Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027973/bi2196sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027973/bi2196Isup2.hkl |
CCDC reference: 1148880
A mixture of FeCl2 (0.5 mmol), pyridine-2,6-dicarboxylic acid (0.5 mmol), NaOH (1 mmol), 4,4'-bipyridine (0.5 mmol), H2O (8 ml) and ethanol (8 ml) were place in a 25 ml Teflon-lined stainless steel autoclave and heated at 433 K for two days. On cooling to room temperature, blue crystals were obtained with a yield of 12%. Elemental analysis calculated: C 47.83, H 5.17, N 10.33, Fe 8.27%; found: C 47.87, H 5.21, N 10.27, Fe 8.16%.
H atoms bound to C atoms were placed geometrically and refined as riding atoms with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the water molecules were located from difference Fourier maps and were refined with distance restraints of O—H = 0.82 (1) Å and H···H = 1.35 (2) Å, and with Uiso(H) = 1.5Ueq(O). The [Fe(C10H8N2)2(H2O)4]2+ cations exhibit non-crystallographic inversion symmetry. The refined Flack parameter (Flack, 1983) from 530 Freidel pairs is 0.36 (3).
Metal-organic frameworks have applications in catalysis, optical materials, membranes, and sorption (Evans, Ngo & Lin, 2001; Vioux et al., 2004; Sanchez et al., 2003; Evans & Lin, 2001; Jannasch, 2003; Javaid et al., 2001; Honma et al., 2001; Sudik et al., 2005; Rowsell et al., 2004; Kitaura et al., 2004; Suzuki et al., 2002).
Design of metal-organic frameworks often utilizes a metal cation, metal cluster, or metal oxide substructure as a node, from which rigid or flexible multitopic organic ligands radiate to act as tethers to adjacent nodes for the bottom-up construction of complex extended architectures. While a variety of organic molecules have been investigated as potential tethers, materials incorporating multitopic carboxylates and pyridine ligands have been employed most extensively.
In the title compound, FeII is hexa-coordinated in an octahedral manner by four water molecules in the equatorial plane and two N atoms in the axial positions from two 4,4'-bipyridine molecules (Fig. 1). The Fe—N and Fe—O bond lengths are in the range 2.265 (4)–2.266 (4) and 2.161 (3)–2.202 (4) Å, respectively. The cations lie in layers in the bc planes. Pyridine-2,6-dicarboxylate anions and water molecules lie between these layers, forming an extensive hydrogen-bond network.
For literature concerning metal–organic frameworks, see: Evans, Ngo & Lin (2001); Vioux et al. (2004); Sanchez et al. (2003); Evans & Lin (2001); Jannasch (2003); Javaid et al. (2001); Honma et al. (2001); Sudik et al. (2005); Rowsell et al. (2004); Kitaura et al. (2004); Suzuki et al. (2002).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids for non-H atoms. |
[Fe(C10H8N2)2(H2O)4](C7H3NO4)·4H2O | F(000) = 1416 |
Mr = 677.45 | Dx = 1.452 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 3290 reflections |
a = 18.201 (1) Å | θ = 2.0–55.0° |
b = 6.900 (1) Å | µ = 0.56 mm−1 |
c = 25.010 (1) Å | T = 293 K |
β = 99.40 (3)° | Block, blue |
V = 3098.9 (5) Å3 | 0.10 × 0.10 × 0.10 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2946 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 25.1°, θmin = 1.7° |
ω scans | h = −19→21 |
5104 measured reflections | k = −8→4 |
3180 independent reflections | l = −29→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0702P)2 + 1.0906P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3180 reflections | Δρmax = 0.35 e Å−3 |
455 parameters | Δρmin = −0.38 e Å−3 |
26 restraints | Absolute structure: Flack (1983), with 530 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.36 (3) |
[Fe(C10H8N2)2(H2O)4](C7H3NO4)·4H2O | V = 3098.9 (5) Å3 |
Mr = 677.45 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 18.201 (1) Å | µ = 0.56 mm−1 |
b = 6.900 (1) Å | T = 293 K |
c = 25.010 (1) Å | 0.10 × 0.10 × 0.10 mm |
β = 99.40 (3)° |
Bruker SMART CCD area-detector diffractometer | 2946 reflections with I > 2σ(I) |
5104 measured reflections | Rint = 0.018 |
3180 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | Δρmax = 0.35 e Å−3 |
S = 1.05 | Δρmin = −0.38 e Å−3 |
3180 reflections | Absolute structure: Flack (1983), with 530 Friedel pairs |
455 parameters | Absolute structure parameter: 0.36 (3) |
26 restraints |
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 | ||
Fe1 | 0.82218 (7) | 0.73736 (9) | 0.62280 (5) | 0.03412 (16) | |
C1 | 0.5731 (3) | 0.1741 (7) | 0.8192 (2) | 0.0385 (11) | |
C2 | 0.5712 (5) | 0.2657 (6) | 0.8733 (4) | 0.0335 (7) | |
C3 | 0.5690 (3) | 0.4671 (6) | 0.8799 (2) | 0.0395 (10) | |
H3A | 0.5680 | 0.5473 | 0.8498 | 0.047* | |
C4 | 0.5683 (3) | 0.5490 (6) | 0.9306 (2) | 0.0405 (10) | |
H4A | 0.5663 | 0.6829 | 0.9343 | 0.049* | |
C5 | 0.5706 (2) | 0.4311 (6) | 0.97538 (19) | 0.0391 (10) | |
H5A | 0.5703 | 0.4866 | 1.0092 | 0.047* | |
C6 | 0.5735 (3) | 0.2278 (6) | 0.9706 (3) | 0.0342 (13) | |
C7 | 0.5791 (2) | 0.0996 (6) | 1.02025 (18) | 0.0347 (9) | |
C8 | 0.8773 (3) | 0.8254 (9) | 0.7460 (2) | 0.0476 (13) | |
H8A | 0.9228 | 0.8122 | 0.7340 | 0.057* | |
C9 | 0.8770 (3) | 0.8418 (8) | 0.8006 (2) | 0.0448 (12) | |
H9A | 0.9220 | 0.8416 | 0.8244 | 0.054* | |
C10 | 0.8112 (3) | 0.8587 (6) | 0.82083 (18) | 0.0279 (9) | |
C11 | 0.7468 (3) | 0.8708 (8) | 0.7815 (2) | 0.0481 (13) | |
H11A | 0.7007 | 0.8911 | 0.7920 | 0.058* | |
C12 | 0.7517 (3) | 0.8526 (9) | 0.7275 (2) | 0.0503 (14) | |
H12A | 0.7079 | 0.8582 | 0.7025 | 0.060* | |
C13 | 0.8081 (2) | 0.8626 (6) | 0.87930 (18) | 0.0287 (10) | |
C14 | 0.8730 (3) | 0.8650 (7) | 0.91726 (18) | 0.0379 (11) | |
H14A | 0.9194 | 0.8654 | 0.9062 | 0.045* | |
C15 | 0.8673 (3) | 0.8668 (7) | 0.9720 (2) | 0.0397 (11) | |
H15A | 0.9111 | 0.8685 | 0.9971 | 0.048* | |
C16 | 0.7424 (3) | 0.8637 (7) | 0.9536 (2) | 0.0450 (12) | |
H16A | 0.6970 | 0.8625 | 0.9661 | 0.054* | |
C17 | 0.7409 (3) | 0.8628 (7) | 0.8989 (2) | 0.0402 (11) | |
H17A | 0.6958 | 0.8623 | 0.8752 | 0.048* | |
C18 | 0.8956 (3) | 0.6415 (7) | 0.51671 (19) | 0.0387 (11) | |
H18A | 0.9401 | 0.6401 | 0.5410 | 0.046* | |
C19 | 0.8987 (3) | 0.6324 (8) | 0.46210 (18) | 0.0414 (12) | |
H19A | 0.9443 | 0.6245 | 0.4501 | 0.050* | |
C20 | 0.8331 (3) | 0.6353 (6) | 0.42539 (18) | 0.0285 (10) | |
C21 | 0.7673 (3) | 0.6404 (7) | 0.4459 (2) | 0.0418 (12) | |
H21A | 0.7218 | 0.6382 | 0.4227 | 0.050* | |
C22 | 0.7698 (3) | 0.6488 (8) | 0.5007 (2) | 0.0457 (12) | |
H22A | 0.7247 | 0.6521 | 0.5137 | 0.055* | |
C23 | 0.8328 (3) | 0.6379 (6) | 0.36586 (18) | 0.0294 (10) | |
C24 | 0.7669 (3) | 0.6306 (8) | 0.3286 (2) | 0.0478 (13) | |
H24A | 0.7214 | 0.6219 | 0.3408 | 0.057* | |
C25 | 0.7689 (3) | 0.6362 (8) | 0.2741 (2) | 0.0482 (13) | |
H25A | 0.7239 | 0.6311 | 0.2502 | 0.058* | |
C26 | 0.8947 (4) | 0.6555 (9) | 0.2887 (2) | 0.0576 (15) | |
H26A | 0.9394 | 0.6641 | 0.2753 | 0.069* | |
C27 | 0.8981 (3) | 0.6507 (8) | 0.3441 (2) | 0.0467 (13) | |
H27A | 0.9439 | 0.6560 | 0.3668 | 0.056* | |
N1 | 0.5734 (3) | 0.1479 (6) | 0.91981 (19) | 0.0466 (10) | |
N2 | 0.8150 (2) | 0.8275 (5) | 0.70892 (16) | 0.0345 (9) | |
N3 | 0.8037 (3) | 0.8662 (5) | 0.99043 (16) | 0.0383 (10) | |
N4 | 0.8316 (2) | 0.6524 (5) | 0.53671 (15) | 0.0322 (9) | |
N5 | 0.8321 (3) | 0.6486 (5) | 0.25322 (17) | 0.0424 (10) | |
O1 | 0.7848 (2) | 1.0205 (5) | 0.59307 (15) | 0.0469 (9) | |
H11 | 0.757 (3) | 1.098 (6) | 0.605 (2) | 0.070* | |
H12 | 0.799 (3) | 1.074 (7) | 0.5671 (17) | 0.070* | |
O2 | 0.9377 (2) | 0.8418 (5) | 0.63036 (16) | 0.0457 (8) | |
H21 | 0.947 (3) | 0.957 (2) | 0.631 (3) | 0.069* | |
H22 | 0.974 (2) | 0.785 (6) | 0.646 (3) | 0.069* | |
O3 | 0.8599 (2) | 0.4528 (5) | 0.65227 (14) | 0.0477 (9) | |
H31 | 0.894 (2) | 0.384 (8) | 0.646 (2) | 0.072* | |
H32 | 0.856 (3) | 0.445 (8) | 0.6841 (8) | 0.072* | |
O4 | 0.70693 (19) | 0.6295 (5) | 0.61352 (15) | 0.0407 (8) | |
H41 | 0.693 (3) | 0.516 (2) | 0.611 (3) | 0.061* | |
H42 | 0.672 (2) | 0.697 (6) | 0.600 (3) | 0.061* | |
O5 | 0.4859 (3) | 0.7286 (6) | 0.6359 (2) | 0.0577 (14) | |
H51 | 0.511 (3) | 0.738 (9) | 0.612 (2) | 0.087* | |
H52 | 0.514 (3) | 0.724 (11) | 0.6650 (14) | 0.087* | |
O6 | 0.5641 (3) | 0.6916 (7) | 0.73867 (17) | 0.0714 (11) | |
H61 | 0.569 (4) | 0.761 (9) | 0.7655 (19) | 0.107* | |
H62 | 0.597 (3) | 0.610 (9) | 0.744 (3) | 0.107* | |
O7 | 0.5641 (3) | 0.1491 (5) | 0.68152 (16) | 0.0554 (10) | |
H71 | 0.571 (4) | 0.180 (8) | 0.7137 (8) | 0.083* | |
H72 | 0.543 (4) | 0.044 (5) | 0.679 (2) | 0.083* | |
O8 | 0.6593 (3) | 0.2454 (5) | 0.6074 (2) | 0.0487 (13) | |
H81 | 0.636 (3) | 0.220 (9) | 0.6318 (17) | 0.073* | |
H82 | 0.635 (3) | 0.209 (9) | 0.5790 (13) | 0.073* | |
O9 | 0.5726 (3) | 0.2898 (6) | 0.77972 (17) | 0.0533 (11) | |
O10 | 0.5739 (2) | −0.0063 (5) | 0.81586 (14) | 0.0472 (8) | |
O11 | 0.5811 (2) | 0.1826 (5) | 1.06512 (14) | 0.0470 (9) | |
O12 | 0.5839 (2) | −0.0786 (4) | 1.01353 (13) | 0.0453 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0355 (3) | 0.0432 (3) | 0.0237 (2) | 0.0010 (3) | 0.00518 (18) | 0.0011 (3) |
C1 | 0.028 (2) | 0.049 (3) | 0.038 (3) | 0.005 (2) | 0.0020 (19) | −0.001 (2) |
C2 | 0.0201 (14) | 0.0445 (18) | 0.0342 (17) | 0.002 (2) | −0.0004 (12) | 0.004 (2) |
C3 | 0.034 (2) | 0.0435 (19) | 0.039 (3) | 0.002 (2) | −0.0002 (19) | 0.003 (2) |
C4 | 0.040 (2) | 0.032 (2) | 0.048 (3) | 0.0044 (19) | 0.002 (2) | −0.003 (2) |
C5 | 0.036 (2) | 0.044 (2) | 0.037 (2) | −0.001 (2) | 0.0022 (19) | −0.012 (2) |
C6 | 0.026 (2) | 0.041 (2) | 0.036 (3) | −0.0011 (19) | 0.006 (2) | −0.007 (2) |
C7 | 0.028 (2) | 0.045 (2) | 0.032 (2) | −0.0034 (19) | 0.0064 (17) | −0.0061 (19) |
C8 | 0.030 (3) | 0.087 (4) | 0.027 (3) | −0.003 (3) | 0.010 (2) | −0.007 (3) |
C9 | 0.024 (2) | 0.081 (4) | 0.027 (3) | −0.002 (2) | −0.002 (2) | −0.005 (2) |
C10 | 0.030 (2) | 0.0301 (19) | 0.023 (2) | 0.0014 (17) | 0.0050 (19) | −0.0006 (17) |
C11 | 0.029 (3) | 0.081 (3) | 0.036 (3) | 0.007 (2) | 0.012 (2) | −0.009 (3) |
C12 | 0.039 (3) | 0.081 (4) | 0.029 (3) | 0.014 (3) | 0.001 (2) | −0.005 (2) |
C13 | 0.033 (3) | 0.0258 (18) | 0.026 (2) | 0.0020 (17) | 0.003 (2) | −0.0030 (16) |
C14 | 0.035 (3) | 0.059 (3) | 0.020 (2) | −0.001 (2) | 0.006 (2) | −0.003 (2) |
C15 | 0.037 (3) | 0.051 (2) | 0.028 (3) | −0.004 (2) | −0.006 (2) | −0.003 (2) |
C16 | 0.044 (3) | 0.059 (3) | 0.035 (3) | 0.002 (2) | 0.016 (2) | 0.000 (2) |
C17 | 0.035 (3) | 0.057 (3) | 0.030 (3) | 0.003 (2) | 0.009 (2) | −0.004 (2) |
C18 | 0.030 (3) | 0.060 (3) | 0.025 (2) | 0.008 (2) | 0.000 (2) | −0.005 (2) |
C19 | 0.033 (3) | 0.070 (3) | 0.021 (2) | 0.004 (2) | 0.003 (2) | −0.003 (2) |
C20 | 0.035 (3) | 0.0285 (18) | 0.022 (2) | 0.0008 (18) | 0.0047 (18) | −0.0012 (16) |
C21 | 0.030 (3) | 0.070 (3) | 0.025 (2) | −0.007 (2) | 0.003 (2) | −0.006 (2) |
C22 | 0.033 (3) | 0.074 (4) | 0.031 (3) | −0.008 (3) | 0.008 (2) | −0.007 (2) |
C23 | 0.034 (3) | 0.0307 (19) | 0.025 (2) | 0.0023 (18) | 0.0105 (19) | −0.0012 (17) |
C24 | 0.034 (3) | 0.075 (3) | 0.035 (3) | 0.002 (2) | 0.008 (2) | 0.000 (2) |
C25 | 0.047 (3) | 0.071 (3) | 0.028 (3) | 0.003 (3) | 0.007 (2) | 0.001 (2) |
C26 | 0.054 (4) | 0.090 (4) | 0.034 (3) | −0.008 (3) | 0.022 (3) | −0.008 (3) |
C27 | 0.034 (3) | 0.074 (3) | 0.033 (3) | −0.005 (2) | 0.006 (2) | −0.005 (2) |
N1 | 0.036 (2) | 0.056 (2) | 0.048 (3) | 0.003 (2) | 0.0065 (19) | −0.002 (2) |
N2 | 0.035 (2) | 0.042 (2) | 0.027 (2) | 0.0029 (17) | 0.0048 (17) | −0.0016 (16) |
N3 | 0.050 (3) | 0.044 (2) | 0.023 (2) | 0.0024 (18) | 0.0102 (18) | −0.0008 (16) |
N4 | 0.033 (2) | 0.041 (2) | 0.022 (2) | −0.0026 (16) | 0.0033 (17) | −0.0015 (16) |
N5 | 0.054 (3) | 0.046 (2) | 0.028 (2) | −0.005 (2) | 0.0100 (19) | −0.0045 (18) |
O1 | 0.061 (2) | 0.0487 (18) | 0.0351 (19) | 0.0179 (17) | 0.0201 (17) | 0.0103 (15) |
O2 | 0.037 (2) | 0.0534 (18) | 0.047 (2) | −0.0058 (16) | 0.0062 (17) | −0.0034 (17) |
O3 | 0.069 (3) | 0.0472 (18) | 0.0299 (17) | 0.0214 (17) | 0.0172 (17) | 0.0102 (15) |
O4 | 0.036 (2) | 0.0444 (16) | 0.0406 (19) | −0.0041 (14) | 0.0036 (16) | 0.0007 (15) |
O5 | 0.054 (3) | 0.067 (3) | 0.058 (3) | 0.008 (2) | 0.026 (3) | 0.014 (2) |
O6 | 0.083 (3) | 0.084 (3) | 0.046 (2) | −0.006 (3) | 0.010 (2) | −0.011 (2) |
O7 | 0.070 (3) | 0.053 (2) | 0.045 (2) | −0.009 (2) | 0.013 (2) | −0.0043 (18) |
O8 | 0.050 (3) | 0.054 (3) | 0.042 (3) | −0.0061 (16) | 0.010 (2) | −0.0065 (16) |
O9 | 0.067 (3) | 0.065 (2) | 0.028 (2) | 0.006 (2) | 0.007 (2) | 0.0021 (19) |
O10 | 0.055 (2) | 0.0498 (19) | 0.0355 (17) | 0.0017 (16) | 0.0048 (15) | −0.0096 (15) |
O11 | 0.052 (2) | 0.059 (2) | 0.0322 (19) | −0.0061 (18) | 0.0110 (16) | −0.0121 (16) |
O12 | 0.057 (2) | 0.0426 (17) | 0.0350 (17) | 0.0006 (16) | 0.0052 (15) | −0.0001 (14) |
Fe1—O1 | 2.161 (3) | C16—H16A | 0.930 |
Fe1—O3 | 2.169 (3) | C17—H17A | 0.930 |
Fe1—O2 | 2.202 (4) | C18—N4 | 1.342 (6) |
Fe1—O4 | 2.202 (4) | C18—C19 | 1.377 (7) |
Fe1—N4 | 2.265 (4) | C18—H18A | 0.930 |
Fe1—N2 | 2.266 (4) | C19—C20 | 1.381 (6) |
C1—O10 | 1.248 (6) | C19—H19A | 0.930 |
C1—O9 | 1.268 (7) | C20—C21 | 1.379 (7) |
C1—C2 | 1.499 (10) | C20—C23 | 1.488 (6) |
C2—C3 | 1.401 (6) | C21—C22 | 1.366 (7) |
C2—N1 | 1.414 (9) | C21—H21A | 0.930 |
C3—C4 | 1.390 (7) | C22—N4 | 1.321 (6) |
C3—H3A | 0.930 | C22—H22A | 0.930 |
C4—C5 | 1.380 (7) | C23—C27 | 1.389 (7) |
C4—H4A | 0.930 | C23—C24 | 1.394 (7) |
C5—C6 | 1.410 (6) | C24—C25 | 1.371 (7) |
C5—H5A | 0.930 | C24—H24A | 0.930 |
C6—N1 | 1.385 (7) | C25—N5 | 1.341 (7) |
C6—C7 | 1.514 (7) | C25—H25A | 0.930 |
C7—O12 | 1.246 (5) | C26—N5 | 1.327 (8) |
C7—O11 | 1.255 (5) | C26—C27 | 1.378 (8) |
C8—N2 | 1.342 (6) | C26—H26A | 0.930 |
C8—C9 | 1.371 (7) | C27—H27A | 0.930 |
C8—H8A | 0.930 | O1—H11 | 0.82 (1) |
C9—C10 | 1.379 (7) | O1—H12 | 0.82 (1) |
C9—H9A | 0.930 | O2—H21 | 0.82 (1) |
C10—C11 | 1.405 (7) | O2—H22 | 0.82 (1) |
C10—C13 | 1.473 (6) | O3—H31 | 0.81 (1) |
C11—C12 | 1.373 (7) | O3—H32 | 0.81 (1) |
C11—H11A | 0.930 | O4—H41 | 0.82 (1) |
C12—N2 | 1.323 (7) | O4—H42 | 0.82 (1) |
C12—H12A | 0.930 | O5—H51 | 0.82 (1) |
C13—C17 | 1.389 (7) | O5—H52 | 0.82 (1) |
C13—C14 | 1.391 (6) | O6—H61 | 0.82 (1) |
C14—C15 | 1.390 (7) | O6—H62 | 0.82 (1) |
C14—H14A | 0.930 | O7—H71 | 0.82 (1) |
C15—N3 | 1.314 (7) | O7—H72 | 0.82 (1) |
C15—H15A | 0.930 | O8—H81 | 0.82 (1) |
C16—N3 | 1.326 (7) | O8—H82 | 0.81 (1) |
C16—C17 | 1.366 (7) | ||
O1—Fe1—O3 | 179.73 (19) | N3—C16—H16A | 117.5 |
O1—Fe1—O2 | 88.66 (15) | C17—C16—H16A | 117.5 |
O3—Fe1—O2 | 91.28 (16) | C16—C17—C13 | 118.6 (5) |
O1—Fe1—O4 | 91.61 (15) | C16—C17—H17A | 120.7 |
O3—Fe1—O4 | 88.44 (15) | C13—C17—H17A | 120.7 |
O2—Fe1—O4 | 178.69 (18) | N4—C18—C19 | 123.4 (4) |
O1—Fe1—N4 | 88.59 (14) | N4—C18—H18A | 118.3 |
O3—Fe1—N4 | 91.14 (13) | C19—C18—H18A | 118.3 |
O2—Fe1—N4 | 86.94 (15) | C18—C19—C20 | 119.2 (5) |
O4—Fe1—N4 | 91.79 (15) | C18—C19—H19A | 120.4 |
O1—Fe1—N2 | 90.87 (14) | C20—C19—H19A | 120.4 |
O3—Fe1—N2 | 89.40 (14) | C21—C20—C19 | 117.5 (4) |
O2—Fe1—N2 | 91.78 (16) | C21—C20—C23 | 120.7 (4) |
O4—Fe1—N2 | 89.50 (15) | C19—C20—C23 | 121.8 (4) |
N4—Fe1—N2 | 178.62 (18) | C22—C21—C20 | 119.1 (5) |
O10—C1—O9 | 125.1 (5) | C22—C21—H21A | 120.5 |
O10—C1—C2 | 118.9 (5) | C20—C21—H21A | 120.5 |
O9—C1—C2 | 116.0 (4) | N4—C22—C21 | 124.7 (5) |
C3—C2—N1 | 118.1 (7) | N4—C22—H22A | 117.7 |
C3—C2—C1 | 122.0 (6) | C21—C22—H22A | 117.7 |
N1—C2—C1 | 119.9 (4) | C27—C23—C24 | 116.0 (5) |
C4—C3—C2 | 121.0 (6) | C27—C23—C20 | 121.9 (4) |
C4—C3—H3A | 119.5 | C24—C23—C20 | 122.1 (4) |
C2—C3—H3A | 119.5 | C25—C24—C23 | 120.3 (5) |
C5—C4—C3 | 119.9 (4) | C25—C24—H24A | 119.8 |
C5—C4—H4A | 120.1 | C23—C24—H24A | 119.8 |
C3—C4—H4A | 120.1 | N5—C25—C24 | 123.5 (5) |
C4—C5—C6 | 121.0 (5) | N5—C25—H25A | 118.3 |
C4—C5—H5A | 119.5 | C24—C25—H25A | 118.3 |
C6—C5—H5A | 119.5 | N5—C26—C27 | 124.4 (6) |
N1—C6—C5 | 118.6 (5) | N5—C26—H26A | 117.8 |
N1—C6—C7 | 120.7 (4) | C27—C26—H26A | 117.8 |
C5—C6—C7 | 120.7 (5) | C26—C27—C23 | 119.7 (5) |
O12—C7—O11 | 125.3 (4) | C26—C27—H27A | 120.2 |
O12—C7—C6 | 117.5 (4) | C23—C27—H27A | 120.2 |
O11—C7—C6 | 117.1 (4) | C6—N1—C2 | 121.5 (4) |
N2—C8—C9 | 123.2 (5) | C12—N2—C8 | 116.4 (4) |
N2—C8—H8A | 118.4 | C12—N2—Fe1 | 124.0 (3) |
C9—C8—H8A | 118.4 | C8—N2—Fe1 | 118.7 (3) |
C8—C9—C10 | 121.1 (5) | C15—N3—C16 | 116.6 (4) |
C8—C9—H9A | 119.4 | C22—N4—C18 | 116.1 (4) |
C10—C9—H9A | 119.4 | C22—N4—Fe1 | 117.6 (3) |
C9—C10—C11 | 115.1 (4) | C18—N4—Fe1 | 125.0 (3) |
C9—C10—C13 | 122.9 (4) | C26—N5—C25 | 116.2 (5) |
C11—C10—C13 | 122.0 (4) | Fe1—O1—H11 | 130 (4) |
C12—C11—C10 | 120.1 (5) | Fe1—O1—H12 | 124 (4) |
C12—C11—H11A | 119.9 | H11—O1—H12 | 106.3 (18) |
C10—C11—H11A | 119.9 | Fe1—O2—H21 | 121 (4) |
N2—C12—C11 | 123.9 (5) | Fe1—O2—H22 | 125 (4) |
N2—C12—H12A | 118.1 | H21—O2—H22 | 107.8 (19) |
C11—C12—H12A | 118.1 | Fe1—O3—H31 | 132 (4) |
C17—C13—C14 | 117.3 (4) | Fe1—O3—H32 | 109 (4) |
C17—C13—C10 | 122.0 (4) | H31—O3—H32 | 109.4 (19) |
C14—C13—C10 | 120.7 (4) | Fe1—O4—H41 | 127 (4) |
C15—C14—C13 | 118.7 (5) | Fe1—O4—H42 | 121 (4) |
C15—C14—H14A | 120.6 | H41—O4—H42 | 107.8 (19) |
C13—C14—H14A | 120.6 | H51—O5—H52 | 108.4 (19) |
N3—C15—C14 | 123.9 (5) | H61—O6—H62 | 107.2 (19) |
N3—C15—H15A | 118.1 | H71—O7—H72 | 106.9 (19) |
C14—C15—H15A | 118.1 | H81—O8—H82 | 108.6 (19) |
N3—C16—C17 | 125.0 (5) | ||
O10—C1—C2—C3 | −179.0 (7) | C19—C20—C23—C24 | 176.6 (4) |
O9—C1—C2—C3 | 0.1 (10) | C27—C23—C24—C25 | 0.0 (8) |
O10—C1—C2—N1 | 2.5 (10) | C20—C23—C24—C25 | 179.0 (4) |
O9—C1—C2—N1 | −178.5 (6) | C23—C24—C25—N5 | 0.0 (9) |
N1—C2—C3—C4 | −0.6 (11) | N5—C26—C27—C23 | 0.0 (9) |
C1—C2—C3—C4 | −179.2 (6) | C24—C23—C27—C26 | 0.0 (7) |
C2—C3—C4—C5 | 0.7 (9) | C20—C23—C27—C26 | −179.0 (5) |
C3—C4—C5—C6 | −0.2 (8) | C5—C6—N1—C2 | 0.5 (9) |
C4—C5—C6—N1 | −0.4 (8) | C7—C6—N1—C2 | −177.4 (6) |
C4—C5—C6—C7 | 177.5 (4) | C3—C2—N1—C6 | −0.1 (11) |
N1—C6—C7—O12 | 0.2 (7) | C1—C2—N1—C6 | 178.6 (5) |
C5—C6—C7—O12 | −177.7 (5) | C11—C12—N2—C8 | −1.8 (8) |
N1—C6—C7—O11 | 177.9 (5) | C11—C12—N2—Fe1 | 167.1 (4) |
C5—C6—C7—O11 | 0.0 (7) | C9—C8—N2—C12 | 2.0 (8) |
N2—C8—C9—C10 | 1.0 (9) | C9—C8—N2—Fe1 | −167.5 (5) |
C8—C9—C10—C11 | −4.1 (8) | O1—Fe1—N2—C12 | 72.5 (4) |
C8—C9—C10—C13 | 175.5 (5) | O3—Fe1—N2—C12 | −107.6 (4) |
C9—C10—C11—C12 | 4.3 (8) | O2—Fe1—N2—C12 | 161.2 (4) |
C13—C10—C11—C12 | −175.3 (5) | O4—Fe1—N2—C12 | −19.1 (4) |
C10—C11—C12—N2 | −1.5 (9) | O1—Fe1—N2—C8 | −118.9 (4) |
C9—C10—C13—C17 | −174.3 (4) | O3—Fe1—N2—C8 | 61.1 (4) |
C11—C10—C13—C17 | 5.2 (7) | O2—Fe1—N2—C8 | −30.2 (4) |
C9—C10—C13—C14 | 5.3 (7) | O4—Fe1—N2—C8 | 149.5 (4) |
C11—C10—C13—C14 | −175.1 (4) | C14—C15—N3—C16 | 0.0 (7) |
C17—C13—C14—C15 | 0.2 (7) | C17—C16—N3—C15 | −0.3 (8) |
C10—C13—C14—C15 | −179.4 (4) | C21—C22—N4—C18 | −1.9 (8) |
C13—C14—C15—N3 | 0.0 (7) | C21—C22—N4—Fe1 | 165.8 (4) |
N3—C16—C17—C13 | 0.6 (8) | C19—C18—N4—C22 | 1.8 (7) |
C14—C13—C17—C16 | −0.6 (7) | C19—C18—N4—Fe1 | −164.9 (4) |
C10—C13—C17—C16 | 179.1 (4) | O1—Fe1—N4—C22 | −63.8 (4) |
N4—C18—C19—C20 | 0.3 (8) | O3—Fe1—N4—C22 | 116.3 (4) |
C18—C19—C20—C21 | −2.2 (7) | O2—Fe1—N4—C22 | −152.5 (4) |
C18—C19—C20—C23 | 176.3 (4) | O4—Fe1—N4—C22 | 27.8 (4) |
C19—C20—C21—C22 | 2.1 (7) | O1—Fe1—N4—C18 | 102.7 (4) |
C23—C20—C21—C22 | −176.4 (4) | O3—Fe1—N4—C18 | −77.2 (4) |
C20—C21—C22—N4 | 0.0 (8) | O2—Fe1—N4—C18 | 14.0 (4) |
C21—C20—C23—C27 | 174.0 (4) | O4—Fe1—N4—C18 | −165.7 (4) |
C19—C20—C23—C27 | −4.4 (7) | C27—C26—N5—C25 | 0.0 (9) |
C21—C20—C23—C24 | −5.0 (7) | C24—C25—N5—C26 | 0.0 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O8i | 0.82 (1) | 2.06 (3) | 2.831 (7) | 156 (6) |
O1—H12···N3ii | 0.82 (1) | 1.98 (3) | 2.759 (5) | 158 (6) |
O2—H21···O5iii | 0.82 (1) | 2.00 (2) | 2.806 (6) | 172 (5) |
O2—H22···O7iii | 0.82 (1) | 1.96 (1) | 2.781 (6) | 178 (8) |
O3—H31···O5iv | 0.81 (1) | 2.04 (1) | 2.851 (7) | 175 (7) |
O3—H32···N5v | 0.81 (1) | 1.96 (2) | 2.745 (5) | 162 (6) |
O4—H41···O8 | 0.82 (1) | 1.97 (1) | 2.785 (5) | 177 (7) |
O4—H42···O11vi | 0.82 (1) | 1.93 (2) | 2.736 (5) | 170 (5) |
O5—H52···O6 | 0.82 (1) | 1.93 (3) | 2.739 (8) | 170 (7) |
O5—H51···O11vi | 0.82 (1) | 1.94 (2) | 2.742 (7) | 166 (7) |
O6—H62···O9 | 0.82 (1) | 2.46 (8) | 2.952 (6) | 120 (7) |
O6—H61···O10i | 0.82 (1) | 2.03 (2) | 2.827 (5) | 164 (7) |
O7—H72···O5vii | 0.82 (1) | 2.57 (2) | 3.349 (7) | 159 (5) |
O7—H71···O9 | 0.82 (1) | 1.81 (2) | 2.622 (6) | 168 (7) |
O8—H81···O7 | 0.82 (1) | 2.01 (3) | 2.817 (7) | 170 (6) |
O8—H82···O12viii | 0.81 (1) | 1.97 (2) | 2.768 (6) | 170 (7) |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+2, z−1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y−1/2, z; (v) x, −y+1, z+1/2; (vi) x, −y+1, z−1/2; (vii) x, y−1, z; (viii) x, −y, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C10H8N2)2(H2O)4](C7H3NO4)·4H2O |
Mr | 677.45 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 293 |
a, b, c (Å) | 18.201 (1), 6.900 (1), 25.010 (1) |
β (°) | 99.40 (3) |
V (Å3) | 3098.9 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.56 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5104, 3180, 2946 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.105, 1.05 |
No. of reflections | 3180 |
No. of parameters | 455 |
No. of restraints | 26 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.38 |
Absolute structure | Flack (1983), with 530 Friedel pairs |
Absolute structure parameter | 0.36 (3) |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O8i | 0.82 (1) | 2.06 (3) | 2.831 (7) | 156 (6) |
O1—H12···N3ii | 0.82 (1) | 1.98 (3) | 2.759 (5) | 158 (6) |
O2—H21···O5iii | 0.82 (1) | 2.00 (2) | 2.806 (6) | 172 (5) |
O2—H22···O7iii | 0.82 (1) | 1.96 (1) | 2.781 (6) | 178 (8) |
O3—H31···O5iv | 0.81 (1) | 2.04 (1) | 2.851 (7) | 175 (7) |
O3—H32···N5v | 0.81 (1) | 1.96 (2) | 2.745 (5) | 162 (6) |
O4—H41···O8 | 0.82 (1) | 1.97 (1) | 2.785 (5) | 177 (7) |
O4—H42···O11vi | 0.82 (1) | 1.93 (2) | 2.736 (5) | 170 (5) |
O5—H52···O6 | 0.82 (1) | 1.93 (3) | 2.739 (8) | 170 (7) |
O5—H51···O11vi | 0.82 (1) | 1.94 (2) | 2.742 (7) | 166 (7) |
O6—H62···O9 | 0.82 (1) | 2.46 (8) | 2.952 (6) | 120 (7) |
O6—H61···O10i | 0.82 (1) | 2.03 (2) | 2.827 (5) | 164 (7) |
O7—H72···O5vii | 0.82 (1) | 2.57 (2) | 3.349 (7) | 159 (5) |
O7—H71···O9 | 0.82 (1) | 1.81 (2) | 2.622 (6) | 168 (7) |
O8—H81···O7 | 0.82 (1) | 2.01 (3) | 2.817 (7) | 170 (6) |
O8—H82···O12viii | 0.81 (1) | 1.97 (2) | 2.768 (6) | 170 (7) |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+2, z−1/2; (iii) x+1/2, y+1/2, z; (iv) x+1/2, y−1/2, z; (v) x, −y+1, z+1/2; (vi) x, −y+1, z−1/2; (vii) x, y−1, z; (viii) x, −y, z−1/2. |
Metal-organic frameworks have applications in catalysis, optical materials, membranes, and sorption (Evans, Ngo & Lin, 2001; Vioux et al., 2004; Sanchez et al., 2003; Evans & Lin, 2001; Jannasch, 2003; Javaid et al., 2001; Honma et al., 2001; Sudik et al., 2005; Rowsell et al., 2004; Kitaura et al., 2004; Suzuki et al., 2002).
Design of metal-organic frameworks often utilizes a metal cation, metal cluster, or metal oxide substructure as a node, from which rigid or flexible multitopic organic ligands radiate to act as tethers to adjacent nodes for the bottom-up construction of complex extended architectures. While a variety of organic molecules have been investigated as potential tethers, materials incorporating multitopic carboxylates and pyridine ligands have been employed most extensively.
In the title compound, FeII is hexa-coordinated in an octahedral manner by four water molecules in the equatorial plane and two N atoms in the axial positions from two 4,4'-bipyridine molecules (Fig. 1). The Fe—N and Fe—O bond lengths are in the range 2.265 (4)–2.266 (4) and 2.161 (3)–2.202 (4) Å, respectively. The cations lie in layers in the bc planes. Pyridine-2,6-dicarboxylate anions and water molecules lie between these layers, forming an extensive hydrogen-bond network.