{2,2-Bis[(4S)-4-isopropyl-4,5-dihydro-1,3-oxazol-2-yl]propane}­bis­(N,N-dimethyl­formamide)­copper(II) bis­[hexa­fluoridoanti­monate(V)]

Zeh, J.; Möller, M.; Strohmann, C.; Preut, H.; Hiersemann, M.

doi:10.1107/S1600536810048658

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1688

https://doi.org/10.1107/S1600536810048658

Open

access

{2,2-Bis[(4S)-4-isopropyl-4,5-dihydro-1,3-oxazol-2-yl]propane}bis(N,N-dimethylformamide)copper(II) bis[hexafluoridoantimonate(V)]

Julia Zeh,^a Melina Möller,^a Carsten Strohmann,^a Hans Preut ^a ^* and Martin Hiersemann ^a

^aFakultät Chemie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44221 Dortmund, Germany
^*Correspondence e-mail: hans.preut@tu-dortmund.de

(Received 17 November 2010; accepted 22 November 2010; online 27 November 2010)

In the title compound, [Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂][SbF₆]₂, which is a potential catalyst in the catalytic asymmetric Gosteli–Claisen rearrangement, the central Cu^II atom is in a nearly square-planar cis-N₂O₂ environment in the cation arising from its coordination by an N,N-bidentate 2,2-bis[(4S)-4-isopropyl-4,5-dihydro-1,3-oxazol-2-yl]propane ligand and two O-bonded N,N-dimethylformamide molecules. Two SbF₆⁻ anions are positioned on opposite sides of the plane through the CuN₂O₂ unit, generating an axially distorted CuN₂O₂F₂ octahedral geometry for the metal ion.

Related literature

For background to the catalytic asymmetric Gosteli–Claisen rearrangement, see: Abraham & Hiersemann (2001 ); Abraham et al. (2001 , 2004 ); Hiersemann & Abraham (2002 ). For further synthetic details, see: Evans et al. (1991 , 1998 ); McKennon et al. (1993 ). For application of the catalytic asymmetric Gosteli–Claisen rearrangement, see: Körner & Hiersemann (2007 ); Pollex & Hiersemann (2005 ).

Experimental

Crystal data

[Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂][SbF₆]₂
M_r = 947.61
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.7256 (2) Å
b = 15.2444 (3) Å
c = 23.2040 (5) Å
V = 3440.25 (12) Å³
Z = 4
Mo Kα radiation
μ = 2.27 mm⁻¹
T = 173 K
0.30 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.820, T_max = 1.000
41873 measured reflections
7479 independent reflections
6078 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.037
S = 1.04
7479 reflections
407 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Absolute structure: Flack (1983 ), 2727 Friedel pairs
Flack parameter: −0.008 (10)

Table 1
Selected geometric parameters (Å, °)

Cu—O2	1.951 (2)
Cu—N4	1.962 (2)
Cu—O1	1.964 (2)
Cu—N3	1.971 (2)
Cu—F7	2.4232 (18)
Cu—F5	2.5452 (19)

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis CCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810048658/hb5747sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810048658/hb5747Isup2.hkl

checkCIF report

Comment top

The title compound, (I), was tested as a catalyst in the catalytic asymmetric Gosteli-Claisen rearrangement (Abraham et al., 2001; Abraham & Hiersemann, 2001; Hiersemann & Abraham, 2002; Abraham et al., 2004). The synthesis of the title compound, (I), was accomplished according to a modified procedure of Evans et al. (1991, 1998). A sequence of Meyers` amino acid reduction of (S)-Valine (McKennon et al., 1993), subsequent condensation with dimethyl malonic acid dichloride and p-TsCl catalyzed cyclization provided the (S,S)-ⁱPr-box ligand. Treatment of the box ligand with CuCl₂ and subsequent anion metathesis with AgSbF₆ provided [Cu{(S,S)-ⁱPr-box}](SbF₆)₂ (Evans et al., 1998). Addition of 2 eq of DMF to a solution of [Cu{(S,S)-ⁱPr-box}](SbF₆)₂ in 1,2-dichloroethane afforded [Cu{(S,S)-ⁱPr-box}(dmf)₂](SbF₆)₂. Crystallization was achieved by vapor diffusion recrystallization at 243 K.

Related literature top

For background to the Gosteli–Claisen rearrangement, see: Abraham & Hiersemann (2001); Abraham et al. (2001, 2004); Hiersemann & Abraham (2002). For further synthetic details, see: Evans et al. (1991, 1998); McKennon et al. (1993). For related literature [on what subject?], see: Körner & Hiersemann (2007); Pollex & Hiersemann (2005).

Experimental top

To a solution of [Cu{(S,S)-ⁱPr-box}](SbF₆)₂ (78.1 mg, 0.094 mmol, 1 eq) in dry 1,2-dichloroethane (1 ml) under argon atmosphere was added DMF (14.5 µL, 0.188 mmol, 2 eq) by a microliter syringe and the resulting deep blue solution was stirred for 15 min at room temperature. Subsequent cooling to 243 K provided (I) as deep blue blocks.

Structure description top

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. : The molecular structure of the title compound with H-atoms are omitted for clarity. Displacement ellipsoids are shown at the 30% probability level.
	Fig. 2. : The molecular structure of the cation [Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂]²⁺.

{2,2-Bis[(4S)-4-isopropyl-4,5-dihydro-1,3-oxazol-2- yl]propane}bis(N,N-dimethylformamide)copper(II) bis[hexafluoridoantimonate(V)] top

Crystal data top

[Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂][SbF₆]₂	F(000) = 1860
M_r = 947.61	D_x = 1.830 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 18634 reflections
a = 9.7256 (2) Å	θ = 2.2–29.1°
b = 15.2444 (3) Å	µ = 2.27 mm⁻¹
c = 23.2040 (5) Å	T = 173 K
V = 3440.25 (12) Å³	Block, blue
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	7479 independent reflections
Radiation source: Enhance (Mo) X-ray Source	6078 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 16.0560 pixels mm^-1	θ_max = 27.0°, θ_min = 2.2°
ω scans	h = −12→13
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −20→20
T_min = 0.820, T_max = 1.000	l = −29→29
41873 measured reflections

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.037	w = 1/[σ²(F_o²) + (0.0104P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.002
7479 reflections	Δρ_max = 0.81 e Å⁻³
407 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3264 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.008 (10)

Crystal data top

[Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂][SbF₆]₂	V = 3440.25 (12) Å³
M_r = 947.61	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.7256 (2) Å	µ = 2.27 mm⁻¹
b = 15.2444 (3) Å	T = 173 K
c = 23.2040 (5) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Oxford Diffraction Xcalibur S CCD diffractometer	7479 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	6078 reflections with I > 2σ(I)
T_min = 0.820, T_max = 1.000	R_int = 0.046
41873 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.037	Δρ_max = 0.81 e Å⁻³
S = 1.04	Δρ_min = −0.52 e Å⁻³
7479 reflections	Absolute structure: Flack (1983), 3264 Friedel pairs
407 parameters	Absolute structure parameter: −0.008 (10)
0 restraints

Special details top

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.37 (release 24-10-2008) Empirical absorption correction using sperical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5137 (4)	−0.0127 (2)	0.49613 (13)	0.0289 (9)
H1	0.4400	−0.0272	0.5213	0.035*
C2	0.6042 (3)	−0.0081 (2)	0.40077 (13)	0.0401 (10)
H2A	0.6808	0.0202	0.4210	0.060*
H2B	0.5682	0.0317	0.3712	0.060*
H2C	0.6367	−0.0622	0.3825	0.060*
C3	0.3714 (4)	−0.0676 (3)	0.41833 (15)	0.0533 (12)
H3A	0.3091	−0.0825	0.4500	0.080*
H3B	0.3947	−0.1209	0.3968	0.080*
H3C	0.3264	−0.0256	0.3925	0.080*
C4	0.4588 (3)	0.1619 (2)	0.58081 (13)	0.0256 (8)
H4	0.5160	0.1732	0.5484	0.031*
C5	0.2758 (4)	0.2059 (3)	0.64305 (15)	0.0542 (12)
H5A	0.2778	0.1441	0.6548	0.081*
H5B	0.1810	0.2231	0.6343	0.081*
H5C	0.3114	0.2425	0.6744	0.081*
C6	0.3425 (4)	0.2977 (2)	0.55892 (15)	0.0454 (10)
H6A	0.3591	0.3486	0.5837	0.068*
H6B	0.2484	0.3001	0.5439	0.068*
H6C	0.4078	0.2982	0.5268	0.068*
C7	0.4543 (3)	0.0165 (2)	0.74066 (13)	0.0287 (9)
H7	0.4068	0.0057	0.7031	0.034*
C8	0.4871 (4)	−0.0730 (2)	0.76668 (15)	0.0483 (12)
H8A	0.5467	−0.1059	0.7403	0.073*
H8B	0.4015	−0.1057	0.7728	0.073*
H8C	0.5342	−0.0651	0.8036	0.073*
C9	0.3533 (4)	0.0675 (3)	0.77929 (14)	0.0444 (11)
H9A	0.3973	0.0803	0.8164	0.067*
H9B	0.2707	0.0320	0.7857	0.067*
H9C	0.3278	0.1226	0.7604	0.067*
C10	0.5804 (3)	0.0722 (2)	0.72801 (12)	0.0211 (8)
H10	0.5518	0.1305	0.7123	0.025*
C11	0.6784 (4)	0.0848 (2)	0.77903 (13)	0.0324 (9)
H11A	0.7194	0.1443	0.7786	0.039*
H11B	0.6298	0.0761	0.8161	0.039*
C12	0.7743 (3)	−0.0033 (2)	0.71476 (13)	0.0253 (8)
C13	0.8862 (3)	−0.0654 (2)	0.69651 (13)	0.0299 (9)
C14	0.8660 (4)	−0.1533 (2)	0.72814 (14)	0.0482 (11)
H14A	0.8620	−0.1428	0.7698	0.072*
H14B	0.9432	−0.1924	0.7194	0.072*
H14C	0.7800	−0.1806	0.7153	0.072*
C15	1.0259 (3)	−0.0252 (3)	0.71247 (15)	0.0457 (11)
H15A	1.0368	0.0312	0.6927	0.069*
H15B	1.0997	−0.0650	0.7006	0.069*
H15C	1.0303	−0.0161	0.7542	0.069*
C16	0.8874 (3)	−0.0824 (2)	0.63266 (13)	0.0241 (8)
C17	0.9624 (4)	−0.1531 (2)	0.55485 (14)	0.0317 (9)
H17A	0.9144	−0.2091	0.5469	0.038*
H17B	1.0517	−0.1530	0.5343	0.038*
C18	0.8747 (3)	−0.0751 (2)	0.53675 (13)	0.0221 (8)
H18	0.7999	−0.0951	0.5103	0.027*
C19	0.9522 (4)	0.0016 (2)	0.50941 (13)	0.0295 (9)
H19	0.8849	0.0508	0.5049	0.035*
C20	1.0693 (4)	0.0358 (2)	0.54629 (15)	0.0429 (10)
H20A	1.0330	0.0564	0.5833	0.064*
H20B	1.1149	0.0845	0.5264	0.064*
H20C	1.1358	−0.0114	0.5530	0.064*
C21	1.0018 (4)	−0.0230 (3)	0.44894 (15)	0.0426 (10)
H21A	1.0490	0.0273	0.4316	0.064*
H21B	0.9227	−0.0393	0.4251	0.064*
H21C	1.0654	−0.0726	0.4515	0.064*
Cu	0.64767 (4)	0.02331 (2)	0.602048 (15)	0.01965 (9)
F1	0.8666 (3)	0.37550 (14)	0.65651 (10)	0.0660 (8)
F2	0.7212 (2)	0.32927 (15)	0.56382 (10)	0.0693 (8)
F3	0.6661 (2)	0.25671 (14)	0.66418 (9)	0.0605 (7)
F4	0.9252 (2)	0.20713 (17)	0.67247 (9)	0.0705 (7)
F5	0.77901 (19)	0.16435 (12)	0.58166 (8)	0.0398 (5)
F6	0.97787 (19)	0.28174 (17)	0.57245 (9)	0.0569 (6)
F7	0.5062 (2)	−0.10547 (12)	0.61729 (9)	0.0539 (6)
F8	0.3044 (3)	−0.15540 (19)	0.54937 (11)	0.0903 (10)
F9	0.5315 (3)	−0.2408 (2)	0.55262 (12)	0.1229 (13)
F10	0.3038 (3)	−0.31014 (16)	0.59552 (11)	0.1034 (10)
F11	0.5076 (3)	−0.26059 (18)	0.66505 (11)	0.0897 (9)
F12	0.2818 (2)	−0.1733 (2)	0.66203 (12)	0.0942 (10)
N1	0.4964 (3)	−0.02873 (19)	0.44157 (11)	0.0281 (7)
N2	0.3604 (3)	0.21768 (18)	0.59222 (10)	0.0273 (7)
N3	0.6737 (3)	0.02687 (16)	0.68626 (9)	0.0188 (6)
N4	0.8145 (3)	−0.04765 (16)	0.59293 (10)	0.0192 (6)
O1	0.6184 (2)	0.01985 (15)	0.51831 (8)	0.0240 (5)
O2	0.4822 (2)	0.09465 (13)	0.60992 (9)	0.0232 (5)
O3	0.7822 (2)	0.01878 (17)	0.77070 (9)	0.0345 (6)
O4	0.9819 (2)	−0.14044 (14)	0.61644 (10)	0.0347 (6)
Sb1	0.82253 (2)	0.270184 (15)	0.619240 (9)	0.02832 (6)
Sb2	0.40579 (2)	−0.208325 (15)	0.607463 (10)	0.03231 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.037 (2)	0.032 (2)	0.0181 (19)	0.007 (2)	0.0039 (16)	0.0065 (17)
C2	0.046 (2)	0.056 (3)	0.0185 (18)	0.013 (2)	0.0007 (17)	−0.0003 (17)
C3	0.058 (3)	0.071 (3)	0.030 (2)	−0.024 (3)	−0.0164 (19)	0.002 (2)
C4	0.026 (2)	0.032 (2)	0.0195 (18)	−0.0009 (19)	0.0029 (15)	−0.0005 (17)
C5	0.046 (2)	0.073 (3)	0.043 (2)	0.040 (3)	0.0168 (18)	0.009 (2)
C6	0.051 (3)	0.034 (2)	0.051 (2)	0.017 (2)	−0.004 (2)	0.0040 (19)
C7	0.033 (2)	0.041 (2)	0.0115 (17)	−0.015 (2)	0.0025 (14)	0.0001 (16)
C8	0.065 (3)	0.048 (3)	0.032 (2)	−0.015 (2)	0.011 (2)	0.007 (2)
C9	0.046 (3)	0.061 (3)	0.026 (2)	−0.014 (2)	0.0115 (18)	−0.0117 (19)
C10	0.0221 (19)	0.028 (2)	0.0135 (16)	0.0001 (18)	−0.0008 (14)	−0.0016 (14)
C11	0.034 (2)	0.041 (2)	0.0223 (18)	0.004 (2)	0.0015 (17)	−0.0109 (16)
C12	0.025 (2)	0.032 (2)	0.0185 (18)	−0.0036 (18)	−0.0003 (14)	0.0049 (16)
C13	0.032 (2)	0.035 (2)	0.0219 (18)	0.005 (2)	−0.0057 (15)	0.0043 (16)
C14	0.066 (3)	0.047 (3)	0.032 (2)	0.014 (2)	0.000 (2)	0.0125 (19)
C15	0.039 (2)	0.072 (3)	0.027 (2)	0.015 (2)	−0.0120 (17)	−0.013 (2)
C16	0.025 (2)	0.0183 (18)	0.0286 (19)	−0.0002 (17)	0.0016 (15)	0.0023 (15)
C17	0.038 (2)	0.023 (2)	0.034 (2)	0.0064 (19)	0.0071 (17)	−0.0083 (17)
C18	0.020 (2)	0.023 (2)	0.0231 (18)	0.0025 (17)	0.0029 (13)	−0.0055 (15)
C19	0.034 (2)	0.030 (2)	0.0244 (19)	0.0044 (19)	0.0065 (15)	−0.0016 (16)
C20	0.046 (3)	0.038 (2)	0.044 (2)	−0.010 (2)	0.008 (2)	0.000 (2)
C21	0.042 (2)	0.050 (3)	0.036 (2)	0.000 (2)	0.0171 (18)	−0.004 (2)
Cu	0.0244 (2)	0.0223 (2)	0.01230 (19)	0.00190 (19)	0.00036 (16)	0.00085 (17)
F1	0.089 (2)	0.0442 (14)	0.0649 (17)	−0.0308 (14)	0.0121 (13)	−0.0198 (12)
F2	0.0860 (19)	0.0492 (16)	0.0727 (18)	0.0242 (14)	−0.0256 (14)	0.0122 (13)
F3	0.0603 (13)	0.0506 (15)	0.0704 (15)	−0.0135 (13)	0.0353 (12)	−0.0259 (12)
F4	0.0802 (17)	0.0779 (18)	0.0534 (14)	0.0076 (17)	−0.0219 (12)	0.0184 (15)
F5	0.0443 (13)	0.0282 (12)	0.0470 (13)	−0.0084 (10)	0.0141 (9)	−0.0097 (10)
F6	0.0401 (12)	0.0687 (18)	0.0618 (14)	−0.0192 (14)	0.0148 (10)	−0.0022 (14)
F7	0.0751 (15)	0.0443 (13)	0.0422 (14)	−0.0327 (11)	−0.0080 (12)	0.0008 (12)
F8	0.0765 (19)	0.108 (2)	0.0861 (19)	−0.0432 (18)	−0.0446 (16)	0.0576 (17)
F9	0.123 (2)	0.145 (3)	0.101 (2)	−0.017 (2)	0.0507 (19)	−0.077 (2)
F10	0.166 (3)	0.0594 (18)	0.085 (2)	−0.0660 (19)	−0.0287 (19)	0.0046 (15)
F11	0.097 (2)	0.068 (2)	0.105 (2)	0.0046 (16)	−0.0373 (16)	0.0335 (18)
F12	0.0541 (17)	0.135 (3)	0.094 (2)	−0.0123 (17)	0.0283 (14)	−0.028 (2)
N1	0.0313 (17)	0.0369 (19)	0.0161 (15)	0.0008 (16)	−0.0018 (13)	0.0025 (14)
N2	0.0270 (15)	0.0310 (17)	0.0238 (14)	0.0080 (16)	−0.0014 (11)	0.0036 (13)
N3	0.0200 (15)	0.0206 (15)	0.0159 (13)	−0.0055 (15)	0.0026 (12)	0.0018 (11)
N4	0.0227 (15)	0.0151 (14)	0.0197 (14)	0.0004 (14)	0.0028 (12)	0.0004 (11)
O1	0.0245 (14)	0.0312 (14)	0.0164 (12)	0.0012 (12)	−0.0031 (9)	−0.0015 (10)
O2	0.0267 (12)	0.0247 (12)	0.0184 (12)	0.0055 (10)	0.0031 (10)	0.0070 (11)
O3	0.0385 (15)	0.0518 (18)	0.0131 (12)	0.0099 (14)	−0.0065 (10)	−0.0055 (12)
O4	0.0393 (14)	0.0307 (14)	0.0340 (15)	0.0170 (12)	−0.0026 (12)	−0.0011 (13)
Sb1	0.03023 (13)	0.02309 (12)	0.03164 (13)	−0.00408 (12)	−0.00031 (11)	−0.00031 (11)
Sb2	0.04411 (15)	0.02205 (13)	0.03076 (13)	−0.00479 (12)	−0.00402 (11)	−0.00098 (11)

Geometric parameters (Å, º) top

C1—O1	1.245 (4)	C13—C14	1.540 (5)
C1—N1	1.300 (4)	C14—H14A	0.9800
C1—H1	0.9500	C14—H14B	0.9800
C2—N1	1.448 (4)	C14—H14C	0.9800
C2—H2A	0.9800	C15—H15A	0.9800
C2—H2B	0.9800	C15—H15B	0.9800
C2—H2C	0.9800	C15—H15C	0.9800
C3—N1	1.456 (4)	C16—N4	1.278 (4)
C3—H3A	0.9800	C16—O4	1.330 (4)
C3—H3B	0.9800	C17—O4	1.455 (4)
C3—H3C	0.9800	C17—C18	1.523 (4)
C4—O2	1.249 (4)	C17—H17A	0.9900
C4—N2	1.307 (4)	C17—H17B	0.9900
C4—H4	0.9500	C18—N4	1.489 (4)
C5—N2	1.450 (4)	C18—C19	1.529 (4)
C5—H5A	0.9800	C18—H18	1.0000
C5—H5B	0.9800	C19—C20	1.517 (4)
C5—H5C	0.9800	C19—C21	1.530 (4)
C6—N2	1.454 (4)	C19—H19	1.0000
C6—H6A	0.9800	C20—H20A	0.9800
C6—H6B	0.9800	C20—H20B	0.9800
C6—H6C	0.9800	C20—H20C	0.9800
C7—C10	1.521 (4)	C21—H21A	0.9800
C7—C8	1.526 (5)	C21—H21B	0.9800
C7—C9	1.540 (5)	C21—H21C	0.9800
C7—H7	1.0000	Cu—O2	1.951 (2)
C8—H8A	0.9800	Cu—N4	1.962 (2)
C8—H8B	0.9800	Cu—O1	1.964 (2)
C8—H8C	0.9800	Cu—N3	1.971 (2)
C9—H9A	0.9800	Cu—F7	2.4232 (18)
C9—H9B	0.9800	Cu—F5	2.5452 (19)
C9—H9C	0.9800	F1—Sb1	1.873 (2)
C10—N3	1.497 (4)	F2—Sb1	1.854 (2)
C10—C11	1.532 (4)	F3—Sb1	1.8560 (18)
C10—H10	1.0000	F4—Sb1	1.856 (2)
C11—O3	1.439 (4)	F5—Sb1	1.8822 (18)
C11—H11A	0.9900	F6—Sb1	1.8687 (19)
C11—H11B	0.9900	F7—Sb2	1.8613 (18)
C12—N3	1.268 (4)	F8—Sb2	1.855 (2)
C12—O3	1.343 (4)	F9—Sb2	1.832 (2)
C12—C13	1.503 (5)	F10—Sb2	1.863 (2)
C13—C16	1.504 (4)	F11—Sb2	1.844 (2)
C13—C15	1.536 (4)	F12—Sb2	1.828 (2)

O1—C1—N1	125.7 (3)	H17A—C17—H17B	109.0
O1—C1—H1	117.1	N4—C18—C17	101.4 (2)
N1—C1—H1	117.1	N4—C18—C19	110.0 (3)
N1—C2—H2A	109.5	C17—C18—C19	115.8 (3)
N1—C2—H2B	109.5	N4—C18—H18	109.7
H2A—C2—H2B	109.5	C17—C18—H18	109.7
N1—C2—H2C	109.5	C19—C18—H18	109.7
H2A—C2—H2C	109.5	C20—C19—C18	113.5 (3)
H2B—C2—H2C	109.5	C20—C19—C21	111.4 (3)
N1—C3—H3A	109.5	C18—C19—C21	110.4 (3)
N1—C3—H3B	109.5	C20—C19—H19	107.1
H3A—C3—H3B	109.5	C18—C19—H19	107.1
N1—C3—H3C	109.5	C21—C19—H19	107.1
H3A—C3—H3C	109.5	C19—C20—H20A	109.5
H3B—C3—H3C	109.5	C19—C20—H20B	109.5
O2—C4—N2	123.9 (3)	H20A—C20—H20B	109.5
O2—C4—H4	118.1	C19—C20—H20C	109.5
N2—C4—H4	118.1	H20A—C20—H20C	109.5
N2—C5—H5A	109.5	H20B—C20—H20C	109.5
N2—C5—H5B	109.5	C19—C21—H21A	109.5
H5A—C5—H5B	109.5	C19—C21—H21B	109.5
N2—C5—H5C	109.5	H21A—C21—H21B	109.5
H5A—C5—H5C	109.5	C19—C21—H21C	109.5
H5B—C5—H5C	109.5	H21A—C21—H21C	109.5
N2—C6—H6A	109.5	H21B—C21—H21C	109.5
N2—C6—H6B	109.5	O2—Cu—N4	179.10 (10)
H6A—C6—H6B	109.5	O2—Cu—O1	89.32 (9)
N2—C6—H6C	109.5	N4—Cu—O1	89.90 (9)
H6A—C6—H6C	109.5	O2—Cu—N3	89.86 (10)
H6B—C6—H6C	109.5	N4—Cu—N3	90.92 (10)
C10—C7—C8	114.1 (3)	O1—Cu—N3	179.05 (10)
C10—C7—C9	110.1 (3)	O2—Cu—F7	88.26 (8)
C8—C7—C9	110.8 (3)	N4—Cu—F7	92.21 (9)
C10—C7—H7	107.2	O1—Cu—F7	92.32 (8)
C8—C7—H7	107.2	N3—Cu—F7	87.16 (9)
C9—C7—H7	107.2	O2—Cu—F5	87.74 (8)
C7—C8—H8A	109.5	N4—Cu—F5	91.75 (8)
C7—C8—H8B	109.5	O1—Cu—F5	84.92 (8)
H8A—C8—H8B	109.5	N3—Cu—F5	95.54 (8)
C7—C8—H8C	109.5	F7—Cu—F5	175.16 (7)
H8A—C8—H8C	109.5	Sb1—F5—Cu	138.67 (9)
H8B—C8—H8C	109.5	Sb2—F7—Cu	164.27 (12)
C7—C9—H9A	109.5	C1—N1—C2	120.1 (3)
C7—C9—H9B	109.5	C1—N1—C3	123.0 (3)
H9A—C9—H9B	109.5	C2—N1—C3	116.8 (3)
C7—C9—H9C	109.5	C4—N2—C5	120.0 (3)
H9A—C9—H9C	109.5	C4—N2—C6	121.7 (3)
H9B—C9—H9C	109.5	C5—N2—C6	117.9 (3)
N3—C10—C7	110.8 (3)	C12—N3—C10	107.3 (2)
N3—C10—C11	100.4 (2)	C12—N3—Cu	127.3 (2)
C7—C10—C11	115.0 (3)	C10—N3—Cu	125.2 (2)
N3—C10—H10	110.1	C16—N4—C18	107.3 (3)
C7—C10—H10	110.1	C16—N4—Cu	127.6 (2)
C11—C10—H10	110.1	C18—N4—Cu	125.06 (19)
O3—C11—C10	104.2 (2)	C1—O1—Cu	122.6 (2)
O3—C11—H11A	110.9	C4—O2—Cu	123.9 (2)
C10—C11—H11A	110.9	C12—O3—C11	105.4 (2)
O3—C11—H11B	110.9	C16—O4—C17	106.0 (2)
C10—C11—H11B	110.9	F2—Sb1—F3	90.45 (11)
H11A—C11—H11B	108.9	F2—Sb1—F4	177.53 (11)
N3—C12—O3	117.2 (3)	F3—Sb1—F4	90.55 (10)
N3—C12—C13	129.8 (3)	F2—Sb1—F6	88.91 (11)
O3—C12—C13	112.9 (3)	F3—Sb1—F6	178.42 (10)
C12—C13—C16	113.1 (3)	F4—Sb1—F6	90.03 (10)
C12—C13—C15	108.7 (3)	F2—Sb1—F1	91.46 (11)
C16—C13—C15	107.4 (3)	F3—Sb1—F1	91.31 (9)
C12—C13—C14	108.8 (3)	F4—Sb1—F1	90.78 (11)
C16—C13—C14	108.7 (3)	F6—Sb1—F1	90.14 (10)
C15—C13—C14	110.2 (3)	F2—Sb1—F5	88.61 (10)
C13—C14—H14A	109.5	F3—Sb1—F5	88.92 (8)
C13—C14—H14B	109.5	F4—Sb1—F5	89.16 (10)
H14A—C14—H14B	109.5	F6—Sb1—F5	89.63 (9)
C13—C14—H14C	109.5	F1—Sb1—F5	179.76 (10)
H14A—C14—H14C	109.5	F12—Sb2—F9	178.67 (15)
H14B—C14—H14C	109.5	F12—Sb2—F11	88.77 (13)
C13—C15—H15A	109.5	F9—Sb2—F11	91.63 (14)
C13—C15—H15B	109.5	F12—Sb2—F8	91.47 (13)
H15A—C15—H15B	109.5	F9—Sb2—F8	88.12 (14)
C13—C15—H15C	109.5	F11—Sb2—F8	179.62 (12)
H15A—C15—H15C	109.5	F12—Sb2—F7	90.88 (11)
H15B—C15—H15C	109.5	F9—Sb2—F7	87.85 (12)
N4—C16—O4	117.1 (3)	F11—Sb2—F7	89.62 (11)
N4—C16—C13	129.4 (3)	F8—Sb2—F7	90.09 (10)
O4—C16—C13	113.5 (3)	F12—Sb2—F10	89.71 (13)
O4—C17—C18	103.9 (2)	F9—Sb2—F10	91.55 (14)
O4—C17—H17A	111.0	F11—Sb2—F10	91.94 (12)
C18—C17—H17A	111.0	F8—Sb2—F10	88.36 (12)
O4—C17—H17B	111.0	F7—Sb2—F10	178.35 (11)
C18—C17—H17B	111.0

C8—C7—C10—N3	59.8 (3)	F7—Cu—N3—C12	97.1 (3)
C9—C7—C10—N3	−174.9 (3)	F5—Cu—N3—C12	−86.9 (3)
C8—C7—C10—C11	−53.1 (4)	O2—Cu—N3—C10	0.8 (2)
C9—C7—C10—C11	72.1 (4)	N4—Cu—N3—C10	−179.7 (2)
N3—C10—C11—O3	−22.7 (3)	F7—Cu—N3—C10	−87.5 (2)
C7—C10—C11—O3	96.3 (3)	F5—Cu—N3—C10	88.5 (2)
N3—C12—C13—C16	9.9 (5)	O4—C16—N4—C18	−8.3 (4)
O3—C12—C13—C16	−173.6 (3)	C13—C16—N4—C18	169.4 (3)
N3—C12—C13—C15	129.1 (4)	O4—C16—N4—Cu	168.4 (2)
O3—C12—C13—C15	−54.4 (4)	C13—C16—N4—Cu	−13.8 (5)
N3—C12—C13—C14	−110.9 (4)	C17—C18—N4—C16	17.6 (3)
O3—C12—C13—C14	65.6 (4)	C19—C18—N4—C16	−105.6 (3)
C12—C13—C16—N4	5.2 (5)	C17—C18—N4—Cu	−159.3 (2)
C15—C13—C16—N4	−114.8 (4)	C19—C18—N4—Cu	77.5 (3)
C14—C13—C16—N4	126.0 (4)	O1—Cu—N4—C16	−171.4 (3)
C12—C13—C16—O4	−177.0 (3)	N3—Cu—N4—C16	8.1 (3)
C15—C13—C16—O4	63.0 (4)	F7—Cu—N4—C16	−79.1 (3)
C14—C13—C16—O4	−56.2 (4)	F5—Cu—N4—C16	103.7 (3)
O4—C17—C18—N4	−20.0 (3)	O1—Cu—N4—C18	4.8 (2)
O4—C17—C18—C19	99.0 (3)	N3—Cu—N4—C18	−175.7 (2)
N4—C18—C19—C20	59.9 (4)	F7—Cu—N4—C18	97.1 (2)
C17—C18—C19—C20	−54.3 (4)	F5—Cu—N4—C18	−80.1 (2)
N4—C18—C19—C21	−174.2 (3)	N1—C1—O1—Cu	−169.4 (3)
C17—C18—C19—C21	71.6 (4)	O2—Cu—O1—C1	−61.1 (3)
O2—Cu—F5—Sb1	62.36 (16)	N4—Cu—O1—C1	119.4 (3)
N4—Cu—F5—Sb1	−118.37 (16)	F7—Cu—O1—C1	27.2 (3)
O1—Cu—F5—Sb1	151.89 (16)	F5—Cu—O1—C1	−148.9 (3)
N3—Cu—F5—Sb1	−27.28 (17)	N2—C4—O2—Cu	−168.2 (2)
O2—Cu—F7—Sb2	106.6 (4)	O1—Cu—O2—C4	−50.1 (2)
N4—Cu—F7—Sb2	−72.7 (4)	N3—Cu—O2—C4	130.4 (3)
O1—Cu—F7—Sb2	17.3 (4)	F7—Cu—O2—C4	−142.4 (3)
N3—Cu—F7—Sb2	−163.5 (4)	F5—Cu—O2—C4	34.9 (2)
O1—C1—N1—C2	−0.3 (5)	N3—C12—O3—C11	−9.1 (4)
O1—C1—N1—C3	179.5 (3)	C13—C12—O3—C11	173.9 (3)
O2—C4—N2—C5	3.6 (5)	C10—C11—O3—C12	20.0 (3)
O2—C4—N2—C6	176.4 (3)	N4—C16—O4—C17	−5.6 (4)
O3—C12—N3—C10	−6.7 (4)	C13—C16—O4—C17	176.3 (3)
C13—C12—N3—C10	169.7 (3)	C18—C17—O4—C16	16.4 (3)
O3—C12—N3—Cu	169.3 (2)	Cu—F5—Sb1—F2	−116.14 (16)
C13—C12—N3—Cu	−14.2 (5)	Cu—F5—Sb1—F3	−25.67 (15)
C7—C10—N3—C12	−103.8 (3)	Cu—F5—Sb1—F4	64.90 (15)
C11—C10—N3—C12	18.2 (3)	Cu—F5—Sb1—F6	154.94 (15)
C7—C10—N3—Cu	80.0 (3)	Cu—F7—Sb2—F12	−145.8 (4)
C11—C10—N3—Cu	−158.0 (2)	Cu—F7—Sb2—F9	33.8 (4)
O2—Cu—N3—C12	−174.6 (3)	Cu—F7—Sb2—F11	125.5 (4)
N4—Cu—N3—C12	4.9 (3)	Cu—F7—Sb2—F8	−54.3 (4)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₅H₂₆N₂O₂)(C₃H₇NO)₂][SbF₆]₂
M_r	947.61
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	9.7256 (2), 15.2444 (3), 23.2040 (5)
V (Å³)	3440.25 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.27
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Diffraction Xcalibur S CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.820, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	41873, 7479, 6078
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.037, 1.04
No. of reflections	7479
No. of parameters	407
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.52
Absolute structure	Flack (1983), 3264 Friedel pairs
Absolute structure parameter	−0.008 (10)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Cu—O2	1.951 (2)	Cu—N3	1.971 (2)
Cu—N4	1.962 (2)	Cu—F7	2.4232 (18)
Cu—O1	1.964 (2)	Cu—F5	2.5452 (19)

N4—Cu—N3	90.92 (10)	Sb2—F7—Cu	164.27 (12)
Sb1—F5—Cu	138.67 (9)

References

Abraham, L., Czerwonka, R. & Hiersemann, M. (2001). Angew. Chem. Int. Ed. 40, 4700–4703. Web of Science CrossRef CAS Google Scholar
Abraham, L. & Hiersemann, M. (2001). Org. Lett. 3, 48–52. Google Scholar
Abraham, L., Körner, M. & Hiersemann, M. (2004). Adv. Synth. Catal. 346, 1281–1294. Web of Science CSD CrossRef CAS Google Scholar
Evans, D. A., Peterson, G. S., Johnson, J. S., Barnes, D. M., Campos, K. R. & Woerpel, K. A. (1998). J. Org. Chem. 63, 4541–4544. Web of Science CSD CrossRef CAS Google Scholar
Evans, D. A., Woerpel, K. A., Hinman, M. M. & Faul, M. M. (1991). J. Am. Chem. Soc. 113, 726–728. CrossRef CAS Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hiersemann, M. & Abraham, L. (2002). Eur. J. Org. Chem. pp. 1461–1471. CrossRef Google Scholar
Körner, M. & Hiersemann, M. (2007). Org. Lett. 9, 4979–4982. Web of Science PubMed Google Scholar
McKennon, M. J., Meyers, A. I., Drauz, K. & Schwarm, M. (1993). J. Org. Chem. 58, 3568–3571. CrossRef CAS Web of Science Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Pollex, A. & Hiersemann, M. (2005). Org. Lett. 7, 5705–5708. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.