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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Pages i61-i62
https://doi.org/10.1107/S1600536810028205

trans-K3[TcO2(CN)4]

Sayandev Chatterjee,a Andrew S. Del Negro,a Matthew K. Edwards,a Brendan Twamley,b Jeanette A. Krausec and Samuel A. Bryana*

aRadiochemical Processing Laboratory, Pacific Northwest National Laboratory, Richland, WA 99357, USA, bDepartment of Chemistry, University of Idaho, Moscow, ID 83844, USA, and cDepartment of Chemistry, University of Cincinnati, Cincinnati, OH 45221-0172, USA
*Correspondence e-mail: sam.bryan@pnl.gov

(Received 8 July 2010; accepted 14 July 2010; online 21 July 2010)

The structure of the title compound, tripotassium trans-tetra­cyanidodioxidotechnetate(V), is isotypic with its Re analogue. The [TcO2(CN)4]3− trans-tetra­cyanido­dioxido­technetate anion has a slightly distorted octa­hedral configuration. The Tc atom is located on a center of inversion and is bound to two O atoms in axial and to four cyanide ligands in equatorial positions. The Tc—O distance is consistent with a double-bond character. The two potassium cations, one located on a center of inversion and one in a general position, reside in octa­hedral or tetra­hedral environments, respectively. K⋯O and K⋯N inter­actions occur in the 2.7877 (19)–2.8598 (15) Å range.

Related literature

The isotypic rhenate(V) analogue was reported by Fenn et al. (1971[Fenn, R. H., Graham, A. J. & Johnson, N. P. (1971). J. Chem. Soc. A, pp. 2880-2883.]) (neutron study) and Murmann & Schlemper (1971[Murmann, R. K. & Schlemper, E. O. (1971). Inorg. Chem. 10, 2352-2354.]) (X-ray study). For further information on dioxidotetra­cyanido anions of Tc and Re, see: Fackler et al. (1985[Fackler, P. H., Lindsay, M. J., Clarke, M. J. & Kastner, M. E. (1985). Inorg. Chim. Acta, 109, 39-49.]); Kastner et al. (1982[Kastner, M. E., Lindsay, M. J. & Clarke, M. J. (1982). Inorg. Chem. 21, 2037-2040.], 1984[Kastner, M. E., Fackler, P. H., Clarke, M. J. & Deutsch, E. (1984). Inorg. Chem. 23, 4683-4688.]); Kremer et al. (1997[Kremer, C., Gancheff, J., Kremer E., Mombru, A. W., Gonzalez, O., Mariezcurrena, R., Suescun, L, Cubas, M. L. & Ventura, O. N. (1997). Polyhedron, 19, 3311-3316.]). Luminescence properties of Tc complexes were reported by Del Negro et al. (2005[Del Negro, A. S., Wang, Z., Seliskar, C. J., Heineman, W. R., Hightower, S. E., Bryan, S. A. & Sullivan, B. P. (2005). J. Am. Chem. Soc. 127, 14978-14979.], 2006[Del Negro, A. S., Seliskar, C. J., Heineman, W. R., Hightower, S. E., Bryan, S. A. & Sullivan, B. P. (2006). J. Am. Chem. Soc. 128, 16494-16495.]). For further information on hydroxidooxidotetra­cyanido or aqua­oxidotetra­cyanido anions of Tc and Re, see: Baldas et al. (1990[Baldas, J., Boas, J. F., Colmanet, S. F. & Mackay, J. F. (1990). Inorg. Chim. Acta, 170, 233-239.]); Purcell et al. (1989[Purcell, W., Roodt, A., Basson, S. S. & Leipoldt, J. G. (1989). Transition Met. Chem. 14, 5-6.], 1990[Purcell, W., Roodt, A., Basson, S. S. & Leipoldt, J. G. (1990). Transition Met. Chem. 15, 239-241.]). For general reviews on technetium structures, see: Bandoli et al. (2001[Bandoli, G., Dolmella, A., Porchia, M., Refosco, F. & Tisato, F. (2001). Coord. Chem. Rev. 214, 43-90.], 2006[Bandoli, G., Tisato, F., Dolmella, A. & Agostini, S. (2006). Coord. Chem. Rev. 250, 561-573.]); Bartholoma et al. (2010[Bartholoma, M. D., Louie, A. S., Valliant, J. F. & Zubieta, J. (2010). Chem. Rev. 110, 2903-2920.]); Tisato et al. (1994[Tisato, F., Refosco, F. & Bandoli, G. (1994). Coord. Chem. Rev. 135-136, 325-397.]). Synthetic details were given by Trop et al. (1980[Trop, H. S., Jones, A. G. & Davison, A. (1980). Inorg. Chem. 19, 1993-1997.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

Experimental

Crystal data

  • K3[TcO2(CN)4]

  • Mr = 351.38

  • Triclinic, [P \overline 1]

  • a = 6.2539 (6) Å

  • b = 6.9389 (6) Å

  • c = 7.4347 (7) Å

  • α = 108.305 (1)°

  • β = 109.816 (2)°

  • γ = 104.143 (1)°

  • V = 265.01 (4) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 2.51 mm−1

  • T = 90 K

  • 0.32 × 0.20 × 0.14 mm
Data collection

  • Bruker SMART APEX diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007[Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany.]) Tmin = 0.490, Tmax = 0.705

  • 3949 measured reflections

  • 1097 independent reflections

  • 1064 reflections with > σ(I)

  • Rint = 0.072
Refinement

  • R[F2 > 2σ(F2)] = 0.020

  • wR(F2) = 0.049

  • S = 1.09

  • 1097 reflections

  • 68 parameters

  • Δρmax = 0.77 e Å−3

  • Δρmin = −0.90 e Å−3

Table 1
Selected geometric parameters (Å, °)

Tc1—O1 1.7721 (12)
Tc1—C1 2.1423 (19)
Tc1—C2 2.145 (2)
N1—C1 1.150 (3)
N2—C2 1.151 (3)
N1—C1—Tc1 177.71 (16)
N2—C2—Tc1 172.74 (15)

Data collection: SMART (Bruker, 2006[Bruker (2006). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810028205/wm2375sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810028205/wm2375Isup2.hkl

checkCIF report


Comment top

99Tc is the most significant long-lived product of uranium fission. In addition to a long half-life (2.13x105 yrs), it is readily water soluble, making it extremely mobile in the environment. This, coupled with its ability to form anionic species, causes major concern when considering long-term disposal of high-level radioactive waste. Thus, it is imperative to provide methods for chemical detection of 99Tc. Under normal environmental conditions, 99Tc composition is dominated by the pertechnetate anion (TcO4-) which lacks a characteristic spectral signature. This prevents its rapid, sensitive and economic in situ detection. In order to address this problem, our research is focused on designing a suitable sensor for the detection of TcO4-. The ultimate aim is to chemically convert the pertechnetate anion to an organic-ligated species that will have a readily characterizable spectral signature. As a first step to address this problem, our group has been able to identify several technetium complexes with long-lived excited states. Thus, the luminescence properties of technetium(V)-dioxidotetrapyridyl and technetium(II)-tris(1,2-bis(dimethylphosphino)ethane) were reported by Del Negro et al. (2005, 2006).

However, the significant dearth of Tc structures in general (Bandoli et al., 2001, 2006; Bartholoma et al., 2010; Tisato et al., 1994) has resulted in a substantial knowledge gap in the structures and bonding of technetium complexes, thereby preventing the correlation of the electronic properties with structural parameters. As a representative comparison, the Cambridge Structural Database (CSD, version 5.31; Allen, 2002) currently contains 21 dioxidotechnetium complexes compared to 141 structures reported for dioxidorhenium and dioxidomanganese complexes. In an attempt to bridge this gap, we are focusing on the structural characterization of a series of dioxidotechnetium(V) complexes. Herein, we report the structure of K3[TcO2(CN)4], (I), a tetracyanidodioxidotechnetium(V) salt.

The unit cell of (I) is comprised of three K+ cations and one discrete [TcO2(CN)4]3- anion. The configuration of the anion is shown in Fig. 1. The Tc atom (located on an inversion center) resides in an octahedral environment defined by two oxido and four cyanido ligands. The trans basal C—Tc—C angles are linear resulting in a square planar arrangement of the tetracyanido groups about the Tc center.

The Tc═O distance (1.7721 (12) Å) is virtually identical to the Re═O distance in K3[ReO2(CN)4] [neutron study: 1.773 (8) Å (Fenn et al., 1971), X-ray study: 1.781 (3) Å (Murmann & Schlemper, 1971)]. An average Tc═O distance of 1.74 Å has been observed for an oxido ligand in cations of the type trans-[O2R4Tc]+ (R = 4-tert-butylpyridine, imidazole, 1-methylimidazole, trimethylenediamine) (Kastner et al., 1984; Fackler et al., 1985; Kremer et al., 1997) or trans-[O2en2Tc]+ (en = ethylenediamine) (Kastner et al., 1982) while a Tc—O distance of 2.559 (9) Å is observed in the [TcN(CN)4(OH2)]2- dianion reported by Baldas et al. (1990).

The Tc—C distances (2.1423 (19) and 2.145 (2) Å) determined in this study are slightly longer than reported by Murmann & Schlemper (1971) and Fenn et al. (1971) for the [ReO2(CN)4]3- anion (Re—Cave = 2.13 Å). In addition, we see a deviation from linearity for one Tc—C—N angle (172.74 (15)° versus 177.71 (16)°). Similar bending is common in the [ReO2(CN)4]3-, [ReO(OH)(CN)4]2- and [ReO(OH2)(CN)4]- anions (ave. 175° versus 178°) (Fenn et al., 1971; Murmann & Schlemper, 1971; Purcell et al., 1989, 1990) and may be a result of inequivalent interactions with the surrounding environment.

(I) shows interionic interactions between the K+ cations and the [TcO2(CN)4]3- anion. The K+ cations reside in two distinct environments [K1 located on a special position with inversion symmetry and K2 is located on a general position] (Fig 2). Each oxygen atom of the anion interacts with one K1 and two K2 atoms. The local environment about K1 is distorted octahedral, consisting of the following interactions: K1···O1 = 2.8235 (13) Å, K1···N1 = 2.8315 (18) Å, K1···N2 = 2.8598 (15) Å and the symmetry equivalents. On the other hand, the local environment about K2 is approximately tetrahedral with interactions of K2···O1 = 2.7936 (12) and 2.8262 (14) Å, K2···N1 = 2.8152 (16) Å and K2···N2 = 2.7877 (19) Å). In addition, there are three significantly longer contacts between K2 and N1 (3.1710 (16) and 3.5715 (16) Å) and K2 and N2 (3.1496 (17) Å).

Related literature top

The isotypic rhenate(V) analogue was reported by Fenn et al. (1971) (neutron study) and Murmann & Schlemper (1971) (X-ray study). For further information on dioxidotetracyanido anions of Tc and Re, see: Fackler et al. (1985); Kastner et al. (1982, 1984); Kremer et al. (1997). Luminescence properties of Tc complexes were reported by Del Negro et al. (2005, 2006). For further information on hydroxidooxidotetracyanido or aquaoxidotetracyanido anions of Tc and Re, see: Baldas et al. (1990); Purcell et al. (1989, 1990). For general reviews on technetium structures, see: Bandoli et al. (2001, 2006); Bartholoma et al. (2010); Tisato et al. (1994). Synthetic details are given by Trop et al. (1980). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

(I) is prepared from [TcO2(py)4]Cl (py = pyridyl) by the method of Trop et al. (1980). Complete cyanide substitution of the pyridyl groups of the starting material is achieved by adding an excess of alkaline cyanide.

In a typical preparation, 0.5 g of [TcO2(py)4]Cl was dissolved in a minimum amount of methanol. Addition of 50 ml of 1.2M KCN in 5:1 (v/v) methanol/water to the above resulted in an immediate green solution which turned yellow in approx. 5 minutes. This was followed by a gradual appearance of a fine yellow precipitate. The mixture was stirred on a hot plate set to low heat for an additional hour to ensure complete conversion. The supernatant was drawn off and the yellow precipitate was washed with diethyl ether. The yellow precipitate was dissolved in a minimal amount of water, followed by slow diffusion of methanol vapors, to yield crystals of (I) suitable for X-ray diffraction.

CAUTION! All syntheses and characterizations were performed with 99Tc, which is a β-emitting isotope with a half-life of 2.13x105 years. The handling of small quantities (generally <100 milligrams) of this material does not pose a serious health hazard since common laboratory materials provide adequate shielding. However, radiation safety procedures must be used to prevent contamination!

Structure description top

99Tc is the most significant long-lived product of uranium fission. In addition to a long half-life (2.13x105 yrs), it is readily water soluble, making it extremely mobile in the environment. This, coupled with its ability to form anionic species, causes major concern when considering long-term disposal of high-level radioactive waste. Thus, it is imperative to provide methods for chemical detection of 99Tc. Under normal environmental conditions, 99Tc composition is dominated by the pertechnetate anion (TcO4-) which lacks a characteristic spectral signature. This prevents its rapid, sensitive and economic in situ detection. In order to address this problem, our research is focused on designing a suitable sensor for the detection of TcO4-. The ultimate aim is to chemically convert the pertechnetate anion to an organic-ligated species that will have a readily characterizable spectral signature. As a first step to address this problem, our group has been able to identify several technetium complexes with long-lived excited states. Thus, the luminescence properties of technetium(V)-dioxidotetrapyridyl and technetium(II)-tris(1,2-bis(dimethylphosphino)ethane) were reported by Del Negro et al. (2005, 2006).

However, the significant dearth of Tc structures in general (Bandoli et al., 2001, 2006; Bartholoma et al., 2010; Tisato et al., 1994) has resulted in a substantial knowledge gap in the structures and bonding of technetium complexes, thereby preventing the correlation of the electronic properties with structural parameters. As a representative comparison, the Cambridge Structural Database (CSD, version 5.31; Allen, 2002) currently contains 21 dioxidotechnetium complexes compared to 141 structures reported for dioxidorhenium and dioxidomanganese complexes. In an attempt to bridge this gap, we are focusing on the structural characterization of a series of dioxidotechnetium(V) complexes. Herein, we report the structure of K3[TcO2(CN)4], (I), a tetracyanidodioxidotechnetium(V) salt.

The unit cell of (I) is comprised of three K+ cations and one discrete [TcO2(CN)4]3- anion. The configuration of the anion is shown in Fig. 1. The Tc atom (located on an inversion center) resides in an octahedral environment defined by two oxido and four cyanido ligands. The trans basal C—Tc—C angles are linear resulting in a square planar arrangement of the tetracyanido groups about the Tc center.

The Tc═O distance (1.7721 (12) Å) is virtually identical to the Re═O distance in K3[ReO2(CN)4] [neutron study: 1.773 (8) Å (Fenn et al., 1971), X-ray study: 1.781 (3) Å (Murmann & Schlemper, 1971)]. An average Tc═O distance of 1.74 Å has been observed for an oxido ligand in cations of the type trans-[O2R4Tc]+ (R = 4-tert-butylpyridine, imidazole, 1-methylimidazole, trimethylenediamine) (Kastner et al., 1984; Fackler et al., 1985; Kremer et al., 1997) or trans-[O2en2Tc]+ (en = ethylenediamine) (Kastner et al., 1982) while a Tc—O distance of 2.559 (9) Å is observed in the [TcN(CN)4(OH2)]2- dianion reported by Baldas et al. (1990).

The Tc—C distances (2.1423 (19) and 2.145 (2) Å) determined in this study are slightly longer than reported by Murmann & Schlemper (1971) and Fenn et al. (1971) for the [ReO2(CN)4]3- anion (Re—Cave = 2.13 Å). In addition, we see a deviation from linearity for one Tc—C—N angle (172.74 (15)° versus 177.71 (16)°). Similar bending is common in the [ReO2(CN)4]3-, [ReO(OH)(CN)4]2- and [ReO(OH2)(CN)4]- anions (ave. 175° versus 178°) (Fenn et al., 1971; Murmann & Schlemper, 1971; Purcell et al., 1989, 1990) and may be a result of inequivalent interactions with the surrounding environment.

(I) shows interionic interactions between the K+ cations and the [TcO2(CN)4]3- anion. The K+ cations reside in two distinct environments [K1 located on a special position with inversion symmetry and K2 is located on a general position] (Fig 2). Each oxygen atom of the anion interacts with one K1 and two K2 atoms. The local environment about K1 is distorted octahedral, consisting of the following interactions: K1···O1 = 2.8235 (13) Å, K1···N1 = 2.8315 (18) Å, K1···N2 = 2.8598 (15) Å and the symmetry equivalents. On the other hand, the local environment about K2 is approximately tetrahedral with interactions of K2···O1 = 2.7936 (12) and 2.8262 (14) Å, K2···N1 = 2.8152 (16) Å and K2···N2 = 2.7877 (19) Å). In addition, there are three significantly longer contacts between K2 and N1 (3.1710 (16) and 3.5715 (16) Å) and K2 and N2 (3.1496 (17) Å).

The isotypic rhenate(V) analogue was reported by Fenn et al. (1971) (neutron study) and Murmann & Schlemper (1971) (X-ray study). For further information on dioxidotetracyanido anions of Tc and Re, see: Fackler et al. (1985); Kastner et al. (1982, 1984); Kremer et al. (1997). Luminescence properties of Tc complexes were reported by Del Negro et al. (2005, 2006). For further information on hydroxidooxidotetracyanido or aquaoxidotetracyanido anions of Tc and Re, see: Baldas et al. (1990); Purcell et al. (1989, 1990). For general reviews on technetium structures, see: Bandoli et al. (2001, 2006); Bartholoma et al. (2010); Tisato et al. (1994). Synthetic details are given by Trop et al. (1980). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. : The structural moieties of (I) with the atomic labelling scheme and 50% probability ellipsoids. [Symmetry code: (i) -x + 1, -y + 1, -z + 1].
[Figure 2] Fig. 2. : The extended packing motif of (I) in the bc plane showing the octahedral and tetrahedral environments about the K+ ions. Dashed lines indicate the K···O (red) and K···N (blue) interionic interactions [K1 in light pink, K2 in dark pink].
tripotassium trans-tetracyanidodioxidotechnetate(V) top
Crystal data top
K3[TcO2(CN)4]Z = 1
Mr = 351.38F(000) = 168
Triclinic, P1Dx = 2.202 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.2539 (6) ÅCell parameters from 3550 reflections
b = 6.9389 (6) Åθ = 3.2–30.0°
c = 7.4347 (7) ŵ = 2.51 mm−1
α = 108.305 (1)°T = 90 K
β = 109.816 (2)°Fragment, yellow
γ = 104.143 (1)°0.32 × 0.20 × 0.14 mm
V = 265.01 (4) Å3
Data collection top
Bruker SMART APEX
diffractometer		1097 independent reflections
Radiation source: normal-focus sealed tube1064 reflections with > σ(I)
Graphite monochromatorRint = 0.072
ω scansθmax = 26.5°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		h = −7→7
Tmin = 0.490, Tmax = 0.705k = −8→8
3949 measured reflectionsl = −9→9
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)] = 0.020 w = 1/[σ2(Fo2) + (0.0114P)2 + 0.0622P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049(Δ/σ)max = 0.001
S = 1.09Δρmax = 0.77 e Å−3
1097 reflectionsΔρmin = −0.90 e Å−3
68 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.024 (3)
Crystal data top
K3[TcO2(CN)4]γ = 104.143 (1)°
Mr = 351.38V = 265.01 (4) Å3
Triclinic, P1Z = 1
a = 6.2539 (6) ÅMo Kα radiation
b = 6.9389 (6) ŵ = 2.51 mm−1
c = 7.4347 (7) ÅT = 90 K
α = 108.305 (1)°0.32 × 0.20 × 0.14 mm
β = 109.816 (2)°
Data collection top
Bruker SMART APEX
diffractometer		1097 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)		1064 reflections with > σ(I)
Tmin = 0.490, Tmax = 0.705Rint = 0.072
3949 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.02068 parameters
wR(F2) = 0.0490 restraints
S = 1.09Δρmax = 0.77 e Å−3
1097 reflectionsΔρmin = −0.90 e Å−3
Special details top

Experimental. A suitable crystal was mounted on a glass fiber and immediately transferred to the goniostat bathed in a cold stream.

CAUTION!All syntheses and characterizations were performed with99Tc, which is a β-emitting isotope with a half-life of 2.13x105 years. The handling of small quantities (generally <100 milligrams) of this material does not pose a serious health hazard since common laboratory materials provide adequate shielding. However, radiation safety procedures must be used to prevent contamination.

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
xyzUiso*/Ueq
K10.50000.00001.00000.01358 (15)
K20.04367 (6)0.33536 (7)0.69923 (6)0.01283 (13)
Tc10.50000.50000.50000.00885 (11)
O10.6628 (2)0.3641 (2)0.39016 (18)0.0123 (3)
N10.6522 (3)0.3389 (3)0.8804 (2)0.0159 (4)
N2−0.0098 (3)0.0509 (3)0.2506 (2)0.0161 (4)
C10.5999 (3)0.3996 (3)0.7507 (3)0.0120 (4)
C20.1707 (3)0.2034 (3)0.3254 (3)0.0123 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.0127 (3)0.0130 (3)0.0118 (3)0.0033 (2)0.0024 (2)0.0064 (2)
K20.0118 (2)0.0155 (3)0.0129 (2)0.00591 (17)0.00588 (15)0.00746 (18)
Tc10.00763 (14)0.01073 (17)0.00889 (14)0.00383 (10)0.00354 (9)0.00513 (10)
O10.0110 (6)0.0132 (7)0.0131 (6)0.0052 (5)0.0050 (5)0.0063 (5)
N10.0157 (7)0.0175 (10)0.0145 (7)0.0059 (7)0.0061 (6)0.0084 (7)
N20.0139 (7)0.0172 (9)0.0164 (7)0.0056 (7)0.0055 (6)0.0085 (7)
C10.0100 (8)0.0120 (10)0.0121 (8)0.0033 (7)0.0055 (6)0.0035 (7)
C20.0136 (8)0.0157 (11)0.0106 (8)0.0084 (8)0.0055 (6)0.0071 (7)
Geometric parameters (Å, º) top
Tc1—O1i1.7721 (12)N2—K2v2.7876 (19)
Tc1—O11.7721 (12)N2—K1vi2.8598 (15)
Tc1—C1i2.1423 (19)K1—O1vii2.8235 (13)
Tc1—C12.1423 (19)K1—O1viii2.8235 (13)
Tc1—C22.145 (2)K1—N12.8315 (18)
Tc1—C2i2.145 (2)K1—N1ix2.8315 (18)
O1—K2ii2.7937 (12)K1—N2x2.8598 (15)
O1—K1iii2.8235 (13)K1—N2v2.8598 (15)
O1—K2i2.8262 (14)K2—N2v2.7877 (19)
N1—C11.150 (3)K2—O1xi2.7936 (12)
N1—K2iv2.8152 (16)K2—N1iv2.8152 (16)
N1—K2ii3.1710 (16)K2—O1i2.8262 (14)
N2—C21.151 (3)K2—N1xi3.1710 (16)
O1i—Tc1—O1180.0C2—N2—K2v124.85 (13)
O1i—Tc1—C1i90.13 (6)C2—N2—K1vi127.59 (15)
O1—Tc1—C1i89.87 (6)K2v—N2—K1vi107.51 (6)
O1i—Tc1—C189.87 (6)O1vii—K1—O1viii180.00 (5)
O1—Tc1—C190.13 (6)O1vii—K1—N197.86 (4)
C1i—Tc1—C1179.999 (1)O1viii—K1—N182.14 (4)
O1i—Tc1—C288.60 (6)O1vii—K1—N1ix82.14 (4)
O1—Tc1—C291.40 (6)O1viii—K1—N1ix97.86 (4)
C1i—Tc1—C292.34 (7)N1—K1—N1ix180.00 (7)
C1—Tc1—C287.66 (7)O1vii—K1—N2x104.18 (4)
O1i—Tc1—C2i91.40 (6)O1viii—K1—N2x75.82 (4)
O1—Tc1—C2i88.60 (6)N1—K1—N2x95.00 (5)
C1i—Tc1—C2i87.66 (7)N1ix—K1—N2x85.00 (5)
C1—Tc1—C2i92.34 (7)O1vii—K1—N2v75.82 (4)
C2—Tc1—C2i180.0O1viii—K1—N2v104.18 (4)
Tc1—O1—K2ii111.70 (5)N1—K1—N2v85.00 (5)
Tc1—O1—K1iii131.58 (5)N1ix—K1—N2v95.00 (5)
K2ii—O1—K1iii107.62 (4)N2x—K1—N2v180.0
Tc1—O1—K2i106.54 (6)N2v—K2—O1xi123.16 (4)
K2ii—O1—K2i98.26 (4)N2v—K2—N1iv101.64 (5)
K1iii—O1—K2i94.38 (4)O1xi—K2—N1iv125.77 (5)
N1—C1—Tc1177.71 (16)N2v—K2—O1i139.59 (4)
N2—C2—Tc1172.74 (15)O1xi—K2—O1i81.74 (4)
C1—N1—K2iv116.78 (14)N1iv—K2—O1i82.38 (5)
C1—N1—K1145.03 (14)N2v—K2—N1xi84.21 (5)
K2iv—N1—K194.44 (5)O1xi—K2—N1xi77.02 (4)
C1—N1—K2ii73.15 (11)N1iv—K2—N1xi79.06 (5)
K2iv—N1—K2ii100.94 (5)O1i—K2—N1xi135.31 (4)
K1—N1—K2ii118.11 (6)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y, z; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+2; (v) −x, −y, −z+1; (vi) x−1, y, z−1; (vii) −x+1, −y, −z+1; (viii) x, y, z+1; (ix) −x+1, −y, −z+2; (x) x+1, y, z+1; (xi) x−1, y, z.

Experimental details

Crystal data
Chemical formulaK3[TcO2(CN)4]
Mr351.38
Crystal system, space groupTriclinic, P1
Temperature (K)90
a, b, c (Å)6.2539 (6), 6.9389 (6), 7.4347 (7)
α, β, γ (°)108.305 (1), 109.816 (2), 104.143 (1)
V (Å3)265.01 (4)
Z1
Radiation typeMo Kα
µ (mm−1)2.51
Crystal size (mm)0.32 × 0.20 × 0.14
Data collection
DiffractometerBruker SMART APEX
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.490, 0.705
No. of measured, independent and
observed [ > σ(I)] reflections		3949, 1097, 1064
Rint0.072
(sin θ/λ)max (Å−1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.049, 1.09
No. of reflections1097
No. of parameters68
Δρmax, Δρmin (e Å−3)0.77, −0.90

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2010).

Selected geometric parameters (Å, º) top
Tc1—O11.7721 (12)N1—C11.150 (3)
Tc1—C12.1423 (19)N2—C21.151 (3)
Tc1—C22.145 (2)
N1—C1—Tc1177.71 (16)N2—C2—Tc1172.74 (15)
 

Acknowledgements

We thank Dr Sean E. Hightower and Mr Chuck Z. Soderquist for helpful discussion during the synthesis and crystallization. Financial support was provided by DOE EMSP grant DE–FG02-07ER51629. The SMART APEX Diffraction Facility (University of Idaho) was funded by NSF-EPSCoR and the M. J. Murdock Charitable Trust, Vancouver, WA. The Radiochemical Processing and the Environmental Mol­ecular Science Laboratories are national scientific user facilities sponsored by the DOE Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the DOE under Contract DE–AC05-76RL01830.

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ISSN: 2056-9890
Volume 66| Part 8| August 2010| Pages i61-i62
https://doi.org/10.1107/S1600536810028205
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