metal-organic compounds
Di-μ-dimethylformamide-κ4O:O-μ-tetrahydrofuran-κ2O:O-bis[(tetrahydrofuran-κO)sodium(I)] bis(μ-3,6-dichlorobenzene-1,2-dithiolato-κ3S,S′:S)bis[(3,6-dichlorobenzene-1,2-dithiolato-κ2S,S′)iron(III)]
aDepartamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049 Madrid, Spain, and bLaboratorio de Difracción de Rayos X de Monocristal, Servicio Interdepartamental de Investigación, Universidad Autónoma de Madrid, 28049 Madrid, Spain
*Correspondence e-mail: josefina.perles@uam.es
The title compound, [Na2(C3H7NO)2(C4H8O)5][Fe2(C6H2Cl2S2)4], was synthesized and its was solved. The ionic crystal contains a [Fe2(S2C6H2Cl2)4]2− dimeric anion and a [Na2(THF)4(μ-THF)(μ-DMF)2]2+ cation, where THF is tetrahydrofuran and DMF is dimethylformamide, comprising two sodium atoms joined by one THF and two DMF molecules bridging through their O atoms. The five-coordinate environment of each Na site is completed by two terminal THF molecules. The contains half a cationic unit (as the cation is placed on a twofold axis) and half an anion, as there is an inversion centre at the midpoint of the Fe—Fe vectors. The cationic and anionic moieties are linked by C—H⋯Cl and C—H⋯S interactions.
CCDC reference: 1474454
Structure description
In the title compound (Fig. 1) the [FeIII(Cl2-bdt)2]− anion (Cl2-bdt is 3,6-dichloro-1,2-benzenedithiolate) forms a centrosymmetric dimer supported by two FeIII—S bonds [Fe1—S4 = 2.4885 (16) Å] in which each iron atom shows the expected 4 + 1 square-pyramidal geometry. This is the typical coordination mode displayed by most of the iron bis(dithiolato) compounds, which is due to the strong dimerization tendency of the monoanionic [Fe(dithiolate)2]− species (Amo-Ochoa et al., 2013; Chen et al., 2012; Sproules & Wieghardt, 2010; Cerdeira et al., 2008). The basal Fe—S bond lengths [Fe1—S1 = 2.2219 (15), Fe1—S2 = 2.2101 (16), Fe1—S3 = 2.2256 (15) and Fe1—S4 = 2.2296 (15) Å] are shorter than the axial one, 2.4885 (16) Å. On the other hand, the two sodium atoms in the cation [Na2(THF)4(μ-THF)(μ-DMF)2]2+ are bridged by one THF and two DMF molecules. To complete the pentacoordination sphere (Fig. 2), each sodium atom is additionally bonded to two terminal THF molecules, at normal distances (Benmansour et al., 2015; Raja et al., 2014; Thirumurugan et al., 2010).
In the crystal, the supramolecular packing is determined by C—H⋯Cl and C—H⋯S interactions between anionic and cationic species (Table 1), yielding a three-dimensional network.
Synthesis and crystallization
An amount of 1,2-HSC6H2Cl2SH (238 mg, 1.1 mmol) was treated with an aqueous solution (10 ml) of NaOH, (5% by weight). Then, FeCl3·6H2O (150 mg, 0.37 mmol) in 10 ml of ethanol/water (1:1) was slowly added. The mixture was stirred at room temperature for 30 min. The solid formed was collected by filtration and washed several times with water and n-hexane. Suitable crystals for X-ray analysis of the title compound were obtained from a solution in THF–DMF/n-hexane, at room temperature.
Refinement
Crystal data, data collection and structure . Several C atoms from the THF molecules coordinated to the Na+ cation (mainly for the bridging THF, see Fig. 2) present high displacement parameters. Alternative positions for disordered C atoms could not be located.
details are summarized in Table 2Structural data
CCDC reference: 1474454
10.1107/S241431461600643X/bh4005sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S241431461600643X/bh4005Isup2.hkl
file with corrected spelling in the name of the first author. DOI:An amount of 1,2-HSC6H2Cl2SH (238 mg, 1.1 mmol) was treated with an aqueous solution (10 ml) of NaOH, (5% by weight). Then, FeCl3·6H2O (150 mg, 0.37 mmol) in 10 ml of ethanol/water (1:1) was slowly added. The mixture was stirred at room temperature for 30 min. The solid formed was collected by filtration and washed several times with water and n-hexane. Suitable crystals for X-ray analysis of the title compound were obtained from a solution in THF–DMF/n-hexane, at room temperature.
Crystal data, data collection and structure
details are summarized in Table 2. Several C atoms from the THF molecules coordinated to the Na+ cation (mainly for the bridging THF, see Fig. 3) present high displacement parameters. Alternative positions for disordered C atoms could not be located.In the title compound (Fig. 1) the [FeIII(Cl2-bdt)2]- anion (Cl2-bdt is 3,6-dichloro-1,2-benzenedithiolate) forms a centrosymmetric dimer supported by two FeIII—S bonds [Fe1—S4 = 2.4885 (16) Å] in which each iron atom shows the expected 4 + 1 square-pyramidal geometry. This is the typical coordination mode displayed by most of the iron bis(dithiolato) compounds, which is due to the strong dimerization tendency of the monoanionic [Fe(dithiolate)2]- species (Amo-Ochoa et al., 2013; Chen et al., 2012; Sproules & Wieghardt, 2010; Cerdeira et al., 2008). The basal Fe—S bond lengths [Fe1—S1 = 2.2219 (15), Fe1—S2 = 2.2101 (16), Fe1—S3 = 2.2256 (15) and Fe1—S4 = 2.2296 (15) Å] are shorter than the axial one, 2.4885 (16) Å (Fig. 2). On the other hand, the two sodium atoms in the cation [Na2(THF)4(µ-THF)(µ-DMF)2]2+ are bridged by one THF and two DMF molecules. To complete the pentacoordination sphere (Fig. 3), each sodium atom is additionally bonded to two terminal THF molecules, at normal distances (Benmansour et al., 2015; Raja et al., 2014; Thirumurugan et al., 2010).
In the crystal, the supramolecular packing is determined by C—H···Cl and C—H···S interactions between anionic and cationic species (Table 1).
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).Fig. 1. Ellipsoid plot (at 50% probability) of the [Fe2(S2C6H2Cl2)4]2- anion with atoms labelled. | |
Fig. 2. Ellipsoid plot (at 50% probability) of the [Na2(THF)4(µ-THF)(µ-DMF)2]2+ cation with non-hydrogen atoms labelled. |
[Na2(C3H7NO)2(C4H8O)5][Fe2(C6H2Cl2S2)4] | F(000) = 3080 |
Mr = 1500.77 | Dx = 1.580 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 29.063 (2) Å | Cell parameters from 3584 reflections |
b = 9.9393 (6) Å | θ = 2.2–22.1° |
c = 25.645 (3) Å | µ = 1.13 mm−1 |
β = 121.609 (3)° | T = 100 K |
V = 6309.0 (9) Å3 | Prismatic, deep purple |
Z = 4 | 0.19 × 0.12 × 0.02 mm |
Bruker Kappa APEXII diffractometer | 3785 reflections with I > 2σ(I) |
Radiation source: molybdenum, x-ray tube | Rint = 0.101 |
Graphite monochromator | θmax = 25.4°, θmin = 1.7° |
θ and φ scans | h = −34→34 |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | k = −11→11 |
Tmin = 0.81, Tmax = 0.98 | l = −30→30 |
43114 measured reflections | 5765 standard reflections every 908 min |
5765 independent reflections | intensity decay: 0.0 (2) |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0854P)2 + 20.9273P] where P = (Fo2 + 2Fc2)/3 |
5762 reflections | (Δ/σ)max < 0.001 |
359 parameters | Δρmax = 1.26 e Å−3 |
2 restraints | Δρmin = −0.46 e Å−3 |
[Na2(C3H7NO)2(C4H8O)5][Fe2(C6H2Cl2S2)4] | V = 6309.0 (9) Å3 |
Mr = 1500.77 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.063 (2) Å | µ = 1.13 mm−1 |
b = 9.9393 (6) Å | T = 100 K |
c = 25.645 (3) Å | 0.19 × 0.12 × 0.02 mm |
β = 121.609 (3)° |
Bruker Kappa APEXII diffractometer | 3785 reflections with I > 2σ(I) |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | Rint = 0.101 |
Tmin = 0.81, Tmax = 0.98 | 5765 standard reflections every 908 min |
43114 measured reflections | intensity decay: 0.0 (2) |
5765 independent reflections |
R[F2 > 2σ(F2)] = 0.062 | 2 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0854P)2 + 20.9273P] where P = (Fo2 + 2Fc2)/3 |
5762 reflections | Δρmax = 1.26 e Å−3 |
359 parameters | Δρmin = −0.46 e Å−3 |
Refinement. There is some disorder in atoms from the coordinated THF molecules, specially in the positions occupied by C21 and C22 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1205 (2) | 0.5476 (6) | 0.1796 (2) | 0.0255 (13) | |
C2 | 0.1666 (2) | 0.6228 (6) | 0.2206 (3) | 0.0324 (14) | |
C3 | 0.2126 (2) | 0.5608 (7) | 0.2674 (3) | 0.0382 (16) | |
H3 | 0.2437 | 0.6124 | 0.2942 | 0.046* | |
C4 | 0.2125 (2) | 0.4236 (7) | 0.2746 (3) | 0.0370 (16) | |
H4 | 0.2438 | 0.38 | 0.3063 | 0.044* | |
C5 | 0.1673 (2) | 0.3495 (6) | 0.2359 (3) | 0.0328 (14) | |
C6 | 0.1201 (2) | 0.4095 (6) | 0.1884 (2) | 0.0257 (13) | |
C7 | −0.1128 (2) | 0.3851 (6) | −0.0270 (2) | 0.0248 (13) | |
C8 | −0.1619 (2) | 0.3163 (6) | −0.0633 (3) | 0.0334 (14) | |
C9 | −0.2079 (2) | 0.3846 (7) | −0.1069 (3) | 0.0377 (16) | |
H9 | −0.2406 | 0.3363 | −0.1316 | 0.045* | |
C10 | 0.2067 (2) | 0.4793 (7) | 0.1147 (3) | 0.0387 (17) | |
H10 | 0.2386 | 0.433 | 0.1437 | 0.046* | |
C11 | 0.1589 (2) | 0.4098 (6) | 0.0804 (3) | 0.0314 (14) | |
C12 | 0.1114 (2) | 0.4770 (6) | 0.0375 (2) | 0.0274 (13) | |
Cl1 | 0.16741 (7) | 0.79653 (16) | 0.21324 (7) | 0.0429 (4) | |
Cl2 | 0.16885 (6) | 0.17555 (17) | 0.24562 (7) | 0.0452 (4) | |
Cl3 | −0.16552 (6) | 0.14461 (18) | −0.05570 (7) | 0.0456 (4) | |
Cl4 | 0.15827 (6) | 0.23673 (17) | 0.08984 (7) | 0.0393 (4) | |
Fe1 | 0.01139 (3) | 0.45371 (7) | 0.06272 (3) | 0.0205 (2) | |
S1 | 0.06380 (5) | 0.62436 (14) | 0.11780 (6) | 0.0229 (3) | |
S2 | 0.06183 (5) | 0.31766 (14) | 0.14040 (6) | 0.0267 (3) | |
S3 | −0.05458 (5) | 0.30212 (14) | 0.02869 (6) | 0.0265 (3) | |
S4 | 0.04882 (5) | 0.39247 (14) | −0.00191 (6) | 0.0231 (3) | |
C13 | 0.0826 (5) | 1.1857 (10) | 0.3275 (6) | 0.105 (4) | |
H13A | 0.0671 | 1.1971 | 0.283 | 0.126* | |
H13B | 0.0531 | 1.1929 | 0.3359 | 0.126* | |
C14 | 0.1240 (7) | 1.2872 (13) | 0.3620 (7) | 0.148 (6) | |
H14A | 0.1343 | 1.332 | 0.3351 | 0.177* | |
H14B | 0.11 | 1.3564 | 0.3779 | 0.177* | |
C15 | 0.1627 (3) | 1.0772 (10) | 0.3994 (4) | 0.076 (3) | |
H15A | 0.19 | 1.0432 | 0.3906 | 0.091* | |
H15B | 0.1674 | 1.0287 | 0.4356 | 0.091* | |
C16 | 0.1703 (6) | 1.2210 (14) | 0.4120 (7) | 0.121 (5) | |
H16A | 0.1728 | 1.2413 | 0.4512 | 0.146* | |
H16B | 0.2039 | 1.2518 | 0.4148 | 0.146* | |
C17 | 0.1423 (4) | 0.6789 (11) | 0.4322 (4) | 0.082 (3) | |
H17A | 0.1119 | 0.6231 | 0.4269 | 0.099* | |
H17B | 0.1475 | 0.7541 | 0.4601 | 0.099* | |
C18 | 0.1906 (3) | 0.5988 (9) | 0.4591 (4) | 0.069 (2) | |
H18A | 0.1826 | 0.5041 | 0.4635 | 0.083* | |
H18B | 0.218 | 0.634 | 0.4999 | 0.083* | |
C19 | 0.2101 (4) | 0.6087 (10) | 0.4164 (4) | 0.081 (3) | |
H19A | 0.2472 | 0.6455 | 0.4377 | 0.098* | |
H19B | 0.2103 | 0.5188 | 0.4 | 0.098* | |
C20 | 0.1741 (5) | 0.6957 (13) | 0.3685 (5) | 0.112 (4) | |
H20A | 0.1607 | 0.6507 | 0.3286 | 0.135* | |
H20B | 0.1936 | 0.7782 | 0.3695 | 0.135* | |
C23 | 0.0411 (3) | 0.9659 (7) | 0.1732 (3) | 0.0423 (16) | |
H23 | 0.0786 | 0.9867 | 0.1968 | 0.051* | |
C24 | 0.0492 (3) | 0.9917 (7) | 0.0845 (3) | 0.0398 (16) | |
H24A | 0.0869 | 1.011 | 0.1158 | 0.06* | |
H24B | 0.0339 | 1.068 | 0.0563 | 0.06* | |
H24C | 0.0476 | 0.9109 | 0.0617 | 0.06* | |
C25 | −0.0394 (3) | 0.9425 (6) | 0.0737 (3) | 0.0408 (16) | |
H25A | −0.0577 | 0.9574 | 0.0962 | 0.061* | |
H25B | −0.0447 | 0.849 | 0.0596 | 0.061* | |
H25C | −0.0546 | 1.0031 | 0.0383 | 0.061* | |
N1 | 0.0182 (2) | 0.9694 (5) | 0.1138 (2) | 0.0317 (12) | |
Na1 | 0.05894 (11) | 0.8688 (3) | 0.30354 (12) | 0.0485 (7) | |
O1 | 0.1100 (2) | 1.0542 (6) | 0.3483 (3) | 0.0744 (17) | |
O2 | 0.1294 (2) | 0.7314 (6) | 0.3744 (3) | 0.0757 (18) | |
O3 | 0.01874 (19) | 0.9381 (4) | 0.2015 (2) | 0.0431 (11) | |
O4 | 0 | 0.6850 (7) | 0.25 | 0.061 (2) | |
C21 | 0.0153 (4) | 0.5972 (8) | 0.2171 (5) | 0.080 (3) | |
H21A | −0.0079 | 0.6157 | 0.1727 | 0.096* | |
H21B | 0.0532 | 0.6163 | 0.2295 | 0.096* | |
C22 | 0.0109 (9) | 0.4696 (10) | 0.2273 (8) | 0.227 (11) | |
H22A | 0.0464 | 0.424 | 0.2462 | 0.272* | |
H22B | −0.0148 | 0.423 | 0.1886 | 0.272* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.014 (3) | 0.049 (4) | 0.010 (3) | 0.001 (2) | 0.004 (2) | −0.005 (2) |
C2 | 0.026 (3) | 0.048 (4) | 0.021 (3) | −0.008 (3) | 0.011 (3) | −0.011 (3) |
C3 | 0.020 (3) | 0.071 (5) | 0.021 (3) | −0.013 (3) | 0.009 (3) | −0.012 (3) |
C4 | 0.017 (3) | 0.073 (5) | 0.011 (3) | 0.005 (3) | 0.001 (3) | 0.004 (3) |
C5 | 0.026 (3) | 0.048 (4) | 0.021 (3) | 0.006 (3) | 0.010 (3) | 0.006 (3) |
C6 | 0.014 (3) | 0.045 (4) | 0.012 (3) | 0.006 (2) | 0.003 (2) | −0.005 (2) |
C7 | 0.013 (3) | 0.044 (3) | 0.015 (3) | −0.002 (2) | 0.006 (2) | −0.005 (2) |
C8 | 0.022 (3) | 0.055 (4) | 0.022 (3) | −0.006 (3) | 0.011 (3) | −0.010 (3) |
C9 | 0.013 (3) | 0.073 (5) | 0.019 (3) | −0.009 (3) | 0.003 (3) | −0.018 (3) |
C10 | 0.016 (3) | 0.075 (5) | 0.014 (3) | 0.010 (3) | 0.001 (3) | −0.007 (3) |
C11 | 0.018 (3) | 0.055 (4) | 0.018 (3) | 0.007 (3) | 0.007 (3) | −0.002 (3) |
C12 | 0.013 (3) | 0.051 (4) | 0.016 (3) | 0.002 (2) | 0.006 (2) | −0.006 (3) |
Cl1 | 0.0403 (9) | 0.0505 (10) | 0.0307 (9) | −0.0171 (7) | 0.0136 (7) | −0.0104 (7) |
Cl2 | 0.0358 (9) | 0.0544 (10) | 0.0291 (9) | 0.0132 (8) | 0.0057 (7) | 0.0141 (7) |
Cl3 | 0.0338 (9) | 0.0593 (11) | 0.0357 (9) | −0.0211 (8) | 0.0127 (8) | −0.0123 (8) |
Cl4 | 0.0278 (8) | 0.0548 (10) | 0.0284 (9) | 0.0184 (7) | 0.0100 (7) | 0.0074 (7) |
Fe1 | 0.0155 (4) | 0.0280 (4) | 0.0147 (4) | 0.0012 (3) | 0.0056 (3) | −0.0010 (3) |
S1 | 0.0184 (7) | 0.0303 (7) | 0.0161 (7) | −0.0007 (5) | 0.0063 (6) | −0.0019 (6) |
S2 | 0.0203 (7) | 0.0322 (7) | 0.0187 (7) | 0.0009 (6) | 0.0041 (6) | 0.0020 (6) |
S3 | 0.0206 (7) | 0.0329 (8) | 0.0195 (7) | −0.0050 (6) | 0.0059 (6) | −0.0009 (6) |
S4 | 0.0163 (7) | 0.0303 (8) | 0.0179 (7) | 0.0036 (5) | 0.0057 (6) | −0.0008 (6) |
C13 | 0.132 (10) | 0.066 (7) | 0.118 (10) | −0.026 (7) | 0.066 (8) | −0.010 (6) |
C14 | 0.221 (19) | 0.094 (10) | 0.165 (16) | −0.054 (11) | 0.127 (15) | −0.058 (10) |
C15 | 0.045 (5) | 0.109 (8) | 0.082 (7) | −0.018 (5) | 0.039 (5) | −0.006 (6) |
C16 | 0.118 (11) | 0.127 (12) | 0.143 (13) | −0.065 (9) | 0.085 (10) | −0.055 (10) |
C17 | 0.073 (6) | 0.129 (9) | 0.046 (5) | 0.035 (6) | 0.032 (5) | 0.030 (5) |
C18 | 0.067 (6) | 0.075 (6) | 0.054 (5) | −0.008 (5) | 0.023 (5) | −0.004 (4) |
C19 | 0.073 (7) | 0.091 (7) | 0.061 (6) | −0.017 (5) | 0.022 (5) | −0.006 (5) |
C20 | 0.114 (9) | 0.175 (12) | 0.091 (8) | 0.075 (9) | 0.084 (8) | 0.061 (8) |
C23 | 0.048 (4) | 0.050 (4) | 0.027 (4) | −0.001 (3) | 0.019 (3) | 0.002 (3) |
C24 | 0.045 (4) | 0.044 (4) | 0.040 (4) | −0.001 (3) | 0.029 (3) | 0.002 (3) |
C25 | 0.050 (4) | 0.039 (4) | 0.036 (4) | −0.012 (3) | 0.024 (3) | −0.010 (3) |
N1 | 0.042 (3) | 0.035 (3) | 0.028 (3) | −0.001 (2) | 0.024 (3) | −0.002 (2) |
Na1 | 0.0597 (18) | 0.0594 (17) | 0.0355 (16) | 0.0062 (14) | 0.0313 (14) | 0.0059 (13) |
O1 | 0.074 (4) | 0.073 (4) | 0.075 (4) | −0.015 (3) | 0.038 (4) | −0.007 (3) |
O2 | 0.086 (4) | 0.097 (4) | 0.055 (4) | 0.029 (4) | 0.045 (3) | 0.030 (3) |
O3 | 0.054 (3) | 0.054 (3) | 0.034 (3) | −0.001 (2) | 0.032 (2) | 0.003 (2) |
O4 | 0.115 (7) | 0.047 (4) | 0.072 (5) | 0 | 0.084 (5) | 0 |
C21 | 0.129 (9) | 0.074 (6) | 0.102 (8) | 0.003 (6) | 0.105 (7) | −0.016 (5) |
C22 | 0.55 (3) | 0.060 (7) | 0.36 (2) | 0.010 (12) | 0.44 (3) | 0.004 (10) |
C1—C6 | 1.393 (8) | S4—Fe1i | 2.2296 (15) |
C1—C2 | 1.407 (8) | C13—C14 | 1.461 (16) |
C1—S1 | 1.753 (5) | C13—O1 | 1.477 (12) |
C2—C3 | 1.388 (8) | C14—C16 | 1.442 (18) |
C2—Cl1 | 1.739 (7) | C15—O1 | 1.419 (10) |
C3—C4 | 1.376 (9) | C15—C16 | 1.456 (15) |
C4—C5 | 1.374 (8) | C17—O2 | 1.425 (9) |
C5—C6 | 1.402 (7) | C17—C18 | 1.436 (11) |
C5—Cl2 | 1.745 (6) | C18—C19 | 1.473 (12) |
C6—S2 | 1.742 (5) | C19—C20 | 1.416 (12) |
C7—C12i | 1.402 (8) | C20—O2 | 1.428 (10) |
C7—C8 | 1.407 (8) | C23—O3 | 1.236 (7) |
C7—S3 | 1.746 (5) | C23—N1 | 1.303 (8) |
C8—C9 | 1.390 (9) | C24—N1 | 1.462 (7) |
C8—Cl3 | 1.727 (7) | C25—N1 | 1.458 (8) |
C9—C10i | 1.371 (9) | Na1—O1 | 2.265 (6) |
C10—C9i | 1.372 (9) | Na1—O3ii | 2.298 (5) |
C10—C11 | 1.377 (8) | Na1—O2 | 2.336 (6) |
C11—C12 | 1.403 (8) | Na1—O3 | 2.341 (5) |
C11—Cl4 | 1.739 (7) | Na1—O4 | 2.385 (6) |
C12—C7i | 1.402 (8) | Na1—Na1ii | 3.069 (5) |
C12—S4 | 1.764 (6) | O3—Na1ii | 2.298 (5) |
Fe1—S2 | 2.2101 (16) | O4—C21ii | 1.438 (7) |
Fe1—S1 | 2.2219 (15) | O4—C21 | 1.438 (7) |
Fe1—S3 | 2.2256 (15) | O4—Na1ii | 2.385 (6) |
Fe1—S4i | 2.2296 (15) | C21—C22 | 1.315 (11) |
Fe1—S4 | 2.4885 (16) | C22—C22ii | 1.593 (17) |
C6—C1—C2 | 119.2 (5) | C14—C13—O1 | 106.0 (11) |
C6—C1—S1 | 119.5 (4) | C16—C14—C13 | 108.2 (12) |
C2—C1—S1 | 121.4 (5) | O1—C15—C16 | 109.1 (9) |
C3—C2—C1 | 121.3 (6) | C14—C16—C15 | 106.8 (11) |
C3—C2—Cl1 | 118.2 (5) | O2—C17—C18 | 111.1 (7) |
C1—C2—Cl1 | 120.5 (5) | C17—C18—C19 | 105.4 (8) |
C4—C3—C2 | 119.2 (6) | C20—C19—C18 | 106.8 (8) |
C5—C4—C3 | 120.1 (6) | C19—C20—O2 | 111.0 (8) |
C4—C5—C6 | 122.0 (6) | O3—C23—N1 | 126.0 (7) |
C4—C5—Cl2 | 119.0 (5) | C23—N1—C25 | 121.0 (5) |
C6—C5—Cl2 | 119.1 (5) | C23—N1—C24 | 121.9 (6) |
C1—C6—C5 | 118.2 (5) | C25—N1—C24 | 117.0 (5) |
C1—C6—S2 | 119.3 (4) | O1—Na1—O3ii | 98.5 (2) |
C5—C6—S2 | 122.5 (5) | O1—Na1—O2 | 90.4 (3) |
C12i—C7—C8 | 117.9 (5) | O3ii—Na1—O2 | 130.9 (2) |
C12i—C7—S3 | 120.5 (4) | O1—Na1—O3 | 97.9 (2) |
C8—C7—S3 | 121.6 (5) | O3ii—Na1—O3 | 87.03 (19) |
C9—C8—C7 | 120.7 (6) | O2—Na1—O3 | 139.6 (2) |
C9—C8—Cl3 | 118.9 (5) | O1—Na1—O4 | 175.4 (2) |
C7—C8—Cl3 | 120.4 (5) | O3ii—Na1—O4 | 79.00 (16) |
C10i—C9—C8 | 120.8 (6) | O2—Na1—O4 | 94.2 (2) |
C9i—C10—C11 | 119.7 (6) | O3—Na1—O4 | 78.16 (15) |
C10—C11—C12 | 120.7 (6) | O1—Na1—Na1ii | 125.53 (17) |
C10—C11—Cl4 | 119.2 (5) | O3ii—Na1—Na1ii | 49.18 (13) |
C12—C11—Cl4 | 120.1 (5) | O2—Na1—Na1ii | 143.93 (18) |
C11—C12—C7i | 120.1 (5) | O3—Na1—Na1ii | 47.98 (13) |
C11—C12—S4 | 121.2 (5) | O4—Na1—Na1ii | 49.97 (12) |
C7i—C12—S4 | 118.7 (4) | C15—O1—C13 | 107.9 (7) |
S2—Fe1—S1 | 89.09 (6) | C15—O1—Na1 | 134.7 (6) |
S2—Fe1—S3 | 88.13 (6) | C13—O1—Na1 | 116.8 (6) |
S1—Fe1—S3 | 158.23 (7) | C17—O2—C20 | 105.1 (6) |
S2—Fe1—S4i | 163.07 (7) | C17—O2—Na1 | 132.0 (5) |
S1—Fe1—S4i | 86.93 (6) | C20—O2—Na1 | 122.6 (5) |
S3—Fe1—S4i | 89.48 (6) | C23—O3—Na1ii | 147.1 (4) |
S2—Fe1—S4 | 97.79 (6) | C23—O3—Na1 | 128.0 (4) |
S1—Fe1—S4 | 102.52 (6) | Na1ii—O3—Na1 | 82.83 (18) |
S3—Fe1—S4 | 99.25 (6) | C21ii—O4—C21 | 105.3 (8) |
S4i—Fe1—S4 | 99.13 (5) | C21ii—O4—Na1ii | 116.9 (4) |
C1—S1—Fe1 | 104.4 (2) | C21—O4—Na1ii | 118.5 (4) |
C6—S2—Fe1 | 104.9 (2) | C21ii—O4—Na1 | 118.5 (4) |
C7—S3—Fe1 | 105.5 (2) | C21—O4—Na1 | 116.9 (4) |
C12—S4—Fe1i | 105.7 (2) | Na1ii—O4—Na1 | 80.1 (2) |
C12—S4—Fe1 | 100.46 (18) | C22—C21—O4 | 112.1 (7) |
Fe1i—S4—Fe1 | 80.87 (5) | C21—C22—C22ii | 105.3 (5) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···Cl2iii | 0.95 | 2.86 | 3.645 (6) | 141 |
C16—H16A···Cl3iv | 0.99 | 2.96 | 3.836 (15) | 148 |
C23—H23···Cl2v | 0.95 | 2.92 | 3.787 (7) | 152 |
C25—H25B···S4i | 0.98 | 2.79 | 3.744 (6) | 165 |
C25—H25C···S3v | 0.98 | 2.98 | 3.711 (7) | 132 |
Symmetry codes: (i) −x, −y+1, −z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x, y+1, −z+1/2; (v) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···Cl2i | 0.95 | 2.86 | 3.645 (6) | 141.0 |
C16—H16A···Cl3ii | 0.99 | 2.96 | 3.836 (15) | 148.4 |
C23—H23···Cl2iii | 0.95 | 2.92 | 3.787 (7) | 152.2 |
C25—H25B···S4iv | 0.98 | 2.79 | 3.744 (6) | 165.3 |
C25—H25C···S3iii | 0.98 | 2.98 | 3.711 (7) | 132.0 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x, y+1, −z+1/2; (iii) x, y+1, z; (iv) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Na2(C3H7NO)2(C4H8O)5][Fe2(C6H2Cl2S2)4] |
Mr | 1500.77 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 29.063 (2), 9.9393 (6), 25.645 (3) |
β (°) | 121.609 (3) |
V (Å3) | 6309.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.19 × 0.12 × 0.02 |
Data collection | |
Diffractometer | Bruker Kappa APEXII |
Absorption correction | Multi-scan (SADABS; Bruker, 2009) |
Tmin, Tmax | 0.81, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43114, 5765, 3785 |
Rint | 0.101 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.062, 0.169, 1.04 |
No. of reflections | 5762 |
No. of parameters | 359 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0854P)2 + 20.9273P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.26, −0.46 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS2013 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2008).
References
Amo-Ochoa, P., Delgado, E., Gómez-García, C. J., Hernández, D., Hernández, E., Martin, A. & Zamora, F. (2013). Inorg. Chem. 52, 5943–5950. CAS PubMed Google Scholar
Benmansour, S., Delgado, E., Gómez-García, C. J., Hernández, D., Hernández, E., Martin, A., Perles, J. & Zamora, F. (2015). Inorg. Chem. 54, 2243–2252. CSD CrossRef CAS PubMed Google Scholar
Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cerdeira, A. C., Simão, D., Santos, I. C., Machado, A., Pereira, L. C. J., Waerenborgh, J. C., Henriques, R. T. & Almeida, M. (2008). Inorg. Chim. Acta, 361, 3836–3841. CSD CrossRef CAS Google Scholar
Chen, X., Lingam, H. K., Meyers, E. A. & Shore, S. G. (2012). J. Organomet. Chem. 721–722, 137–143. CSD CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Raja, D.-S., Luo, J.-H., Yeh, C.-T., Jiang, Y.-C., Hsu, K.-F. & Lin, C.-H. (2014). CrystEngComm, 16, 1985–1994. CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sproules, S. & Wieghardt, K. (2010). Coord. Chem. Rev. 254, 1358–1382. CrossRef CAS Google Scholar
Thirumurugan, A., Tan, J.-C. & Cheetham, A. K. (2010). Cryst. Growth Des. 10, 1736–1741. CrossRef CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.