Literature DB >> 21588082

trans-K(3)[TcO(2)(CN)(4)].

Sayandev Chatterjee, Andrew S Del Negro, Matthew K Edwards, Brendan Twamley, Jeanette A Krause, Samuel A Bryan.

Abstract

The structure of the title compound, tripotassium trans-tetra-cyanidodioxidotechnetate(V), is isotypic with its Re analogue. The [TcO(2)(CN)(4)](3-)trans-tetra-cyanido-dioxido-technetate anion has a slightly distorted octa-hedral 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 octa-hedral or tetra-hedral environments, respectively. K⋯O and K⋯N inter-actions occur in the 2.7877 (19)-2.8598 (15) Å range.

Entities: Chemical Disease Species

Year: 2010 PMID： 21588082 PMCID： PMC3007308 DOI： 10.1107/S1600536810028205

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

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 were given by Trop et al. (1980 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

K3[TcO2(CN)4] M = 351.38 Triclinic, 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 ▶) T min = 0.490, T max = 0.705 3949 measured reflections 1097 independent reflections 1064 reflections with > σ(I) R int = 0.072

Refinement

R[F 2 > 2σ(F 2)] = 0.020 wR(F 2) = 0.049 S = 1.09 1097 reflections 68 parameters Δρmax = 0.77 e Å−3 Δρmin = −0.90 e Å−3 Data collection: SMART (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028205/wm2375sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028205/wm2375Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

K3[TcO₂(CN)₄]	Z = 1
M_r = 351.38	F(000) = 168
Triclinic, P1	D_x = 2.202 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2539 (6) Å	Cell parameters from 3550 reflections
b = 6.9389 (6) Å	θ = 3.2–30.0°
c = 7.4347 (7) Å	µ = 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

Bruker SMART APEX diffractometer	1097 independent reflections
Radiation source: normal-focus sealed tube	1064 reflections with > σ(I)
graphite	R_int = 0.072
ω scans	θ_max = 26.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −7→7
T_min = 0.490, T_max = 0.705	k = −8→8
3949 measured reflections	l = −9→9

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.020	w = 1/[σ²(F_o²) + (0.0114P)² + 0.0622P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.049	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.77 e Å⁻³
1097 reflections	Δρ_min = −0.90 e Å⁻³
68 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.024 (3)

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.

	x	y	z	U_iso*/U_eq
K1	0.5000	0.0000	1.0000	0.01358 (15)
K2	0.04367 (6)	0.33536 (7)	0.69923 (6)	0.01283 (13)
Tc1	0.5000	0.5000	0.5000	0.00885 (11)
O1	0.6628 (2)	0.3641 (2)	0.39016 (18)	0.0123 (3)
N1	0.6522 (3)	0.3389 (3)	0.8804 (2)	0.0159 (4)
N2	−0.0098 (3)	0.0509 (3)	0.2506 (2)	0.0161 (4)
C1	0.5999 (3)	0.3996 (3)	0.7507 (3)	0.0120 (4)
C2	0.1707 (3)	0.2034 (3)	0.3254 (3)	0.0123 (4)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
K1	0.0127 (3)	0.0130 (3)	0.0118 (3)	0.0033 (2)	0.0024 (2)	0.0064 (2)
K2	0.0118 (2)	0.0155 (3)	0.0129 (2)	0.00591 (17)	0.00588 (15)	0.00746 (18)
Tc1	0.00763 (14)	0.01073 (17)	0.00889 (14)	0.00383 (10)	0.00354 (9)	0.00513 (10)
O1	0.0110 (6)	0.0132 (7)	0.0131 (6)	0.0052 (5)	0.0050 (5)	0.0063 (5)
N1	0.0157 (7)	0.0175 (10)	0.0145 (7)	0.0059 (7)	0.0061 (6)	0.0084 (7)
N2	0.0139 (7)	0.0172 (9)	0.0164 (7)	0.0056 (7)	0.0055 (6)	0.0085 (7)
C1	0.0100 (8)	0.0120 (10)	0.0121 (8)	0.0033 (7)	0.0055 (6)	0.0035 (7)
C2	0.0136 (8)	0.0157 (11)	0.0106 (8)	0.0084 (8)	0.0055 (6)	0.0071 (7)

Tc1—O1ⁱ	1.7721 (12)	N2—K2^v	2.7876 (19)
Tc1—O1	1.7721 (12)	N2—K1^vi	2.8598 (15)
Tc1—C1ⁱ	2.1423 (19)	K1—O1^vii	2.8235 (13)
Tc1—C1	2.1423 (19)	K1—O1^viii	2.8235 (13)
Tc1—C2	2.145 (2)	K1—N1	2.8315 (18)
Tc1—C2ⁱ	2.145 (2)	K1—N1^ix	2.8315 (18)
O1—K2ⁱⁱ	2.7937 (12)	K1—N2^x	2.8598 (15)
O1—K1ⁱⁱⁱ	2.8235 (13)	K1—N2^v	2.8598 (15)
O1—K2ⁱ	2.8262 (14)	K2—N2^v	2.7877 (19)
N1—C1	1.150 (3)	K2—O1^xi	2.7936 (12)
N1—K2^iv	2.8152 (16)	K2—N1^iv	2.8152 (16)
N1—K2ⁱⁱ	3.1710 (16)	K2—O1ⁱ	2.8262 (14)
N2—C2	1.151 (3)	K2—N1^xi	3.1710 (16)

O1ⁱ—Tc1—O1	180.0	C2—N2—K2^v	124.85 (13)
O1ⁱ—Tc1—C1ⁱ	90.13 (6)	C2—N2—K1^vi	127.59 (15)
O1—Tc1—C1ⁱ	89.87 (6)	K2^v—N2—K1^vi	107.51 (6)
O1ⁱ—Tc1—C1	89.87 (6)	O1^vii—K1—O1^viii	180.00 (5)
O1—Tc1—C1	90.13 (6)	O1^vii—K1—N1	97.86 (4)
C1ⁱ—Tc1—C1	179.999 (1)	O1^viii—K1—N1	82.14 (4)
O1ⁱ—Tc1—C2	88.60 (6)	O1^vii—K1—N1^ix	82.14 (4)
O1—Tc1—C2	91.40 (6)	O1^viii—K1—N1^ix	97.86 (4)
C1ⁱ—Tc1—C2	92.34 (7)	N1—K1—N1^ix	180.00 (7)
C1—Tc1—C2	87.66 (7)	O1^vii—K1—N2^x	104.18 (4)
O1ⁱ—Tc1—C2ⁱ	91.40 (6)	O1^viii—K1—N2^x	75.82 (4)
O1—Tc1—C2ⁱ	88.60 (6)	N1—K1—N2^x	95.00 (5)
C1ⁱ—Tc1—C2ⁱ	87.66 (7)	N1^ix—K1—N2^x	85.00 (5)
C1—Tc1—C2ⁱ	92.34 (7)	O1^vii—K1—N2^v	75.82 (4)
C2—Tc1—C2ⁱ	180.0	O1^viii—K1—N2^v	104.18 (4)
Tc1—O1—K2ⁱⁱ	111.70 (5)	N1—K1—N2^v	85.00 (5)
Tc1—O1—K1ⁱⁱⁱ	131.58 (5)	N1^ix—K1—N2^v	95.00 (5)
K2ⁱⁱ—O1—K1ⁱⁱⁱ	107.62 (4)	N2^x—K1—N2^v	180.0
Tc1—O1—K2ⁱ	106.54 (6)	N2^v—K2—O1^xi	123.16 (4)
K2ⁱⁱ—O1—K2ⁱ	98.26 (4)	N2^v—K2—N1^iv	101.64 (5)
K1ⁱⁱⁱ—O1—K2ⁱ	94.38 (4)	O1^xi—K2—N1^iv	125.77 (5)
N1—C1—Tc1	177.71 (16)	N2^v—K2—O1ⁱ	139.59 (4)
N2—C2—Tc1	172.74 (15)	O1^xi—K2—O1ⁱ	81.74 (4)
C1—N1—K2^iv	116.78 (14)	N1^iv—K2—O1ⁱ	82.38 (5)
C1—N1—K1	145.03 (14)	N2^v—K2—N1^xi	84.21 (5)
K2^iv—N1—K1	94.44 (5)	O1^xi—K2—N1^xi	77.02 (4)
C1—N1—K2ⁱⁱ	73.15 (11)	N1^iv—K2—N1^xi	79.06 (5)
K2^iv—N1—K2ⁱⁱ	100.94 (5)	O1ⁱ—K2—N1^xi	135.31 (4)
K1—N1—K2ⁱⁱ	118.11 (6)

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)

5 in total

1. The Cambridge Structural Database: a quarter of a million crystal structures and rising.

Authors: Frank H Allen
Journal: Acta Crystallogr B Date: 2002-05-29

Review 2. Technetium and gallium derived radiopharmaceuticals: comparing and contrasting the chemistry of two important radiometals for the molecular imaging era.

Authors: Mark D Bartholomä; Anika S Louie; John F Valliant; Jon Zubieta
Journal: Chem Rev Date: 2010-05-12 Impact factor: 60.622