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The conversion of the spin state of complexes exhibiting thermal spin crossover from the 1A1 low-spin (LS) state to the 5T2 high-spin (HS) state is accompanied by a deformation of the lattice due to the larger bond lengths in the HS state as compared with the LS state. In a previous work [Kusz et al. (2000). J. Appl. Cryst. 33, 201–205], it has been shown that the deformation of the lattice, corrected for its temperature dependence, can be described by an almost temperature-independent tensor ![[epsilon]](/logos/entities/epsiv_rmgif.gif)
multiplied by the fraction of molecules in the HS state, γHS. Here the dependence of in a mixed single crystal of [Fe0.46Zn0.54(ptz)6](BF4)2 (ptz = propyltetrazole) with a transition temperature near 110 K is reported. In order to study the dependence of the metal–ligand bond length on the concentration of Zn, five structures were determined at 10 K: the neat iron and the mixed-crystal compound in both the excited HS state (LIESST) and the LS state, and the neat Zn compound. The comparison of the structures shows that neither the bond lengths nor their differences in the HS and LS states depend linearly on the Zn concentration. These deviations can be considered as consequences of elastic interactions directly observed by X-ray diffraction analysis. The lattice constants a and c also do not depend linearly on the Zn concentration, contrary to the unit-cell volume and the differences of a and c between the HS and LS states, a fact which is in agreement with the observed linear dependence of these parameters on the temperature-dependent HS fraction.
multiplied by the fraction of molecules in the HS state, γHS. Here the dependence of in a mixed single crystal of [Fe0.46Zn0.54(ptz)6](BF4)2 (ptz = propyltetrazole) with a transition temperature near 110 K is reported. In order to study the dependence of the metal–ligand bond length on the concentration of Zn, five structures were determined at 10 K: the neat iron and the mixed-crystal compound in both the excited HS state (LIESST) and the LS state, and the neat Zn compound. The comparison of the structures shows that neither the bond lengths nor their differences in the HS and LS states depend linearly on the Zn concentration. These deviations can be considered as consequences of elastic interactions directly observed by X-ray diffraction analysis. The lattice constants a and c also do not depend linearly on the Zn concentration, contrary to the unit-cell volume and the differences of a and c between the HS and LS states, a fact which is in agreement with the observed linear dependence of these parameters on the temperature-dependent HS fraction.Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0021889804011720/ko5005sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0021889804011720/ko5005Isup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0021889804011720/ko5005IIsup3.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0021889804011720/ko5005IIIsup4.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0021889804011720/ko5005IVsup5.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0021889804011720/ko5005Vsup6.hkl |
CCDC references: 251390; 251391; 251392; 251393; 251394
Computing details top
For all compounds, data collection: CrysAlis (Oxford Diffraction, 2002); cell refinement: STADI4 (Stoe, 1995); data reduction: CrysAlis (Oxford Diffraction, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: PLATON (Spek,2003). Software used to prepare material for publication: SHELXL93 (Sheldrick, 1993) for (I), (II), (IV), (V); PLATON (Spek,2003) for (III).
![[Figure 1]](http://journals.iucr.org/j/issues/2004/04/00/ko5005/ko5005fig1thm.gif)
![[Figure 2]](http://journals.iucr.org/j/issues/2004/04/00/ko5005/ko5005fig2thm.gif)
(I) top
Crystal data top
| C24H48N24Zn·2(BF2) | Dx = 1.412 Mg m−3 |
| Mr = 911.85 | Mo Kα radiation, λ = 0.71073 Å |
| Hexagonal, R3 | Cell parameters from 60 reflections |
| a = 10.8429 (7) Å | θ = 30–40° |
| c = 31.607 (3) Å | µ = 0.66 mm−1 |
| V = 3218.1 (4) Å3 | T = 10 K |
| Z = 3 | Plate, colourless |
| F(000) = 1416 | 0.6 × 0.6 × 0.3 mm |
Data collection top
| CCD-Kuma Difraction diffractometer | 1478 independent reflections |
| Radiation source: fine-focus sealed tube | 1439 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.039 |
| ϕ–scan | θmax = 26.8°, θmin = 3.4° |
| Absorption correction: multi-scan ? | h = −13→13 |
| Tmin = 0.681, Tmax = 0.821 | k = −9→13 |
| 7605 measured reflections | l = −38→39 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.061 | Calculated w = 1/[σ2(Fo2) + (0.0247P)2 + 6.3194P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.09 | (Δ/σ)max < 0.001 |
| 1478 reflections | Δρmax = 0.30 e Å−3 |
| 122 parameters | Δρmin = −0.34 e Å−3 |
| 0 restraints |
Crystal data top
| C24H48N24Zn·2(BF2) | Z = 3 |
| Mr = 911.85 | Mo Kα radiation |
| Hexagonal, R3 | µ = 0.66 mm−1 |
| a = 10.8429 (7) Å | T = 10 K |
| c = 31.607 (3) Å | 0.6 × 0.6 × 0.3 mm |
| V = 3218.1 (4) Å3 |
Data collection top
| CCD-Kuma Difraction diffractometer | 1478 independent reflections |
| Absorption correction: multi-scan ? | 1439 reflections with I > 2σ(I) |
| Tmin = 0.681, Tmax = 0.821 | Rint = 0.039 |
| 7605 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.026 | 122 parameters |
| wR(F2) = 0.061 | 0 restraints |
| S = 1.09 | Δρmax = 0.30 e Å−3 |
| 1478 reflections | Δρmin = −0.34 e Å−3 |
Special details top
Experimental. 'CrysAlis (Oxford Diffraction, 2002)' |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.0000 | 0.0000 | 0.0000 | 0.00361 (11) | |
| N4 | 0.04742 (11) | −0.13522 (11) | 0.03879 (3) | 0.0062 (2) | |
| C1 | −0.01774 (13) | −0.27580 (14) | 0.04096 (4) | 0.0063 (2) | |
| H1 | −0.0931 (19) | −0.3373 (19) | 0.0266 (5) | 0.012 (4)* | |
| N3 | 0.15957 (11) | −0.08552 (12) | 0.06627 (3) | 0.0077 (2) | |
| N2 | 0.16222 (11) | −0.19178 (11) | 0.08422 (3) | 0.0080 (2) | |
| N1 | 0.05113 (11) | −0.31173 (11) | 0.06857 (3) | 0.0059 (2) | |
| C4 | −0.12058 (15) | −0.46411 (15) | 0.14385 (4) | 0.0116 (3) | |
| H6 | −0.1361 (19) | −0.491 (2) | 0.1741 (6) | 0.019 (4)* | |
| H7 | −0.209 (2) | −0.528 (2) | 0.1281 (6) | 0.020 (5)* | |
| H8 | −0.0996 (19) | −0.367 (2) | 0.1401 (6) | 0.020 (4)* | |
| C2 | 0.02678 (14) | −0.45410 (13) | 0.08019 (4) | 0.0078 (3) | |
| H2 | −0.0539 (18) | −0.5201 (18) | 0.0645 (5) | 0.010 (4)* | |
| H3 | 0.1077 (18) | −0.4586 (17) | 0.0699 (5) | 0.008 (4)* | |
| C3 | 0.00274 (14) | −0.48068 (14) | 0.12752 (4) | 0.0089 (3) | |
| H5 | −0.0149 (18) | −0.5765 (19) | 0.1312 (5) | 0.014 (4)* | |
| H4 | 0.0895 (18) | −0.4163 (18) | 0.1430 (5) | 0.010 (4)* | |
| F2 | −0.04678 (9) | −0.13801 (8) | 0.33486 (2) | 0.0122 (2) | |
| F1 | 0.0000 | 0.0000 | 0.27606 (4) | 0.0124 (3) | |
| B | 0.0000 | 0.0000 | 0.32021 (8) | 0.0070 (5) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.00263 (13) | 0.00263 (13) | 0.0056 (2) | 0.00131 (7) | 0.000 | 0.000 |
| N4 | 0.0043 (5) | 0.0061 (5) | 0.0074 (5) | 0.0021 (4) | 0.0001 (4) | −0.0003 (4) |
| C1 | 0.0059 (6) | 0.0062 (6) | 0.0067 (6) | 0.0030 (5) | 0.0002 (5) | 0.0001 (5) |
| N3 | 0.0068 (5) | 0.0081 (5) | 0.0090 (5) | 0.0043 (4) | −0.0008 (4) | 0.0001 (4) |
| N2 | 0.0062 (5) | 0.0055 (5) | 0.0113 (5) | 0.0022 (4) | −0.0005 (4) | 0.0002 (4) |
| N1 | 0.0051 (5) | 0.0043 (5) | 0.0082 (5) | 0.0023 (4) | 0.0007 (4) | 0.0000 (4) |
| C4 | 0.0112 (7) | 0.0109 (7) | 0.0115 (6) | 0.0047 (6) | 0.0017 (5) | 0.0007 (5) |
| C2 | 0.0099 (6) | 0.0036 (6) | 0.0114 (6) | 0.0045 (5) | 0.0000 (5) | 0.0012 (5) |
| C3 | 0.0096 (6) | 0.0062 (6) | 0.0110 (6) | 0.0040 (5) | −0.0006 (5) | 0.0015 (5) |
| F2 | 0.0143 (4) | 0.0054 (4) | 0.0152 (4) | 0.0036 (3) | −0.0029 (3) | 0.0014 (3) |
| F1 | 0.0137 (4) | 0.0137 (4) | 0.0098 (6) | 0.0068 (2) | 0.000 | 0.000 |
| B | 0.0054 (7) | 0.0054 (7) | 0.0101 (11) | 0.0027 (3) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
| Zn1—N4i | 2.1613 (10) | C4—C3 | 1.525 (2) |
| Zn1—N4ii | 2.1614 (10) | C4—H6 | 0.99 (2) |
| Zn1—N4iii | 2.1613 (10) | C4—H7 | 0.99 (2) |
| Zn1—N4iv | 2.1613 (10) | C4—H8 | 0.97 (2) |
| Zn1—N4 | 2.1613 (10) | C2—C3 | 1.521 (2) |
| Zn1—N4v | 2.1613 (10) | C2—H2 | 0.95 (2) |
| N4—C1 | 1.323 (2) | C2—H3 | 0.96 (2) |
| N4—N3 | 1.3667 (15) | C3—H5 | 0.96 (2) |
| C1—N1 | 1.327 (2) | C3—H4 | 0.98 (2) |
| C1—H1 | 0.88 (2) | F2—B | 1.3971 (11) |
| N3—N2 | 1.297 (2) | F1—B | 1.396 (3) |
| N2—N1 | 1.3491 (15) | B—F2ii | 1.3971 (11) |
| N1—C2 | 1.477 (2) | B—F2iii | 1.3971 (11) |
| N4i—Zn1—N4ii | 180.0 | N2—N1—C2 | 121.57 (10) |
| N4i—Zn1—N4iii | 89.01 (4) | C3—C4—H6 | 108.8 (10) |
| N4ii—Zn1—N4iii | 90.99 (4) | C3—C4—H7 | 110.0 (11) |
| N4i—Zn1—N4iv | 90.99 (4) | H6—C4—H7 | 108.4 (15) |
| N4ii—Zn1—N4iv | 89.01 (4) | C3—C4—H8 | 110.1 (11) |
| N4iii—Zn1—N4iv | 89.01 (4) | H6—C4—H8 | 110.8 (15) |
| N4i—Zn1—N4 | 89.01 (4) | H7—C4—H8 | 108.8 (15) |
| N4ii—Zn1—N4 | 90.99 (4) | N1—C2—C3 | 111.51 (10) |
| N4iii—Zn1—N4 | 90.99 (4) | N1—C2—H2 | 105.9 (10) |
| N4iv—Zn1—N4 | 180.0 | C3—C2—H2 | 111.5 (10) |
| N4i—Zn1—N4v | 90.99 (4) | N1—C2—H3 | 106.2 (10) |
| N4ii—Zn1—N4v | 89.01 (4) | C3—C2—H3 | 113.5 (9) |
| N4iii—Zn1—N4v | 180.0 | H2—C2—H3 | 107.8 (13) |
| N4iv—Zn1—N4v | 90.99 (4) | C2—C3—C4 | 112.81 (11) |
| N4—Zn1—N4v | 89.01 (4) | C2—C3—H5 | 104.1 (10) |
| C1—N4—N3 | 106.18 (10) | C4—C3—H5 | 111.9 (10) |
| C1—N4—Zn1 | 129.78 (9) | C2—C3—H4 | 110.2 (9) |
| N3—N4—Zn1 | 124.02 (8) | C4—C3—H4 | 109.5 (10) |
| N4—C1—N1 | 108.51 (11) | H5—C3—H4 | 108.1 (13) |
| N4—C1—H1 | 127.3 (11) | F1—B—F2 | 109.35 (10) |
| N1—C1—H1 | 124.2 (11) | F1—B—F2ii | 109.35 (10) |
| N2—N3—N4 | 109.76 (10) | F2—B—F2ii | 109.59 (10) |
| N3—N2—N1 | 106.88 (10) | F1—B—F2iii | 109.35 (10) |
| C1—N1—N2 | 108.67 (10) | F2—B—F2iii | 109.59 (10) |
| C1—N1—C2 | 129.61 (11) | F2ii—B—F2iii | 109.59 (10) |
| N4i—Zn1—N4—C1 | −15.05 (11) | Zn1—N4—C1—N1 | 178.50 (8) |
| N4ii—Zn1—N4—C1 | 164.95 (11) | C1—N4—N3—N2 | 0.16 (13) |
| N4iii—Zn1—N4—C1 | 73.94 (13) | Zn1—N4—N3—N2 | −178.50 (8) |
| N4iv—Zn1—N4—C1 | −133.41 (11) | N4—N3—N2—N1 | −0.19 (13) |
| N4v—Zn1—N4—C1 | −106.06 (13) | N4—C1—N1—N2 | −0.06 (14) |
| N4i—Zn1—N4—N3 | 163.27 (10) | N4—C1—N1—C2 | −175.60 (11) |
| N4ii—Zn1—N4—N3 | −16.73 (10) | N3—N2—N1—C1 | 0.16 (13) |
| N4iii—Zn1—N4—N3 | −107.73 (7) | N3—N2—N1—C2 | 176.12 (11) |
| N4iv—Zn1—N4—N3 | 44.92 (8) | C1—N1—C2—C3 | −123.94 (14) |
| N4v—Zn1—N4—N3 | 72.27 (7) | N2—N1—C2—C3 | 61.03 (15) |
| N3—N4—C1—N1 | −0.06 (14) | N1—C2—C3—C4 | 56.60 (15) |
| Symmetry codes: (i) y, −x+y, −z; (ii) −y, x−y, z; (iii) −x+y, −x, z; (iv) −x, −y, −z; (v) x−y, x, −z. |
(II) top
Crystal data top
| C24H48N24Fe·2(BF2) | Dx = 1.393 Mg m−3 |
| Mr = 902.33 | Mo Kα radiation, λ = 0.71073 Å |
| Hexagonal, R3 | Cell parameters from 60 reflections |
| a = 10.881 (2) Å | θ = 30–40° |
| c = 31.480 (8) Å | µ = 0.44 mm−1 |
| V = 3227.8 (12) Å3 | T = 10 K |
| Z = 3 | Plate, colourless |
| F(000) = 1404 | 0.7 × 0.5 × 0.3 mm |
Data collection top
| CCD-Kuma Difraction diffractometer | 1554 independent reflections |
| Radiation source: fine-focus rotating anode | 1257 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.085 |
| ϕ–scan | θmax = 27.5°, θmin = 3.7° |
| Absorption correction: multi-scan ? | h = −13→13 |
| Tmin = 0.770, Tmax = 0.877 | k = −8→13 |
| 12546 measured reflections | l = −39→39 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.076 | Calculated w = 1/[σ2(Fo2) + (0.0331P)2 + 1.398P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max < 0.001 |
| 1554 reflections | Δρmax = 0.23 e Å−3 |
| 122 parameters | Δρmin = −0.57 e Å−3 |
| 0 restraints |
Crystal data top
| C24H48N24Fe·2(BF2) | Z = 3 |
| Mr = 902.33 | Mo Kα radiation |
| Hexagonal, R3 | µ = 0.44 mm−1 |
| a = 10.881 (2) Å | T = 10 K |
| c = 31.480 (8) Å | 0.7 × 0.5 × 0.3 mm |
| V = 3227.8 (12) Å3 |
Data collection top
| CCD-Kuma Difraction diffractometer | 1554 independent reflections |
| Absorption correction: multi-scan ? | 1257 reflections with I > 2σ(I) |
| Tmin = 0.770, Tmax = 0.877 | Rint = 0.085 |
| 12546 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.032 | 122 parameters |
| wR(F2) = 0.076 | 0 restraints |
| S = 1.08 | Δρmax = 0.23 e Å−3 |
| 1554 reflections | Δρmin = −0.57 e Å−3 |
Special details top
Experimental. 'CrysAlis (Oxford Diffraction, 2002)' |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.0053 (2) | |
| N4 | 0.04711 (13) | −0.13647 (13) | 0.03938 (3) | 0.0069 (3) | |
| C1 | −0.0186 (2) | −0.2766 (2) | 0.04160 (4) | 0.0069 (3) | |
| H1 | −0.0992 (18) | −0.3415 (18) | 0.0277 (5) | 0.006 (4)* | |
| N3 | 0.16026 (14) | −0.08745 (14) | 0.06660 (4) | 0.0084 (3) | |
| N2 | 0.16291 (14) | −0.19392 (14) | 0.08426 (4) | 0.0087 (3) | |
| N1 | 0.05097 (13) | −0.31330 (13) | 0.06879 (4) | 0.0065 (3) | |
| C4 | −0.1209 (2) | −0.4652 (2) | 0.14404 (5) | 0.0130 (4) | |
| H6 | −0.139 (2) | −0.492 (2) | 0.1744 (6) | 0.022 (5)* | |
| H7 | −0.209 (2) | −0.525 (2) | 0.1277 (5) | 0.018 (5)* | |
| H8 | −0.0990 (19) | −0.363 (2) | 0.1405 (5) | 0.017 (5)* | |
| C2 | 0.0266 (2) | −0.4550 (2) | 0.08031 (5) | 0.0084 (3) | |
| H2 | −0.0585 (18) | −0.5226 (17) | 0.0644 (5) | 0.002 (4)* | |
| H3 | 0.109 (2) | −0.4624 (19) | 0.0699 (5) | 0.012 (4)* | |
| C3 | 0.0015 (2) | −0.4821 (2) | 0.12776 (5) | 0.0098 (3) | |
| H5 | −0.0158 (19) | −0.576 (2) | 0.1319 (5) | 0.014 (5)* | |
| H4 | 0.0869 (18) | −0.4177 (18) | 0.1430 (5) | 0.004 (4)* | |
| F2 | −0.04656 (10) | −0.13762 (10) | 0.33474 (2) | 0.0120 (2) | |
| F1 | 0.0000 | 0.0000 | 0.27571 (4) | 0.0128 (4) | |
| B | 0.0000 | 0.0000 | 0.32016 (8) | 0.0071 (6) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0054 (2) | 0.0054 (2) | 0.0053 (2) | 0.00268 (10) | 0.000 | 0.000 |
| N4 | 0.0057 (7) | 0.0077 (7) | 0.0070 (6) | 0.0030 (6) | −0.0001 (5) | −0.0007 (5) |
| C1 | 0.0059 (8) | 0.0085 (8) | 0.0067 (6) | 0.0039 (7) | 0.0002 (6) | −0.0001 (6) |
| N3 | 0.0079 (7) | 0.0095 (7) | 0.0085 (6) | 0.0049 (6) | −0.0015 (5) | 0.0002 (5) |
| N2 | 0.0081 (7) | 0.0064 (7) | 0.0102 (6) | 0.0026 (6) | −0.0003 (5) | −0.0003 (5) |
| N1 | 0.0069 (7) | 0.0061 (7) | 0.0067 (6) | 0.0033 (6) | −0.0003 (5) | −0.0006 (5) |
| C4 | 0.0143 (9) | 0.0126 (9) | 0.0105 (7) | 0.0057 (8) | 0.0011 (6) | 0.0008 (6) |
| C2 | 0.0100 (8) | 0.0057 (8) | 0.0105 (7) | 0.0045 (7) | −0.0002 (6) | 0.0008 (6) |
| C3 | 0.0117 (9) | 0.0080 (9) | 0.0100 (7) | 0.0051 (7) | −0.0007 (6) | 0.0019 (6) |
| F2 | 0.0153 (5) | 0.0078 (5) | 0.0130 (4) | 0.0057 (4) | −0.0020 (4) | 0.0015 (4) |
| F1 | 0.0154 (6) | 0.0154 (6) | 0.0077 (7) | 0.0077 (3) | 0.000 | 0.000 |
| B | 0.0075 (10) | 0.0075 (10) | 0.0062 (12) | 0.0037 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
| Fe1—N4i | 2.1831 (12) | C4—C3 | 1.521 (2) |
| Fe1—N4ii | 2.1831 (12) | C4—H6 | 0.99 (2) |
| Fe1—N4iii | 2.1831 (12) | C4—H7 | 0.99 (2) |
| Fe1—N4 | 2.1831 (12) | C4—H8 | 1.02 (2) |
| Fe1—N4iv | 2.1831 (12) | C2—C3 | 1.521 (2) |
| Fe1—N4v | 2.1831 (12) | C2—H2 | 0.98 (2) |
| N4—C1 | 1.323 (2) | C2—H3 | 0.99 (2) |
| N4—N3 | 1.370 (2) | C3—H5 | 0.95 (2) |
| C1—N1 | 1.329 (2) | C3—H4 | 0.97 (2) |
| C1—H1 | 0.92 (2) | F2—B | 1.3969 (13) |
| N3—N2 | 1.298 (2) | F1—B | 1.399 (3) |
| N2—N1 | 1.351 (2) | B—F2i | 1.3969 (13) |
| N1—C2 | 1.473 (2) | B—F2iii | 1.3969 (13) |
| N4i—Fe1—N4ii | 180.0 | N2—N1—C2 | 121.45 (12) |
| N4i—Fe1—N4iii | 90.93 (4) | C3—C4—H6 | 110.4 (11) |
| N4ii—Fe1—N4iii | 89.07 (4) | C3—C4—H7 | 111.2 (10) |
| N4i—Fe1—N4 | 90.93 (4) | H6—C4—H7 | 108.9 (15) |
| N4ii—Fe1—N4 | 89.07 (4) | C3—C4—H8 | 110.7 (10) |
| N4iii—Fe1—N4 | 90.93 (4) | H6—C4—H8 | 109.0 (15) |
| N4i—Fe1—N4iv | 89.07 (4) | H7—C4—H8 | 106.6 (15) |
| N4ii—Fe1—N4iv | 90.93 (4) | N1—C2—C3 | 111.41 (12) |
| N4iii—Fe1—N4iv | 89.07 (4) | N1—C2—H2 | 105.5 (9) |
| N4—Fe1—N4iv | 180.0 | C3—C2—H2 | 110.2 (9) |
| N4i—Fe1—N4v | 89.07 (4) | N1—C2—H3 | 107.7 (10) |
| N4ii—Fe1—N4v | 90.93 (4) | C3—C2—H3 | 113.1 (9) |
| N4iii—Fe1—N4v | 180.0 | H2—C2—H3 | 108.6 (13) |
| N4—Fe1—N4v | 89.07 (4) | C2—C3—C4 | 113.02 (13) |
| N4iv—Fe1—N4v | 90.93 (4) | C2—C3—H5 | 105.1 (10) |
| C1—N4—N3 | 106.14 (12) | C4—C3—H5 | 111.7 (11) |
| C1—N4—Fe1 | 129.68 (10) | C2—C3—H4 | 109.4 (9) |
| N3—N4—Fe1 | 124.14 (10) | C4—C3—H4 | 109.2 (10) |
| N4—C1—N1 | 108.63 (13) | H5—C3—H4 | 108.3 (14) |
| N4—C1—H1 | 128.3 (10) | F2i—B—F2 | 109.75 (11) |
| N1—C1—H1 | 123.1 (10) | F2i—B—F2iii | 109.75 (11) |
| N2—N3—N4 | 109.69 (12) | F2—B—F2iii | 109.75 (11) |
| N3—N2—N1 | 106.99 (11) | F2i—B—F1 | 109.19 (11) |
| C1—N1—N2 | 108.55 (12) | F2—B—F1 | 109.19 (11) |
| C1—N1—C2 | 129.87 (13) | F2iii—B—F1 | 109.19 (11) |
| N4i—Fe1—N4—C1 | 164.76 (12) | Fe1—N4—C1—N1 | 177.48 (9) |
| N4ii—Fe1—N4—C1 | −15.24 (12) | C1—N4—N3—N2 | 0.4 (2) |
| N4iii—Fe1—N4—C1 | 73.81 (15) | Fe1—N4—N3—N2 | −177.59 (9) |
| N4iv—Fe1—N4—C1 | −5.E1 (10) | N4—N3—N2—N1 | −0.26 (15) |
| N4v—Fe1—N4—C1 | −106.19 (15) | N4—C1—N1—N2 | 0.2 (2) |
| N4i—Fe1—N4—N3 | −17.77 (11) | N4—C1—N1—C2 | −175.67 (13) |
| N4ii—Fe1—N4—N3 | 162.22 (11) | N3—N2—N1—C1 | 0.05 (15) |
| N4iii—Fe1—N4—N3 | −108.72 (8) | N3—N2—N1—C2 | 176.32 (12) |
| N4iv—Fe1—N4—N3 | 12.E1 (10) | C1—N1—C2—C3 | −122.4 (2) |
| N4v—Fe1—N4—N3 | 71.28 (8) | N2—N1—C2—C3 | 62.2 (2) |
| N3—N4—C1—N1 | −0.3 (2) | N1—C2—C3—C4 | 56.3 (2) |
| Symmetry codes: (i) −y, x−y, z; (ii) y, −x+y, −z; (iii) −x+y, −x, z; (iv) −x, −y, −z; (v) x−y, x, −z. |
(III) top
Crystal data top
| C24H48N24Fe·2(BF2) | Dx = 1.421 Mg m−3 |
| Mr = 902.33 | Mo Kα radiation, λ = 0.71073 Å |
| Hexagonal, R3 | Cell parameters from 60 reflections |
| a = 10.701 (2) Å | θ = 30–40° |
| c = 31.900 (8) Å | µ = 0.45 mm−1 |
| V = 3163.5 (12) Å3 | T = 10 K |
| Z = 3 | Plate, red |
| F(000) = 1404 | 0.7 × 0.5 × 0.3 mm |
Data collection top
| CCD-Kuma Difraction diffractometer | 1563 independent reflections |
| Radiation source: fine-focus rotating anode | 1322 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.063 |
| ϕ–scan | θmax = 27.8°, θmin = 3.4° |
| Absorption correction: multi-scan ? | h = −8→13 |
| Tmin = 0.732, Tmax = 0.766 | k = −13→13 |
| 9516 measured reflections | l = −39→40 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.088 | Calculated w = 1/[σ2(Fo2) + (0.0368P)2 + 5.8158P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max < 0.001 |
| 1563 reflections | Δρmax = 0.32 e Å−3 |
| 122 parameters | Δρmin = −0.58 e Å−3 |
| 0 restraints |
Crystal data top
| C24H48N24Fe·2(BF2) | Z = 3 |
| Mr = 902.33 | Mo Kα radiation |
| Hexagonal, R3 | µ = 0.45 mm−1 |
| a = 10.701 (2) Å | T = 10 K |
| c = 31.900 (8) Å | 0.7 × 0.5 × 0.3 mm |
| V = 3163.5 (12) Å3 |
Data collection top
| CCD-Kuma Difraction diffractometer | 1563 independent reflections |
| Absorption correction: multi-scan ? | 1322 reflections with I > 2σ(I) |
| Tmin = 0.732, Tmax = 0.766 | Rint = 0.063 |
| 9516 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.036 | 122 parameters |
| wR(F2) = 0.088 | 0 restraints |
| S = 1.11 | Δρmax = 0.32 e Å−3 |
| 1563 reflections | Δρmin = −0.58 e Å−3 |
Special details top
Experimental. CrysAlis (Oxford Diffraction, 2002) |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.0052 (2) | |
| N4 | 0.04737 (14) | −0.12355 (14) | 0.03562 (4) | 0.0063 (3) | |
| C1 | −0.0194 (2) | −0.2659 (2) | 0.03935 (5) | 0.0069 (3) | |
| H1 | −0.104 (2) | −0.336 (2) | 0.0255 (6) | 0.008 (4)* | |
| N3 | 0.16515 (15) | −0.07062 (15) | 0.06153 (4) | 0.0084 (3) | |
| N2 | 0.16943 (15) | −0.17690 (15) | 0.07978 (4) | 0.0086 (3) | |
| N1 | 0.05403 (14) | −0.29931 (14) | 0.06613 (4) | 0.0068 (3) | |
| C4 | −0.1091 (2) | −0.4528 (2) | 0.14330 (5) | 0.0127 (4) | |
| H6 | −0.121 (2) | −0.480 (2) | 0.1736 (7) | 0.019 (5)* | |
| H7 | −0.205 (2) | −0.524 (2) | 0.1291 (6) | 0.017 (5)* | |
| H8 | −0.095 (3) | −0.354 (3) | 0.1394 (7) | 0.024 (6)* | |
| C2 | 0.0314 (2) | −0.4425 (2) | 0.07803 (5) | 0.0085 (3) | |
| H2 | −0.059 (2) | −0.518 (2) | 0.0634 (5) | 0.008 (5)* | |
| H3 | 0.115 (2) | −0.450 (2) | 0.0672 (5) | 0.007 (4)* | |
| C3 | 0.0158 (2) | −0.4658 (2) | 0.12530 (5) | 0.0099 (3) | |
| H5 | 0.004 (2) | −0.559 (2) | 0.1295 (6) | 0.012 (5)* | |
| H4 | 0.104 (2) | −0.399 (2) | 0.1389 (6) | 0.006 (4)* | |
| F2 | −0.03774 (11) | −0.13765 (10) | 0.33170 (3) | 0.0114 (2) | |
| F1 | 0.0000 | 0.0000 | 0.27326 (5) | 0.0116 (4) | |
| B | 0.0000 | 0.0000 | 0.31716 (9) | 0.0075 (6) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0049 (2) | 0.0049 (2) | 0.0058 (3) | 0.00247 (10) | 0.000 | 0.000 |
| N4 | 0.0046 (6) | 0.0076 (7) | 0.0059 (6) | 0.0024 (6) | 0.0004 (5) | −0.0005 (5) |
| C1 | 0.0070 (8) | 0.0073 (8) | 0.0064 (7) | 0.0034 (7) | 0.0010 (6) | −0.0005 (6) |
| N3 | 0.0078 (7) | 0.0095 (7) | 0.0090 (6) | 0.0052 (6) | −0.0015 (5) | 0.0000 (5) |
| N2 | 0.0080 (7) | 0.0064 (7) | 0.0106 (6) | 0.0029 (6) | −0.0006 (5) | 0.0001 (5) |
| N1 | 0.0071 (7) | 0.0063 (7) | 0.0070 (6) | 0.0034 (6) | 0.0011 (5) | 0.0001 (5) |
| C4 | 0.0139 (9) | 0.0131 (9) | 0.0103 (8) | 0.0062 (7) | 0.0025 (6) | 0.0012 (6) |
| C2 | 0.0091 (8) | 0.0070 (8) | 0.0101 (7) | 0.0045 (7) | −0.0002 (6) | 0.0007 (6) |
| C3 | 0.0121 (8) | 0.0093 (8) | 0.0085 (7) | 0.0055 (7) | 0.0009 (6) | 0.0027 (6) |
| F2 | 0.0136 (5) | 0.0078 (5) | 0.0128 (5) | 0.0054 (4) | −0.0018 (4) | 0.0014 (4) |
| F1 | 0.0139 (5) | 0.0139 (5) | 0.0070 (7) | 0.0069 (3) | 0.000 | 0.000 |
| B | 0.0071 (9) | 0.0071 (9) | 0.0083 (13) | 0.0035 (5) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
| Fe1—N4i | 1.9915 (13) | C4—C3 | 1.524 (2) |
| Fe1—N4ii | 1.9915 (13) | C4—H6 | 1.00 (2) |
| Fe1—N4iii | 1.9915 (13) | C4—H7 | 1.03 (2) |
| Fe1—N4 | 1.9915 (13) | C4—H8 | 1.00 (2) |
| Fe1—N4iv | 1.9915 (13) | C2—C3 | 1.524 (2) |
| Fe1—N4v | 1.9915 (13) | C2—H2 | 1.02 (2) |
| N4—C1 | 1.325 (2) | C2—H3 | 0.99 (2) |
| N4—N3 | 1.371 (2) | C3—H5 | 0.94 (2) |
| C1—N1 | 1.326 (2) | C3—H4 | 0.96 (2) |
| C1—H1 | 0.95 (2) | F2—B | 1.3975 (14) |
| N3—N2 | 1.299 (2) | F1—B | 1.400 (3) |
| N2—N1 | 1.346 (2) | B—F2i | 1.3975 (14) |
| N1—C2 | 1.476 (2) | B—F2iv | 1.3975 (14) |
| N4i—Fe1—N4ii | 180.0 | N2—N1—C2 | 121.42 (13) |
| N4i—Fe1—N4iii | 89.33 (5) | C3—C4—H6 | 108.9 (12) |
| N4ii—Fe1—N4iii | 90.67 (5) | C3—C4—H7 | 111.5 (12) |
| N4i—Fe1—N4 | 90.67 (5) | H6—C4—H7 | 106.3 (17) |
| N4ii—Fe1—N4 | 89.33 (5) | C3—C4—H8 | 111.8 (14) |
| N4iii—Fe1—N4 | 89.33 (5) | H6—C4—H8 | 111.1 (18) |
| N4i—Fe1—N4iv | 90.67 (5) | H7—C4—H8 | 107.2 (18) |
| N4ii—Fe1—N4iv | 89.33 (5) | N1—C2—C3 | 111.85 (13) |
| N4iii—Fe1—N4iv | 180.0 | N1—C2—H2 | 107.9 (11) |
| N4—Fe1—N4iv | 90.67 (5) | C3—C2—H2 | 109.9 (10) |
| N4i—Fe1—N4v | 89.33 (5) | N1—C2—H3 | 107.7 (11) |
| N4ii—Fe1—N4v | 90.67 (5) | C3—C2—H3 | 111.0 (10) |
| N4iii—Fe1—N4v | 90.67 (5) | H2—C2—H3 | 108.3 (15) |
| N4—Fe1—N4v | 180.0 | C4—C3—C2 | 112.77 (13) |
| N4iv—Fe1—N4v | 89.33 (5) | C4—C3—H5 | 112.4 (12) |
| C1—N4—N3 | 106.08 (13) | C2—C3—H5 | 104.9 (11) |
| C1—N4—Fe1 | 130.10 (11) | C4—C3—H4 | 110.1 (11) |
| N3—N4—Fe1 | 123.81 (10) | C2—C3—H4 | 109.9 (11) |
| N4—C1—N1 | 108.43 (14) | H5—C3—H4 | 106.6 (16) |
| N4—C1—H1 | 128.1 (12) | F2i—B—F2 | 109.57 (12) |
| N1—C1—H1 | 123.5 (12) | F2i—B—F2iv | 109.57 (12) |
| N2—N3—N4 | 109.64 (13) | F2—B—F2iv | 109.57 (12) |
| N3—N2—N1 | 106.88 (13) | F2i—B—F1 | 109.38 (12) |
| C1—N1—N2 | 108.96 (13) | F2—B—F1 | 109.38 (12) |
| C1—N1—C2 | 129.36 (14) | F2iv—B—F1 | 109.38 (12) |
| N4i—Fe1—N4—C1 | 161.56 (13) | Fe1—N4—C1—N1 | 178.40 (10) |
| N4ii—Fe1—N4—C1 | −18.44 (13) | C1—N4—N3—N2 | 0.5 (2) |
| N4iii—Fe1—N4—C1 | −109.1 (2) | Fe1—N4—N3—N2 | −178.30 (10) |
| N4iv—Fe1—N4—C1 | 70.9 (2) | N4—N3—N2—N1 | −0.5 (2) |
| N4v—Fe1—N4—C1 | 6.E1 (8) | N4—C1—N1—N2 | 0.0 (2) |
| N4i—Fe1—N4—N3 | −19.91 (12) | N4—C1—N1—C2 | −174.17 (14) |
| N4ii—Fe1—N4—N3 | 160.09 (12) | N3—N2—N1—C1 | 0.3 (2) |
| N4iii—Fe1—N4—N3 | 69.41 (9) | N3—N2—N1—C2 | 175.04 (13) |
| N4iv—Fe1—N4—N3 | −110.59 (9) | C1—N1—C2—C3 | −125.3 (2) |
| N4v—Fe1—N4—N3 | −12.E1 (8) | N2—N1—C2—C3 | 61.1 (2) |
| N3—N4—C1—N1 | −0.3 (2) | N1—C2—C3—C4 | 58.6 (2) |
| Symmetry codes: (i) −y, x−y, z; (ii) y, −x+y, −z; (iii) x−y, x, −z; (iv) −x+y, −x, z; (v) −x, −y, −z. |
(IV) top
Crystal data top
| C24H48N24Fe0.46Zn0.54·2(BF2) | Dx = 1.403 Mg m−3 |
| Mr = 907.47 | Mo Kα radiation, λ = 0.71073 Å |
| Hexagonal, R3 | Cell parameters from 60 reflections |
| a = 10.8575 (5) Å | θ = 30–40° |
| c = 31.560 (3) Å | µ = 0.56 mm−1 |
| V = 3222.0 (4) Å3 | T = 10 K |
| Z = 3 | Plate, colourless |
| F(000) = 1410 | 0.6 × 0.5 × 0.3 mm |
Data collection top
| CCD-Kuma Difraction diffractometer | 1469 independent reflections |
| Radiation source: fine-focus rotating anode | 1433 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.028 |
| ϕ–scan | θmax = 26.8°, θmin = 3.8° |
| Absorption correction: multi-scan ? | h = −13→13 |
| Tmin = 0.724, Tmax = 0.846 | k = −13→10 |
| 7865 measured reflections | l = −38→38 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.072 | Calculated w = 1/[σ2(Fo2) + (0.0368P)2 + 5.8158P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 1469 reflections | Δρmax = 0.29 e Å−3 |
| 122 parameters | Δρmin = −0.37 e Å−3 |
| 0 restraints |
Crystal data top
| C24H48N24Fe0.46Zn0.54·2(BF2) | Z = 3 |
| Mr = 907.47 | Mo Kα radiation |
| Hexagonal, R3 | µ = 0.56 mm−1 |
| a = 10.8575 (5) Å | T = 10 K |
| c = 31.560 (3) Å | 0.6 × 0.5 × 0.3 mm |
| V = 3222.0 (4) Å3 |
Data collection top
| CCD-Kuma Difraction diffractometer | 1469 independent reflections |
| Absorption correction: multi-scan ? | 1433 reflections with I > 2σ(I) |
| Tmin = 0.724, Tmax = 0.846 | Rint = 0.028 |
| 7865 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.027 | 122 parameters |
| wR(F2) = 0.072 | 0 restraints |
| S = 1.10 | Δρmax = 0.29 e Å−3 |
| 1469 reflections | Δρmin = −0.37 e Å−3 |
Special details top
Experimental. 'CrysAlis (Oxford Diffraction, 2002)' |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.00420 (13) | 0.46 |
| Zn1 | 0.0000 | 0.0000 | 0.0000 | 0.00420 (13) | 0.54 |
| N4 | 0.04733 (11) | −0.13580 (12) | 0.03912 (3) | 0.0064 (2) | |
| C1 | −0.01807 (14) | −0.27608 (14) | 0.04125 (4) | 0.0069 (3) | |
| H1 | −0.0939 (19) | −0.3387 (18) | 0.0269 (5) | 0.010 (4)* | |
| N3 | 0.15982 (12) | −0.08657 (12) | 0.06643 (3) | 0.0078 (2) | |
| N2 | 0.16259 (12) | −0.19269 (12) | 0.08427 (4) | 0.0080 (2) | |
| N1 | 0.05095 (12) | −0.31233 (11) | 0.06871 (3) | 0.0061 (2) | |
| C4 | −0.12076 (15) | −0.46450 (15) | 0.14387 (4) | 0.0115 (3) | |
| H6 | −0.1372 (19) | −0.4909 (19) | 0.1744 (6) | 0.015 (4)* | |
| H7 | −0.209 (2) | −0.528 (2) | 0.1281 (6) | 0.017 (4)* | |
| H8 | −0.1011 (19) | −0.366 (2) | 0.1404 (6) | 0.016 (4)* | |
| C2 | 0.02658 (15) | −0.45451 (14) | 0.08022 (4) | 0.0081 (3) | |
| H2 | −0.0551 (19) | −0.5227 (18) | 0.0640 (5) | 0.012 (4)* | |
| H3 | 0.1071 (18) | −0.4603 (17) | 0.0702 (5) | 0.006 (4)* | |
| C3 | 0.00216 (15) | −0.48146 (14) | 0.12766 (4) | 0.0092 (3) | |
| H5 | −0.0145 (18) | −0.577 (2) | 0.1320 (5) | 0.015 (4)* | |
| H4 | 0.0895 (19) | −0.4172 (18) | 0.1435 (5) | 0.010 (4)* | |
| F2 | −0.04693 (9) | −0.13781 (8) | 0.33484 (2) | 0.0124 (2) | |
| F1 | 0.0000 | 0.0000 | 0.27594 (4) | 0.0127 (3) | |
| B | 0.0000 | 0.0000 | 0.32018 (8) | 0.0068 (5) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0036 (2) | 0.0036 (2) | 0.0054 (2) | 0.00179 (8) | 0.000 | 0.000 |
| Zn1 | 0.0036 (2) | 0.0036 (2) | 0.0054 (2) | 0.00179 (8) | 0.000 | 0.000 |
| N4 | 0.0049 (5) | 0.0067 (5) | 0.0072 (5) | 0.0027 (4) | −0.0002 (4) | −0.0004 (4) |
| C1 | 0.0062 (6) | 0.0073 (6) | 0.0071 (6) | 0.0035 (5) | 0.0002 (5) | 0.0000 (5) |
| N3 | 0.0070 (5) | 0.0081 (5) | 0.0084 (5) | 0.0039 (4) | −0.0010 (4) | 0.0006 (4) |
| N2 | 0.0066 (5) | 0.0057 (5) | 0.0106 (5) | 0.0022 (4) | −0.0005 (4) | 0.0000 (4) |
| N1 | 0.0054 (5) | 0.0053 (5) | 0.0077 (5) | 0.0028 (4) | 0.0003 (4) | 0.0000 (4) |
| C4 | 0.0116 (7) | 0.0111 (7) | 0.0111 (7) | 0.0051 (6) | 0.0016 (5) | 0.0006 (5) |
| C2 | 0.0104 (6) | 0.0044 (6) | 0.0110 (6) | 0.0047 (5) | 0.0001 (5) | 0.0010 (5) |
| C3 | 0.0106 (7) | 0.0076 (6) | 0.0100 (6) | 0.0050 (5) | −0.0010 (5) | 0.0019 (5) |
| F2 | 0.0149 (4) | 0.0060 (4) | 0.0150 (4) | 0.0042 (3) | −0.0031 (3) | 0.0014 (3) |
| F1 | 0.0151 (5) | 0.0151 (5) | 0.0079 (6) | 0.0075 (2) | 0.000 | 0.000 |
| B | 0.0062 (7) | 0.0062 (7) | 0.0081 (11) | 0.0031 (4) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
| Fe1—N4i | 2.1726 (11) | N3—N2 | 1.296 (2) |
| Fe1—N4ii | 2.1726 (11) | N2—N1 | 1.3502 (15) |
| Fe1—N4iii | 2.1726 (11) | N1—C2 | 1.475 (2) |
| Fe1—N4iv | 2.1726 (11) | C4—C3 | 1.524 (2) |
| Fe1—N4v | 2.1726 (11) | C4—H6 | 1.00 (2) |
| Fe1—N4 | 2.1726 (11) | C4—H7 | 0.99 (2) |
| Zn1—N4i | 2.1726 (11) | C4—H8 | 0.98 (2) |
| Zn1—N4ii | 2.1726 (11) | C2—C3 | 1.523 (2) |
| Zn1—N4iii | 2.1726 (11) | C2—H2 | 0.97 (2) |
| Zn1—N4iv | 2.1726 (11) | C2—H3 | 0.96 (2) |
| Zn1—N4v | 2.1726 (11) | C3—H5 | 0.97 (2) |
| Zn1—N4 | 2.1726 (11) | C3—H4 | 0.99 (2) |
| N4—C1 | 1.322 (2) | F2—B | 1.3965 (11) |
| N4—N3 | 1.3664 (15) | F1—B | 1.396 (3) |
| C1—N1 | 1.328 (2) | B—F2iv | 1.3965 (11) |
| C1—H1 | 0.89 (2) | B—F2i | 1.3965 (11) |
| N4i—Fe1—N4ii | 180.0 | N3—N4—Fe1 | 124.15 (8) |
| N4i—Fe1—N4iii | 89.11 (4) | Zn1—N4—Fe1 | 0.0 |
| N4ii—Fe1—N4iii | 90.89 (4) | N4—C1—N1 | 108.49 (12) |
| N4i—Fe1—N4iv | 90.89 (4) | N4—C1—H1 | 128.0 (11) |
| N4ii—Fe1—N4iv | 89.11 (4) | N1—C1—H1 | 123.5 (11) |
| N4iii—Fe1—N4iv | 89.11 (4) | N2—N3—N4 | 109.85 (10) |
| N4i—Fe1—N4v | 89.11 (4) | N3—N2—N1 | 106.78 (10) |
| N4ii—Fe1—N4v | 90.89 (4) | C1—N1—N2 | 108.69 (10) |
| N4iii—Fe1—N4v | 90.89 (4) | C1—N1—C2 | 129.68 (11) |
| N4iv—Fe1—N4v | 180.0 | N2—N1—C2 | 121.48 (11) |
| N4i—Fe1—N4 | 90.89 (4) | C3—C4—H6 | 109.4 (10) |
| N4ii—Fe1—N4 | 89.11 (4) | C3—C4—H7 | 110.2 (11) |
| N4iii—Fe1—N4 | 180.0 | H6—C4—H7 | 108.3 (15) |
| N4iv—Fe1—N4 | 90.89 (4) | C3—C4—H8 | 111.4 (11) |
| N4v—Fe1—N4 | 89.11 (4) | H6—C4—H8 | 109.3 (15) |
| N4i—Zn1—N4ii | 180.0 | H7—C4—H8 | 108.2 (15) |
| N4i—Zn1—N4iii | 89.11 (4) | N1—C2—C3 | 111.47 (10) |
| N4ii—Zn1—N4iii | 90.89 (4) | N1—C2—H2 | 106.6 (10) |
| N4i—Zn1—N4iv | 90.89 (4) | C3—C2—H2 | 111.5 (10) |
| N4ii—Zn1—N4iv | 89.11 (4) | N1—C2—H3 | 107.1 (10) |
| N4iii—Zn1—N4iv | 89.11 (4) | C3—C2—H3 | 112.8 (9) |
| N4i—Zn1—N4v | 89.11 (4) | H2—C2—H3 | 107.0 (14) |
| N4ii—Zn1—N4v | 90.89 (4) | C2—C3—C4 | 112.68 (11) |
| N4iii—Zn1—N4v | 90.89 (4) | C2—C3—H5 | 105.4 (10) |
| N4iv—Zn1—N4v | 180.0 | C4—C3—H5 | 112.1 (10) |
| N4i—Zn1—N4 | 90.89 (4) | C2—C3—H4 | 110.4 (10) |
| N4ii—Zn1—N4 | 89.11 (4) | C4—C3—H4 | 109.5 (10) |
| N4iii—Zn1—N4 | 180.0 | H5—C3—H4 | 106.6 (14) |
| N4iv—Zn1—N4 | 90.89 (4) | F1—B—F2iv | 109.35 (10) |
| N4v—Zn1—N4 | 89.11 (4) | F1—B—F2i | 109.35 (10) |
| C1—N4—N3 | 106.20 (10) | F2iv—B—F2i | 109.59 (10) |
| C1—N4—Zn1 | 129.63 (9) | F1—B—F2 | 109.35 (10) |
| N3—N4—Zn1 | 124.15 (8) | F2iv—B—F2 | 109.59 (10) |
| C1—N4—Fe1 | 129.63 (9) | F2i—B—F2 | 109.59 (10) |
| N4i—Zn1—N4—C1 | 164.91 (11) | N4iii—Fe1—N4—N3 | −4.13 (9) |
| N4ii—Zn1—N4—C1 | −15.09 (11) | N4iv—Fe1—N4—N3 | −108.21 (7) |
| N4iii—Zn1—N4—C1 | 178.08 (11) | N4v—Fe1—N4—N3 | 71.79 (7) |
| N4iv—Zn1—N4—C1 | 74.00 (13) | N4i—Fe1—N4—Zn1 | 0.0 |
| N4v—Zn1—N4—C1 | −106.00 (13) | N4ii—Fe1—N4—Zn1 | 0.0 |
| N4i—Zn1—N4—N3 | −17.31 (10) | N4iii—Fe1—N4—Zn1 | 0.0 |
| N4ii—Zn1—N4—N3 | 162.69 (10) | N4iv—Fe1—N4—Zn1 | 0.0 |
| N4iii—Zn1—N4—N3 | −4.13 (9) | N4v—Fe1—N4—Zn1 | 0.0 |
| N4iv—Zn1—N4—N3 | −108.21 (7) | N3—N4—C1—N1 | −0.01 (14) |
| N4v—Zn1—N4—N3 | 71.79 (7) | Zn1—N4—C1—N1 | 178.08 (8) |
| N4i—Zn1—N4—Fe1 | 0.0 | Fe1—N4—C1—N1 | 178.08 (8) |
| N4ii—Zn1—N4—Fe1 | 0.0 | C1—N4—N3—N2 | 0.16 (14) |
| N4iii—Zn1—N4—Fe1 | 0.0 | Zn1—N4—N3—N2 | −178.07 (8) |
| N4iv—Zn1—N4—Fe1 | 0.0 | Fe1—N4—N3—N2 | −178.07 (8) |
| N4v—Zn1—N4—Fe1 | 0.0 | N4—N3—N2—N1 | −0.23 (13) |
| N4i—Fe1—N4—C1 | 164.91 (11) | N4—C1—N1—N2 | −0.13 (14) |
| N4ii—Fe1—N4—C1 | −15.09 (11) | N4—C1—N1—C2 | −175.55 (12) |
| N4iii—Fe1—N4—C1 | 178.08 (11) | N3—N2—N1—C1 | 0.22 (13) |
| N4iv—Fe1—N4—C1 | 74.00 (13) | N3—N2—N1—C2 | 176.10 (11) |
| N4v—Fe1—N4—C1 | −106.00 (13) | C1—N1—C2—C3 | −123.48 (14) |
| N4i—Fe1—N4—N3 | −17.31 (10) | N2—N1—C2—C3 | 61.61 (15) |
| N4ii—Fe1—N4—N3 | 162.69 (10) | N1—C2—C3—C4 | 56.40 (15) |
| Symmetry codes: (i) −y, x−y, z; (ii) y, −x+y, −z; (iii) −x, −y, −z; (iv) −x+y, −x, z; (v) x−y, x, −z. |
(V) top
Crystal data top
| C24H48N24Fe0.46Zn0.54·2(BF2) | Dx = 1.416 Mg m−3 |
| Mr = 907.47 | Mo Kα radiation, λ = 0.71073 Å |
| Hexagonal, R3 | Cell parameters from 60 reflections |
| a = 10.7719 (6) Å | θ = 30–40° |
| c = 31.763 (3) Å | µ = 0.56 mm−1 |
| V = 3191.8 (4) Å3 | T = 10 K |
| Z = 3 | Plate, red |
| F(000) = 1410 | 0.6 × 0.5 × 0.3 mm |
Data collection top
| CCD-Kuma Difraction diffractometer | 1462 independent reflections |
| Radiation source: fine-focus rotating anode | 1433 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.030 |
| ϕ–scan | θmax = 26.8°, θmin = 3.8° |
| Absorption correction: multi-scan ? | h = −13→13 |
| Tmin = 0.721, Tmax = 0.845 | k = −13→10 |
| 7725 measured reflections | l = −38→38 |
Refinement top
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.070 | Calculated w = 1/[σ2(Fo2) + (0.0368P)2 + 5.8158P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 1462 reflections | Δρmax = 0.33 e Å−3 |
| 122 parameters | Δρmin = −0.37 e Å−3 |
| 0 restraints |
Crystal data top
| C24H48N24Fe0.46Zn0.54·2(BF2) | Z = 3 |
| Mr = 907.47 | Mo Kα radiation |
| Hexagonal, R3 | µ = 0.56 mm−1 |
| a = 10.7719 (6) Å | T = 10 K |
| c = 31.763 (3) Å | 0.6 × 0.5 × 0.3 mm |
| V = 3191.8 (4) Å3 |
Data collection top
| CCD-Kuma Difraction diffractometer | 1462 independent reflections |
| Absorption correction: multi-scan ? | 1433 reflections with I > 2σ(I) |
| Tmin = 0.721, Tmax = 0.845 | Rint = 0.030 |
| 7725 measured reflections |
Refinement top
| R[F2 > 2σ(F2)] = 0.027 | 122 parameters |
| wR(F2) = 0.070 | 0 restraints |
| S = 1.06 | Δρmax = 0.33 e Å−3 |
| 1462 reflections | Δρmin = −0.37 e Å−3 |
Special details top
Experimental. 'CrysAlis (Oxford Diffraction, 2002)' |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Fe1 | 0.0000 | 0.0000 | 0.0000 | 0.00389 (12) | 0.46 |
| Zn1 | 0.0000 | 0.0000 | 0.0000 | 0.00389 (12) | 0.54 |
| N4 | 0.04743 (11) | −0.12938 (12) | 0.03725 (3) | 0.0084 (2) | |
| C1 | −0.01872 (13) | −0.27080 (14) | 0.04016 (4) | 0.0083 (3) | |
| H1 | −0.0985 (19) | −0.3355 (18) | 0.0264 (5) | 0.011 (4)* | |
| N3 | 0.16227 (12) | −0.07833 (12) | 0.06396 (3) | 0.0108 (2) | |
| N2 | 0.16574 (12) | −0.18443 (12) | 0.08212 (4) | 0.0115 (2) | |
| N1 | 0.05210 (11) | −0.30596 (11) | 0.06742 (3) | 0.0084 (2) | |
| C4 | −0.1153 (2) | −0.4589 (2) | 0.14362 (4) | 0.0137 (3) | |
| H6 | −0.1270 (19) | −0.483 (2) | 0.1738 (6) | 0.018 (4)* | |
| H7 | −0.206 (2) | −0.525 (2) | 0.1289 (6) | 0.024 (5)* | |
| H8 | −0.0983 (18) | −0.3618 (19) | 0.1401 (5) | 0.015 (4)* | |
| C2 | 0.02879 (14) | −0.44852 (14) | 0.07912 (4) | 0.0103 (3) | |
| H2 | −0.0556 (19) | −0.5191 (18) | 0.0643 (5) | 0.013 (4)* | |
| H3 | 0.1101 (18) | −0.4543 (17) | 0.0689 (5) | 0.009 (4)* | |
| C3 | 0.00890 (15) | −0.4737 (2) | 0.12641 (4) | 0.0118 (3) | |
| H5 | −0.0058 (18) | −0.5686 (19) | 0.1305 (5) | 0.013 (4)* | |
| H4 | 0.0960 (18) | −0.4089 (18) | 0.1406 (5) | 0.010 (4)* | |
| F2 | −0.04224 (9) | −0.13801 (8) | 0.33332 (2) | 0.0118 (2) | |
| F1 | 0.0000 | 0.0000 | 0.27475 (4) | 0.0129 (3) | |
| B | 0.0000 | 0.0000 | 0.31871 (8) | 0.0071 (5) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.00328 (15) | 0.00328 (15) | 0.0051 (2) | 0.00164 (7) | 0.000 | 0.000 |
| Zn1 | 0.00328 (15) | 0.00328 (15) | 0.0051 (2) | 0.00164 (7) | 0.000 | 0.000 |
| N4 | 0.0048 (5) | 0.0096 (5) | 0.0087 (5) | 0.0020 (4) | 0.0005 (4) | −0.0032 (4) |
| C1 | 0.0058 (6) | 0.0100 (6) | 0.0078 (6) | 0.0030 (5) | 0.0005 (4) | −0.0021 (5) |
| N3 | 0.0069 (5) | 0.0132 (6) | 0.0117 (5) | 0.0045 (5) | −0.0019 (4) | −0.0037 (4) |
| N2 | 0.0074 (5) | 0.0116 (6) | 0.0138 (5) | 0.0034 (4) | −0.0020 (4) | −0.0044 (4) |
| N1 | 0.0055 (5) | 0.0098 (5) | 0.0090 (5) | 0.0032 (4) | −0.0005 (4) | −0.0031 (4) |
| C4 | 0.0146 (7) | 0.0150 (7) | 0.0121 (6) | 0.0078 (6) | 0.0015 (5) | −0.0005 (5) |
| C2 | 0.0105 (6) | 0.0099 (6) | 0.0120 (6) | 0.0062 (5) | −0.0010 (5) | −0.0019 (5) |
| C3 | 0.0126 (7) | 0.0136 (7) | 0.0112 (6) | 0.0081 (6) | −0.0020 (5) | −0.0009 (5) |
| F2 | 0.0133 (4) | 0.0064 (4) | 0.0150 (4) | 0.0043 (3) | −0.0019 (3) | 0.0016 (3) |
| F1 | 0.0151 (4) | 0.0151 (4) | 0.0084 (6) | 0.0076 (2) | 0.000 | 0.000 |
| B | 0.0062 (7) | 0.0062 (7) | 0.0089 (11) | 0.0031 (3) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
| Fe1—N4i | 2.0774 (11) | N3—N2 | 1.297 (2) |
| Fe1—N4ii | 2.0774 (11) | N2—N1 | 1.3519 (15) |
| Fe1—N4 | 2.0774 (11) | N1—C2 | 1.474 (2) |
| Fe1—N4iii | 2.0774 (11) | C4—C3 | 1.526 (2) |
| Fe1—N4iv | 2.0774 (11) | C4—H6 | 0.99 (2) |
| Fe1—N4v | 2.0774 (11) | C4—H7 | 0.99 (2) |
| Zn1—N4i | 2.0774 (11) | C4—H8 | 0.97 (2) |
| Zn1—N4ii | 2.0774 (11) | C2—C3 | 1.522 (2) |
| Zn1—N4 | 2.0774 (11) | C2—H2 | 0.97 (2) |
| Zn1—N4iii | 2.0774 (11) | C2—H3 | 0.97 (2) |
| Zn1—N4iv | 2.0774 (11) | C3—H5 | 0.96 (2) |
| Zn1—N4v | 2.0774 (11) | C3—H4 | 0.96 (2) |
| N4—C1 | 1.323 (2) | F2—B | 1.3986 (11) |
| N4—N3 | 1.3682 (15) | F1—B | 1.396 (3) |
| C1—N1 | 1.328 (2) | B—F2iii | 1.3986 (11) |
| C1—H1 | 0.90 (2) | B—F2i | 1.3986 (11) |
| N4i—Fe1—N4ii | 180.0 | N3—N4—Fe1 | 124.04 (8) |
| N4i—Fe1—N4 | 90.77 (4) | Zn1—N4—Fe1 | 0.0 |
| N4ii—Fe1—N4 | 89.23 (4) | N4—C1—N1 | 108.56 (11) |
| N4i—Fe1—N4iii | 90.77 (4) | N4—C1—H1 | 127.7 (10) |
| N4ii—Fe1—N4iii | 89.23 (4) | N1—C1—H1 | 123.8 (10) |
| N4—Fe1—N4iii | 90.77 (4) | N2—N3—N4 | 109.88 (10) |
| N4i—Fe1—N4iv | 89.23 (4) | N3—N2—N1 | 106.77 (10) |
| N4ii—Fe1—N4iv | 90.77 (4) | C1—N1—N2 | 108.67 (11) |
| N4—Fe1—N4iv | 180.0 | C1—N1—C2 | 129.67 (11) |
| N4iii—Fe1—N4iv | 89.23 (4) | N2—N1—C2 | 121.45 (11) |
| N4i—Fe1—N4v | 89.23 (4) | C3—C4—H6 | 108.8 (10) |
| N4ii—Fe1—N4v | 90.77 (4) | C3—C4—H7 | 111.3 (11) |
| N4—Fe1—N4v | 89.23 (4) | H6—C4—H7 | 108.6 (15) |
| N4iii—Fe1—N4v | 180.0 | C3—C4—H8 | 111.6 (10) |
| N4iv—Fe1—N4v | 90.77 (4) | H6—C4—H8 | 109.1 (15) |
| N4i—Zn1—N4ii | 180.0 | H7—C4—H8 | 107.4 (15) |
| N4i—Zn1—N4 | 90.77 (4) | N1—C2—C3 | 111.71 (11) |
| N4ii—Zn1—N4 | 89.23 (4) | N1—C2—H2 | 107.5 (10) |
| N4i—Zn1—N4iii | 90.77 (4) | C3—C2—H2 | 110.2 (10) |
| N4ii—Zn1—N4iii | 89.23 (4) | N1—C2—H3 | 107.1 (10) |
| N4—Zn1—N4iii | 90.77 (4) | C3—C2—H3 | 111.9 (9) |
| N4i—Zn1—N4iv | 89.23 (4) | H2—C2—H3 | 108.2 (13) |
| N4ii—Zn1—N4iv | 90.77 (4) | C2—C3—C4 | 112.79 (11) |
| N4—Zn1—N4iv | 180.0 | C2—C3—H5 | 104.8 (10) |
| N4iii—Zn1—N4iv | 89.23 (4) | C4—C3—H5 | 112.1 (10) |
| N4i—Zn1—N4v | 89.23 (4) | C2—C3—H4 | 109.5 (10) |
| N4ii—Zn1—N4v | 90.77 (4) | C4—C3—H4 | 110.3 (10) |
| N4—Zn1—N4v | 89.23 (4) | H5—C3—H4 | 107.1 (13) |
| N4iii—Zn1—N4v | 180.0 | F1—B—F2iii | 109.38 (10) |
| N4iv—Zn1—N4v | 90.77 (4) | F1—B—F2i | 109.38 (10) |
| C1—N4—N3 | 106.12 (11) | F2iii—B—F2i | 109.57 (10) |
| C1—N4—Zn1 | 129.83 (9) | F1—B—F2 | 109.38 (10) |
| N3—N4—Zn1 | 124.04 (8) | F2iii—B—F2 | 109.57 (10) |
| C1—N4—Fe1 | 129.83 (9) | F2i—B—F2 | 109.57 (10) |
| N4i—Zn1—N4—C1 | 163.25 (10) | N4iii—Fe1—N4—N3 | −109.14 (7) |
| N4ii—Zn1—N4—C1 | −16.75 (10) | N4iv—Fe1—N4—N3 | 13.E1 (10) |
| N4iii—Zn1—N4—C1 | 72.48 (13) | N4v—Fe1—N4—N3 | 70.86 (7) |
| N4iv—Zn1—N4—C1 | −5.E1 (10) | N4i—Fe1—N4—Zn1 | 0.0 |
| N4v—Zn1—N4—C1 | −107.52 (13) | N4ii—Fe1—N4—Zn1 | 0.0 |
| N4i—Zn1—N4—N3 | −18.36 (10) | N4iii—Fe1—N4—Zn1 | 0.0 |
| N4ii—Zn1—N4—N3 | 161.64 (10) | N4iv—Fe1—N4—Zn1 | 0.0 |
| N4iii—Zn1—N4—N3 | −109.14 (7) | N4v—Fe1—N4—Zn1 | 0.0 |
| N4iv—Zn1—N4—N3 | 13.E1 (10) | N3—N4—C1—N1 | −0.10 (13) |
| N4v—Zn1—N4—N3 | 70.86 (7) | Zn1—N4—C1—N1 | 178.50 (8) |
| N4i—Zn1—N4—Fe1 | 0.0 | Fe1—N4—C1—N1 | 178.50 (8) |
| N4ii—Zn1—N4—Fe1 | 0.0 | C1—N4—N3—N2 | 0.25 (13) |
| N4iii—Zn1—N4—Fe1 | 0.0 | Zn1—N4—N3—N2 | −178.46 (8) |
| N4iv—Zn1—N4—Fe1 | 0.0 | Fe1—N4—N3—N2 | −178.46 (8) |
| N4v—Zn1—N4—Fe1 | 0.0 | N4—N3—N2—N1 | −0.30 (13) |
| N4i—Fe1—N4—C1 | 163.25 (10) | N4—C1—N1—N2 | −0.07 (14) |
| N4ii—Fe1—N4—C1 | −16.75 (10) | N4—C1—N1—C2 | −174.71 (11) |
| N4iii—Fe1—N4—C1 | 72.48 (13) | N3—N2—N1—C1 | 0.23 (13) |
| N4iv—Fe1—N4—C1 | −5.E1 (10) | N3—N2—N1—C2 | 175.39 (11) |
| N4v—Fe1—N4—C1 | −107.52 (13) | C1—N1—C2—C3 | −124.81 (14) |
| N4i—Fe1—N4—N3 | −18.36 (10) | N2—N1—C2—C3 | 61.14 (15) |
| N4ii—Fe1—N4—N3 | 161.64 (10) | N1—C2—C3—C4 | 57.49 (15) |
| Symmetry codes: (i) −y, x−y, z; (ii) y, −x+y, −z; (iii) −x+y, −x, z; (iv) −x, −y, −z; (v) x−y, x, −z. |
Experimental details
| (I) | (II) | (III) | (IV) | |
| Crystal data | ||||
| Chemical formula | C24H48N24Zn·2(BF2) | C24H48N24Fe·2(BF2) | C24H48N24Fe·2(BF2) | C24H48N24Fe0.46Zn0.54·2(BF2) |
| Mr | 911.85 | 902.33 | 902.33 | 907.47 |
| Crystal system, space group | Hexagonal, R3 | Hexagonal, R3 | Hexagonal, R3 | Hexagonal, R3 |
| Temperature (K) | 10 | 10 | 10 | 10 |
| a, c (Å) | 10.8429 (7), 31.607 (3) | 10.881 (2), 31.480 (8) | 10.701 (2), 31.900 (8) | 10.8575 (5), 31.560 (3) |
| V (Å3) | 3218.1 (4) | 3227.8 (12) | 3163.5 (12) | 3222.0 (4) |
| Z | 3 | 3 | 3 | 3 |
| Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
| µ (mm−1) | 0.66 | 0.44 | 0.45 | 0.56 |
| Crystal size (mm) | 0.6 × 0.6 × 0.3 | 0.7 × 0.5 × 0.3 | 0.7 × 0.5 × 0.3 | 0.6 × 0.5 × 0.3 |
| Data collection | ||||
| Diffractometer | CCD-Kuma Difraction diffractometer | CCD-Kuma Difraction diffractometer | CCD-Kuma Difraction diffractometer | CCD-Kuma Difraction diffractometer |
| Absorption correction | Multi-scan | Multi-scan | Multi-scan | Multi-scan |
| Tmin, Tmax | 0.681, 0.821 | 0.770, 0.877 | 0.732, 0.766 | 0.724, 0.846 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7605, 1478, 1439 | 12546, 1554, 1257 | 9516, 1563, 1322 | 7865, 1469, 1433 |
| Rint | 0.039 | 0.085 | 0.063 | 0.028 |
| (sin θ/λ)max (Å−1) | 0.634 | 0.649 | 0.656 | 0.634 |
| Refinement | ||||
| R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.061, 1.09 | 0.032, 0.076, 1.08 | 0.036, 0.088, 1.11 | 0.027, 0.072, 1.10 |
| No. of reflections | 1478 | 1554 | 1563 | 1469 |
| No. of parameters | 122 | 122 | 122 | 122 |
| Δρmax, Δρmin (e Å−3) | 0.30, −0.34 | 0.23, −0.57 | 0.32, −0.58 | 0.29, −0.37 |
| (V) | |
| Crystal data | |
| Chemical formula | C24H48N24Fe0.46Zn0.54·2(BF2) |
| Mr | 907.47 |
| Crystal system, space group | Hexagonal, R3 |
| Temperature (K) | 10 |
| a, c (Å) | 10.7719 (6), 31.763 (3) |
| V (Å3) | 3191.8 (4) |
| Z | 3 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.56 |
| Crystal size (mm) | 0.6 × 0.5 × 0.3 |
| Data collection | |
| Diffractometer | CCD-Kuma Difraction diffractometer |
| Absorption correction | Multi-scan |
| Tmin, Tmax | 0.721, 0.845 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7725, 1462, 1433 |
| Rint | 0.030 |
| (sin θ/λ)max (Å−1) | 0.634 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.070, 1.06 |
| No. of reflections | 1462 |
| No. of parameters | 122 |
| Δρmax, Δρmin (e Å−3) | 0.33, −0.37 |
Computer programs: CrysAlis (Oxford Diffraction, 2002), STADI4 (Stoe, 1995), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), PLATON (Spek,2003).
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