Solvent water tapes in two hydrates of μ-oxo-bis[bis(2,2′-bipyridine-κ2N,N′)(sulfato-κO)iron(III)]
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106034275/bg3017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106034275/bg3017Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106034275/bg3017IIsup3.hkl |
CCDC references: 625678; 625679
For the preparation of compound (I), ferric sulfate (0.800 g, 2.00 mmol) and sodium acetate (0.656 g, 8.00 mmol) were stirred in water (40 ml) and the mixture was heated. 2,2'-Bipyridine (0.312 g, 2.00 mmol) was dissolved in ethanol (5 ml) and added to the hot solution. The mixture was stirred continuously and heated to 353 K for 10 min. The small amount of light-brown precipitate that formed was filtered off and the brown–red solution kept for crystallization. From this solution, shiny dark-red crystals of (I) formed after 10 d. CHN analysis, calculated for C40H54Fe2N8O20S2: C 42.04, H 4.76, N 9.80, S 5.61; found C 42.03, H 4.58, N 9.81, S 5.54%. IR (KBr disk, cm−1): 3400, 1645, 1599, 1495, 1474, 1440, 1317, 1109, 1022, 823, 767, 617.
Compound (II) was prepared by a similar method, but with 1,2-diaminoethane (0.165 ml, 2.36 mmol) used in place of sodium acetate. Wine-red crystals were formed after 10 d. CHN analysis, calculated for C40H62Fe2N8O24S2: C 39.55, H 5.14, N 9.22, S 5.28; found C 39.61, H 5.11, N 9.24, S 5.18%. IR (KBr disk, cm−1): 3400, 1645, 1599, 1495, 1475, 1441, 1317, 1149, 1022, 825, 769, 654.
In compound (II), one of the O atoms of the sulfate ion is disordered over two positions, O4A and O4B, with occupancy factors of 0.73 and 0.27, respectively. H atoms were positioned geometrically and treated as riding, with C—H = 0.95 Å and O—H = 0.72–0.94 Å, and with Uiso(H) = 1.2Ueq(C,O). [Please check added text and correct as necessary]
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.
[Fe2O(SO4)2(C10H8N2)4]·11H2O | F(000) = 2376 |
Mr = 1142.73 | Dx = 1.585 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3943 reflections |
a = 13.7244 (8) Å | θ = 2.2–26.7° |
b = 21.6461 (13) Å | µ = 0.78 mm−1 |
c = 16.1238 (9) Å | T = 100 K |
β = 90.680 (1)° | Block, red |
V = 4789.7 (5) Å3 | 0.20 × 0.08 × 0.07 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 5757 independent reflections |
Radiation source: sealed tube | 4601 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
ϕ and ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −18→18 |
Tmin = 0.783, Tmax = 0.947 | k = −28→28 |
27533 measured reflections | l = −21→21 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0436P)2 + 10.7762P] where P = (Fo2 + 2Fc2)/3 |
5757 reflections | (Δ/σ)max = 0.001 |
327 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
[Fe2O(SO4)2(C10H8N2)4]·11H2O | V = 4789.7 (5) Å3 |
Mr = 1142.73 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.7244 (8) Å | µ = 0.78 mm−1 |
b = 21.6461 (13) Å | T = 100 K |
c = 16.1238 (9) Å | 0.20 × 0.08 × 0.07 mm |
β = 90.680 (1)° |
Bruker SMART CCD area-detector diffractometer | 5757 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4601 reflections with I > 2σ(I) |
Tmin = 0.783, Tmax = 0.947 | Rint = 0.069 |
27533 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0436P)2 + 10.7762P] where P = (Fo2 + 2Fc2)/3 |
5757 reflections | Δρmax = 0.70 e Å−3 |
327 parameters | Δρmin = −0.42 e Å−3 |
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 | ||
Fe | 0.89374 (3) | 0.361349 (19) | 0.18585 (3) | 0.00755 (11) | |
S | 0.75448 (5) | 0.25781 (3) | 0.27524 (5) | 0.01082 (16) | |
C1 | 1.0107 (2) | 0.25701 (14) | 0.11149 (19) | 0.0121 (6) | |
H1 | 1.0399 | 0.2573 | 0.1652 | 0.014* | |
C2 | 1.0491 (2) | 0.21849 (14) | 0.0517 (2) | 0.0153 (7) | |
H2 | 1.1023 | 0.1920 | 0.0645 | 0.018* | |
C3 | 1.0084 (2) | 0.21942 (15) | −0.0272 (2) | 0.0174 (7) | |
H3 | 1.0349 | 0.1947 | −0.0701 | 0.021* | |
C4 | 0.9283 (2) | 0.25703 (14) | −0.0429 (2) | 0.0143 (6) | |
H4 | 0.8987 | 0.2580 | −0.0964 | 0.017* | |
C5 | 0.8921 (2) | 0.29306 (13) | 0.02067 (18) | 0.0109 (6) | |
C6 | 0.8054 (2) | 0.33338 (13) | 0.01061 (18) | 0.0099 (6) | |
C7 | 0.7472 (2) | 0.33297 (14) | −0.06027 (19) | 0.0131 (6) | |
H7 | 0.7618 | 0.3063 | −0.1052 | 0.016* | |
C8 | 0.6671 (2) | 0.37215 (14) | −0.06470 (19) | 0.0135 (6) | |
H8 | 0.6262 | 0.3727 | −0.1127 | 0.016* | |
C9 | 0.6478 (2) | 0.41032 (15) | 0.00166 (19) | 0.0142 (6) | |
H9 | 0.5939 | 0.4378 | 0.0000 | 0.017* | |
C10 | 0.7084 (2) | 0.40782 (14) | 0.0706 (2) | 0.0145 (6) | |
H10 | 0.6941 | 0.4338 | 0.1164 | 0.017* | |
C11 | 0.7553 (2) | 0.45487 (15) | 0.27228 (19) | 0.0134 (6) | |
H11 | 0.7289 | 0.4191 | 0.2978 | 0.016* | |
C12 | 0.7093 (2) | 0.51153 (14) | 0.2843 (2) | 0.0154 (6) | |
H12 | 0.6533 | 0.5146 | 0.3181 | 0.018* | |
C13 | 0.7472 (2) | 0.56329 (14) | 0.2456 (2) | 0.0149 (7) | |
H13 | 0.7165 | 0.6023 | 0.2515 | 0.018* | |
C14 | 0.8302 (2) | 0.55756 (14) | 0.1986 (2) | 0.0141 (6) | |
H14 | 0.8575 | 0.5927 | 0.1722 | 0.017* | |
C15 | 0.8732 (2) | 0.50009 (13) | 0.19031 (18) | 0.0104 (6) | |
C16 | 0.9620 (2) | 0.48979 (13) | 0.14169 (18) | 0.0101 (6) | |
C17 | 1.0253 (2) | 0.53757 (14) | 0.12081 (19) | 0.0126 (6) | |
H17 | 1.0132 | 0.5787 | 0.1384 | 0.015* | |
C18 | 1.1059 (2) | 0.52361 (15) | 0.07389 (19) | 0.0149 (6) | |
H18 | 1.1504 | 0.5552 | 0.0589 | 0.018* | |
C19 | 1.1216 (2) | 0.46332 (15) | 0.04878 (19) | 0.0141 (6) | |
H19 | 1.1757 | 0.4532 | 0.0151 | 0.017* | |
C20 | 1.0572 (2) | 0.41832 (14) | 0.07369 (18) | 0.0119 (6) | |
H20 | 1.0692 | 0.3768 | 0.0579 | 0.014* | |
N1 | 0.93417 (17) | 0.29386 (11) | 0.09689 (15) | 0.0099 (5) | |
N2 | 0.78655 (17) | 0.37049 (11) | 0.07615 (15) | 0.0103 (5) | |
N3 | 0.83536 (17) | 0.44889 (11) | 0.22607 (15) | 0.0096 (5) | |
N4 | 0.97839 (17) | 0.43057 (11) | 0.11926 (15) | 0.0095 (5) | |
O1 | 1.0000 | 0.34810 (13) | 0.2500 | 0.0099 (6) | |
O2 | 0.78998 (15) | 0.32051 (10) | 0.24725 (14) | 0.0147 (5) | |
O3 | 0.82641 (16) | 0.21163 (10) | 0.25062 (14) | 0.0180 (5) | |
O4 | 0.74220 (17) | 0.26031 (11) | 0.36499 (14) | 0.0206 (5) | |
O5 | 0.66033 (15) | 0.24639 (10) | 0.23353 (14) | 0.0177 (5) | |
O1W | 0.5387 (2) | 0.42336 (12) | 0.36311 (17) | 0.0361 (7) | |
H1A | 0.5167 | 0.3908 | 0.3294 | 0.047* | |
H1B | 0.5015 | 0.4488 | 0.3496 | 0.047* | |
O2W | 0.5000 | 0.32706 (15) | 0.2500 | 0.0225 (8) | |
H2A | 0.5545 | 0.3035 | 0.2401 | 0.029* | |
O3W | 0.5000 | 0.16114 (15) | 0.2500 | 0.0260 (8) | |
H3A | 0.5515 | 0.1791 | 0.2484 | 0.034* | |
O4W | 0.28414 (17) | 0.16941 (10) | 0.01046 (15) | 0.0212 (5) | |
H4A | 0.2720 | 0.1877 | −0.0367 | 0.028* | |
H4B | 0.2851 | 0.1956 | 0.0494 | 0.028* | |
O5W | 0.14739 (18) | 0.07350 (11) | 0.00661 (18) | 0.0315 (6) | |
H5A | 0.1221 | 0.0809 | −0.0427 | 0.041* | |
H5B | 0.1848 | 0.1095 | 0.0153 | 0.041* | |
O6W | 0.03174 (18) | 0.04151 (12) | 0.13628 (16) | 0.0283 (6) | |
H6A | 0.0657 | 0.0511 | 0.0954 | 0.037* | |
H6B | 0.0212 | 0.0712 | 0.1675 | 0.037* | |
O7W | 0.0000 | 0.14195 (14) | 0.2500 | 0.0180 (7) | |
H7A | 0.0477 | 0.1666 | 0.2415 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0084 (2) | 0.0054 (2) | 0.0088 (2) | −0.00001 (16) | −0.00074 (14) | −0.00033 (17) |
S | 0.0117 (4) | 0.0088 (4) | 0.0119 (4) | −0.0015 (3) | −0.0007 (3) | 0.0010 (3) |
C1 | 0.0111 (14) | 0.0112 (15) | 0.0138 (16) | −0.0024 (11) | −0.0016 (11) | 0.0008 (12) |
C2 | 0.0127 (15) | 0.0098 (15) | 0.0234 (18) | 0.0009 (11) | −0.0001 (13) | −0.0015 (13) |
C3 | 0.0206 (17) | 0.0149 (16) | 0.0168 (17) | 0.0021 (13) | 0.0049 (13) | −0.0055 (13) |
C4 | 0.0181 (16) | 0.0136 (15) | 0.0113 (15) | 0.0004 (12) | −0.0014 (12) | −0.0006 (12) |
C5 | 0.0131 (15) | 0.0081 (14) | 0.0115 (15) | −0.0029 (11) | −0.0008 (11) | 0.0005 (11) |
C6 | 0.0114 (14) | 0.0072 (14) | 0.0109 (15) | −0.0040 (11) | −0.0006 (11) | 0.0027 (11) |
C7 | 0.0165 (15) | 0.0111 (15) | 0.0116 (15) | −0.0043 (12) | 0.0001 (12) | −0.0028 (12) |
C8 | 0.0150 (15) | 0.0120 (16) | 0.0133 (15) | −0.0050 (12) | −0.0043 (12) | 0.0042 (12) |
C9 | 0.0080 (14) | 0.0175 (16) | 0.0170 (16) | 0.0015 (12) | −0.0032 (12) | 0.0046 (13) |
C10 | 0.0138 (15) | 0.0142 (16) | 0.0155 (16) | 0.0022 (12) | −0.0004 (12) | −0.0020 (12) |
C11 | 0.0134 (15) | 0.0135 (16) | 0.0131 (16) | −0.0015 (12) | −0.0022 (12) | 0.0000 (12) |
C12 | 0.0122 (15) | 0.0160 (16) | 0.0179 (17) | 0.0021 (12) | −0.0006 (12) | −0.0027 (13) |
C13 | 0.0165 (16) | 0.0096 (15) | 0.0185 (17) | 0.0048 (12) | −0.0038 (12) | −0.0022 (12) |
C14 | 0.0175 (16) | 0.0079 (15) | 0.0168 (16) | −0.0012 (12) | −0.0028 (12) | 0.0027 (12) |
C15 | 0.0126 (14) | 0.0098 (14) | 0.0086 (14) | −0.0023 (11) | −0.0028 (11) | −0.0008 (11) |
C16 | 0.0105 (14) | 0.0110 (14) | 0.0086 (14) | 0.0014 (11) | −0.0040 (11) | 0.0015 (11) |
C17 | 0.0167 (15) | 0.0069 (14) | 0.0140 (16) | −0.0008 (11) | −0.0034 (12) | 0.0024 (12) |
C18 | 0.0143 (16) | 0.0143 (16) | 0.0160 (16) | −0.0054 (12) | −0.0027 (12) | 0.0060 (13) |
C19 | 0.0115 (14) | 0.0187 (17) | 0.0121 (16) | 0.0017 (12) | 0.0013 (12) | 0.0004 (12) |
C20 | 0.0134 (15) | 0.0101 (15) | 0.0123 (15) | 0.0013 (11) | −0.0018 (11) | 0.0012 (12) |
N1 | 0.0095 (12) | 0.0081 (12) | 0.0122 (13) | −0.0009 (9) | −0.0001 (10) | 0.0008 (10) |
N2 | 0.0087 (11) | 0.0102 (13) | 0.0121 (13) | −0.0004 (9) | −0.0021 (9) | −0.0001 (10) |
N3 | 0.0107 (12) | 0.0088 (12) | 0.0095 (13) | −0.0001 (9) | −0.0006 (9) | −0.0023 (9) |
N4 | 0.0103 (12) | 0.0092 (12) | 0.0090 (12) | 0.0003 (9) | −0.0018 (9) | −0.0031 (10) |
O1 | 0.0127 (14) | 0.0065 (14) | 0.0104 (15) | 0.000 | −0.0028 (11) | 0.000 |
O2 | 0.0149 (11) | 0.0084 (11) | 0.0210 (12) | −0.0027 (8) | 0.0053 (9) | 0.0025 (9) |
O3 | 0.0168 (12) | 0.0117 (11) | 0.0254 (13) | 0.0017 (9) | −0.0047 (9) | −0.0022 (10) |
O4 | 0.0242 (13) | 0.0217 (13) | 0.0158 (12) | −0.0038 (10) | −0.0007 (9) | 0.0026 (10) |
O5 | 0.0114 (11) | 0.0212 (12) | 0.0205 (12) | −0.0028 (9) | −0.0030 (9) | −0.0024 (10) |
O1W | 0.0453 (17) | 0.0267 (15) | 0.0365 (17) | −0.0030 (13) | 0.0096 (13) | −0.0033 (13) |
O2W | 0.0162 (17) | 0.0149 (17) | 0.036 (2) | 0.000 | −0.0026 (15) | 0.000 |
O3W | 0.0160 (17) | 0.0142 (17) | 0.048 (2) | 0.000 | 0.0014 (16) | 0.000 |
O4W | 0.0256 (13) | 0.0146 (12) | 0.0235 (13) | 0.0008 (10) | 0.0028 (10) | −0.0028 (10) |
O5W | 0.0253 (14) | 0.0182 (13) | 0.0512 (18) | −0.0010 (11) | 0.0060 (12) | −0.0043 (12) |
O6W | 0.0291 (14) | 0.0274 (14) | 0.0283 (15) | −0.0006 (11) | −0.0022 (11) | −0.0075 (11) |
O7W | 0.0146 (15) | 0.0105 (15) | 0.0290 (19) | 0.000 | 0.0000 (13) | 0.000 |
Fe—O1 | 1.8009 (6) | C11—C12 | 1.394 (4) |
Fe—O2 | 1.955 (2) | C11—H11 | 0.9500 |
Fe—N1 | 2.126 (2) | C12—C13 | 1.386 (4) |
Fe—N3 | 2.160 (2) | C12—H12 | 0.9500 |
Fe—N4 | 2.186 (3) | C13—C14 | 1.382 (4) |
Fe—N2 | 2.296 (2) | C13—H13 | 0.9500 |
S—O4 | 1.460 (2) | C14—C15 | 1.384 (4) |
S—O3 | 1.463 (2) | C14—H14 | 0.9500 |
S—O5 | 1.471 (2) | C15—N3 | 1.356 (4) |
S—O2 | 1.513 (2) | C15—C16 | 1.474 (4) |
C1—N1 | 1.338 (4) | C16—N4 | 1.351 (4) |
C1—C2 | 1.384 (4) | C16—C17 | 1.394 (4) |
C1—H1 | 0.9500 | C17—C18 | 1.382 (4) |
C2—C3 | 1.383 (5) | C17—H17 | 0.9500 |
C2—H2 | 0.9500 | C18—C19 | 1.384 (4) |
C3—C4 | 1.389 (4) | C18—H18 | 0.9500 |
C3—H3 | 0.9500 | C19—C20 | 1.378 (4) |
C4—C5 | 1.384 (4) | C19—H19 | 0.9500 |
C4—H4 | 0.9500 | C20—N4 | 1.342 (4) |
C5—N1 | 1.352 (4) | C20—H20 | 0.9500 |
C5—C6 | 1.482 (4) | O1—Fei | 1.8009 (6) |
C6—N2 | 1.355 (4) | O1W—H1A | 0.9383 |
C6—C7 | 1.387 (4) | O1W—H1B | 0.7786 |
C7—C8 | 1.389 (4) | O2W—H2A | 0.9206 |
C7—H7 | 0.9500 | O3W—H3A | 0.8076 |
C8—C9 | 1.380 (4) | O4W—H4A | 0.8721 |
C8—H8 | 0.9500 | O4W—H4B | 0.8461 |
C9—C10 | 1.381 (4) | O5W—H5A | 0.8781 |
C9—H9 | 0.9500 | O5W—H5B | 0.9417 |
C10—N2 | 1.345 (4) | O6W—H6A | 0.8377 |
C10—H10 | 0.9500 | O6W—H6B | 0.8299 |
C11—N3 | 1.342 (4) | O7W—H7A | 0.8572 |
O1—Fe—O2 | 103.12 (8) | C9—C10—H10 | 118.3 |
O1—Fe—N1 | 93.56 (9) | N3—C11—C12 | 122.5 (3) |
O2—Fe—N1 | 103.21 (9) | N3—C11—H11 | 118.8 |
O1—Fe—N3 | 105.55 (10) | C12—C11—H11 | 118.8 |
O2—Fe—N3 | 88.26 (9) | C13—C12—C11 | 118.4 (3) |
N1—Fe—N3 | 154.99 (10) | C13—C12—H12 | 120.8 |
O1—Fe—N4 | 87.69 (9) | C11—C12—H12 | 120.8 |
O2—Fe—N4 | 162.41 (9) | C14—C13—C12 | 119.4 (3) |
N1—Fe—N4 | 89.72 (9) | C14—C13—H13 | 120.3 |
N3—Fe—N4 | 75.36 (9) | C12—C13—H13 | 120.3 |
O1—Fe—N2 | 164.45 (7) | C13—C14—C15 | 119.2 (3) |
O2—Fe—N2 | 88.00 (9) | C13—C14—H14 | 120.4 |
N1—Fe—N2 | 73.10 (9) | C15—C14—H14 | 120.4 |
N3—Fe—N2 | 85.36 (9) | N3—C15—C14 | 121.9 (3) |
N4—Fe—N2 | 84.37 (9) | N3—C15—C16 | 115.2 (3) |
O4—S—O3 | 112.36 (14) | C14—C15—C16 | 122.9 (3) |
O4—S—O5 | 110.39 (14) | N4—C16—C17 | 122.2 (3) |
O3—S—O5 | 110.67 (13) | N4—C16—C15 | 115.3 (3) |
O4—S—O2 | 107.70 (13) | C17—C16—C15 | 122.5 (3) |
O3—S—O2 | 108.14 (13) | C18—C17—C16 | 118.4 (3) |
O5—S—O2 | 107.38 (13) | C18—C17—H17 | 120.8 |
N1—C1—C2 | 122.8 (3) | C16—C17—H17 | 120.8 |
N1—C1—H1 | 118.6 | C17—C18—C19 | 119.7 (3) |
C2—C1—H1 | 118.6 | C17—C18—H18 | 120.2 |
C3—C2—C1 | 118.7 (3) | C19—C18—H18 | 120.2 |
C3—C2—H2 | 120.7 | C20—C19—C18 | 118.6 (3) |
C1—C2—H2 | 120.7 | C20—C19—H19 | 120.7 |
C2—C3—C4 | 119.0 (3) | C18—C19—H19 | 120.7 |
C2—C3—H3 | 120.5 | N4—C20—C19 | 123.0 (3) |
C4—C3—H3 | 120.5 | N4—C20—H20 | 118.5 |
C5—C4—C3 | 119.1 (3) | C19—C20—H20 | 118.5 |
C5—C4—H4 | 120.5 | C1—N1—C5 | 118.6 (3) |
C3—C4—H4 | 120.5 | C1—N1—Fe | 120.1 (2) |
N1—C5—C4 | 121.8 (3) | C5—N1—Fe | 120.7 (2) |
N1—C5—C6 | 115.2 (3) | C10—N2—C6 | 117.6 (3) |
C4—C5—C6 | 123.0 (3) | C10—N2—Fe | 127.3 (2) |
N2—C6—C7 | 122.2 (3) | C6—N2—Fe | 115.04 (19) |
N2—C6—C5 | 115.1 (3) | C11—N3—C15 | 118.6 (3) |
C7—C6—C5 | 122.7 (3) | C11—N3—Fe | 124.1 (2) |
C6—C7—C8 | 119.1 (3) | C15—N3—Fe | 116.37 (19) |
C6—C7—H7 | 120.4 | C20—N4—C16 | 118.1 (3) |
C8—C7—H7 | 120.4 | C20—N4—Fe | 124.8 (2) |
C9—C8—C7 | 119.0 (3) | C16—N4—Fe | 115.34 (19) |
C9—C8—H8 | 120.5 | Fei—O1—Fe | 161.67 (17) |
C7—C8—H8 | 120.5 | S—O2—Fe | 142.73 (14) |
C8—C9—C10 | 118.8 (3) | H1A—O1W—H1B | 99.5 |
C8—C9—H9 | 120.6 | H4A—O4W—H4B | 110.1 |
C10—C9—H9 | 120.6 | H5A—O5W—H5B | 101.2 |
N2—C10—C9 | 123.3 (3) | H6A—O6W—H6B | 112.9 |
N2—C10—H10 | 118.3 |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.94 | 1.89 | 2.816 (4) | 167 |
O1W—H1B···O6Wii | 0.78 | 2.07 | 2.734 (4) | 143 |
O2W—H2A···O5 | 0.92 | 1.91 | 2.824 (3) | 170 |
O3W—H3A···O5 | 0.81 | 2.10 | 2.886 (3) | 163 |
O4W—H4A···O4iii | 0.87 | 1.98 | 2.849 (3) | 172 |
O4W—H4B···O4iv | 0.85 | 2.00 | 2.838 (3) | 168 |
O5W—H5A···O1Wiii | 0.88 | 1.89 | 2.739 (4) | 161 |
O5W—H5B···O4W | 0.94 | 1.88 | 2.799 (3) | 162 |
O6W—H6A···O5W | 0.84 | 1.89 | 2.729 (4) | 177 |
O6W—H6B···O7W | 0.83 | 2.05 | 2.880 (3) | 176 |
O7W—H7A···O3iv | 0.86 | 1.99 | 2.820 (3) | 163 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, y, −z+1/2. |
[Fe2O(SO4)2(C10H8N2)4]·15H2O | F(000) = 2536 |
Mr = 1214.80 | Dx = 1.502 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 2734 reflections |
a = 12.8303 (18) Å | θ = 2.7–19.5° |
b = 21.819 (3) Å | µ = 0.71 mm−1 |
c = 19.312 (3) Å | T = 298 K |
β = 96.288 (3)° | Block, red |
V = 5373.6 (13) Å3 | 0.30 × 0.12 × 0.12 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 5272 independent reflections |
Radiation source: fine-focus sealed tube | 2798 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.094 |
ϕ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −15→15 |
Tmin = 0.738, Tmax = 0.919 | k = −26→25 |
12439 measured reflections | l = −23→11 |
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.84 | w = 1/[σ2(Fo2) + (0.0091P)2] where P = (Fo2 + 2Fc2)/3 |
5272 reflections | (Δ/σ)max < 0.001 |
353 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Fe2O(SO4)2(C10H8N2)4]·15H2O | V = 5373.6 (13) Å3 |
Mr = 1214.80 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.8303 (18) Å | µ = 0.71 mm−1 |
b = 21.819 (3) Å | T = 298 K |
c = 19.312 (3) Å | 0.30 × 0.12 × 0.12 mm |
β = 96.288 (3)° |
Bruker SMART CCD area-detector diffractometer | 5272 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2798 reflections with I > 2σ(I) |
Tmin = 0.738, Tmax = 0.919 | Rint = 0.094 |
12439 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 0.84 | Δρmax = 0.49 e Å−3 |
5272 reflections | Δρmin = −0.31 e Å−3 |
353 parameters |
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 | Occ. (<1) | |
Fe | 0.89766 (4) | 0.13570 (2) | 0.18047 (3) | 0.03141 (17) | |
S | 0.73904 (9) | 0.24448 (6) | 0.21837 (6) | 0.0486 (3) | |
C1 | 1.0379 (3) | 0.23811 (18) | 0.1363 (2) | 0.0415 (11) | |
H1 | 1.0672 | 0.2348 | 0.1823 | 0.050* | |
C2 | 1.0804 (3) | 0.27871 (19) | 0.0938 (2) | 0.0496 (12) | |
H2 | 1.1373 | 0.3030 | 0.1105 | 0.060* | |
C3 | 1.0367 (4) | 0.2829 (2) | 0.0254 (2) | 0.0552 (13) | |
H3 | 1.0648 | 0.3100 | −0.0048 | 0.066* | |
C4 | 0.9526 (3) | 0.24746 (19) | 0.0019 (2) | 0.0464 (11) | |
H4 | 0.9229 | 0.2501 | −0.0441 | 0.056* | |
C5 | 0.9124 (3) | 0.20763 (17) | 0.04782 (19) | 0.0317 (9) | |
C6 | 0.8209 (3) | 0.16756 (18) | 0.02842 (19) | 0.0346 (10) | |
C7 | 0.7653 (3) | 0.16842 (19) | −0.0366 (2) | 0.0438 (11) | |
H7 | 0.7848 | 0.1947 | −0.0708 | 0.053* | |
C8 | 0.6813 (3) | 0.1304 (2) | −0.0505 (2) | 0.0543 (13) | |
H8 | 0.6429 | 0.1306 | −0.0943 | 0.065* | |
C9 | 0.6538 (3) | 0.0916 (2) | 0.0006 (2) | 0.0553 (13) | |
H9 | 0.5975 | 0.0648 | −0.0080 | 0.066* | |
C10 | 0.7120 (3) | 0.0937 (2) | 0.0647 (2) | 0.0502 (12) | |
H10 | 0.6926 | 0.0684 | 0.0999 | 0.060* | |
C11 | 0.7565 (3) | 0.0464 (2) | 0.2534 (2) | 0.0512 (12) | |
H11 | 0.7271 | 0.0824 | 0.2684 | 0.061* | |
C12 | 0.7198 (4) | −0.0085 (2) | 0.2747 (2) | 0.0675 (15) | |
H12 | 0.6671 | −0.0100 | 0.3041 | 0.081* | |
C13 | 0.7627 (4) | −0.0613 (2) | 0.2515 (3) | 0.0691 (15) | |
H13 | 0.7393 | −0.0994 | 0.2649 | 0.083* | |
C14 | 0.8400 (4) | −0.0572 (2) | 0.2086 (2) | 0.0553 (13) | |
H14 | 0.8694 | −0.0928 | 0.1927 | 0.066* | |
C15 | 0.8747 (3) | −0.00177 (19) | 0.18884 (19) | 0.0368 (10) | |
C16 | 0.9583 (3) | 0.00621 (18) | 0.14335 (19) | 0.0351 (10) | |
C17 | 1.0081 (4) | −0.0425 (2) | 0.1154 (2) | 0.0571 (13) | |
H17 | 0.9878 | −0.0826 | 0.1236 | 0.068* | |
C18 | 1.0880 (4) | −0.0310 (2) | 0.0751 (3) | 0.0648 (15) | |
H18 | 1.1227 | −0.0634 | 0.0564 | 0.078* | |
C19 | 1.1160 (4) | 0.0275 (2) | 0.0629 (2) | 0.0592 (13) | |
H19 | 1.1696 | 0.0360 | 0.0355 | 0.071* | |
C20 | 1.0632 (3) | 0.0741 (2) | 0.0919 (2) | 0.0486 (12) | |
H20 | 1.0828 | 0.1143 | 0.0839 | 0.058* | |
N1 | 0.9559 (2) | 0.20288 (13) | 0.11433 (15) | 0.0310 (8) | |
N2 | 0.7950 (2) | 0.13039 (14) | 0.07900 (15) | 0.0339 (8) | |
N3 | 0.8341 (2) | 0.05052 (15) | 0.21133 (15) | 0.0363 (8) | |
N4 | 0.9848 (2) | 0.06455 (14) | 0.13131 (15) | 0.0351 (8) | |
O1 | 1.0000 | 0.14584 (15) | 0.2500 | 0.0377 (9) | |
O2 | 0.7855 (2) | 0.18168 (12) | 0.21883 (13) | 0.0486 (8) | |
O3 | 0.8176 (2) | 0.28896 (13) | 0.20367 (17) | 0.0741 (10) | |
O4A | 0.7127 (7) | 0.2603 (3) | 0.2861 (5) | 0.063 (2) | 0.73 |
O4B | 0.6799 (18) | 0.2344 (7) | 0.2884 (12) | 0.042 (5) | 0.27 |
O5 | 0.6494 (2) | 0.24552 (14) | 0.16478 (13) | 0.0586 (9) | |
O1W | 0.5232 (3) | −0.05293 (16) | 0.14043 (17) | 0.1062 (13) | |
H1A | 0.5705 | −0.0694 | 0.1179 | 0.149* | |
H1B | 0.5386 | −0.0499 | 0.1851 | 0.149* | |
O2W | 0.5439 (2) | 0.31039 (13) | 0.34690 (15) | 0.0749 (10) | |
H2A | 0.4952 | 0.2850 | 0.3461 | 0.105* | |
H2B | 0.5790 | 0.2902 | 0.3303 | 0.105* | |
O3W | 0.3343 (3) | 0.06428 (16) | −0.04512 (18) | 0.1130 (14) | |
H3A | 0.3589 | 0.0600 | −0.0100 | 0.158* | |
H3B | 0.2831 | 0.0844 | −0.0513 | 0.158* | |
O4W | 0.3144 (3) | 0.34396 (17) | 0.03695 (18) | 0.1123 (14) | |
H4A | 0.2869 | 0.3385 | −0.0046 | 0.157* | |
H4B | 0.3405 | 0.3204 | 0.0717 | 0.157* | |
O5W | 0.0000 | 0.35972 (19) | 0.2500 | 0.0686 (13) | |
H5A | 0.0400 | 0.3302 | 0.2396 | 0.096* | |
O6W | 0.2770 (3) | 0.1732 (2) | 0.10101 (19) | 0.1309 (16) | |
H6A | 0.2831 | 0.1985 | 0.1347 | 0.183* | |
H6B | 0.3112 | 0.1408 | 0.1005 | 0.183* | |
O7W | 0.4279 (3) | 0.05275 (18) | 0.0935 (2) | 0.1252 (15) | |
H7A | 0.4825 | 0.0268 | 0.0926 | 0.175* | |
H7B | 0.4611 | 0.0781 | 0.1285 | 0.175* | |
O8W | 0.5046 (3) | 0.15009 (18) | 0.1765 (2) | 0.1422 (17) | |
H8A | 0.4501 | 0.1730 | 0.1854 | 0.199* | |
H8B | 0.5313 | 0.1785 | 0.1662 | 0.199* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0316 (3) | 0.0338 (3) | 0.0290 (3) | −0.0002 (3) | 0.0038 (2) | −0.0007 (3) |
S | 0.0460 (8) | 0.0631 (9) | 0.0356 (6) | 0.0235 (7) | −0.0005 (6) | −0.0037 (6) |
C1 | 0.044 (3) | 0.038 (3) | 0.040 (3) | −0.004 (2) | −0.003 (2) | −0.003 (2) |
C2 | 0.050 (3) | 0.043 (3) | 0.057 (3) | −0.007 (2) | 0.010 (2) | 0.005 (2) |
C3 | 0.054 (3) | 0.062 (3) | 0.053 (3) | −0.007 (3) | 0.019 (2) | 0.019 (3) |
C4 | 0.049 (3) | 0.052 (3) | 0.039 (3) | −0.004 (2) | 0.007 (2) | 0.008 (2) |
C5 | 0.034 (3) | 0.030 (2) | 0.031 (2) | 0.0062 (19) | 0.0041 (19) | −0.0012 (19) |
C6 | 0.035 (3) | 0.040 (3) | 0.029 (2) | 0.012 (2) | 0.0020 (19) | −0.004 (2) |
C7 | 0.035 (3) | 0.058 (3) | 0.038 (3) | 0.007 (2) | 0.000 (2) | 0.002 (2) |
C8 | 0.047 (3) | 0.064 (3) | 0.047 (3) | 0.009 (3) | −0.017 (2) | −0.010 (3) |
C9 | 0.044 (3) | 0.056 (3) | 0.064 (3) | −0.006 (2) | −0.008 (3) | −0.004 (3) |
C10 | 0.048 (3) | 0.057 (3) | 0.046 (3) | −0.015 (2) | 0.003 (2) | 0.003 (2) |
C11 | 0.049 (3) | 0.055 (3) | 0.053 (3) | −0.003 (3) | 0.019 (2) | −0.009 (3) |
C12 | 0.072 (4) | 0.062 (4) | 0.074 (4) | −0.021 (3) | 0.031 (3) | 0.001 (3) |
C13 | 0.077 (4) | 0.049 (3) | 0.083 (4) | −0.029 (3) | 0.013 (3) | 0.015 (3) |
C14 | 0.063 (4) | 0.038 (3) | 0.066 (3) | −0.006 (3) | 0.013 (3) | −0.006 (3) |
C15 | 0.043 (3) | 0.031 (2) | 0.036 (2) | −0.004 (2) | 0.001 (2) | −0.002 (2) |
C16 | 0.035 (3) | 0.032 (3) | 0.036 (2) | 0.006 (2) | −0.0030 (19) | −0.004 (2) |
C17 | 0.058 (4) | 0.035 (3) | 0.079 (3) | 0.004 (2) | 0.010 (3) | −0.005 (3) |
C18 | 0.068 (4) | 0.045 (3) | 0.085 (4) | 0.021 (3) | 0.025 (3) | −0.018 (3) |
C19 | 0.055 (3) | 0.065 (4) | 0.062 (3) | 0.016 (3) | 0.025 (3) | −0.006 (3) |
C20 | 0.047 (3) | 0.048 (3) | 0.054 (3) | 0.002 (2) | 0.018 (2) | 0.000 (2) |
N1 | 0.036 (2) | 0.0279 (19) | 0.0283 (18) | −0.0061 (16) | 0.0009 (15) | 0.0039 (15) |
N2 | 0.031 (2) | 0.033 (2) | 0.0370 (19) | −0.0007 (17) | 0.0016 (15) | −0.0038 (17) |
N3 | 0.034 (2) | 0.044 (2) | 0.0314 (19) | −0.0052 (17) | 0.0072 (16) | −0.0005 (17) |
N4 | 0.036 (2) | 0.035 (2) | 0.0344 (19) | 0.0034 (17) | 0.0069 (16) | −0.0034 (17) |
O1 | 0.040 (2) | 0.038 (2) | 0.035 (2) | 0.000 | 0.0009 (18) | 0.000 |
O2 | 0.0440 (19) | 0.0472 (18) | 0.0577 (18) | 0.0174 (15) | 0.0191 (15) | 0.0017 (15) |
O3 | 0.065 (2) | 0.045 (2) | 0.108 (3) | −0.0047 (18) | −0.007 (2) | −0.007 (2) |
O4A | 0.076 (6) | 0.075 (6) | 0.040 (3) | 0.021 (4) | 0.015 (4) | −0.006 (4) |
O4B | 0.059 (13) | 0.031 (10) | 0.040 (7) | 0.013 (7) | 0.024 (8) | 0.006 (8) |
O5 | 0.0423 (19) | 0.085 (2) | 0.0461 (17) | 0.0111 (17) | −0.0068 (15) | 0.0130 (17) |
O1W | 0.111 (3) | 0.119 (3) | 0.084 (3) | −0.001 (3) | −0.011 (2) | 0.001 (2) |
O2W | 0.065 (2) | 0.064 (2) | 0.100 (3) | −0.0165 (18) | 0.0280 (19) | −0.022 (2) |
O3W | 0.124 (4) | 0.102 (3) | 0.114 (3) | 0.009 (3) | 0.018 (3) | 0.020 (3) |
O4W | 0.110 (3) | 0.139 (4) | 0.085 (3) | 0.028 (3) | −0.001 (2) | 0.012 (3) |
O5W | 0.072 (3) | 0.058 (3) | 0.077 (3) | 0.000 | 0.014 (3) | 0.000 |
O6W | 0.112 (3) | 0.181 (4) | 0.100 (3) | 0.027 (3) | 0.013 (3) | −0.033 (3) |
O7W | 0.103 (3) | 0.141 (4) | 0.131 (4) | −0.001 (3) | 0.011 (3) | 0.028 (3) |
O8W | 0.124 (4) | 0.106 (4) | 0.202 (5) | −0.015 (3) | 0.038 (3) | 0.026 (3) |
Fe—O1 | 1.7860 (7) | C12—C13 | 1.374 (6) |
Fe—O2 | 1.965 (3) | C12—H12 | 0.9300 |
Fe—N1 | 2.132 (3) | C13—C14 | 1.362 (6) |
Fe—N3 | 2.140 (3) | C13—H13 | 0.9300 |
Fe—N4 | 2.190 (3) | C14—C15 | 1.358 (5) |
Fe—N2 | 2.241 (3) | C14—H14 | 0.9300 |
S—O4A | 1.429 (9) | C15—N3 | 1.346 (4) |
S—O3 | 1.450 (3) | C15—C16 | 1.470 (5) |
S—O5 | 1.461 (3) | C16—N4 | 1.344 (4) |
S—O2 | 1.494 (3) | C16—C17 | 1.380 (5) |
S—O4B | 1.64 (2) | C17—C18 | 1.375 (6) |
C1—N1 | 1.334 (4) | C17—H17 | 0.9300 |
C1—C2 | 1.361 (5) | C18—C19 | 1.354 (6) |
C1—H1 | 0.9300 | C18—H18 | 0.9300 |
C2—C3 | 1.381 (5) | C19—C20 | 1.375 (5) |
C2—H2 | 0.9300 | C19—H19 | 0.9300 |
C3—C4 | 1.364 (5) | C20—N4 | 1.342 (5) |
C3—H3 | 0.9300 | C20—H20 | 0.9300 |
C4—C5 | 1.381 (5) | O1—Fei | 1.7860 (7) |
C4—H4 | 0.9300 | O1W—H1A | 0.8618 |
C5—N1 | 1.347 (4) | O1W—H1B | 0.8671 |
C5—C6 | 1.479 (5) | O2W—H2A | 0.8330 |
C6—N2 | 1.339 (4) | O2W—H2B | 0.7293 |
C6—C7 | 1.375 (5) | O3W—H3A | 0.7218 |
C7—C8 | 1.364 (5) | O3W—H3B | 0.7883 |
C7—H7 | 0.9300 | O4W—H4A | 0.8498 |
C8—C9 | 1.374 (6) | O4W—H4B | 0.8816 |
C8—H8 | 0.9300 | O5W—H5A | 0.8613 |
C9—C10 | 1.376 (5) | O6W—H6A | 0.8499 |
C9—H9 | 0.9300 | O6W—H6B | 0.8318 |
C10—N2 | 1.337 (5) | O7W—H7A | 0.9019 |
C10—H10 | 0.9300 | O7W—H7B | 0.9381 |
C11—N3 | 1.355 (5) | O8W—H8A | 0.8917 |
C11—C12 | 1.367 (6) | O8W—H8B | 0.7465 |
C11—H11 | 0.9300 | ||
O1—Fe—O2 | 99.32 (10) | C9—C10—H10 | 118.4 |
O1—Fe—N1 | 95.06 (11) | N3—C11—C12 | 122.5 (4) |
O2—Fe—N1 | 101.19 (11) | N3—C11—H11 | 118.8 |
O1—Fe—N3 | 99.75 (12) | C12—C11—H11 | 118.8 |
O2—Fe—N3 | 91.21 (12) | C11—C12—C13 | 118.3 (5) |
N1—Fe—N3 | 158.88 (11) | C11—C12—H12 | 120.8 |
O1—Fe—N4 | 92.60 (11) | C13—C12—H12 | 120.8 |
O2—Fe—N4 | 162.84 (12) | C14—C13—C12 | 119.2 (5) |
N1—Fe—N4 | 89.91 (12) | C14—C13—H13 | 120.4 |
N3—Fe—N4 | 74.54 (13) | C12—C13—H13 | 120.4 |
O1—Fe—N2 | 167.70 (9) | C15—C14—C13 | 120.8 (5) |
O2—Fe—N2 | 88.36 (11) | C15—C14—H14 | 119.6 |
N1—Fe—N2 | 73.91 (12) | C13—C14—H14 | 119.6 |
N3—Fe—N2 | 89.60 (11) | N3—C15—C14 | 121.0 (4) |
N4—Fe—N2 | 82.15 (11) | N3—C15—C16 | 115.2 (4) |
O4A—S—O3 | 104.9 (3) | C14—C15—C16 | 123.8 (4) |
O4A—S—O5 | 113.5 (4) | N4—C16—C17 | 121.7 (4) |
O3—S—O5 | 111.18 (18) | N4—C16—C15 | 115.5 (4) |
O4A—S—O2 | 110.5 (4) | C17—C16—C15 | 122.8 (4) |
O3—S—O2 | 109.25 (17) | C18—C17—C16 | 119.0 (4) |
O5—S—O2 | 107.51 (17) | C18—C17—H17 | 120.5 |
O3—S—O4B | 130.3 (6) | C16—C17—H17 | 120.5 |
O5—S—O4B | 100.8 (9) | C19—C18—C17 | 120.0 (4) |
O2—S—O4B | 95.3 (7) | C19—C18—H18 | 120.0 |
N1—C1—C2 | 122.6 (4) | C17—C18—H18 | 120.0 |
N1—C1—H1 | 118.7 | C18—C19—C20 | 118.2 (4) |
C2—C1—H1 | 118.7 | C18—C19—H19 | 120.9 |
C1—C2—C3 | 118.2 (4) | C20—C19—H19 | 120.9 |
C1—C2—H2 | 120.9 | N4—C20—C19 | 123.3 (4) |
C3—C2—H2 | 120.9 | N4—C20—H20 | 118.3 |
C4—C3—C2 | 120.2 (4) | C19—C20—H20 | 118.3 |
C4—C3—H3 | 119.9 | C1—N1—C5 | 119.2 (3) |
C2—C3—H3 | 119.9 | C1—N1—Fe | 121.5 (3) |
C3—C4—C5 | 118.8 (4) | C5—N1—Fe | 119.2 (3) |
C3—C4—H4 | 120.6 | C10—N2—C6 | 117.9 (3) |
C5—C4—H4 | 120.6 | C10—N2—Fe | 126.1 (3) |
N1—C5—C4 | 121.0 (4) | C6—N2—Fe | 115.9 (2) |
N1—C5—C6 | 115.5 (3) | C15—N3—C11 | 118.3 (3) |
C4—C5—C6 | 123.5 (4) | C15—N3—Fe | 118.3 (3) |
N2—C6—C7 | 122.0 (4) | C11—N3—Fe | 123.4 (3) |
N2—C6—C5 | 115.3 (3) | C20—N4—C16 | 117.7 (4) |
C7—C6—C5 | 122.8 (4) | C20—N4—Fe | 125.8 (3) |
C8—C7—C6 | 119.4 (4) | C16—N4—Fe | 116.5 (3) |
C8—C7—H7 | 120.3 | Fe—O1—Fei | 165.8 (2) |
C6—C7—H7 | 120.3 | S—O2—Fe | 140.75 (17) |
C7—C8—C9 | 119.5 (4) | H1A—O1W—H1B | 115.9 |
C7—C8—H8 | 120.3 | H2A—O2W—H2B | 95.2 |
C9—C8—H8 | 120.3 | H3A—O3W—H3B | 119.1 |
C8—C9—C10 | 118.0 (4) | H4A—O4W—H4B | 136.2 |
C8—C9—H9 | 121.0 | H6A—O6W—H6B | 123.7 |
C10—C9—H9 | 121.0 | H7A—O7W—H7B | 95.3 |
N2—C10—C9 | 123.2 (4) | H8A—O8W—H8B | 88.8 |
N2—C10—H10 | 118.4 |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O3Wii | 0.86 | 1.96 | 2.744 (5) | 150 |
O1W—H1B···O5Wiii | 0.87 | 2.42 | 2.887 (4) | 115 |
O2W—H2A···O5iv | 0.83 | 2.04 | 2.843 (4) | 163 |
O2W—H2B···O4A | 0.73 | 2.10 | 2.797 (9) | 160 |
O3W—H3A···O7W | 0.72 | 2.10 | 2.825 (5) | 177 |
O3W—H3B···O4Wv | 0.79 | 2.04 | 2.782 (5) | 157 |
O4W—H4A···O6Wv | 0.85 | 1.97 | 2.816 (5) | 179 |
O4W—H4B···O2Wiv | 0.88 | 2.05 | 2.825 (5) | 146 |
O5W—H5A···O3iv | 0.86 | 2.22 | 2.864 (4) | 132 |
O6W—H6A···O4Aiv | 0.85 | 2.04 | 2.884 (3) | 176 |
O6W—H6B···O7W | 0.83 | 2.45 | 3.277 (6) | 173 |
O7W—H7A···O1W | 0.90 | 2.01 | 2.717 (5) | 134 |
O7W—H7B···O8W | 0.94 | 1.88 | 2.774 (6) | 159 |
O8W—H8A···O4Biv | 0.89 | 2.24 | 3.131 (6) | 176 |
O8W—H8B···O5 | 0.75 | 2.11 | 2.816 (5) | 159 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x+1/2, y−1/2, z; (iv) −x+1, y, −z+1/2; (v) −x+1/2, −y+1/2, −z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Fe2O(SO4)2(C10H8N2)4]·11H2O | [Fe2O(SO4)2(C10H8N2)4]·15H2O |
Mr | 1142.73 | 1214.80 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 100 | 298 |
a, b, c (Å) | 13.7244 (8), 21.6461 (13), 16.1238 (9) | 12.8303 (18), 21.819 (3), 19.312 (3) |
β (°) | 90.680 (1) | 96.288 (3) |
V (Å3) | 4789.7 (5) | 5373.6 (13) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.78 | 0.71 |
Crystal size (mm) | 0.20 × 0.08 × 0.07 | 0.30 × 0.12 × 0.12 |
Data collection | ||
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.783, 0.947 | 0.738, 0.919 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27533, 5757, 4601 | 12439, 5272, 2798 |
Rint | 0.069 | 0.094 |
(sin θ/λ)max (Å−1) | 0.667 | 0.618 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.121, 1.14 | 0.057, 0.107, 0.84 |
No. of reflections | 5757 | 5272 |
No. of parameters | 327 | 353 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0436P)2 + 10.7762P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0091P)2] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.70, −0.42 | 0.49, −0.31 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Mercury (Macrae et al., 2006), SHELXL97.
Fe—O1 | 1.8009 (6) | Fe—N3 | 2.160 (2) |
Fe—O2 | 1.955 (2) | Fe—N4 | 2.186 (3) |
Fe—N1 | 2.126 (2) | Fe—N2 | 2.296 (2) |
Fei—O1—Fe | 161.67 (17) |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O2W | 0.94 | 1.89 | 2.816 (4) | 167 |
O1W—H1B···O6Wii | 0.78 | 2.07 | 2.734 (4) | 143 |
O2W—H2A···O5 | 0.92 | 1.91 | 2.824 (3) | 170 |
O3W—H3A···O5 | 0.81 | 2.10 | 2.886 (3) | 163 |
O4W—H4A···O4iii | 0.87 | 1.98 | 2.849 (3) | 172 |
O4W—H4B···O4iv | 0.85 | 2.00 | 2.838 (3) | 168 |
O5W—H5A···O1Wiii | 0.88 | 1.89 | 2.739 (4) | 161 |
O5W—H5B···O4W | 0.94 | 1.88 | 2.799 (3) | 162 |
O6W—H6A···O5W | 0.84 | 1.89 | 2.729 (4) | 177 |
O6W—H6B···O7W | 0.83 | 2.05 | 2.880 (3) | 176 |
O7W—H7A···O3iv | 0.86 | 1.99 | 2.820 (3) | 163 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, y, −z+1/2. |
Fe—O1 | 1.7860 (7) | Fe—N3 | 2.140 (3) |
Fe—O2 | 1.965 (3) | Fe—N4 | 2.190 (3) |
Fe—N1 | 2.132 (3) | Fe—N2 | 2.241 (3) |
Fe—O1—Fei | 165.8 (2) |
Symmetry code: (i) −x+2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O3Wii | 0.86 | 1.96 | 2.744 (5) | 150 |
O1W—H1B···O5Wiii | 0.87 | 2.42 | 2.887 (4) | 115 |
O2W—H2A···O5iv | 0.83 | 2.04 | 2.843 (4) | 163 |
O2W—H2B···O4A | 0.73 | 2.10 | 2.797 (9) | 160 |
O3W—H3A···O7W | 0.72 | 2.10 | 2.825 (5) | 177 |
O3W—H3B···O4Wv | 0.79 | 2.04 | 2.782 (5) | 157 |
O4W—H4A···O6Wv | 0.85 | 1.97 | 2.816 (5) | 179 |
O4W—H4B···O2Wiv | 0.88 | 2.05 | 2.825 (5) | 146 |
O5W—H5A···O3iv | 0.86 | 2.22 | 2.864 (4) | 132 |
O6W—H6A···O4Aiv | 0.85 | 2.04 | 2.884 (3) | 176 |
O6W—H6B···O7W | 0.83 | 2.45 | 3.277 (6) | 173 |
O7W—H7A···O1W | 0.90 | 2.01 | 2.717 (5) | 134 |
O7W—H7B···O8W | 0.94 | 1.88 | 2.774 (6) | 159 |
O8W—H8A···O4Biv | 0.89 | 2.24 | 3.131 (6) | 176 |
O8W—H8B···O5 | 0.75 | 2.11 | 2.816 (5) | 159 |
Symmetry codes: (ii) −x+1, −y, −z; (iii) x+1/2, y−1/2, z; (iv) −x+1, y, −z+1/2; (v) −x+1/2, −y+1/2, −z. |
Oxo-bridged dinuclear FeIII complexes are of interest due to their magnetic properties resulting from superexchange via the oxo-bridge (Wernsdorfer & Sessoli, 1999). Moreover, they have been studied as potential models for several non-haem iron centres in biological systems (Feig & Lippard, 1994). Compounds with a single oxo-bridge are less common than those containing additional multi-atom bridges, notably carboxylate bridges (Kurtz, 1990). It has long been known that the treatment of FeIII salts with 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) in an aqueous medium results in dinuclear complexes (Khedekar et al., 1967). Several complexes having the [Fe2O(phen)4]4+ core have been structurally characterized to date. However, the structures of only two bpy complexes of this type (Xiang et al., 1998; Choudhury et al., 1997) and its 4,4-dimethyl-2,2'-bipyridine analogue (Collomb et al., 1999; Menage et al., 1993) have so far been reported. In this paper, we report the structures of two hydrates of the bpy complex obtained with FeIII sulfate, [Fe2(µ-O)(SO4)2(C10H8N2)4].11H2O, (I), and [Fe2(µ-O)(SO4)2(C10H8N2)4].15H2O, (II). A previous preparation is said to have yielded a precipitate having 3.5 water molecules per dimer, but this has not been structurally characterized (Reiff et al., 1968).
We obtained both hydrates (I) and (II) in an attempt to prepare mixed-ligand complexes. Compound (I) was obtained in a reaction of ferric sulfate with bpy and sodium acetate, while (II) was obtained when 1,2-diaminoethane was used in place of sodium acetate. Both structures consist of a dinuclear molecule in which two symmetry-related FeIII atoms are bridged by an oxide ion situated on a twofold axis (Figs. 1 and 2). Selected bond distances and angles and hydrogen-bond parameters are shown in Tables 1–4.
The coordination around each metal atom, which may be described as cis-distorted octahedral, is completed by an O atom from the sulfate ion and two chelating bpy ligands. The Fe—N bonds trans to the O atoms in the equatorial plane are significantly longer than the axial Fe—N bonds. The equatorial atoms (Fe, O1, O2, N2 and N4) are only approximately coplanar in both structures [r.m.s. deviations 0.2173 for (I) and 0.1890 Å for (II)]. The Fe—O—Fei angle deviates appreciably from linearity, at 161.7 (2)° in (I) and 165.8 (2)° in (II). The Fe···Fei distance is 3.556 (4) Å in (I) and 3.544 (1) Å in (II). The corresponding values in the analogous phenanthroline complex (Odoko & Okabe, 2005) are 172.8 (1)° and 3.555 (2) Å.
A comparison between the structures of the dinuclear complex molecules in the two hydrates is in order. The two pyridyl rings of bpy are appreciably twisted with respect to each other in (I), while they are nearly coplanar in (II). The C4—C5—C6—C7 and C14—C15—C16—C17 torsion angles are, respectively, 7.5 (4) and 19.3 (4)° in (I), and −2.7 (6) and 1.3 (6)° in (II). These distortions are within the normal range of 0–26° seen in coordinated bpy ligands (Xiang et al., 1998). The ligands in the two halves are disposed in such a manner as to reduce the repulsion between the sulfate ions without compromising the attractive π–π stacking interaction between the pyridyl rings. The O2—Fe—Fei—O2i torsion angle is 123.4 (1)° in (I) and −116.7 (1)° in (II).
One pair of symmetry-related bpy ligands participates in intramolecular π–π stacking. This interaction is stronger in (I), with eight C···C contacts in the range 3.33–3.68 Å, while in (II) the contacts are all greater than 3.62 Å. The bpy molecules with the largest twist angle are involved in the intramolecular stacking of (I). Intermolecular stacking involving all the bpy ligands is observed in both structures, with several C···C contacts in the range 3.38–3.69 Å in (I) and 3.36–3.70 Å in (II). It is noteworthy that in (I), the bpy ligand having the highest twist angle is involved in intramolecular stacking as well as intermolecular stacking. It appears that the high twist facilitates this `conjugation' of the two types of interactions.
Considering the crystal packing, in both compounds the complex molecules assemble together to produce oval-shaped channels, with an average diameter of about 6.5 Å along the c axis. The sulfate O atoms line the inside of these channels, while the hydrophobic parts of the bpy ligands are on the outside. The solvent water molecules forming hydrogen-bonded ribbons occupy these channels. The ribbons in (I) consists of two types of six-membered rings fused together, while in (II) there are alternate six- and seven-membered rings. In (I), there is an additional water molecule hydrogen-bonded to one six-membered ring (Fig. 3). In (II), there is a cluster of three water molecules interacting with each six-membered ring (Fig. 4). In both structures, the tapes are bonded to the channels through these extra water molecules via hydrogen-bonding interactions with sulfate O atoms (Figs. 5 and 6).
It is remarkable that the presence of sodium acetate and 1,2-diaminoethane in the reaction medium led to the formation of crystals of two different hydrates of a compound which has been previously obtained only as precipitates. Other than adjusting the pH, the role of these substances which are themselves coordinating ligands, in the crystallization process is not known.