Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042170/hg6264sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042170/hg6264Isup2.hkl |
CCDC reference: 296566
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.033
- wR factor = 0.085
- Data-to-parameter ratio = 11.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 4 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Fe1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
Iron(II) sulfate heptahydrate (0.278 g, 1 mmol) was dissolved in DMF (7 ml) under constant stirring. A drop of concentrated sulfuric acid (0.06 ml, 1 mmol) was added, followed by piperazine (0.086 g, 1 mmol). The final mixture was placed in a 15 ml Teflon-lined Parr bomb, which was heated at 383 K for 2 d. The bomb was cooled and opened to reveal pale-green block-shaped crystals in about 40% yield with respect to Fe.
H atoms were located in difference Fourier maps and were refined with distance restraints of O—H = N—H = 0.85 (1) Å and C—H =0.95 (1) Å; their displacement parameters were refined freely.
Data collection: SMART (Bruker, 2002); cell refinement: SMART; data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELX97.
Fig. 1. ORTEPII plot (Johnson, 1976) of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probablility level. |
(C4H12N2)[Fe(H2O)6](SO4)2 | F(000) = 464 |
Mr = 444.22 | Dx = 1.809 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 7.8345 (6) Å | θ = 2.8–27.0° |
b = 9.3814 (8) Å | µ = 1.25 mm−1 |
c = 11.0965 (9) Å | T = 273 K |
β = 91.284 (1)° | Block, pale green |
V = 815.37 (11) Å3 | 0.18 × 0.15 × 0.14 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 1763 independent reflections |
Radiation source: fine-focus sealed tube | 1679 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→10 |
Tmin = 0.806, Tmax = 0.844 | k = −10→11 |
4636 measured reflections | l = −10→14 |
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)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0439P)2 + 0.5012P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1763 reflections | Δρmax = 0.63 e Å−3 |
155 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (2) |
(C4H12N2)[Fe(H2O)6](SO4)2 | V = 815.37 (11) Å3 |
Mr = 444.22 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.8345 (6) Å | µ = 1.25 mm−1 |
b = 9.3814 (8) Å | T = 273 K |
c = 11.0965 (9) Å | 0.18 × 0.15 × 0.14 mm |
β = 91.284 (1)° |
Bruker SMART CCD area-detector diffractometer | 1763 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1679 reflections with I > 2σ(I) |
Tmin = 0.806, Tmax = 0.844 | Rint = 0.021 |
4636 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.63 e Å−3 |
1763 reflections | Δρmin = −0.36 e Å−3 |
155 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.0000 | 0.5000 | 0.5000 | 0.02379 (16) | |
S1 | 0.52503 (6) | 0.45971 (6) | 0.77949 (5) | 0.02620 (17) | |
O1 | 0.1949 (2) | 0.36551 (19) | 0.43356 (17) | 0.0362 (4) | |
O2 | 0.1901 (2) | 0.6046 (2) | 0.60118 (19) | 0.0436 (5) | |
O3 | 0.0411 (3) | 0.6370 (2) | 0.35063 (17) | 0.0417 (4) | |
O4 | 0.3852 (2) | 0.35897 (18) | 0.79981 (17) | 0.0406 (4) | |
O5 | 0.5180 (2) | 0.5102 (2) | 0.65443 (16) | 0.0423 (5) | |
O6 | 0.6905 (2) | 0.3888 (2) | 0.80446 (17) | 0.0466 (5) | |
C2 | 0.0810 (3) | 0.5914 (3) | 0.9133 (2) | 0.0354 (5) | |
O7 | 0.5067 (3) | 0.5777 (2) | 0.86399 (19) | 0.0534 (5) | |
N1 | 0.1743 (3) | 0.4728 (3) | 0.9743 (2) | 0.0375 (5) | |
C1 | −0.0584 (3) | 0.6459 (3) | 0.9928 (3) | 0.0404 (6) | |
H9 | 0.157 (4) | 0.664 (3) | 0.898 (3) | 0.046 (8)* | |
H3 | 0.174 (4) | 0.674 (4) | 0.642 (3) | 0.050 (9)* | |
H5 | 0.023 (4) | 0.721 (4) | 0.352 (3) | 0.047 (9)* | |
H7 | −0.121 (4) | 0.717 (4) | 0.953 (3) | 0.056 (9)* | |
H2 | 0.177 (4) | 0.293 (4) | 0.386 (3) | 0.060 (10)* | |
H1 | 0.281 (5) | 0.397 (4) | 0.408 (3) | 0.057 (10)* | |
H4 | 0.274 (4) | 0.578 (3) | 0.620 (3) | 0.042 (9)* | |
H11 | 0.250 (5) | 0.433 (4) | 0.926 (3) | 0.074 (11)* | |
H8 | −0.016 (4) | 0.686 (3) | 1.073 (3) | 0.049 (8)* | |
H6 | 0.134 (5) | 0.631 (4) | 0.312 (3) | 0.067 (11)* | |
H10 | 0.037 (4) | 0.562 (3) | 0.836 (3) | 0.050 (8)* | |
H12 | 0.233 (5) | 0.506 (4) | 1.037 (4) | 0.067 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0207 (2) | 0.0218 (2) | 0.0290 (3) | 0.00017 (14) | 0.00509 (16) | −0.00031 (15) |
S1 | 0.0224 (3) | 0.0259 (3) | 0.0305 (3) | −0.00013 (18) | 0.0054 (2) | 0.00480 (19) |
O1 | 0.0287 (8) | 0.0283 (9) | 0.0521 (10) | −0.0005 (6) | 0.0132 (7) | −0.0076 (7) |
O2 | 0.0307 (9) | 0.0352 (10) | 0.0646 (13) | 0.0045 (7) | −0.0107 (9) | −0.0148 (9) |
O3 | 0.0477 (11) | 0.0303 (10) | 0.0479 (10) | 0.0083 (8) | 0.0201 (8) | 0.0085 (8) |
O4 | 0.0352 (9) | 0.0344 (9) | 0.0526 (10) | −0.0091 (7) | 0.0107 (7) | 0.0029 (8) |
O5 | 0.0275 (8) | 0.0641 (13) | 0.0353 (9) | −0.0002 (7) | 0.0034 (7) | 0.0169 (8) |
O6 | 0.0293 (9) | 0.0603 (12) | 0.0505 (11) | 0.0129 (8) | 0.0087 (7) | 0.0195 (9) |
C2 | 0.0324 (11) | 0.0418 (13) | 0.0325 (12) | −0.0044 (10) | 0.0080 (9) | 0.0028 (10) |
O7 | 0.0713 (13) | 0.0325 (10) | 0.0569 (12) | −0.0076 (9) | 0.0159 (10) | −0.0056 (8) |
N1 | 0.0223 (9) | 0.0501 (13) | 0.0406 (12) | 0.0029 (8) | 0.0095 (9) | 0.0005 (9) |
C1 | 0.0385 (13) | 0.0330 (13) | 0.0502 (15) | 0.0059 (10) | 0.0107 (11) | 0.0019 (11) |
Fe1—O2 | 2.0894 (18) | O2—H4 | 0.73 (3) |
Fe1—O2i | 2.0894 (18) | O3—H5 | 0.80 (3) |
Fe1—O1 | 2.1253 (16) | O3—H6 | 0.86 (4) |
Fe1—O1i | 2.1253 (16) | C2—N1 | 1.486 (3) |
Fe1—O3i | 2.1273 (18) | C2—C1 | 1.509 (3) |
Fe1—O3 | 2.1273 (18) | C2—H9 | 0.92 (3) |
S1—O7 | 1.460 (2) | C2—H10 | 0.96 (3) |
S1—O5 | 1.4663 (18) | N1—C1ii | 1.487 (3) |
S1—O4 | 1.4678 (16) | N1—H11 | 0.89 (4) |
S1—O6 | 1.4781 (17) | N1—H12 | 0.88 (5) |
O1—H2 | 0.87 (4) | C1—N1ii | 1.487 (3) |
O1—H1 | 0.79 (4) | C1—H7 | 0.93 (3) |
O2—H3 | 0.80 (4) | C1—H8 | 1.01 (3) |
O2—Fe1—O2i | 180.0 | Fe1—O2—H3 | 124 (2) |
O2—Fe1—O1 | 87.49 (8) | Fe1—O2—H4 | 128 (3) |
O2i—Fe1—O1 | 92.51 (8) | H3—O2—H4 | 106 (3) |
O2—Fe1—O1i | 92.51 (8) | Fe1—O3—H5 | 123 (2) |
O2i—Fe1—O1i | 87.49 (8) | Fe1—O3—H6 | 120 (2) |
O1—Fe1—O1i | 180.00 (9) | H5—O3—H6 | 103 (3) |
O2—Fe1—O3i | 89.05 (8) | N1—C2—C1 | 110.0 (2) |
O2i—Fe1—O3i | 90.95 (8) | N1—C2—H9 | 108.8 (18) |
O1—Fe1—O3i | 91.96 (7) | C1—C2—H9 | 109.3 (18) |
O1i—Fe1—O3i | 88.04 (7) | N1—C2—H10 | 110.8 (19) |
O2—Fe1—O3 | 90.95 (8) | C1—C2—H10 | 111.7 (18) |
O2i—Fe1—O3 | 89.05 (8) | H9—C2—H10 | 106 (3) |
O1—Fe1—O3 | 88.04 (7) | C2—N1—C1ii | 112.0 (2) |
O1i—Fe1—O3 | 91.96 (7) | C2—N1—H11 | 111 (3) |
O3i—Fe1—O3 | 180.0 | C1ii—N1—H11 | 105 (3) |
O7—S1—O5 | 111.14 (12) | C2—N1—H12 | 110 (2) |
O7—S1—O4 | 107.77 (11) | C1ii—N1—H12 | 112 (2) |
O5—S1—O4 | 109.95 (11) | H11—N1—H12 | 106 (3) |
O7—S1—O6 | 108.62 (13) | N1ii—C1—C2 | 110.1 (2) |
O5—S1—O6 | 109.70 (10) | N1ii—C1—H7 | 110 (2) |
O4—S1—O6 | 109.63 (11) | C2—C1—H7 | 110.4 (19) |
Fe1—O1—H2 | 124 (2) | N1ii—C1—H8 | 104.5 (17) |
Fe1—O1—H1 | 121 (2) | C2—C1—H8 | 114.3 (17) |
H2—O1—H1 | 102 (3) | H7—C1—H8 | 108 (3) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H12···O7iii | 0.88 (5) | 2.43 (4) | 3.080 (3) | 131 (3) |
N1—H12···O6iii | 0.88 (5) | 2.10 (5) | 2.953 (3) | 165 (3) |
O3—H6···O6iv | 0.86 (4) | 1.91 (4) | 2.757 (2) | 167 (3) |
N1—H11···O7 | 0.89 (4) | 2.54 (4) | 3.065 (3) | 119 (3) |
O2—H4···O5 | 0.73 (3) | 2.04 (3) | 2.768 (3) | 174 (3) |
O1—H1···O5iv | 0.79 (4) | 1.94 (4) | 2.733 (2) | 175 (3) |
O1—H2···O6v | 0.87 (4) | 1.94 (4) | 2.783 (3) | 164 (3) |
O3—H5···O7vi | 0.80 (3) | 1.90 (4) | 2.695 (3) | 173 (3) |
O2—H3···O4vii | 0.80 (4) | 1.91 (4) | 2.698 (3) | 165 (3) |
Symmetry codes: (iii) −x+1, −y+1, −z+2; (iv) −x+1, −y+1, −z+1; (v) x−1/2, −y+1/2, z−1/2; (vi) x−1/2, −y+3/2, z−1/2; (vii) −x+1/2, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N2)[Fe(H2O)6](SO4)2 |
Mr | 444.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 7.8345 (6), 9.3814 (8), 11.0965 (9) |
β (°) | 91.284 (1) |
V (Å3) | 815.37 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.18 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.806, 0.844 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4636, 1763, 1679 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.085, 1.10 |
No. of reflections | 1763 |
No. of parameters | 155 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.63, −0.36 |
Computer programs: SMART (Bruker, 2002), SMART, SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELX97.
Fe1—O2 | 2.0894 (18) | Fe1—O3 | 2.1273 (18) |
Fe1—O1 | 2.1253 (16) | ||
O2—Fe1—O1 | 87.49 (8) | O2—Fe1—O3 | 90.95 (8) |
O2i—Fe1—O1 | 92.51 (8) | O1—Fe1—O3 | 88.04 (7) |
O2—Fe1—O3i | 89.05 (8) | O1i—Fe1—O3 | 91.96 (7) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H12···O7ii | 0.88 (5) | 2.43 (4) | 3.080 (3) | 131 (3) |
N1—H12···O6ii | 0.88 (5) | 2.10 (5) | 2.953 (3) | 165 (3) |
O3—H6···O6iii | 0.86 (4) | 1.91 (4) | 2.757 (2) | 167 (3) |
N1—H11···O7 | 0.89 (4) | 2.54 (4) | 3.065 (3) | 119 (3) |
O2—H4···O5 | 0.73 (3) | 2.04 (3) | 2.768 (3) | 174 (3) |
O1—H1···O5iii | 0.79 (4) | 1.94 (4) | 2.733 (2) | 175 (3) |
O1—H2···O6iv | 0.87 (4) | 1.94 (4) | 2.783 (3) | 164 (3) |
O3—H5···O7v | 0.80 (3) | 1.90 (4) | 2.695 (3) | 173 (3) |
O2—H3···O4vi | 0.80 (4) | 1.91 (4) | 2.698 (3) | 165 (3) |
Symmetry codes: (ii) −x+1, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x−1/2, −y+1/2, z−1/2; (v) x−1/2, −y+3/2, z−1/2; (vi) −x+1/2, y+1/2, −z+3/2. |
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This report describes a study on the reactions of iron(II) sulfate and piperazine under solvothermal conditions. We have previously described a 4,4-bipyridine salt of hexaquairon(II) sulfate, accompanied by two uncoordinated water molecules (Fu et al., 2005). A similar reaction with N,N-diethylformamide (DMF) as solvent and piperazine as diamine yielded the title compound, (I) (Fig. 1), although DMF was not incorporated into the crystal structure. The compound can be regarded as a double salt of piperazinium sulfate and hexaquairon(II) sulfate.
The [Fe(H2O)6]2+ and C4H12N22+ cations and the sulfate anions interact through hydrogen bonds (Table 2), forming a three-dimensional network. The organic cation and the Fe atom each lie on an inversion center. There are only four examples in the literature of a hexaaquametal sulfate salt having an organic piperazine cation. The structures of piperazinium hexaquacobalt(II) disulfate (Pan et al., 2003) and piperazinium hexaquanickel(II) disulfate (Meng et al., 2004) are similar to that of the title compound, but hemi(piperazinium) hexaquaaluminium(III) bis(sulfate) tetrahydrate (Bataille, 2003) and piperazinium hexaquazinc(II) bis(sulfate) (Rekik et al., 2005) have additional hydrogen-bond interactions with uncoordinated water molecules.