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The two title compounds, [Re(C10H10N6)(CO)3]Br and [Re(C11H12N6)(CO)3]I·0.5C2H6O, have slightly distorted octahedral geometries about the rhenium centers. The distortions result from the constraints of the η3-coordinated tris­(pyrazol-1-yl)­methane ligands in each case which reduce the N—Re—N bond angles well below the preferred value of 90° for facially disposed ligands at a six-coordinate metal center.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009349/bk1610sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009349/bk1610Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009349/bk1610IIsup3.hkl
Contains datablock II

CCDC references: 174792; 174793

Comment top

The title compounds, (I) and (II), respectively, have been prepared as part of a general study of ligand systems which are capable of variable denticity. The tris(pyrazol-1-yl)methane ligand [HC(pz)3] has previously demonstrated the capacity for either bidentate or tridentate coordination (Macchioni et al., 1998). Flexibility in changing between these two coordination modes may play an important role in catalytic processes, as demonstrated for some of the closely related tris(pyrazol-1-yl)borate complexes (Bromberg et al., 1996). Compounds (I) and (II) have been characterized in order to increase our knowledge of the structural charcterstics of metal complexes with this ligand.

Fig. 1 shows an ORTEP-3 diagram (Farrugia, 1997) illustrating the cation of (I). The constraints of the η3-coordinated HC(pz)3 ligand reduce the N—Re—N bond angles well below the preferred value of 90°. The N—Re—N bond angles in (I) are also smaller [average 81.4 (1)°] than those in [HC(3-iPrpz)3Mn(CO)3](SO3CF3) (Reger et al., 2000), which average 85.0 (3)°. The C—Re—C bond angles associated with the three facial carbonyl groups in (I) average 88.8 (3)°, whereas the corresponding angles in the Mn complex are slightly greater, with an average of 89.6 (5)°. The constraints of the HC(pz)3 ligand in (I) also ensure that trans arrangements such as C3—Re—N1 will be well below 180°; they range from 173.5 (2)° for C3—Re—N1 to 176.4 (2)° for C1—Re—N5, and all are bent toward the HC(pz)3 ligand. The corresponding angles in the manganese complex are slightly larger, ranging from 175.7 (4) to 177.7 (4)°, reflecting the influence of the isopropyl substituents at position 3 of the pyrazole ring.

An ORTEP-3 diagram (Farrugia, 1997) of the cation of (II) is shown in Fig. 2; similar distortions are seen in (II). The bond angles for trans groups, such as C3—Re—N1, are again well below 180°; they range from 172.4 (3)° for C2—Re—N3 to 174.9 (3)° for C3—Re—N1. The N—Re—N bond angles are even smaller in (II) than in (I) [average 80.5 (2)°], but the C—Re—C bond angles associated with the three facial carbonyl groups are slightly larger than the corresponding angles in (I) [average 89.4 (4)°]. Replacement of hydrogen by methyl in CH3C(pz)3 does not appear to cause any significant distortions in the complex.

Experimental top

The synthesis of (I) was carried out by refluxing Re(CO)5Br and tris(pyrazol-1-yl)methane (1:1) in ethanol for 4 h. Crystals were obtained after allowing the solution to cool overnight to 295 K. Stirring (I) with sodium methoxide (1:1) in methanol for 30 min effected its deprotonation; the neutral product was isolated by evaporation of solvent followed by extraction into CH2Cl2. Addition of excess CH3I to this extract, followed by stirring for 4 h, converted the neutral compound to (II). The crude product, (II), was isolated as a colorless solid by evaporating the methylene chloride. Crystals of (II) were obtained by dissolving the product in ethanol and allowing the solution to stand for several days at 253 K.

Refinement top

H-atom positions were all calculated and their refinement was constrained with C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C) for the pyrazole, methylene and methine H atoms. For the methyl groups, the torsion angle which defined the orientation was not allowed to refine, and these atoms were assigned Uiso(H) = 1.5Ueq(C). The occupancy factor of the ethanol solvate was varied during the initial stages of the refinement; since the value converged to about 0.5 it was set at 0.5 for the final cycles. The highest peak in (I) is located 0.93 Å from Re, 1.39 Å from C1 and 1.93 Å from N3, and the deepest trough is 0.98 Å from Re and 1.35 Å from N5. In (II), the highest peak and deepest trough are 1.24 Å from Re and 1.02 Å from C2, respectively.

Computing details top

For both compounds, data collection: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Diffractometer Control Software; data reduction: SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I) showing 45% displacement ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. ORTEP-3 (Farrugia, 1997) view of (II) showing 45% displacement ellipsoids. H atoms and the label for C13 have been omitted for clarity.
(I) tricarbonyl-tris(pyrazol-1-yl)methane rhenium(I) bromide top
Crystal data top
[Re(C10H10N6)(CO)3]BrF(000) = 2112
Mr = 564.38Dx = 2.183 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 21.565 (4) ÅCell parameters from 25 reflections
b = 9.002 (2) Åθ = 15.0–18.0°
c = 18.396 (4) ŵ = 9.43 mm1
β = 105.93 (3)°T = 293 K
V = 3434 (1) Å3Block, colorless
Z = 80.33 × 0.26 × 0.17 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
3172 reflections with I > 2σ(I)
Radiation source: normal focus Philips sealed tubeRint = 0.036
Equatorial mounted graphite monochromatorθmax = 27.5°, θmin = 2.3°
ω/2θ scansh = 027
Absorption correction: ψ scan
(North et al., 1968)
k = 110
Tmin = 0.07, Tmax = 0.21l = 2323
4033 measured reflections3 standard reflections every 60 min
3929 independent reflections intensity decay: <2%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters not refined
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0412P)2 + 1.98P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.01
3929 reflectionsΔρmax = 0.55 e Å3
218 parametersΔρmin = 0.59 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00343 (9)
Crystal data top
[Re(C10H10N6)(CO)3]BrV = 3434 (1) Å3
Mr = 564.38Z = 8
Monoclinic, C2/cMo Kα radiation
a = 21.565 (4) ŵ = 9.43 mm1
b = 9.002 (2) ÅT = 293 K
c = 18.396 (4) Å0.33 × 0.26 × 0.17 mm
β = 105.93 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
3172 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.036
Tmin = 0.07, Tmax = 0.213 standard reflections every 60 min
4033 measured reflections intensity decay: <2%
3929 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.071H-atom parameters not refined
S = 1.06Δρmax = 0.55 e Å3
3929 reflectionsΔρmin = 0.59 e Å3
218 parameters
Special details top

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.

The coordinates for the highest peak are (0.3734, 0.8890, 0.2270) locating it 0.93 Å from Re, 1.39 Å from C1 and 1.93 Å from N3. The deepest trough is found at (0.3133, 0.8349, 0.1508) which is 0.98 Å from Re and 1.35 Å from N5.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Re0.330173 (9)0.88021 (2)0.200909 (10)0.03940 (9)
Br0.41970 (3)0.30361 (6)0.03315 (3)0.05823 (16)
N10.37570 (19)0.6766 (4)0.2542 (2)0.0392 (8)
O10.4131 (3)1.0946 (6)0.3166 (3)0.0975 (19)
C10.3828 (3)1.0137 (6)0.2729 (3)0.0608 (15)
C20.2659 (3)0.8897 (6)0.2546 (3)0.0513 (13)
O20.2253 (2)0.8932 (6)0.2839 (3)0.0786 (15)
N20.39157 (18)0.5692 (4)0.2103 (2)0.0385 (8)
N30.4001 (2)0.8491 (4)0.1368 (2)0.0419 (9)
O30.2657 (3)1.1480 (5)0.1075 (3)0.0898 (17)
C30.2899 (3)1.0497 (7)0.1431 (3)0.0567 (14)
N40.40772 (19)0.7119 (4)0.1092 (2)0.0426 (9)
C40.3749 (2)0.5861 (5)0.1292 (3)0.0410 (10)
H4A0.38850.49660.10740.049*
N50.27532 (18)0.7188 (5)0.1207 (2)0.0417 (9)
C50.3949 (3)0.6235 (6)0.3244 (3)0.0488 (12)
H5A0.39060.67310.36710.059*
N60.30618 (19)0.6022 (4)0.0992 (2)0.0396 (9)
C60.4224 (3)0.4825 (6)0.3249 (3)0.0579 (14)
H6A0.43930.42280.36700.070*
C70.4197 (2)0.4504 (6)0.2525 (3)0.0478 (12)
H7A0.43420.36400.23480.057*
C80.4393 (3)0.9367 (7)0.1121 (3)0.0551 (13)
H8A0.44441.03800.12190.066*
C90.4718 (3)0.8564 (6)0.0695 (4)0.0585 (15)
H9A0.50160.89300.04590.070*
C100.4518 (2)0.7169 (6)0.0691 (3)0.0507 (13)
H10A0.46550.63690.04550.061*
C110.2646 (3)0.5066 (6)0.0549 (3)0.0511 (13)
H11A0.27470.41860.03430.061*
C120.2043 (3)0.5642 (8)0.0463 (3)0.0636 (15)
H12A0.16540.52420.01790.076*
C130.2128 (3)0.6945 (7)0.0884 (3)0.0546 (13)
H13A0.17950.75610.09330.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re0.04381 (13)0.03421 (12)0.04082 (12)0.00841 (8)0.01270 (8)0.00313 (8)
Br0.0784 (4)0.0437 (3)0.0612 (3)0.0076 (3)0.0336 (3)0.0052 (2)
N10.040 (2)0.036 (2)0.041 (2)0.0048 (17)0.0114 (17)0.0002 (17)
O10.100 (4)0.062 (3)0.103 (4)0.005 (3)0.017 (3)0.029 (3)
C10.064 (4)0.043 (3)0.069 (4)0.009 (3)0.007 (3)0.007 (3)
C20.054 (3)0.057 (3)0.042 (2)0.019 (3)0.011 (2)0.002 (2)
O20.073 (3)0.113 (4)0.061 (3)0.034 (3)0.037 (2)0.006 (2)
N20.039 (2)0.0323 (19)0.046 (2)0.0009 (16)0.0143 (17)0.0026 (16)
N30.042 (2)0.030 (2)0.058 (2)0.0004 (16)0.0207 (18)0.0045 (17)
O30.137 (5)0.056 (3)0.064 (3)0.040 (3)0.007 (3)0.007 (2)
C30.073 (4)0.047 (3)0.048 (3)0.019 (3)0.013 (3)0.007 (2)
N40.046 (2)0.033 (2)0.056 (2)0.0020 (17)0.0268 (19)0.0012 (17)
C40.046 (3)0.035 (2)0.048 (3)0.004 (2)0.023 (2)0.0002 (19)
N50.040 (2)0.046 (2)0.0386 (19)0.0029 (18)0.0108 (16)0.0032 (17)
C50.046 (3)0.055 (3)0.039 (2)0.002 (2)0.002 (2)0.001 (2)
N60.047 (2)0.037 (2)0.0385 (19)0.0011 (17)0.0177 (17)0.0009 (16)
C60.058 (3)0.054 (3)0.053 (3)0.001 (3)0.000 (3)0.017 (3)
C70.040 (3)0.036 (3)0.066 (3)0.006 (2)0.012 (2)0.009 (2)
C80.052 (3)0.040 (3)0.075 (4)0.000 (2)0.020 (3)0.012 (3)
C90.053 (3)0.059 (4)0.073 (4)0.005 (3)0.034 (3)0.019 (3)
C100.049 (3)0.051 (3)0.061 (3)0.012 (3)0.030 (2)0.012 (3)
C110.063 (3)0.051 (3)0.036 (2)0.009 (3)0.009 (2)0.005 (2)
C120.058 (3)0.075 (4)0.050 (3)0.013 (3)0.001 (3)0.002 (3)
C130.040 (3)0.072 (4)0.049 (3)0.002 (3)0.008 (2)0.003 (3)
Geometric parameters (Å, º) top
Re—C11.913 (6)N5—C131.335 (6)
Re—C21.911 (5)N5—N61.359 (5)
Re—C31.925 (6)C5—C61.400 (8)
Re—N12.181 (4)C5—H5A0.93
Re—N32.172 (4)N6—C111.345 (6)
Re—N52.175 (4)C6—C71.349 (8)
N1—C51.333 (6)C6—H6A0.93
N1—N21.361 (5)C7—H7A0.93
O1—C11.146 (7)C8—C91.388 (8)
C2—O21.150 (7)C8—H8A0.93
N2—C71.362 (6)C9—C101.327 (8)
N2—C41.444 (6)C9—H9A0.93
N3—C81.326 (7)C10—H10A0.93
N3—N41.362 (5)C11—C121.367 (8)
O3—C31.139 (7)C11—H11A0.93
N4—C101.354 (6)C12—C131.389 (9)
N4—C41.436 (6)C12—H12A0.93
C4—N61.439 (6)C13—H13A0.93
C4—H4A0.98
C1—Re—C289.5 (3)N2—C4—H4A108.6
C1—Re—C388.6 (3)C13—N5—N6105.0 (4)
C2—Re—C388.2 (2)C13—N5—Re135.0 (4)
C1—Re—N196.2 (2)N6—N5—Re119.7 (3)
C1—Re—N395.1 (2)N1—C5—C6110.5 (5)
C1—Re—N5176.4 (2)N1—C5—H5A124.8
C2—Re—N196.1 (2)C6—C5—H5A124.8
C2—Re—N3174.8 (2)C11—N6—N5111.8 (4)
C2—Re—N592.5 (2)C11—N6—C4127.8 (4)
C3—Re—N1173.5 (2)N5—N6—C4120.1 (4)
C3—Re—N394.4 (2)C7—C6—C5106.5 (5)
C3—Re—N594.4 (2)C7—C6—H6A126.8
N1—Re—N380.9 (1)C5—C6—H6A126.8
N1—Re—N580.6 (1)C6—C7—N2106.6 (5)
N3—Re—N582.8 (1)C6—C7—H7A126.7
C5—N1—N2104.9 (4)N2—C7—H7A126.7
C5—N1—Re135.9 (4)N3—C8—C9110.6 (5)
N2—N1—Re119.1 (3)N3—C8—H8A124.7
O1—C1—Re178.4 (6)C9—C8—H8A124.7
O2—C2—Re176.9 (5)C10—C9—C8106.4 (5)
N1—N2—C7111.4 (4)C10—C9—H9A126.8
N1—N2—C4120.3 (4)C8—C9—H9A126.8
C7—N2—C4128.1 (4)C9—C10—N4107.7 (5)
C8—N3—N4104.9 (4)C9—C10—H10A126.1
C8—N3—Re135.5 (4)N4—C10—H10A126.1
N4—N3—Re119.5 (3)N6—C11—C12106.4 (5)
O3—C3—Re178.4 (5)N6—C11—H11A126.8
C10—N4—N3110.3 (4)C12—C11—H11A126.8
C10—N4—C4129.4 (4)C11—C12—C13106.3 (5)
N3—N4—C4120.0 (4)C11—C12—H12A126.8
N6—C4—N4110.5 (4)C13—C12—H12A126.8
N6—C4—N2110.3 (4)N5—C13—C12110.4 (5)
N4—C4—N2110.3 (4)N5—C13—H13A124.8
N6—C4—H4A108.6C12—C13—H13A124.8
N4—C4—H4A108.6
(II) tricarbonyl-methyltris(pyrazol-1-yl)methane rhenium(I) iodide ethanol solvate top
Crystal data top
[Re(C11H12N6)(CO)3]I·0.5C2H6OF(000) = 1233
Mr = 648.44Dx = 2.022 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.361 (3) ÅCell parameters from 25 reflections
b = 11.803 (2) Åθ = 15.0–18.0°
c = 15.543 (3) ŵ = 7.13 mm1
β = 108.83 (3)°T = 293 K
V = 2146.3 (7) Å3Block, colorless
Z = 40.41 × 0.23 × 0.23 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
4128 reflections with I > 2σ(I)
Radiation source: normal focus Philips sealed tubeRint = 0.068
Equatorial mounted graphite monochromatorθmax = 27.5°, θmin = 2.2°
ω/2θ scansh = 1616
Absorption correction: ψ scan
North et al. (1968)
k = 015
Tmin = 0.08, Tmax = 0.20l = 020
5073 measured reflections3 standard reflections every 60 min
4896 independent reflections intensity decay: <2%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters not refined
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0778P)2 + 1.9504P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.014
4896 reflectionsΔρmax = 1.37 e Å3
254 parametersΔρmin = 1.29 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0094 (5)
Crystal data top
[Re(C11H12N6)(CO)3]I·0.5C2H6OV = 2146.3 (7) Å3
Mr = 648.44Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.361 (3) ŵ = 7.13 mm1
b = 11.803 (2) ÅT = 293 K
c = 15.543 (3) Å0.41 × 0.23 × 0.23 mm
β = 108.83 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
4128 reflections with I > 2σ(I)
Absorption correction: ψ scan
North et al. (1968)
Rint = 0.068
Tmin = 0.08, Tmax = 0.203 standard reflections every 60 min
5073 measured reflections intensity decay: <2%
4896 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.123H-atom parameters not refined
S = 1.12Δρmax = 1.37 e Å3
4896 reflectionsΔρmin = 1.29 e Å3
254 parameters
Special details top

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.

The coordinates for the highest peak are (0.2837, 1.0333, 0.0653) and for the deepest trough are (0.1779, 0.9883, 0.1437) which is 1.24 Å from Re and 1.02 Å from C2.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Re0.26460 (2)0.99066 (2)0.120017 (16)0.04659 (13)
I0.32805 (5)0.93586 (4)0.33990 (4)0.07274 (19)
N10.1725 (4)0.8358 (4)0.0678 (3)0.0474 (11)
O10.3584 (6)0.9032 (7)0.3157 (4)0.102 (2)
C10.3234 (7)0.9381 (7)0.2419 (5)0.0660 (18)
N20.1740 (4)0.7893 (4)0.0111 (3)0.0461 (10)
C20.1396 (6)1.0643 (6)0.1452 (5)0.0595 (16)
O20.0643 (5)1.1101 (5)0.1566 (5)0.0850 (17)
C30.3506 (6)1.1280 (6)0.1567 (5)0.0612 (16)
N30.3912 (4)0.9044 (5)0.0744 (4)0.0504 (11)
O30.4005 (6)1.2099 (5)0.1777 (5)0.0906 (18)
C40.2417 (5)0.8414 (5)0.0634 (4)0.0463 (12)
N40.3612 (4)0.8459 (4)0.0059 (4)0.0499 (11)
N50.2010 (4)1.0334 (4)0.0221 (4)0.0473 (11)
C50.1075 (6)0.7677 (6)0.0984 (5)0.0593 (16)
H50.09150.77910.15230.071*
N60.2013 (5)0.9564 (4)0.0880 (4)0.0489 (11)
C60.0674 (6)0.6790 (6)0.0408 (6)0.0678 (19)
H60.02030.62040.04720.081*
C70.1109 (5)0.6950 (5)0.0281 (5)0.0557 (15)
H70.09890.64830.07850.067*
C80.5045 (6)0.8925 (7)0.1097 (6)0.0649 (18)
H80.54920.92500.16410.078*
C90.5454 (7)0.8271 (8)0.0558 (7)0.085 (3)
H90.62110.80590.06680.102*
C100.4538 (7)0.7982 (7)0.0181 (6)0.070 (2)
H100.45550.75400.06720.084*
C110.1638 (7)1.0057 (6)0.1708 (5)0.0572 (16)
H110.15760.97110.22600.069*
C120.1370 (6)1.1148 (6)0.1592 (5)0.0595 (16)
H120.10791.16900.20420.071*
C130.1621 (5)1.1284 (6)0.0667 (5)0.0537 (14)
H130.15281.19590.03910.064*
C140.2297 (7)0.7714 (6)0.1479 (5)0.0644 (18)
H14A0.27420.80510.18160.097*
H14B0.15080.76900.18510.097*
H14C0.25640.69570.13050.097*
O200.112 (2)1.065 (3)0.3861 (15)0.188 (12)0.50
C200.099 (3)0.968 (2)0.3882 (19)0.140 (14)0.50
C210.0366 (14)0.9400 (13)0.3796 (9)0.066 (4)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re0.04932 (18)0.04296 (17)0.04910 (18)0.00482 (9)0.01813 (12)0.00250 (9)
I0.1069 (4)0.0458 (3)0.0779 (4)0.0022 (2)0.0470 (3)0.0021 (2)
N10.049 (3)0.045 (3)0.054 (3)0.002 (2)0.024 (2)0.005 (2)
O10.105 (5)0.129 (6)0.063 (4)0.015 (4)0.012 (3)0.021 (4)
C10.079 (5)0.062 (4)0.054 (4)0.008 (4)0.017 (4)0.002 (3)
N20.048 (2)0.037 (2)0.056 (3)0.0013 (19)0.020 (2)0.004 (2)
C20.065 (4)0.056 (4)0.064 (4)0.006 (3)0.031 (3)0.005 (3)
O20.080 (4)0.079 (4)0.113 (5)0.023 (3)0.054 (4)0.010 (3)
C30.070 (4)0.055 (4)0.063 (4)0.005 (3)0.027 (3)0.006 (3)
N30.048 (3)0.048 (3)0.054 (3)0.000 (2)0.014 (2)0.008 (2)
O30.107 (5)0.057 (3)0.104 (5)0.020 (3)0.030 (4)0.023 (3)
C40.053 (3)0.038 (3)0.053 (3)0.003 (2)0.023 (3)0.001 (2)
N40.046 (3)0.044 (3)0.065 (3)0.000 (2)0.026 (2)0.002 (2)
N50.053 (3)0.032 (2)0.060 (3)0.001 (2)0.022 (2)0.002 (2)
C50.061 (4)0.052 (4)0.076 (4)0.008 (3)0.038 (3)0.015 (3)
N60.059 (3)0.033 (2)0.057 (3)0.003 (2)0.022 (2)0.001 (2)
C60.066 (4)0.045 (4)0.102 (6)0.008 (3)0.041 (4)0.007 (4)
C70.052 (3)0.039 (3)0.077 (4)0.006 (2)0.021 (3)0.001 (3)
C80.042 (3)0.066 (4)0.085 (5)0.001 (3)0.018 (3)0.008 (4)
C90.055 (4)0.079 (6)0.132 (8)0.007 (4)0.044 (5)0.016 (5)
C100.057 (4)0.061 (4)0.107 (6)0.002 (3)0.046 (4)0.019 (4)
C110.071 (4)0.052 (4)0.049 (3)0.008 (3)0.019 (3)0.005 (3)
C120.061 (4)0.054 (4)0.061 (4)0.004 (3)0.017 (3)0.016 (3)
C130.050 (3)0.043 (3)0.066 (4)0.005 (2)0.016 (3)0.006 (3)
C140.093 (5)0.043 (3)0.067 (4)0.003 (3)0.039 (4)0.011 (3)
O200.18 (2)0.27 (3)0.108 (15)0.08 (2)0.034 (15)0.06 (2)
C200.19 (3)0.055 (11)0.12 (2)0.015 (15)0.03 (2)0.025 (13)
C210.088 (10)0.056 (8)0.046 (7)0.006 (7)0.011 (7)0.016 (6)
Geometric parameters (Å, º) top
Re—C11.901 (8)C5—C61.363 (11)
Re—C21.920 (7)C5—H50.9300
Re—C31.922 (8)N6—C111.351 (9)
Re—N52.152 (6)C6—C71.358 (10)
Re—N12.168 (5)C6—H60.9300
Re—N32.169 (5)C7—H70.9300
Re—N52.152 (6)C8—C91.351 (11)
N1—C51.328 (8)C8—H80.9300
N1—N21.349 (7)C9—C101.371 (13)
O1—C11.163 (9)C9—H90.9300
N2—C71.336 (8)C10—H100.9300
N2—C41.474 (7)C11—C121.356 (10)
C2—O21.139 (8)C11—H110.9300
C3—O31.135 (9)C12—C131.379 (9)
N3—C81.336 (8)C12—H120.9300
N3—N41.369 (7)C13—H130.9300
C4—N61.455 (8)C14—H14A0.9600
C4—N41.460 (8)C14—H14B0.9600
C4—C141.518 (9)C14—H14C0.9600
N4—C101.344 (8)O20—C201.16 (4)
N5—C131.324 (8)C20—C211.67 (4)
N5—N61.371 (7)
C1—Re—C291.1 (3)N6—N5—Re121.6 (4)
C1—Re—C389.0 (3)N1—C5—C6111.3 (6)
C2—Re—C387.8 (3)N1—C5—H5124.4
C1—Re—N194.8 (3)C6—C5—H5124.4
C1—Re—N395.1 (3)C11—N6—N5110.1 (5)
C1—Re—N5174.3 (3)C11—N6—C4129.5 (6)
C2—Re—N195.6 (3)N5—N6—C4120.3 (5)
C2—Re—N3172.8 (3)C7—C6—C5105.0 (6)
C2—Re—N592.9 (3)C7—C6—H6127.5
C3—Re—N595.2 (3)C5—C6—H6127.5
C3—Re—N396.0 (2)N2—C7—C6108.3 (6)
C3—Re—N1174.8 (2)N2—C7—H7125.8
N1—Re—N380.17 (18)C6—C7—H7125.8
N1—Re—N580.77 (19)N3—C8—C9111.0 (7)
N3—Re—N580.7 (2)N3—C8—H8124.5
C5—N1—N2105.5 (5)C9—C8—H8124.5
C5—N1—Re132.9 (5)C8—C9—C10106.8 (7)
N2—N1—Re121.5 (3)C8—C9—H9126.6
O1—C1—Re178.3 (8)C10—C9—H9126.6
C7—N2—N1109.9 (5)N4—C10—C9106.7 (7)
C7—N2—C4129.6 (5)N4—C10—H10126.7
N1—N2—C4120.5 (5)C9—C10—H10126.7
O2—C2—Re177.1 (7)N6—C11—C12107.8 (7)
O3—C3—Re179.2 (8)N6—C11—H11126.1
C8—N3—N4105.1 (5)C12—C11—H11126.1
C8—N3—Re133.4 (5)C11—C12—C13105.5 (6)
N4—N3—Re121.5 (4)C11—C12—H12127.3
N6—C4—N4108.7 (5)C13—C12—H12127.3
N6—C4—N2109.1 (5)N5—C13—C12111.7 (6)
N4—C4—N2108.7 (5)N5—C13—H13124.2
N6—C4—C14110.5 (5)C12—C13—H13124.2
N4—C4—C14110.3 (5)C4—C14—H14A109.5
N2—C4—C14109.6 (5)C4—C14—H14B109.5
C10—N4—N3110.4 (6)H14A—C14—H14B109.5
C10—N4—C4129.6 (6)C4—C14—H14C109.5
N3—N4—C4119.9 (5)H14A—C14—H14C109.5
C13—N5—N6104.9 (5)H14B—C14—H14C109.5
C13—N5—Re133.4 (4)O20—C20—C21110 (3)

Experimental details

(I)(II)
Crystal data
Chemical formula[Re(C10H10N6)(CO)3]Br[Re(C11H12N6)(CO)3]I·0.5C2H6O
Mr564.38648.44
Crystal system, space groupMonoclinic, C2/cMonoclinic, P21/n
Temperature (K)293293
a, b, c (Å)21.565 (4), 9.002 (2), 18.396 (4)12.361 (3), 11.803 (2), 15.543 (3)
β (°) 105.93 (3) 108.83 (3)
V3)3434 (1)2146.3 (7)
Z84
Radiation typeMo KαMo Kα
µ (mm1)9.437.13
Crystal size (mm)0.33 × 0.26 × 0.170.41 × 0.23 × 0.23
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
ψ scan
North et al. (1968)
Tmin, Tmax0.07, 0.210.08, 0.20
No. of measured, independent and
observed [I > 2σ(I)] reflections
4033, 3929, 3172 5073, 4896, 4128
Rint0.0360.068
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.071, 1.06 0.045, 0.123, 1.12
No. of reflections39294896
No. of parameters218254
H-atom treatmentH-atom parameters not refinedH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.55, 0.591.37, 1.29

Computer programs: CAD-4 Diffractometer Control Software (Enraf-Nonius, 1988), CAD-4 Diffractometer Control Software, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
Re—C11.913 (6)Re—N12.181 (4)
Re—C21.911 (5)Re—N32.172 (4)
Re—C31.925 (6)Re—N52.175 (4)
C1—Re—C289.5 (3)C2—Re—N592.5 (2)
C1—Re—C388.6 (3)C3—Re—N1173.5 (2)
C2—Re—C388.2 (2)C3—Re—N394.4 (2)
C1—Re—N196.2 (2)C3—Re—N594.4 (2)
C1—Re—N395.1 (2)N1—Re—N380.9 (1)
C1—Re—N5176.4 (2)N1—Re—N580.6 (1)
C2—Re—N196.1 (2)N3—Re—N582.8 (1)
C2—Re—N3174.8 (2)
Selected geometric parameters (Å, º) for (II) top
Re—C11.901 (8)Re—N12.168 (5)
Re—C21.920 (7)Re—N32.169 (5)
Re—C31.922 (8)Re—N52.152 (6)
Re—N52.152 (6)
C1—Re—C291.1 (3)C2—Re—N592.9 (3)
C1—Re—C389.0 (3)C3—Re—N595.2 (3)
C2—Re—C387.8 (3)C3—Re—N396.0 (2)
C1—Re—N194.8 (3)C3—Re—N1174.8 (2)
C1—Re—N395.1 (3)N1—Re—N380.17 (18)
C1—Re—N5174.3 (3)N1—Re—N580.77 (19)
C2—Re—N195.6 (3)N3—Re—N580.7 (2)
C2—Re—N3172.8 (3)
 

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