Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107018471/gz3084sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107018471/gz3084Isup2.hkl | |
Text file https://doi.org/10.1107/S0108270107018471/gz3084sup3.txt |
CCDC references: 652487; 653160
The compound was prepared from a solution of Cu2(BBI)2.xDMF in CH2Cl2 by addition of an excess of 3,5-lutidine, where BBI is 5-tert-butyl-m-xylylenebis(acetylacetone iminate) (Bradbury et al., 1989). Over a period of 1–2 weeks, the CH2Cl2 evaporated, and blue crystals formed in the residual liquid. However, those crystals were not of sufficient quality for crystal structure determination, and the sample was retained in a sealed vial. After approximately 18 years, high-quality blue prisms of (I) were discovered in the sample.
For sp2 C atoms, a C—H distance of 0.95 Å was used, with Uiso(H) = 1.2Ueq(C). For the methyl group, C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C), and a torsional parameter was refined.
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[CuCl2(C7H9N)4] | Dx = 1.337 Mg m−3 |
Mr = 563.05 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/nnc | Cell parameters from 3012 reflections |
Hall symbol: -P 4a 2bc | θ = 2.5–35.0° |
a = 11.3324 (15) Å | µ = 1.00 mm−1 |
c = 10.894 (2) Å | T = 110 K |
V = 1399.0 (4) Å3 | Prism, blue |
Z = 2 | 0.20 × 0.20 × 0.17 mm |
F(000) = 590 |
Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler | 1547 independent reflections |
Radiation source: fine-focus sealed tube | 1195 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans with κ offsets | θmax = 35.0°, θmin = 2.5° |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | h = −18→18 |
Tmin = 0.826, Tmax = 0.849 | k = −12→12 |
13834 measured reflections | l = −14→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.034P)2 + 0.5672P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1547 reflections | Δρmax = 0.40 e Å−3 |
45 parameters | Δρmin = −0.65 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0064 (13) |
[CuCl2(C7H9N)4] | Z = 2 |
Mr = 563.05 | Mo Kα radiation |
Tetragonal, P4/nnc | µ = 1.00 mm−1 |
a = 11.3324 (15) Å | T = 110 K |
c = 10.894 (2) Å | 0.20 × 0.20 × 0.17 mm |
V = 1399.0 (4) Å3 |
Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler | 1547 independent reflections |
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997) | 1195 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 0.849 | Rint = 0.035 |
13834 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.40 e Å−3 |
1547 reflections | Δρmin = −0.65 e Å−3 |
45 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.7500 | 0.7500 | 0.2500 | 0.01052 (10) | |
Cl1 | 0.7500 | 0.7500 | 0.50380 (5) | 0.01531 (11) | |
N1 | 0.62202 (7) | 0.62202 (7) | 0.2500 | 0.0113 (2) | |
C1 | 0.62762 (9) | 0.53069 (9) | 0.17179 (11) | 0.01328 (19) | |
H1 | 0.6913 | 0.5275 | 0.1152 | 0.016* | |
C2 | 0.54443 (9) | 0.44044 (9) | 0.16975 (11) | 0.0144 (2) | |
C3 | 0.44920 (9) | 0.44920 (9) | 0.2500 | 0.0158 (3) | |
H3 | 0.3899 | 0.3899 | 0.2500 | 0.019* | |
C4 | 0.55841 (11) | 0.33732 (11) | 0.08414 (13) | 0.0238 (3) | |
H4A | 0.6120 | 0.2794 | 0.1208 | 0.036* | |
H4B | 0.5910 | 0.3647 | 0.0059 | 0.036* | |
H4C | 0.4813 | 0.3007 | 0.0699 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.00625 (11) | 0.00625 (11) | 0.01905 (18) | 0.000 | 0.000 | 0.000 |
Cl1 | 0.01361 (14) | 0.01361 (14) | 0.0187 (2) | 0.000 | 0.000 | 0.000 |
N1 | 0.0090 (3) | 0.0090 (3) | 0.0160 (5) | −0.0001 (4) | 0.0009 (3) | −0.0009 (3) |
C1 | 0.0120 (4) | 0.0119 (4) | 0.0159 (5) | −0.0010 (3) | 0.0024 (4) | −0.0025 (4) |
C2 | 0.0132 (4) | 0.0115 (4) | 0.0185 (5) | −0.0023 (3) | 0.0005 (4) | −0.0043 (4) |
C3 | 0.0121 (3) | 0.0121 (3) | 0.0231 (7) | −0.0038 (4) | 0.0014 (4) | −0.0014 (4) |
C4 | 0.0225 (5) | 0.0181 (5) | 0.0308 (6) | −0.0054 (4) | 0.0052 (5) | −0.0131 (5) |
Cu1—Cl1 | 2.7649 (7) | C2—C4 | 1.5034 (16) |
Cu1—N1 | 2.0510 (12) | C3—H3 | 0.9500 |
N1—C1 | 1.3422 (12) | C4—H4A | 0.9800 |
C1—C2 | 1.3912 (14) | C4—H4B | 0.9800 |
C1—H1 | 0.9500 | C4—H4C | 0.9800 |
C2—C3 | 1.3924 (13) | ||
N1i—Cu1—N1 | 90 | C1—N1—Cu1 | 120.79 (6) |
N1i—Cu1—N1ii | 180 | N1—C1—C2 | 123.03 (10) |
N1—Cu1—N1ii | 90 | N1—C1—H1 | 118.5 |
N1i—Cu1—N1iii | 90 | C2—C1—H1 | 118.5 |
N1—Cu1—N1iii | 180 | C1—C2—C3 | 117.57 (10) |
N1ii—Cu1—N1iii | 90 | C1—C2—C4 | 120.66 (10) |
N1i—Cu1—Cl1i | 90 | C3—C2—C4 | 121.77 (10) |
N1—Cu1—Cl1i | 90 | C2iv—C3—C2 | 120.32 (13) |
N1ii—Cu1—Cl1i | 90 | C2iv—C3—H3 | 119.8 |
N1iii—Cu1—Cl1i | 90 | C2—C3—H3 | 119.8 |
N1i—Cu1—Cl1 | 90 | C2—C4—H4A | 109.5 |
N1—Cu1—Cl1 | 90 | C2—C4—H4B | 109.5 |
N1ii—Cu1—Cl1 | 90 | H4A—C4—H4B | 109.5 |
N1iii—Cu1—Cl1 | 90 | C2—C4—H4C | 109.5 |
Cl1i—Cu1—Cl1 | 180 | H4A—C4—H4C | 109.5 |
C1iv—N1—C1 | 118.42 (12) | H4B—C4—H4C | 109.5 |
C1iv—N1—Cu1 | 120.79 (6) | ||
N1i—Cu1—N1—C1iv | −47.65 (6) | Cu1—N1—C1—C2 | 178.68 (8) |
Cl1i—Cu1—N1—C1iv | −137.65 (6) | N1—C1—C2—C3 | 2.54 (16) |
Cl1—Cu1—N1—C1iv | 42.35 (6) | N1—C1—C2—C4 | −177.05 (10) |
N1i—Cu1—N1—C1 | 132.35 (6) | C1—C2—C3—C2iv | −1.19 (8) |
Cl1—Cu1—N1—C1 | −137.65 (6) | C4—C2—C3—C2iv | 178.40 (13) |
C1iv—N1—C1—C2 | −1.32 (8) |
Symmetry codes: (i) x, −y+3/2, −z+1/2; (ii) −x+3/2, y, −z+1/2; (iii) −x+3/2, −y+3/2, z; (iv) y, x, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [CuCl2(C7H9N)4] |
Mr | 563.05 |
Crystal system, space group | Tetragonal, P4/nnc |
Temperature (K) | 110 |
a, c (Å) | 11.3324 (15), 10.894 (2) |
V (Å3) | 1399.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.20 × 0.20 × 0.17 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler |
Absorption correction | Multi-scan (SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.826, 0.849 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13834, 1547, 1195 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.807 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.081, 1.06 |
No. of reflections | 1547 |
No. of parameters | 45 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.65 |
Computer programs: COLLECT (Nonius, 2000), SCALEPACK (Otwinowski & Minor 1997), DENZO (Otwinowski & Minor 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
Cu1—Cl1 | 2.7649 (7) | C1—C2 | 1.3912 (14) |
Cu1—N1 | 2.0510 (12) | C2—C3 | 1.3924 (13) |
N1—C1 | 1.3422 (12) | C2—C4 | 1.5034 (16) |
Cl1—Cu1—N1—C1i | 42.35 (6) |
Symmetry code: (i) y, x, −z+1/2. |
The title compound, (I), was prepared during an investigation of the reactions of a cofacial binuclear bis(ketoenamine) complex, Cu2(BBI)2, where BBI is 5-tert-butyl-m-xylylenebis(acetylacetone iminate) (Bradbury et al., 1989), with 3,5-lutidine and related Lewis bases. Electronic spectroscopic changes during these reactions suggested that simple adducts, such as Cu2(BBI)2L2, were forming. However, these products could not be isolated. Instead, the complex apparently decomposed, and the title compound fortuitously crystallized after many years. No chloride was added to the Cu2(BBI)2–3,5-lutidine solution, nor were any other copper sources present. However, dichloromethane is known to be attacked by amines, with displacement of a Cl- anion (Fronczek et al., 1990; Maverick et al., 1990). Thus, formation of the title compound may have occurred by slow hydrolysis of Cu2(BBI)2 to release Cu2+, and subsequent combination with displaced Cl- anion and excess lutidine.
The molecule of (I) lies on a site of 42 symmetry and Z'= 1/8. Space group P4/nnc is uncommon, with only three occurrences reported by Brock & Dunitz (1994) in their compilation of well determined structures from the Cambridge Structural Database (CSD; Allen, 2002). All three have Z'= 1/8. A search of the complete database (Version 5.28, November 2006) yielded 101 hits, of which 65 have Z' = 1/8, 34 have Z' = 1/4, one has Z' = 9/8 and one has Z' = 2.
The crystallographic symmetry requires strict square-planar geometry of the CuN4 unit, and the axial octahedral elongation is likewise undistorted. The Cu—N distance is comparable with those in trans-dichlorotetrakis(pyridine)copper(II) dipyridine solvate [2.028 (3)–2.064 (4) Å; CSD refcode OMIROR; Bond et al., 2003], but that compound has a somewhat longer Cu—Cl distance [2.957 (2) Å] than in (I). Likewise, in trans-dichlorotetrakis(pyrid-3-ylmethanol-N) copper(II) (CSD refcode PACYUO; Moncol et al., 2004), the Cu—N distances are comparable, at 2.0322 (15)–2.0747 (17) Å, and the Cu—Cl distance is even longer, at 3.0752 (8) Å.
There are differences among these three structures with respect to the twisting of the pyridine ring out of the coordination plane, as measured by the Cl—Cu—N—C torsion angles. Compound (I) has a torsion angle of 42.35 (6)°, OMIROR has torsion angles of 25.4 and 32.0°, while PACYUO has torsion angles within the range 10.1–32.8°.
Compound (I) is isomorphous with the analogous NiII compound (Xu et al., 2005). The CoII analogue (refcode YIZSIJ; Kansikas et al., 1994) has been reported in space group Pnnn, with a = b, the molecule lying on a site of 222 (D2) symmetry and one full 3,5-lutidine ligand in the asymmetric unit. However, the coordinates of the lutidine conform to twofold symmetry, with a maximum deviation of 0.013 Å. Thus, it appears that the structure should be properly described in space group P4/nnc, isomorphous with the Ni and Cu compounds. Symmetrized coordinates for YIZSIJ in the tetragonal space group are provided as supplementary material.