Bis{2-[(diisopropyl­phosphan­yl)amino]­pyridine-κ2N1,P}copper(I) hexa­fluorido­phosphate

Öztopcu, Ö.; Kirchner, K.; Mereiter, K.

doi:10.1107/S1600536810020283

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m729-m730

doi:10.1107/S1600536810020283

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Bis{2-[(diisopropylphosphanyl)amino]pyridine-κ²N¹,P}copper(I) hexafluoridophosphate

Özgür Öztopcu,^a Karl Kirchner ^a and Kurt Mereiter ^b ^*

^aInstitute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, A-1060 Vienna, Austria, and ^bInstitute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 1 May 2010; accepted 28 May 2010; online 5 June 2010)

The crystal structure of the title compound, [Cu(C₁₁H₁₉N₂P)₂]PF₆, is composed of discrete [Cu(PN-iPr)₂]⁺ cations [PN-iPr is 2-(diisopropylphosphanylamino)pyridine] and PF₆⁻ anions. The Cu(I) atom is bis-chelated by two independent PN-iPr ligands. It has a distorted tetrahedral coordination by two P atoms [Cu—P = 2.2277 (4) and 2.2257 (4) Å] and two pyridine N atoms [Cu—N = 2.0763 (11) and 2.0845 (12) Å]. Bond angles about Cu vary from 85.11 (3) (P—Cu—N) to 130.37 (2)° (P—Cu—P). In the crystal, N—H⋯F hydrogen bonds link the Cu complexes and the PF₆⁻ anions into continuous chains, which show a cross-bedded spatial arrangement. In addition, several weaker C—H⋯F interactions contribute to the coherence of the structure.

Related literature

For the synthesis and crystal structures of PN-complexes [PN are 2-(phosphanylamino)pyridines], see: Aucott et al. (2000 ); Benito-Garagorri, Mereiter & Kirchner (2007 ); Standfest-Hauser et al. (2009 ). For applications of PN-complexes in catalysis, see: Aguirre et al. (2007 ); Benito-Garagorri, Wiedermann et al. (2007 ). For the chemistry and crystal structures of related PNP-complexes [PNP = 2,6-bis(phosphanylamino)pyridine], see: Benito-Garagorri et al. (2006 ). For crystal structures of other related Cu(I) complexes, see: Hursthouse et al. (2003 ); Healy (2008 ).

Experimental

Crystal data

[Cu(C₁₁H₁₉N₂P)₂]PF₆
M_r = 629.01
Monoclinic, P n
a = 11.0357 (13) Å
b = 9.2129 (11) Å
c = 14.4282 (17) Å
β = 96.723 (1)°
V = 1456.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 100 K
0.45 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.65, T_max = 0.75
21170 measured reflections
8422 independent reflections
8187 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.054
S = 1.02
8422 reflections
334 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ), 4180 Friedel pairs, merohedral twin with twin proportions refined
Flack parameter: 0.410 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯F1ⁱ	0.88	2.24	3.1038 (15)	167
N4—H4N⋯F3ⁱⁱ	0.88	2.26	3.1185 (16)	167
C2—H2⋯F4ⁱ	0.95	2.41	3.306 (2)	158
C20—H20⋯F4	1.00	2.53	3.502 (2)	164
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT, SADABS and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020283/zs2038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020283/zs2038Isup2.hkl

checkCIF report

Comment top

Heterobidentate pyridylphosphane ligands (PN-ligands) in which 2-pyridyl and phosphane moieties are linked by an amino group as spacer are of interest in organometallic chemistry because they contain both hard (nitrogen) and soft (phosphorus) donor atoms at P—N distances of about 3 Å, very suitable for the chelation of transition metals. Moreover, they are readily accessible in a modular fashion via the ease of phosphane-nitrogen bond-forming reactions (e.g. Benito-Garagorri et al., 2006). Some transition metal complexes of these ligands, mainly with diphenylphosphane moieties, are catalytically active and have been applied for carbonylation of olefins and other transformations (Aguirre et al., 2007; Benito-Garagorri, Wiedermann et al., 2007). In continuation of earlier work on Ni(II), Pd(II), and Mo(0/II)-complexes of such ligands (Benito-Garagorri, Mereiter & Kirchner, 2007; Standfest-Hauser et al., 2009) we recently focused on Cu(I) complexes and report here the synthesis and crystal structure of the title compound [Cu(PN-iPr)₂]PF₆. A view of the asymmetric unit is shown in Fig. 1. Copper is bis-chelated by two independent PN-iPr ligands and adopts a strongly distorted tetrahedral coordination by two P and two N atoms with well-balanced bond distances of Cu1—P1 = 2.2277 (4) Å, Cu1—P2 = 2.2257 (4) Å, Cu1—N1 = 2.0763 (11) Å, and Cu1—N3 = 2.0845 (12) Å. Bond angles about Cu vary from ca. 85° for the two bite angles P1—Cu1—N1 and P2—Cu1—N3 to 130.37 (2)° for P1—Cu1—P2. The twist angle between the planes P1—Cu1—P2 and N1—Cu—N3 is 60.50 (3)° and thus about 30° off from 90°, the value for an ideal undistorted coordination tetrahedron. The complex approaches a molecular non-crystallographic C₂ symmetry, which makes both PN-iPr ligands pseudo-equivalent; this includes also the isopropyl groups and their orientations (Fig. 1). A Cu(I)(PN)₂ complex closely related in ligand characteristics to that of the title compound was reported for bis(6-chloro-2-(diphenylphosphinoamino)benzothiazole)copper(I) hexafluoridophosphate (Hursthouse et al., 2003); it has Cu—P ≈ 2.26 Å, Cu—N ≈ 2.06 Å, and a twist angle P—Cu—P vs. N—Cu—N of 63.2°. Cu(I) complexes with separate non-chelating two P- and two N-ligands have generally more regular CuP₂N₂ tetrahedra with twist angles P—Cu—P vs. N—Cu—N near 90°, e.g. bis(pyridine)-bis(triphenylphosphane)copper(I) tetrafluoridoborate (Healy, 2008).

A characteristic feature of PN-iPr ligands and their homologues is the acidity of the N—H bond (here N2—H2N and N4—H4N), which is a good hydrogen bond donor. In the title compound each NH group is hydrogen bonded to the F-atom of an adjacent PF₆ octahedron at N···F distances of ca. 3.1 Å (Table 1). These hydrogen bonds link the cation and anion complexes into infinite chains, which extend parallel to [110] at z ≈ 0.15 and parallel to [110] at z ≈ 0.65 resulting in a cross-bedded arangement (Fig. 2). Several weaker C—H···F interactions contribute to the coherence of the structure. The most significant two of them with H···F < 2.6 Å are included in Table 1, seven more have H···F distances in the range 2.60 to 2.70 Å.

Related literature top

For the synthesis and crystal structures of PN-complexes [PN are 2-(phosphanylamino)pyridines], see: Aucott et al. (2000); Benito-Garagorri, Mereiter & Kirchner (2007); Standfest-Hauser et al. (2009). For applications of PN-complexes in catalysis, see: Aguirre et al. (2007); Benito-Garagorri, Wiedermann et al. (2007). For the chemistry and crystal structures of related PNP-complexes [PNP = 2,6-bis(phosphanylamino)pyridine], see: Benito-Garagorri et al. (2006). For crystal structures of other related Cu(I) complexes, see: Hursthouse et al. (2003); Healy (2008).

Experimental top

To a solution of [Cu(CH₃CN)₄]PF₆ (100 mg, 0.27 mmol) in THF (10 ml) 2-(diisopropylphosphanylamino)pyridine (PN-iPr; 112.8 mg, 0.54 mmol; for synthesis, see: Benito-Garagorri, Mereiter & Kirchner, 2007) was added and the solution was stirred for 12 h. After removal of the solvent a white powder was obtained which was washed with Et₂O and dried under vacuum. Yield: 100 mg (89%). ¹H-NMR (δ, acetone, 20 °C): 7.83 (s, 1H, py), 7.69 (s, 1H, py), 7.23 (s, 1H, py), 7.06 (s, 1H, py), 6.78 (s, 1H, NH), 2.90 (s, 2H, CH), 1.22 (s, 12H, CH₃). ³¹P{¹H} NMR (δ, acetone, 20 °C): 50.53. Colourless crystals for X-ray diffraction were obtained by evaporation crystallization from acetone.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT, SADABS and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. The red broken line shows one of the C—H···F interactions listed in Table 1.
	Fig. 2. Packing diagram of (I) showing two N—H···F hydrogen bonded chains of [Cu(PN-iPr)₂]⁺ cations and PF₆^- anions. Upper chain extends parallel to [110], lower chain parallel to [110], C-bonded H atoms omitted for clarity.

Bis{2-[(diisopropylphosphanyl)amino]pyridine-κ²N¹,P}copper(I) hexafluoridophosphate top

Crystal data top

[Cu(C₁₁H₁₉N₂P)₂]PF₆	F(000) = 652
M_r = 629.01	D_x = 1.434 Mg m⁻³
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 9966 reflections
a = 11.0357 (13) Å	θ = 2.5–30.0°
b = 9.2129 (11) Å	µ = 0.97 mm⁻¹
c = 14.4282 (17) Å	T = 100 K
β = 96.723 (1)°	Block, colourless
V = 1456.8 (3) Å³	0.45 × 0.22 × 0.20 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	8422 independent reflections
Radiation source: fine-focus sealed tube	8187 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
T_min = 0.65, T_max = 0.75	k = −12→12
21170 measured reflections	l = −20→20

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)] = 0.021	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0327P)² + 0.1922P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
8422 reflections	Δρ_max = 0.35 e Å⁻³
334 parameters	Δρ_min = −0.26 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 4180 Friedel pairs, merohedral twin with twin proportions refined
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.410 (4)

Crystal data top

[Cu(C₁₁H₁₉N₂P)₂]PF₆	V = 1456.8 (3) Å³
M_r = 629.01	Z = 2
Monoclinic, Pn	Mo Kα radiation
a = 11.0357 (13) Å	µ = 0.97 mm⁻¹
b = 9.2129 (11) Å	T = 100 K
c = 14.4282 (17) Å	0.45 × 0.22 × 0.20 mm
β = 96.723 (1)°

Data collection top

Bruker APEXII CCD diffractometer	8422 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	8187 reflections with I > 2σ(I)
T_min = 0.65, T_max = 0.75	R_int = 0.021
21170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.054	Δρ_max = 0.35 e Å⁻³
S = 1.02	Δρ_min = −0.26 e Å⁻³
8422 reflections	Absolute structure: Flack (1983), 4180 Friedel pairs, merohedral twin with twin proportions refined
334 parameters	Absolute structure parameter: 0.410 (4)
2 restraints

Special details top

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

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
Cu1	0.545130 (11)	0.141471 (15)	0.626623 (10)	0.01477 (4)
P1	0.38719 (3)	0.26283 (4)	0.55383 (2)	0.01685 (6)
P2	0.72626 (3)	0.09024 (3)	0.58123 (2)	0.01465 (6)
N1	0.50957 (10)	0.25486 (12)	0.74483 (8)	0.0155 (2)
N2	0.34515 (12)	0.35253 (13)	0.64884 (8)	0.0209 (2)
H2N	0.2830	0.4129	0.6411	0.025*
N3	0.54844 (10)	−0.07232 (12)	0.67416 (8)	0.0168 (2)
N4	0.74461 (10)	−0.07879 (12)	0.62954 (8)	0.0180 (2)
H4N	0.8145	−0.1241	0.6281	0.022*
C1	0.40583 (12)	0.33308 (14)	0.73755 (9)	0.0164 (2)
C2	0.36015 (13)	0.39407 (15)	0.81595 (10)	0.0198 (2)
H2	0.2852	0.4459	0.8095	0.024*
C3	0.42655 (14)	0.37681 (15)	0.90213 (10)	0.0215 (3)
H3	0.3978	0.4173	0.9560	0.026*
C4	0.53606 (13)	0.29988 (15)	0.91019 (9)	0.0207 (3)
H4	0.5842	0.2893	0.9688	0.025*
C5	0.57229 (12)	0.23970 (14)	0.83056 (9)	0.0178 (2)
H5	0.6455	0.1844	0.8362	0.021*
C6	0.24294 (13)	0.18007 (18)	0.50231 (11)	0.0249 (3)
H6	0.1814	0.2584	0.4860	0.030*
C7	0.26381 (16)	0.0977 (2)	0.41411 (12)	0.0325 (3)
H7A	0.3187	0.0157	0.4304	0.049*
H7B	0.3005	0.1629	0.3715	0.049*
H7C	0.1856	0.0616	0.3836	0.049*
C8	0.19540 (16)	0.0774 (3)	0.57232 (13)	0.0435 (5)
H8A	0.2568	0.0027	0.5906	0.065*
H8B	0.1201	0.0311	0.5439	0.065*
H8C	0.1786	0.1321	0.6276	0.065*
C9	0.41591 (14)	0.40856 (16)	0.47148 (10)	0.0228 (3)
H9	0.4234	0.3609	0.4101	0.027*
C10	0.53711 (19)	0.4818 (2)	0.50186 (15)	0.0423 (4)
H10A	0.5560	0.5500	0.4535	0.063*
H10B	0.6015	0.4082	0.5114	0.063*
H10C	0.5322	0.5344	0.5603	0.063*
C11	0.3130 (2)	0.5190 (3)	0.45456 (15)	0.0473 (5)
H11A	0.3089	0.5764	0.5113	0.071*
H11B	0.2354	0.4682	0.4383	0.071*
H11C	0.3285	0.5835	0.4032	0.071*
C12	0.65306 (12)	−0.14630 (13)	0.67082 (9)	0.0161 (2)
C13	0.67045 (13)	−0.28684 (15)	0.70895 (11)	0.0218 (3)
H13	0.7447	−0.3376	0.7055	0.026*
C14	0.57773 (14)	−0.34880 (15)	0.75124 (12)	0.0269 (3)
H14	0.5874	−0.4432	0.7775	0.032*
C15	0.46883 (14)	−0.27208 (17)	0.75539 (12)	0.0280 (3)
H15	0.4039	−0.3128	0.7846	0.034*
C16	0.45880 (13)	−0.13615 (15)	0.71590 (11)	0.0220 (3)
H16	0.3848	−0.0843	0.7181	0.026*
C17	0.87311 (12)	0.17551 (15)	0.62197 (10)	0.0195 (2)
H17	0.9400	0.1074	0.6099	0.023*
C18	0.88851 (16)	0.31683 (17)	0.56853 (12)	0.0278 (3)
H18A	0.8217	0.3834	0.5778	0.042*
H18B	0.8871	0.2955	0.5019	0.042*
H18C	0.9666	0.3620	0.5918	0.042*
C19	0.88143 (15)	0.20342 (19)	0.72714 (10)	0.0278 (3)
H19A	0.9629	0.2401	0.7497	0.042*
H19B	0.8667	0.1126	0.7594	0.042*
H19C	0.8200	0.2754	0.7396	0.042*
C20	0.73108 (13)	0.05665 (15)	0.45568 (9)	0.0205 (2)
H20	0.7185	0.1517	0.4224	0.025*
C21	0.62513 (16)	−0.0434 (2)	0.41957 (11)	0.0319 (3)
H21A	0.6225	−0.0543	0.3518	0.048*
H21B	0.5482	−0.0012	0.4344	0.048*
H21C	0.6369	−0.1387	0.4494	0.048*
C22	0.85233 (15)	−0.00667 (18)	0.43271 (11)	0.0284 (3)
H22A	0.8741	−0.0907	0.4729	0.043*
H22B	0.9163	0.0672	0.4434	0.043*
H22C	0.8441	−0.0371	0.3672	0.043*
P3	0.55962 (3)	0.31567 (4)	0.21299 (3)	0.01976 (7)
F1	0.62918 (10)	0.43352 (14)	0.15595 (8)	0.0398 (3)
F2	0.48767 (9)	0.20025 (11)	0.26926 (7)	0.0333 (2)
F3	0.46624 (12)	0.28652 (18)	0.12151 (7)	0.0542 (4)
F4	0.65102 (12)	0.34760 (14)	0.30470 (9)	0.0516 (4)
F5	0.64776 (15)	0.19392 (16)	0.18453 (16)	0.0785 (6)
F6	0.47085 (12)	0.43906 (12)	0.24247 (9)	0.0434 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01443 (6)	0.01369 (7)	0.01602 (7)	0.00390 (6)	0.00110 (5)	−0.00054 (6)
P1	0.01635 (13)	0.01949 (15)	0.01425 (13)	0.00588 (12)	−0.00017 (11)	−0.00045 (12)
P2	0.01461 (13)	0.01342 (14)	0.01588 (14)	0.00242 (11)	0.00163 (10)	0.00086 (11)
N1	0.0170 (5)	0.0150 (5)	0.0149 (5)	0.0012 (4)	0.0026 (4)	0.0010 (4)
N2	0.0227 (5)	0.0232 (6)	0.0166 (5)	0.0126 (4)	0.0011 (4)	0.0002 (4)
N3	0.0160 (5)	0.0143 (5)	0.0201 (5)	0.0010 (4)	0.0017 (4)	−0.0007 (4)
N4	0.0152 (5)	0.0154 (5)	0.0236 (5)	0.0045 (4)	0.0031 (4)	0.0051 (4)
C1	0.0191 (6)	0.0135 (5)	0.0166 (6)	0.0022 (4)	0.0026 (4)	0.0003 (4)
C2	0.0250 (6)	0.0142 (6)	0.0215 (6)	0.0028 (5)	0.0086 (5)	−0.0007 (5)
C3	0.0300 (7)	0.0174 (6)	0.0184 (6)	−0.0044 (5)	0.0088 (5)	−0.0032 (5)
C4	0.0262 (6)	0.0211 (6)	0.0148 (5)	−0.0068 (5)	0.0019 (5)	0.0010 (5)
C5	0.0181 (5)	0.0168 (6)	0.0181 (6)	−0.0018 (4)	0.0009 (4)	0.0024 (4)
C6	0.0180 (6)	0.0313 (7)	0.0239 (7)	0.0052 (5)	−0.0038 (5)	−0.0009 (6)
C7	0.0363 (8)	0.0344 (8)	0.0256 (7)	−0.0071 (7)	−0.0008 (6)	−0.0060 (6)
C8	0.0217 (7)	0.0752 (15)	0.0336 (9)	−0.0164 (8)	0.0036 (6)	0.0046 (9)
C9	0.0270 (7)	0.0248 (7)	0.0162 (6)	0.0058 (5)	0.0010 (5)	0.0019 (5)
C10	0.0443 (10)	0.0269 (8)	0.0513 (11)	−0.0091 (7)	−0.0123 (8)	0.0144 (8)
C11	0.0472 (11)	0.0484 (12)	0.0475 (11)	0.0239 (9)	0.0106 (9)	0.0275 (9)
C12	0.0150 (5)	0.0146 (5)	0.0182 (6)	0.0005 (4)	0.0000 (4)	−0.0010 (4)
C13	0.0204 (6)	0.0139 (6)	0.0304 (7)	0.0019 (5)	0.0007 (5)	0.0021 (5)
C14	0.0256 (7)	0.0151 (6)	0.0399 (9)	−0.0017 (5)	0.0038 (6)	0.0056 (6)
C15	0.0242 (7)	0.0209 (7)	0.0406 (8)	−0.0029 (5)	0.0105 (6)	0.0057 (6)
C16	0.0175 (6)	0.0200 (6)	0.0290 (7)	0.0006 (5)	0.0056 (5)	0.0007 (5)
C17	0.0178 (6)	0.0192 (6)	0.0216 (6)	−0.0013 (5)	0.0020 (5)	0.0007 (5)
C18	0.0316 (7)	0.0235 (7)	0.0287 (7)	−0.0067 (6)	0.0056 (6)	0.0017 (6)
C19	0.0268 (7)	0.0336 (8)	0.0217 (7)	−0.0065 (6)	−0.0034 (5)	−0.0007 (6)
C20	0.0250 (6)	0.0197 (6)	0.0169 (6)	0.0061 (5)	0.0024 (5)	0.0005 (5)
C21	0.0324 (8)	0.0368 (9)	0.0251 (7)	0.0005 (7)	−0.0024 (6)	−0.0088 (6)
C22	0.0309 (7)	0.0307 (8)	0.0253 (6)	0.0071 (6)	0.0104 (6)	−0.0018 (6)
P3	0.01635 (14)	0.02039 (15)	0.02286 (16)	−0.00373 (12)	0.00365 (12)	−0.00201 (13)
F1	0.0306 (5)	0.0534 (7)	0.0353 (5)	−0.0215 (5)	0.0030 (4)	0.0106 (5)
F2	0.0329 (5)	0.0303 (5)	0.0366 (5)	−0.0113 (4)	0.0039 (4)	0.0085 (4)
F3	0.0530 (7)	0.0899 (10)	0.0193 (4)	−0.0476 (7)	0.0026 (4)	−0.0051 (5)
F4	0.0451 (7)	0.0571 (8)	0.0453 (7)	−0.0261 (6)	−0.0252 (5)	0.0224 (6)
F5	0.0594 (9)	0.0427 (8)	0.1435 (17)	0.0108 (7)	0.0543 (10)	−0.0213 (9)
F6	0.0505 (6)	0.0329 (6)	0.0500 (6)	0.0158 (5)	0.0188 (5)	0.0059 (5)

Geometric parameters (Å, º) top

Cu1—N1	2.0763 (11)	C10—H10A	0.9800
Cu1—N3	2.0845 (12)	C10—H10B	0.9800
Cu1—P2	2.2257 (4)	C10—H10C	0.9800
Cu1—P1	2.2277 (4)	C11—H11A	0.9800
P1—N2	1.7107 (12)	C11—H11B	0.9800
P1—C6	1.8415 (16)	C11—H11C	0.9800
P1—C9	1.8446 (15)	C12—C13	1.4112 (18)
P2—N4	1.7084 (12)	C13—C14	1.375 (2)
P2—C17	1.8347 (14)	C13—H13	0.9500
P2—C20	1.8446 (14)	C14—C15	1.401 (2)
N1—C1	1.3464 (16)	C14—H14	0.9500
N1—C5	1.3521 (16)	C15—C16	1.375 (2)
N2—C1	1.3850 (17)	C15—H15	0.9500
N2—H2N	0.8800	C16—H16	0.9500
N3—C12	1.3464 (16)	C17—C19	1.531 (2)
N3—C16	1.3516 (18)	C17—C18	1.533 (2)
N4—C12	1.3795 (17)	C17—H17	1.0000
N4—H4N	0.8800	C18—H18A	0.9800
C1—C2	1.4080 (18)	C18—H18B	0.9800
C2—C3	1.377 (2)	C18—H18C	0.9800
C2—H2	0.9500	C19—H19A	0.9800
C3—C4	1.394 (2)	C19—H19B	0.9800
C3—H3	0.9500	C19—H19C	0.9800
C4—C5	1.3766 (19)	C20—C22	1.531 (2)
C4—H4	0.9500	C20—C21	1.531 (2)
C5—H5	0.9500	C20—H20	1.0000
C6—C8	1.522 (3)	C21—H21A	0.9800
C6—C7	1.522 (2)	C21—H21B	0.9800
C6—H6	1.0000	C21—H21C	0.9800
C7—H7A	0.9800	C22—H22A	0.9800
C7—H7B	0.9800	C22—H22B	0.9800
C7—H7C	0.9800	C22—H22C	0.9800
C8—H8A	0.9800	P3—F5	1.5704 (13)
C8—H8B	0.9800	P3—F6	1.5907 (11)
C8—H8C	0.9800	P3—F4	1.5944 (12)
C9—C10	1.516 (2)	P3—F3	1.5993 (11)
C9—C11	1.523 (2)	P3—F2	1.6036 (10)
C9—H9	1.0000	P3—F1	1.6103 (11)

N1—Cu1—N3	101.70 (4)	H10B—C10—H10C	109.5
N1—Cu1—P2	127.66 (3)	C9—C11—H11A	109.5
N3—Cu1—P2	85.11 (3)	C9—C11—H11B	109.5
N1—Cu1—P1	85.53 (3)	H11A—C11—H11B	109.5
N3—Cu1—P1	127.73 (3)	C9—C11—H11C	109.5
P2—Cu1—P1	130.374 (15)	H11A—C11—H11C	109.5
N2—P1—C6	102.75 (7)	H11B—C11—H11C	109.5
N2—P1—C9	104.34 (7)	N3—C12—N4	117.49 (12)
C6—P1—C9	104.30 (7)	N3—C12—C13	121.91 (12)
N2—P1—Cu1	97.78 (4)	N4—C12—C13	120.59 (12)
C6—P1—Cu1	125.04 (5)	C14—C13—C12	118.66 (13)
C9—P1—Cu1	119.02 (5)	C14—C13—H13	120.7
N4—P2—C17	101.62 (6)	C12—C13—H13	120.7
N4—P2—C20	103.42 (6)	C13—C14—C15	119.73 (13)
C17—P2—C20	105.10 (6)	C13—C14—H14	120.1
N4—P2—Cu1	98.10 (4)	C15—C14—H14	120.1
C17—P2—Cu1	127.23 (5)	C16—C15—C14	118.00 (13)
C20—P2—Cu1	117.04 (5)	C16—C15—H15	121.0
C1—N1—C5	117.79 (11)	C14—C15—H15	121.0
C1—N1—Cu1	116.49 (9)	N3—C16—C15	123.59 (13)
C5—N1—Cu1	125.01 (9)	N3—C16—H16	118.2
C1—N2—P1	122.07 (9)	C15—C16—H16	118.2
C1—N2—H2N	119.0	C19—C17—C18	111.02 (13)
P1—N2—H2N	119.0	C19—C17—P2	109.74 (10)
C12—N3—C16	118.11 (12)	C18—C17—P2	110.39 (10)
C12—N3—Cu1	116.65 (9)	C19—C17—H17	108.5
C16—N3—Cu1	124.90 (9)	C18—C17—H17	108.5
C12—N4—P2	121.95 (9)	P2—C17—H17	108.5
C12—N4—H4N	119.0	C17—C18—H18A	109.5
P2—N4—H4N	119.0	C17—C18—H18B	109.5
N1—C1—N2	117.13 (12)	H18A—C18—H18B	109.5
N1—C1—C2	122.14 (12)	C17—C18—H18C	109.5
N2—C1—C2	120.73 (12)	H18A—C18—H18C	109.5
C3—C2—C1	118.48 (13)	H18B—C18—H18C	109.5
C3—C2—H2	120.8	C17—C19—H19A	109.5
C1—C2—H2	120.8	C17—C19—H19B	109.5
C2—C3—C4	119.91 (12)	H19A—C19—H19B	109.5
C2—C3—H3	120.0	C17—C19—H19C	109.5
C4—C3—H3	120.0	H19A—C19—H19C	109.5
C5—C4—C3	117.96 (13)	H19B—C19—H19C	109.5
C5—C4—H4	121.0	C22—C20—C21	110.42 (13)
C3—C4—H4	121.0	C22—C20—P2	113.76 (10)
N1—C5—C4	123.66 (13)	C21—C20—P2	109.05 (10)
N1—C5—H5	118.2	C22—C20—H20	107.8
C4—C5—H5	118.2	C21—C20—H20	107.8
C8—C6—C7	110.05 (15)	P2—C20—H20	107.8
C8—C6—P1	109.78 (11)	C20—C21—H21A	109.5
C7—C6—P1	109.61 (11)	C20—C21—H21B	109.5
C8—C6—H6	109.1	H21A—C21—H21B	109.5
C7—C6—H6	109.1	C20—C21—H21C	109.5
P1—C6—H6	109.1	H21A—C21—H21C	109.5
C6—C7—H7A	109.5	H21B—C21—H21C	109.5
C6—C7—H7B	109.5	C20—C22—H22A	109.5
H7A—C7—H7B	109.5	C20—C22—H22B	109.5
C6—C7—H7C	109.5	H22A—C22—H22B	109.5
H7A—C7—H7C	109.5	C20—C22—H22C	109.5
H7B—C7—H7C	109.5	H22A—C22—H22C	109.5
C6—C8—H8A	109.5	H22B—C22—H22C	109.5
C6—C8—H8B	109.5	F5—P3—F6	179.62 (11)
H8A—C8—H8B	109.5	F5—P3—F4	89.87 (10)
C6—C8—H8C	109.5	F6—P3—F4	89.76 (8)
H8A—C8—H8C	109.5	F5—P3—F3	91.33 (10)
H8B—C8—H8C	109.5	F6—P3—F3	89.04 (8)
C10—C9—C11	111.42 (16)	F4—P3—F3	178.79 (9)
C10—C9—P1	110.47 (11)	F5—P3—F2	90.99 (8)
C11—C9—P1	114.10 (12)	F6—P3—F2	88.94 (6)
C10—C9—H9	106.8	F4—P3—F2	90.28 (6)
C11—C9—H9	106.8	F3—P3—F2	89.83 (6)
P1—C9—H9	106.8	F5—P3—F1	90.06 (8)
C9—C10—H10A	109.5	F6—P3—F1	90.01 (7)
C9—C10—H10B	109.5	F4—P3—F1	90.38 (6)
H10A—C10—H10B	109.5	F3—P3—F1	89.49 (6)
C9—C10—H10C	109.5	F2—P3—F1	178.76 (6)
H10A—C10—H10C	109.5

N1—Cu1—P1—N2	−3.58 (6)	N2—C1—C2—C3	−177.28 (13)
N3—Cu1—P1—N2	97.77 (6)	C1—C2—C3—C4	−0.2 (2)
P2—Cu1—P1—N2	−141.14 (5)	C2—C3—C4—C5	−1.8 (2)
N1—Cu1—P1—C6	−115.16 (7)	C1—N1—C5—C4	−0.2 (2)
N3—Cu1—P1—C6	−13.82 (8)	Cu1—N1—C5—C4	−170.10 (10)
P2—Cu1—P1—C6	107.27 (6)	C3—C4—C5—N1	2.1 (2)
N1—Cu1—P1—C9	107.62 (6)	N2—P1—C6—C8	−60.40 (14)
N3—Cu1—P1—C9	−151.03 (7)	C9—P1—C6—C8	−169.05 (13)
P2—Cu1—P1—C9	−29.94 (6)	Cu1—P1—C6—C8	48.75 (14)
N1—Cu1—P2—N4	94.55 (6)	N2—P1—C6—C7	178.60 (11)
N3—Cu1—P2—N4	−6.47 (5)	C9—P1—C6—C7	69.95 (13)
P1—Cu1—P2—N4	−143.64 (4)	Cu1—P1—C6—C7	−72.24 (13)
N1—Cu1—P2—C17	−16.78 (7)	N2—P1—C9—C10	75.95 (13)
N3—Cu1—P2—C17	−117.80 (7)	C6—P1—C9—C10	−176.57 (13)
P1—Cu1—P2—C17	105.03 (6)	Cu1—P1—C9—C10	−31.59 (14)
N1—Cu1—P2—C20	−155.83 (6)	N2—P1—C9—C11	−50.50 (15)
N3—Cu1—P2—C20	103.16 (6)	C6—P1—C9—C11	56.98 (15)
P1—Cu1—P2—C20	−34.02 (6)	Cu1—P1—C9—C11	−158.05 (13)
N3—Cu1—N1—C1	−118.85 (9)	C16—N3—C12—N4	−178.83 (12)
P2—Cu1—N1—C1	148.29 (8)	Cu1—N3—C12—N4	−5.15 (16)
P1—Cu1—N1—C1	8.79 (9)	C16—N3—C12—C13	0.3 (2)
N3—Cu1—N1—C5	51.21 (11)	Cu1—N3—C12—C13	173.97 (10)
P2—Cu1—N1—C5	−41.64 (12)	P2—N4—C12—N3	−1.76 (17)
P1—Cu1—N1—C5	178.85 (11)	P2—N4—C12—C13	179.10 (11)
C6—P1—N2—C1	127.56 (12)	N3—C12—C13—C14	−0.5 (2)
C9—P1—N2—C1	−123.82 (12)	N4—C12—C13—C14	178.60 (14)
Cu1—P1—N2—C1	−1.12 (12)	C12—C13—C14—C15	0.1 (2)
N1—Cu1—N3—C12	−120.07 (10)	C13—C14—C15—C16	0.4 (2)
P2—Cu1—N3—C12	7.42 (9)	C12—N3—C16—C15	0.3 (2)
P1—Cu1—N3—C12	146.52 (8)	Cu1—N3—C16—C15	−172.84 (12)
N1—Cu1—N3—C16	53.13 (12)	C14—C15—C16—N3	−0.6 (3)
P2—Cu1—N3—C16	−179.38 (11)	N4—P2—C17—C19	−70.36 (11)
P1—Cu1—N3—C16	−40.29 (13)	C20—P2—C17—C19	−177.88 (10)
C17—P2—N4—C12	137.45 (11)	Cu1—P2—C17—C19	39.33 (12)
C20—P2—N4—C12	−113.74 (11)	N4—P2—C17—C18	166.96 (10)
Cu1—P2—N4—C12	6.67 (11)	C20—P2—C17—C18	59.45 (12)
C5—N1—C1—N2	177.49 (12)	Cu1—P2—C17—C18	−83.34 (11)
Cu1—N1—C1—N2	−11.70 (15)	N4—P2—C20—C22	−62.05 (12)
C5—N1—C1—C2	−2.08 (19)	C17—P2—C20—C22	44.15 (12)
Cu1—N1—C1—C2	168.72 (10)	Cu1—P2—C20—C22	−168.57 (9)
P1—N2—C1—N1	8.39 (18)	N4—P2—C20—C21	61.68 (11)
P1—N2—C1—C2	−172.03 (11)	C17—P2—C20—C21	167.88 (10)
N1—C1—C2—C3	2.3 (2)	Cu1—P2—C20—C21	−44.84 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···F1ⁱ	0.88	2.24	3.1038 (15)	167
N4—H4N···F3ⁱⁱ	0.88	2.26	3.1185 (16)	167
C2—H2···F4ⁱ	0.95	2.41	3.306 (2)	158
C20—H20···F4	1.00	2.53	3.502 (2)	164

Symmetry codes: (i) x−1/2, −y+1, z+1/2; (ii) x+1/2, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₁₉N₂P)₂]PF₆
M_r	629.01
Crystal system, space group	Monoclinic, Pn
Temperature (K)	100
a, b, c (Å)	11.0357 (13), 9.2129 (11), 14.4282 (17)
β (°)	96.723 (1)
V (Å³)	1456.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.45 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.65, 0.75
No. of measured, independent and observed [I > 2σ(I)] reflections	21170, 8422, 8187
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.054, 1.02
No. of reflections	8422
No. of parameters	334
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.26
Absolute structure	Flack (1983), 4180 Friedel pairs, merohedral twin with twin proportions refined
Absolute structure parameter	0.410 (4)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SAINT, SADABS and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···F1ⁱ	0.88	2.24	3.1038 (15)	167.3
N4—H4N···F3ⁱⁱ	0.88	2.26	3.1185 (16)	166.7
C2—H2···F4ⁱ	0.95	2.41	3.306 (2)	157.8
C20—H20···F4	1.00	2.53	3.502 (2)	163.7

Symmetry codes: (i) x−1/2, −y+1, z+1/2; (ii) x+1/2, −y, z+1/2.

References

Aguirre, P. A., Lagos, C. A., Moya, S. A., Zúñiga, C., Vera-Oyarce, C., Sola, E., Peris, G. & Bayón, J. C. (2007). Dalton Trans. pp. 5419–5426 CrossRef Google Scholar
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Benito-Garagorri, D., Wiedermann, J., Pollak, M., Mereiter, K. & Kirchner, K. (2007). Organometallics, 26, 217–222. Web of Science CSD CrossRef CAS Google Scholar
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Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Volume 66| Part 7| July 2010| Pages m729-m730

doi:10.1107/S1600536810020283

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