Iron(II) hydrazinium sulfate

Srinivasan, K.; Govindarajan, S.; Harrison, W.T.A.

doi:10.1107/S1600536806056509

inorganic compounds

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Volume 63| Part 2| February 2007| Pages i41-i42

https://doi.org/10.1107/S1600536806056509

Iron(II) hydrazinium sulfate

Krishnan Srinivasan,^a Subbaiah Govindarajan ^a and William T. A. Harrison ^b ^*

^aDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, India, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 22 December 2006; accepted 29 December 2006; online 12 January 2007)

The title compound, poly[[dihydraziniumiron(II)]-di-μ-sulfato-κ⁴O:O′], [Fe(SO₄)₂(N₂H₅)₂]_n, contains fairly regular trans-FeN₂O₄ octahedra. The Fe atoms (site symmetry $[\overline{1}]$ ) are bridged by pairs of sulfate groups into infinite [100] chains, which are cross-linked by a network of N—H⋯O hydrogen bonds. Fe(N₂H₅)₂(SO₄)₂ is isostructural with its zinc, chromium(II) and cadmium-containing analogues.

Comment

The divalent-metal–hydrazinium sulfates of general formula M(N₂H₅)₂(SO₄)₂, where M = Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd can be readily prepared by reacting a salt of the respective metal with hydrazinium sulfate in dilute sulfuric acid (Hand & Prout, 1966 ), although this method usually results in a microcrystalline product. Recently, we described the single-crystal structure of Cd(N₂H₅)₂(SO₄)₂ (Srinivasan et al., 2006 ) and we now report the isostructural title compound, (I), Fe(N₂H₅)₂(SO₄)₂. The compounds Zn(N₂H₅)₂(SO₄)₂ (Prout & Powell, 1961 ) and Cr(N₂H₅)₂(SO₄)₂ (Parkins et al., 2001 ) also share the same stucture.

Compound (I) contains trans-FeN₂O₄ octahedra (Fig. 1), in which the N atom is part of a hydrazinium (N₂H₅⁺) cation. The Fe atoms (site symmetry $[\overline{1}]$ ) are connected by pairs of sulfate groups into infinite chains that propagate in [100]. The intra-chain Fe⋯Fe separation in (I) is equal to the a unit-cell dimension, i.e. 5.3306 (3) Å. The two distinct Fe—O bond lengths in (I) are similar (Table 1) and do not show the gross differences seen in the chromium and zinc analogues.

The iron–sulfate chains in (I) are cross-linked by N—H⋯O hydrogen bonds (Table 2), resulting in the same hydrogen-bonding network seen in the other analogues noted above. A well defined trifurcated N2—H3C⋯(O,O,O) interaction occurs (mean bond angle about H3C = 107.3°).

Figure 1
The asymmetric unit of (I) expanded to show the iron coordination (50% displacement ellipsoids; arbitrary spheres for the H atoms). Symmetry codes: (i) −x, −y, −z; (ii) x − 1, y, z; (iii) 1 − x, −y, −z.

Figure 2
Polyhedral view of a fragment of the chain structure of (I). Colour key: Fe octahedra green, S tetrahedra yellow, O pink, N blue, H grey. The H⋯O portions of the hydrogen bonds are coloured light blue.

Experimental

The reaction of hydrazine monohydrate (N₂H₄·H₂O; 0.50 g, 10 mmol) and ethyl bromoacetate (1.671 g, 10 mmol) in 5 ml of dry ethanol resulted in the formation of a white solid containing hydrazinium bromide and ethyl hydrazinoacetate, as reported earlier (Srinivasan et al., 2006). This white solid (0.236 g) was dissolved in water (30 ml) and mixed with an aqueous solution (30 ml) of FeSO₄·7H₂O (0.278 g, 1 mmol) and a few drops of conc. H₂SO₄. The resulting clear solution, with a pH of 2, was concentrated over a water bath to 20 ml and kept for crystallization at room temperature. After three days, many block-shaped light-green crystals of (I) had formed. These were recovered by filtration, washed with cold water and dried in air.

Crystal data

[Fe(SO₄)₂(N₂H₅)₂]
M_r = 314.08
Triclinic, $[P \overline 1]$
a = 5.3306 (3) Å
b = 5.8205 (3) Å
c = 7.3835 (4) Å
α = 92.034 (3)°
β = 103.313 (3)°
γ = 99.237 (3)°
V = 219.41 (2) Å³
Z = 1
D_x = 2.377 Mg m⁻³
Mo Kα radiation
μ = 2.23 mm⁻¹
T = 120 (2) K
Lath, pale green
0.05 × 0.02 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.897, T_max = 0.978
3957 measured reflections
1004 independent reflections
911 reflections with I > 2σ(I)
R_int = 0.043
θ_max = 28.0°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.076
S = 1.12
1004 reflections
90 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0127P)² + 0.6538P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—O1	2.109 (2)
Fe1—O2ⁱ	2.147 (2)
Fe1—N1	2.184 (2)

S1—O1—Fe1	142.94 (13)
S1—O2—Fe1ⁱⁱ	128.85 (12)
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱⁱⁱ	0.82 (4)	2.37 (4)	3.070 (3)	143 (3)
N1—H1B⋯O4^iv	0.82 (4)	2.12 (4)	2.867 (3)	151 (4)
N2—H2A⋯O4ⁱⁱⁱ	0.88 (4)	1.96 (4)	2.799 (3)	160 (4)
N2—H2B⋯O3	0.80 (4)	2.02 (4)	2.769 (4)	156 (4)
N2—H2C⋯O2^v	0.82 (4)	2.51 (4)	2.849 (3)	106 (3)
N2—H2C⋯O2^iv	0.82 (4)	2.32 (4)	3.011 (4)	141 (4)
N2—H2C⋯O1^vi	0.82 (4)	2.45 (4)	3.073 (3)	133 (4)
Symmetry codes: (iii) -x+1, -y, -z+1; (iv) x-1, y-1, z; (v) -x+1, -y, -z; (vi) x, y-1, z.

The H atoms were located in difference maps and their positions and U_iso values were freely refined.

Data collection: Collect (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) & SORTAV (Blessing 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806056509/br2024sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806056509/br2024Isup2.hkl

Computing details top

Data collection: Collect (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) & SORTAV (Blessing 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

Fe(N₂H₅)₂(SO₄)₂	Z = 1
M_r = 314.08	F(000) = 160
Triclinic, P1	D_x = 2.377 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3306 (3) Å	Cell parameters from 984 reflections
b = 5.8205 (3) Å	θ = 2.9–27.5°
c = 7.3835 (4) Å	µ = 2.23 mm⁻¹
α = 92.034 (3)°	T = 120 K
β = 103.313 (3)°	Lath, pale green
γ = 99.237 (3)°	0.05 × 0.02 × 0.01 mm
V = 219.41 (2) Å³

Data collection top

Nonius KappaCCD diffractometer	1004 independent reflections
Radiation source: fine-focus sealed tube	911 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω and φ scans	θ_max = 28.0°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −6→6
T_min = 0.897, T_max = 0.978	k = −7→7
3957 measured reflections	l = −9→9

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	All H-atom parameters refined
S = 1.12	w = 1/[σ²(F_o²) + (0.0127P)² + 0.6538P] where P = (F_o² + 2F_c²)/3
1004 reflections	(Δ/σ)_max < 0.001
90 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Fe1	0.0000	0.0000	0.0000	0.01099 (17)
S1	0.63302 (12)	0.24660 (11)	0.21899 (9)	0.00929 (18)
O1	0.3609 (4)	0.2280 (4)	0.0944 (3)	0.0142 (4)
O2	0.8223 (4)	0.2674 (3)	0.1024 (3)	0.0131 (4)
O3	0.6559 (4)	0.0411 (3)	0.3285 (3)	0.0130 (4)
O4	0.6932 (4)	0.4606 (3)	0.3470 (3)	0.0122 (4)
N1	0.0660 (5)	−0.1738 (5)	0.2599 (4)	0.0117 (5)
H1A	0.129 (7)	−0.079 (7)	0.350 (5)	0.017 (9)*
H1B	−0.077 (8)	−0.249 (7)	0.265 (5)	0.022 (10)*
N2	0.2501 (5)	−0.3342 (5)	0.2854 (4)	0.0144 (5)
H2A	0.281 (7)	−0.403 (7)	0.390 (6)	0.021 (10)*
H2B	0.391 (8)	−0.256 (7)	0.293 (6)	0.023 (10)*
H2C	0.188 (8)	−0.442 (7)	0.204 (6)	0.026 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0100 (3)	0.0120 (3)	0.0110 (3)	0.0012 (2)	0.0031 (2)	0.0007 (2)
S1	0.0085 (3)	0.0102 (3)	0.0094 (3)	0.0007 (2)	0.0033 (3)	0.0001 (3)
O1	0.0095 (9)	0.0156 (10)	0.0162 (10)	0.0006 (8)	0.0014 (8)	0.0011 (8)
O2	0.0136 (10)	0.0131 (10)	0.0141 (10)	0.0020 (8)	0.0063 (8)	0.0013 (8)
O3	0.0157 (10)	0.0118 (10)	0.0126 (10)	0.0017 (8)	0.0058 (8)	0.0024 (8)
O4	0.0151 (10)	0.0112 (10)	0.0105 (10)	0.0009 (8)	0.0048 (8)	−0.0015 (8)
N1	0.0079 (11)	0.0138 (12)	0.0136 (12)	0.0014 (10)	0.0033 (10)	0.0006 (10)
N2	0.0151 (13)	0.0145 (13)	0.0133 (13)	0.0034 (11)	0.0023 (11)	0.0012 (11)

Geometric parameters (Å, º) top

Fe1—O1	2.109 (2)	S1—O1	1.513 (2)
Fe1—O1ⁱ	2.109 (2)	O2—Fe1^iv	2.147 (2)
Fe1—O2ⁱⁱ	2.147 (2)	N1—N2	1.446 (4)
Fe1—O2ⁱⁱⁱ	2.147 (2)	N1—H1A	0.82 (4)
Fe1—N1	2.184 (2)	N1—H1B	0.82 (4)
Fe1—N1ⁱ	2.184 (2)	N2—H2A	0.88 (4)
S1—O2	1.464 (2)	N2—H2B	0.80 (4)
S1—O3	1.473 (2)	N2—H2C	0.82 (4)
S1—O4	1.482 (2)

O1—Fe1—O1ⁱ	180.0	O2—S1—O1	108.74 (12)
O1—Fe1—O2ⁱⁱ	87.04 (8)	O3—S1—O1	111.25 (12)
O1ⁱ—Fe1—O2ⁱⁱ	92.96 (8)	O4—S1—O1	109.43 (12)
O1—Fe1—O2ⁱⁱⁱ	92.96 (8)	S1—O1—Fe1	142.94 (13)
O1ⁱ—Fe1—O2ⁱⁱⁱ	87.04 (8)	S1—O2—Fe1^iv	128.85 (12)
O2ⁱⁱ—Fe1—O2ⁱⁱⁱ	180.0	N2—N1—Fe1	118.02 (18)
O1—Fe1—N1	90.79 (9)	N2—N1—H1A	102 (3)
O1ⁱ—Fe1—N1	89.21 (9)	Fe1—N1—H1A	111 (3)
O2ⁱⁱ—Fe1—N1	95.14 (9)	N2—N1—H1B	107 (3)
O2ⁱⁱⁱ—Fe1—N1	84.86 (9)	Fe1—N1—H1B	107 (3)
O1—Fe1—N1ⁱ	89.21 (9)	H1A—N1—H1B	112 (4)
O1ⁱ—Fe1—N1ⁱ	90.79 (9)	N1—N2—H2A	119 (3)
O2ⁱⁱ—Fe1—N1ⁱ	84.86 (9)	N1—N2—H2B	106 (3)
O2ⁱⁱⁱ—Fe1—N1ⁱ	95.14 (9)	H2A—N2—H2B	101 (4)
N1—Fe1—N1ⁱ	180.0	N1—N2—H2C	106 (3)
O2—S1—O3	109.79 (12)	H2A—N2—H2C	105 (4)
O2—S1—O4	107.99 (12)	H2B—N2—H2C	122 (4)
O3—S1—O4	109.57 (12)

O2—S1—O1—Fe1	114.0 (2)	O3—S1—O2—Fe1^iv	24.58 (19)
O3—S1—O1—Fe1	−7.1 (3)	O4—S1—O2—Fe1^iv	143.99 (14)
O4—S1—O1—Fe1	−128.3 (2)	O1—S1—O2—Fe1^iv	−97.35 (16)
O2ⁱⁱ—Fe1—O1—S1	124.1 (2)	O1—Fe1—N1—N2	−76.0 (2)
O2ⁱⁱⁱ—Fe1—O1—S1	−55.9 (2)	O1ⁱ—Fe1—N1—N2	104.0 (2)
N1—Fe1—O1—S1	29.0 (2)	O2ⁱⁱ—Fe1—N1—N2	−163.1 (2)
N1ⁱ—Fe1—O1—S1	−151.0 (2)	O2ⁱⁱⁱ—Fe1—N1—N2	16.9 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3^v	0.82 (4)	2.37 (4)	3.070 (3)	143 (3)
N1—H1B···O4^vi	0.82 (4)	2.12 (4)	2.867 (3)	151 (4)
N2—H2A···O4^v	0.88 (4)	1.96 (4)	2.799 (3)	160 (4)
N2—H2B···O3	0.80 (4)	2.02 (4)	2.769 (4)	156 (4)
N2—H2C···O2ⁱⁱⁱ	0.82 (4)	2.51 (4)	2.849 (3)	106 (3)
N2—H2C···O2^vi	0.82 (4)	2.32 (4)	3.011 (4)	141 (4)
N2—H2C···O1^vii	0.82 (4)	2.45 (4)	3.073 (3)	133 (4)

Symmetry codes: (iii) −x+1, −y, −z; (v) −x+1, −y, −z+1; (vi) x−1, y−1, z; (vii) x, y−1, z.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

References

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inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Iron(II) hydrazinium sulfate

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

inorganic compounds