develop new mixed-ligand complexes and [Ni(C5O5)(2,2'-bipy)2] was thus obtained (Chen, Fang & Yu, 2008). This complex is isostructural with [Ni(C5O5)(phen)2] and also shows an isolated structure. Recently, we synthesized the title mixed-ligand complex, {[Mn(C5O5)(2,2'-bipy)(H2O)].H2O}n, (I), which shows a bis-bidentate bridging mode and a one-dimensional polymeric structure. We report here its crystal structure at 135 K. The structure at 291 K has also been determined; it is essentially the same as that at 135 K, and the data have been deposited in the Supplementary Material. Note that in all of our previous or present mixed-ligand complexes, the neutral phen or 2,2'-bipy ligands are essentially lipophilic, while the croconate anion is prone to be hydrophilic, and its alkali metal salts can easily dissolve in water.
As shown in Fig. 1, the asymmetric unit of (I) comprises an MnII ion and three different ligands, with a solvent water molecule linking to the aqua ligand via a hydrogen bond. The seven coordinating atoms make up a severely distorted pentagonal bipyramid. Atoms O6 and N1 are in axial positions, with the O6—Mn1—N1 moiety being essentially collinear [170.14 (3)°] and with the Mn1—O6(aqua) bond length [2.1484 (8) Å] being the shortest in the MnO5N2 coordination polyhedron. Among the five equatorial atoms, O1 and N2 are displaced by -0.800 (1) and 1.582 (1) Å, respectively, on opposite sides of the plane defined by atoms O2, O3 and O4. The terminal C15—O5 bond shows the `ketonic' C═O bond length [1.2360 (10) Å], while the other four C—O bonds involved in coordination show longer C—O distances.
The croconate ligand is bridging, and exhibits a bis-bidentate chelation mode through four O atoms to two MnII ions. In this way, an infinite one-dimensional coordination chain is formed along the [001] direction (Fig. 2), in which the zigzag-arranged MnII ions are the nodes connecting a series of planar croconate ligands. The planes of two neighbouring croconate ligands in the chain have a dihedral angle of 22.7 (1)° and the two carbonyl groups point to opposite sides of the chain. Along the [Mn(C5O5)]n chain, 2,2'-bipy ligands are attached to the same side, forming the lipophilic side of the chain. The least-squares plane of the 2,2'-bipy ligand is roughly perpendicular to those of the two croconate ligands coordinated to the same MnII ion, with dihedral angles of 89.3 (1) and 84.6 (1)°. The aqua ligands, which lie trans to the 2,2'-bipy ligands, form the hydrophilic side of the [Mn(C5O5)]n chain. The [Mn(C5O5)]n chains run parallel to c-glide planes, with the croconate ligands lying across these glide planes. The dihedral angle between the glide plane and the plane of the croconate ligand is 81.5 (1)°, and that between the glide plane and the plane of the 2,2'-bipy ligand is 77.9 (1)°.
To date, several polymeric mixed-ligand croconate complexes have been reported. In the one-dimensional coordination polymer {[Co2(C5O5)2(bpds)2(H2O)4].3H2O}n (bpds = 4,4'-bipyridyl disulfide), the terminal-bidentate croconate ligand is at the side of the [Co(bpds)]n main chain (Manna et al., 2007). In comparison with 2,2'-bipy, 4,4'-bipyridine (4,4'-bipy) is a bridging ligand that is useful for the construction of two-dimensional frameworks. The [Cd2(C5O5)2(4,4'-bipy)(H2O)]n complex (Wang et al., 2003) and the isostructural {[Cd2(C5O5)2(bipye)(H2O)].2H2O}n [bipye = 1,2-bis(4-pyridyl)ethylene; Wang, Tseng et al., 2007] complexes exhibit a tightly-bonded bilayer two-dimensional framework, which is characterized by a tris-bidentate bridging mode in the [Cd(C5O5)]n chain. The {[Cu2(C5O5)2(bipye)2].H2O}n complex shows an undulating monolayer two-dimensional framework (Ghoshal et al., 2005), while {[Zn2(C5O5)2(bipye)2].H2O}n (Wang, Tseng et al., 2007) exhibits a brick-wall-like two-dimensional structure. Similar bilayer two-dimensional frameworks can be found in the group of isostructural complexes [M(C5O5)(bipya)]n [M = Mn, Fe, Co, Cd; bipya = 1,2-bis(4-pyridyl)ethane; Wang, Dai et al., 2007]. Small ligands such as pyrazine (Maji et al., 2004) or polydentate N,N'-bis(3-aminopropyl)oxamide (Castro et al., 2001) are also involved in two-dimensional mixed-ligand frameworks. One could consider that the 2,2'-bipyrimidine (bipym) ligand combines the properties of bidentate 2,2'-bipy and bridgeable 4,4'-bipy, and it has thus been employed to enhance dimensionality. However, the [Cd2(C5O5)2(bipym)(H2O)2]n structure also shows a two-dimensional framework (Wang, Kuo et al., 2007), in which the [Cd(C5O5)]n chain is similar to the [Mn(C5O5)]n chain of (I).
Fig. 3 shows a projection looking along a bundle of polymeric coordination chains of (I) (along the c direction), which are cross-linked by hydrogen bonding and π–π interactions. Coordinated water and solvent water molecules from neighbouring chains come together to form a hydrophilic layer, and 2,2'-bipy ligands from adjacent chains form a lipophilic layer. The hydrophilic and lipophilic layers are stacked alternately to build a layer structure.
The detailed hydrophilic–hydrophilic interactions are exhibited in Fig. 2 and Table 2, and involve four unique O—H···O hydrogen bonds. Both the coordinated water and the solvent water molecules act as double hydrogen-bond donors in these hydrogen bonds, and the latter also acts as a single hydrogen-bond acceptor. Besides hydrogen bonding, there are several short intermolecular C···O and C···C contacts involving the C═O group in the hydrophilic layer: the C14···O5iv, C14···C15iv and C15···C15iv distances are 2.9002 (11), 3.1888 (12) and 3.1170 (12) Å, respectively [symmetry code: (iv) -x + 1, -y + 1, -z + 2]. These interactions may also considered to be π–π interactions between the C═O group and an adjacent croconate C5 ring, as these two entities are parallel.
As shown in Fig. 2, the lipophilic layer is characterized by π–π interactions in 2,2'-bipy pairs between neighbouring [Mn(C5O5)]n chains. The cross-linking of the chains through these π–π interactions is further assisted by the C7—H7···O2(-x + 2, -y, -z + 2) interaction. The 2,2'-bipy ligand is basically planar, with a small dihedral angle of 9.4 (1)° between its two pyridine rings as a result of the bidentate chelation balance and intra-ligand H···H repulsion. The two 2,2'-bipy ligands in the π–π interaction are approximately half-overlapped, with the interplanar spacing being 3.429 (5) Å (the spacing is based on the least-squares plane of the 2,2'-bipy ligand). The C5···C7(-x + 2, -y, -z + 2) distance of 3.2664 (13) Å in the 2,2'-bipy pair is slightly shorter than the interplanar spacing and is nearly perpendicular [85.1 (1)°] to these planes. Thus, the structural flexibility of the 2,2'-bipy ligand is manifested in (I). Using the rigid phen ligand and similar synthetic methods, the resultant [Mn(C5O5)(phen)2] complex does not show a network structure (Reference?). Note that [Ni(C5O5)(2,2'-bipy)2] also fails to form a network structure (Reference?). The half-empty d shell and the relatively large size of the Mn atom, which accommodates higher coordination numbers and has longer Mn—X bond lengths, may account for this difference. For example, the average Mn—N bond length in (I) [2.300 (2) Å] is much longer than the average Ni—N length [2.063 (3) Å] in [Ni(C5O5)(2,2'-bipy)2] at the same temperature (i.e. room temperature).
The unit-cell dimensions at 291 K are a = 11.3911 (2), b = 9.4023 (1) and c = 14.4361 (2) Å, β = 104.740 (1)° and V = 1495.26 (3) Å3 (see Supplementary Material). The cell dimensions contract anisotropically with decreasing temperature, with the largest contractions being perpendicular to the direction of the rigid chain, i.e. adjacent chains may be able to nestle closer to one another at lower temperature, thus increasing the strength of the intermolecular interactions.
The thermogravimetry (TG) curve (Fig. 4) of the title crystal exhibits three weight-loss steps. The first weight loss begins at 366 K and the weight approaches 95.4% of the original weight at 393 K, corresponding to the loss of a solvent water molecule. The differential thermal analysis (DTA) curve gives an enthalpy change of 46.8 kJ mol-1 for this dehydration process, indicating the very strong hydrogen bonding. The second weight loss begins at 422 K and the weight approaches 90.7% of the original weight at 503 K, which can be assigned to the release of the coordinated water molecule. In the DTA curve, the corresponding second valley suggests an enthalpy change of 43.1 kJ mol-1. The strength of hydrogen bonding here is comparable with the aqua coordination of the water molecule.
In conclusion, the one-dimensional molecular fibres of (I) have been woven into a three-dimensional structure by alternating layers of strong hydrophilic–hydrophilic interactions and lipophilic–lipophilic interactions.