

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989014026188/wm5094sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S2056989014026188/wm5094Isup2.hkl |
![]() | Chemdraw file https://doi.org/10.1107/S2056989014026188/wm5094Isup3.cdx |
CCDC reference: 1036669
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(N-C) = 0.011 Å
- R factor = 0.038
- wR factor = 0.106
- Data-to-parameter ratio = 26.9
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of . 390 Ang3
Author Response: highly porous polycyanide complex |
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.972 Note PLAT242_ALERT_2_C Low Ueq as Compared to Neighbors for ..... Fe Check PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 40 Report
Alert level G PLAT004_ALERT_5_G Polymeric Structure Found with Dimension ....... 2 Info PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF Please Do ! PLAT040_ALERT_1_G No H-atoms in this Carbon Containing Compound .. Please Check PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 15.45 Why ? PLAT180_ALERT_4_G Check Cell Rounding: # of Values Ending with 0 = 3 PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K) 293 Check PLAT200_ALERT_1_G Reported _diffrn_ambient_temperature ..... (K) 293 Check PLAT794_ALERT_5_G Tentative Bond Valency for Pt1 (II) ..... 2.09 Note PLAT794_ALERT_5_G Tentative Bond Valency for Pt2 (II) ..... 2.17 Note PLAT794_ALERT_5_G Tentative Bond Valency for Fe (II) ..... 2.08 Note PLAT899_ALERT_4_G SHELXL97 is Deprecated and Succeeded by SHELXL 2014 Note PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) ..... 3 Report PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 11 Note
1 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 3 ALERT level C = Check. Ensure it is not caused by an omission or oversight 13 ALERT level G = General information/check it is not something unexpected 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 5 ALERT type 5 Informative message, check
Single crystals of the title compound were grown using a slow diffusion technique. During the reaction time a side product had formed serendipitously due to oxidation of the initial FeII salt. One side of a multi-arm shaped vessel contained (NH4)2Fe(SO4)2·6H2O (20 mg, 51 mmol) dissolved in water (0.5 mL). The second arm contained K2[Pt(CN)4]·3H2O (22 mg, 51 mmol) in water (0.5 ml). The vessel was filled with a water/methanol (1:1) solution. Square shaped orange crystals suitable for single crystal X-ray analysis were obtained after several weeks.
The highest and lowest remaining electron density are located 3.66 and 0.83 Å, respectively, from the Pt atom. The highest electron densities are connected with positions in the voids of the framework. However, modelling of the electron density e.g. under consideration of disordered (partially occupied) water molecules lead to implausible models.
Coordination compounds have interesting properties in catalysis (Kanderal et al., 2005; Penkova et al., 2009) or as photoactive materials (Yan et al., 2012). Magnetically active polycyanidometallate network complexes of FeII [FeIIL2{MI(CN)2}2] or [FeIIL2{MII(CN)4}] (MI = Ag, Au; MII = Ni, Pd, Pt; L = N-heterocyclic ligand) have been studied because they show versatile polymeric structures (Piñeiro-López et al. 2014; Seredyuk et al., 2007, 2009), spin transition (Muñoz & Real, 2013) and functionalities such as sorption–desorption of organic and inorganic molecules (Muñoz & Real, 2013) or reversible chemosorption (Arcís-Castillo et al., 2013).
Single crystals of the title compound were grown using a slow diffusion technique. During the reaction time a side product had formed serendipitously due to oxidation of the initial FeII salt. One side of a multi-arm shaped vessel contained (NH4)2Fe(SO4)2·6H2O (20 mg, 51 mmol) dissolved in water (0.5 mL). The second arm contained K2[Pt(CN)4]·3H2O (22 mg, 51 mmol) in water (0.5 ml). The vessel was filled with a water/methanol (1:1) solution. Square shaped orange crystals suitable for single crystal X-ray analysis were obtained after several weeks.
The highest and lowest remaining electron density are located 3.66 and 0.83 Å, respectively, from the Pt atom. The highest electron densities are connected with positions in the voids of the framework. However, modelling of the electron density e.g. under consideration of disordered (partially occupied) water molecules lead to implausible models.
Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).
[Fe2Pt3(CN)12] | F(000) = 884 |
Mr = 1009.18 | Dx = 2.051 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2y | Cell parameters from 200 reflections |
a = 16.0140 (5) Å | θ = 12–20° |
b = 13.8250 (5) Å | µ = 13.68 mm−1 |
c = 7.5720 (2) Å | T = 293 K |
β = 102.946 (2)° | Prismatic, orange |
V = 1633.78 (9) Å3 | 0.04 × 0.04 × 0.02 mm |
Z = 2 |
Oxford Diffraction Gemini S Ultra diffractometer | 1909 independent reflections |
Radiation source: fine-focus sealed tube | 1568 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (Blessing, 1995) | h = −20→20 |
Tmin = 0.611, Tmax = 0.772 | k = −17→16 |
3358 measured reflections | l = −9→9 |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.038 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0615P)2 + 15.455P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | (Δ/σ)max < 0.001 |
1909 reflections | Δρmax = 1.25 e Å−3 |
71 parameters | Δρmin = −1.33 e Å−3 |
0 restraints |
[Fe2Pt3(CN)12] | V = 1633.78 (9) Å3 |
Mr = 1009.18 | Z = 2 |
Monoclinic, C2/m | Mo Kα radiation |
a = 16.0140 (5) Å | µ = 13.68 mm−1 |
b = 13.8250 (5) Å | T = 293 K |
c = 7.5720 (2) Å | 0.04 × 0.04 × 0.02 mm |
β = 102.946 (2)° |
Oxford Diffraction Gemini S Ultra diffractometer | 1909 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1568 reflections with I > 2σ(I) |
Tmin = 0.611, Tmax = 0.772 | Rint = 0.038 |
3358 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0615P)2 + 15.455P] where P = (Fo2 + 2Fc2)/3 |
S = 0.97 | Δρmax = 1.25 e Å−3 |
1909 reflections | Δρmin = −1.33 e Å−3 |
71 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 | ||
Pt1 | 0.0000 | 0.0000 | 0.0000 | 0.02376 (17) | |
Pt2 | 0.19452 (3) | 0.5000 | 0.47749 (5) | 0.02524 (16) | |
Fe | 0.2500 | 0.2500 | 0.0000 | 0.0215 (3) | |
N1 | 0.1335 (5) | 0.1622 (5) | −0.0284 (10) | 0.0368 (17) | |
N2 | 0.2081 (6) | 0.3449 (5) | 0.1843 (10) | 0.0400 (18) | |
N3 | 0.3039 (6) | 0.1577 (5) | 0.2273 (10) | 0.0385 (17) | |
C1 | 0.0859 (5) | 0.1023 (6) | −0.0190 (12) | 0.0310 (17) | |
C2 | 0.2001 (6) | 0.4002 (6) | 0.2915 (11) | 0.0335 (19) | |
C3 | 0.3072 (6) | 0.1012 (6) | 0.3373 (10) | 0.0312 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0208 (3) | 0.0167 (3) | 0.0343 (3) | 0.000 | 0.0073 (2) | 0.000 |
Pt2 | 0.0389 (3) | 0.0182 (2) | 0.0195 (2) | 0.000 | 0.00824 (18) | 0.000 |
Fe | 0.0294 (8) | 0.0165 (7) | 0.0199 (7) | −0.0040 (6) | 0.0083 (6) | −0.0004 (5) |
N1 | 0.041 (4) | 0.026 (4) | 0.042 (4) | −0.009 (3) | 0.008 (4) | −0.002 (3) |
N2 | 0.056 (5) | 0.030 (4) | 0.038 (4) | −0.004 (4) | 0.017 (4) | −0.006 (3) |
N3 | 0.053 (5) | 0.026 (4) | 0.037 (4) | 0.002 (4) | 0.011 (4) | 0.006 (3) |
C1 | 0.028 (4) | 0.023 (4) | 0.043 (4) | 0.000 (3) | 0.011 (4) | 0.004 (3) |
C2 | 0.050 (6) | 0.026 (4) | 0.026 (4) | 0.003 (4) | 0.012 (4) | −0.001 (3) |
C3 | 0.045 (5) | 0.021 (4) | 0.025 (4) | −0.001 (4) | 0.004 (4) | 0.000 (3) |
Pt1—C1 | 2.000 (8) | Fe—N2 | 2.130 (7) |
Pt1—C1i | 2.000 (8) | Fe—N3vii | 2.161 (7) |
Pt1—C1ii | 2.000 (8) | Fe—N3 | 2.161 (7) |
Pt1—C1iii | 2.000 (8) | Fe—N1vii | 2.195 (7) |
Pt2—C3iv | 1.986 (8) | Fe—N1 | 2.195 (7) |
Pt2—C3v | 1.986 (8) | N1—C1 | 1.139 (10) |
Pt2—C2 | 1.988 (8) | N2—C2 | 1.143 (11) |
Pt2—C2vi | 1.988 (8) | N3—C3 | 1.134 (10) |
Fe—N2vii | 2.130 (7) | C3—Pt2v | 1.986 (8) |
C1—Pt1—C1i | 90.0 (5) | N3vii—Fe—N3 | 180.0 (3) |
C1—Pt1—C1ii | 180.0 (6) | N2vii—Fe—N1vii | 91.1 (3) |
C1i—Pt1—C1ii | 90.0 (5) | N2—Fe—N1vii | 88.9 (3) |
C1—Pt1—C1iii | 90.0 (5) | N3vii—Fe—N1vii | 86.0 (3) |
C1i—Pt1—C1iii | 180.0 (6) | N3—Fe—N1vii | 94.0 (3) |
C1ii—Pt1—C1iii | 90.0 (5) | N2vii—Fe—N1 | 88.9 (3) |
C3iv—Pt2—C3v | 89.6 (4) | N2—Fe—N1 | 91.1 (3) |
C3iv—Pt2—C2 | 178.1 (4) | N3vii—Fe—N1 | 94.0 (3) |
C3v—Pt2—C2 | 91.2 (3) | N3—Fe—N1 | 86.0 (3) |
C3iv—Pt2—C2vi | 91.2 (3) | N1vii—Fe—N1 | 180.0 (2) |
C3v—Pt2—C2vi | 178.1 (4) | C1—N1—Fe | 164.2 (7) |
C2—Pt2—C2vi | 87.9 (5) | C2—N2—Fe | 168.3 (8) |
N2vii—Fe—N2 | 180.0 (5) | C3—N3—Fe | 159.4 (8) |
N2vii—Fe—N3vii | 88.3 (3) | N1—C1—Pt1 | 178.3 (7) |
N2—Fe—N3vii | 91.7 (3) | N2—C2—Pt2 | 175.9 (9) |
N2vii—Fe—N3 | 91.7 (3) | N3—C3—Pt2v | 176.4 (8) |
N2—Fe—N3 | 88.3 (3) |
Symmetry codes: (i) x, −y, z; (ii) −x, −y, −z; (iii) −x, y, −z; (iv) −x+1/2, y+1/2, −z+1; (v) −x+1/2, −y+1/2, −z+1; (vi) x, −y+1, z; (vii) −x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Fe2Pt3(CN)12] |
Mr | 1009.18 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 16.0140 (5), 13.8250 (5), 7.5720 (2) |
β (°) | 102.946 (2) |
V (Å3) | 1633.78 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 13.68 |
Crystal size (mm) | 0.04 × 0.04 × 0.02 |
Data collection | |
Diffractometer | Oxford Diffraction Gemini S Ultra |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.611, 0.772 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3358, 1909, 1568 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 0.97 |
No. of reflections | 1909 |
No. of parameters | 71 |
w = 1/[σ2(Fo2) + (0.0615P)2 + 15.455P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.25, −1.33 |
Computer programs: COLLECT (Nonius, 1999), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).