The title compound, (C
10H
10N
2)
2[Fe(C
2O
4)
2(H
2O)
2](C
2HO
4)
2, appears to be a modular associate consisting of a complex anion containing bivalent Fe as the central atom, a bridging hydrogen oxalate anion and a diprotonated 4,4-bipyridine acting as the counter-cation. The Fe
II ion in the complex anion occupies a position on a centre of inversion. Its coordination environment is formed by six O atoms from two bidentate oxalate ligands, forming a basal plane, and two water molecules approximately perpendicular to the plane, representing a distorted octahedral geometry. These three kinds of ions are connected by strong hydrogen bonds, with donor-acceptor distances (N
O and O
O) lying in the range 2.54-2.98 Å, and
-
stacking interactions between the 4,4'-bipyridinium cations, thus forming a three-dimensional supramolecular structure.
Supporting information
CCDC reference: 645522
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,
1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
bis(4,4'-bipyridinium) diaquadioxalatoferrate(II) bis(hydrogen oxalate)
top
Crystal data top
(C10H10N2)2[Fe(C2O4)2(H2O)2](C2HO4)2 | Z = 1 |
Mr = 762.38 | F(000) = 392 |
Triclinic, P1 | Dx = 1.734 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0927 (14) Å | Cell parameters from 3878 reflections |
b = 10.092 (2) Å | θ = 2.0–27.1° |
c = 10.633 (2) Å | µ = 0.62 mm−1 |
α = 101.76 (3)° | T = 293 K |
β = 96.29 (3)° | Prism, brown |
γ = 98.09 (3)° | 0.16 × 0.08 × 0.08 mm |
V = 730.2 (3) Å3 | |
Data collection top
Bruker P4 diffractometer | 1934 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −8→8 |
3600 measured reflections | k = −11→11 |
2474 independent reflections | l = −11→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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0477P)2 + 0.6889P] where P = (Fo2 + 2Fc2)/3 |
2474 reflections | (Δ/σ)max < 0.001 |
244 parameters | Δρmax = 0.29 e Å−3 |
4 restraints | Δρmin = −0.37 e Å−3 |
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 | |
Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.0299 (3) | |
O1 | 0.4358 (4) | 1.5647 (3) | 0.6837 (3) | 0.0426 (7) | |
O2 | 0.3026 (5) | 1.4917 (3) | 0.8857 (3) | 0.0404 (7) | |
O3 | 0.3562 (5) | 1.7086 (3) | 0.9973 (3) | 0.0452 (8) | |
O4 | 0.4985 (4) | 1.7842 (3) | 0.7880 (3) | 0.0458 (8) | |
O5 | 0.1688 (4) | 0.4186 (2) | 0.0784 (2) | 0.0404 (7) | |
O6 | 0.0415 (5) | 0.3428 (3) | 0.2880 (2) | 0.0442 (8) | |
O7 | −0.0075 (4) | 0.1243 (2) | 0.1827 (2) | 0.0333 (6) | |
O8 | 0.2922 (4) | −0.0179 (3) | 0.0597 (4) | 0.0536 (9) | |
O9 | 0.0999 (4) | 0.1993 (2) | −0.0298 (2) | 0.0326 (6) | |
C1 | 0.1588 (7) | 0.7030 (4) | 0.2554 (4) | 0.0500 (12) | |
H1A | 0.1447 | 0.6768 | 0.1654 | 0.060* | |
C2 | 0.1916 (7) | 0.8391 (4) | 0.3154 (4) | 0.0495 (12) | |
H2B | 0.1974 | 0.9048 | 0.2654 | 0.059* | |
C3 | 0.2924 (7) | 1.1294 (4) | 0.4491 (4) | 0.0411 (11) | |
H3 | 0.2866 | 1.1064 | 0.3593 | 0.049* | |
C4 | 0.3346 (6) | 1.2635 (4) | 0.5133 (4) | 0.0410 (10) | |
H4 | 0.3595 | 1.3313 | 0.4669 | 0.049* | |
C5 | 0.3076 (7) | 1.2047 (4) | 0.7096 (4) | 0.0502 (12) | |
H5 | 0.3118 | 1.2312 | 0.7991 | 0.060* | |
C6 | 0.2671 (7) | 1.0680 (4) | 0.6493 (4) | 0.0440 (11) | |
H6 | 0.2455 | 1.0024 | 0.6984 | 0.053* | |
C7 | 0.2582 (5) | 1.0272 (3) | 0.5168 (3) | 0.0243 (8) | |
C8 | 0.2162 (5) | 0.8808 (3) | 0.4489 (3) | 0.0239 (8) | |
C9 | 0.1999 (7) | 0.7784 (4) | 0.5176 (4) | 0.0465 (12) | |
H9 | 0.2114 | 0.8010 | 0.6077 | 0.056* | |
C10 | 0.1666 (7) | 0.6438 (4) | 0.4529 (4) | 0.0500 (12) | |
H10 | 0.1576 | 0.5754 | 0.4998 | 0.060* | |
C11 | 0.3614 (5) | 1.6229 (4) | 0.9004 (4) | 0.0291 (9) | |
C12 | 0.4401 (6) | 1.6608 (4) | 0.7805 (4) | 0.0318 (9) | |
C13 | 0.1105 (5) | 0.2936 (3) | 0.0692 (3) | 0.0281 (9) | |
C14 | 0.0426 (5) | 0.2510 (3) | 0.1907 (3) | 0.0288 (9) | |
N1 | 0.1471 (5) | 0.6094 (3) | 0.3249 (3) | 0.0347 (8) | |
H1 | 0.1264 | 0.5239 | 0.2864 | 0.042* | |
N2 | 0.3408 (5) | 1.2992 (3) | 0.6407 (3) | 0.0328 (8) | |
H2A | 0.3667 | 1.3846 | 0.6793 | 0.039* | |
H7 | 0.341 (6) | −0.083 (3) | 0.025 (5) | 0.08 (2)* | |
H8 | 0.378 (5) | 0.051 (3) | 0.082 (5) | 0.080 (19)* | |
H2 | 0.256 (7) | 1.472 (5) | 0.949 (3) | 0.070 (17)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe1 | 0.0422 (5) | 0.0190 (4) | 0.0261 (4) | 0.0027 (3) | 0.0055 (3) | 0.0007 (3) |
O1 | 0.068 (2) | 0.0280 (14) | 0.0294 (15) | −0.0028 (13) | 0.0142 (14) | 0.0038 (12) |
O2 | 0.070 (2) | 0.0219 (14) | 0.0299 (16) | 0.0005 (13) | 0.0203 (15) | 0.0049 (12) |
O3 | 0.078 (2) | 0.0242 (14) | 0.0338 (16) | 0.0093 (14) | 0.0178 (15) | 0.0012 (13) |
O4 | 0.068 (2) | 0.0263 (15) | 0.0357 (16) | −0.0104 (14) | 0.0035 (14) | 0.0052 (12) |
O5 | 0.070 (2) | 0.0201 (14) | 0.0317 (16) | 0.0019 (13) | 0.0174 (14) | 0.0064 (11) |
O6 | 0.081 (2) | 0.0232 (14) | 0.0268 (15) | 0.0020 (14) | 0.0201 (14) | 0.0008 (12) |
O7 | 0.0536 (18) | 0.0196 (13) | 0.0262 (14) | −0.0007 (12) | 0.0120 (12) | 0.0050 (11) |
O8 | 0.044 (2) | 0.0274 (16) | 0.079 (2) | 0.0052 (15) | −0.0020 (17) | −0.0066 (16) |
O9 | 0.0532 (18) | 0.0219 (13) | 0.0221 (13) | 0.0027 (12) | 0.0118 (12) | 0.0024 (11) |
C1 | 0.087 (4) | 0.034 (2) | 0.025 (2) | 0.009 (2) | 0.009 (2) | −0.0024 (19) |
C2 | 0.094 (4) | 0.028 (2) | 0.025 (2) | 0.008 (2) | 0.011 (2) | 0.0035 (17) |
C3 | 0.069 (3) | 0.029 (2) | 0.024 (2) | 0.003 (2) | 0.005 (2) | 0.0066 (17) |
C4 | 0.061 (3) | 0.026 (2) | 0.037 (2) | 0.0042 (19) | 0.010 (2) | 0.0089 (18) |
C5 | 0.085 (4) | 0.035 (2) | 0.027 (2) | 0.002 (2) | 0.017 (2) | −0.0011 (19) |
C6 | 0.082 (3) | 0.023 (2) | 0.030 (2) | 0.006 (2) | 0.022 (2) | 0.0077 (17) |
C7 | 0.0247 (19) | 0.0250 (18) | 0.0235 (19) | 0.0053 (15) | 0.0064 (15) | 0.0040 (15) |
C8 | 0.026 (2) | 0.0228 (18) | 0.0232 (18) | 0.0046 (15) | 0.0053 (15) | 0.0051 (15) |
C9 | 0.084 (4) | 0.031 (2) | 0.021 (2) | 0.003 (2) | 0.003 (2) | 0.0050 (17) |
C10 | 0.086 (4) | 0.024 (2) | 0.037 (3) | 0.001 (2) | 0.003 (2) | 0.0093 (19) |
C11 | 0.036 (2) | 0.0223 (19) | 0.030 (2) | 0.0065 (16) | 0.0036 (17) | 0.0060 (17) |
C12 | 0.041 (2) | 0.022 (2) | 0.029 (2) | −0.0014 (17) | −0.0005 (17) | 0.0046 (16) |
C13 | 0.039 (2) | 0.0208 (19) | 0.026 (2) | 0.0058 (16) | 0.0090 (17) | 0.0062 (16) |
C14 | 0.039 (2) | 0.0212 (19) | 0.025 (2) | 0.0040 (16) | 0.0057 (16) | 0.0029 (16) |
N1 | 0.046 (2) | 0.0197 (16) | 0.0338 (19) | 0.0038 (14) | 0.0049 (15) | −0.0034 (14) |
N2 | 0.043 (2) | 0.0198 (15) | 0.0334 (19) | 0.0033 (14) | 0.0089 (15) | 0.0001 (14) |
Geometric parameters (Å, º) top
Fe1—O7i | 2.097 (2) | C2—H2B | 0.9300 |
Fe1—O7 | 2.097 (2) | C3—C4 | 1.361 (5) |
Fe1—O9 | 2.134 (2) | C3—C7 | 1.383 (5) |
Fe1—O9i | 2.134 (2) | C3—H3 | 0.9300 |
Fe1—O8 | 2.143 (3) | C4—N2 | 1.322 (5) |
Fe1—O8i | 2.143 (3) | C4—H4 | 0.9300 |
O1—C12 | 1.257 (4) | C5—N2 | 1.328 (5) |
O2—C11 | 1.303 (4) | C5—C6 | 1.372 (5) |
O2—H2 | 0.83 (2) | C5—H5 | 0.9300 |
O3—C11 | 1.211 (4) | C6—C7 | 1.377 (5) |
O4—C12 | 1.239 (4) | C6—H6 | 0.9300 |
O5—C13 | 1.251 (4) | C7—C8 | 1.478 (5) |
O6—C14 | 1.242 (4) | C8—C9 | 1.381 (5) |
O7—C14 | 1.261 (4) | C9—C10 | 1.365 (5) |
O8—H7 | 0.824 (19) | C9—H9 | 0.9300 |
O8—H8 | 0.832 (19) | C10—N1 | 1.321 (5) |
O9—C13 | 1.255 (4) | C10—H10 | 0.9300 |
C1—N1 | 1.313 (5) | C11—C12 | 1.542 (5) |
C1—C2 | 1.366 (5) | C13—C14 | 1.546 (5) |
C1—H1A | 0.9300 | N1—H1 | 0.8600 |
C2—C8 | 1.380 (5) | N2—H2A | 0.8600 |
| | | |
O7i—Fe1—O7 | 180.00 (15) | C6—C5—H5 | 119.9 |
O7i—Fe1—O9 | 101.47 (9) | C5—C6—C7 | 120.6 (4) |
O7—Fe1—O9 | 78.53 (9) | C5—C6—H6 | 119.7 |
O7i—Fe1—O9i | 78.53 (9) | C7—C6—H6 | 119.7 |
O7—Fe1—O9i | 101.47 (9) | C6—C7—C3 | 117.0 (3) |
O9—Fe1—O9i | 180.0 (2) | C6—C7—C8 | 122.0 (3) |
O7i—Fe1—O8 | 90.03 (12) | C3—C7—C8 | 121.0 (3) |
O7—Fe1—O8 | 89.97 (12) | C2—C8—C9 | 116.6 (3) |
O9—Fe1—O8 | 88.92 (12) | C2—C8—C7 | 122.5 (3) |
O9i—Fe1—O8 | 91.08 (12) | C9—C8—C7 | 120.9 (3) |
O7i—Fe1—O8i | 89.97 (12) | C10—C9—C8 | 119.9 (4) |
O7—Fe1—O8i | 90.03 (12) | C10—C9—H9 | 120.1 |
O9—Fe1—O8i | 91.08 (12) | C8—C9—H9 | 120.1 |
O9i—Fe1—O8i | 88.92 (12) | N1—C10—C9 | 121.1 (4) |
O8—Fe1—O8i | 180.00 (16) | N1—C10—H10 | 119.5 |
C11—O2—H2 | 113 (3) | C9—C10—H10 | 119.5 |
C14—O7—Fe1 | 114.4 (2) | O3—C11—O2 | 124.6 (4) |
Fe1—O8—H7 | 122 (3) | O3—C11—C12 | 122.1 (3) |
Fe1—O8—H8 | 121 (3) | O2—C11—C12 | 113.3 (3) |
H7—O8—H8 | 108 (3) | O4—C12—O1 | 126.1 (4) |
C13—O9—Fe1 | 113.5 (2) | O4—C12—C11 | 116.6 (3) |
N1—C1—C2 | 120.0 (4) | O1—C12—C11 | 117.3 (3) |
N1—C1—H1A | 120.0 | O5—C13—O9 | 126.2 (3) |
C2—C1—H1A | 120.0 | O5—C13—C14 | 117.1 (3) |
C1—C2—C8 | 121.2 (4) | O9—C13—C14 | 116.7 (3) |
C1—C2—H2B | 119.4 | O6—C14—O7 | 125.0 (3) |
C8—C2—H2B | 119.4 | O6—C14—C13 | 118.2 (3) |
C4—C3—C7 | 120.2 (4) | O7—C14—C13 | 116.8 (3) |
C4—C3—H3 | 119.9 | C1—N1—C10 | 121.2 (3) |
C7—C3—H3 | 119.9 | C1—N1—H1 | 119.4 |
N2—C4—C3 | 121.1 (4) | C10—N1—H1 | 119.4 |
N2—C4—H4 | 119.4 | C4—N2—C5 | 120.7 (3) |
C3—C4—H4 | 119.4 | C4—N2—H2A | 119.6 |
N2—C5—C6 | 120.2 (4) | C5—N2—H2A | 119.6 |
N2—C5—H5 | 119.9 | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O5ii | 0.83 (4) | 1.72 (2) | 2.548 (4) | 175 (5) |
O8—H7···O3iii | 0.83 (4) | 2.09 (3) | 2.817 (4) | 148 (5) |
O8—H8···O4iv | 0.83 (4) | 1.95 (3) | 2.705 (4) | 149 (5) |
N1—H1···O5 | 0.86 | 2.32 | 2.952 (4) | 130 |
N1—H1···O6 | 0.86 | 1.85 | 2.625 (4) | 150 |
N2—H2A···O1 | 0.86 | 1.80 | 2.601 (4) | 153 |
N2—H2A···O2 | 0.86 | 2.36 | 2.979 (4) | 129 |
Symmetry codes: (ii) x, y+1, z+1; (iii) x, y−2, z−1; (iv) −x+1, −y+2, −z+1. |