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Acta Cryst. (2005). C61, m231-m233
https://doi.org/10.1107/S0108270105008693
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Two square-pyramidal chromium(V)–nitride complexes: bis­(2-methyl­quinolin-8-olato)nitridochromium(V) and nitridobis(2-sulfidopyridine N-oxide)chromium(V)

T. Birk, H. O. Sørensen and J. Bendix
Two new chromium(V)–nitride complexes with a coordination sphere completed by bidentate ligands have been synthesized and structurally characterized. Bis(2-methyl­quinolin-8-olato)nitridochromium(V), [Cr(C10H8NO)2(N)], has the coordination sphere completed by an equatorial N2O2 set of ligators. The compound crystallizes with the five-coordinate complexes at sites with twofold rotational symmetry and all Cr—N bond directions aligned with the crystallographic b axis. Nitridobis(2-sulfidopyridine N-oxide)chromium(V), [Cr(C5H4NOS)2(N)], crystallizes with the mol­ecules on general positions and has an equatorial S2O2 coordination environment, which is unprecedented among nitride complexes of the first-row transition metals. In both systems, Cr[triple bond]N bonds are short at ca 1.56 Å.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105008693/bg1000sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105008693/bg1000Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105008693/bg1000IIsup3.hkl
Contains datablock II

CCDC references: 273026; 273027

Comment top

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).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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?).

Figures top
[Figure 1] Fig. 1. A drawing of the molecular structure of (I), including labelling of the atoms. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. Molecular structure of (II), including labelling of the atoms. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radii.
[Figure 3] Fig. 3. The crystal packing in (I), showing the parallel and anti-parallel Cr≡N orientations. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
(I) bis(2-methylquinolin-8-olato)nitridochromium(V) top
Crystal data top
[Cr(C10H8NO)2N]F(000) = 788
Mr = 382.36Dx = 1.516 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 31996 reflections
a = 16.8980 (14) Åθ = 2.9–39.9°
b = 7.6853 (7) ŵ = 0.70 mm−1
c = 13.2955 (12) ÅT = 122 K
β = 103.967 (7)°Prism, orange
V = 1675.6 (3) Å30.44 × 0.37 × 0.17 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		5177 independent reflections
Radiation source: fine-focus sealed tube4523 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 40.0°, θmin = 2.9°
Absorption correction: numerical
Gaussian integration (Coppens, 1970)		h = −30→30
Tmin = 0.813, Tmax = 0.918k = −13→13
49933 measured reflectionsl = −24→24
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)] = 0.028Hydrogen site location: difference Fourier map
wR(F2) = 0.085H-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 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.50 e Å−3
Crystal data top
[Cr(C10H8NO)2N]V = 1675.6 (3) Å3
Mr = 382.36Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.8980 (14) ŵ = 0.70 mm−1
b = 7.6853 (7) ÅT = 122 K
c = 13.2955 (12) Å0.44 × 0.37 × 0.17 mm
β = 103.967 (7)°
Data collection top
Nonius KappaCCD
diffractometer		5177 independent reflections
Absorption correction: numerical
Gaussian integration (Coppens, 1970)		4523 reflections with I > 2σ(I)
Tmin = 0.813, Tmax = 0.918Rint = 0.036
49933 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.14Δρmax = 0.56 e Å−3
5177 reflectionsΔρmin = −0.50 e Å−3
120 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cr10.00000.22857 (2)0.25000.01337 (4)
C10.10441 (4)0.33551 (9)0.12170 (5)0.01426 (10)
C20.14601 (4)0.36423 (10)0.22685 (6)0.01602 (11)
C30.22434 (5)0.43091 (12)0.24758 (7)0.02135 (14)
C40.26199 (5)0.46655 (13)0.16573 (8)0.02351 (15)
C50.22225 (5)0.43762 (12)0.06387 (7)0.02212 (14)
C60.14149 (5)0.37214 (10)0.03976 (6)0.01699 (11)
C70.09385 (5)0.34031 (11)−0.06183 (6)0.02052 (13)
C80.01626 (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)
N10.00000.02569 (14)0.25000.02243 (18)
N20.02679 (4)0.27016 (8)0.10699 (5)0.01422 (9)
O10.10634 (3)0.32522 (9)0.29926 (4)0.01886 (10)
H10A−0.10050.07600.04840.033*0.633 (18)
H10B−0.11340.1013−0.07390.033*0.633 (18)
H10C−0.13990.2520−0.00570.033*0.633 (18)
H11A−0.09740.0379−0.02640.033*0.367 (18)
H11B−0.13760.2233−0.06220.033*0.367 (18)
H11C−0.11880.16810.05730.033*0.367 (18)
H30.25300.45280.31720.026*
H40.31600.51150.18140.028*
H50.24880.46140.01010.027*
H70.11560.3629−0.12010.025*
H8−0.01600.2574−0.14360.023*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0122 (2)0.0135 (2)0.0175 (3)0.00081 (18)0.00448 (19)−0.00045 (19)
C100.0166 (3)0.0254 (4)0.0224 (3)−0.0034 (2)0.0009 (2)−0.0043 (3)
C20.0117 (2)0.0181 (3)0.0183 (3)0.0000 (2)0.0038 (2)−0.0024 (2)
C30.0130 (3)0.0261 (4)0.0248 (3)−0.0032 (2)0.0044 (2)−0.0042 (3)
C40.0153 (3)0.0253 (4)0.0316 (4)−0.0044 (2)0.0089 (3)−0.0024 (3)
C50.0195 (3)0.0217 (3)0.0285 (4)−0.0030 (2)0.0122 (3)0.0007 (3)
C60.0177 (3)0.0145 (3)0.0205 (3)0.0002 (2)0.0080 (2)0.0012 (2)
C70.0253 (3)0.0194 (3)0.0185 (3)0.0006 (2)0.0085 (2)0.0027 (2)
C80.0235 (3)0.0187 (3)0.0158 (3)0.0014 (2)0.0036 (2)0.0006 (2)
C90.0159 (3)0.0152 (3)0.0162 (3)0.0010 (2)0.0021 (2)−0.0009 (2)
Cr10.01149 (6)0.01431 (7)0.01440 (6)0.0000.00334 (4)0.000
N10.0312 (5)0.0160 (4)0.0198 (4)0.0000.0057 (3)0.000
N20.0124 (2)0.0146 (2)0.0155 (2)−0.00011 (17)0.00333 (17)−0.00123 (18)
O10.01330 (19)0.0271 (3)0.0166 (2)−0.00266 (19)0.00454 (16)−0.00379 (19)
Geometric parameters (Å, º) top
Cr1—N11.5591 (11)C9—C101.4974 (11)
Cr1—O11.9082 (6)C7—H70.9500
Cr1—N22.0827 (6)C5—C41.3767 (13)
O1—C21.3333 (9)C5—H50.9500
C1—N21.3738 (9)C3—C41.4137 (12)
C1—C61.4099 (10)C3—H30.9500
C1—C21.4224 (10)C4—H40.9500
C6—C71.4168 (12)C10—H10A0.9800
C6—C51.4168 (11)C10—H10B0.9800
N2—C91.3327 (10)C10—H10C0.9800
C8—C71.3697 (12)C10—H11A0.9800
C8—C91.4186 (11)C10—H11B0.9800
C8—H80.9500C10—H11C0.9800
C2—C31.3837 (10)
N1—Cr1—O1112.91 (2)C8—C7—C6119.54 (7)
O1—Cr1—O1i134.18 (4)C8—C7—H7120.2
O1—Cr1—N2i91.21 (2)C6—C7—H7120.2
N1—Cr1—N298.828 (18)C4—C5—C6119.64 (7)
O1—Cr1—N281.92 (2)C4—C5—H5120.2
N2i—Cr1—N2162.34 (4)C6—C5—H5120.2
C2—O1—Cr1115.83 (5)C2—C3—C4120.33 (8)
N2—C1—C6123.37 (7)C2—C3—H3119.8
N2—C1—C2115.15 (6)C4—C3—H3119.8
C6—C1—C2121.48 (6)C5—C4—C3121.51 (7)
C1—C6—C7116.49 (7)C5—C4—H4119.2
C1—C6—C5118.65 (7)C3—C4—H4119.2
C7—C6—C5124.86 (7)C9—C10—H10A109.5
C9—N2—C1119.11 (6)C9—C10—H10B109.5
C9—N2—Cr1131.18 (5)H10A—C10—H10B109.5
C1—N2—Cr1109.67 (5)C9—C10—H10C109.5
C7—C8—C9120.94 (7)H10A—C10—H10C109.5
C7—C8—H8119.5H10B—C10—H10C109.5
C9—C8—H8119.5C9—C10—H11A109.5
O1—C2—C3124.26 (7)C9—C10—H11B109.5
O1—C2—C1117.36 (6)H11A—C10—H11B109.5
C3—C2—C1118.38 (7)C9—C10—H11C109.5
N2—C9—C8120.52 (7)H11A—C10—H11C109.5
N2—C9—C10119.93 (7)H11B—C10—H11C109.5
C8—C9—C10119.53 (7)
N1—Cr1—O1—C293.82 (6)Cr1—O1—C2—C12.02 (9)
O1i—Cr1—O1—C2−86.18 (6)N2—C1—C2—O10.15 (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—C70.85 (11)C6—C1—C2—C30.49 (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—C50.52 (11)C1—N2—C9—C10177.13 (7)
C6—C1—N2—C9−0.12 (11)Cr1—N2—C9—C10−0.40 (11)
C2—C1—N2—C9180.00 (7)C7—C8—C9—N21.90 (12)
C6—C1—N2—Cr1177.91 (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—C968.00 (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—C4178.73 (8)
N1—Cr1—N2—C1−109.72 (5)O1—C2—C3—C4179.26 (8)
O1—Cr1—N2—C12.36 (5)C1—C2—C3—C4−0.98 (12)
O1i—Cr1—N2—C1136.88 (5)C6—C5—C4—C30.58 (14)
N2i—Cr1—N2—C170.29 (5)C2—C3—C4—C50.46 (14)
Cr1—O1—C2—C3−178.22 (7)
Symmetry code: (i) −x, y, −z+1/2.
(II) nitridobis(2-sulfidopyridine N-oxide)chromium(V) top
Crystal data top
[Cr(C5H4NOS)2N]F(000) = 1288
Mr = 318.31Dx = 1.773 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 47810 reflections
a = 11.0511 (12) Åθ = 2.7–35°
b = 14.1558 (12) ŵ = 1.30 mm−1
c = 15.2486 (11) ÅT = 122 K
V = 2385.4 (4) Å3Block, dark red
Z = 80.34 × 0.32 × 0.17 mm
Data collection top
Nonius KappaCCD
diffractometer		5236 independent reflections
Radiation source: fine-focus sealed tube4479 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
φ and ω scansθmax = 35.0°, θmin = 2.7°
Absorption correction: numerical
gaussian numerical integration (Coppens, 1970)		h = −17→17
Tmin = 0.710, Tmax = 0.856k = −22→22
85248 measured reflectionsl = −24→24
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)] = 0.025Hydrogen site location: difference Fourier map
wR(F2) = 0.074H-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 parametersΔρmax = 1.18 e Å−3
0 restraintsΔρmin = −0.43 e Å−3
Crystal data top
[Cr(C5H4NOS)2N]V = 2385.4 (4) Å3
Mr = 318.31Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.0511 (12) ŵ = 1.30 mm−1
b = 14.1558 (12) ÅT = 122 K
c = 15.2486 (11) Å0.34 × 0.32 × 0.17 mm
Data collection top
Nonius KappaCCD
diffractometer		5236 independent reflections
Absorption correction: numerical
gaussian numerical integration (Coppens, 1970)		4479 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.856Rint = 0.043
85248 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.074H-atom parameters constrained
S = 1.07Δρmax = 1.18 e Å−3
5236 reflectionsΔρmin = −0.43 e Å−3
163 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.150718 (16)0.403096 (12)0.078491 (12)0.01248 (4)
N30.25475 (11)0.37550 (8)0.14282 (7)0.0213 (2)
S10.23750 (3)0.37689 (2)−0.060213 (19)0.01581 (6)
O10.05758 (8)0.29140 (6)0.04969 (6)0.01724 (15)
N10.09790 (8)0.23336 (7)−0.01433 (6)0.01300 (15)
C10.18627 (10)0.26250 (8)−0.06994 (7)0.01355 (17)
C20.22459 (12)0.19791 (9)−0.13436 (8)0.0190 (2)
H20.28820.2148−0.17330.023*
C30.17083 (13)0.11044 (9)−0.14157 (8)0.0206 (2)
H30.19750.0670−0.18500.025*
C40.07672 (12)0.08590 (9)−0.08458 (8)0.0194 (2)
H40.03740.0265−0.08990.023*
C50.04200 (11)0.14852 (8)−0.02105 (8)0.01635 (19)
H5−0.02130.13250.01840.020*
S110.17019 (3)0.56583 (2)0.06097 (2)0.01734 (6)
N110.00946 (9)0.52577 (7)0.18492 (6)0.01339 (15)
O110.01309 (8)0.43684 (6)0.15243 (6)0.01775 (16)
C110.07867 (10)0.59451 (7)0.14809 (7)0.01295 (17)
C120.06965 (11)0.68604 (8)0.18362 (8)0.01715 (19)
H120.11760.73570.16010.021*
C13−0.00837 (12)0.70427 (9)0.25243 (8)0.0196 (2)
H13−0.01370.76600.27650.023*
C14−0.07907 (11)0.63134 (9)0.28629 (8)0.0197 (2)
H14−0.13390.64320.33300.024*
C15−0.06893 (11)0.54209 (9)0.25157 (8)0.01692 (19)
H15−0.11680.49200.27420.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.01444 (8)0.01070 (7)0.01229 (7)0.00035 (5)−0.00110 (6)−0.00006 (5)
N30.0231 (5)0.0218 (5)0.0189 (4)0.0034 (4)−0.0055 (4)0.0002 (4)
S10.01571 (11)0.01588 (11)0.01583 (11)−0.00325 (9)0.00164 (9)0.00016 (9)
O10.0201 (4)0.0149 (3)0.0168 (3)−0.0018 (3)0.0053 (3)−0.0039 (3)
N10.0134 (4)0.0124 (4)0.0133 (4)−0.0006 (3)−0.0005 (3)−0.0005 (3)
C10.0128 (4)0.0154 (4)0.0125 (4)0.0001 (3)−0.0005 (3)0.0007 (3)
C20.0208 (5)0.0195 (5)0.0166 (5)0.0012 (4)0.0032 (4)−0.0018 (4)
C30.0276 (6)0.0177 (5)0.0166 (5)0.0022 (4)0.0008 (4)−0.0042 (4)
C40.0250 (5)0.0156 (5)0.0175 (5)−0.0020 (4)−0.0028 (4)−0.0022 (4)
C50.0178 (5)0.0142 (4)0.0170 (4)−0.0034 (4)−0.0011 (4)−0.0006 (4)
S110.02033 (13)0.01345 (11)0.01822 (12)−0.00135 (9)0.00600 (10)0.00070 (9)
N110.0130 (4)0.0139 (4)0.0132 (4)−0.0006 (3)−0.0004 (3)0.0011 (3)
O110.0215 (4)0.0106 (3)0.0211 (4)−0.0013 (3)0.0021 (3)−0.0019 (3)
C110.0129 (4)0.0119 (4)0.0140 (4)0.0002 (3)−0.0006 (3)0.0011 (3)
C120.0182 (5)0.0136 (4)0.0196 (5)0.0001 (4)−0.0013 (4)−0.0004 (4)
C130.0211 (5)0.0179 (5)0.0197 (5)0.0038 (4)−0.0021 (4)−0.0043 (4)
C140.0181 (5)0.0241 (5)0.0170 (5)0.0032 (4)0.0009 (4)−0.0029 (4)
C150.0157 (4)0.0205 (5)0.0145 (4)0.0000 (4)0.0014 (3)0.0013 (4)
Geometric parameters (Å, º) top
Cr1—N31.5609 (11)C4—H40.9500
Cr1—O11.9371 (9)C5—H50.9500
Cr1—O111.9526 (9)S11—C111.7183 (11)
Cr1—S112.3290 (4)N11—O111.3534 (13)
Cr1—S12.3517 (4)N11—C151.3553 (15)
S1—C11.7217 (12)N11—C111.3592 (14)
O1—N11.3515 (12)C11—C121.4080 (16)
N1—C51.3545 (14)C12—C131.3823 (18)
N1—C11.3577 (14)C12—H120.9500
C1—C21.4072 (16)C13—C141.3939 (19)
C2—C31.3778 (18)C13—H130.9500
C2—H20.9500C14—C151.3745 (18)
C3—C41.3991 (19)C14—H140.9500
C3—H30.9500C15—H150.9500
C4—C51.3680 (17)
N3—Cr1—O1109.24 (5)C5—C4—H4120.4
N3—Cr1—O11105.79 (5)C3—C4—H4120.4
O1—Cr1—O1185.22 (4)N1—C5—C4120.01 (11)
N3—Cr1—S11104.57 (5)N1—C5—H5120.0
O1—Cr1—S11146.14 (3)C4—C5—H5120.0
O11—Cr1—S1184.05 (3)C11—S11—Cr195.20 (4)
N3—Cr1—S1103.02 (5)O11—N11—C15116.87 (9)
O1—Cr1—S183.34 (3)O11—N11—C11119.87 (9)
O11—Cr1—S1151.11 (3)C15—N11—C11123.20 (10)
S11—Cr1—S190.870 (12)N11—O11—Cr1117.51 (7)
C1—S1—Cr195.27 (4)N11—C11—C12117.39 (10)
N1—O1—Cr1119.00 (7)N11—C11—S11118.78 (8)
O1—N1—C5116.32 (9)C12—C11—S11123.82 (9)
O1—N1—C1120.24 (9)C13—C12—C11120.53 (11)
C5—N1—C1123.39 (10)C13—C12—H12119.7
N1—C1—C2117.06 (10)C11—C12—H12119.7
N1—C1—S1117.94 (8)C12—C13—C14119.51 (11)
C2—C1—S1124.91 (9)C12—C13—H13120.2
C3—C2—C1120.66 (11)C14—C13—H13120.2
C3—C2—H2119.7C15—C14—C13119.50 (11)
C1—C2—H2119.7C15—C14—H14120.3
C2—C3—C4119.60 (11)C13—C14—H14120.3
C2—C3—H3120.2N11—C15—C14119.85 (11)
C4—C3—H3120.2N11—C15—H15120.1
C5—C4—C3119.18 (11)C14—C15—H15120.1
N3—Cr1—S1—C192.38 (6)N3—Cr1—S11—C11−89.05 (6)
O1—Cr1—S1—C1−15.89 (5)O1—Cr1—S11—C1187.95 (6)
O11—Cr1—S1—C1−83.24 (7)O11—Cr1—S11—C1115.76 (5)
S11—Cr1—S1—C1−162.45 (4)S1—Cr1—S11—C11167.26 (4)
N3—Cr1—O1—N1−82.99 (9)C15—N11—O11—Cr1−164.90 (8)
O11—Cr1—O1—N1171.95 (8)C11—N11—O11—Cr117.89 (13)
S11—Cr1—O1—N1100.09 (8)N3—Cr1—O11—N1183.20 (9)
S1—Cr1—O1—N118.52 (7)O1—Cr1—O11—N11−168.14 (8)
Cr1—O1—N1—C5168.54 (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—C2179.34 (10)O11—N11—C11—C12178.92 (10)
C5—N1—C1—C2−3.51 (16)C15—N11—C11—C121.90 (16)
O1—N1—C1—S1−3.88 (13)O11—N11—C11—S11−0.38 (14)
C5—N1—C1—S1173.27 (9)C15—N11—C11—S11−177.40 (9)
Cr1—S1—C1—N114.90 (9)Cr1—S11—C11—N11−12.80 (9)
Cr1—S1—C1—C2−168.60 (10)Cr1—S11—C11—C12167.95 (9)
N1—C1—C2—C32.15 (17)N11—C11—C12—C13−0.92 (17)
S1—C1—C2—C3−174.39 (10)S11—C11—C12—C13178.35 (9)
C1—C2—C3—C40.39 (19)C11—C12—C13—C14−0.44 (18)
C2—C3—C4—C5−1.75 (19)C12—C13—C14—C150.91 (19)
O1—N1—C5—C4179.48 (11)O11—N11—C15—C14−178.57 (10)
C1—N1—C5—C42.23 (17)C11—N11—C15—C14−1.46 (17)
C3—C4—C5—N10.52 (18)C13—C14—C15—N110.00 (18)

Experimental details

(I)(II)
Crystal data
Chemical formula[Cr(C10H8NO)2N][Cr(C5H4NOS)2N]
Mr382.36318.31
Crystal system, space groupMonoclinic, C2/cOrthorhombic, Pbca
Temperature (K)122122
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), 9090, 90, 90
V (Å3)1675.6 (3)2385.4 (4)
Z48
Radiation typeMo KαMo Kα
µ (mm−1)0.701.30
Crystal size (mm)0.44 × 0.37 × 0.170.34 × 0.32 × 0.17
Data collection
DiffractometerNonius KappaCCDNonius KappaCCD
Absorption correctionNumerical
Gaussian integration (Coppens, 1970)		Numerical
gaussian numerical integration (Coppens, 1970)
Tmin, Tmax0.813, 0.9180.710, 0.856
No. of measured, independent and
observed [I > 2σ(I)] reflections		49933, 5177, 4523 85248, 5236, 4479
Rint0.0360.043
(sin θ/λ)max (Å−1)0.9040.807
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.085, 1.14 0.025, 0.074, 1.07
No. of reflections51775236
No. of parameters120163
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.56, −0.501.18, −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?).

Selected geometric parameters (Å,°) for nitride complexes (I) and (II) top
Compound (I)
Cr1-N11.5591 (11)N1-Cr1-N298.828 (18)
Cr1-O11.9082 (6)N1-Cr1-O2112.91 (2)
Cr1-N22.0827 (6)O1-Cr1-O1134.18 (4)
O1-C21.3333 (9)O1-Cr1-N291.21 (2)
C1-N21.3738 (9)O1-Cr1-N281.92 (2)
N2-C91.3327 (10)N2-Cr1-N2162.34 (4)
Cr-out-of-plane0.5312 (5) Å
Compound (II)
Cr1-N31.5609 (11)N3-Cr1-O1109.24 (5)
Cr1-O11.9371 (9)N3-Cr1-O11105.79 (5)
Cr1-O111.9526 (9)N3-Cr1-S1103.02 (5)
Cr1-S12.3517 (4)N3-Cr1-S11104.57 (5)
Cr1-S112.3290 (4)O1-Cr1-O1185.22 (4)
O1-N11.3515 (12)S1-Cr1-S1190.870 (12)
Cr-out-of-plane0.5724 (4) Å
Comparative Geometric Parameters (Å,°) for Vanadyl Complexes. top
V(O)(quinald)2 (a)
V-O(oxo)1.600 (8)
V-O1.921 (5)O(oxo)-V-O116.4 (7)
V-N2.136 (6)O(oxo)-V-N99.5 (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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