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Chromium(III) complexes of two ethyl­ene cross-bridged tetra­aza­macrocycles were prepared and structurally characterized in order to extend the coordination chemistry of this ligand type farther towards the early transition metals.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536814019072/wm5051sup1.cif
Contains datablocks I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536814019072/wm5051Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536814019072/wm5051IIsup3.hkl
Contains datablock II

CCDC references: 1020729; 1020730

Key indicators

Structure: I
  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.041
  • wR factor = 0.096
  • Data-to-parameter ratio = 19.2
Structure: II
  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.045
  • wR factor = 0.109
  • Data-to-parameter ratio = 16.3

checkCIF/PLATON results

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Datablock: I

No errors found in this datablock



Datablock: II


Alert level C GOODF01_ALERT_2_C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 0.784
Author Response: The crystal was relatively weakly scattering. A fair proportion of weak data are included in the final refinement. This leads to a slightly low GooF value.

0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 0 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
Author Response: The compound and crystal sample was produced as part of an undergraduate laboratory experiment supervised by Hubin at both Southwestern Oklahoma State University and McPherson College. One compound was produced by D. L. Maples and R. D. Maples. The other was synthesised by Hoffert and Parsell. We strongly feel they all deserve credit for this research contribution. Prior, Archibald, and Silversides carried out the crystallographic analysis. Hubin is the research supervisor for the synthesis.

1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Chemical context top

Ethyl­ene cross-bridged tetra­aza­macrocycles were introduced to coordination chemists in 1990 by Weisman and Wong (Weisman et al., 1990). Since then, their transition metal complexes have become important to the fields of oxidation catalysis (Yin et al., 2007; Dong et al., 2013), medical/biological imaging (Boswell et al., 2004; Sprague et al., 2007; Silversides et al., 2011) and chemokine receptor antagonism (Lewis et al., 2005; Valks et al., 2006; Smith et al., 2012) due to the combination of restricted macrocycle configuration and kinetic inertness inherent to these ligands. Chromium(III) complexes have played an important role in characterizing new ligands due to their relative kinetic inertness (Cotton & Wilkinson, 1988). Yet, to date, only one report of the chromium coordination chemistry of these macrobicyclic ligands has appeared in the literature (Maples et al., 2009). In order to expand the range of metal ions that can be coordinated by these remarkable ligands (Hubin, 2003), we are exploring further the structural chemistry of chromium cross-bridged tetra­aza­macrocyclic complexes and report synthesis and crystal structures of dichlorido(4,10-di­methyl-1,4,7,10-tetra­aza­bicyclo­[5.5.2]tetra­decane)­chromium(III) hexafluoridophosphate, (I), and dichlorido(4,11-di­methyl-1,4,8,11-tetra­aza­bicyclo­[6.6.2]hexa­decane)­chromium(III) hexafluoridophosphate, (II),

Structural commentary top

Each of the title compounds crystallizes with a single positively-charged metal complex and one PF6- anion in the asymmetric unit. The metal ion in each complex adopts a distorted o­cta­hedral geometry. The N atoms of each macrocycle occupy four coordination sites, while two chloride ions in a cis arrangement complete the coordination of CrIII. This so-called cis-V conformation, expected to be di­cta­ted by the ligand cross-bridge, is apparent for both of the complexes structurally characterized here. Figs. 1 and 2 illustrate the local geometry about CrIII in (I) (di­methyl bridged cyclen complex) and (II) (di­methyl bridged cyclam complex), respectively. Apparently, neither the identity of the metal ion, nor that of the alkyl substituents affects this conformation. This same conformation has been seen in all known metal complexes with ethyl­ene cross-bridged cyclam and cyclen ligands.

The ring size of the parent macrocycle alters the degree to which the metal ion is engulfed by the bridged macrocycle. This is most clearly evident in the N2—Cr1—N4 bond angle between two axially bound nitro­gen atoms. This bond angle is 161.62 (11)° in the case of the smaller macrocycle, cylcen, while it is 171.44 (14)° for the cyclam complex. A larger bond angle, closer to linearity, indicates a better fit, or complementarity, between the ligand and the preferred o­cta­hedral geometry of the CrIII ion. A more subtle difference in the N1—Cr1—N3 bond angles, viz. the equatorially bound N atoms, shows the same trend: this angle is 83.23 (10)° for the cyclen complex and 84.18 (13)° for the cyclam complex. Finally, the Cr—N bond lengths are somewhat affected by the ligand size as well. The mean of the four Cr—N bond lengths is 2.08 Å in (I), while this average is 2.12 Å in (II). The mean value for a number of Cr—NR3 bonds in the literature is 2.093 Å (σ = 0.044 Å) (Orpen et al., 1989).

Supra­molecular features top

There are no classical hydrogen bonds present in either (I) and (II) but each structure contains a great many C—H···F and C—H···Cl inter­actions which generate three-dimensional arrays. These inter­actions were identified from the standard criterion that the distance from the hydrogen atom to the hydrogen-bond acceptor should not exceed the sum of the radius of the acceptor plus 2 Å. Tables 1 and 2 contain full details of these inter­actions for (I) and (II), respectively.

For (I), each PF6- anion resides in a pocket between six metal complexes and there are C—H···F inter­actions to each of them. The mean C···F distance of those in Table 1 is 3.35 Å. Supplementary C—H···Cl intra­molecular contacts are present and inter­molecular inter­actions between neighbouring metal complexes are also observed. The overall effect of these inter­molecular inter­actions is to generate an extended network. One way to describe this is in terms of puckered sheets of the cationic complex and PF6- anions that extend in the bc plane. Between these sheets further C—H···F and C—H···Cl inter­actions assemble these layers in an ABAB fashion along a to generate a densely packed three-dimensional array as shown in Fig. 3.

For (II), the arrangement is rather similar and again a three-dimensional array is constructed from nonclassical hydrogen bonds between the cations and anions. The PF6- anion is located in a pocket formed from four metal complexes in a distorted tetra­hedral arrangement and forms C—H···F inter­actions to each of them, with a mean C···F distance of 3.23 Å. Further C—H···Cl inter­actions are also present. In a similar fashion to (I), these nonclassical inter­actions assemble the cations and anions into puckered sheets that extend in the bc plane. The sheets are then ABAB stacked along a as shown in Fig. 4.

Database survey top

The structures of three complexes that are directly analogous to (I) have been reported. These are the manganese (Hubin et al., 2001), iron (McClain et al., 2006) and cobalt (Hubin et al., 2002) analogues. Each of these contains the metal in the trivalent state. For the Mn and Fe examples, the geometry about the metal is similar to that for Cr, but the bond angles formed by the two axially bound N atoms are smaller [155.01 (11) and 153.20 (9) °, respectively]. Similarly, the bite angles of the two equatorially bound N atoms are also noticeably smaller; these are 81.29 (11) and 78.62 (8)° for Mn and Fe analogues, respectively. However, the mean M—N bond length is longer for Mn and Fe examples: 2.153 and 2.167 Å, respectively. These differences in geometry reflect the smaller size of the MnIII and FeIII ions, but the greater ligand field stabilization energy (LFSE) for CrIII yields shorter bond lengths. The CoIII analogue is rather different because it is in a low spin state. The axial N—Co—N bond angle is 168.8 (4)° and the equatorial bond angle is 87.2 (4)°. As expected, the mean bond length is shorter for the Co case at 1.978 Å. The smaller, low-spin CoIII ion fits into the pocket of the macrocyle better than CrIII.

Chromium(III) complexes similar to (I) and (II) but crystallized with different anions have been reported before (Maples et al., 2009). The chloride analogue of (I) has bond angles of 160.83 (19) and 83.50 (18)° about the chromium ion and a mean Cr—N bond length of 2.08 Å, which are in good agreement with (I), demonstrating the counter-anion has very little effect on the coordination about the metal. A cyclen-based macrocycle with benzyl groups replacing the methyl groups in (I), has key bond angles 160.35 (19) and 83.6 (2)° and a mean Cr—N bond length of 2.09 Å (Maples et al., 2009). The pocket in the macrocycle is of a similar shape in this example but slightly enlarged because of the pendant benzyl groups.

The chloride analogue of (II) (Maples et al., 2009) displays a similarly sized pocket; the N—Cr—N axial bond angle is 172.46 (11)° and the equatorial angle is 84.63 (11)°, while mean Cr—N bond length is 2.12 Å. In line with the observation in (I) and (II), the pocket of the cyclam-derived ligand is better able to accomodate the o­cta­hedrally surrounded CrIII ion and displays larger bond lengths than the cyclen equivalent.

Synthesis and crystallization top

The cross-bridged ligands were prepared according to literature procedures (Weisman et al., 1990; Wong et al., 2000). The title complexes were prepared by a procedure slightly modified from those found in Hubin et al. (2001) for other trivalent metal ions. In an inert atmosphere glove-box, 1 mmol of the respective ligand was dissolved in 20 ml of anhydrous di­methyl­formamide in a 50 ml Erlenmeyer flask. 1 mmol of anhydrous chromium(II) chloride was added to the stirring ligand solution. The reaction was allowed to stir at room temperature overnight. The solution was then filtered through filter paper and the solvent was removed under vacuum to give blue–violet solids. In the glove-box, this divalent complex was dissolved in 20 ml of methanol in a round-bottomed flask. Five equivalents of NH4PF6 (5 mmol, 0.815 g) were dissolved in the solution. The flask was removed from the glove-box with a stopper to protect it from air. In a fume hood, a stream of nitro­gen gas was directed over the surface of the solution. Four to six drops of Br2 were added and the reaction was stirred for 15 min. Bright-purple precipitates formed immediately. The nitro­gen gas was then allowed to bubble through the solution for 15 min to remove excess Br2. The flask was then stoppered and placed in a freezer for 30 min to complete the precipitation. The purple solid product was collected by vacuum filtration on a glass frit and washed with methanol and then ether. Crystals suitable for X-ray diffraction (purple blocks) were grown from the slow evaporation of aqueous solutions of the product.

Refinement top

H atoms were placed in idealised positions and refined using a riding model, with C—H = 0.98 and 0.99 Å for –CH3 and –CH2– groups, respectively, and with Uiso(H) values of, respectively, 1.5 and 1.2 times Ueq of the carrier atom.

In (I), there is evidence for a very small degree of disorder (~10%) in the position of the PF6- anions. Refinement with a second orientation for this anion did not lead to a substantial improve in the fit. A model with a single orientation was therefore retained.

The structure of (II) is presented in P21/n, consistent with manganese and cobalt analogues (Hubin et al., 2001, 2002), rather than the P21/c setting of the iron analogue (McClain et al., 2006) which has β 120°.

Related literature top

For related literature, see: Boswell et al. (2004); Cotton & Wilkinson (1988); Dong et al. (2013); Hubin (2003); Hubin et al. (2001, 2002); Lewis et al. (2005); Maples et al. (2009); McClain et al. (2006); Orpen et al. (1989); Silversides et al. (2011); Smith et al. (2012); Sprague et al. (2007); Valks et al. (2006); Weisman et al. (1990); Wong et al. (2000); Yin et al. (2007).

Computing details top

For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular entities of (I), with atoms shown as displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The molecular entities of (II), with atoms shown as displacement ellipsoids at the 50% probability level.
[Figure 3] Fig. 3. Crystal packing of (I), viewed perpendicular to the bc plane. Dashed lines represent halide···H—C interactions.
[Figure 4] Fig. 4. Crystal packing of (II), viewed perpendicular to the bc plane. Dashed lines represent halide···H—C interactions.
(I) Dichlorido(4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane)chromium(III) hexafluoridophosphate top
Crystal data top
[CrCl2(C12H26N4)]PF6F(000) = 1012
Mr = 494.24Dx = 1.670 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.2271 (10) ÅCell parameters from 12040 reflections
b = 19.957 (2) Åθ = 2.7–31.2°
c = 12.0474 (17) ŵ = 1.00 mm1
β = 96.374 (11)°T = 150 K
V = 1965.8 (4) Å3Block, purple
Z = 40.10 × 0.10 × 0.08 mm
Data collection top
Stoe IPDS2
diffractometer
4501 independent reflections
Radiation source: fine-focus sealed tube2798 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm-1Rint = 0.091
ω–scansθmax = 27.5°, θmin = 2.7°
Absorption correction: analytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
h = 1010
Tmin = 0.827, Tmax = 0.915k = 2525
22999 measured reflectionsl = 1415
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0474P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.88(Δ/σ)max < 0.001
4501 reflectionsΔρmax = 0.77 e Å3
235 parametersΔρmin = 0.49 e Å3
Crystal data top
[CrCl2(C12H26N4)]PF6V = 1965.8 (4) Å3
Mr = 494.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2271 (10) ŵ = 1.00 mm1
b = 19.957 (2) ÅT = 150 K
c = 12.0474 (17) Å0.10 × 0.10 × 0.08 mm
β = 96.374 (11)°
Data collection top
Stoe IPDS2
diffractometer
4501 independent reflections
Absorption correction: analytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
2798 reflections with I > 2σ(I)
Tmin = 0.827, Tmax = 0.915Rint = 0.091
22999 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.096H-atom parameters constrained
S = 0.88Δρmax = 0.77 e Å3
4501 reflectionsΔρmin = 0.49 e Å3
235 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.21553 (5)0.19169 (2)0.20979 (4)0.02173 (12)
Cl10.06600 (7)0.20275 (4)0.17145 (7)0.03159 (19)
Cl20.25268 (8)0.23403 (4)0.03552 (7)0.03325 (19)
N10.2035 (3)0.15406 (14)0.3675 (2)0.0274 (6)
N20.2399 (3)0.09097 (13)0.1641 (2)0.0276 (6)
N30.4628 (3)0.18082 (13)0.2517 (2)0.0234 (5)
N40.2408 (3)0.28159 (14)0.2997 (2)0.0296 (6)
C10.1252 (4)0.08715 (17)0.3466 (3)0.0348 (8)
H1A0.00990.09270.31440.042*
H1B0.12670.06210.41770.042*
C20.2193 (4)0.04929 (17)0.2664 (3)0.0340 (7)
H2A0.16060.00740.24350.041*
H2B0.32830.03710.30420.041*
C30.4087 (3)0.08276 (17)0.1267 (3)0.0328 (8)
H3A0.39760.07760.04450.039*
H3B0.45860.04120.15990.039*
C40.5235 (3)0.14187 (17)0.1595 (3)0.0300 (7)
H4A0.63480.12490.18370.036*
H4B0.52960.17140.09400.036*
C50.5233 (3)0.25153 (16)0.2599 (3)0.0298 (7)
H5A0.51180.27260.18500.036*
H5B0.64020.25240.28990.036*
C60.4221 (3)0.28971 (17)0.3373 (3)0.0325 (8)
H6A0.44670.27260.41450.039*
H6B0.45150.33780.33720.039*
C70.1464 (4)0.27476 (19)0.3992 (3)0.0370 (8)
H7A0.04460.30140.38580.044*
H7B0.21240.29370.46550.044*
C80.1016 (4)0.20179 (19)0.4244 (3)0.0379 (8)
H8A0.11860.19400.50610.045*
H8B0.01540.19390.39880.045*
C90.3681 (3)0.14731 (18)0.4344 (3)0.0321 (7)
H9A0.36970.10620.48050.038*
H9B0.38670.18610.48540.038*
C100.5051 (3)0.14384 (16)0.3594 (3)0.0275 (7)
H10A0.60590.16330.39930.033*
H10B0.52760.09630.34290.033*
C110.1158 (4)0.06839 (19)0.0721 (3)0.0377 (8)
H11A0.00590.07420.09470.057*
H11B0.13380.02100.05590.057*
H11C0.12620.09510.00500.057*
C120.1830 (4)0.34219 (19)0.2353 (4)0.0428 (9)
H12A0.06600.33780.21030.064*
H12B0.24370.34690.17010.064*
H12C0.20120.38190.28290.064*
P10.74031 (9)0.44740 (4)0.22662 (7)0.0291 (2)
F10.8570 (3)0.43093 (16)0.3353 (2)0.0756 (8)
F20.8987 (2)0.46269 (12)0.1662 (2)0.0570 (6)
F30.6248 (3)0.46395 (16)0.1167 (2)0.0744 (8)
F40.5828 (3)0.43324 (12)0.2878 (2)0.0604 (7)
F50.7476 (3)0.37224 (11)0.1869 (3)0.0675 (8)
F60.7324 (3)0.52314 (12)0.2644 (3)0.0639 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.01590 (19)0.0277 (3)0.0219 (3)0.00047 (18)0.00316 (17)0.0011 (2)
Cl10.0156 (3)0.0430 (5)0.0361 (5)0.0006 (3)0.0023 (3)0.0020 (4)
Cl20.0254 (3)0.0468 (5)0.0273 (4)0.0002 (3)0.0018 (3)0.0092 (4)
N10.0232 (11)0.0368 (16)0.0228 (14)0.0009 (10)0.0049 (10)0.0025 (12)
N20.0241 (11)0.0302 (15)0.0279 (15)0.0014 (10)0.0011 (10)0.0035 (12)
N30.0173 (10)0.0293 (14)0.0237 (13)0.0008 (9)0.0030 (9)0.0003 (11)
N40.0233 (11)0.0322 (15)0.0331 (16)0.0037 (10)0.0024 (11)0.0033 (12)
C10.0297 (15)0.042 (2)0.0334 (19)0.0101 (14)0.0055 (14)0.0085 (16)
C20.0342 (15)0.0284 (18)0.038 (2)0.0054 (13)0.0005 (14)0.0049 (16)
C30.0265 (14)0.0368 (19)0.036 (2)0.0060 (13)0.0067 (13)0.0101 (16)
C40.0200 (13)0.0403 (19)0.0306 (18)0.0043 (12)0.0073 (12)0.0006 (15)
C50.0197 (12)0.0329 (18)0.0364 (19)0.0056 (12)0.0014 (12)0.0017 (15)
C60.0244 (14)0.0320 (19)0.040 (2)0.0022 (12)0.0011 (13)0.0051 (15)
C70.0319 (15)0.047 (2)0.0324 (19)0.0083 (15)0.0065 (14)0.0095 (17)
C80.0336 (15)0.052 (2)0.0302 (18)0.0077 (15)0.0137 (14)0.0011 (17)
C90.0321 (15)0.0389 (19)0.0248 (17)0.0005 (14)0.0011 (13)0.0016 (15)
C100.0249 (13)0.0317 (17)0.0244 (17)0.0008 (12)0.0035 (12)0.0032 (14)
C110.0313 (15)0.045 (2)0.035 (2)0.0027 (14)0.0049 (14)0.0101 (17)
C120.0393 (17)0.034 (2)0.053 (3)0.0085 (15)0.0046 (16)0.0024 (18)
P10.0267 (4)0.0287 (4)0.0326 (5)0.0003 (3)0.0059 (3)0.0026 (4)
F10.0721 (16)0.109 (2)0.0429 (15)0.0339 (15)0.0032 (13)0.0063 (16)
F20.0442 (11)0.0542 (14)0.0786 (18)0.0083 (10)0.0329 (11)0.0070 (13)
F30.0674 (15)0.107 (2)0.0452 (15)0.0192 (15)0.0114 (12)0.0022 (15)
F40.0486 (12)0.0574 (15)0.0815 (19)0.0082 (10)0.0357 (12)0.0007 (13)
F50.0616 (14)0.0366 (13)0.109 (2)0.0068 (10)0.0292 (14)0.0234 (14)
F60.0456 (12)0.0412 (14)0.107 (2)0.0014 (10)0.0159 (12)0.0269 (14)
Geometric parameters (Å, º) top
Cr1—N32.053 (2)C5—C61.522 (4)
Cr1—N12.056 (3)C5—H5A0.9900
Cr1—N42.094 (3)C5—H5B0.9900
Cr1—N22.100 (3)C6—H6A0.9900
Cr1—Cl22.3147 (9)C6—H6B0.9900
Cr1—Cl12.3215 (8)C7—C81.541 (5)
N1—C81.486 (4)C7—H7A0.9900
N1—C11.492 (4)C7—H7B0.9900
N1—C91.503 (4)C8—H8A0.9900
N2—C111.491 (4)C8—H8B0.9900
N2—C21.512 (4)C9—C101.523 (4)
N2—C31.516 (3)C9—H9A0.9900
N3—C41.486 (4)C9—H9B0.9900
N3—C51.496 (4)C10—H10A0.9900
N3—C101.499 (4)C10—H10B0.9900
N4—C121.486 (5)C11—H11A0.9800
N4—C71.505 (4)C11—H11B0.9800
N4—C61.519 (4)C11—H11C0.9800
C1—C21.507 (5)C12—H12A0.9800
C1—H1A0.9900C12—H12B0.9800
C1—H1B0.9900C12—H12C0.9800
C2—H2A0.9900P1—F11.570 (3)
C2—H2B0.9900P1—F31.577 (3)
C3—C41.535 (5)P1—F51.578 (2)
C3—H3A0.9900P1—F61.582 (2)
C3—H3B0.9900P1—F41.585 (2)
C4—H4A0.9900P1—F21.591 (2)
C4—H4B0.9900
N3—Cr1—N183.23 (10)N3—C5—C6108.2 (2)
N3—Cr1—N485.68 (10)N3—C5—H5A110.1
N1—Cr1—N481.21 (11)C6—C5—H5A110.1
N3—Cr1—N280.93 (9)N3—C5—H5B110.1
N1—Cr1—N284.74 (11)C6—C5—H5B110.1
N4—Cr1—N2161.62 (11)H5A—C5—H5B108.4
N3—Cr1—Cl291.97 (7)N4—C6—C5110.5 (3)
N1—Cr1—Cl2175.19 (7)N4—C6—H6A109.6
N4—Cr1—Cl298.09 (8)C5—C6—H6A109.6
N2—Cr1—Cl294.91 (8)N4—C6—H6B109.6
N3—Cr1—Cl1177.18 (8)C5—C6—H6B109.6
N1—Cr1—Cl193.99 (7)H6A—C6—H6B108.1
N4—Cr1—Cl193.50 (7)N4—C7—C8113.5 (3)
N2—Cr1—Cl199.27 (7)N4—C7—H7A108.9
Cl2—Cr1—Cl190.81 (3)C8—C7—H7A108.9
C8—N1—C1113.3 (2)N4—C7—H7B108.9
C8—N1—C9109.3 (3)C8—C7—H7B108.9
C1—N1—C9110.9 (3)H7A—C7—H7B107.7
C8—N1—Cr1106.2 (2)N1—C8—C7110.8 (2)
C1—N1—Cr1103.6 (2)N1—C8—H8A109.5
C9—N1—Cr1113.31 (17)C7—C8—H8A109.5
C11—N2—C2108.1 (2)N1—C8—H8B109.5
C11—N2—C3108.7 (2)C7—C8—H8B109.5
C2—N2—C3111.8 (2)H8A—C8—H8B108.1
C11—N2—Cr1114.0 (2)N1—C9—C10111.6 (3)
C2—N2—Cr1106.88 (19)N1—C9—H9A109.3
C3—N2—Cr1107.38 (18)C10—C9—H9A109.3
C4—N3—C5114.0 (2)N1—C9—H9B109.3
C4—N3—C10108.9 (2)C10—C9—H9B109.3
C5—N3—C10111.3 (2)H9A—C9—H9B108.0
C4—N3—Cr1106.11 (18)N3—C10—C9112.0 (2)
C5—N3—Cr1103.27 (17)N3—C10—H10A109.2
C10—N3—Cr1113.16 (16)C9—C10—H10A109.2
C12—N4—C7109.0 (3)N3—C10—H10B109.2
C12—N4—C6108.4 (2)C9—C10—H10B109.2
C7—N4—C6110.4 (3)H10A—C10—H10B107.9
C12—N4—Cr1114.8 (2)N2—C11—H11A109.5
C7—N4—Cr1107.7 (2)N2—C11—H11B109.5
C6—N4—Cr1106.47 (18)H11A—C11—H11B109.5
N1—C1—C2108.3 (2)N2—C11—H11C109.5
N1—C1—H1A110.0H11A—C11—H11C109.5
C2—C1—H1A110.0H11B—C11—H11C109.5
N1—C1—H1B110.0N4—C12—H12A109.5
C2—C1—H1B110.0N4—C12—H12B109.5
H1A—C1—H1B108.4H12A—C12—H12B109.5
C1—C2—N2111.0 (3)N4—C12—H12C109.5
C1—C2—H2A109.4H12A—C12—H12C109.5
N2—C2—H2A109.4H12B—C12—H12C109.5
C1—C2—H2B109.4F1—P1—F3179.36 (15)
N2—C2—H2B109.4F1—P1—F590.78 (16)
H2A—C2—H2B108.0F3—P1—F589.08 (17)
N2—C3—C4113.5 (2)F1—P1—F690.07 (16)
N2—C3—H3A108.9F3—P1—F690.06 (16)
C4—C3—H3A108.9F5—P1—F6179.05 (17)
N2—C3—H3B108.9F1—P1—F491.76 (15)
C4—C3—H3B108.9F3—P1—F488.88 (15)
H3A—C3—H3B107.7F5—P1—F491.85 (13)
N3—C4—C3110.3 (2)F6—P1—F488.55 (13)
N3—C4—H4A109.6F1—P1—F288.05 (14)
C3—C4—H4A109.6F3—P1—F291.32 (15)
N3—C4—H4B109.6F5—P1—F289.00 (12)
C3—C4—H4B109.6F6—P1—F290.60 (13)
H4A—C4—H4B108.1F4—P1—F2179.13 (14)
C8—N1—C1—C2167.0 (3)C7—N4—C6—C5141.4 (3)
C9—N1—C1—C269.6 (3)Cr1—N4—C6—C524.8 (3)
Cr1—N1—C1—C252.3 (3)N3—C5—C6—N452.8 (3)
N1—C1—C2—N251.4 (3)C12—N4—C7—C8140.9 (3)
C11—N2—C2—C1100.3 (3)C6—N4—C7—C8100.1 (3)
C3—N2—C2—C1140.1 (3)Cr1—N4—C7—C815.7 (3)
Cr1—N2—C2—C122.8 (3)C1—N1—C8—C7155.4 (3)
C11—N2—C3—C4138.1 (3)C9—N1—C8—C780.4 (3)
C2—N2—C3—C4102.6 (3)Cr1—N1—C8—C742.3 (3)
Cr1—N2—C3—C414.3 (3)N4—C7—C8—N117.3 (4)
C5—N3—C4—C3157.4 (3)C8—N1—C9—C10140.2 (3)
C10—N3—C4—C377.6 (3)C1—N1—C9—C1094.1 (3)
Cr1—N3—C4—C344.5 (3)Cr1—N1—C9—C1021.9 (3)
N2—C3—C4—N319.5 (4)C4—N3—C10—C9140.6 (3)
C4—N3—C5—C6166.7 (3)C5—N3—C10—C992.9 (3)
C10—N3—C5—C669.7 (3)Cr1—N3—C10—C922.9 (3)
Cr1—N3—C5—C652.0 (3)N1—C9—C10—N328.9 (4)
C12—N4—C6—C599.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···F6i0.992.533.347 (4)140
C1—H1B···F3ii0.992.463.410 (5)162
C2—H2A···F4i0.992.483.407 (4)155
C3—H3A···F1iii0.992.513.500 (4)177
C4—H4A···F6iv0.992.363.175 (4)139
C6—H6B···F40.992.303.238 (4)158
C1—H1A···Cl10.992.823.393 (4)118
C4—H4B···Cl20.992.633.137 (3)112
C5—H5A···Cl20.992.743.324 (3)118
C6—H6A···Cl2v0.992.773.447 (3)126
C8—H8B···Cl10.992.733.203 (4)110
C12—H12B···Cl20.982.783.329 (4)116
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+3/2, y1/2, z+1/2; (v) x+1/2, y+1/2, z+1/2.
(II) Dichlorido(4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane)chromium(III) hexafluorophosphate top
Crystal data top
[CrCl2(C14H30N4)]PF6F(000) = 1076
Mr = 522.29Dx = 1.683 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 13.6801 (19) ÅCell parameters from 9091 reflections
b = 12.437 (2) Åθ = 2.6–27.9°
c = 12.3864 (17) ŵ = 0.95 mm1
β = 102.028 (11)°T = 150 K
V = 2061.1 (5) Å3Block, purple
Z = 40.15 × 0.15 × 0.06 mm
Data collection top
Stoe IPDS2
diffractometer
4158 independent reflections
Radiation source: fine-focus sealed tube2073 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm-1Rint = 0.091
ω–scansθmax = 26.3°, θmin = 2.6°
Absorption correction: analytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
h = 1716
Tmin = 0.778, Tmax = 0.901k = 1513
13450 measured reflectionsl = 1515
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.109 w = 1/[σ2(Fo2) + (0.052P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.78(Δ/σ)max < 0.001
4158 reflectionsΔρmax = 0.33 e Å3
255 parametersΔρmin = 0.79 e Å3
Crystal data top
[CrCl2(C14H30N4)]PF6V = 2061.1 (5) Å3
Mr = 522.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.6801 (19) ŵ = 0.95 mm1
b = 12.437 (2) ÅT = 150 K
c = 12.3864 (17) Å0.15 × 0.15 × 0.06 mm
β = 102.028 (11)°
Data collection top
Stoe IPDS2
diffractometer
4158 independent reflections
Absorption correction: analytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
2073 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 0.901Rint = 0.091
13450 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 0.78Δρmax = 0.33 e Å3
4158 reflectionsΔρmin = 0.79 e Å3
255 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cr10.32108 (5)0.56984 (5)0.21705 (5)0.03357 (19)
Cl10.46100 (9)0.62992 (9)0.33888 (8)0.0431 (3)
Cl20.36519 (9)0.66096 (9)0.07251 (8)0.0423 (3)
N10.2651 (3)0.4975 (3)0.3442 (3)0.0367 (8)
N20.2251 (3)0.7026 (3)0.2372 (2)0.0368 (9)
N30.1984 (3)0.4956 (3)0.1138 (2)0.0331 (8)
N40.3972 (3)0.4231 (3)0.1961 (3)0.0384 (9)
C10.2305 (4)0.5917 (3)0.4026 (3)0.0406 (11)
H1A0.28920.63110.44440.049*
H1B0.19100.56560.45580.049*
C20.1674 (4)0.6666 (4)0.3209 (3)0.0401 (11)
H2A0.10570.62910.28340.048*
H2B0.14780.72980.36000.048*
C30.1559 (3)0.7420 (4)0.1358 (3)0.0396 (10)
H3A0.19660.77330.08630.048*
H3B0.11510.80080.15730.048*
C40.0858 (3)0.6599 (4)0.0706 (3)0.0421 (11)
H4A0.04190.63160.11830.051*
H4B0.04250.69680.00740.051*
C50.1360 (3)0.5661 (4)0.0269 (3)0.0388 (10)
H5A0.08380.52110.01930.047*
H5B0.17930.59430.02140.047*
C60.2446 (4)0.4113 (4)0.0536 (3)0.0426 (11)
H6A0.27680.44600.00200.051*
H6B0.19200.36230.01440.051*
C70.3218 (4)0.3474 (4)0.1338 (3)0.0416 (11)
H7A0.28910.30730.18560.050*
H7B0.35490.29490.09310.050*
C80.4513 (3)0.3706 (4)0.3011 (3)0.0408 (11)
H8A0.50600.41900.33710.049*
H8B0.48250.30350.28160.049*
C90.3879 (4)0.3433 (4)0.3847 (3)0.0421 (11)
H9A0.33530.29220.34960.051*
H9B0.43090.30550.44740.051*
C100.3379 (3)0.4366 (4)0.4302 (3)0.0405 (11)
H10A0.30210.40890.48620.049*
H10B0.39010.48690.46790.049*
C110.1794 (3)0.4237 (4)0.3005 (3)0.0395 (10)
H11A0.12860.43160.34630.047*
H11B0.20380.34850.30800.047*
C120.1300 (3)0.4441 (4)0.1802 (3)0.0402 (11)
H12A0.10560.37490.14540.048*
H12B0.07130.49130.17770.048*
C130.2856 (4)0.7989 (4)0.2819 (3)0.0443 (11)
H13A0.32620.78200.35480.053*
H13B0.24070.85890.28830.053*
H13C0.32940.81890.23180.053*
C140.4760 (4)0.4407 (4)0.1303 (4)0.0469 (12)
H14A0.52340.49520.16660.056*
H14B0.44470.46530.05600.056*
H14C0.51160.37310.12520.056*
P10.12310 (10)0.10057 (10)0.18374 (9)0.0430 (3)
F10.0182 (2)0.0745 (3)0.1049 (2)0.0696 (9)
F20.0958 (3)0.0212 (2)0.2740 (2)0.0688 (9)
F30.2260 (2)0.1297 (3)0.2639 (2)0.0718 (9)
F40.1495 (2)0.1810 (2)0.0940 (2)0.0637 (8)
F50.1746 (2)0.0057 (2)0.1317 (2)0.0615 (8)
F60.0718 (2)0.1974 (2)0.2371 (2)0.0664 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cr10.0378 (4)0.0298 (4)0.0323 (3)0.0011 (3)0.0054 (3)0.0001 (3)
Cl10.0451 (7)0.0383 (6)0.0423 (5)0.0058 (5)0.0008 (5)0.0013 (4)
Cl20.0466 (7)0.0428 (7)0.0379 (5)0.0023 (5)0.0096 (5)0.0057 (4)
N10.040 (2)0.0317 (19)0.0366 (17)0.0027 (17)0.0037 (16)0.0002 (14)
N20.045 (2)0.033 (2)0.0333 (16)0.0000 (17)0.0082 (16)0.0005 (14)
N30.032 (2)0.0315 (19)0.0345 (16)0.0029 (16)0.0053 (15)0.0008 (14)
N40.043 (2)0.035 (2)0.0374 (17)0.0034 (18)0.0077 (16)0.0012 (15)
C10.052 (3)0.035 (3)0.035 (2)0.002 (2)0.011 (2)0.0052 (17)
C20.047 (3)0.031 (2)0.044 (2)0.003 (2)0.013 (2)0.0005 (18)
C30.040 (3)0.036 (3)0.040 (2)0.004 (2)0.0009 (19)0.0013 (18)
C40.042 (3)0.040 (3)0.042 (2)0.004 (2)0.003 (2)0.004 (2)
C50.039 (3)0.037 (3)0.037 (2)0.001 (2)0.0000 (19)0.0011 (18)
C60.050 (3)0.037 (3)0.041 (2)0.002 (2)0.008 (2)0.0053 (19)
C70.052 (3)0.034 (2)0.040 (2)0.003 (2)0.011 (2)0.0031 (19)
C80.043 (3)0.036 (3)0.040 (2)0.010 (2)0.003 (2)0.0025 (18)
C90.044 (3)0.040 (3)0.040 (2)0.004 (2)0.005 (2)0.0066 (19)
C100.045 (3)0.038 (3)0.035 (2)0.001 (2)0.002 (2)0.0054 (18)
C110.043 (3)0.038 (2)0.037 (2)0.005 (2)0.007 (2)0.0022 (19)
C120.047 (3)0.035 (3)0.039 (2)0.009 (2)0.009 (2)0.0011 (18)
C130.051 (3)0.031 (3)0.049 (2)0.004 (2)0.007 (2)0.0061 (19)
C140.042 (3)0.050 (3)0.050 (2)0.004 (2)0.014 (2)0.005 (2)
P10.0498 (8)0.0337 (7)0.0480 (6)0.0055 (6)0.0157 (6)0.0035 (5)
F10.057 (2)0.078 (2)0.0717 (18)0.0152 (17)0.0075 (15)0.0207 (16)
F20.097 (3)0.057 (2)0.0623 (16)0.0099 (18)0.0399 (17)0.0102 (14)
F30.061 (2)0.088 (3)0.0633 (17)0.0109 (18)0.0054 (15)0.0088 (16)
F40.079 (2)0.0471 (18)0.0706 (17)0.0034 (16)0.0279 (16)0.0136 (14)
F50.084 (2)0.0391 (16)0.0712 (17)0.0070 (16)0.0400 (16)0.0038 (13)
F60.069 (2)0.0465 (18)0.092 (2)0.0049 (16)0.0352 (17)0.0261 (15)
Geometric parameters (Å, º) top
Cr1—N12.093 (3)C6—C71.516 (6)
Cr1—N32.100 (3)C6—H6A0.9900
Cr1—N42.143 (4)C6—H6B0.9900
Cr1—N22.155 (4)C7—H7A0.9900
Cr1—Cl12.3012 (13)C7—H7B0.9900
Cr1—Cl22.3031 (12)C8—C91.520 (6)
N1—C111.499 (5)C8—H8A0.9900
N1—C101.502 (5)C8—H8B0.9900
N1—C11.504 (5)C9—C101.516 (6)
N2—C31.490 (5)C9—H9A0.9900
N2—C131.495 (5)C9—H9B0.9900
N2—C21.497 (5)C10—H10A0.9900
N3—C61.500 (5)C10—H10B0.9900
N3—C51.507 (5)C11—C121.524 (5)
N3—C121.511 (5)C11—H11A0.9900
N4—C71.487 (6)C11—H11B0.9900
N4—C141.498 (5)C12—H12A0.9900
N4—C81.505 (5)C12—H12B0.9900
C1—C21.508 (6)C13—H13A0.9800
C1—H1A0.9900C13—H13B0.9800
C1—H1B0.9900C13—H13C0.9800
C2—H2A0.9900C14—H14A0.9800
C2—H2B0.9900C14—H14B0.9800
C3—C41.514 (6)C14—H14C0.9800
C3—H3A0.9900P1—F51.579 (3)
C3—H3B0.9900P1—F31.587 (3)
C4—C51.510 (6)P1—F11.592 (3)
C4—H4A0.9900P1—F41.592 (3)
C4—H4B0.9900P1—F21.593 (3)
C5—H5A0.9900P1—F61.605 (3)
C5—H5B0.9900
N1—Cr1—N384.18 (13)N3—C6—C7110.4 (3)
N1—Cr1—N489.33 (13)N3—C6—H6A109.6
N3—Cr1—N484.16 (14)C7—C6—H6A109.6
N1—Cr1—N285.11 (13)N3—C6—H6B109.6
N3—Cr1—N288.80 (14)C7—C6—H6B109.6
N4—Cr1—N2171.44 (14)H6A—C6—H6B108.1
N1—Cr1—Cl191.75 (10)N4—C7—C6108.7 (4)
N3—Cr1—Cl1172.78 (10)N4—C7—H7A109.9
N4—Cr1—Cl189.84 (10)C6—C7—H7A109.9
N2—Cr1—Cl196.82 (10)N4—C7—H7B109.9
N1—Cr1—Cl2173.17 (11)C6—C7—H7B109.9
N3—Cr1—Cl292.77 (9)H7A—C7—H7B108.3
N4—Cr1—Cl296.45 (9)N4—C8—C9115.9 (4)
N2—Cr1—Cl288.73 (9)N4—C8—H8A108.3
Cl1—Cr1—Cl291.90 (5)C9—C8—H8A108.3
C11—N1—C10107.4 (3)N4—C8—H8B108.3
C11—N1—C1110.5 (3)C9—C8—H8B108.3
C10—N1—C1106.3 (3)H8A—C8—H8B107.4
C11—N1—Cr1111.9 (2)C10—C9—C8116.6 (4)
C10—N1—Cr1117.3 (3)C10—C9—H9A108.1
C1—N1—Cr1103.2 (2)C8—C9—H9A108.1
C3—N2—C13104.7 (3)C10—C9—H9B108.1
C3—N2—C2110.4 (3)C8—C9—H9B108.1
C13—N2—C2108.3 (3)H9A—C9—H9B107.3
C3—N2—Cr1116.7 (2)N1—C10—C9114.0 (3)
C13—N2—Cr1110.7 (3)N1—C10—H10A108.8
C2—N2—Cr1105.9 (2)C9—C10—H10A108.8
C6—N3—C5106.6 (3)N1—C10—H10B108.8
C6—N3—C12110.3 (3)C9—C10—H10B108.8
C5—N3—C12108.2 (3)H10A—C10—H10B107.7
C6—N3—Cr1104.1 (3)N1—C11—C12113.9 (3)
C5—N3—Cr1116.2 (3)N1—C11—H11A108.8
C12—N3—Cr1111.2 (2)C12—C11—H11A108.8
C7—N4—C14108.1 (3)N1—C11—H11B108.8
C7—N4—C8109.7 (3)C12—C11—H11B108.8
C14—N4—C8104.7 (3)H11A—C11—H11B107.7
C7—N4—Cr1107.5 (3)N3—C12—C11113.9 (4)
C14—N4—Cr1111.4 (3)N3—C12—H12A108.8
C8—N4—Cr1115.4 (2)C11—C12—H12A108.8
N1—C1—C2110.6 (3)N3—C12—H12B108.8
N1—C1—H1A109.5C11—C12—H12B108.8
C2—C1—H1A109.5H12A—C12—H12B107.7
N1—C1—H1B109.5N2—C13—H13A109.5
C2—C1—H1B109.5N2—C13—H13B109.5
H1A—C1—H1B108.1H13A—C13—H13B109.5
N2—C2—C1109.8 (4)N2—C13—H13C109.5
N2—C2—H2A109.7H13A—C13—H13C109.5
C1—C2—H2A109.7H13B—C13—H13C109.5
N2—C2—H2B109.7N4—C14—H14A109.5
C1—C2—H2B109.7N4—C14—H14B109.5
H2A—C2—H2B108.2H14A—C14—H14B109.5
N2—C3—C4116.7 (4)N4—C14—H14C109.5
N2—C3—H3A108.1H14A—C14—H14C109.5
C4—C3—H3A108.1H14B—C14—H14C109.5
N2—C3—H3B108.1F5—P1—F390.73 (18)
C4—C3—H3B108.1F5—P1—F191.12 (17)
H3A—C3—H3B107.3F3—P1—F1178.15 (19)
C5—C4—C3115.3 (4)F5—P1—F489.96 (15)
C5—C4—H4A108.5F3—P1—F489.57 (17)
C3—C4—H4A108.5F1—P1—F490.36 (17)
C5—C4—H4B108.5F5—P1—F290.75 (16)
C3—C4—H4B108.5F3—P1—F290.55 (17)
H4A—C4—H4B107.5F1—P1—F289.50 (18)
N3—C5—C4115.2 (3)F4—P1—F2179.28 (19)
N3—C5—H5A108.5F5—P1—F6179.47 (19)
C4—C5—H5A108.5F3—P1—F688.75 (17)
N3—C5—H5B108.5F1—P1—F689.40 (17)
C4—C5—H5B108.5F4—P1—F689.91 (17)
H5A—C5—H5B107.5F2—P1—F689.38 (16)
C11—N1—C1—C271.2 (4)C8—N4—C7—C6159.7 (3)
C10—N1—C1—C2172.6 (4)Cr1—N4—C7—C633.5 (4)
Cr1—N1—C1—C248.6 (4)N3—C6—C7—N456.2 (5)
C3—N2—C2—C1159.5 (3)C7—N4—C8—C964.3 (5)
C13—N2—C2—C186.4 (4)C14—N4—C8—C9180.0 (4)
Cr1—N2—C2—C132.3 (4)Cr1—N4—C8—C957.2 (4)
N1—C1—C2—N256.7 (5)N4—C8—C9—C1061.3 (5)
C13—N2—C3—C4178.8 (4)C11—N1—C10—C966.6 (5)
C2—N2—C3—C464.9 (5)C1—N1—C10—C9175.1 (4)
Cr1—N2—C3—C456.0 (5)Cr1—N1—C10—C960.3 (4)
N2—C3—C4—C560.3 (5)C8—C9—C10—N161.5 (5)
C6—N3—C5—C4177.6 (4)C10—N1—C11—C12149.2 (4)
C12—N3—C5—C463.7 (5)C1—N1—C11—C1295.2 (4)
Cr1—N3—C5—C462.1 (4)Cr1—N1—C11—C1219.2 (5)
C3—C4—C5—N362.9 (5)C6—N3—C12—C1195.5 (4)
C5—N3—C6—C7170.9 (4)C5—N3—C12—C11148.2 (4)
C12—N3—C6—C771.8 (4)Cr1—N3—C12—C1119.6 (4)
Cr1—N3—C6—C747.6 (4)N1—C11—C12—N325.8 (5)
C14—N4—C7—C686.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···F5i0.992.413.318 (5)153
C2—H2A···F1ii0.992.503.094 (5)119
C2—H2A···F6ii0.992.533.223 (6)127
C7—H7A···F40.992.553.098 (6)115
C12—H12B···F2ii0.992.513.393 (6)149
C3—H3A···Cl20.992.733.280 (5)115
C5—H5B···Cl20.992.703.287 (5)119
C8—H8A···Cl10.992.703.258 (5)116
C8—H8B···Cl1iii0.992.823.778 (4)162
C10—H10B···Cl10.992.703.270 (5)117
C13—H13A···Cl10.982.683.157 (5)111
C13—H13A···Cl2iv0.982.733.572 (4)144
C14—H14B···Cl20.982.693.141 (5)108
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y+3/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···F6i0.992.533.347 (4)140.1
C1—H1B···F3ii0.992.463.410 (5)161.8
C2—H2A···F4i0.992.483.407 (4)154.9
C3—H3A···F1iii0.992.513.500 (4)176.8
C4—H4A···F6iv0.992.363.175 (4)139.4
C6—H6B···F40.992.303.238 (4)157.6
C1—H1A···Cl10.992.823.393 (4)117.7
C4—H4B···Cl20.992.633.137 (3)112.2
C5—H5A···Cl20.992.743.324 (3)117.9
C6—H6A···Cl2v0.992.773.447 (3)126.2
C8—H8B···Cl10.992.733.203 (4)109.7
C12—H12B···Cl20.982.783.329 (4)116.0
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1/2; (iii) x1/2, y+1/2, z1/2; (iv) x+3/2, y1/2, z+1/2; (v) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···F5i0.992.413.318 (5)153.0
C2—H2A···F1ii0.992.503.094 (5)118.6
C2—H2A···F6ii0.992.533.223 (6)126.5
C7—H7A···F40.992.553.098 (6)114.8
C12—H12B···F2ii0.992.513.393 (6)148.6
C3—H3A···Cl20.992.733.280 (5)115.3
C5—H5B···Cl20.992.703.287 (5)118.5
C8—H8A···Cl10.992.703.258 (5)116.3
C8—H8B···Cl1iii0.992.823.778 (4)162.4
C10—H10B···Cl10.992.703.270 (5)116.7
C13—H13A···Cl10.982.683.157 (5)110.5
C13—H13A···Cl2iv0.982.733.572 (4)144.2
C14—H14B···Cl20.982.693.141 (5)108.4
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x, y+3/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formula[CrCl2(C12H26N4)]PF6[CrCl2(C14H30N4)]PF6
Mr494.24522.29
Crystal system, space groupMonoclinic, P21/nMonoclinic, P21/c
Temperature (K)150150
a, b, c (Å)8.2271 (10), 19.957 (2), 12.0474 (17)13.6801 (19), 12.437 (2), 12.3864 (17)
β (°) 96.374 (11) 102.028 (11)
V3)1965.8 (4)2061.1 (5)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.000.95
Crystal size (mm)0.10 × 0.10 × 0.080.15 × 0.15 × 0.06
Data collection
DiffractometerStoe IPDS2
diffractometer
Stoe IPDS2
diffractometer
Absorption correctionAnalytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
Analytical
[a face-indexed absorption correction was applied; X-AREA (Stoe & Cie, 2002)]
Tmin, Tmax0.827, 0.9150.778, 0.901
No. of measured, independent and
observed [I > 2σ(I)] reflections
22999, 4501, 2798 13450, 4158, 2073
Rint0.0910.091
(sin θ/λ)max1)0.6500.622
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.096, 0.88 0.045, 0.109, 0.78
No. of reflections45014158
No. of parameters235255
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.77, 0.490.33, 0.79

Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS86 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

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