Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615015739/ov3065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015739/ov30652sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015739/ov30653sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015739/ov30651sup4.hkl |
CCDC reference: 1420167
Homoleptic octahedral compounds of CrII are invaluable synthons in the coordination chemistry of chromium. However, despite their synthetic utility, very few examples have been crystallographically characterized. Such compounds are also interesting from a fundamental perspective, as they have partially filled d orbitals in a degenerate ground state. The Jahn–Teller effect distorts the nuclei from octahedral symmetry to remove the orbital degeneracy. The distortion can in principle lie anywhere along the Jahn–Teller minimum potential energy surface, the so-called `Mexican hat diagram' and the Jahn–Teller distortion is usually fluxional (Falvello, 1997). However, in the crystal structures of related six-coordinate Cr2+ (high-spin) and Cu2+ compounds, they usually distort by elongation of a single pair of metal–ligand bonds [see, for example, Figgis et al. (1990, 2000)]. In the environment of a rigid solid, interchange between different elongations along the molecular x, y and z axes involves breaking the bonds which hold the ligand molecules (hydrogen bonds etc.) in the crystal structure. Jahn–Teller distortions are a challenge for molecular modelling since they are essentially dynamic in nature. Since octahedral systems involve minimal steric repulsion about ligand atoms with maximal symmetry it is difficult or impossible to determine a priori in which direction the distortion will occur. We report the structure and electron density (ED) of [Cr(CH3CN)6](BPh4)2·CH3CN, (I), a compound representing a rare well ordered Jahn–Teller-distorted CrII species. A detailed picture of the electronic structure allows us to assess the extent and directionality of the Jahn–Teller distortion away from idealized octahedral symmetry and observe the influence on the bonding with ligand N atoms. Examinations of the electronic structure at the Jahn–Teller minimum also provide detailed insights into the electronic structure of synthetically valuable homoleptic six-coordinate CrII species. To study the title compound in more detail than possible with the conventional independent atom model (IAM), we have carried out a combined X-ray diffraction study (XD) with free refinement of the multipoles and a computational study where we have projected (Dittrich et al., 2005) the theoretical ED from a wavefunction onto the multipole model (Hansen & Coppens, 1978). The resulting scattering factors were fixed in the least-squares refinement. An advantage of this approach is that it gives a complete static distribution of the ED that can be compared directly with densities from the free multipolar refinement. Both sets of multipole populations were evaluated to give d-orbital populations (Holladay et al., 1983).
The title compound, [Cr(CH3CN)6](BPh4)2·CH3CN, was synthesized inside a glove-box by combining CrCl2 and NaBPh4 in a scintillation vial and stirring overnight in anhydrous acetonitrile (10 ml). A white precipitate was allowed to settle, the pale-blue solution was filtered over a fine-porosity fritted glass funnel, and the remaining solid was rinsed with acetonitrile (5 ml). The clear pale-blue acetonitrile solution was concentrated in vacuo to one half of the original volume and stored at ambient temperature to afford single crystals of the title compound over a period of 4 d.
Crystal data, data collection and structure refinement details are summarized in Table 1. Data were measured at 110 K using ω scans using Mo Kα radiation (fine-focus sealed tube, 45 kV, 35 mA). The total number of runs and images was based on the strategy calculation from the program APEXII (Bruker, 2014), giving redundant and 100% complete diffraction data to 0.5 Å (2θ = 90°) and a highest resolution of 0.481 Å (2θ = 95°). Multipole refinements were initiated with the results from a SHELXL refinement (Sheldrick, 2008) and carried out with the XD2006 suite of programs (Volkov et al., 2006). Local coordinate systems were set for each atom and local site symmetry employed to restrict the number of multipoles to be refined, for example, chemically equivalent phenyl ring C and H atoms. However, chemical constraints were not used for the refinement of the [Cr(CH3CN)6]2+ cation, which resides on a crystallographic twofold axis. Hence, its x and z coordinates were fixed and the U12 and U23 tensor components were set to zero. The site symmetry also requires a particular choice of coordinate system and restricts which multipole populations are refined. For a site with site symmetry 2, the z axis must be parallel to the twofold axis and the multipole populations with indices (l, 2µ, ±) are refined (Koritsanszky et al., 2007; Table 2). The Su–Coppens–Macchi databank with relativistic Dirac–Fock wavefunctions for the core, valence and deformation density was used (Su & Coppens, 1998). The refinements with a 3d4 valence configuration gave a slightly better electron density (ED) than when a neutral-atom scattering factor for the Cr atom was used. The total charge of the asymmetric unit was constrained to be zero, allowing charge transfer between the molecules. All atomic positions, except H atoms, were refined freely. [H atoms fully refined in (2)?] The C—H distances were constrained to their neutron values (Allen & Bruno, 2010). Only reflections with intensities I > 3σ(I) were included in the refinement.
A second refinement was performed using scattering factors derived from a theoretical B3LYP/TZVP ED of the isolated [Cr(CH3CN)6]2+ cation using the same starting structure. In this refinement, only the atomic positions and the anisotropic displacement parameters were adjusted. The experimental refinement data contained atomic positions, anisotropic displacement parameters and multipoles. Care was taken to preserve the local coordinate system (i.e. the chemical environment of the atom) and the overall charge constraints in both sets of refinements. The [Cr(CH3CN)6]2+ cation was assigned a dipositive charge. Charge transfer between molecules was only allowed in the experimental multipole refinement, leading to a slight discrepancy between monopole populations for the [Cr(CH3CN)6]2+ cation in the refinement with theoretical scattering factors (which sum to 2+). The program invariomtool (Hübschle et al., 2007) was used in setting the local coordinate system and preparing the master and input files for multipole refinement with the XDLSM program of the XD2006 suite (Farrugia, 2007; Volkov et al., 2006).
Unrestricted density functional theory (DFT) calculations were carried out for [Cr(CH3CN)6] using the B3LYP functional (Becke, 1993; Lee et al., 1988) and a triple ζ valence (TZVP) basis set (Schäfer et al., 1994), as implemented in the GAUSSIAN09 suite of programs (Frisch et al., 2009). The molecule was assigned a pentet spin state and an overall charge of 2+ for the calculations. An integration grid having 99 radial shells and 590 angular points per shell was used during the numerical integrations. Calculations were carried out using 504 basis functions and 860 primitives, of which 36 basis functions (6 s, 12 p and 18 d functions) and 86 primitives were from the Cr basis. The molecular wavefunction was calculated for the nuclear configuration taken from the crystal structure but with C—H distances normalized to neutron values (Allen & Bruno, 2010). Topological analysis of the electron-density distribution (EDD) was carried out with the program AIMALL (Keith, 2013). The program TONTO (Jayatilaka & Grimwood, 2003) was used to project the EDD onto the multipole model. The Fourier transform of the electron densities placed in an artificial unit cell then gave simulated X-ray structure factors (Jayatilaka, 1994; Jayatilaka & Dittrich, 2008). The space group P2/n was chosen to mimic the crystallographic symmetry at the Cr2+ site, and the twofold axis intersects the cation at the CrII atom in both the experimental and artificial crystal structures. The unit cell was large and the fragments thus sufficiently far from each other to be non-interacting. The structure factors (a Fourier transform of the ED) were generated by TONTO up to a resolution of (sinθ)/λ = 1.15 Å-1. The above procedure is analogous to the one used in invariom modeling (Dittrich et al., 2006, 2013), which has been recently extended to coordination compounds (Dittrich et al., 2015).
Results from the XD refinements with spherical atoms, denoted (1), with freely refined, denoted (2), and with predicted, denoted (3), multipolar parameters are shown in Table 3. The free multipolar refinement lowered R(F) from 0.047 to 0.035 and improved the goodness-of-fit from 1.71 to 1.15. The fixed multipolar parameters led to an R(F) value of 0.036 with a goodness-of-fit value of 1.12. Both sets of multipolar parameter significantly lowered the differences between the mean-square displacement amplitudes (DMSDA – the Hirshfeld test) along interatomic vectors (Rosenfield et al., 1978) compared with those from a spherical atom refinement. The refinement with the theoretical multipolar gave the best DMSDA's along the Cr—N bonds (Table 4). The r.m.s. deviation (0.053) of the final difference maps was the same for both sets of aspherical-atom refinements. The largest residual peak and hole (±0.46 e Å-3) are greater in magnitude with predicted than with experimental scattering factors (±0.33 e Å-3). The largest residuals occurred within 0.5 to 1 Å to the Cr atom. There are small but significant displacements in the C- and N-atom positions relative to those of the spherical atom refinements (about 0.005 Å) and these are similar for the two sets of aspherical-atom refinements, indicating better treatment of the electron distribution about the Cr atom than in the IAM refinement.
The asymmetric unit (half the formula given in Table 1) contains the [Cr(CH3CN)6]2+ cation, with the CrII atom in the special position (1/2, y, 1/4), and a [B(C6H5)4]- anion and an acetonitrile solvent molecule in general positions (Fig. 1). The Cr2+ cation is highly distorted: the four equatorial bonds [2.0665 (6) and 2.0904 (6) Å] are considerably shorter than the two axial bonds [2.4259 (8) Å]. The two axial nitrile angles (Cr—N—C) are bent (Tables 5 and 6). Intermolecular C—H···π interactions occur between the acetonitrile H atoms and the aromatic rings of the [B(C6H5)4]- anion, and there are favorable interactions between the acetonitrile H atoms and the nitrile N atom. The stronger metal–ligand bonding in the equatorial plane constrains these angles towards linearity as this would minimize steric repulsion between ligands. The weakly bound axial atoms are further apart, and are freer to move when perturbed by intermolecular forces.
This arrangement of ligands and the corresponding electronic interaction between these ligands and the Cr atom is of interest in Jahn–Teller theory. Difference-density maps were calculated using the differences between the structure-factor amplitudes from the multipole and independent atom models. Fourier deformation density maps in the plane of equatorial ligands calculated for both aspherical-atom models are compared in Fig. 2. A representation of the three-dimensional deformation ED from theoretical multipolar parameters (which reveals the character of the chemical bonding) is shown in Fig. 3. The deformation density shows four lobes of positive ED (and four lobes of negative density along the Cr—N bonds). This shape corresponds to the shape of a dx2–y2 orbital when the equatorial plane is the xy plane. The experimental ED distribution has a pronounced charge accumulation along an axis bisecting a pair of alternate trans N—Cr—N angles (N1—Cr—N1' and N3—Cr—N3') and a weakened positive density in the adjacent bisector (N1—Cr—N3 and N1'—Cr—N3'). The experimental ED is smeared due to thermal motion, especially close to the Cr nucleus. Both maps show similar dative N—Cr bonding, with the lone pairs of the N atoms migrating to the CrII cation. The degree of migration of charge from the N atoms to the metal ion is remarkably similar in both models, despite the assumption of full charge transfer for predicted multipoles. The residual density from both sets of aspherical-atom refinements in the same plane is shown in Fig. 4. Both maps show some aspherical density features not modelled by the multipolar models, with maximum peak heights of 0.44 (Fig. 4a) and 0.32 e Å-3 (Fig. 4b).
As there is no disorder, the six ligands are the same and the CrII cation is in an electronic degenerate state, the title compound is an excellent candidate for the investigation of the Jahn–Teller effect by an analysis of the charge density. The d-orbital populations can be derived from the multipole populations (Holladay et al., 1983) for both aspherical atom refinements and we will discuss the results using the point of view of classic crystal field theory first. In a standard textbook description of electrostatic crystal field theory, the Cr atom would generally be described as having tetragonal distortion along the z axis. The z axis is defined to be the axial bond direction and the symmetry properties of the orbitals are referred to using the D4 h point group (Huheey et al., 1993). In crystal field theory, the dxy and dyz orbitals are degenerate (eg) and lowest in energy when the Cr atom has tetragonal (D4h) symmetry. Crystal field theory predicts the highest energy orbital to be the dx2–y2 orbital (b1g) with the standard orientation of the axes. In (I), the CrII cation is located on a site with site symmetry 2 and the z axis must be parallel to the twofold axis. This z axis subtends the equatorial N—Cr—N bond angles, while the x axis is the axial bond direction. This reorientation of axes transforms the dx2–y2 orbital to the orbital that subtends the x, y axes (i.e. the dyz orbital). The d-orbital populations are presented in Table 7. The multipole analysis gives roughly equal populations for the dx2–y2, dxz, dxy and dz2 orbitals, but with far fewer electrons in the orbital directed towards the equatorial ligands (the dyz orbital). One can conclude from the experimental data in Table 7 that the highest-energy orbital is the dyz orbital (it is the lowest populated orbital and is directed towards the equatorial ligands) and that the dz2 orbital is stabilized by Jahn–Teller distortion. The qualitative agreement between the orbital populations from the refinements with calculated structure factors from theory and from the experimental diffraction data is satisfactory. Both theory and experiment indicate a significant increase in energy of the dyz orbital with respect to the other orbitals and that the remaining orbitals are similar in energy.
The classical crystal field description is next complemented by an atoms in molecules (AIM) analysis (Bader, 1990) of the EDD from the B3LYP/TZVP wavefunction. The electron densities at the bond critical point (BCP) ρ(rbcp) for the metal–ligand and the ligand C—N bonds are shown in Table 8. BCP's occur roughly midway between the Cr and N nuclei. The equatorial Cr—N BCP's have nearly twice the ED of the axial Cr1—N2 bond, which is due to the Jahn–Teller effect. In organic compounds, the charge concentrations occur close to the midpoints of bonds and ρ(rbcp) correlates well with the strength of the bond. The outer electrons of a transition metal are more diffuse and the location of the valence electrons is less certain. Therefore, the values of these ρ(rbcp) are low compared with the bonds in the ligands (Table 8). Also, the values of \nabla2ρ(r) are positive. Thus, there is little accumulation of electrons along these bond paths. However, there is significant ligand-to-metal charge migration (Fig. 2) between the Cr and the ligand N atoms. This not only indicates a strong electrostatic interaction but also significant electron-pair density between the CrII cation and its ligands (and the bond-order sum for these six bonds is close to 2.0). This result is entirely consistent with a bonding picture where vacant orbitals centered on the metal atom have the correct symmetry to overlap with occupied orbitals on the donor atoms.
Contour maps of the Laplacian [\nabla2(r)ρ(r)] are shown in Fig. 5. As in the deformation maps, the Laplacian shows the aspherical d-electron density about the CrII cation. The lobes of metal [electron?] density are directed between the ligands in the equatorial plane, and there is significant valence charge concentration about the Cr nucleus directed towards the two N atoms along the axial Cr—N axis. These are revealed as (3,+3) critical points of \nabla2(r)ρ(r) where the electron densities are at local maxima. There are four of these critical points in the equatorial plane and two along the axial Cr—N axis. The equatorial angle LCP—Cr—LCP is 90°, and the angle LCP—LCP—Cr is 45°. Moreover, there are four (3,-3) critical points of \nabla2(r)ρ(r), where the EDD is at a local minimum along the equatorial Cr—N bond paths. This topology corresponds to that expected for a high-spin d4 Cr2+ cation in a tetragonal field. It is clearly evident that this arrangement entails minimal electrostatic repulsion between the t2g electrons centered on the Cr and the donor electrons on the ligand atoms, and also the Jahn–Teller distortion has stabilized the dz2 electron in the eg set.
In this work, the electron density of an ordered Jahn–Teller complex was investigated. A sense of the accuracy of the computed and experimental electron densities was obtained from a comparison of two aspherical-atom models. The theoretical multipolar model significantly improved the structural model from spherical-atom refinements, as shown by the lower mean-square displacement amplitudes, the goodness-of-fit values and the R indices. The multipole analysis gave d-orbital populations in agreement with classical crystal field theory. The deformation maps and the Laplacian densities from IAM analysis provide a more detailed description and show the aspherical d-electron density to be in rough agreement with classical crystal field theory.
In conclusion, aspherical-atom modeling provides a significant improvement on the spherical-atom model. For traditional multipole refinements, data collected at even lower temperatures and higher resolution would be needed to vouchsafe the veracity of the theoretical models.
Data collection: APEX2 v2014.1-1 (Bruker, 2014) for (1); APEX2 (Bruker, 2014) for (2), (3). Cell refinement: SAINT v8.34A (Bruker, 2013) for (1); SAINT(Bruker, 2014) for (2); SAINT (Bruker, 2014) for (3). Data reduction: SAINT v8.34A (Bruker, 2013) for (1); SAINT (Bruker, 2014) for (2), (3). Program(s) used to solve structure: SHELXS97 for (1); SHELXS97 (Sheldrick, 2008) for (2), (3). Program(s) used to refine structure: SHELXL (Sheldrick, 2008) for (1); XD2006 (Volkov et al., 2006) for (2), (3). Molecular graphics: XD2006 (Volkov et al., 2006), X-SEED (Barbour, 2001) and AIMALL (Keith, 2013) for (2), (3). Software used to prepare material for publication: SHELXL (Sheldrick, 2008) for (1); XD2006 (Volkov et al., 2006) and publCIF (Westrip, 2010) for (2), (3).
C12H18CrN6·2(C24H20B)·2(C2H3N) | F(000) = 2152 |
Mr = 1018.92 | Dx = 1.183 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.8632 (3) Å | Cell parameters from 9787 reflections |
b = 14.6756 (2) Å | θ = 2.6–47.0° |
c = 20.7596 (3) Å | µ = 0.25 mm−1 |
β = 95.230 (1)° | T = 110 K |
V = 5722.93 (15) Å3 | Prism, green |
Z = 4 | 0.37 × 0.34 × 0.18 mm |
Bruker APEX-II CCD diffractometer | 26260 independent reflections |
Radiation source: fine-focus sealed tube | 14506 reflections with I > 2σ(I) |
Graphite monochromator | θmax = 47.6°, θmin = 1.8° |
φ and ω scans | h = −34→39 |
Absorption correction: multi-scan SADABS2012/1 (Bruker, 2012) was used for absorption correction. wR2(int) was 0.0831 before and 0.0669 after correction. The Ratio of minimum to maximum transmission is 0.7925. The λ/2 correction factor is 0.0015. | k = −29→30 |
Tmin = 0.594, Tmax = 0.749 | l = −42→42 |
127361 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.055 | w = 1/[σ2(Fo2) + (0.0567P)2 + 1.2339P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.147 | (Δ/σ)max = 0.007 |
S = 1.00 | Δρmax = 0.60 e Å−3 |
26260 reflections | Δρmin = −0.78 e Å−3 |
395 parameters |
C12H18CrN6·2(C24H20B)·2(C2H3N) | V = 5722.93 (15) Å3 |
Mr = 1018.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.8632 (3) Å | µ = 0.25 mm−1 |
b = 14.6756 (2) Å | T = 110 K |
c = 20.7596 (3) Å | 0.37 × 0.34 × 0.18 mm |
β = 95.230 (1)° |
Bruker APEX-II CCD diffractometer | 127361 measured reflections |
Absorption correction: multi-scan SADABS2012/1 (Bruker, 2012) was used for absorption correction. wR2(int) was 0.0831 before and 0.0669 after correction. The Ratio of minimum to maximum transmission is 0.7925. The λ/2 correction factor is 0.0015. | 26260 independent reflections |
Tmin = 0.594, Tmax = 0.749 | 14506 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.60 e Å−3 |
26260 reflections | Δρmin = −0.78 e Å−3 |
395 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.5000 | 0.73355 (2) | 0.2500 | 0.01640 (4) | |
N1 | 0.50959 (4) | 0.63183 (5) | 0.32082 (3) | 0.01992 (11) | |
N3 | 0.50456 (4) | 0.83129 (5) | 0.32198 (4) | 0.02043 (12) | |
C13 | 0.81869 (4) | 0.38610 (5) | 0.44096 (3) | 0.01381 (10) | |
C7 | 0.71091 (4) | 0.43579 (5) | 0.35133 (3) | 0.01434 (10) | |
C25 | 0.72388 (4) | 0.52060 (5) | 0.46146 (3) | 0.01511 (10) | |
C19 | 0.82989 (4) | 0.53866 (5) | 0.38073 (3) | 0.01469 (10) | |
N2 | 0.62917 (4) | 0.73312 (6) | 0.25873 (4) | 0.02444 (13) | |
C14 | 0.83946 (4) | 0.31192 (5) | 0.40421 (4) | 0.01765 (12) | |
C1 | 0.52280 (4) | 0.57464 (5) | 0.35739 (4) | 0.01813 (12) | |
C30 | 0.69365 (4) | 0.47063 (5) | 0.50982 (4) | 0.01677 (11) | |
C24 | 0.86456 (4) | 0.60751 (5) | 0.41895 (4) | 0.01833 (12) | |
C18 | 0.84833 (4) | 0.38859 (5) | 0.50557 (4) | 0.01767 (12) | |
C20 | 0.85517 (4) | 0.52512 (6) | 0.31975 (4) | 0.01876 (12) | |
C3 | 0.68363 (4) | 0.75396 (6) | 0.28292 (4) | 0.02033 (13) | |
C12 | 0.67617 (4) | 0.35098 (5) | 0.35367 (4) | 0.01776 (12) | |
C8 | 0.68534 (4) | 0.49354 (5) | 0.30034 (4) | 0.01801 (12) | |
C5 | 0.50666 (4) | 0.87916 (5) | 0.36561 (4) | 0.01844 (12) | |
C15 | 0.88532 (5) | 0.24403 (5) | 0.43019 (5) | 0.02284 (15) | |
C21 | 0.90975 (4) | 0.57754 (7) | 0.29757 (4) | 0.02410 (15) | |
C23 | 0.91917 (4) | 0.66079 (6) | 0.39745 (5) | 0.02318 (15) | |
C11 | 0.62105 (4) | 0.32514 (6) | 0.30788 (4) | 0.02224 (14) | |
C9 | 0.63010 (4) | 0.46870 (6) | 0.25431 (4) | 0.02218 (14) | |
H9 | 0.6145 | 0.5100 | 0.2207 | 0.027* | |
C29 | 0.65150 (4) | 0.51110 (6) | 0.55377 (4) | 0.02108 (13) | |
C17 | 0.89389 (4) | 0.32103 (6) | 0.53242 (4) | 0.02310 (14) | |
C2 | 0.53907 (5) | 0.50189 (7) | 0.40354 (4) | 0.02463 (15) | |
H2A | 0.5611 | 0.4511 | 0.3821 | 0.037* | |
H2B | 0.4951 | 0.4810 | 0.4206 | 0.037* | |
H2C | 0.5721 | 0.5244 | 0.4392 | 0.037* | |
B1 | 0.77067 (4) | 0.47031 (5) | 0.40855 (4) | 0.01357 (11) | |
C26 | 0.70633 (5) | 0.61363 (5) | 0.45842 (4) | 0.02233 (14) | |
H26 | 0.7237 | 0.6498 | 0.4253 | 0.027* | |
C10 | 0.59787 (4) | 0.38383 (7) | 0.25744 (4) | 0.02399 (15) | |
H10 | 0.5608 | 0.3661 | 0.2259 | 0.029* | |
C16 | 0.91229 (5) | 0.24770 (6) | 0.49482 (5) | 0.02551 (16) | |
H16 | 0.9427 | 0.2010 | 0.5130 | 0.031* | |
C22 | 0.94157 (5) | 0.64660 (6) | 0.33625 (5) | 0.02556 (16) | |
H22 | 0.9780 | 0.6834 | 0.3210 | 0.031* | |
C6 | 0.50900 (5) | 0.93856 (6) | 0.42156 (4) | 0.02116 (13) | |
H6A | 0.4906 | 0.9988 | 0.4083 | 0.032* | |
H6B | 0.5583 | 0.9444 | 0.4405 | 0.032* | |
H6C | 0.4797 | 0.9126 | 0.4537 | 0.032* | |
C28 | 0.63725 (5) | 0.60413 (6) | 0.55074 (5) | 0.02572 (16) | |
H28 | 0.6096 | 0.6322 | 0.5812 | 0.031* | |
N4 | 0.83715 (5) | 0.54081 (7) | 0.64758 (5) | 0.03448 (19) | |
C4 | 0.75343 (5) | 0.77978 (7) | 0.31291 (5) | 0.02819 (17) | |
H4A | 0.7757 | 0.8227 | 0.2848 | 0.042* | |
H4B | 0.7833 | 0.7253 | 0.3194 | 0.042* | |
H4C | 0.7483 | 0.8087 | 0.3548 | 0.042* | |
C31 | 0.80675 (5) | 0.47468 (7) | 0.65530 (4) | 0.02435 (15) | |
C27 | 0.66431 (5) | 0.65515 (6) | 0.50210 (5) | 0.02820 (18) | |
H27 | 0.6542 | 0.7185 | 0.4986 | 0.034* | |
C32 | 0.76930 (5) | 0.38963 (6) | 0.66481 (4) | 0.02645 (16) | |
H32A | 0.7622 | 0.3567 | 0.6236 | 0.040* | |
H32B | 0.7230 | 0.4029 | 0.6805 | 0.040* | |
H32C | 0.7975 | 0.3521 | 0.6967 | 0.040* | |
H12 | 0.6909 (7) | 0.3110 (9) | 0.3892 (6) | 0.023 (3)* | |
H30 | 0.7018 (7) | 0.4056 (9) | 0.5124 (6) | 0.021 (3)* | |
H18 | 0.8372 (7) | 0.4404 (9) | 0.5318 (6) | 0.024 (3)* | |
H14 | 0.8219 (7) | 0.3082 (9) | 0.3561 (6) | 0.023 (3)* | |
H8 | 0.7074 (7) | 0.5554 (8) | 0.2974 (6) | 0.019 (3)* | |
H24 | 0.8505 (7) | 0.6196 (9) | 0.4634 (6) | 0.022 (3)* | |
H20 | 0.8329 (7) | 0.4765 (9) | 0.2920 (6) | 0.024 (3)* | |
H17 | 0.9126 (8) | 0.3259 (10) | 0.5780 (7) | 0.032 (3)* | |
H21 | 0.9250 (7) | 0.5653 (9) | 0.2561 (7) | 0.025 (3)* | |
H23 | 0.9429 (8) | 0.7090 (10) | 0.4255 (7) | 0.034 (4)* | |
H29 | 0.6343 (8) | 0.4714 (9) | 0.5883 (7) | 0.030 (3)* | |
H11 | 0.5999 (8) | 0.2657 (9) | 0.3113 (7) | 0.029 (3)* | |
H15 | 0.8995 (8) | 0.1961 (10) | 0.4035 (7) | 0.031 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.01779 (7) | 0.01403 (7) | 0.01726 (7) | 0.000 | 0.00093 (5) | 0.000 |
N1 | 0.0201 (3) | 0.0190 (3) | 0.0204 (3) | 0.0010 (2) | 0.0009 (2) | 0.0005 (2) |
N3 | 0.0199 (3) | 0.0182 (3) | 0.0232 (3) | −0.0010 (2) | 0.0023 (2) | −0.0019 (2) |
C13 | 0.0129 (2) | 0.0132 (2) | 0.0154 (2) | −0.00052 (19) | 0.00216 (18) | 0.00055 (19) |
C7 | 0.0125 (2) | 0.0143 (3) | 0.0164 (2) | 0.00031 (19) | 0.00184 (19) | −0.0005 (2) |
C25 | 0.0140 (3) | 0.0138 (3) | 0.0178 (3) | 0.0000 (2) | 0.0026 (2) | −0.0008 (2) |
C19 | 0.0134 (3) | 0.0134 (2) | 0.0172 (3) | −0.0002 (2) | 0.00076 (19) | 0.0011 (2) |
N2 | 0.0195 (3) | 0.0255 (3) | 0.0282 (3) | 0.0002 (3) | 0.0012 (2) | 0.0020 (3) |
C14 | 0.0166 (3) | 0.0148 (3) | 0.0217 (3) | 0.0006 (2) | 0.0024 (2) | −0.0017 (2) |
C1 | 0.0144 (3) | 0.0201 (3) | 0.0198 (3) | 0.0008 (2) | 0.0009 (2) | 0.0002 (2) |
C30 | 0.0148 (3) | 0.0174 (3) | 0.0183 (3) | 0.0014 (2) | 0.0033 (2) | 0.0007 (2) |
C24 | 0.0160 (3) | 0.0140 (3) | 0.0248 (3) | −0.0005 (2) | 0.0006 (2) | −0.0016 (2) |
C18 | 0.0153 (3) | 0.0212 (3) | 0.0165 (3) | 0.0001 (2) | 0.0015 (2) | 0.0013 (2) |
C20 | 0.0155 (3) | 0.0239 (3) | 0.0170 (3) | −0.0030 (2) | 0.0020 (2) | 0.0015 (2) |
C3 | 0.0185 (3) | 0.0193 (3) | 0.0236 (3) | 0.0012 (2) | 0.0041 (2) | 0.0030 (2) |
C12 | 0.0151 (3) | 0.0161 (3) | 0.0220 (3) | −0.0018 (2) | 0.0010 (2) | 0.0000 (2) |
C8 | 0.0150 (3) | 0.0188 (3) | 0.0200 (3) | 0.0010 (2) | 0.0003 (2) | 0.0025 (2) |
C5 | 0.0169 (3) | 0.0162 (3) | 0.0223 (3) | −0.0007 (2) | 0.0019 (2) | −0.0001 (2) |
C15 | 0.0178 (3) | 0.0144 (3) | 0.0365 (4) | 0.0019 (2) | 0.0035 (3) | −0.0005 (3) |
C21 | 0.0168 (3) | 0.0344 (4) | 0.0213 (3) | −0.0047 (3) | 0.0026 (2) | 0.0067 (3) |
C23 | 0.0162 (3) | 0.0153 (3) | 0.0374 (4) | −0.0026 (2) | −0.0012 (3) | 0.0009 (3) |
C11 | 0.0155 (3) | 0.0222 (3) | 0.0287 (4) | −0.0046 (3) | 0.0003 (3) | −0.0036 (3) |
C9 | 0.0157 (3) | 0.0299 (4) | 0.0205 (3) | 0.0035 (3) | −0.0010 (2) | 0.0025 (3) |
C29 | 0.0184 (3) | 0.0255 (4) | 0.0201 (3) | 0.0023 (3) | 0.0058 (2) | 0.0001 (3) |
C17 | 0.0169 (3) | 0.0290 (4) | 0.0229 (3) | 0.0003 (3) | −0.0007 (2) | 0.0087 (3) |
C2 | 0.0181 (3) | 0.0290 (4) | 0.0269 (4) | 0.0044 (3) | 0.0033 (3) | 0.0104 (3) |
B1 | 0.0131 (3) | 0.0123 (3) | 0.0154 (3) | −0.0002 (2) | 0.0019 (2) | 0.0004 (2) |
C26 | 0.0235 (3) | 0.0145 (3) | 0.0305 (4) | 0.0016 (3) | 0.0104 (3) | 0.0005 (3) |
C10 | 0.0138 (3) | 0.0332 (4) | 0.0242 (3) | −0.0009 (3) | −0.0022 (2) | −0.0052 (3) |
C16 | 0.0177 (3) | 0.0204 (3) | 0.0379 (4) | 0.0027 (3) | 0.0000 (3) | 0.0100 (3) |
C22 | 0.0155 (3) | 0.0254 (4) | 0.0356 (4) | −0.0052 (3) | 0.0012 (3) | 0.0103 (3) |
C6 | 0.0204 (3) | 0.0201 (3) | 0.0229 (3) | −0.0010 (3) | 0.0020 (2) | −0.0046 (3) |
C28 | 0.0233 (4) | 0.0251 (4) | 0.0303 (4) | 0.0015 (3) | 0.0106 (3) | −0.0078 (3) |
N4 | 0.0354 (5) | 0.0369 (5) | 0.0314 (4) | −0.0089 (4) | 0.0047 (3) | −0.0058 (3) |
C4 | 0.0184 (3) | 0.0312 (4) | 0.0345 (4) | −0.0038 (3) | −0.0001 (3) | 0.0013 (3) |
C31 | 0.0248 (4) | 0.0291 (4) | 0.0192 (3) | 0.0000 (3) | 0.0019 (3) | −0.0043 (3) |
C27 | 0.0286 (4) | 0.0161 (3) | 0.0421 (5) | 0.0018 (3) | 0.0153 (4) | −0.0051 (3) |
C32 | 0.0308 (4) | 0.0244 (4) | 0.0240 (4) | −0.0002 (3) | 0.0014 (3) | 0.0008 (3) |
Cr1—N1i | 2.0915 (7) | C5—C6 | 1.4496 (11) |
Cr1—N1 | 2.0916 (7) | C15—C16 | 1.3920 (14) |
Cr1—N3i | 2.0673 (7) | C15—H15 | 0.949 (14) |
Cr1—N3 | 2.0673 (7) | C21—C22 | 1.3944 (14) |
Cr1—N2 | 2.4267 (8) | C21—H21 | 0.949 (13) |
Cr1—N2i | 2.4267 (8) | C23—C22 | 1.3906 (14) |
N1—C1 | 1.1438 (11) | C23—H23 | 0.997 (15) |
N3—C5 | 1.1441 (11) | C11—C10 | 1.3949 (13) |
C13—C14 | 1.4054 (10) | C11—H11 | 0.965 (14) |
C13—C18 | 1.4059 (10) | C9—H9 | 0.9500 |
C13—B1 | 1.6400 (10) | C9—C10 | 1.3900 (13) |
C7—C12 | 1.4095 (10) | C29—C28 | 1.3919 (13) |
C7—C8 | 1.4064 (10) | C29—H29 | 1.001 (14) |
C7—B1 | 1.6414 (11) | C17—C16 | 1.3918 (14) |
C25—C30 | 1.4054 (10) | C17—H17 | 0.982 (15) |
C25—B1 | 1.6453 (10) | C2—H2A | 0.9800 |
C25—C26 | 1.4049 (11) | C2—H2B | 0.9800 |
C19—C24 | 1.4083 (10) | C2—H2C | 0.9800 |
C19—C20 | 1.4069 (10) | C26—H26 | 0.9500 |
C19—B1 | 1.6448 (10) | C26—C27 | 1.3975 (11) |
N2—C3 | 1.1433 (12) | C10—H10 | 0.9500 |
C14—C15 | 1.3953 (11) | C16—H16 | 0.9500 |
C14—H14 | 1.025 (13) | C22—H22 | 0.9500 |
C1—C2 | 1.4485 (11) | C6—H6A | 0.9800 |
C30—C29 | 1.3963 (10) | C6—H6B | 0.9800 |
C30—H30 | 0.968 (13) | C6—H6C | 0.9800 |
C24—C23 | 1.3985 (11) | C28—H28 | 0.9500 |
C24—H24 | 0.999 (13) | C28—C27 | 1.3909 (13) |
C18—C17 | 1.3946 (12) | N4—C31 | 1.1459 (14) |
C18—H18 | 0.970 (13) | C4—H4A | 0.9800 |
C20—C21 | 1.3965 (11) | C4—H4B | 0.9800 |
C20—H20 | 0.986 (13) | C4—H4C | 0.9800 |
C3—C4 | 1.4544 (13) | C31—C32 | 1.4565 (13) |
C12—C11 | 1.3959 (11) | C27—H27 | 0.9500 |
C12—H12 | 0.963 (13) | C32—H32A | 0.9800 |
C8—C9 | 1.3965 (11) | C32—H32B | 0.9800 |
C8—H8 | 1.002 (12) | C32—H32C | 0.9800 |
N1i—Cr1—N1 | 88.91 (4) | C22—C23—H23 | 118.8 (9) |
N1i—Cr1—N2i | 85.62 (3) | C12—C11—H11 | 118.9 (9) |
N1i—Cr1—N2 | 94.16 (3) | C10—C11—C12 | 120.43 (8) |
N1—Cr1—N2i | 94.16 (3) | C10—C11—H11 | 120.7 (9) |
N1—Cr1—N2 | 85.63 (3) | C8—C9—H9 | 119.9 |
N3—Cr1—N1i | 176.88 (3) | C10—C9—C8 | 120.27 (8) |
N3i—Cr1—N1 | 176.88 (3) | C10—C9—H9 | 119.9 |
N3—Cr1—N1 | 89.54 (3) | C30—C29—H29 | 117.5 (8) |
N3i—Cr1—N1i | 89.54 (3) | C28—C29—C30 | 120.45 (7) |
N3i—Cr1—N3 | 92.14 (4) | C28—C29—H29 | 122.0 (8) |
N3i—Cr1—N2i | 88.42 (3) | C18—C17—H17 | 119.2 (9) |
N3—Cr1—N2i | 91.79 (3) | C16—C17—C18 | 120.11 (8) |
N3—Cr1—N2 | 88.42 (3) | C16—C17—H17 | 120.7 (9) |
N3i—Cr1—N2 | 91.79 (3) | C1—C2—H2A | 109.5 |
N2i—Cr1—N2 | 179.70 (4) | C1—C2—H2B | 109.5 |
C1—N1—Cr1 | 171.86 (7) | C1—C2—H2C | 109.5 |
C5—N3—Cr1 | 173.92 (7) | H2A—C2—H2B | 109.5 |
C14—C13—C18 | 115.58 (7) | H2A—C2—H2C | 109.5 |
C14—C13—B1 | 122.14 (6) | H2B—C2—H2C | 109.5 |
C18—C13—B1 | 121.91 (6) | C13—B1—C7 | 112.43 (6) |
C12—C7—B1 | 122.57 (6) | C13—B1—C25 | 111.96 (6) |
C8—C7—C12 | 115.43 (7) | C13—B1—C19 | 103.66 (5) |
C8—C7—B1 | 121.63 (6) | C7—B1—C25 | 104.29 (5) |
C30—C25—B1 | 121.34 (6) | C7—B1—C19 | 112.20 (6) |
C26—C25—C30 | 115.46 (6) | C19—B1—C25 | 112.56 (6) |
C26—C25—B1 | 122.98 (6) | C25—C26—H26 | 118.7 |
C24—C19—B1 | 122.35 (6) | C27—C26—C25 | 122.67 (8) |
C20—C19—C24 | 115.48 (7) | C27—C26—H26 | 118.7 |
C20—C19—B1 | 121.77 (6) | C11—C10—H10 | 120.7 |
C3—N2—Cr1 | 152.62 (7) | C9—C10—C11 | 118.68 (8) |
C13—C14—H14 | 119.3 (7) | C9—C10—H10 | 120.7 |
C15—C14—C13 | 122.48 (8) | C15—C16—C17 | 118.85 (8) |
C15—C14—H14 | 118.2 (7) | C15—C16—H16 | 120.6 |
N1—C1—C2 | 179.59 (10) | C17—C16—H16 | 120.6 |
C25—C30—H30 | 118.8 (7) | C21—C22—H22 | 120.5 |
C29—C30—C25 | 122.49 (7) | C23—C22—C21 | 118.96 (7) |
C29—C30—H30 | 118.7 (7) | C23—C22—H22 | 120.5 |
C19—C24—H24 | 120.0 (8) | C5—C6—H6A | 109.5 |
C23—C24—C19 | 122.62 (8) | C5—C6—H6B | 109.5 |
C23—C24—H24 | 117.4 (8) | C5—C6—H6C | 109.5 |
C13—C18—H18 | 118.0 (8) | H6A—C6—H6B | 109.5 |
C17—C18—C13 | 122.67 (7) | H6A—C6—H6C | 109.5 |
C17—C18—H18 | 119.3 (8) | H6B—C6—H6C | 109.5 |
C19—C20—H20 | 117.8 (8) | C29—C28—H28 | 120.7 |
C21—C20—C19 | 122.65 (8) | C27—C28—C29 | 118.61 (7) |
C21—C20—H20 | 119.6 (8) | C27—C28—H28 | 120.7 |
N2—C3—C4 | 179.13 (10) | C3—C4—H4A | 109.5 |
C7—C12—H12 | 117.5 (8) | C3—C4—H4B | 109.5 |
C11—C12—C7 | 122.42 (7) | C3—C4—H4C | 109.5 |
C11—C12—H12 | 120.1 (8) | H4A—C4—H4B | 109.5 |
C7—C8—H8 | 118.4 (7) | H4A—C4—H4C | 109.5 |
C9—C8—C7 | 122.75 (7) | H4B—C4—H4C | 109.5 |
C9—C8—H8 | 118.8 (7) | N4—C31—C32 | 178.91 (11) |
N3—C5—C6 | 179.05 (9) | C26—C27—H27 | 119.9 |
C14—C15—H15 | 120.1 (9) | C28—C27—C26 | 120.24 (8) |
C16—C15—C14 | 120.28 (8) | C28—C27—H27 | 119.9 |
C16—C15—H15 | 119.6 (9) | C31—C32—H32A | 109.5 |
C20—C21—H21 | 119.3 (8) | C31—C32—H32B | 109.5 |
C22—C21—C20 | 120.14 (8) | C31—C32—H32C | 109.5 |
C22—C21—H21 | 120.6 (8) | H32A—C32—H32B | 109.5 |
C24—C23—H23 | 121.0 (9) | H32A—C32—H32C | 109.5 |
C22—C23—C24 | 120.13 (8) | H32B—C32—H32C | 109.5 |
C13—C14—C15—C16 | 0.20 (12) | C20—C19—C24—C23 | 1.65 (11) |
C13—C18—C17—C16 | 0.60 (12) | C20—C19—B1—C13 | 84.34 (8) |
C7—C12—C11—C10 | −0.29 (12) | C20—C19—B1—C7 | −37.21 (9) |
C7—C8—C9—C10 | −0.12 (12) | C20—C19—B1—C25 | −154.48 (7) |
C25—C30—C29—C28 | 0.54 (13) | C20—C21—C22—C23 | 1.42 (14) |
C25—C26—C27—C28 | −0.71 (16) | C12—C7—C8—C9 | −0.97 (11) |
C19—C24—C23—C22 | −0.31 (13) | C12—C7—B1—C13 | 34.25 (9) |
C19—C20—C21—C22 | 0.00 (14) | C12—C7—B1—C25 | −87.25 (8) |
C14—C13—C18—C17 | −1.65 (11) | C12—C7—B1—C19 | 150.63 (6) |
C14—C13—B1—C7 | 36.67 (9) | C12—C11—C10—C9 | −0.86 (13) |
C14—C13—B1—C25 | 153.70 (6) | C8—C7—C12—C11 | 1.17 (11) |
C14—C13—B1—C19 | −84.72 (8) | C8—C7—B1—C13 | −153.03 (6) |
C14—C15—C16—C17 | −1.32 (13) | C8—C7—B1—C25 | 85.46 (7) |
C30—C25—B1—C13 | −36.61 (9) | C8—C7—B1—C19 | −36.65 (9) |
C30—C25—B1—C7 | 85.20 (8) | C8—C9—C10—C11 | 1.06 (12) |
C30—C25—B1—C19 | −152.92 (7) | C29—C28—C27—C26 | −1.57 (16) |
C30—C25—C26—C27 | 2.75 (13) | B1—C13—C14—C15 | 174.35 (7) |
C30—C29—C28—C27 | 1.65 (14) | B1—C13—C18—C17 | −174.77 (7) |
C24—C19—C20—C21 | −1.49 (12) | B1—C7—C12—C11 | 174.30 (7) |
C24—C19—B1—C13 | −88.08 (8) | B1—C7—C8—C9 | −174.17 (7) |
C24—C19—B1—C7 | 150.37 (7) | B1—C25—C30—C29 | −177.52 (7) |
C24—C19—B1—C25 | 33.10 (9) | B1—C25—C26—C27 | 177.51 (9) |
C24—C23—C22—C21 | −1.27 (13) | B1—C19—C24—C23 | 174.51 (7) |
C18—C13—C14—C15 | 1.25 (11) | B1—C19—C20—C21 | −174.40 (8) |
C18—C13—B1—C7 | −150.66 (6) | C26—C25—C30—C29 | −2.66 (12) |
C18—C13—B1—C25 | −33.63 (9) | C26—C25—B1—C13 | 148.92 (7) |
C18—C13—B1—C19 | 87.95 (7) | C26—C25—B1—C7 | −89.26 (8) |
C18—C17—C16—C15 | 0.94 (13) | C26—C25—B1—C19 | 32.61 (10) |
Symmetry code: (i) −x+1, y, −z+1/2. |
[Cr(C2H3N)6](C24H20B)2·2C2H3N | F(000) = 2152 |
Mr = 1018.92 | Dx = 1.183 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.8632 (3) Å | Cell parameters from 9787 reflections |
b = 14.6756 (2) Å | θ = 2.6–47.0° |
c = 20.7596 (3) Å | µ = 0.25 mm−1 |
β = 95.230 (1)° | T = 110 K |
V = 5722.93 (15) Å3 | Prism, green |
Z = 4 | 0.37 × 0.34 × 0.18 mm |
Bruker APEXII CCD area-detector diffractometer | 26260 independent reflections |
Radiation source: fine-focus sealed tube | 12685 reflections with I ≥ 3σ(I) |
Graphite monochromator | Rint = 0.05 |
φ and ω scans | θmax = 47.6°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −39→38 |
Tmin = 0.594, Tmax = 0.749 | k = 0→30 |
129273 measured reflections | l = 0→42 |
Refinement on F | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.035 | , w1 = [Fo*sqrt(w2) + sqrt(Fo2w22 + sqrt(w22))]2
where w2 = q/[s2(Fo2) + (0.05 P)2 + 0.00 P + 0.00 + 0.00 sin(th)] where P = (0.3333 Fo2 + 0.667 Fc2) q = 1.0 |
wR(F2) = 0.043 | (Δ/σ)max = 0.012 |
S = 1.15 | Δρmax = 0.33 e Å−3 |
12582 reflections | Δρmin = −0.33 e Å−3 |
629 parameters |
[Cr(C2H3N)6](C24H20B)2·2C2H3N | V = 5722.93 (15) Å3 |
Mr = 1018.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.8632 (3) Å | µ = 0.25 mm−1 |
b = 14.6756 (2) Å | T = 110 K |
c = 20.7596 (3) Å | 0.37 × 0.34 × 0.18 mm |
β = 95.230 (1)° |
Bruker APEXII CCD area-detector diffractometer | 26260 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 12685 reflections with I ≥ 3σ(I) |
Tmin = 0.594, Tmax = 0.749 | Rint = 0.05 |
129273 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.043 | All H-atom parameters refined |
S = 1.15 | Δρmax = 0.33 e Å−3 |
12582 reflections | Δρmin = −0.33 e Å−3 |
629 parameters |
Experimental. Absorption correction: SADABS-2012/1 (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0831 before and 0.0669 after correction. The Ratio of minimum to maximum transmission is 0.7925. The λ/2 correction factor is 0.0015. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.5 | 0.733568 (19) | 0.25 | 0.016 | |
N1 | 0.50950 (6) | 0.63177 (8) | 0.32079 (5) | 0.019 | |
N2 | 0.62897 (7) | 0.73303 (9) | 0.25852 (6) | 0.024 | |
N3 | 0.50456 (6) | 0.83125 (8) | 0.32189 (6) | 0.02 | |
N4 | 0.83713 (9) | 0.54132 (14) | 0.64749 (7) | 0.033 | |
C1 | 0.52292 (5) | 0.57447 (7) | 0.35753 (5) | 0.018 | |
C2 | 0.53904 (5) | 0.50184 (8) | 0.40340 (5) | 0.024 | |
C3 | 0.68377 (6) | 0.75398 (7) | 0.28291 (5) | 0.02 | |
C4 | 0.75345 (6) | 0.77953 (8) | 0.31288 (6) | 0.027 | |
C5 | 0.50667 (5) | 0.87936 (7) | 0.36574 (5) | 0.018 | |
C6 | 0.50899 (5) | 0.93858 (7) | 0.42149 (5) | 0.02 | |
C7 | 0.71086 (3) | 0.43574 (5) | 0.35129 (3) | 0.014 | |
C8 | 0.68534 (4) | 0.49372 (5) | 0.30031 (3) | 0.017 | |
C9 | 0.63005 (4) | 0.46889 (6) | 0.25418 (4) | 0.022 | |
C10 | 0.59776 (4) | 0.38373 (7) | 0.25730 (4) | 0.023 | |
C11 | 0.62104 (4) | 0.32495 (6) | 0.30786 (4) | 0.022 | |
C12 | 0.67622 (4) | 0.35094 (5) | 0.35377 (3) | 0.017 | |
C13 | 0.81873 (3) | 0.38602 (5) | 0.44096 (3) | 0.013 | |
C14 | 0.83941 (4) | 0.31190 (5) | 0.40409 (3) | 0.017 | |
C15 | 0.88529 (4) | 0.24393 (5) | 0.43008 (4) | 0.022 | |
C16 | 0.91253 (4) | 0.24743 (6) | 0.49485 (5) | 0.025 | |
C17 | 0.89388 (4) | 0.32114 (6) | 0.53253 (4) | 0.022 | |
C18 | 0.84825 (4) | 0.38873 (5) | 0.50561 (3) | 0.017 | |
C19 | 0.82990 (3) | 0.53875 (4) | 0.38071 (3) | 0.014 | |
C20 | 0.85515 (4) | 0.52500 (5) | 0.31971 (3) | 0.018 | |
C21 | 0.90974 (4) | 0.57739 (6) | 0.29744 (4) | 0.023 | |
C22 | 0.94176 (4) | 0.64675 (6) | 0.33613 (5) | 0.025 | |
C23 | 0.91911 (4) | 0.66089 (5) | 0.39756 (4) | 0.022 | |
C24 | 0.86452 (4) | 0.60756 (5) | 0.41902 (4) | 0.018 | |
C25 | 0.72387 (3) | 0.52063 (5) | 0.46149 (3) | 0.014 | |
C26 | 0.70630 (4) | 0.61381 (5) | 0.45835 (4) | 0.022 | |
C27 | 0.66426 (5) | 0.65535 (6) | 0.50204 (5) | 0.028 | |
C28 | 0.63712 (5) | 0.60416 (6) | 0.55088 (4) | 0.025 | |
C29 | 0.65152 (4) | 0.51098 (6) | 0.55386 (3) | 0.02 | |
C30 | 0.69369 (4) | 0.47048 (5) | 0.50985 (3) | 0.016 | |
C31 | 0.80665 (5) | 0.47441 (10) | 0.65537 (4) | 0.024 | |
C32 | 0.76930 (5) | 0.38967 (8) | 0.66486 (4) | 0.026 | |
B1 | 0.77072 (4) | 0.47034 (5) | 0.40857 (3) | 0.013 | |
H2A | 0.498 (3) | 0.487 (2) | 0.4170 (15) | 0.091 (9) | |
H2B | 0.570 (2) | 0.524 (2) | 0.435 (2) | 0.096 (10) | |
H2C | 0.5564 (17) | 0.456 (3) | 0.3819 (16) | 0.083 (8) | |
H4A | 0.7810 (15) | 0.723 (2) | 0.3177 (11) | 0.064 (6) | |
H4B | 0.7465 (12) | 0.8074 (18) | 0.3561 (19) | 0.076 (7) | |
H4C | 0.7759 (15) | 0.820 (2) | 0.2813 (15) | 0.078 (7) | |
H6A | 0.483 (2) | 0.913 (2) | 0.450 (2) | 0.092 (9) | |
H6B | 0.4927 (18) | 0.991 (4) | 0.4084 (15) | 0.097 (10) | |
H6C | 0.555 (3) | 0.9443 (17) | 0.4368 (15) | 0.086 (9) | |
H8 | 0.7080 (8) | 0.5575 (14) | 0.2967 (6) | 0.040 (4) | |
H9 | 0.6140 (9) | 0.5136 (13) | 0.2182 (10) | 0.056 (4) | |
H10 | 0.5570 (13) | 0.3652 (11) | 0.2233 (11) | 0.062 (5) | |
H11 | 0.5975 (9) | 0.2626 (15) | 0.3105 (7) | 0.051 (4) | |
H12 | 0.6913 (8) | 0.3072 (12) | 0.3899 (9) | 0.040 (4) | |
H14 | 0.8216 (8) | 0.3084 (9) | 0.3564 (10) | 0.041 (4) | |
H15 | 0.9001 (9) | 0.1912 (15) | 0.4016 (9) | 0.061 (5) | |
H16 | 0.9466 (12) | 0.1972 (16) | 0.5137 (9) | 0.058 (5) | |
H17 | 0.9145 (9) | 0.3263 (10) | 0.5794 (12) | 0.056 (4) | |
H18 | 0.8369 (7) | 0.4431 (13) | 0.5331 (8) | 0.040 (4) | |
H20 | 0.8341 (8) | 0.4735 (13) | 0.2907 (8) | 0.045 (4) | |
H21 | 0.9261 (8) | 0.5640 (10) | 0.2530 (11) | 0.052 (4) | |
H22 | 0.9836 (13) | 0.6853 (14) | 0.3204 (8) | 0.061 (5) | |
H23 | 0.9438 (10) | 0.7103 (15) | 0.4255 (9) | 0.059 (5) | |
H24 | 0.8486 (7) | 0.6207 (9) | 0.4644 (9) | 0.035 (3) | |
H26 | 0.7242 (8) | 0.6533 (12) | 0.4235 (9) | 0.045 (4) | |
H27 | 0.6538 (9) | 0.7224 (17) | 0.4988 (8) | 0.059 (5) | |
H28 | 0.6082 (11) | 0.6346 (12) | 0.5827 (11) | 0.056 (5) | |
H29 | 0.6316 (8) | 0.4708 (12) | 0.5895 (9) | 0.047 (4) | |
H30 | 0.7025 (7) | 0.4020 (14) | 0.5128 (6) | 0.038 (3) | |
H32A | 0.7626 (8) | 0.3589 (16) | 0.6268 (17) | 0.082 (6) | |
H32B | 0.7262 (17) | 0.4041 (12) | 0.6810 (9) | 0.074 (5) | |
H32C | 0.7961 (14) | 0.3542 (18) | 0.6948 (14) | 0.086 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.01741 (12) | 0.01404 (11) | 0.01707 (11) | 0 | 0.00101 (8) | 0 |
N1 | 0.0204 (4) | 0.0180 (4) | 0.0188 (4) | 0.0014 (3) | 0.0004 (3) | 0.0024 (3) |
N2 | 0.0163 (4) | 0.0264 (5) | 0.0281 (5) | −0.0014 (4) | −0.0007 (4) | 0.0013 (4) |
N3 | 0.0210 (4) | 0.0173 (4) | 0.0207 (4) | −0.0014 (3) | 0.0027 (3) | −0.0047 (3) |
N4 | 0.0347 (7) | 0.0332 (7) | 0.0313 (6) | −0.0115 (6) | 0.0056 (5) | −0.0056 (5) |
C1 | 0.0159 (3) | 0.0188 (4) | 0.0180 (3) | 0.0018 (3) | 0.0002 (3) | 0.0027 (3) |
C2 | 0.0172 (4) | 0.0288 (5) | 0.0256 (4) | 0.0041 (3) | 0.0032 (3) | 0.0099 (4) |
C3 | 0.0156 (4) | 0.0207 (4) | 0.0231 (4) | 0.0000 (3) | 0.0025 (3) | 0.0023 (3) |
C4 | 0.0188 (4) | 0.0298 (5) | 0.0329 (5) | −0.0030 (4) | −0.0001 (4) | 0.0013 (4) |
C5 | 0.0183 (4) | 0.0159 (4) | 0.0194 (4) | −0.0004 (3) | 0.0019 (3) | −0.0032 (3) |
C6 | 0.0196 (4) | 0.0196 (4) | 0.0223 (4) | −0.0008 (3) | 0.0022 (3) | −0.0045 (3) |
C7 | 0.0119 (2) | 0.0136 (3) | 0.0152 (2) | −0.00058 (19) | 0.00049 (19) | 0.00021 (19) |
C8 | 0.0147 (3) | 0.0185 (3) | 0.0184 (3) | 0.0006 (2) | −0.0006 (2) | 0.0032 (2) |
C9 | 0.0151 (3) | 0.0295 (4) | 0.0194 (3) | 0.0021 (2) | −0.0020 (2) | 0.0026 (3) |
C10 | 0.0138 (3) | 0.0316 (4) | 0.0231 (3) | −0.0013 (3) | −0.0026 (2) | −0.0043 (3) |
C11 | 0.0152 (3) | 0.0224 (3) | 0.0269 (3) | −0.0049 (2) | −0.0013 (2) | −0.0027 (3) |
C12 | 0.0148 (3) | 0.0159 (3) | 0.0209 (3) | −0.0029 (2) | 0.0000 (2) | 0.0000 (2) |
C13 | 0.0130 (2) | 0.0127 (2) | 0.0138 (2) | 0.00057 (19) | 0.00163 (18) | 0.00023 (19) |
C14 | 0.0165 (3) | 0.0144 (3) | 0.0200 (3) | 0.0017 (2) | 0.0018 (2) | −0.0022 (2) |
C15 | 0.0177 (3) | 0.0142 (3) | 0.0346 (4) | 0.0028 (2) | 0.0026 (3) | −0.0006 (3) |
C16 | 0.0184 (3) | 0.0202 (3) | 0.0350 (4) | 0.0033 (3) | −0.0006 (3) | 0.0088 (3) |
C17 | 0.0166 (3) | 0.0286 (4) | 0.0215 (3) | 0.0017 (3) | −0.0011 (2) | 0.0082 (3) |
C18 | 0.0151 (3) | 0.0206 (3) | 0.0151 (2) | 0.0008 (2) | 0.00065 (19) | 0.0011 (2) |
C19 | 0.0131 (2) | 0.0133 (2) | 0.0157 (2) | −0.00122 (19) | 0.00122 (18) | 0.00033 (19) |
C20 | 0.0150 (3) | 0.0242 (3) | 0.0154 (2) | −0.0040 (2) | 0.00233 (19) | 0.0013 (2) |
C21 | 0.0164 (3) | 0.0340 (4) | 0.0200 (3) | −0.0063 (3) | 0.0026 (2) | 0.0062 (3) |
C22 | 0.0155 (3) | 0.0252 (4) | 0.0331 (4) | −0.0060 (3) | 0.0014 (3) | 0.0091 (3) |
C23 | 0.0157 (3) | 0.0155 (3) | 0.0352 (4) | −0.0036 (2) | −0.0003 (3) | 0.0004 (3) |
C24 | 0.0152 (3) | 0.0141 (3) | 0.0233 (3) | −0.0017 (2) | 0.0007 (2) | −0.0023 (2) |
C25 | 0.0143 (2) | 0.0127 (3) | 0.0165 (2) | 0.00037 (19) | 0.00345 (19) | −0.00026 (19) |
C26 | 0.0237 (3) | 0.0134 (3) | 0.0302 (3) | 0.0023 (2) | 0.0115 (3) | 0.0003 (2) |
C27 | 0.0290 (4) | 0.0155 (3) | 0.0409 (4) | 0.0020 (3) | 0.0169 (3) | −0.0051 (3) |
C28 | 0.0239 (3) | 0.0233 (4) | 0.0293 (4) | 0.0018 (3) | 0.0115 (3) | −0.0068 (3) |
C29 | 0.0186 (3) | 0.0239 (3) | 0.0193 (3) | 0.0028 (2) | 0.0065 (2) | 0.0001 (2) |
C30 | 0.0147 (3) | 0.0172 (3) | 0.0171 (2) | 0.0016 (2) | 0.00390 (19) | 0.0010 (2) |
C31 | 0.0243 (3) | 0.0272 (4) | 0.0192 (3) | −0.0020 (4) | 0.0021 (2) | −0.0036 (3) |
C32 | 0.0302 (4) | 0.0236 (4) | 0.0226 (3) | −0.0006 (3) | 0.0013 (3) | 0.0008 (3) |
B1 | 0.0121 (3) | 0.0120 (3) | 0.0140 (3) | −0.0005 (2) | 0.0017 (2) | 0.0004 (2) |
Cr1—N1 | 2.0918 (11) | C1—C2 | 1.4432 (14) |
Cr1—N2 | 2.4231 (13) | C3—C4 | 1.4513 (16) |
Cr1—N3 | 2.0655 (12) | C5—C6 | 1.4448 (14) |
N1—C1 | 1.1480 (14) | C4—H4A | 0.98 (4) |
N2—C3 | 1.1507 (15) | C4—H4B | 1.01 (4) |
N3—C5 | 1.1499 (13) | C4—H4C | 1.01 (4) |
N1—Cr1—N2 | 85.71 (4) | Cr1—N3—C5 | 173.90 (11) |
N1—Cr1—N3 | 89.59 (5) | C3—C4—H4B | 107.5 (13) |
N1—Cr1—N2i | 94.02 (4) | C3—C4—H4C | 106.9 (13) |
N2i—Cr1—N3i | 88.52 (4) | H4A—C4—H4B | 111.5 (17) |
Cr1—N1—C1 | 171.71 (10) | H4A—C4—H4C | 108.5 (17) |
Cr1—N2—C3 | 152.49 (11) |
Symmetry code: (i) −x+1, y, −z+1/2. |
[Cr(C2H3N)6](C24H20B)2·2C2H3N | F(000) = 2152 |
Mr = 1018.92 | Dx = 1.183 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.8632 (3) Å | Cell parameters from 9787 reflections |
b = 14.6756 (2) Å | µ = 0.25 mm−1 |
c = 20.7596 (3) Å | T = 110 K |
β = 95.230 (1)° | Prism, green |
V = 5722.93 (15) Å3 | 0.37 × 0.34 × 0.18 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 26260 independent reflections |
Radiation source: fine-focus sealed tube | 12685 reflections with I ≥ 3σ(I) |
Graphite monochromator | Rint = 0.05 |
φ and ω scans | θmax = 47.6°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | h = −39→38 |
Tmin = 0.594, Tmax = 0.749 | k = 0→30 |
129273 measured reflections | l = 0→42 |
Refinement on F | 0 restraints |
Least-squares matrix: full | Only H-atom displacement parameters refined |
R[F2 > 2σ(F2)] = 0.036 | , w1 = [Fo*sqrt(w2) + sqrt(Fo2w22 + sqrt(w22))]2
where w2 = q/[s2(Fo2) + (0.05 P)2 + 0.00 P + 0.00 + 0.00 sin(th)] where P = (0.3333 Fo2 + 0.6667 Fc2) q = 1.0 |
wR(F2) = 0.044 | (Δ/σ)max = 0.001 |
S = 1.20 | Δρmax = 0.44 e Å−3 |
12582 reflections | Δρmin = −0.48 e Å−3 |
495 parameters |
[Cr(C2H3N)6](C24H20B)2·2C2H3N | V = 5722.93 (15) Å3 |
Mr = 1018.92 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.8632 (3) Å | µ = 0.25 mm−1 |
b = 14.6756 (2) Å | T = 110 K |
c = 20.7596 (3) Å | 0.37 × 0.34 × 0.18 mm |
β = 95.230 (1)° |
Bruker APEXII CCD area-detector diffractometer | 26260 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | 12685 reflections with I ≥ 3σ(I) |
Tmin = 0.594, Tmax = 0.749 | Rint = 0.05 |
129273 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.044 | Only H-atom displacement parameters refined |
S = 1.20 | Δρmax = 0.44 e Å−3 |
12582 reflections | Δρmin = −0.48 e Å−3 |
495 parameters |
Experimental. Absorption correction: SADABS-2012/1 (Bruker, 2014) was used for absorption correction. wR2(int) was 0.0831 before and 0.0669 after correction. The Ratio of minimum to maximum transmission is 0.7925. The λ/2 correction factor is 0.0015. |
x | y | z | Uiso*/Ueq | ||
Cr1 | 0.5 | 0.733561 (11) | 0.25 | 0.016 | |
N1 | 0.50956 (4) | 0.63191 (4) | 0.32080 (3) | 0.02 | |
N2 | 0.62912 (4) | 0.73310 (5) | 0.25868 (4) | 0.025 | |
N3 | 0.50453 (4) | 0.83122 (4) | 0.32197 (3) | 0.02 | |
N4 | 0.83713 (5) | 0.54131 (7) | 0.64750 (4) | 0.033 | |
C1 | 0.52284 (4) | 0.57455 (5) | 0.35745 (3) | 0.018 | |
C2 | 0.53904 (5) | 0.50195 (8) | 0.40335 (5) | 0.024 | |
C3 | 0.68386 (4) | 0.75402 (5) | 0.28296 (4) | 0.02 | |
C4 | 0.75340 (6) | 0.77950 (8) | 0.31285 (6) | 0.028 | |
C5 | 0.50665 (4) | 0.87930 (5) | 0.36568 (3) | 0.018 | |
C6 | 0.50897 (5) | 0.93851 (7) | 0.42144 (4) | 0.021 | |
C7 | 0.71085 (4) | 0.43574 (5) | 0.35128 (3) | 0.014 | |
C8 | 0.68531 (4) | 0.49359 (5) | 0.30033 (3) | 0.018 | |
C9 | 0.63009 (4) | 0.46879 (6) | 0.25426 (4) | 0.022 | |
C10 | 0.59784 (4) | 0.38375 (7) | 0.25737 (4) | 0.024 | |
C11 | 0.62107 (4) | 0.32508 (6) | 0.30784 (4) | 0.022 | |
C12 | 0.67620 (4) | 0.35102 (5) | 0.35370 (4) | 0.018 | |
C13 | 0.81873 (3) | 0.38602 (5) | 0.44096 (3) | 0.014 | |
C14 | 0.83944 (4) | 0.31191 (5) | 0.40417 (4) | 0.017 | |
C15 | 0.88526 (4) | 0.24404 (5) | 0.43012 (5) | 0.023 | |
C16 | 0.91246 (4) | 0.24753 (6) | 0.49483 (5) | 0.025 | |
C17 | 0.89384 (4) | 0.32114 (6) | 0.53243 (4) | 0.023 | |
C18 | 0.84825 (4) | 0.38865 (5) | 0.50555 (3) | 0.017 | |
C19 | 0.82990 (4) | 0.53876 (5) | 0.38070 (3) | 0.015 | |
C20 | 0.85518 (4) | 0.52508 (5) | 0.31976 (3) | 0.019 | |
C21 | 0.90970 (4) | 0.57742 (6) | 0.29755 (4) | 0.024 | |
C22 | 0.94169 (4) | 0.64667 (6) | 0.33618 (5) | 0.025 | |
C23 | 0.91907 (4) | 0.66081 (5) | 0.39750 (4) | 0.023 | |
C24 | 0.86453 (4) | 0.60752 (5) | 0.41895 (4) | 0.018 | |
C25 | 0.72387 (4) | 0.52063 (5) | 0.46151 (3) | 0.015 | |
C26 | 0.70626 (4) | 0.61374 (5) | 0.45842 (4) | 0.023 | |
C27 | 0.66427 (5) | 0.65522 (6) | 0.50203 (5) | 0.028 | |
C28 | 0.63717 (5) | 0.60410 (6) | 0.55082 (4) | 0.026 | |
C29 | 0.65156 (4) | 0.51107 (6) | 0.55379 (4) | 0.021 | |
C30 | 0.69369 (4) | 0.47060 (5) | 0.50983 (3) | 0.017 | |
C31 | 0.80665 (5) | 0.47447 (8) | 0.65536 (4) | 0.024 | |
C32 | 0.76939 (5) | 0.38988 (8) | 0.66485 (4) | 0.026 | |
B1 | 0.77072 (4) | 0.47032 (5) | 0.40857 (4) | 0.013 | |
H2A | 0.490322 | 0.478607 | 0.422591 | 0.064 (9) | |
H2B | 0.57583 | 0.526667 | 0.44305 | 0.074 (10) | |
H2C | 0.563541 | 0.445224 | 0.379751 | 0.062 (9) | |
H4A | 0.786294 | 0.718765 | 0.320845 | 0.067 (8) | |
H4B | 0.747747 | 0.812894 | 0.359001 | 0.078 (10) | |
H4C | 0.778691 | 0.826234 | 0.281158 | 0.073 (9) | |
H6A | 0.477802 | 0.908644 | 0.457794 | 0.072 (9) | |
H6B | 0.486795 | 1.004853 | 0.407162 | 0.084 (11) | |
H6C | 0.563896 | 0.946878 | 0.441849 | 0.076 (10) | |
H8 | 0.709473 | 0.560129 | 0.29675 | 0.024 (3) | |
H9 | 0.612246 | 0.516029 | 0.216094 | 0.038 (4) | |
H10 | 0.555677 | 0.36348 | 0.221306 | 0.045 (5) | |
H11 | 0.596222 | 0.258975 | 0.311455 | 0.033 (4) | |
H12 | 0.692885 | 0.30422 | 0.392488 | 0.027 (4) | |
H14 | 0.819112 | 0.30733 | 0.35377 | 0.029 (4) | |
H15 | 0.900025 | 0.188206 | 0.399959 | 0.044 (5) | |
H16 | 0.947296 | 0.194456 | 0.515605 | 0.040 (4) | |
H17 | 0.91486 | 0.325532 | 0.582647 | 0.039 (4) | |
H18 | 0.835211 | 0.445256 | 0.535788 | 0.027 (4) | |
H20 | 0.831271 | 0.471908 | 0.288789 | 0.033 (4) | |
H21 | 0.927276 | 0.564723 | 0.25014 | 0.035 (4) | |
H22 | 0.983241 | 0.688596 | 0.318894 | 0.046 (5) | |
H23 | 0.943855 | 0.713433 | 0.428444 | 0.041 (5) | |
H24 | 0.848412 | 0.619657 | 0.466963 | 0.021 (3) | |
H26 | 0.726295 | 0.654963 | 0.420787 | 0.031 (4) | |
H27 | 0.652651 | 0.727389 | 0.498159 | 0.041 (5) | |
H28 | 0.605875 | 0.635975 | 0.585812 | 0.040 (5) | |
H29 | 0.630122 | 0.469865 | 0.590705 | 0.030 (4) | |
H30 | 0.703416 | 0.397963 | 0.513286 | 0.026 (4) | |
H32A | 0.761316 | 0.35311 | 0.619153 | 0.064 (9) | |
H32B | 0.717914 | 0.404371 | 0.682562 | 0.040 (7) | |
H32C | 0.800769 | 0.347898 | 0.700159 | 0.056 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cr1 | 0.01708 (7) | 0.01467 (7) | 0.01684 (6) | 0 | 0.00072 (5) | 0 |
N1 | 0.0215 (3) | 0.0185 (3) | 0.0196 (2) | 0.0014 (2) | 0.00049 (19) | 0.0023 (2) |
N2 | 0.0175 (3) | 0.0272 (3) | 0.0283 (3) | −0.0009 (2) | −0.0005 (2) | 0.0016 (2) |
N3 | 0.0214 (3) | 0.0185 (3) | 0.0213 (2) | −0.0011 (2) | 0.0023 (2) | −0.0040 (2) |
N4 | 0.0350 (4) | 0.0338 (4) | 0.0318 (4) | −0.0112 (3) | 0.0056 (3) | −0.0058 (3) |
C1 | 0.0158 (3) | 0.0198 (3) | 0.0187 (2) | 0.0015 (2) | 0.0005 (2) | 0.0024 (2) |
C2 | 0.0175 (4) | 0.0293 (5) | 0.0262 (4) | 0.0039 (3) | 0.0033 (3) | 0.0096 (4) |
C3 | 0.0163 (3) | 0.0214 (3) | 0.0235 (3) | 0.0000 (2) | 0.0024 (2) | 0.0024 (2) |
C4 | 0.0195 (4) | 0.0301 (5) | 0.0334 (5) | −0.0029 (4) | 0.0001 (4) | 0.0011 (4) |
C5 | 0.0183 (3) | 0.0165 (3) | 0.0202 (3) | −0.0005 (2) | 0.0020 (2) | −0.0025 (2) |
C6 | 0.0199 (4) | 0.0202 (4) | 0.0229 (4) | −0.0007 (3) | 0.0022 (3) | −0.0042 (3) |
C7 | 0.0125 (2) | 0.0141 (3) | 0.0160 (2) | −0.00060 (19) | 0.00067 (19) | 0.00026 (19) |
C8 | 0.0153 (3) | 0.0188 (3) | 0.0192 (3) | 0.0004 (2) | −0.0005 (2) | 0.0032 (2) |
C9 | 0.0159 (3) | 0.0299 (4) | 0.0199 (3) | 0.0023 (3) | −0.0021 (2) | 0.0030 (3) |
C10 | 0.0144 (3) | 0.0323 (4) | 0.0236 (3) | −0.0016 (3) | −0.0030 (2) | −0.0043 (3) |
C11 | 0.0159 (3) | 0.0225 (3) | 0.0277 (3) | −0.0052 (2) | −0.0011 (2) | −0.0026 (3) |
C12 | 0.0156 (3) | 0.0163 (3) | 0.0214 (3) | −0.0028 (2) | −0.0001 (2) | 0.0003 (2) |
C13 | 0.0136 (2) | 0.0133 (2) | 0.0144 (2) | 0.0006 (2) | 0.00176 (18) | 0.00017 (19) |
C14 | 0.0172 (3) | 0.0150 (3) | 0.0202 (3) | 0.0018 (2) | 0.0017 (2) | −0.0022 (2) |
C15 | 0.0184 (3) | 0.0144 (3) | 0.0354 (4) | 0.0029 (2) | 0.0027 (3) | −0.0009 (3) |
C16 | 0.0191 (3) | 0.0204 (3) | 0.0358 (4) | 0.0037 (3) | −0.0007 (3) | 0.0089 (3) |
C17 | 0.0175 (3) | 0.0292 (4) | 0.0218 (3) | 0.0017 (3) | −0.0012 (2) | 0.0081 (3) |
C18 | 0.0158 (3) | 0.0209 (3) | 0.0156 (2) | 0.0010 (2) | 0.00073 (19) | 0.0008 (2) |
C19 | 0.0137 (2) | 0.0138 (2) | 0.0163 (2) | −0.0012 (2) | 0.00134 (19) | 0.0003 (2) |
C20 | 0.0156 (3) | 0.0247 (3) | 0.0160 (2) | −0.0042 (2) | 0.0023 (2) | 0.0010 (2) |
C21 | 0.0173 (3) | 0.0348 (4) | 0.0203 (3) | −0.0063 (3) | 0.0029 (2) | 0.0061 (3) |
C22 | 0.0161 (3) | 0.0257 (4) | 0.0339 (4) | −0.0064 (3) | 0.0017 (3) | 0.0092 (3) |
C23 | 0.0163 (3) | 0.0159 (3) | 0.0358 (4) | −0.0039 (2) | −0.0003 (3) | 0.0001 (3) |
C24 | 0.0160 (3) | 0.0147 (3) | 0.0236 (3) | −0.0018 (2) | 0.0009 (2) | −0.0024 (2) |
C25 | 0.0149 (2) | 0.0132 (3) | 0.0171 (2) | 0.00040 (19) | 0.0036 (2) | −0.0002 (2) |
C26 | 0.0246 (3) | 0.0138 (3) | 0.0308 (3) | 0.0022 (2) | 0.0119 (3) | 0.0005 (2) |
C27 | 0.0300 (4) | 0.0156 (3) | 0.0418 (4) | 0.0021 (3) | 0.0171 (3) | −0.0052 (3) |
C28 | 0.0249 (4) | 0.0237 (4) | 0.0299 (4) | 0.0020 (3) | 0.0121 (3) | −0.0068 (3) |
C29 | 0.0194 (3) | 0.0244 (3) | 0.0198 (3) | 0.0028 (2) | 0.0068 (2) | 0.0004 (2) |
C30 | 0.0155 (3) | 0.0173 (3) | 0.0179 (2) | 0.0017 (2) | 0.0041 (2) | 0.0010 (2) |
C31 | 0.0247 (3) | 0.0277 (4) | 0.0196 (3) | −0.0019 (3) | 0.0022 (2) | −0.0036 (3) |
C32 | 0.0308 (4) | 0.0246 (4) | 0.0230 (3) | −0.0002 (4) | 0.0013 (3) | 0.0007 (3) |
B1 | 0.0128 (3) | 0.0126 (3) | 0.0147 (3) | −0.0005 (2) | 0.0018 (2) | 0.0004 (2) |
Cr1—N1 | 2.0904 (6) | C5—C6 | 1.4437 (11) |
Cr1—N2 | 2.4259 (8) | C2—H2A | 1.0900 |
Cr1—N3 | 2.0665 (6) | C2—H2B | 1.0900 |
N1—C1 | 1.1469 (10) | C2—H2C | 1.0900 |
N2—C3 | 1.1485 (11) | C4—H4A | 1.0900 |
N3—C5 | 1.1472 (10) | C4—H4B | 1.0900 |
C1—C2 | 1.4422 (12) | C4—H4C | 1.0900 |
C3—C4 | 1.4467 (14) | ||
N1—Cr1—N2 | 85.65 (3) | Cr1—N2—C3 | 152.63 (7) |
N1—Cr1—N3 | 89.51 (2) | Cr1—N3—C5 | 174.02 (6) |
N2—Cr1—N3 | 88.46 (3) | H4A—C4—H4B | 109.41 |
N1i—Cr1—N2 | 94.12 (3) | H4A—C4—H4C | 109.32 |
Cr1—N1—C1 | 171.81 (7) | H4B—C4—H4C | 109.24 |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
(1) | (3) | |
Crystal data | ||
Chemical formula | C12H18CrN6·2(C24H20B)·2(C2H3N) | [Cr(C2H3N)6](C24H20B)2·2C2H3N |
Mr | 1018.92 | 1018.92 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 110 | 110 |
a, b, c (Å) | 18.8632 (3), 14.6756 (2), 20.7596 (3) | 18.8632 (3), 14.6756 (2), 20.7596 (3) |
β (°) | 95.230 (1) | 95.230 (1) |
V (Å3) | 5722.93 (15) | 5722.93 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.25 |
Crystal size (mm) | 0.37 × 0.34 × 0.18 | 0.37 × 0.34 × 0.18 |
Data collection | ||
Diffractometer | Bruker APEX-II CCD diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS2012/1 (Bruker, 2012) was used for absorption correction. wR2(int) was 0.0831 before and 0.0669 after correction. The Ratio of minimum to maximum transmission is 0.7925. The λ/2 correction factor is 0.0015. | Multi-scan (SADABS; Bruker, 2014) |
Tmin, Tmax | 0.594, 0.749 | 0.594, 0.749 |
No. of measured, independent and observed reflections | 127361, 26260, 14506 [I > 2σ(I)] | 129273, 26260, 12685 [I ≥ 3σ(I)] |
Rint | ? | 0.05 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.147, 1.00 | 0.036, 0.044, 1.20 |
No. of reflections | 26260 | 12582 |
No. of parameters | 395 | 495 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.60, −0.78 | 0.44, −0.48 |
Computer programs: APEX2 v2014.1-1 (Bruker, 2014), APEX2 (Bruker, 2014), SAINT v8.34A (Bruker, 2013), SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008), SHELXL (Sheldrick, 2008), XD2006 (Volkov et al., 2006), X-SEED (Barbour, 2001) and AIMALL (Keith, 2013), XD2006 (Volkov et al., 2006) and publCIF (Westrip, 2010).
(2) | (3) | |
Pval | 4.32 (7) | 4.482 |
Kappa | 1.250 (19) | 1.067 |
Kappa | 1.019 | 1.015 |
Net charge | +1.67 (7) | +1.5182 |
D10 | 0.02 (3) | 0.007 |
Q20 | 0.16 (4) | -0.108 |
Q22+ | 0.18 (4) | 0.178 |
Q22- | -0.12 (4) | 0.016 |
O30 | -0.03 (3) | 0.000 |
O32+ | -0.01 (3) | 0.000 |
O32- | 0.05 (2) | -0.001 |
H40 | 0.27 (3) | 0.235 |
H42+ | 0.28 (3) | 0.188 |
H42- | -0.10 (3) | 0.019 |
H44+ | 0.05 (3) | 0.007 |
H44- | 0.11 (3) | 0.000 |
(1) | (2) | (3) | |
R[F > 2σ(F)] | 0.047, 0.088, 1.71 | 0.035, 0.043, 1.15 | 0.036, 0.044, 1.12 |
No. of reflections | 12685 | 12685 | 12685 |
No. of parameters | 467 | 629 | 495 |
Δρmax, Δρmin (e Å-3) | 0.62, -0.68 | 0.33, -0.33 | 0.44, -0.48 |
(1) | (2) | (3) | |
Cr1—N1 | 46 | 4 | 10 |
Cr1—N3 | 43 | -13 | 5 |
Cr1—N2 | 26 | -10 | 2 |
N1—C1 | 11 | -4 | 0 |
C1—C2 | -37 | 18 | 16 |
N3—C5 | 11 | 1 | 0 |
Cr1—N1 | 2.0918 (11) | C1—C2 | 1.4432 (14) |
Cr1—N2 | 2.4231 (13) | C3—C4 | 1.4513 (16) |
Cr1—N3 | 2.0655 (12) | C5—C6 | 1.4448 (14) |
N1—C1 | 1.1480 (14) | C4—H4A | 0.98 (4) |
N2—C3 | 1.1507 (15) | C4—H4B | 1.01 (4) |
N3—C5 | 1.1499 (13) | C4—H4C | 1.01 (4) |
N1—Cr1—N2 | 85.71 (4) | Cr1—N3—C5 | 173.90 (11) |
N1—Cr1—N3 | 89.59 (5) | C3—C4—H4B | 107.5 (13) |
N1—Cr1—N2i | 94.02 (4) | C3—C4—H4C | 106.9 (13) |
N2i—Cr1—N3i | 88.52 (4) | H4A—C4—H4B | 111.5 (17) |
Cr1—N1—C1 | 171.71 (10) | H4A—C4—H4C | 108.5 (17) |
Cr1—N2—C3 | 152.49 (11) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Cr1—N1 | 2.0904 (6) | C5—C6 | 1.4437 (11) |
Cr1—N2 | 2.4259 (8) | C2—H2A | 1.0900 |
Cr1—N3 | 2.0665 (6) | C2—H2B | 1.0900 |
N1—C1 | 1.1469 (10) | C2—H2C | 1.0900 |
N2—C3 | 1.1485 (11) | C4—H4A | 1.0900 |
N3—C5 | 1.1472 (10) | C4—H4B | 1.0900 |
C1—C2 | 1.4422 (12) | C4—H4C | 1.0900 |
C3—C4 | 1.4467 (14) | ||
N1—Cr1—N2 | 85.65 (3) | Cr1—N2—C3 | 152.63 (7) |
N1—Cr1—N3 | 89.51 (2) | Cr1—N3—C5 | 174.02 (6) |
N2—Cr1—N3 | 88.46 (3) | H4A—C4—H4B | 109.41 |
N1i—Cr1—N2 | 94.12 (3) | H4A—C4—H4C | 109.32 |
Cr1—N1—C1 | 171.81 (7) | H4B—C4—H4C | 109.24 |
Symmetry code: (i) −x+1, y, −z+1/2. |
Orbital | (2) | (3) |
z2 | 31.7 | 23.9 |
xz | 27.4 | 22.3 |
yz | 6.0 | 7.5 |
x2 – y2 | 19.1 | 23.8 |
xy | 15.9 | 23.3 |
Atoms | Cr1—BCP (Å) | BCP—N (Å) | ρ(r) (e Å-3) | \nabla2ρ(r) (e e Å-5) | Ellipticity, ε |
Cr1—BCP(1)–N1 | 1.004 | 1.086 | 0.436 | +8.509 | 0.17 |
Cr1—BCP(2)–N2 | 1.200 | 1.224 | 0.240 | +2.874 | 0.00 |
Cr1—BCP(3)–N3 | 0.995 | 1.070 | 0.465 | +9.202 | 0.16 |
N—BCP (Å) | BCP–C (Å) | ||||
N1—BCP(4)–C1 | 0.748 | 0.403 | 3.263 | -5.148 | 0.00 |
N2—BCP(5)–C3 | 0.749 | 0.403 | 3.293 | -6.552 | 0.00 |
N3—BCP(6)–C5 | 0.748 | 0.403 | 3.263 | -5.062 | 0.00 |
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