Crystal structure of tetra­aqua­(5,5′-dimethyl-2,2′-bipyridyl-κ2N,N′)iron(II) sulfate

Belamri, Y.; Setifi, F.; Francuski, B.M.; Novaković, S.B.; Zouaoui, S.

doi:10.1107/S1600536814024982

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages 544-546

doi:10.1107/S1600536814024982

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Crystal structure of tetraaqua(5,5′-dimethyl-2,2′-bipyridyl-κ²N,N′)iron(II) sulfate

Yamine Belamri,^a Fatima Setifi,^a ^* Bojana M. Francuski,^b Sladjana B. Novaković ^b and Setifi Zouaoui ^c,^d

^aLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas Sétif 1, Sétif 19000, Algeria, ^bVinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, PO Box 522, University of Belgrade, 11001 Belgrade, Serbia, ^cDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955-Skikda, BP 26, Route d'El-Hadaiek, Skikda 21000, Algeria, and ^dUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Constantine 1, Constantine 25000, Algeria
^*Correspondence e-mail: setifi_zouaoui@yahoo.fr

Edited by A. Van der Lee, Université de Montpellier II, France (Received 31 October 2014; accepted 13 November 2014; online 21 November 2014)

In the title compound, [Fe(C₁₂H₁₂N₂)(H₂O)₄]SO₄, the central Fe^II ion is coordinated by two N atoms from the 5,5′-dimethyl-2,2′-bipyridine ligand and four water O atoms in a distorted octahedral geometry. The Fe—O coordination bond lengths vary from 2.080 (3) to 2.110 (3) Å, while the two Fe—N coordination bonds have practically identical lengths [2.175 (3) and 2.177 (3) Å]. The chelating N—Fe—N angle of 75.6 (1)° shows the largest deviation from an ideal octahedral geometry; the other coordination angles deviate from ideal values by 0.1 (1) to 9.1 (1)°. O—H⋯O hydrogen bonding between the four aqua ligands of the cationic complex and four O-atom acceptors of the anion leads to the formation of layers parallel to the ab plane. Neighbouring layers further interact by means of C—H⋯O and π–π interactions involving the laterally positioned bipyridine rings. The perpendicular distance between π–π interacting rings is 3.365 (2) Å, with a centroid–centroid distance of 3.702 (3) Å.

Keywords: crystal structure; 5,5′-dimethyl-2,2′-dipyridyl; tetraaquairon(II) complex; sulfate; bipyridine ligand; hydrogen bonding; π–π interactions.

CCDC reference: 1034106

1. Chemical context

The crystal structures of several complexes with general formula [M(bpy)(H₂O)₄]²⁺ comprising bipyridine derivatives as ligands have been reported previously (Boonlue et al., 2012 ; Harvey et al., 1999 ; Kwak et al., 2007 ; Suarez et al., 2013 ; Xiao et al., 2003 ; Yang, 2009 ; Yu et al., 2007 ; Zhang et al., 2008 ; Zhao & Bai, 2009 ). This is the first complex of this type with Fe^II as the central ion.

2. Structural commentary

A molecular view of complex (I), together with the atom-numbering scheme is given in Fig. 1. The crystal structure of (I) consists of the cationic complex [Fe(dmbpy)(H₂O)₄]²⁺ and a free [SO₄]²⁻ counter-ion. The Fe^II atom is in a distorted octahedral coordination environment and the equatorial plane of the octahedron is formed by a pair of nitrogen donors from the 5,5′-dimethyl-2,2′-bipyridyl ligand and two molecules of water, while the axial sites are occupied by two other water molecules. The equatorial donor atoms are nearly coplanar (r.m.s. deviation = 0.0062 Å), while the deviation of the Fe atom from the least-squares plane is somewhat larger [0.021 (2) Å]. The bipyridine chelating angle N1—Fe—N2 of 75.6 (1)° shows the most significant deviation from an ideal octahedral geometry. The other angular distortions from an ideal octahedral geometry are in the range 0.1 (1) to 9.1 (1)°. The S—O bond lengths [1.466 (3)–1.480 (3) Å] and O—S—O angles [108.8 (2)–109.9 (2)°] indicate a nearly ideal tetrahedral geometry for the anion.

Figure 1
The molecular structure of (I)

, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Hydrogen bonds are indicated by dashed lines.

3. Supramolecular features

Within the crystal packing, the charged components are connected by an extensive hydrogen-bonding network (Table 1). Each of the [Fe(dmbpy)(H₂O)₄]²⁺ cations engages all four coordinating water molecules in hydrogen bonding to four [SO₄]²⁻ anions (Fig. 2a). The anions surrounding the cationic unit are positioned at similar Fe⋯S distance of $[\simeq]$ 4.9 Å. On the other hand, each of the [SO₄]²⁻ anions appears surrounded with four cationic units, where its four O atoms engage as acceptors in bifurcated O—H⋯O hydrogen bonds towards neighbouring cations (Fig. 2a). Such a mutual arrangement leads to the formation of a two-dimensional hydrogen-bonded network parallel to the ab plane (Fig. 2b). Laterally arranged aromatic rings of the 5,5′-dimethyl-2,2′-bipyridine ligand in neighbouring layers interact by means of weak C—H⋯O and π–π interactions, forming the three-dimensional crystal packing (Table 1 and Fig. 3). The centroid–centroid distance for the latter interaction is 3.702 (3) Å.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1O5⋯O4ⁱ	0.83	1.92	2.734 (4)	165
O5—H2O5⋯O2ⁱⁱ	0.96	1.94	2.794 (4)	147
O6—H1O6⋯O1	0.94	1.90	2.820 (4)	167
O6—H2O6⋯O3ⁱⁱⁱ	0.83	1.95	2.765 (4)	165
O7—H1O7⋯O4ⁱⁱ	0.83	1.89	2.722 (4)	175
O7—H2O7⋯O2	0.82	1.89	2.697 (4)	167
O8—H1O8⋯O1ⁱⁱⁱ	0.77	1.95	2.719 (4)	175
O8—H2O8⋯O3ⁱ	0.89	1.91	2.792 (5)	174
C4—H4⋯O4^iv	0.93	2.54	3.232 (5)	132
Symmetry codes: (i) x, y+1, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
(a) O—H⋯O interactions (dashed lines) connect the cations and anions into layers parallel to the ab plane. (b) View of a single layer down the a axis.

Figure 3
(a) The bipyridine rings from neighbouring layers interact via C—H⋯O and π–π interactions. (b) Orthogonal projection of the central fragment.

4. Synthesis and crystallization

The title compound, (I), was synthesized hydrothermally from a mixture of iron(II) sulfate heptahydrate (28 mg, 0.1 mmol), 5,5′-dimethyl-2,2′-bipyridyl (18 mg, 0.1 mmol) and potassium tricyanomethanide KC(CN)₃ (26 mg, 0.2 mmol) in water–ethanol (4:1 v/v, 20 ml). The mixture was transferred to a Teflon-lined autoclave and heated at 410 K for 3 d. The autoclave was then allowed to cool to ambient temperature. Red crystals of (I) were collected by filtration, washed with water and dried in air (yield 35%).

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms bonded to C atoms were placed at geometrically calculated positions and refined using a riding model. C—H distances were fixed at 0.93 and 0.96 Å from aromatic and methyl C atoms, respectively. The U_iso(H) values were equal to 1.2 and 1.5 times U_eq of the corresponding C(sp²) and C(sp³) atoms. The H atoms of the four water molecules were initially located in a difference Fourier map. During the refinement, these H atoms were allowed to ride on their parent O atoms and also to rotate about the corresponding Fe—O bonds. The U_iso(H) values were set equal to 1.2 times U_eq of the parent O atom. The reflections (100) and (002) were excluded from the refinement because they were nearly completely obscured by the beamstop.

Table 2
Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₁₂N₂)(H₂O)₄]SO₄
M_r	408.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.5790 (7), 9.6190 (9), 18.5500 (12)
β (°)	101.527 (5)
V (Å³)	1674.7 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.07
Crystal size (mm)	0.28 × 0.14 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.792, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	14477, 4868, 3305
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.196, 1.08
No. of reflections	4867
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −1.33
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ).

Supporting information

CCDC reference: 1034106

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814024982/vn2087sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814024982/vn2087Isup2.hkl

checkCIF report

Chemical context top

Coordination compounds containing polynitrile anions as ligands are of current interest for their magnetic properties and their rich architectures and topologies (Setifi et al., 2003; Gaamoune et al., 2010; Váhovská & Potočňák, 2012; Setifi, Setifi et al., 2013; Setifi, Domasevitsch et al., 2013; Potočňák et al., 2014). Given the crucial role of these anionic ligands, we are interested in using them in combination with other chelating or bridging neutral co-ligands to explore their structural and electronic characteristics in the large field of molecular materials exhibiting the spin crossover (SCO) phenomenon. In an attempt to prepare such a complex, we obtained the title compound, [Fe(dmbpy)(H₂O)₄]SO₄, (I), where dmbpy is 5,5'-dimethyl-2,2'-bipyridyl. The crystal structures of several complexes with general formula [M(bpy)(H₂O)₄]²⁺ comprising bypiridine derivatives as ligands have been reported previously (Boonlue et al., 2012; Harvey et al., 1999; Kwak et al., 2007; Suarez et al., 2013; Xiao et al., 2003; Yang, 2009; Yu et al., 2007; Zhang et al., 2008; Zhao & Bai, 2009). This is the first complex of this type with Fe^II as the central ion.

Structural commentary top

A molecular view of complex (I), together with the atom-numbering scheme is given in Fig. 1. The crystal structure of (I) consists of the cationic complex [Fe(dmbpy)(H₂O)₄]²⁺ and a free [SO₄]^2- counter-ion. The Fe^II atom is in a distorted octahedral coordination environment and the equatorial plane of the octahedron is formed by a pair of nitrogen donors from the 5,5'-dimethyl-2,2'-bipyridyl ligand and two molecules of water, while the axial sites are occupied by two other water molecules. The equatorial donor atoms are nearly co-planar (r.m.s. deviation = 0.0062 Å), while the deviation of the Fe atom from the least-squares plane is somewhat larger [0.021 (2) Å]. The bipyridine chelating angle N1—Fe—N2 of 75.6 (1)° shows the most significant deviation from an ideal octahedral geometry. The other angular distortions from an ideal octahedral geometry are in the range 0.1 (1) to 9.1 (1)°. The S—O bond lengths [1.466 (3)–1.480 (3) Å] and O—S—O angles [108.8 (2)–109.9 (2)°] indicate a nearly ideal tetrahedral geometry for the anion.

Supramolecular features top

Within the crystal packing, the charged components are connected by an extensive hydrogen-bonding network (Table 1). Each of the [Fe(dmbpy)(H₂O)₄]²⁺ cations engages all four coordinating water molecules in hydrogen bonding to four [SO₄]^2- anions (Fig. 2a). The anions surrounding cationic unit are positioned at similar Fe···S distance of 4.9?? (su?) Å. On the other hand, each of the [SO₄]^2- anions appears surrounded with four cationic units, where its four O atoms engage as acceptors in bifurcated O—H···O hydrogen bonds towards neighbouring cations (Fig. 2a). Such a mutual arrangement leads to the formation of a two-dimensional hydrogen-bonded network parallel to the ab plane (Fig. 2b). Laterally arranged aromatic rings of the 5,5'-dimethyl-2,2'-bipyridine ligand in neighbouring layers interact by means of weak C—H···O and π–π interactions, forming the three-dimensional crystal packing (Table 1, Fig. 3). The centroid–centroid distance for the latter interaction is 3.702 (3) Å.

Synthesis and crystallization top

The title compound, (I), was synthesized hydrothermally from a mixture of iron(II) sulfate heptahydrate (28 mg, 0.1 mmol), 5,5'-dimethyl-2,2'-bipyridyl (18 mg, 0.1 mmol) and potassium tricyanomethanide KC(CN)₃ (26 mg, 0.2 mmol) in water–ethanol (4:1 v/v, 20 ml). The mixture was transferred to a Teflon-lined autoclave and heated at 410 K for 3 d. The autoclave was then allowed to cool to ambient temperature. Red crystals of (I) were collected by filtration, washed with water and dried in air (yield 35%).

Refinement details top

H atoms bonded to C atoms were placed at geometrically calculated positions and refined using a riding model. C—H distances were fixed at 0.93 and 0.96 Å from aromatic and methyl C atoms, respectively. The U_iso(H) values were equal to 1.2 and 1.5 times U_eq of the corresponding C(sp²) and C(sp³) atoms. The H atoms of the four water molecules were initially located in a difference Fourier map. During the refinement, these H atoms were allowed to ride on their parent O atoms and also to rotate about the corresponding Fe—O bonds. The U_iso(H) values were set equal to 1.2 times U_eq of the parent O atom. The reflections (100) and (002) were excluded from the refinement because they were nearly completely obscured by the beamstop.

Related literature top

For related literature, see: Boonlue et al. (2012); Gaamoune et al. (2010); Harvey et al. (1999); Kwak et al. (2007); Potočňák et al. (2014); Setifi et al. (2003); Setifi, Domasevitch, Setifi, Mach, Ng, Petříček & Dušek (2013); Setifi, Setifi, Ng, Oudahmane, El–Ghozzi & Avignant (2013); Suarez et al. (2013); Váhovská & Potočňák (2012); Xiao, –P, Shi, Zhu, –G, Xu, –R, Pang & –Q (2003); Yang (2009); Yu et al. (2007); Zhang, –Y, Nie, –J, Xu & –J (2008); Zhao, –L, Bai & –F (2009).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: CALC-OH (Nardelli, 1999).

Figures top

The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

(a) O—H···O interactions (dashed lines) connect the cations and anions into layers parallel to the ab plane. (b) View of a single layer down the a axis.

(a) The bypyridine rings from neighbouring layers interact via C—H···O and π–π interactions. (b) Orthogonal projection of the central fragment.

Tetraaqua(5,5'-dimethyl-2,2'-bipyridyl-κ²N,N')iron(II) sulfate top

Crystal data top

[Fe(C₁₂H₁₂N₂)(H₂O)₄]SO₄	F(000) = 848
M_r = 408.21	D_x = 1.619 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4857 reflections
a = 9.5790 (7) Å	θ = 2.2–29.9°
b = 9.6190 (9) Å	µ = 1.07 mm⁻¹
c = 18.5500 (12) Å	T = 293 K
β = 101.527 (5)°	Block, red
V = 1674.7 (2) Å³	0.28 × 0.14 × 0.09 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4868 independent reflections
Radiation source: fine-focus sealed tube	3305 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.117
ω–2θ scans	θ_max = 30.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
T_min = 0.792, T_max = 0.881	k = −13→13
14477 measured reflections	l = −26→26

Refinement top

Refinement on F²	223 parameters
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.065	w = 1/[σ²(F_o²) + (0.0821P)² + 2.0315P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.196	(Δ/σ)_max = 0.002
S = 1.08	Δρ_max = 0.84 e Å⁻³
4867 reflections	Δρ_min = −1.33 e Å⁻³

Crystal data top

[Fe(C₁₂H₁₂N₂)(H₂O)₄]SO₄	V = 1674.7 (2) Å³
M_r = 408.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.5790 (7) Å	µ = 1.07 mm⁻¹
b = 9.6190 (9) Å	T = 293 K
c = 18.5500 (12) Å	0.28 × 0.14 × 0.09 mm
β = 101.527 (5)°

Data collection top

Bruker APEXII CCD diffractometer	4868 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3305 reflections with I > 2σ(I)
T_min = 0.792, T_max = 0.881	R_int = 0.117
14477 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	223 parameters
wR(F²) = 0.196	H-atom parameters constrained
S = 1.08	Δρ_max = 0.84 e Å⁻³
4867 reflections	Δρ_min = −1.33 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Fe1	0.77171 (5)	0.13308 (6)	0.80535 (3)	0.02534 (17)
S1	0.75114 (9)	−0.36313 (10)	0.75262 (5)	0.0251 (2)
O3	0.6693 (3)	−0.4269 (3)	0.80282 (17)	0.0376 (7)
O1	0.6620 (3)	−0.2600 (3)	0.70522 (17)	0.0364 (7)
O2	0.8783 (3)	−0.2931 (3)	0.79546 (16)	0.0338 (6)
O4	0.7980 (3)	−0.4722 (3)	0.70641 (16)	0.0347 (6)
O5	0.8418 (3)	0.2477 (3)	0.72229 (16)	0.0361 (7)
H1O5	0.8129	0.3296	0.7171	0.043*
H2O5	0.9194	0.2065	0.7043	0.043*
O6	0.6213 (3)	0.0261 (3)	0.72705 (17)	0.0399 (7)
H1O6	0.6389	−0.0652	0.7130	0.048*
H2O6	0.5378	0.0556	0.7195	0.048*
O7	0.9191 (3)	−0.0166 (3)	0.7871 (2)	0.0489 (9)
H1O7	1.0046	−0.0016	0.7863	0.059*
H2O7	0.8929	−0.0981	0.7879	0.059*
O8	0.6224 (3)	0.2876 (4)	0.8109 (2)	0.0619 (11)
H1O8	0.5422	0.2701	0.8053	0.074*
H2O8	0.6333	0.3793	0.8107	0.074*
N1	0.7224 (4)	0.0244 (4)	0.90015 (19)	0.0340 (8)
N2	0.9173 (4)	0.2218 (4)	0.89908 (19)	0.0337 (8)
C1	0.6251 (5)	−0.0763 (5)	0.8969 (3)	0.0390 (10)
H1	0.5747	−0.1028	0.8508	0.047*
C2	0.5945 (5)	−0.1437 (5)	0.9581 (3)	0.0424 (10)
C3	0.6691 (6)	−0.0975 (5)	1.0262 (3)	0.0452 (11)
H3	0.6497	−0.1362	1.0691	0.054*
C4	0.7709 (5)	0.0043 (5)	1.0307 (2)	0.0412 (10)
H4	0.8219	0.0327	1.0763	0.049*
C5	0.7973 (4)	0.0650 (5)	0.9666 (2)	0.0341 (9)
C6	0.9054 (4)	0.1741 (4)	0.9658 (2)	0.0316 (8)
C7	0.9931 (5)	0.2257 (5)	1.0288 (2)	0.0440 (11)
H7	0.9845	0.1926	1.0748	0.053*
C8	1.0931 (5)	0.3265 (5)	1.0230 (3)	0.0436 (11)
H8	1.1512	0.3617	1.0653	0.052*
C9	1.1071 (5)	0.3750 (5)	0.9549 (3)	0.0411 (10)
C10	1.0156 (5)	0.3184 (5)	0.8947 (2)	0.0381 (9)
H10	1.0231	0.3496	0.8482	0.046*
C11	0.4852 (6)	−0.2566 (6)	0.9492 (3)	0.0594 (14)
H11A	0.3987	−0.2243	0.9184	0.089*
H11B	0.4670	−0.2817	0.9966	0.089*
H11C	0.5198	−0.3363	0.9270	0.089*
C12	1.2165 (5)	0.4814 (6)	0.9444 (3)	0.0553 (13)
H12A	1.2919	0.4366	0.9261	0.083*
H12B	1.2548	0.5249	0.9907	0.083*
H12C	1.1726	0.5504	0.9099	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0228 (3)	0.0200 (3)	0.0332 (3)	0.0001 (2)	0.00542 (19)	0.0011 (2)
S1	0.0219 (4)	0.0171 (4)	0.0374 (5)	0.0005 (3)	0.0084 (3)	0.0000 (4)
O3	0.0387 (16)	0.0309 (16)	0.0461 (17)	−0.0077 (13)	0.0152 (13)	0.0018 (13)
O1	0.0323 (15)	0.0262 (15)	0.0500 (17)	0.0075 (12)	0.0067 (12)	0.0064 (13)
O2	0.0223 (12)	0.0289 (16)	0.0499 (17)	−0.0067 (11)	0.0065 (11)	−0.0046 (13)
O4	0.0371 (15)	0.0236 (14)	0.0455 (16)	0.0052 (12)	0.0135 (12)	−0.0051 (12)
O5	0.0361 (15)	0.0212 (14)	0.0536 (18)	−0.0039 (12)	0.0151 (13)	0.0065 (13)
O6	0.0266 (14)	0.0299 (16)	0.0601 (19)	−0.0038 (12)	0.0013 (13)	−0.0091 (15)
O7	0.0286 (15)	0.0234 (15)	0.098 (3)	0.0025 (12)	0.0207 (17)	0.0004 (17)
O8	0.0270 (16)	0.0275 (17)	0.134 (4)	0.0013 (13)	0.022 (2)	0.000 (2)
N1	0.0345 (17)	0.0336 (19)	0.0351 (18)	0.0003 (15)	0.0102 (14)	0.0042 (15)
N2	0.0352 (18)	0.0307 (18)	0.0336 (17)	−0.0043 (14)	0.0033 (14)	−0.0016 (14)
C1	0.039 (2)	0.036 (2)	0.042 (2)	−0.0060 (19)	0.0111 (18)	0.0020 (19)
C2	0.045 (2)	0.035 (2)	0.051 (3)	0.001 (2)	0.017 (2)	0.009 (2)
C3	0.059 (3)	0.042 (3)	0.040 (2)	0.002 (2)	0.024 (2)	0.012 (2)
C4	0.050 (3)	0.043 (3)	0.033 (2)	0.003 (2)	0.0133 (19)	0.0032 (19)
C5	0.037 (2)	0.032 (2)	0.034 (2)	0.0064 (17)	0.0093 (16)	0.0015 (17)
C6	0.0318 (19)	0.030 (2)	0.034 (2)	0.0048 (16)	0.0078 (16)	0.0014 (16)
C7	0.049 (3)	0.047 (3)	0.034 (2)	0.002 (2)	0.0034 (19)	−0.003 (2)
C8	0.044 (2)	0.040 (3)	0.044 (3)	−0.005 (2)	0.0012 (19)	−0.012 (2)
C9	0.040 (2)	0.035 (2)	0.047 (3)	−0.0016 (19)	0.0050 (18)	−0.005 (2)
C10	0.040 (2)	0.036 (2)	0.038 (2)	−0.0048 (19)	0.0059 (17)	0.0020 (19)
C11	0.061 (3)	0.050 (3)	0.073 (4)	−0.006 (3)	0.028 (3)	0.014 (3)
C12	0.042 (3)	0.051 (3)	0.069 (3)	−0.017 (2)	0.003 (2)	−0.007 (3)

Geometric parameters (Å, º) top

Fe1—O8	2.080 (3)	C1—H1	0.9300
Fe1—O7	2.091 (3)	C2—C3	1.394 (7)
Fe1—O6	2.099 (3)	C2—C11	1.494 (7)
Fe1—O5	2.110 (3)	C3—C4	1.373 (7)
Fe1—N2	2.175 (3)	C3—H3	0.9300
Fe1—N1	2.177 (3)	C4—C5	1.392 (6)
S1—O3	1.466 (3)	C4—H4	0.9300
S1—O2	1.477 (3)	C5—C6	1.477 (6)
S1—O1	1.479 (3)	C6—C7	1.388 (6)
S1—O4	1.480 (3)	C7—C8	1.382 (7)
O5—H1O5	0.8346	C7—H7	0.9300
O5—H2O5	0.9588	C8—C9	1.379 (7)
O6—H1O6	0.9409	C8—H8	0.9300
O6—H2O6	0.8339	C9—C10	1.385 (6)
O7—H1O7	0.8346	C9—C12	1.504 (7)
O7—H2O7	0.8248	C10—H10	0.9300
O8—H1O8	0.7727	C11—H11A	0.9600
O8—H2O8	0.8889	C11—H11B	0.9600
N1—C1	1.337 (6)	C11—H11C	0.9600
N1—C5	1.354 (5)	C12—H12A	0.9600
N2—C10	1.336 (5)	C12—H12B	0.9600
N2—C6	1.345 (5)	C12—H12C	0.9600
C1—C2	1.389 (6)

O8—Fe1—O7	173.50 (16)	C2—C1—H1	117.9
O8—Fe1—O6	90.06 (14)	C1—C2—C3	116.0 (4)
O7—Fe1—O6	86.71 (13)	C1—C2—C11	120.5 (5)
O8—Fe1—O5	89.18 (14)	C3—C2—C11	123.6 (4)
O7—Fe1—O5	85.26 (13)	C4—C3—C2	120.7 (4)
O6—Fe1—O5	91.46 (12)	C4—C3—H3	119.6
O8—Fe1—N2	90.98 (15)	C2—C3—H3	119.6
O7—Fe1—N2	93.10 (14)	C3—C4—C5	119.7 (4)
O6—Fe1—N2	170.92 (13)	C3—C4—H4	120.1
O5—Fe1—N2	97.58 (13)	C5—C4—H4	120.1
O8—Fe1—N1	92.32 (15)	N1—C5—C4	120.2 (4)
O7—Fe1—N1	93.60 (14)	N1—C5—C6	116.1 (4)
O6—Fe1—N1	95.39 (13)	C4—C5—C6	123.7 (4)
O5—Fe1—N1	172.99 (13)	N2—C6—C7	120.3 (4)
N2—Fe1—N1	75.55 (14)	N2—C6—C5	116.1 (4)
O3—S1—O2	109.72 (18)	C7—C6—C5	123.6 (4)
O3—S1—O1	109.88 (18)	C8—C7—C6	119.8 (4)
O2—S1—O1	109.25 (18)	C8—C7—H7	120.1
O3—S1—O4	109.51 (18)	C6—C7—H7	120.1
O2—S1—O4	108.76 (17)	C9—C8—C7	120.3 (4)
O1—S1—O4	109.70 (18)	C9—C8—H8	119.8
Fe1—O5—H1O5	115.4	C7—C8—H8	119.8
Fe1—O5—H2O5	114.8	C8—C9—C10	116.3 (4)
H1O5—O5—H2O5	127.9	C8—C9—C12	123.1 (4)
Fe1—O6—H1O6	120.9	C10—C9—C12	120.6 (4)
Fe1—O6—H2O6	116.9	N2—C10—C9	124.4 (4)
H1O6—O6—H2O6	119.3	N2—C10—H10	117.8
Fe1—O7—H1O7	125.5	C9—C10—H10	117.8
Fe1—O7—H2O7	115.7	C2—C11—H11A	109.5
H1O7—O7—H2O7	118.0	C2—C11—H11B	109.5
Fe1—O8—H1O8	120.9	H11A—C11—H11B	109.5
Fe1—O8—H2O8	128.8	C2—C11—H11C	109.5
H1O8—O8—H2O8	109.3	H11A—C11—H11C	109.5
C1—N1—C5	119.2 (4)	H11B—C11—H11C	109.5
C1—N1—Fe1	125.0 (3)	C9—C12—H12A	109.5
C5—N1—Fe1	115.8 (3)	C9—C12—H12B	109.5
C10—N2—C6	118.9 (4)	H12A—C12—H12B	109.5
C10—N2—Fe1	124.9 (3)	C9—C12—H12C	109.5
C6—N2—Fe1	116.3 (3)	H12A—C12—H12C	109.5
N1—C1—C2	124.1 (4)	H12B—C12—H12C	109.5
N1—C1—H1	117.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O4ⁱ	0.83	1.92	2.734 (4)	165
O5—H2O5···O2ⁱⁱ	0.96	1.94	2.794 (4)	147
O6—H1O6···O1	0.94	1.90	2.820 (4)	167
O6—H2O6···O3ⁱⁱⁱ	0.83	1.95	2.765 (4)	165
O7—H1O7···O4ⁱⁱ	0.83	1.89	2.722 (4)	175
O7—H2O7···O2	0.82	1.89	2.697 (4)	167
O8—H1O8···O1ⁱⁱⁱ	0.77	1.95	2.719 (4)	175
O8—H2O8···O3ⁱ	0.89	1.91	2.792 (5)	174
C4—H4···O4^iv	0.93	2.54	3.232 (5)	132

Symmetry codes: (i) x, y+1, z; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y−1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1O5···O4ⁱ	0.83	1.92	2.734 (4)	165
O5—H2O5···O2ⁱⁱ	0.96	1.94	2.794 (4)	147
O6—H1O6···O1	0.94	1.90	2.820 (4)	167
O6—H2O6···O3ⁱⁱⁱ	0.83	1.95	2.765 (4)	165
O7—H1O7···O4ⁱⁱ	0.83	1.89	2.722 (4)	175
O7—H2O7···O2	0.82	1.89	2.697 (4)	167
O8—H1O8···O1ⁱⁱⁱ	0.77	1.95	2.719 (4)	175
O8—H2O8···O3ⁱ	0.89	1.91	2.792 (5)	174
C4—H4···O4^iv	0.93	2.54	3.232 (5)	132

Symmetry codes: (i) x, y+1, z; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+3/2; (iv) x, −y−1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₁₂N₂)(H₂O)₄]SO₄
M_r	408.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	9.5790 (7), 9.6190 (9), 18.5500 (12)
β (°)	101.527 (5)
V (Å³)	1674.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.28 × 0.14 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.792, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	14477, 4868, 3305
R_int	0.117
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.196, 1.08
No. of reflections	4867
No. of parameters	223
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −1.33

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006), CALC-OH (Nardelli, 1999).

Acknowledgements

The authors acknowledge the Algerian Ministry of Higher Education and Scientific Research, the Algerian Directorate General for Scientific Research and Technological Development and Ferhat Abbas Sétif 1 University for financial support. The Ministry of Education and Science of the Republic of Serbia is also thanked for support of the work of BMF and SBN (project Nos. 172014 and 172035).

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