Crystal structure of high-spin tetra­aqua­bis­(2-chloro­pyrazine-κN4)iron(II) bis­(4-methyl­benzene­sulfonate)

Golub, B.O.; Shylin, S.I.; Dechert, S.; Malysheva, M.L.; Gural`skiy, I.A.

doi:10.1107/S2056989015010713

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ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages 776-778

doi:10.1107/S2056989015010713

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Crystal structure of high-spin tetraaquabis(2-chloropyrazine-κN⁴)iron(II) bis(4-methylbenzenesulfonate)

Bohdan O. Golub,^a ^* Sergii I. Shylin,^a Sebastian Dechert,^b Maria L. Malysheva ^a and Il`ya A. Gural`skiy ^a

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska st. 64/13, Kyiv 01601, Ukraine, and ^bInstitute of Inorganic Chemistry, Georg-August-University Göttingen, Tammannstrasse 4, Göttingen D-37077, Germany
^*Correspondence e-mail: bohdan.golub.knu@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 28 May 2015; accepted 3 June 2015; online 13 June 2015)

The title salt, [Fe^II(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂, contains a complex cation with point group symmetry 2/m. The high-spin Fe^II cation is hexacoordinated by four symmetry-related water and two N-bound 2-chloropyrazine molecules in a trans arrangement, forming a distorted FeN₂O₄ octahedron. The three-dimensional supramolecular structure is supported by intermolecular O—H⋯O hydrogen bonds between the complex cations and tosylate anions, and additional π–π interactions between benzene and pyrazine rings. The methyl H atoms of the tosylate anion are equally disordered over two positions.

Keywords: crystal structure; iron(II) complex; 2-chloropyrazine; hydrogen bonding; π–π contacts.

CCDC reference: 1404715

1. Chemical context

Transition metal complexes containing pyrazine or substituted pyrazines as ligands are of current interest due to their supramolecular arrangements and the probability of being spin-crossover compounds. Spin crossover, sometimes referred to as a spin transition or a spin equilibrium behaviour, is a phenomenon that occurs in some metal complexes wherein the spin state of a compound changes via influence of external stimuli such as temperature, pressure, light irradiation, magnetic field or guest effects (Gütlich & Goodwin, 2004 ). As a result of the appearance of such features as thermochromic effects, magnetic susceptibility changes, changes of cell volume, etc. that accompany the molecular switching between high-spin and low-spin states, they can be applied in the development of micro-thermometers and photonic devices (Gural'skiy et al., 2012 ).

Aromatic ligands bearing two or more N atoms are known for their ability to form different coordination polymers and molecular complexes. Thus, a number of mononuclear high-spin Fe^II complexes with substituted pyrazines have been reported recently (Shylin et al., 2015 ). These heterocyclic ligands are also known for their ability to create three-dimensional metal-organic framework structures, so called analogues of Hofmann clathrates with general formula {Fe(L)_x[M_y(CN)_z]}_∞ where M = Ni, Pd, Pt, etc. Series of thiocyanato coordination polymers [M(NCS)₂L₂]_∞ (with M = Mn, Fe, Co, Ni, and L = pyrazine) in which the small-sized thiocyanate anions are terminally N-bound and therefore not involved in any magnetic exchange interactions are also known (Wriedt & Näther, 2011 ). Although 2-chloropyrazine could possess a N,N′-manner of coordination, it is frequently found to act as a monodentate ligand due to the bulky chlorine atom being in direct proximity to one of the nitrogen atoms (Wöhlert & Näther, 2013 ).

In this paper, we report on the crystal structure of [Fe^II(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂ containing a cationic iron(II) complex with 2-chloropyrazine and aqua ligands, and tosylate as an anion.

2. Structural commentary

The structure of the title compound consists of a complex cation [Fe(2-chloropyrazine)₂(H₂O)₄]²⁺ and two tosylate anions. The Fe^II atom, located on a special position with site symmetry 2/m, is sixfold coordinated by two N atoms of two symmetry-related 2-chloropyrazine ligands occupying the axial positions and four O atoms of four H₂O molecules forming the equatorial plane (Fig. 1). The distances between Fe^II and the O atoms [2.1004 (14) Å] of the H₂O molecules are significantly shorter than those between Fe^II and N [2.200 (2) Å] atoms of the two 2-chloropyrazine ligands, hence the resulting FeO₄N₂ octahedron is distorted. The metal-to-ligand distances clearly signalize the high-spin nature of the complex described in here (Shylin et al., 2015). Similar structural features have been reported for other related compounds (Shylin et al., 2013 ). The angles between the coordinating O atoms [O1ⁱ—Fe1—O1ⁱⁱⁱ = 90.83 (11)°; for symmetry codes see caption to Fig. 1], and coordinating N and O atoms [O1ⁱⁱ—Fe1—N1 = 90.68 (5)°] indicate only a small angular distortion.

Figure 1
The structure of the cationic and anionic components in the title salt. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) 1 − x, −y, 1 − z; (ii) 1 − x, y, 1 − z; (iii) x, −y, z; (iv) x, 1 − y, z; (v) 1 − x, −1 + y, 1 − z.]

3. Supramolecular features

In the title compound, the crystal packing is stabilized by O1—H1A⋯O2 and O1—H1B⋯O3ⁱ hydrogen bonds (Table 1) between the complex cations and the counter-anions (Figs. 1 and 2). Only two O atoms of the tosylate anion are involved in hydrogen bonding. Additional π –π stacking interactions (for numerical details, see: Table 2) between the pyrazine and benzene rings of the tosylate anion contribute to the stabilization (Fritsky et al., 2004 ) of the three-dimensional network (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82 (2)	1.91 (2)	2.7238 (19)	171 (4)
O1—H1B⋯O3ⁱ	0.81 (2)	1.95 (2)	2.7624 (19)	177 (3)
Symmetry code: (i) -x+1, y, -z+2.

Table 2
Geometric parameters of π–π stacking (Å, °)

centroid (2-chloropyrazine)—centroid (tosylate anion)	3.7098 (1)
centroid (2-chloropyrazine)—centroid (tosylate anion)—centroid (2-chloropyrazine)	130.283 (1)

Figure 2
The crystal structure of the title compound, showing hydrogen bonds as dashed cyan lines and π–π contacts as green lines. Colour key: orange Fe, yellow S, blue N, grey C, green Cl, red O and white H.

4. Synthesis and crystallization

Crystals of the title compound were obtained by adding 2-chloropyrazine (0.046 g, 0.4 mmol) to Fe(OTs)₂·6H₂O (0.096 g, 0.2 mmol) (OTs = p-toluenesulfonate) and ascorbic acid (0.001 g) in water (5 ml). After seven days this yielded colourless blocks of the title compound that were collected, washed with water and dried in air. Yield 0.090 g (64%).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All non-water H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.95 Å for aromatic and 0.98 Å for CH₃ hydrogen atoms. Because of the symmetry of the complete complex cation, methyl H atoms were modelled as equally disordered over two sets of sites. The H atoms of the water molecule were located from a difference Fourier map and were modelled with a common isotropic displacement parameter fixed at 0.08 Å². The O—H bonds lengths were constrained to 0.82 Å. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms.

Table 3
Experimental details

Crystal data
Chemical formula	[Fe(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂
M_r	699.35
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	133
a, b, c (Å)	30.691 (3), 6.7321 (3), 6.9435 (6)
β (°)	99.811 (7)
V (Å³)	1413.63 (19)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.93
Crystal size (mm)	0.26 × 0.14 × 0.06

Data collection
Diffractometer	Stoe IPDS II
Absorption correction	Numerical (X-RED; Stoe & Cie, 2002 )
T_min, T_max	0.697, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	9102, 1630, 1380
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.00
No. of reflections	1630
No. of parameters	126
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.36
Computer programs: X-AREA and X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1404715

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015010713/wm5168sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015010713/wm5168Isup2.hkl

checkCIF report

Chemical context top

Transition metal complexes containing pyrazine or substituted pyrazines as ligands are of current interest due to their supramolecular arrangements and the probability of being spin-crossover compounds. Spin crossover, sometimes referred to as a spin transition or a spin equilibrium behaviour, is a phenomenon that occurs in some metal complexes wherein the spin state of a compound changes via influence of external stimuli such as temperature, pressure, light irradiation, magnetic field or guest effect (Gütlich & Goodwin, 2004). As a result of the appearance of such features as thermochromic effects, magnetic susceptibility changes, changes of cell volume, etc. that accompany the molecular switching between high-spin and low-spin states, they can be applied in the development of micro-thermometers and photonic devices (Gural'skiy et al., 2012).

Aromatic ligands bearing two or more N atoms are known for their ability to form different coordination polymers and molecular complexes. Thus, a number of mononuclear high-spin Fe^II complexes with substituted pyrazines have been reported recently (Shylin et al., 2015). These heterocyclic ligands are also known for their ability to create three-dimensional metal-organic framework structures, so called analogues of Hofmann clathrates with general formula {Fe(L)_x[M_y(CN)_z]}_∞ where M = Ni, Pd, Pt, etc. Series of thiocyanato coordination polymers [M(NCS)₂L₂]_∞ (with M = Mn, Fe, Co, Ni, and L = pyrazine) are also known in which the small-sized thiocyanate anions are terminally N-bound and therefore not involved in any magnetic exchange interactions (Wriedt & Näther, 2011). Although 2-chloropyrazine could possess a N,N'-manner of coordination, it is frequently found to act as a monodentate ligand due to the bulky chlorine atom being in direct proximity to one of the nitrogen atoms (Wöhlert & Näther, 2013).

Structural commentary top

The structure of the title compound consists of a complex cation [Fe(2-chloropyrazine)₂(H₂O)₄]²⁺ and two tosylate anions. The Fe^II atom, located on a special position with site symmetry 2/m, is sixfold coordinated by two N atoms of two symmetry-related 2-chloropyrazine ligands occupying the axial positions and four O atoms of four H₂O molecules forming the equatorial plane (Fig. 1). The distances between Fe^II and the O atoms [2.1004 (14) Å] of the H₂O molecules are significantly shorter than those between Fe^II and N [2.200 (2) Å] atoms of the two 2-chloropyrazine ligands, hence the resulting FeO₄N₂ octahedron is slightly distorted. The metal-to-ligand distances clearly signalize the high-spin nature of the complex described in here (Shylin et al., 2015). Similar structural features have been reported for other related compounds (Shylin et al., 2013). The angles between the coordinating O atoms [O1ⁱ—Fe1—O1ⁱⁱⁱ = 90.83 (11)°; for symmetry codes see caption to Fig. 1], and coordinating N and O atoms [O1ⁱⁱ—Fe1—N1 = 90.68 (5)°] indicate only a small angular distortion.

Supramolecular features top

In the title compound, the crystal packing is stabilized by O1—H1A···O2 and O1—H1B···O3ⁱ hydrogen bonds (Table 1) between the complex cations and the counter-anions (Figs. 1 and 2). Only two O atoms of the tosylate anion are involved in hydrogen bonding. Additional π –π stacking interactions (for numerical details, see: Table 2) between the pyrazine and benzene rings of the tosylate anion contribute to the stabilization (Fritsky et al., 2004) of the three-dimensional network (Fig. 2).

Synthesis and crystallization top

Refinement top

Related literature top

For related literature, see: Fritsky et al. (2004); Gütlich & Goodwin (2004); Gural'skiy, Quintero, Abdul-Kader, Lopes, Bartual-Murgui, Salmon, Zhao, Molnar, Astruc & Bousseksou (2012); Shylin et al. (2013, 2015); Wöhlert & Näther (2013); Wriedt & Näther (2011).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of the molecular components in the title salt. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are indicated by dashed lines. [Symmetry codes: (i) 1 - x, -y, 1 - z; (ii) 1 - x, y, 1 - z; (iii) x, -y, z; (iv) x, 1 - y, z; (v) 1 - x, -1 + y, 1 - z.]
	Fig. 2. The crystal structure of the title compound, showing hydrogen bonds as dashed cyan lines and π–π contacts as green lines. Colour key: orange Fe, yellow S, blue N, grey C, green Cl, red O and white H.

Tetraaquabis(2-chloropyrazine-κN⁴)iron(II) bis(4-methylbenxenesulfonate) top

Crystal data top

[Fe(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂	F(000) = 720
M_r = 699.35	D_x = 1.643 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 30.691 (3) Å	Cell parameters from 9102 reflections
b = 6.7321 (3) Å	θ = 1.4–26.7°
c = 6.9435 (6) Å	µ = 0.93 mm⁻¹
β = 99.811 (7)°	T = 133 K
V = 1413.63 (19) Å³	Block, colourless
Z = 2	0.26 × 0.14 × 0.06 mm

Data collection top

Stoe IPDS II diffractometer	1380 reflections with I > 2σ(I)
ϕ scans and ω scans with κ offset	R_int = 0.066
Absorption correction: numerical (X-RED; Stoe & Cie, 2002)	θ_max = 26.7°, θ_min = 1.4°
T_min = 0.697, T_max = 0.925	h = −38→38
9102 measured reflections	k = −8→6
1630 independent reflections	l = −8→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0395P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
1630 reflections	Δρ_max = 0.38 e Å⁻³
126 parameters	Δρ_min = −0.35 e Å⁻³
2 restraints

Crystal data top

[Fe(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂	V = 1413.63 (19) Å³
M_r = 699.35	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 30.691 (3) Å	µ = 0.93 mm⁻¹
b = 6.7321 (3) Å	T = 133 K
c = 6.9435 (6) Å	0.26 × 0.14 × 0.06 mm
β = 99.811 (7)°

Data collection top

Stoe IPDS II diffractometer	1630 independent reflections
Absorption correction: numerical (X-RED; Stoe & Cie, 2002)	1380 reflections with I > 2σ(I)
T_min = 0.697, T_max = 0.925	R_int = 0.066
9102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	2 restraints
wR(F²) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.38 e Å⁻³
1630 reflections	Δρ_min = −0.35 e Å⁻³
126 parameters

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Fe1	0.5000	0.0000	0.5000	0.01386 (13)
Cl1	0.68495 (2)	0.0000	0.84806 (9)	0.02791 (16)
O1	0.51119 (5)	0.2190 (3)	0.7183 (2)	0.0399 (4)
N1	0.57111 (7)	0.0000	0.4870 (3)	0.0161 (4)
N2	0.66150 (7)	0.0000	0.4683 (3)	0.0206 (4)
C1	0.60191 (8)	0.0000	0.6491 (3)	0.0171 (5)
H1	0.5932	0.0000	0.7741	0.021*
C2	0.64619 (8)	0.0000	0.6350 (3)	0.0184 (5)
C3	0.58590 (8)	0.0000	0.3161 (3)	0.0192 (5)
H3	0.5652	0.0000	0.1977	0.023*
C4	0.63061 (8)	0.0000	0.3081 (3)	0.0211 (5)
H4	0.6396	0.0000	0.1839	0.025*
S1	0.41620 (2)	0.5000	0.91435 (8)	0.01630 (14)
O2	0.45581 (6)	0.5000	0.8231 (2)	0.0206 (4)
O3	0.41275 (4)	0.32011 (19)	1.02718 (16)	0.0237 (3)
C5	0.37118 (8)	0.5000	0.7189 (3)	0.0165 (5)
C6	0.32788 (8)	0.5000	0.7567 (3)	0.0223 (5)
H6	0.3226	0.5000	0.8876	0.027*
C7	0.29303 (8)	0.5000	0.6040 (4)	0.0239 (5)
H7	0.2637	0.5000	0.6308	0.029*
C8	0.29970 (8)	0.5000	0.4102 (3)	0.0205 (5)
C9	0.34283 (8)	0.5000	0.3749 (3)	0.0211 (5)
H9	0.3480	0.5000	0.2438	0.025*
C10	0.37849 (8)	0.5000	0.5263 (3)	0.0188 (5)
H10	0.4078	0.5000	0.4993	0.023*
C11	0.26090 (9)	0.5000	0.2452 (4)	0.0283 (6)
H11A	0.2351	0.4424	0.2904	0.042*	0.5
H11B	0.2681	0.4209	0.1364	0.042*	0.5
H11C	0.2542	0.6367	0.2013	0.042*	0.5
H1A	0.4925 (10)	0.299 (5)	0.740 (5)	0.080*
H1B	0.5338 (8)	0.251 (5)	0.791 (4)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0130 (2)	0.0152 (2)	0.0129 (2)	0.000	0.00075 (16)	0.000
Cl1	0.0162 (3)	0.0456 (4)	0.0203 (3)	0.000	−0.0017 (2)	0.000
O1	0.0192 (7)	0.0481 (10)	0.0481 (9)	0.0068 (7)	−0.0063 (6)	−0.0343 (7)
N1	0.0165 (10)	0.0157 (10)	0.0159 (9)	0.000	0.0021 (7)	0.000
N2	0.0182 (10)	0.0241 (11)	0.0202 (9)	0.000	0.0051 (8)	0.000
C1	0.0183 (12)	0.0194 (12)	0.0139 (10)	0.000	0.0033 (9)	0.000
C2	0.0178 (12)	0.0194 (12)	0.0168 (10)	0.000	−0.0002 (9)	0.000
C3	0.0212 (13)	0.0210 (12)	0.0155 (10)	0.000	0.0032 (9)	0.000
C4	0.0216 (13)	0.0255 (13)	0.0170 (11)	0.000	0.0054 (9)	0.000
S1	0.0149 (3)	0.0189 (3)	0.0142 (3)	0.000	−0.0001 (2)	0.000
O2	0.0143 (8)	0.0235 (9)	0.0240 (8)	0.000	0.0030 (7)	0.000
O3	0.0224 (7)	0.0263 (7)	0.0203 (6)	−0.0031 (5)	−0.0025 (5)	0.0066 (5)
C5	0.0163 (12)	0.0173 (11)	0.0155 (10)	0.000	0.0014 (9)	0.000
C6	0.0190 (13)	0.0338 (15)	0.0139 (10)	0.000	0.0025 (9)	0.000
C7	0.0138 (12)	0.0354 (15)	0.0229 (12)	0.000	0.0040 (9)	0.000
C8	0.0183 (12)	0.0234 (13)	0.0181 (11)	0.000	−0.0018 (9)	0.000
C9	0.0211 (13)	0.0268 (13)	0.0153 (11)	0.000	0.0028 (9)	0.000
C10	0.0176 (12)	0.0223 (12)	0.0171 (10)	0.000	0.0046 (9)	0.000
C11	0.0217 (13)	0.0391 (16)	0.0216 (12)	0.000	−0.0030 (10)	0.000

Geometric parameters (Å, º) top

Fe1—O1ⁱ	2.1004 (14)	S1—O2	1.4632 (17)
Fe1—O1ⁱⁱ	2.1004 (14)	S1—O3^iv	1.4560 (12)
Fe1—O1ⁱⁱⁱ	2.1004 (14)	S1—O3	1.4560 (12)
Fe1—O1	2.1004 (14)	S1—C5	1.764 (2)
Fe1—N1ⁱ	2.200 (2)	C5—C6	1.398 (3)
Fe1—N1	2.200 (2)	C5—C10	1.393 (3)
Cl1—C2	1.733 (2)	C6—H6	0.9500
O1—H1A	0.820 (18)	C6—C7	1.372 (3)
O1—H1B	0.814 (18)	C7—H7	0.9500
N1—C1	1.341 (3)	C7—C8	1.395 (3)
N1—C3	1.341 (3)	C8—C9	1.387 (3)
N2—C2	1.321 (3)	C8—C11	1.506 (3)
N2—C4	1.333 (3)	C9—H9	0.9500
C1—H1	0.9500	C9—C10	1.383 (3)
C1—C2	1.379 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—H11A	0.9800
C3—C4	1.383 (4)	C11—H11B	0.9800
C4—H4	0.9500	C11—H11C	0.9800

O1ⁱ—Fe1—O1ⁱⁱⁱ	90.83 (11)	N2—C4—H4	118.8
O1ⁱ—Fe1—O1	180.0	C3—C4—H4	118.8
O1ⁱⁱⁱ—Fe1—O1	89.17 (11)	O2—S1—C5	105.44 (10)
O1ⁱⁱⁱ—Fe1—O1ⁱⁱ	180.0	O3^iv—S1—O2	112.02 (6)
O1ⁱ—Fe1—O1ⁱⁱ	89.17 (11)	O3—S1—O2	112.02 (6)
O1ⁱⁱ—Fe1—O1	90.83 (11)	O3—S1—O3^iv	112.56 (10)
O1ⁱⁱⁱ—Fe1—N1	89.32 (5)	O3—S1—C5	107.14 (7)
O1ⁱⁱ—Fe1—N1ⁱ	89.32 (5)	O3^iv—S1—C5	107.14 (7)
O1ⁱ—Fe1—N1ⁱ	89.32 (5)	C6—C5—S1	120.03 (17)
O1ⁱⁱ—Fe1—N1	90.68 (5)	C10—C5—S1	120.37 (18)
O1—Fe1—N1	89.32 (5)	C10—C5—C6	119.6 (2)
O1ⁱ—Fe1—N1	90.68 (5)	C5—C6—H6	120.1
O1ⁱⁱⁱ—Fe1—N1ⁱ	90.68 (5)	C7—C6—C5	119.7 (2)
O1—Fe1—N1ⁱ	90.68 (5)	C7—C6—H6	120.1
N1ⁱ—Fe1—N1	180.0	C6—C7—H7	119.3
Fe1—O1—H1A	124 (3)	C6—C7—C8	121.5 (2)
Fe1—O1—H1B	131 (2)	C8—C7—H7	119.3
H1A—O1—H1B	105 (3)	C7—C8—C11	120.5 (2)
C1—N1—Fe1	121.88 (15)	C9—C8—C7	118.2 (2)
C1—N1—C3	116.5 (2)	C9—C8—C11	121.4 (2)
C3—N1—Fe1	121.60 (16)	C8—C9—H9	119.3
C2—N2—C4	115.0 (2)	C10—C9—C8	121.4 (2)
N1—C1—H1	119.9	C10—C9—H9	119.3
N1—C1—C2	120.2 (2)	C5—C10—H10	120.2
C2—C1—H1	119.9	C9—C10—C5	119.6 (2)
N2—C2—Cl1	116.93 (19)	C9—C10—H10	120.2
N2—C2—C1	124.4 (2)	C8—C11—H11A	109.5
C1—C2—Cl1	118.71 (18)	C8—C11—H11B	109.5
N1—C3—H3	119.2	C8—C11—H11C	109.5
N1—C3—C4	121.6 (2)	H11A—C11—H11B	109.5
C4—C3—H3	119.2	H11A—C11—H11C	109.5
N2—C4—C3	122.4 (2)	H11B—C11—H11C	109.5

Fe1—N1—C1—C2	180.000 (1)	O2—S1—C5—C10	0.000 (1)
Fe1—N1—C3—C4	180.000 (1)	O3^iv—S1—C5—C6	−60.51 (6)
N1—C1—C2—Cl1	180.000 (1)	O3—S1—C5—C6	60.51 (6)
N1—C1—C2—N2	0.000 (1)	O3^iv—S1—C5—C10	119.49 (6)
N1—C3—C4—N2	0.000 (1)	O3—S1—C5—C10	−119.49 (6)
C1—N1—C3—C4	0.000 (1)	C5—C6—C7—C8	0.000 (1)
C2—N2—C4—C3	0.000 (1)	C6—C5—C10—C9	0.000 (1)
C3—N1—C1—C2	0.000 (1)	C6—C7—C8—C9	0.000 (1)
C4—N2—C2—Cl1	180.000 (1)	C6—C7—C8—C11	180.000 (1)
C4—N2—C2—C1	0.000 (1)	C7—C8—C9—C10	0.000 (1)
S1—C5—C6—C7	180.000 (1)	C8—C9—C10—C5	0.000 (1)
S1—C5—C10—C9	180.000 (1)	C10—C5—C6—C7	0.000 (1)
O2—S1—C5—C6	180.000 (1)	C11—C8—C9—C10	180.000 (1)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y, −z+1; (iii) x, −y, z; (iv) x, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82 (2)	1.91 (2)	2.7238 (19)	171 (4)
O1—H1B···O3^v	0.81 (2)	1.95 (2)	2.7624 (19)	177 (3)

Symmetry code: (v) −x+1, y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.820 (18)	1.911 (19)	2.7238 (19)	171 (4)
O1—H1B···O3ⁱ	0.814 (18)	1.949 (18)	2.7624 (19)	177 (3)

Symmetry code: (i) −x+1, y, −z+2.

Geometric parameters of π–π stacking (Å, °) top

centroid (2-chloropyrazine)—centroid (tosylate anion)	3.7098 (1)
centroid (2-chloropyrazine)—centroid (tosylate anion)—centroid (2-chloropyrazine)	130.283 (1)

Experimental details

Crystal data
Chemical formula	[Fe(C₄H₃ClN₂)₂(H₂O)₄](C₇H₇O₃S)₂
M_r	699.35
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	133
a, b, c (Å)	30.691 (3), 6.7321 (3), 6.9435 (6)
β (°)	99.811 (7)
V (Å³)	1413.63 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.93
Crystal size (mm)	0.26 × 0.14 × 0.06

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Numerical (X-RED; Stoe & Cie, 2002)
T_min, T_max	0.697, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	9102, 1630, 1380
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.00
No. of reflections	1630
No. of parameters	126
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.35

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Acknowledgements

SIS and IAG acknowledge a Leonhard Euler fellowship from DAAD and the kind hospitality of Professor Franc Meyer's group. The authors also appreciate some useful comments on the manuscript from Professor Igor O. Fritsky.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Volume 71| Part 7| July 2015| Pages 776-778

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