Hexacarbonyl-technetium(I) perchlorate.

The title compound, [Tc(CO)(6)]ClO(4), was synthesized by the reaction of [TcCl(CO)(5)] with AgClO(4), followed by acidification with HClO(4) under a CO atmosphere. The [Tc(CO)(6)](+) cation has close to idealized octa-hedral geometry, with the bond angles between cis-CO groups close to 90° and the Tc-C bond lengths in the range 2.025 (3)-2.029 (3)Å. The perchlorate anion is disordered over two crystallographically equivalent half-occupied positions. The Tc atom in the [Tc(CO)(6)](+) cation is located on an inversion centre.

Related literature

For the first report on the [Tc(CO)6]+ cation, see: Hieber et al. (1965 ▶). For related literature, see: Aebischer et al. (2000 ▶); Alberto et al. (1996 ▶, 1998 ▶); Baturin et al. (1994a ▶,b ▶); Grigor’ev et al. (1997a ▶,b ▶); Miroslavov et al. (2008a ▶,b ▶); Schwochau (2000 ▶).

Experimental

Crystal data

[Tc(CO)6]ClO4

M = 366.42

Monoclinic,

a = 13.227 (4) Å

b = 6.8002 (18) Å

c = 13.616 (3) Å

β = 112.56 (2)°

V = 1131.0 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.55 mm−1

T = 293 (2) K

0.20 × 0.18 × 0.10 mm

Data collection

Stoe IPDS-2 diffractometer

Absorption correction: integration (X-RED and X-SHAPE; Stoe & Cie, 2005 ▶) T min = 0.620, T max = 0.723

4935 measured reflections

1508 independent reflections

1224 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.067

S = 1.06

1508 reflections

99 parameters

Δρmax = 0.32 e Å−3

Δρmin = −0.44 e Å−3

Data collection: X-AREA (Stoe & Cie, 2007 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2005 ▶); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 2000 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025208/fj2134sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025208/fj2134Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Tc(CO)6]ClO4	F000 = 704
Mr = 366.42	Dx = 2.152 Mg m−3
Monoclinic, C2/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5446 reflections
a = 13.227 (4) Å	θ = 2.0–29.6º
b = 6.8002 (18) Å	µ = 1.55 mm−1
c = 13.616 (3) Å	T = 293 (2) K
β = 112.56 (2)º	Prism, colorless
V = 1131.0 (5) Å3	0.20 × 0.18 × 0.10 mm
Z = 4

Stoe IPDS-2 diffractometer	1508 independent reflections
Radiation source: fine-focus sealed tube	1224 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.035
Detector resolution: 6.67 pixels mm-1	θmax = 29.2º
T = 293(2) K	θmin = 3.2º
rotation method scans	h = −18→18
Absorption correction: integration(X-RED and X-SHAPE; Stoe & Cie, 2005)	k = −9→8
Tmin = 0.620, Tmax = 0.723	l = −18→18
4935 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0289P)2 + 1.543P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.031	(Δ/σ)max < 0.001
wR(F2) = 0.067	Δρmax = 0.32 e Å−3
S = 1.06	Δρmin = −0.44 e Å−3
1508 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
99 parameters	Extinction coefficient: 0.0043 (12)
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
Tc1	0.2500	0.2500	0.0000	0.03673 (14)
C1	0.2509 (2)	0.1350 (5)	0.1375 (2)	0.0484 (7)
C2	0.3021 (2)	−0.0119 (5)	−0.0345 (2)	0.0446 (6)
C3	0.4088 (2)	0.3328 (5)	0.0721 (3)	0.0501 (7)
O1	0.3312 (2)	−0.1557 (4)	−0.0529 (2)	0.0632 (6)
O2	0.49658 (19)	0.3762 (4)	0.1078 (3)	0.0774 (8)
O3	0.2481 (2)	0.0685 (5)	0.2111 (2)	0.0778 (8)
O4	0.0932 (2)	−0.2268 (5)	−0.1933 (3)	0.0814 (9)
O5	0.503 (3)	0.0179 (9)	0.2724 (16)	0.109 (7)	0.50
O6	0.5401 (5)	−0.1423 (12)	0.1398 (5)	0.0856 (18)	0.50
Cl1	0.50996 (15)	−0.1697 (2)	0.22853 (14)	0.0480 (4)	0.50

	U11	U22	U33	U12	U13	U23
Tc1	0.03421 (17)	0.04318 (19)	0.03316 (17)	0.00255 (14)	0.01331 (11)	−0.00340 (15)
C1	0.0481 (15)	0.0592 (18)	0.0423 (16)	0.0126 (13)	0.0222 (12)	0.0041 (13)
C2	0.0403 (13)	0.0519 (15)	0.0404 (14)	0.0037 (12)	0.0141 (11)	−0.0028 (12)
C3	0.0418 (14)	0.0527 (15)	0.0545 (18)	0.0005 (13)	0.0172 (13)	−0.0074 (14)
O1	0.0693 (15)	0.0567 (14)	0.0658 (16)	0.0148 (12)	0.0284 (12)	−0.0076 (12)
O2	0.0433 (12)	0.0782 (18)	0.105 (2)	−0.0091 (12)	0.0216 (13)	−0.0225 (16)
O3	0.0830 (18)	0.105 (2)	0.0609 (16)	0.0297 (16)	0.0444 (14)	0.0249 (16)
O4	0.0566 (14)	0.096 (2)	0.087 (2)	−0.0202 (14)	0.0229 (14)	−0.0261 (16)
O5	0.077 (4)	0.074 (3)	0.155 (19)	−0.002 (8)	0.021 (12)	−0.052 (8)
O6	0.072 (3)	0.120 (5)	0.061 (3)	−0.019 (3)	0.021 (3)	0.019 (4)
Cl1	0.0366 (7)	0.0512 (6)	0.0497 (12)	−0.0023 (6)	0.0094 (6)	−0.0015 (6)

Tc1—C1i	2.025 (3)	O5—O5iv	0.59 (4)
Tc1—C1	2.025 (3)	O5—Cl1iv	1.286 (8)
Tc1—C3i	2.027 (3)	O5—Cl1	1.428 (11)
Tc1—C3	2.027 (3)	O6—Cl1	1.422 (6)
Tc1—C2i	2.029 (3)	O6—Cl1iv	2.144 (6)
Tc1—C2	2.029 (3)	Cl1—Cl1iv	0.728 (3)
C1—O3	1.113 (4)	Cl1—O5iv	1.286 (8)
C2—O1	1.114 (4)	Cl1—O4v	1.393 (3)
C3—O2	1.113 (4)	Cl1—O4iii	1.444 (3)
O4—Cl1ii	1.393 (3)	Cl1—O6iv	2.144 (6)
O4—Cl1iii	1.444 (3)
C1i—Tc1—C1	180.0 (2)	O1—C2—Tc1	179.6 (3)
C1i—Tc1—C3i	91.27 (14)	O2—C3—Tc1	177.0 (3)
C1—Tc1—C3i	88.73 (14)	O5iv—Cl1—O4v	124.7 (11)
C1i—Tc1—C3	88.73 (14)	O4v—Cl1—O5	107.0 (10)
C1—Tc1—C3	91.27 (14)	O5iv—Cl1—O6	86.5 (11)
C3i—Tc1—C3	180.0 (3)	O4v—Cl1—O6	108.6 (3)
C1i—Tc1—C2i	89.61 (12)	O5—Cl1—O6	108.9 (9)
C1—Tc1—C2i	90.39 (12)	O5iv—Cl1—O4iii	112.3 (14)
C3i—Tc1—C2i	88.56 (12)	O4v—Cl1—O4iii	112.1 (3)
C3—Tc1—C2i	91.44 (12)	O5—Cl1—O4iii	111.5 (13)
C1i—Tc1—C2	90.39 (12)	O6—Cl1—O4iii	108.6 (3)
C1—Tc1—C2	89.61 (12)	O5iv—Cl1—O6iv	80.9 (11)
C3i—Tc1—C2	91.44 (12)	O4v—Cl1—O6iv	79.2 (2)
C3—Tc1—C2	88.56 (12)	O5—Cl1—O6iv	58.6 (10)
C2i—Tc1—C2	180.00 (17)	O6—Cl1—O6iv	167.4 (6)
O3—C1—Tc1	177.6 (3)	O4iii—Cl1—O6iv	76.4 (2)