supplementary materials


zl2548 scheme

Acta Cryst. (2013). E69, m320-m321    [ doi:10.1107/S1600536813012312 ]

catena-Poly[[[diaquabis(selenocyanato-[kappa]N)iron(II)]-[mu]-1,2-bis(pyridin-4-yl)ethane-[kappa]2N:N'] 1,2-bis(pyridin-4-yl)ethane disolvate dihydrate]

S. Wöhlert, I. Jess and C. Näther

Abstract top

The title compound, {[Fe(NCSe)2(C12H12N2)(H2O)2]·2C12H12N2·2H2O}n, was obtained by the reaction of iron(II) sulfate heptahydrate and potassium selenocyanate with 1,2-bis(pyridin-4-yl)ethane (bpa) in water. The FeII cation is coordinated by two N-bonded selenocyanate anions, two water molecules and two 1,2-bis(pyridin-4-yl)ethane (bpa) ligands in a slightly distorted octahedral geometry. In addition, two non-coordinating bpa molecules and two water molecules are present. The FeII cation is located on a center of inversion while the coordinating bpa ligand is located on a twofold rotation axis. The FeII cations are linked by the bpa ligands into chains along the b-axis direction, which are further connected into layers perpedicular to the c axis by O-H...N and O-H...O hydrogen bonds to the non-coordinating bpa and the water molecules. The crystal studied was twinned by pseudo-merohedry (180° rotation along c*; contribution of the minor twin component 3.7%).

Comment top

In our recent work we have reported on the synthesis and characterization of cobalt(II) and iron(II) selenocyanate coordination polymers that show coexistence of metamagnetism and a slow relaxation of the magnetization (Boeckmann & Näther, 2011; Wöhlert et al., 2012 and Boeckmann et al., 2012). These compounds can be prepared by thermal decomposition of suitable precursor compounds that contain volatile ligands like e.g. water in hydrates and therefore, such compounds are of extreme importance for our project. In the course of these investigations we obtained such a precursor based on 1,2-bis(pyridin-4-yl)ethane (bpa), which was characterized by single-crystal X-ray diffraction.

In the crystal structure of the title compound Fe(NCSe)2(C12H12N2)(H2O)2]n.2C12H12N2.2H2O solvate each FeII cation is coordinated by two N-bonded selenocyanate anions, two water molecules and two bpa ligands (Fig. 1). The FeN4O2 octahedra are slightly distorted with distances in the range of 2.071 (4) Å to 2.344 (4) Å. The angles arround the FeII cations are in the range of 86.91 (16) ° to 93.09 (16) ° and of 180 ° (Tab. 1). Each FeII cation is located on a center of inversion while the coordinating bpa ligand is located on a twofold rotation axis. The iron(II) cations are connected by the bpa ligands into one dimensional polymeric chains, which elongate in the direction of the crystallographic b-axis (Fig. 2). These chains are linked by intermolecular O—H···N and O—H···O hydrogen bonding into layers by non-coordinating bpa ligands and water molecules perpedicular to c (Fig. 2, Tab. 2).

Related literature top

For background to this work see: Boeckmann & Näther (2011); Wöhlert et al. (2012); Boeckmann et al. (2012).

Experimental top

FeSO4×7H2O, KNCSe and 1,2-bis(pyridin-4-yl)ethane were obtained from Alfa Aesar. All chemicals were used without further purification. 0.15 mmol (43 mg) FeSO4×7H2O and 0.2 mmol (28 mg) KNCSe were reacted with 0.6 mmol (109 mg) 1,2-bis(pyridin-4-yl)ethane in 1 ml water. Red single-crystals of the title compound were obtained after three days.

Refinement top

All H atoms were positions with idealized geometry and were refined isotropically with Uiso(H) = 1.2 Ueq(C) using a riding model with C—H = 0.93 Å and C—H2 = 0.97 Å. The O—H hydrogen atom were located in a difference map, their bond lengths were set to an ideal value of 0.82 Å, and finally they were refined using a riding model with Uiso(H) = 1.5 Ueq(O). Twinning by pseudo-merohedry of the crystal by a 180° rotation along c* was taken into account, using a twin matrix (-1 0 0 0 -1 0 1 0 1; BASF parameter: 0.03696) which lowered the R value from 6.16 to 4.5%.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = -x + 2, -y, -z + 1; ii = -x + 2, -y + 1, -z + 1; iii = x, y - 1, z.
[Figure 2] Fig. 2. : Crystal structure of the title compound with O–H–N and O–H–O hydrogen bonding shown as dashed lines (black = iron, blue = nitrogen, orange = selenium, red = oxygen, grey = carbon, white = hydrogen).
catena-Poly[[[diaquabis(selenocyanato-κN)iron(II)]-µ-1,2-bis(pyridin-4-yl)ethane-κ2N:N'] 1,2-bis(pyridin-4-yl)ethane disolvate dihydrate] top
Crystal data top
[Fe(NCSe)2(C12H12N2)(H2O)2]·2C12H12N2·2H2OF(000) = 908
Mr = 890.58Dx = 1.498 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 20183 reflections
a = 8.0790 (6) Åθ = 2.4–27.5°
b = 14.1870 (7) ŵ = 2.28 mm1
c = 17.6553 (12) ÅT = 293 K
β = 102.645 (8)°Block, red
V = 1974.5 (2) Å30.23 × 0.16 × 0.09 mm
Z = 2
Data collection top
Stoe IPDS-2
diffractometer
4540 independent reflections
Radiation source: fine-focus sealed tube3659 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.095
ω scanθmax = 27.5°, θmin = 2.4°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 1010
Tmin = 0.645, Tmax = 0.818k = 1818
20183 measured reflectionsl = 2222
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0393P)2 + 4.2316P]
where P = (Fo2 + 2Fc2)/3
4540 reflections(Δ/σ)max = 0.001
242 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.88 e Å3
Crystal data top
[Fe(NCSe)2(C12H12N2)(H2O)2]·2C12H12N2·2H2OV = 1974.5 (2) Å3
Mr = 890.58Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.0790 (6) ŵ = 2.28 mm1
b = 14.1870 (7) ÅT = 293 K
c = 17.6553 (12) Å0.23 × 0.16 × 0.09 mm
β = 102.645 (8)°
Data collection top
Stoe IPDS-2
diffractometer
4540 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
3659 reflections with I > 2σ(I)
Tmin = 0.645, Tmax = 0.818Rint = 0.095
20183 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.119Δρmax = 0.58 e Å3
S = 1.09Δρmin = 0.88 e Å3
4540 reflectionsAbsolute structure: ?
242 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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 > 2sigma(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
xyzUiso*/Ueq
Fe11.00000.00000.50000.01501 (15)
N11.0298 (4)0.0036 (2)0.62294 (18)0.0224 (6)
C10.9954 (4)0.0081 (2)0.6834 (2)0.0174 (7)
Se10.94592 (5)0.01632 (3)0.77704 (2)0.02554 (12)
N100.9925 (4)0.16528 (19)0.50356 (18)0.0189 (6)
C101.0341 (5)0.2181 (2)0.4477 (2)0.0229 (8)
H101.07570.18780.40900.028*
C111.0186 (5)0.3159 (2)0.4442 (2)0.0246 (8)
H111.04940.34890.40400.030*
C120.9576 (5)0.3639 (2)0.5007 (2)0.0223 (8)
C130.9174 (6)0.3093 (2)0.5604 (2)0.0251 (8)
H130.87800.33790.60040.030*
C140.9370 (5)0.2119 (2)0.5591 (2)0.0229 (8)
H140.90990.17700.59940.027*
C150.9243 (6)0.4693 (2)0.4954 (3)0.0353 (11)
H15A0.85060.48260.44540.042*
H15B0.86310.48640.53490.042*
N200.5764 (5)0.1671 (2)0.6762 (2)0.0319 (8)
C200.6829 (6)0.2156 (3)0.7307 (3)0.0319 (9)
H200.76990.18300.76350.038*
C210.6708 (6)0.3120 (3)0.7410 (3)0.0296 (9)
H210.74740.34290.78010.036*
C220.5421 (5)0.3616 (2)0.6920 (2)0.0254 (8)
C230.4316 (6)0.3110 (3)0.6357 (3)0.0320 (9)
H230.34330.34140.60200.038*
C240.4532 (6)0.2150 (3)0.6300 (3)0.0342 (10)
H240.37750.18210.59180.041*
C250.5290 (6)0.4669 (3)0.6976 (2)0.0291 (9)
H25A0.60280.48880.74530.035*
H25B0.41350.48440.69870.035*
C260.5799 (6)0.5132 (3)0.6283 (2)0.0277 (8)
H26A0.68990.48910.62410.033*
H26B0.49860.49550.58150.033*
C270.5889 (5)0.6193 (2)0.6332 (2)0.0229 (8)
C280.6949 (5)0.6639 (3)0.6955 (2)0.0253 (8)
H280.75950.62880.73590.030*
C290.7026 (5)0.7616 (3)0.6964 (2)0.0283 (8)
H290.77590.79090.73760.034*
C300.5083 (7)0.7723 (3)0.5820 (3)0.0365 (10)
H300.44360.80910.54290.044*
C310.4938 (6)0.6753 (3)0.5756 (3)0.0329 (9)
H310.42090.64800.53320.039*
N210.6101 (5)0.8156 (2)0.6412 (2)0.0309 (8)
O11.2588 (3)0.00213 (19)0.50632 (15)0.0241 (5)
H1O11.29760.00040.46720.036*
H2O11.34300.00610.54120.036*
O21.4393 (4)0.00140 (17)0.39471 (15)0.0227 (5)
H1O21.39850.03710.36120.034*
H2O21.39420.05260.38280.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0173 (3)0.0124 (3)0.0164 (3)0.0008 (2)0.0059 (3)0.0003 (2)
N10.0271 (16)0.0203 (14)0.0197 (15)0.0008 (12)0.0049 (13)0.0006 (11)
C10.0183 (16)0.0117 (14)0.0204 (17)0.0007 (12)0.0007 (13)0.0002 (11)
Se10.0285 (2)0.03071 (19)0.01874 (19)0.00250 (16)0.00811 (15)0.00011 (14)
N100.0242 (15)0.0135 (13)0.0199 (14)0.0008 (11)0.0067 (12)0.0008 (10)
C100.032 (2)0.0146 (15)0.0268 (19)0.0005 (14)0.0168 (17)0.0018 (13)
C110.034 (2)0.0159 (15)0.029 (2)0.0030 (14)0.0198 (18)0.0026 (13)
C120.0263 (19)0.0118 (15)0.032 (2)0.0015 (13)0.0132 (17)0.0007 (13)
C130.037 (2)0.0166 (16)0.0266 (19)0.0007 (15)0.0166 (17)0.0031 (14)
C140.034 (2)0.0151 (15)0.0214 (17)0.0023 (14)0.0110 (16)0.0017 (13)
C150.045 (3)0.0125 (16)0.059 (3)0.0014 (16)0.034 (2)0.0004 (16)
N200.044 (2)0.0205 (15)0.0312 (18)0.0000 (14)0.0075 (17)0.0019 (13)
C200.034 (2)0.0256 (19)0.036 (2)0.0033 (16)0.0073 (19)0.0017 (16)
C210.033 (2)0.0226 (18)0.034 (2)0.0059 (15)0.0077 (18)0.0015 (15)
C220.031 (2)0.0181 (16)0.032 (2)0.0014 (14)0.0172 (18)0.0003 (14)
C230.038 (2)0.0248 (19)0.032 (2)0.0006 (16)0.0034 (19)0.0013 (15)
C240.048 (3)0.0226 (18)0.029 (2)0.0054 (17)0.003 (2)0.0039 (15)
C250.034 (2)0.0204 (17)0.037 (2)0.0012 (15)0.0168 (19)0.0042 (15)
C260.037 (2)0.0181 (16)0.030 (2)0.0010 (15)0.0115 (18)0.0013 (14)
C270.0235 (19)0.0179 (16)0.029 (2)0.0002 (13)0.0098 (16)0.0015 (13)
C280.025 (2)0.0213 (17)0.032 (2)0.0019 (14)0.0101 (17)0.0002 (14)
C290.031 (2)0.0211 (17)0.034 (2)0.0025 (15)0.0099 (18)0.0030 (15)
C300.047 (3)0.0242 (19)0.037 (2)0.0062 (18)0.007 (2)0.0079 (16)
C310.040 (2)0.0262 (19)0.030 (2)0.0027 (17)0.0022 (19)0.0004 (15)
N210.040 (2)0.0194 (15)0.036 (2)0.0017 (14)0.0137 (17)0.0011 (13)
O10.0186 (13)0.0350 (14)0.0195 (12)0.0013 (10)0.0059 (11)0.0015 (10)
O20.0271 (14)0.0174 (11)0.0231 (13)0.0031 (10)0.0043 (11)0.0012 (9)
Geometric parameters (Å, º) top
Fe1—O12.069 (3)C21—H210.9300
Fe1—O1i2.069 (3)C22—C231.383 (6)
Fe1—N1i2.132 (3)C22—C251.503 (5)
Fe1—N12.132 (3)C23—C241.379 (6)
Fe1—N10i2.347 (3)C23—H230.9300
Fe1—N102.347 (3)C24—H240.9300
N1—C11.162 (5)C25—C261.522 (6)
C1—Se11.788 (4)C25—H25A0.9700
N10—C101.339 (5)C25—H25B0.9700
N10—C141.339 (5)C26—C271.508 (5)
C10—C111.393 (5)C26—H26A0.9700
C10—H100.9300C26—H26B0.9700
C11—C121.384 (5)C27—C311.383 (6)
C11—H110.9300C27—C281.390 (5)
C12—C131.402 (5)C28—C291.388 (5)
C12—C151.519 (5)C28—H280.9300
C13—C141.392 (5)C29—N211.333 (5)
C13—H130.9300C29—H290.9300
C14—H140.9300C30—N211.330 (6)
C15—C15ii1.481 (9)C30—C311.384 (6)
C15—H15A0.9700C30—H300.9300
C15—H15B0.9700C31—H310.9300
N20—C241.327 (6)O1—H1O10.8201
N20—C201.333 (6)O1—H2O10.8201
C20—C211.386 (5)O2—H1O20.8199
C20—H200.9300O2—H2O20.8200
C21—C221.390 (6)
O1—Fe1—O1i180.000 (1)C20—C21—C22118.9 (4)
O1—Fe1—N1i86.68 (12)C20—C21—H21120.5
O1i—Fe1—N1i93.32 (12)C22—C21—H21120.5
O1—Fe1—N193.32 (12)C23—C22—C21117.5 (3)
O1i—Fe1—N186.68 (12)C23—C22—C25121.3 (4)
N1i—Fe1—N1180.000 (1)C21—C22—C25121.1 (4)
O1—Fe1—N10i89.09 (11)C24—C23—C22119.6 (4)
O1i—Fe1—N10i90.91 (11)C24—C23—H23120.2
N1i—Fe1—N10i89.69 (11)C22—C23—H23120.2
N1—Fe1—N10i90.31 (11)N20—C24—C23123.4 (4)
O1—Fe1—N1090.91 (11)N20—C24—H24118.3
O1i—Fe1—N1089.09 (11)C23—C24—H24118.3
N1i—Fe1—N1090.31 (11)C22—C25—C26109.9 (3)
N1—Fe1—N1089.69 (11)C22—C25—H25A109.7
N10i—Fe1—N10180.000 (1)C26—C25—H25A109.7
C1—N1—Fe1160.1 (3)C22—C25—H25B109.7
N1—C1—Se1178.9 (3)C26—C25—H25B109.7
C10—N10—C14116.2 (3)H25A—C25—H25B108.2
C10—N10—Fe1121.8 (2)C27—C26—C25113.8 (3)
C14—N10—Fe1121.8 (2)C27—C26—H26A108.8
N10—C10—C11123.7 (3)C25—C26—H26A108.8
N10—C10—H10118.1C27—C26—H26B108.8
C11—C10—H10118.1C25—C26—H26B108.8
C12—C11—C10120.1 (3)H26A—C26—H26B107.7
C12—C11—H11120.0C31—C27—C28117.9 (3)
C10—C11—H11120.0C31—C27—C26121.3 (4)
C11—C12—C13116.5 (3)C28—C27—C26120.8 (3)
C11—C12—C15121.8 (3)C29—C28—C27118.8 (4)
C13—C12—C15121.6 (3)C29—C28—H28120.6
C14—C13—C12119.4 (3)C27—C28—H28120.6
C14—C13—H13120.3N21—C29—C28123.3 (4)
C12—C13—H13120.3N21—C29—H29118.3
N10—C14—C13124.0 (3)C28—C29—H29118.3
N10—C14—H14118.0N21—C30—C31123.3 (4)
C13—C14—H14118.0N21—C30—H30118.3
C15ii—C15—C12116.2 (5)C31—C30—H30118.3
C15ii—C15—H15A108.2C27—C31—C30119.2 (4)
C12—C15—H15A108.2C27—C31—H31120.4
C15ii—C15—H15B108.2C30—C31—H31120.4
C12—C15—H15B108.2C30—N21—C29117.4 (3)
H15A—C15—H15B107.4Fe1—O1—H1O1121.5
C24—N20—C20117.3 (3)Fe1—O1—H2O1134.5
N20—C20—C21123.4 (4)H1O1—O1—H2O1102.6
N20—C20—H20118.3H1O2—O2—H2O2108.6
C21—C20—H20118.3
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O20.821.892.696 (4)166
O1—H2O1···O2iii0.821.872.672 (4)165
O2—H1O2···N20i0.821.982.688 (4)144
O2—H2O2···N21ii0.821.922.682 (4)155
Symmetry codes: (i) x+2, y, z+1; (ii) x+2, y+1, z+1; (iii) x+3, y, z+1.
Selected bond lengths (Å) top
Fe1—O12.069 (3)Fe1—N102.347 (3)
Fe1—N12.132 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O20.821.892.696 (4)165.5
O1—H2O1···O2i0.821.872.672 (4)164.6
O2—H1O2···N20ii0.821.982.688 (4)143.6
O2—H2O2···N21iii0.821.922.682 (4)155.2
Symmetry codes: (i) x+3, y, z+1; (ii) x+2, y, z+1; (iii) x+2, y+1, z+1.
Acknowledgements top

We gratefully acknowledge financial support by the DFG (project No. NA 720/5–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facility.

references
References top

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Boeckmann, J., Wriedt, M. & Näther, C. (2012). Chem. Eur. J. 18, 5284–5289.

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Stoe & Cie (2008). X-AREA, X-RED32 and X-SHAPE. Stoe & Cie, Darmstadt, Germany.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Wöhlert, S., Ruschewitz, U. & Näther, C. (2012). Cryst. Growth Des. 12, 2715–2718.