Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105008693/bg1000sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105008693/bg1000Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105008693/bg1000IIsup3.hkl |
CCDC references: 273026; 273027
For the synthesis of (I), to a solution resulting from an N-atom transfer reaction between Mn(N)(salen) (0.810 g; 2.4 mmol) and CrCl3(THF)3 (0.906 g; 2.416 mmol) in acetonitrile (20 ml) was added a solution of 8-hydroxyquinaldine (1.559 g, 9.79 mmol, Aldrich 98%) in acetonitrile (6 ml) with precipitation commencing immediately. The resulting orange product (0.626 g, 68%) was washed by methanol and recrystallized from boiling toluene (180 ml). Slow evaporation afforded crystals of X-ray quality. For the synthesis of (II), a solution of the sodium salt of 2-mercaptopyridine-N-oxide hydrate (0.735 g, 4.93 mmol, Aldrich) in methanol (11 ml) was added to the solution resulting from N-atom transfer between Mn(N)(salen) and CrCl3(THF)3 prepared as described above. The resulting red precipitate (0.490 g, 64%) was collected by filtration and washed by methanol. Crystals suitable for X-ray diffraction were obtained by slow evaporation of an acetonitrile solution.
All hydrogen atoms were identified in the difference Fourier map, but were placed in idealized positions (C—Harom:0.95, C—Hmethyl:0.98 Å). Their isotropic displacement parameters were constrained to 1.2Ueq of the connected non-hydrogen atom (1.5Ueq for methyl groups). Disorder of the methyl group in (I) could be resolved in two well separated conformations with populations 0.633 (18) and 0.367 (18), respectively.
The nitride ligand (N3-) is the strongest electron donating ligand known (Nugent & Mayer, 1988). It also stands out by having a much more developed chemistry of second- and third-row transition metals than of their first-row congeners. The first example of a nitride complex of the first-row transition metals, Cr(N)(salen), was, therefore, prepared as late as 1981 by photolysis of the corresponding CrIII–azide complex (Arshankow & Poznjak, 1981). A few other CrV– and MnV–nitride complexes have been prepared by this route, e.g. [M(N)(cyclam)(CH3CN)]2+ [cyclam is 1,4,7,11-tetraazacyclotetradecane; M = Cr (Meyer, Bendix, Bill et al., 1998) and Mn (Meyer, Bendix, Metzler-Nolte et al., 1998)], and [Cr(N)(tacn)(acac)]+ (Niemann et al., 1996), but the method fails for systems where the auxilliary ligand sphere is labile. The lack of general methods of synthesis has been the primary obstacle in the development of the nitride chemistry for the first-row transition metals. Recently, we have found (Birk & Bendix, 2003; Bendix, 2003) that N-atom transfer from the easily accessible Mn(N)(salen) to CrCl3(THF)3 followed by ligand metathesis is a very general synthetic route to chromium(V)– nitride complexes. By this method, the uncharged complexes Cr(N)(quinald)2, (I), and Cr(N)(tpno)2, (II), have been prepared.
Complexes (I) and (II) are both five-coordinate with approximately square-pyramidal coordination around CrV and with the metal displaced ca 0.5 Å out of the plane of the basal ligators towards the nitride ligand (Figs. 1 and 2, and Table 1). Complex (I) crystallizes with CrV≡N in a crystallographic twofold axis, making the basal ligators equivalent in pairs. Interestingly, even though complex (II) has the possibility for a molecular mirror plane (Fig. 2), this is not utilized in the crystal packing. The short Cr≡N bonds of 1.5609 (11) and 1.5591 (11) Å in (II) and (I), respectively, are both within the range of those found for other five-coordinate CrV–nitride complexes and ca 0.05 Å longer than average MnV≡N bond lengths. In both structures, the nitride ligands are non-bridging. This is also evidenced by high ν(Cr—N) stretching frequencies of 1016 and 1007 cm-1, for (I) and (II), respectively. In accordance with the low basicity and nucleophilicity normally observed for [Cr≡N]2+ and [Mn≡N]2+ moieties (Meyer, Bendix, Bill et al., 1998; Meyer, Bendix, Metzler et al., 1998).
The vanadyl analogs of both (I) and (II) have been structurally characterized (Shiro & Fernando, 1971; Higes-Rolando et al., 1994, respectively) and are isostructural with their [Cr≡N]2+ counterparts. The bond lengths to the auxilliary ligands in the VIV(O) complexes are slightly longer than those found in the CrV(N) systems and the pyramidalization is slightly larger for the vanadyl systems (cf. Table 2).
Complexes (I) and (II) differ in the configuration of the bidentate ligands, being trans and cis, respectively. This difference is common for these ligands and thus unrelated to the metal centre. A rare exception to these preferred configurations is [Co(py)(tpno)2], wherein the tpno ligands are in the unusual trans configuration (Kang et al., 1993).
The difference in angle between the nitride ligand and equatorial O donors [112.91 (2)°] and N donors [98.828 (18)°] in (I) reflects a significant distortion towards a trigonal bipyramidal structure (with apical N-atom donors from the bidentate ligands). This contrast to the parent Cr(N)(quinolin-8-olate)2 complex, which features a regular square-pyramidal coordination of chromium, is caused by the steric demands of the 2-methyl substituents in (I). The packing of the Cr(N)(quinald)2 molecules is also influenced by the methyl groups, which prevent the π-stacking dominating the structure of Cr(N)(quinolin-8-olate)2. Nevertheless, a similar overall situation (cf. Fig. 3) with aligned (parallel and anti-parallel) Cr≡ N units results also for (I). This packing mode in combination with the electronically isolated molecules (the shortest Cr—Cr distance is 7.519 Å) makes the compound well suited for single-crystal EPR studies of the bonding anisotropy in the metal–nitride bond (Bendix et al., 2000).
Data collection: EVALCCD (Duisenberg et al., 2003) for (I); COLLECT (Nonius, 1999) for (II). Cell refinement: COLLECT (Nonius, 1999) for (I); COLLECT for (II). Data reduction: EVALCCD for (I); EVALCCD (Duisenberg et al., 2003) for (II). For both compounds, program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: program (reference?).
[Cr(C10H8NO)2N] | F(000) = 788 |
Mr = 382.36 | Dx = 1.516 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 31996 reflections |
a = 16.8980 (14) Å | θ = 2.9–39.9° |
b = 7.6853 (7) Å | µ = 0.70 mm−1 |
c = 13.2955 (12) Å | T = 122 K |
β = 103.967 (7)° | Prism, orange |
V = 1675.6 (3) Å3 | 0.44 × 0.37 × 0.17 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 5177 independent reflections |
Radiation source: fine-focus sealed tube | 4523 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 40.0°, θmin = 2.9° |
Absorption correction: numerical Gaussian integration (Coppens, 1970) | h = −30→30 |
Tmin = 0.813, Tmax = 0.918 | k = −13→13 |
49933 measured reflections | l = −24→24 |
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)] = 0.028 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0361P)2 + 1.038P] where P = (Fo2 + 2Fc2)/3 |
5177 reflections | (Δ/σ)max < 0.001 |
120 parameters | Δρmax = 0.56 e Å−3 |
0 restraints | Δρmin = −0.50 e Å−3 |
[Cr(C10H8NO)2N] | V = 1675.6 (3) Å3 |
Mr = 382.36 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.8980 (14) Å | µ = 0.70 mm−1 |
b = 7.6853 (7) Å | T = 122 K |
c = 13.2955 (12) Å | 0.44 × 0.37 × 0.17 mm |
β = 103.967 (7)° |
Nonius KappaCCD diffractometer | 5177 independent reflections |
Absorption correction: numerical Gaussian integration (Coppens, 1970) | 4523 reflections with I > 2σ(I) |
Tmin = 0.813, Tmax = 0.918 | Rint = 0.036 |
49933 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.56 e Å−3 |
5177 reflections | Δρmin = −0.50 e Å−3 |
120 parameters |
Experimental. Analysis Calculated for C20H16N3O2Cr: C: 62.83%; H: 4.22%; N: 10.99%. Found: C: 62.82%; H: 4.08%; N: 10.95%. IR: ν(Cr—N) 1016 cm-1 (s). MS FAB+: m/z 383.03 (M, rel intensity 10%). UV/vis (CH2Cl2, RT), λMax. [nm] (ε) [m2 mol-1]: 391.30 (56.55), 379.77 (54.70), 316.80 (27.07), 303.93 (26.21), 267.47 (418.7), 264.47 (418.4) |
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 > 2σ(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) | |
Cr1 | 0.0000 | 0.22857 (2) | 0.2500 | 0.01337 (4) | |
C1 | 0.10441 (4) | 0.33551 (9) | 0.12170 (5) | 0.01426 (10) | |
C2 | 0.14601 (4) | 0.36423 (10) | 0.22685 (6) | 0.01602 (11) | |
C3 | 0.22434 (5) | 0.43091 (12) | 0.24758 (7) | 0.02135 (14) | |
C4 | 0.26199 (5) | 0.46655 (13) | 0.16573 (8) | 0.02351 (15) | |
C5 | 0.22225 (5) | 0.43762 (12) | 0.06387 (7) | 0.02212 (14) | |
C6 | 0.14149 (5) | 0.37214 (10) | 0.03976 (6) | 0.01699 (11) | |
C7 | 0.09385 (5) | 0.34031 (11) | −0.06183 (6) | 0.02052 (13) | |
C8 | 0.01626 (5) | 0.27672 (11) | −0.07544 (6) | 0.01953 (12) | |
C9 | −0.01658 (4) | 0.23936 (10) | 0.01081 (6) | 0.01604 (11) | |
C10 | −0.09979 (5) | 0.16034 (12) | −0.00662 (7) | 0.02214 (14) | |
N1 | 0.0000 | 0.02569 (14) | 0.2500 | 0.02243 (18) | |
N2 | 0.02679 (4) | 0.27016 (8) | 0.10699 (5) | 0.01422 (9) | |
O1 | 0.10634 (3) | 0.32522 (9) | 0.29926 (4) | 0.01886 (10) | |
H10A | −0.1005 | 0.0760 | 0.0484 | 0.033* | 0.633 (18) |
H10B | −0.1134 | 0.1013 | −0.0739 | 0.033* | 0.633 (18) |
H10C | −0.1399 | 0.2520 | −0.0057 | 0.033* | 0.633 (18) |
H11A | −0.0974 | 0.0379 | −0.0264 | 0.033* | 0.367 (18) |
H11B | −0.1376 | 0.2233 | −0.0622 | 0.033* | 0.367 (18) |
H11C | −0.1188 | 0.1681 | 0.0573 | 0.033* | 0.367 (18) |
H3 | 0.2530 | 0.4528 | 0.3172 | 0.026* | |
H4 | 0.3160 | 0.5115 | 0.1814 | 0.028* | |
H5 | 0.2488 | 0.4614 | 0.0101 | 0.027* | |
H7 | 0.1156 | 0.3629 | −0.1201 | 0.025* | |
H8 | −0.0160 | 0.2574 | −0.1436 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0122 (2) | 0.0135 (2) | 0.0175 (3) | 0.00081 (18) | 0.00448 (19) | −0.00045 (19) |
C10 | 0.0166 (3) | 0.0254 (4) | 0.0224 (3) | −0.0034 (2) | 0.0009 (2) | −0.0043 (3) |
C2 | 0.0117 (2) | 0.0181 (3) | 0.0183 (3) | 0.0000 (2) | 0.0038 (2) | −0.0024 (2) |
C3 | 0.0130 (3) | 0.0261 (4) | 0.0248 (3) | −0.0032 (2) | 0.0044 (2) | −0.0042 (3) |
C4 | 0.0153 (3) | 0.0253 (4) | 0.0316 (4) | −0.0044 (2) | 0.0089 (3) | −0.0024 (3) |
C5 | 0.0195 (3) | 0.0217 (3) | 0.0285 (4) | −0.0030 (2) | 0.0122 (3) | 0.0007 (3) |
C6 | 0.0177 (3) | 0.0145 (3) | 0.0205 (3) | 0.0002 (2) | 0.0080 (2) | 0.0012 (2) |
C7 | 0.0253 (3) | 0.0194 (3) | 0.0185 (3) | 0.0006 (2) | 0.0085 (2) | 0.0027 (2) |
C8 | 0.0235 (3) | 0.0187 (3) | 0.0158 (3) | 0.0014 (2) | 0.0036 (2) | 0.0006 (2) |
C9 | 0.0159 (3) | 0.0152 (3) | 0.0162 (3) | 0.0010 (2) | 0.0021 (2) | −0.0009 (2) |
Cr1 | 0.01149 (6) | 0.01431 (7) | 0.01440 (6) | 0.000 | 0.00334 (4) | 0.000 |
N1 | 0.0312 (5) | 0.0160 (4) | 0.0198 (4) | 0.000 | 0.0057 (3) | 0.000 |
N2 | 0.0124 (2) | 0.0146 (2) | 0.0155 (2) | −0.00011 (17) | 0.00333 (17) | −0.00123 (18) |
O1 | 0.01330 (19) | 0.0271 (3) | 0.0166 (2) | −0.00266 (19) | 0.00454 (16) | −0.00379 (19) |
Cr1—N1 | 1.5591 (11) | C9—C10 | 1.4974 (11) |
Cr1—O1 | 1.9082 (6) | C7—H7 | 0.9500 |
Cr1—N2 | 2.0827 (6) | C5—C4 | 1.3767 (13) |
O1—C2 | 1.3333 (9) | C5—H5 | 0.9500 |
C1—N2 | 1.3738 (9) | C3—C4 | 1.4137 (12) |
C1—C6 | 1.4099 (10) | C3—H3 | 0.9500 |
C1—C2 | 1.4224 (10) | C4—H4 | 0.9500 |
C6—C7 | 1.4168 (12) | C10—H10A | 0.9800 |
C6—C5 | 1.4168 (11) | C10—H10B | 0.9800 |
N2—C9 | 1.3327 (10) | C10—H10C | 0.9800 |
C8—C7 | 1.3697 (12) | C10—H11A | 0.9800 |
C8—C9 | 1.4186 (11) | C10—H11B | 0.9800 |
C8—H8 | 0.9500 | C10—H11C | 0.9800 |
C2—C3 | 1.3837 (10) | ||
N1—Cr1—O1 | 112.91 (2) | C8—C7—C6 | 119.54 (7) |
O1—Cr1—O1i | 134.18 (4) | C8—C7—H7 | 120.2 |
O1—Cr1—N2i | 91.21 (2) | C6—C7—H7 | 120.2 |
N1—Cr1—N2 | 98.828 (18) | C4—C5—C6 | 119.64 (7) |
O1—Cr1—N2 | 81.92 (2) | C4—C5—H5 | 120.2 |
N2i—Cr1—N2 | 162.34 (4) | C6—C5—H5 | 120.2 |
C2—O1—Cr1 | 115.83 (5) | C2—C3—C4 | 120.33 (8) |
N2—C1—C6 | 123.37 (7) | C2—C3—H3 | 119.8 |
N2—C1—C2 | 115.15 (6) | C4—C3—H3 | 119.8 |
C6—C1—C2 | 121.48 (6) | C5—C4—C3 | 121.51 (7) |
C1—C6—C7 | 116.49 (7) | C5—C4—H4 | 119.2 |
C1—C6—C5 | 118.65 (7) | C3—C4—H4 | 119.2 |
C7—C6—C5 | 124.86 (7) | C9—C10—H10A | 109.5 |
C9—N2—C1 | 119.11 (6) | C9—C10—H10B | 109.5 |
C9—N2—Cr1 | 131.18 (5) | H10A—C10—H10B | 109.5 |
C1—N2—Cr1 | 109.67 (5) | C9—C10—H10C | 109.5 |
C7—C8—C9 | 120.94 (7) | H10A—C10—H10C | 109.5 |
C7—C8—H8 | 119.5 | H10B—C10—H10C | 109.5 |
C9—C8—H8 | 119.5 | C9—C10—H11A | 109.5 |
O1—C2—C3 | 124.26 (7) | C9—C10—H11B | 109.5 |
O1—C2—C1 | 117.36 (6) | H11A—C10—H11B | 109.5 |
C3—C2—C1 | 118.38 (7) | C9—C10—H11C | 109.5 |
N2—C9—C8 | 120.52 (7) | H11A—C10—H11C | 109.5 |
N2—C9—C10 | 119.93 (7) | H11B—C10—H11C | 109.5 |
C8—C9—C10 | 119.53 (7) | ||
N1—Cr1—O1—C2 | 93.82 (6) | Cr1—O1—C2—C1 | 2.02 (9) |
O1i—Cr1—O1—C2 | −86.18 (6) | N2—C1—C2—O1 | 0.15 (10) |
N2i—Cr1—O1—C2 | −166.07 (6) | C6—C1—C2—O1 | −179.73 (7) |
N2—Cr1—O1—C2 | −2.39 (6) | N2—C1—C2—C3 | −179.62 (7) |
N2—C1—C6—C7 | 0.85 (11) | C6—C1—C2—C3 | 0.49 (11) |
C2—C1—C6—C7 | −179.27 (7) | C1—N2—C9—C8 | −1.24 (11) |
N2—C1—C6—C5 | −179.35 (7) | Cr1—N2—C9—C8 | −178.78 (6) |
C2—C1—C6—C5 | 0.52 (11) | C1—N2—C9—C10 | 177.13 (7) |
C6—C1—N2—C9 | −0.12 (11) | Cr1—N2—C9—C10 | −0.40 (11) |
C2—C1—N2—C9 | 180.00 (7) | C7—C8—C9—N2 | 1.90 (12) |
C6—C1—N2—Cr1 | 177.91 (6) | C7—C8—C9—C10 | −176.48 (8) |
C2—C1—N2—Cr1 | −1.98 (8) | C9—C8—C7—C6 | −1.12 (12) |
N1—Cr1—N2—C9 | 68.00 (7) | C1—C6—C7—C8 | −0.20 (11) |
O1—Cr1—N2—C9 | −179.93 (7) | C5—C6—C7—C8 | −179.98 (8) |
O1i—Cr1—N2—C9 | −45.41 (7) | C1—C6—C5—C4 | −1.05 (12) |
N2i—Cr1—N2—C9 | −112.00 (7) | C7—C6—C5—C4 | 178.73 (8) |
N1—Cr1—N2—C1 | −109.72 (5) | O1—C2—C3—C4 | 179.26 (8) |
O1—Cr1—N2—C1 | 2.36 (5) | C1—C2—C3—C4 | −0.98 (12) |
O1i—Cr1—N2—C1 | 136.88 (5) | C6—C5—C4—C3 | 0.58 (14) |
N2i—Cr1—N2—C1 | 70.29 (5) | C2—C3—C4—C5 | 0.46 (14) |
Cr1—O1—C2—C3 | −178.22 (7) |
Symmetry code: (i) −x, y, −z+1/2. |
[Cr(C5H4NOS)2N] | F(000) = 1288 |
Mr = 318.31 | Dx = 1.773 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 47810 reflections |
a = 11.0511 (12) Å | θ = 2.7–35° |
b = 14.1558 (12) Å | µ = 1.30 mm−1 |
c = 15.2486 (11) Å | T = 122 K |
V = 2385.4 (4) Å3 | Block, dark red |
Z = 8 | 0.34 × 0.32 × 0.17 mm |
Nonius KappaCCD diffractometer | 5236 independent reflections |
Radiation source: fine-focus sealed tube | 4479 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
φ and ω scans | θmax = 35.0°, θmin = 2.7° |
Absorption correction: numerical gaussian numerical integration (Coppens, 1970) | h = −17→17 |
Tmin = 0.710, Tmax = 0.856 | k = −22→22 |
85248 measured reflections | l = −24→24 |
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)] = 0.025 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0294P)2 + 2.1443P] where P = (Fo2 + 2Fc2)/3 |
5236 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 1.18 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
[Cr(C5H4NOS)2N] | V = 2385.4 (4) Å3 |
Mr = 318.31 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.0511 (12) Å | µ = 1.30 mm−1 |
b = 14.1558 (12) Å | T = 122 K |
c = 15.2486 (11) Å | 0.34 × 0.32 × 0.17 mm |
Nonius KappaCCD diffractometer | 5236 independent reflections |
Absorption correction: numerical gaussian numerical integration (Coppens, 1970) | 4479 reflections with I > 2σ(I) |
Tmin = 0.710, Tmax = 0.856 | Rint = 0.043 |
85248 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.18 e Å−3 |
5236 reflections | Δρmin = −0.43 e Å−3 |
163 parameters |
Experimental. Analysis Calculated for C10H8N3O2S2Cr: C: 37.73%; H: 2.53%; N: 13.20%. Found: C: 37.94%; H: 2.41%; N: 13.07%. IR: ν(Cr—N) 1007 cm-1 (s). MS FAB+: m/z 318.8 (M, rel intensity 4%). UV/vis (CH2Cl2, RT), λMax. [nm] (ε) [m2 mol-1]: 545.1 (8.92), 408.8 (21.74),328.0 (54.62), 244.9 (907.7). |
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 > 2σ(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 | ||
Cr1 | 0.150718 (16) | 0.403096 (12) | 0.078491 (12) | 0.01248 (4) | |
N3 | 0.25475 (11) | 0.37550 (8) | 0.14282 (7) | 0.0213 (2) | |
S1 | 0.23750 (3) | 0.37689 (2) | −0.060213 (19) | 0.01581 (6) | |
O1 | 0.05758 (8) | 0.29140 (6) | 0.04969 (6) | 0.01724 (15) | |
N1 | 0.09790 (8) | 0.23336 (7) | −0.01433 (6) | 0.01300 (15) | |
C1 | 0.18627 (10) | 0.26250 (8) | −0.06994 (7) | 0.01355 (17) | |
C2 | 0.22459 (12) | 0.19791 (9) | −0.13436 (8) | 0.0190 (2) | |
H2 | 0.2882 | 0.2148 | −0.1733 | 0.023* | |
C3 | 0.17083 (13) | 0.11044 (9) | −0.14157 (8) | 0.0206 (2) | |
H3 | 0.1975 | 0.0670 | −0.1850 | 0.025* | |
C4 | 0.07672 (12) | 0.08590 (9) | −0.08458 (8) | 0.0194 (2) | |
H4 | 0.0374 | 0.0265 | −0.0899 | 0.023* | |
C5 | 0.04200 (11) | 0.14852 (8) | −0.02105 (8) | 0.01635 (19) | |
H5 | −0.0213 | 0.1325 | 0.0184 | 0.020* | |
S11 | 0.17019 (3) | 0.56583 (2) | 0.06097 (2) | 0.01734 (6) | |
N11 | 0.00946 (9) | 0.52577 (7) | 0.18492 (6) | 0.01339 (15) | |
O11 | 0.01309 (8) | 0.43684 (6) | 0.15243 (6) | 0.01775 (16) | |
C11 | 0.07867 (10) | 0.59451 (7) | 0.14809 (7) | 0.01295 (17) | |
C12 | 0.06965 (11) | 0.68604 (8) | 0.18362 (8) | 0.01715 (19) | |
H12 | 0.1176 | 0.7357 | 0.1601 | 0.021* | |
C13 | −0.00837 (12) | 0.70427 (9) | 0.25243 (8) | 0.0196 (2) | |
H13 | −0.0137 | 0.7660 | 0.2765 | 0.023* | |
C14 | −0.07907 (11) | 0.63134 (9) | 0.28629 (8) | 0.0197 (2) | |
H14 | −0.1339 | 0.6432 | 0.3330 | 0.024* | |
C15 | −0.06893 (11) | 0.54209 (9) | 0.25157 (8) | 0.01692 (19) | |
H15 | −0.1168 | 0.4920 | 0.2742 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.01444 (8) | 0.01070 (7) | 0.01229 (7) | 0.00035 (5) | −0.00110 (6) | −0.00006 (5) |
N3 | 0.0231 (5) | 0.0218 (5) | 0.0189 (4) | 0.0034 (4) | −0.0055 (4) | 0.0002 (4) |
S1 | 0.01571 (11) | 0.01588 (11) | 0.01583 (11) | −0.00325 (9) | 0.00164 (9) | 0.00016 (9) |
O1 | 0.0201 (4) | 0.0149 (3) | 0.0168 (3) | −0.0018 (3) | 0.0053 (3) | −0.0039 (3) |
N1 | 0.0134 (4) | 0.0124 (4) | 0.0133 (4) | −0.0006 (3) | −0.0005 (3) | −0.0005 (3) |
C1 | 0.0128 (4) | 0.0154 (4) | 0.0125 (4) | 0.0001 (3) | −0.0005 (3) | 0.0007 (3) |
C2 | 0.0208 (5) | 0.0195 (5) | 0.0166 (5) | 0.0012 (4) | 0.0032 (4) | −0.0018 (4) |
C3 | 0.0276 (6) | 0.0177 (5) | 0.0166 (5) | 0.0022 (4) | 0.0008 (4) | −0.0042 (4) |
C4 | 0.0250 (5) | 0.0156 (5) | 0.0175 (5) | −0.0020 (4) | −0.0028 (4) | −0.0022 (4) |
C5 | 0.0178 (5) | 0.0142 (4) | 0.0170 (4) | −0.0034 (4) | −0.0011 (4) | −0.0006 (4) |
S11 | 0.02033 (13) | 0.01345 (11) | 0.01822 (12) | −0.00135 (9) | 0.00600 (10) | 0.00070 (9) |
N11 | 0.0130 (4) | 0.0139 (4) | 0.0132 (4) | −0.0006 (3) | −0.0004 (3) | 0.0011 (3) |
O11 | 0.0215 (4) | 0.0106 (3) | 0.0211 (4) | −0.0013 (3) | 0.0021 (3) | −0.0019 (3) |
C11 | 0.0129 (4) | 0.0119 (4) | 0.0140 (4) | 0.0002 (3) | −0.0006 (3) | 0.0011 (3) |
C12 | 0.0182 (5) | 0.0136 (4) | 0.0196 (5) | 0.0001 (4) | −0.0013 (4) | −0.0004 (4) |
C13 | 0.0211 (5) | 0.0179 (5) | 0.0197 (5) | 0.0038 (4) | −0.0021 (4) | −0.0043 (4) |
C14 | 0.0181 (5) | 0.0241 (5) | 0.0170 (5) | 0.0032 (4) | 0.0009 (4) | −0.0029 (4) |
C15 | 0.0157 (4) | 0.0205 (5) | 0.0145 (4) | 0.0000 (4) | 0.0014 (3) | 0.0013 (4) |
Cr1—N3 | 1.5609 (11) | C4—H4 | 0.9500 |
Cr1—O1 | 1.9371 (9) | C5—H5 | 0.9500 |
Cr1—O11 | 1.9526 (9) | S11—C11 | 1.7183 (11) |
Cr1—S11 | 2.3290 (4) | N11—O11 | 1.3534 (13) |
Cr1—S1 | 2.3517 (4) | N11—C15 | 1.3553 (15) |
S1—C1 | 1.7217 (12) | N11—C11 | 1.3592 (14) |
O1—N1 | 1.3515 (12) | C11—C12 | 1.4080 (16) |
N1—C5 | 1.3545 (14) | C12—C13 | 1.3823 (18) |
N1—C1 | 1.3577 (14) | C12—H12 | 0.9500 |
C1—C2 | 1.4072 (16) | C13—C14 | 1.3939 (19) |
C2—C3 | 1.3778 (18) | C13—H13 | 0.9500 |
C2—H2 | 0.9500 | C14—C15 | 1.3745 (18) |
C3—C4 | 1.3991 (19) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.3680 (17) | ||
N3—Cr1—O1 | 109.24 (5) | C5—C4—H4 | 120.4 |
N3—Cr1—O11 | 105.79 (5) | C3—C4—H4 | 120.4 |
O1—Cr1—O11 | 85.22 (4) | N1—C5—C4 | 120.01 (11) |
N3—Cr1—S11 | 104.57 (5) | N1—C5—H5 | 120.0 |
O1—Cr1—S11 | 146.14 (3) | C4—C5—H5 | 120.0 |
O11—Cr1—S11 | 84.05 (3) | C11—S11—Cr1 | 95.20 (4) |
N3—Cr1—S1 | 103.02 (5) | O11—N11—C15 | 116.87 (9) |
O1—Cr1—S1 | 83.34 (3) | O11—N11—C11 | 119.87 (9) |
O11—Cr1—S1 | 151.11 (3) | C15—N11—C11 | 123.20 (10) |
S11—Cr1—S1 | 90.870 (12) | N11—O11—Cr1 | 117.51 (7) |
C1—S1—Cr1 | 95.27 (4) | N11—C11—C12 | 117.39 (10) |
N1—O1—Cr1 | 119.00 (7) | N11—C11—S11 | 118.78 (8) |
O1—N1—C5 | 116.32 (9) | C12—C11—S11 | 123.82 (9) |
O1—N1—C1 | 120.24 (9) | C13—C12—C11 | 120.53 (11) |
C5—N1—C1 | 123.39 (10) | C13—C12—H12 | 119.7 |
N1—C1—C2 | 117.06 (10) | C11—C12—H12 | 119.7 |
N1—C1—S1 | 117.94 (8) | C12—C13—C14 | 119.51 (11) |
C2—C1—S1 | 124.91 (9) | C12—C13—H13 | 120.2 |
C3—C2—C1 | 120.66 (11) | C14—C13—H13 | 120.2 |
C3—C2—H2 | 119.7 | C15—C14—C13 | 119.50 (11) |
C1—C2—H2 | 119.7 | C15—C14—H14 | 120.3 |
C2—C3—C4 | 119.60 (11) | C13—C14—H14 | 120.3 |
C2—C3—H3 | 120.2 | N11—C15—C14 | 119.85 (11) |
C4—C3—H3 | 120.2 | N11—C15—H15 | 120.1 |
C5—C4—C3 | 119.18 (11) | C14—C15—H15 | 120.1 |
N3—Cr1—S1—C1 | 92.38 (6) | N3—Cr1—S11—C11 | −89.05 (6) |
O1—Cr1—S1—C1 | −15.89 (5) | O1—Cr1—S11—C11 | 87.95 (6) |
O11—Cr1—S1—C1 | −83.24 (7) | O11—Cr1—S11—C11 | 15.76 (5) |
S11—Cr1—S1—C1 | −162.45 (4) | S1—Cr1—S11—C11 | 167.26 (4) |
N3—Cr1—O1—N1 | −82.99 (9) | C15—N11—O11—Cr1 | −164.90 (8) |
O11—Cr1—O1—N1 | 171.95 (8) | C11—N11—O11—Cr1 | 17.89 (13) |
S11—Cr1—O1—N1 | 100.09 (8) | N3—Cr1—O11—N11 | 83.20 (9) |
S1—Cr1—O1—N1 | 18.52 (7) | O1—Cr1—O11—N11 | −168.14 (8) |
Cr1—O1—N1—C5 | 168.54 (8) | S11—Cr1—O11—N11 | −20.30 (7) |
Cr1—O1—N1—C1 | −14.11 (13) | S1—Cr1—O11—N11 | −101.24 (8) |
O1—N1—C1—C2 | 179.34 (10) | O11—N11—C11—C12 | 178.92 (10) |
C5—N1—C1—C2 | −3.51 (16) | C15—N11—C11—C12 | 1.90 (16) |
O1—N1—C1—S1 | −3.88 (13) | O11—N11—C11—S11 | −0.38 (14) |
C5—N1—C1—S1 | 173.27 (9) | C15—N11—C11—S11 | −177.40 (9) |
Cr1—S1—C1—N1 | 14.90 (9) | Cr1—S11—C11—N11 | −12.80 (9) |
Cr1—S1—C1—C2 | −168.60 (10) | Cr1—S11—C11—C12 | 167.95 (9) |
N1—C1—C2—C3 | 2.15 (17) | N11—C11—C12—C13 | −0.92 (17) |
S1—C1—C2—C3 | −174.39 (10) | S11—C11—C12—C13 | 178.35 (9) |
C1—C2—C3—C4 | 0.39 (19) | C11—C12—C13—C14 | −0.44 (18) |
C2—C3—C4—C5 | −1.75 (19) | C12—C13—C14—C15 | 0.91 (19) |
O1—N1—C5—C4 | 179.48 (11) | O11—N11—C15—C14 | −178.57 (10) |
C1—N1—C5—C4 | 2.23 (17) | C11—N11—C15—C14 | −1.46 (17) |
C3—C4—C5—N1 | 0.52 (18) | C13—C14—C15—N11 | 0.00 (18) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cr(C10H8NO)2N] | [Cr(C5H4NOS)2N] |
Mr | 382.36 | 318.31 |
Crystal system, space group | Monoclinic, C2/c | Orthorhombic, Pbca |
Temperature (K) | 122 | 122 |
a, b, c (Å) | 16.8980 (14), 7.6853 (7), 13.2955 (12) | 11.0511 (12), 14.1558 (12), 15.2486 (11) |
α, β, γ (°) | 90, 103.967 (7), 90 | 90, 90, 90 |
V (Å3) | 1675.6 (3) | 2385.4 (4) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.70 | 1.30 |
Crystal size (mm) | 0.44 × 0.37 × 0.17 | 0.34 × 0.32 × 0.17 |
Data collection | ||
Diffractometer | Nonius KappaCCD | Nonius KappaCCD |
Absorption correction | Numerical Gaussian integration (Coppens, 1970) | Numerical gaussian numerical integration (Coppens, 1970) |
Tmin, Tmax | 0.813, 0.918 | 0.710, 0.856 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 49933, 5177, 4523 | 85248, 5236, 4479 |
Rint | 0.036 | 0.043 |
(sin θ/λ)max (Å−1) | 0.904 | 0.807 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.085, 1.14 | 0.025, 0.074, 1.07 |
No. of reflections | 5177 | 5236 |
No. of parameters | 120 | 163 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.50 | 1.18, −0.43 |
Computer programs: EVALCCD (Duisenberg et al., 2003), COLLECT (Nonius, 1999), COLLECT, EVALCCD, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), program (reference?).
Compound (I) | |||||
Cr1-N1 | 1.5591 (11) | N1-Cr1-N2 | 98.828 (18) | ||
Cr1-O1 | 1.9082 (6) | N1-Cr1-O2 | 112.91 (2) | ||
Cr1-N2 | 2.0827 (6) | O1-Cr1-O1 | 134.18 (4) | ||
O1-C2 | 1.3333 (9) | O1-Cr1-N2 | 91.21 (2) | ||
C1-N2 | 1.3738 (9) | O1-Cr1-N2 | 81.92 (2) | ||
N2-C9 | 1.3327 (10) | N2-Cr1-N2 | 162.34 (4) | ||
Cr-out-of-plane | 0.5312 (5) Å | ||||
Compound (II) | |||||
Cr1-N3 | 1.5609 (11) | N3-Cr1-O1 | 109.24 (5) | ||
Cr1-O1 | 1.9371 (9) | N3-Cr1-O11 | 105.79 (5) | ||
Cr1-O11 | 1.9526 (9) | N3-Cr1-S1 | 103.02 (5) | ||
Cr1-S1 | 2.3517 (4) | N3-Cr1-S11 | 104.57 (5) | ||
Cr1-S11 | 2.3290 (4) | O1-Cr1-O11 | 85.22 (4) | ||
O1-N1 | 1.3515 (12) | S1-Cr1-S11 | 90.870 (12) | ||
Cr-out-of-plane | 0.5724 (4) Å |
V(O)(quinald)2 (a) | ||||
V-O(oxo) | 1.600 (8) | |||
V-O | 1.921 (5) | O(oxo)-V-O | 116.4 (7) | |
V-N | 2.136 (6) | O(oxo)-V-N | 99.5 (5) | |
V(O)(tpno)2 (b) | ||||
V-O(oxo) | 1.593 (3) | |||
V-O(av.) | 1.956 (3) | O(oxo)-V-O(av.) | 108.5 (1) | |
V-S(av.) | 2.373 (2) | O(oxo)-V-S(av.) | 106.4 (1) |
Notes: (a) Shiro & Fernando (1971); (b) Higes-Rolando et al. (1994); |
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The nitride ligand (N3-) is the strongest electron donating ligand known (Nugent & Mayer, 1988). It also stands out by having a much more developed chemistry of second- and third-row transition metals than of their first-row congeners. The first example of a nitride complex of the first-row transition metals, Cr(N)(salen), was, therefore, prepared as late as 1981 by photolysis of the corresponding CrIII–azide complex (Arshankow & Poznjak, 1981). A few other CrV– and MnV–nitride complexes have been prepared by this route, e.g. [M(N)(cyclam)(CH3CN)]2+ [cyclam is 1,4,7,11-tetraazacyclotetradecane; M = Cr (Meyer, Bendix, Bill et al., 1998) and Mn (Meyer, Bendix, Metzler-Nolte et al., 1998)], and [Cr(N)(tacn)(acac)]+ (Niemann et al., 1996), but the method fails for systems where the auxilliary ligand sphere is labile. The lack of general methods of synthesis has been the primary obstacle in the development of the nitride chemistry for the first-row transition metals. Recently, we have found (Birk & Bendix, 2003; Bendix, 2003) that N-atom transfer from the easily accessible Mn(N)(salen) to CrCl3(THF)3 followed by ligand metathesis is a very general synthetic route to chromium(V)– nitride complexes. By this method, the uncharged complexes Cr(N)(quinald)2, (I), and Cr(N)(tpno)2, (II), have been prepared.
Complexes (I) and (II) are both five-coordinate with approximately square-pyramidal coordination around CrV and with the metal displaced ca 0.5 Å out of the plane of the basal ligators towards the nitride ligand (Figs. 1 and 2, and Table 1). Complex (I) crystallizes with CrV≡N in a crystallographic twofold axis, making the basal ligators equivalent in pairs. Interestingly, even though complex (II) has the possibility for a molecular mirror plane (Fig. 2), this is not utilized in the crystal packing. The short Cr≡N bonds of 1.5609 (11) and 1.5591 (11) Å in (II) and (I), respectively, are both within the range of those found for other five-coordinate CrV–nitride complexes and ca 0.05 Å longer than average MnV≡N bond lengths. In both structures, the nitride ligands are non-bridging. This is also evidenced by high ν(Cr—N) stretching frequencies of 1016 and 1007 cm-1, for (I) and (II), respectively. In accordance with the low basicity and nucleophilicity normally observed for [Cr≡N]2+ and [Mn≡N]2+ moieties (Meyer, Bendix, Bill et al., 1998; Meyer, Bendix, Metzler et al., 1998).
The vanadyl analogs of both (I) and (II) have been structurally characterized (Shiro & Fernando, 1971; Higes-Rolando et al., 1994, respectively) and are isostructural with their [Cr≡N]2+ counterparts. The bond lengths to the auxilliary ligands in the VIV(O) complexes are slightly longer than those found in the CrV(N) systems and the pyramidalization is slightly larger for the vanadyl systems (cf. Table 2).
Complexes (I) and (II) differ in the configuration of the bidentate ligands, being trans and cis, respectively. This difference is common for these ligands and thus unrelated to the metal centre. A rare exception to these preferred configurations is [Co(py)(tpno)2], wherein the tpno ligands are in the unusual trans configuration (Kang et al., 1993).
The difference in angle between the nitride ligand and equatorial O donors [112.91 (2)°] and N donors [98.828 (18)°] in (I) reflects a significant distortion towards a trigonal bipyramidal structure (with apical N-atom donors from the bidentate ligands). This contrast to the parent Cr(N)(quinolin-8-olate)2 complex, which features a regular square-pyramidal coordination of chromium, is caused by the steric demands of the 2-methyl substituents in (I). The packing of the Cr(N)(quinald)2 molecules is also influenced by the methyl groups, which prevent the π-stacking dominating the structure of Cr(N)(quinolin-8-olate)2. Nevertheless, a similar overall situation (cf. Fig. 3) with aligned (parallel and anti-parallel) Cr≡ N units results also for (I). This packing mode in combination with the electronically isolated molecules (the shortest Cr—Cr distance is 7.519 Å) makes the compound well suited for single-crystal EPR studies of the bonding anisotropy in the metal–nitride bond (Bendix et al., 2000).