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)]

Barrio, J.; Delgado, E.; Hernández, D.; Hernández, E.; Perles, J.; Zamora, F.

doi:10.1107/S241431461600643X

metal-organic compounds

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ISSN: 2414-3146

Volume 1| Part 4| April 2016| x160643

doi:10.1107/S241431461600643X

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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)]

Jesús Barrio,^a Esther Delgado,^a Diego Hernández,^a Elisa Hernández,^a Josefina Perles ^b ^* and Félix Zamora ^a

^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

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 20 March 2016; accepted 15 April 2016; online 22 April 2016)

The title compound, [Na₂(C₃H₇NO)₂(C₄H₈O)₅][Fe₂(C₆H₂Cl₂S₂)₄], was synthesized and its crystal structure 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 asymmetric unit 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.

Keywords: crystal structure; iron dithiolate; coordination compound; sodium compound.

CCDC reference: 1474454

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Chemical scheme

Structure description

In the title compound (Fig. 1) the [Fe^III(Cl₂-bdt)₂]⁻ anion (Cl₂-bdt is 3,6-dichloro-1,2-benzenedithiolate) forms a centrosymmetric dimer supported by two Fe^III—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 ).

Figure 1
Ellipsoid plot (at 50% probability) of the [Fe₂(S₂C₆H₂Cl₂)₄]²⁻ anion with atoms labelled.

Figure 2
Ellipsoid plot (at 50% probability) of the [Na₂(THF)₄(μ-THF)(μ-DMF)₂]²⁺ cation with non-hydrogen atoms labelled.

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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯Cl2ⁱ	0.95	2.86	3.645 (6)	141
C16—H16A⋯Cl3ⁱⁱ	0.99	2.96	3.836 (15)	148
C23—H23⋯Cl2ⁱⁱⁱ	0.95	2.92	3.787 (7)	152
C25—H25B⋯S4^iv	0.98	2.79	3.744 (6)	165
C25—H25C⋯S3ⁱⁱⁱ	0.98	2.98	3.711 (7)	132
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y+1, -z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) -x, -y+1, -z.

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 refinement 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. 2) present high displacement parameters. Alternative positions for disordered C atoms could not be located.

Table 2
Experimental details

Crystal data
Chemical formula	[Na₂(C₃H₇NO)₂(C₄H₈O)₅][Fe₂(C₆H₂Cl₂S₂)₄]
M_r	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 )
T_min, T_max	0.81, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	43114, 5765, 3785
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	1.26, −0.46
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1474454

Crystal structure: contains datablock I. DOI: 10.1107/S241431461600643X/bh4005sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461600643X/bh4005Isup2.hkl

.cif file with corrected spelling in the name of the first author. DOI: 10.1107/S241431461600643X/bh4005sup3.txt

checkCIF report

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Experimental top

Structure description top

In the title compound (Fig. 1) the [Fe^III(Cl₂-bdt)₂]^- anion (Cl₂-bdt is 3,6-dichloro-1,2-benzenedithiolate) forms a centrosymmetric dimer supported by two Fe^III—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).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: 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).

Figures top

	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.

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)] top

Crystal data top

[Na₂(C₃H₇NO)₂(C₄H₈O)₅][Fe₂(C₆H₂Cl₂S₂)₄]	F(000) = 3080
M_r = 1500.77	D_x = 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

Data collection top

Bruker Kappa APEXII diffractometer	3785 reflections with I > 2σ(I)
Radiation source: molybdenum, x-ray tube	R_int = 0.101
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
θ and φ scans	h = −34→34
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −11→11
T_min = 0.81, T_max = 0.98	l = −30→30
43114 measured reflections	5765 standard reflections every 908 min
5765 independent reflections	intensity decay: 0.0 (2)

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.169	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0854P)² + 20.9273P] where P = (F_o² + 2F_c²)/3
5762 reflections	(Δ/σ)_max < 0.001
359 parameters	Δρ_max = 1.26 e Å⁻³
2 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Na₂(C₃H₇NO)₂(C₄H₈O)₅][Fe₂(C₆H₂Cl₂S₂)₄]	V = 6309.0 (9) Å³
M_r = 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)°

Data collection top

Bruker Kappa APEXII diffractometer	3785 reflections with I > 2σ(I)
Absorption correction: multi-scan (SADABS; Bruker, 2009)	R_int = 0.101
T_min = 0.81, T_max = 0.98	5765 standard reflections every 908 min
43114 measured reflections	intensity decay: 0.0 (2)
5765 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	2 restraints
wR(F²) = 0.169	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0854P)² + 20.9273P] where P = (F_o² + 2F_c²)/3
5762 reflections	Δρ_max = 1.26 e Å⁻³
359 parameters	Δρ_min = −0.46 e Å⁻³

Special details top

Refinement. There is some disorder in atoms from the coordinated THF molecules, specially in the positions occupied by C21 and C22

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···Cl3^iv	0.99	2.96	3.836 (15)	148
C23—H23···Cl2^v	0.95	2.92	3.787 (7)	152
C25—H25B···S4ⁱ	0.98	2.79	3.744 (6)	165
C25—H25C···S3^v	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.

Hydrogen-bond geometry (Å, º) top

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···S4^iv	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]
M_r	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)
T_min, T_max	0.81, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	43114, 5765, 3785
R_int	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(F_o²) + (0.0854P)² + 20.9273P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (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

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Volume 1| Part 4| April 2016| x160643

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