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

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.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.021
• wR factor = 0.054
• Data-to-parameter ratio = 25.2

checkCIF/PLATON results

No syntax errors found



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.410
           From the CIF: _refine_ls_abs_structure_Flack_su    0.004

Author Response: Racemic compound crystallizing in a non-centrosymmetric polar lattice, space-group Pn. According to structure refinement the investigated crystal is a merohedral (polar) twin. In the final refinement this was taken into account by the use of the instructions TWIN and BASF of program SHELXL97. The amounts of the two twin components are 0.590(4) and 0.410(4).

PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of          P3

Author Response: PF~6~ octahedron shows larger librational motions for the fluorine atoms with phosphorus essentially at rest.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               8422
           Count of symmetry unique reflns         4245
           Completeness (_total/calc)            198.40%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      4177
           Fraction of Friedel pairs measured     0.984
           Are heavy atom types Z>Si present        yes

Author Response: The exact number of measured Friedel pairs is 4180. For further explanation see VRF STRVA01.

PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2

Author Response: The two restraints are origin fixing (polar space group)

PLAT033_ALERT_4_G Flack x Parameter Value Deviates from Zero .....       0.41

Author Response: For further explanation see VRF STRVA01.

PLAT128_ALERT_4_G Alternate Setting of Space-group Pc      .......      Pn

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

All H atoms were placed in calculated positions and thereafter treated as riding. A torsional parameter was refined for each methyl group. U_iso(H) = 1.2U_eq(C_non-methyl) and U_iso(H) = 1.5U_eq(C_methyl) were used. The title compound is racemic but crystallizes in a non-centrosymmetric polar lattice, space group Pn. The Flack test indicated that the investigated crystal is a merohedral (polar) twin. In the final refinement this was taken into account by the use of the instructions TWIN and BASF of program SHELXL97 (Sheldrick, 2008). According to this refinement the amounts of the two twin components are 0.590 (4) and 0.410 (4).

Computing details

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

	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

Crystal data

[Cu(C11H19N2P)2]PF6	F(000) = 652
Mr = 629.01	Dx = 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) Å^3	0.45 × 0.22 × 0.20 mm
Z = 2

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0327P)^2 + 0.1922P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
8422 reflections	Δρmax = 0.35 e Å^−3
334 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···F1^i	0.88	2.24	3.1038 (15)	167
N4—H4N···F3^ii	0.88	2.26	3.1185 (16)	167
C2—H2···F4^i	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.