The title compound, [(NH
3)
2(CH
2)
2][Fe(SO
4)
2(H
2O)
4], contains centrosymmetric [Fe(H
2O)
4(SO
4)
2]
2− anions, with a coordination octahedron around iron(II) built up from four water molecules and two sulfate groups. The anions are linked by hydrogen bonds of medium strength, forming a three-dimensional framework. The linkage is reinforced by N—H
O bridges from the centrosymmetric [NH
3(CH
2)
2NH
3]
2+ cations, located in the centre of the interstices.
Supporting information
CCDC reference: 209899
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.022
- wR factor = 0.062
- Data-to-parameter ratio = 21.3
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The title compound was prepared in the course of systematic search for new `double salts' of ethylenediammonium and divalent cations with various inorganic acids. It crystallizes from aqueous solution containing iron sulfate, ethylenediamine and sulfuric acid (in ratio 1:1:1) by slow evaporation at room temperature in form of yellow crystals with dimensions up to 4 mm.
Data collection: MACH3 (Enraf-Nonius, 1993); cell refinement: MACH3; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 2002) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Iron ethylenediammonium bis(sulfate) tetrahydrate
top
Crystal data top
(C2H10N2)[Fe(SO4)2(H2O)4] | Z = 1 |
Mr = 382.15 | F(000) = 198 |
Triclinic, P1 | Dx = 1.974 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8350 (3) Å | Cell parameters from 25 reflections |
b = 7.1253 (3) Å | θ = 12.3–19.3° |
c = 7.2235 (4) Å | µ = 1.56 mm−1 |
α = 75.012 (4)° | T = 293 K |
β = 72.355 (4)° | Parallelepiped, pale yellow |
γ = 79.185 (4)° | 0.25 × 0.23 × 0.21 mm |
V = 321.55 (3) Å3 | |
Data collection top
Nonius MACH3 diffractometer | 2393 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.040 |
Graphite monochromator | θmax = 34.2°, θmin = 3.0° |
ω/2θ scans | h = −10→10 |
Absorption correction: ψ scan (MolEN; Fair, 1990) | k = −11→10 |
Tmin = 0.686, Tmax = 0.721 | l = −11→11 |
4830 measured reflections | 3 standard reflections every 100 reflections |
2660 independent reflections | intensity decay: −4.9% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.022 | All H-atom parameters refined |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0214P)2 + 0.0617P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
2660 reflections | Δρmax = 0.74 e Å−3 |
125 parameters | Δρmin = −0.43 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.190 (6) |
Crystal data top
(C2H10N2)[Fe(SO4)2(H2O)4] | γ = 79.185 (4)° |
Mr = 382.15 | V = 321.55 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8350 (3) Å | Mo Kα radiation |
b = 7.1253 (3) Å | µ = 1.56 mm−1 |
c = 7.2235 (4) Å | T = 293 K |
α = 75.012 (4)° | 0.25 × 0.23 × 0.21 mm |
β = 72.355 (4)° | |
Data collection top
Nonius MACH3 diffractometer | 2393 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MolEN; Fair, 1990) | Rint = 0.040 |
Tmin = 0.686, Tmax = 0.721 | 3 standard reflections every 100 reflections |
4830 measured reflections | intensity decay: −4.9% |
2660 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.022 | 0 restraints |
wR(F2) = 0.063 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.74 e Å−3 |
2660 reflections | Δρmin = −0.43 e Å−3 |
125 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. |
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 | Uiso*/Ueq | |
Fe | 0.0000 | 0.0000 | 0.0000 | 0.01379 (6) | |
S | 0.19821 (3) | 0.22418 (3) | 0.24875 (3) | 0.01323 (6) | |
O1 | 0.3119 (1) | 0.3974 (1) | 0.1827 (1) | 0.0215 (1) | |
O2 | −0.0033 (1) | 0.2640 (2) | 0.3890 (1) | 0.0256 (2) | |
O3 | 0.3202 (1) | 0.0546 (1) | 0.3414 (1) | 0.0246 (2) | |
O4 | 0.1634 (1) | 0.1884 (1) | 0.0675 (1) | 0.0220 (2) | |
OW1 | 0.0850 (2) | −0.2454 (1) | 0.2089 (1) | 0.0316 (2) | |
H1W1 | 0.068 (3) | −0.247 (3) | 0.327 (3) | 0.040 (5)* | |
H2W1 | 0.158 (3) | −0.350 (4) | 0.196 (3) | 0.045 (6)* | |
OW2 | 0.2627 (1) | −0.0627 (2) | −0.2374 (1) | 0.0243 (2) | |
H1W2 | 0.259 (3) | −0.034 (3) | −0.354 (3) | 0.042 (5)* | |
H2W2 | 0.380 (3) | −0.057 (3) | −0.244 (3) | 0.037 (5)* | |
C | 0.4514 (2) | 0.4182 (2) | −0.4187 (1) | 0.0200 (2) | |
H1C | 0.552 (3) | 0.309 (3) | −0.369 (3) | 0.033 (5)* | |
H2C | 0.352 (3) | 0.363 (3) | −0.465 (2) | 0.022 (4)* | |
N | 0.3282 (2) | 0.4960 (2) | −0.2425 (1) | 0.0209 (2) | |
H1N | 0.406 (3) | 0.548 (3) | −0.199 (3) | 0.032 (4)* | |
H2N | 0.273 (3) | 0.400 (3) | −0.148 (3) | 0.045 (6)* | |
H3N | 0.225 (3) | 0.588 (4) | −0.265 (3) | 0.047 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Fe | 0.01487 (9) | 0.01384 (8) | 0.01346 (8) | −0.00331 (6) | −0.00449 (6) | −0.00235 (6) |
S | 0.01272 (9) | 0.0160 (1) | 0.01160 (9) | −0.00280 (7) | −0.00459 (6) | −0.00177 (6) |
O1 | 0.0249 (3) | 0.0193 (3) | 0.0242 (3) | −0.0094 (3) | −0.0100 (3) | −0.0029 (3) |
O2 | 0.0171 (3) | 0.0378 (5) | 0.0172 (3) | 0.0012 (3) | −0.0006 (2) | −0.0059 (3) |
O3 | 0.0203 (3) | 0.0227 (3) | 0.0264 (4) | 0.0002 (3) | −0.0092 (3) | 0.0041 (3) |
O4 | 0.0294 (4) | 0.0278 (4) | 0.0137 (3) | −0.0151 (3) | −0.0067 (2) | −0.0035 (2) |
OW1 | 0.0529 (6) | 0.0218 (4) | 0.0195 (3) | 0.0092 (4) | −0.0169 (3) | −0.0044 (3) |
OW2 | 0.0158 (3) | 0.0380 (5) | 0.0192 (3) | −0.0031 (3) | −0.0034 (2) | −0.0079 (3) |
C | 0.0246 (4) | 0.0186 (4) | 0.0154 (4) | −0.0064 (3) | −0.0024 (3) | −0.0021 (3) |
N | 0.0215 (4) | 0.0249 (4) | 0.0145 (3) | −0.0045 (3) | −0.0030 (3) | −0.0021 (3) |
Geometric parameters (Å, º) top
Fe—OW1i | 2.1111 (9) | S—O2 | 1.4699 (8) |
Fe—OW1 | 2.1111 (9) | S—O1 | 1.4782 (8) |
Fe—O4i | 2.1260 (7) | S—O4 | 1.4899 (7) |
Fe—O4 | 2.1260 (7) | C—N | 1.476 (1) |
Fe—OW2i | 2.1430 (8) | C—Cii | 1.513 (2) |
Fe—OW2 | 2.1430 (8) | C—H1C | 1.01 (2) |
S—O3 | 1.4649 (8) | C—H2C | 1.02 (2) |
| | | |
OW1i—Fe—OW1 | 180.00 (4) | O1—S—O4 | 106.54 (4) |
OW1i—Fe—O4 | 86.39 (4) | S—O4—Fe | 137.20 (4) |
OW1—Fe—O4 | 93.61 (4) | H1W1—OW1—H2W1 | 102 (2) |
O4i—Fe—O4 | 180.00 (4) | H1W2—OW2—H2W2 | 104 (2) |
O4—Fe—OW2i | 89.51 (3) | N—C—Cii | 109.7 (1) |
OW1i—Fe—OW2 | 86.44 (4) | Cii—C—H1C | 115 (1) |
OW1—Fe—OW2 | 93.56 (4) | Cii—C—H2C | 109.9 (9) |
O4—Fe—OW2 | 90.49 (3) | H1C—C—H2C | 110 (1) |
OW2i—Fe—OW2 | 180.00 (4) | C—N—H1N | 110 (1) |
O3—S—O2 | 110.32 (5) | C—N—H2N | 109 (2) |
O3—S—O1 | 110.17 (5) | C—N—H3N | 114 (2) |
O2—S—O1 | 110.32 (5) | H1N—N—H2N | 109 (2) |
O3—S—O4 | 110.57 (5) | H1N—N—H3N | 107 (2) |
O2—S—O4 | 108.85 (5) | H2N—N—H3N | 107 (3) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y+1, −z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W1···O2iii | 0.82 (2) | 1.94 (2) | 2.759 (1) | 174 (2) |
OW1—H2W1···O1iv | 0.83 (2) | 1.91 (3) | 2.741 (1) | 176 (2) |
OW2—H1W2···O3v | 0.82 (2) | 2.06 (2) | 2.862 (1) | 166 (2) |
OW2—H2W2···O3vi | 0.80 (2) | 1.96 (2) | 2.727 (1) | 162 (2) |
N—H1N···O1vii | 0.87 (2) | 2.08 (2) | 2.887 (1) | 154 (2) |
N—H2N···O4 | 0.88 (2) | 1.94 (2) | 2.818 (1) | 177 (2) |
N—H3N···O2viii | 0.89 (2) | 1.98 (2) | 2.835 (1) | 159 (2) |
Symmetry codes: (iii) −x, −y, −z+1; (iv) x, y−1, z; (v) x, y, z−1; (vi) −x+1, −y, −z; (vii) −x+1, −y+1, −z; (viii) −x, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | (C2H10N2)[Fe(SO4)2(H2O)4] |
Mr | 382.15 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8350 (3), 7.1253 (3), 7.2235 (4) |
α, β, γ (°) | 75.012 (4), 72.355 (4), 79.185 (4) |
V (Å3) | 321.55 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.56 |
Crystal size (mm) | 0.25 × 0.23 × 0.21 |
|
Data collection |
Diffractometer | Nonius MACH3 diffractometer |
Absorption correction | ψ scan (MolEN; Fair, 1990) |
Tmin, Tmax | 0.686, 0.721 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4830, 2660, 2393 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.791 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.022, 0.063, 1.07 |
No. of reflections | 2660 |
No. of parameters | 125 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.74, −0.43 |
Selected bond lengths (Å) topFe—OW1 | 2.1111 (9) | S—O1 | 1.4782 (8) |
Fe—O4 | 2.1260 (7) | S—O4 | 1.4899 (7) |
Fe—OW2 | 2.1430 (8) | C—N | 1.476 (1) |
S—O3 | 1.4649 (8) | C—Ci | 1.513 (2) |
S—O2 | 1.4699 (8) | | |
Symmetry code: (i) −x+1, −y+1, −z−1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
OW1—H1W1···O2ii | 0.82 (2) | 1.94 (2) | 2.759 (1) | 174 (2) |
OW1—H2W1···O1iii | 0.83 (2) | 1.91 (3) | 2.741 (1) | 176 (2) |
OW2—H1W2···O3iv | 0.82 (2) | 2.06 (2) | 2.862 (1) | 166 (2) |
OW2—H2W2···O3v | 0.80 (2) | 1.96 (2) | 2.727 (1) | 162 (2) |
N—H1N···O1vi | 0.87 (2) | 2.08 (2) | 2.887 (1) | 154 (2) |
N—H2N···O4 | 0.88 (2) | 1.94 (2) | 2.818 (1) | 177 (2) |
N—H3N···O2vii | 0.89 (2) | 1.98 (2) | 2.835 (1) | 159 (2) |
Symmetry codes: (ii) −x, −y, −z+1; (iii) x, y−1, z; (iv) x, y, z−1; (v) −x+1, −y, −z; (vi) −x+1, −y+1, −z; (vii) −x, −y+1, −z. |
The title compound, (I), crystallize sisostructurally with the analogous manganese compound (Chaabouni et al., 1996). The Fe atom is surrounded by six O atoms of four H2O molecules and of two SO4 groups, forming a slightly distorted octahedron. The Fe atom is placed in special Wykoff position 1a on an inversion centre. The structure is built of [Fe(H2O)4(SO4)2]2− anions, in which the SO4 tetrahedron is vertex-linked to the central Fe2+ ion sharing a common O atom (Fig. 1). Hydrogen bonds of mean strength from H2O molecules to O atoms (O2 and O3) of the SO4 groups interconnect neighbouring [Fe(H2O)4(SO4)2], forming a three-dimensional primitive framework (Fig. 2). Placed at the centre of each interstice, [NH3(CH2)2NH3]2+ cations form N—H···O bonds to six surrounding [Fe(H2O)4(SO4)2] groups. Every NH3 group bounds to two O atoms (O1 and O2) of two different SO4 groups and to one O atom (O4) of an iron–sulfur bridge. The organic ethylenediammonium cation is centrosymmetric with NH3 tails in a trans configuration. Both anionic and cationic structure parts show no deviation from the usual geometry and conformation.