supplementary materials


mw2090 scheme

Acta Cryst. (2012). E68, m1396-m1397    [ doi:10.1107/S1600536812043346 ]

(Nitrato-[kappa]O)tris[tris(4-fluorophenyl)phosphane-[kappa]P]copper(I)

T. N. Hill and A. Roodt

Abstract top

In the title complex, [Cu(NO3)(C18H12F3P)3], the ligating atoms define a distorted tetrahedon with the three tris(4-fluorophenyl)phosphane ligands in the basal positions and the nitrate ligand in the axial position. The intramolecular [pi]-[pi] interaction [centroid-centroid distance = 3.6113 (11) Å] between two of the 4-fluorophenyl groups is complemented by both C-H...F and C-H...O interactions with distances in the range 2.51-2.60 Å, resulting in a tight head-to-tail packing.

Comment top

The title compound (I) has a copper(I) metal center co-ordinated by three tris-4-fluorophenylphosphane ligands ((p-FPh)3P) and a nitrato ligand. The ligating atoms define a distorted trigonal pyramid which is similar to what was found for [Cu(PPh3)3(X)] X = ClO4-, BF4-,NO3-, HCO2- (Hanna et al., 2005) complexes, where the average P—Cu—P angles are in the range 112.29 (4)° - 121.37 (6)°. While markedly different, the P—Cu—P bond angles for for I (Table 1) fall within this range with an average of 116 (2)°. The dissimilarity observed for the O—Cu—P bond angles (Table 1) are as a result of C—H···O (Figure 4) and O2···π (centroid C221-C226) interactions contributing to the non-linearity of the N1—O1—Cu1 angle and the deviation (14.39 (5)°) of the nitrato ligand from the axial position. The average Cu—P bond lengths for [Cu(PPh3)3(NO3)].EtOH (Dyason et al., 1986), [Cu(PPh3)3(NO3)].MeOH (Steyl, 2009) and I were observed to be 2.329 (9) Å, 2.326 (10) Å and 2.300 (13) Å respectively.

An intermolecular ππ interaction is observed for A (centroid C131—C136)···B (centroid C211—C216) with a distance of 3.6113 (11) Å and is stabilized by the bifurcated hydrogen fluorine interaction C215—H215···F21iii and C215—H215···F13iii with H···F distances of 2.61 Å and 2.51 Å respectively (see Figure 2). An additional stabilizing effect arises from the C135ii—H135ii···O2 and C136ii—H136ii···O3 interactions (Figure 4) with H···O distances of 2.58 Å and 2.53 Å. Additional C—H···F interactions are illustrated in Figure 3. All of these interactions contribute to tight packing of I.

Related literature top

For related complexes, see: Hanna et al. (2005); Steyl (2009); Saravanabharathi et al. (2002); Dyason et al. (1986); Matthew et al. (1971).

Experimental top

tris-4-fluorophenylphosphane (2 mmol) was added to a solution of CuNO3 (1 mmol) in warm MeOH (15 ml, 70 °C) and the resulting solution was stirred for c.a. 1 h. The solution was filtered and allowed to cool slowly. Crystals suitable for single-crystal X-ray diffraction were obtained from the slow evaporation of the solution.

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 Å and Uiso(H) = 1.2 Ueq(C) for aromatic H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. View of I (50% probability displacement ellipsoids). Phenyl rings are numbered Cxyz where x represents the phosphane to which the ring is attached, y represents the ring number and z the atom number in the ring. Only the first phenyl ring is completely numbered for illustrative purpose Hydrogen atoms have been omitted for clarity.
[Figure 2] Fig. 2. Intermolecular C—H···F and intramolecular ππ interactions (dashed bonds) for I. Symmetry code (iii) -x + 1, -y + 1, -z + 1. Non-relavent hydrogen atoms and phenyl rings have been omitted for clarity.
[Figure 3] Fig. 3. Intermolecular C—H···F (dashed bonds) for I. Symmetry codes (i) x - 1, y + 1, z, (iv) x, y - 1, z and (vi) -x + 2, -y + 2, -z. Non-relevant hydrogen atoms and phenyl rings have been omitted for clarity.
[Figure 4] Fig. 4. Inter- and intramolecular C—H···O interactions (dashed bonds) for I. Symmetry code (iii) x - 1, y, z. Non-relevant hydrogen atoms and phenyl rings have been omitted for clarity.
(Nitrato-κO)tris[tris(4-fluorophenyl)phosphane-κP]copper(I) top
Crystal data top
[Cu(NO3)(C18H12F3P)3]Z = 2
Mr = 1074.29F(000) = 1092
Triclinic, P1Dx = 1.501 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.3861 (3) ÅCell parameters from 9076 reflections
b = 12.2552 (4) Åθ = 2.5–28.2°
c = 21.4820 (7) ŵ = 0.64 mm1
α = 85.274 (2)°T = 100 K
β = 86.843 (1)°Column, colourless
γ = 74.954 (1)°0.38 × 0.11 × 0.08 mm
V = 2376.76 (13) Å3
Data collection top
Bruker X8 APEXII 4K KappaCCD
diffractometer
11760 independent reflections
Radiation source: sealed tube9439 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 512 pixels mm-1θmax = 28.5°, θmin = 2.4°
φ and ω scansh = 912
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
k = 1616
Tmin = 0.792, Tmax = 0.950l = 2827
28458 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035 w = 1/[σ2(Fo2) + (0.0333P)2 + 0.8637P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max = 0.001
S = 1.05Δρmax = 0.40 e Å3
11760 reflectionsΔρmin = 0.41 e Å3
640 parameters
Crystal data top
[Cu(NO3)(C18H12F3P)3]γ = 74.954 (1)°
Mr = 1074.29V = 2376.76 (13) Å3
Triclinic, P1Z = 2
a = 9.3861 (3) ÅMo Kα radiation
b = 12.2552 (4) ŵ = 0.64 mm1
c = 21.4820 (7) ÅT = 100 K
α = 85.274 (2)°0.38 × 0.11 × 0.08 mm
β = 86.843 (1)°
Data collection top
Bruker X8 APEXII 4K KappaCCD
diffractometer
11760 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
9439 reflections with I > 2σ(I)
Tmin = 0.792, Tmax = 0.950Rint = 0.030
28458 measured reflectionsθmax = 28.5°
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.085Δρmax = 0.40 e Å3
S = 1.05Δρmin = 0.41 e Å3
11760 reflectionsAbsolute structure: ?
640 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1110.64094 (18)1.01573 (14)0.27195 (8)0.0156 (3)
C1120.68685 (19)1.07502 (15)0.21964 (9)0.0188 (4)
H1120.78941.06320.20970.023*
C1130.5860 (2)1.15064 (16)0.18194 (9)0.0214 (4)
H1130.61791.19050.14630.026*
C1140.4384 (2)1.16645 (16)0.19755 (9)0.0224 (4)
C1150.3879 (2)1.11255 (17)0.24917 (9)0.0236 (4)
H1150.28511.12690.25920.028*
C1160.49013 (19)1.03644 (16)0.28659 (9)0.0200 (4)
H1160.45690.99810.32250.024*
C1210.88511 (18)0.99336 (15)0.35054 (8)0.0164 (4)
C1221.0241 (2)0.93895 (17)0.37273 (9)0.0235 (4)
H1221.06360.86040.36790.028*
C1231.1054 (2)0.99874 (18)0.40190 (10)0.0302 (5)
H1231.20020.96210.41720.036*
C1241.0452 (2)1.11196 (18)0.40800 (10)0.0300 (5)
C1250.9084 (2)1.16862 (18)0.38719 (11)0.0338 (5)
H1250.86961.24710.39250.041*
C1260.8282 (2)1.10793 (16)0.35806 (10)0.0261 (4)
H1260.73331.14540.34310.031*
C1310.67292 (18)0.86418 (15)0.38106 (8)0.0155 (3)
C1320.67507 (19)0.89769 (15)0.44123 (8)0.0183 (4)
H1320.73720.94430.44970.022*
C1330.5868 (2)0.86338 (16)0.48895 (9)0.0217 (4)
H1330.58920.8850.53030.026*
C1340.4963 (2)0.79770 (16)0.47510 (9)0.0214 (4)
C1350.49013 (19)0.76214 (15)0.41629 (9)0.0202 (4)
H1350.42580.7170.40820.024*
C1360.58129 (19)0.79473 (15)0.36951 (9)0.0177 (4)
H1360.58170.76950.32880.021*
C2110.84201 (19)0.55517 (15)0.36385 (8)0.0169 (4)
C2120.88652 (19)0.60020 (16)0.41492 (9)0.0203 (4)
H2120.9560.64460.40860.024*
C2130.8305 (2)0.58076 (18)0.47462 (9)0.0259 (4)
H2130.8610.61060.50950.031*
C2140.7292 (2)0.51683 (18)0.48172 (9)0.0286 (5)
C2150.6808 (2)0.47230 (17)0.43309 (10)0.0296 (5)
H2150.61020.4290.43990.036*
C2160.7382 (2)0.49225 (16)0.37315 (9)0.0225 (4)
H2160.7060.46260.33850.027*
C2211.10916 (18)0.48680 (15)0.29250 (8)0.0161 (4)
C2221.2149 (2)0.49938 (16)0.24626 (9)0.0225 (4)
H2221.18690.55080.21080.027*
C2231.3602 (2)0.43753 (17)0.25149 (11)0.0288 (5)
H2231.43230.44550.21980.035*
C2241.3979 (2)0.36487 (17)0.30303 (10)0.0269 (4)
C2251.2974 (2)0.34649 (18)0.34868 (10)0.0297 (5)
H2251.32650.29310.38320.036*
C2261.1516 (2)0.40819 (17)0.34301 (9)0.0249 (4)
H2261.07970.39670.3740.03*
C2310.83035 (18)0.52013 (15)0.23431 (8)0.0155 (3)
C2320.70057 (19)0.58837 (16)0.20949 (8)0.0182 (4)
H2320.66220.66240.22320.022*
C2330.6262 (2)0.55066 (17)0.16533 (9)0.0236 (4)
H2330.53810.59780.14820.028*
C2340.6842 (2)0.44263 (18)0.14708 (9)0.0238 (4)
C2350.8096 (2)0.37125 (17)0.17122 (10)0.0263 (4)
H2350.84510.29640.15820.032*
C2360.8839 (2)0.41083 (16)0.21519 (9)0.0224 (4)
H2360.97160.3630.23220.027*
C3111.04880 (18)0.69465 (14)0.10744 (8)0.0140 (3)
C3121.18958 (18)0.70551 (15)0.08908 (8)0.0168 (4)
H3121.21720.77210.09720.02*
C3131.2899 (2)0.62024 (16)0.05907 (9)0.0214 (4)
H3131.38520.62830.04590.026*
C3141.2481 (2)0.52395 (16)0.04881 (9)0.0212 (4)
C3151.1117 (2)0.50835 (16)0.06709 (9)0.0224 (4)
H3151.08650.44040.05980.027*
C3161.0117 (2)0.59482 (15)0.09661 (9)0.0192 (4)
H3160.91680.58580.10960.023*
C3210.74569 (18)0.81865 (14)0.10980 (8)0.0144 (3)
C3220.61174 (19)0.85818 (15)0.14206 (9)0.0177 (4)
H3220.61080.87020.18520.021*
C3230.4793 (2)0.88015 (16)0.11152 (10)0.0244 (4)
H3230.38760.90720.13320.029*
C3240.4848 (2)0.86173 (16)0.04930 (10)0.0241 (4)
C3250.6133 (2)0.82046 (17)0.01569 (9)0.0248 (4)
H3250.61230.80710.02720.03*
C3260.7452 (2)0.79875 (16)0.04667 (8)0.0196 (4)
H3260.83610.77010.02460.024*
C3310.96604 (18)0.93534 (14)0.12332 (8)0.0137 (3)
C3320.8948 (2)1.00834 (15)0.07499 (9)0.0200 (4)
H3320.82370.98680.05220.024*
C3330.9262 (2)1.11221 (16)0.05949 (9)0.0225 (4)
H3330.87621.16250.0270.027*
C3341.0311 (2)1.13997 (15)0.09233 (9)0.0190 (4)
C3351.1049 (2)1.07060 (16)0.14004 (9)0.0210 (4)
H3351.17741.09240.16180.025*
C3361.07114 (19)0.96782 (15)0.15582 (9)0.0182 (4)
H3361.12010.91910.18910.022*
N11.24915 (16)0.72517 (14)0.29043 (8)0.0232 (4)
O11.14700 (13)0.76757 (11)0.25203 (6)0.0228 (3)
O21.21663 (16)0.68829 (12)0.34380 (7)0.0288 (3)
O31.37844 (15)0.71966 (15)0.27340 (8)0.0413 (4)
F110.33854 (12)1.23879 (10)0.16002 (6)0.0319 (3)
F121.12332 (15)1.17149 (11)0.43652 (7)0.0458 (4)
F130.40845 (13)0.76620 (10)0.52191 (6)0.0330 (3)
F210.67367 (15)0.49784 (12)0.54008 (6)0.0447 (4)
F221.54253 (12)0.30798 (11)0.30944 (7)0.0418 (3)
F230.61304 (14)0.40369 (11)0.10379 (6)0.0355 (3)
F311.34503 (13)0.44073 (10)0.01912 (6)0.0320 (3)
F320.35528 (12)0.88451 (11)0.01908 (6)0.0364 (3)
F331.06177 (12)1.24204 (9)0.07802 (5)0.0261 (3)
P10.78177 (5)0.90846 (4)0.31532 (2)0.01394 (9)
P20.92541 (5)0.58263 (4)0.28780 (2)0.01375 (9)
P30.91661 (5)0.80309 (4)0.15007 (2)0.01231 (9)
Cu10.92130 (2)0.766649 (17)0.258012 (10)0.01294 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1110.0158 (8)0.0129 (9)0.0179 (9)0.0022 (7)0.0035 (7)0.0036 (7)
C1120.0167 (8)0.0160 (9)0.0234 (10)0.0028 (7)0.0020 (7)0.0035 (7)
C1130.0265 (10)0.0166 (9)0.0217 (10)0.0066 (8)0.0040 (8)0.0000 (7)
C1140.0231 (9)0.0154 (9)0.0281 (11)0.0017 (8)0.0144 (8)0.0006 (8)
C1150.0145 (8)0.0253 (11)0.0304 (11)0.0027 (8)0.0071 (8)0.0021 (8)
C1160.0172 (8)0.0226 (10)0.0202 (10)0.0046 (8)0.0029 (7)0.0012 (7)
C1210.0139 (8)0.0164 (9)0.0190 (9)0.0034 (7)0.0020 (7)0.0020 (7)
C1220.0201 (9)0.0185 (10)0.0297 (11)0.0007 (8)0.0072 (8)0.0029 (8)
C1230.0207 (9)0.0300 (12)0.0405 (13)0.0047 (9)0.0131 (9)0.0029 (9)
C1240.0306 (11)0.0278 (11)0.0375 (12)0.0154 (9)0.0142 (9)0.0013 (9)
C1250.0368 (12)0.0165 (10)0.0497 (14)0.0053 (9)0.0207 (10)0.0040 (9)
C1260.0228 (9)0.0181 (10)0.0370 (12)0.0013 (8)0.0143 (9)0.0036 (8)
C1310.0134 (8)0.0139 (9)0.0173 (9)0.0002 (7)0.0016 (7)0.0001 (7)
C1320.0196 (9)0.0149 (9)0.0199 (9)0.0026 (7)0.0021 (7)0.0027 (7)
C1330.0258 (10)0.0186 (10)0.0177 (10)0.0002 (8)0.0014 (7)0.0020 (7)
C1340.0200 (9)0.0182 (10)0.0231 (10)0.0021 (8)0.0053 (7)0.0026 (7)
C1350.0162 (8)0.0158 (9)0.0276 (10)0.0029 (7)0.0026 (7)0.0012 (7)
C1360.0167 (8)0.0150 (9)0.0204 (9)0.0012 (7)0.0023 (7)0.0025 (7)
C2110.0161 (8)0.0134 (9)0.0179 (9)0.0010 (7)0.0020 (7)0.0012 (7)
C2120.0165 (8)0.0199 (10)0.0211 (10)0.0007 (7)0.0007 (7)0.0019 (7)
C2130.0228 (9)0.0292 (11)0.0185 (10)0.0056 (8)0.0010 (8)0.0001 (8)
C2140.0302 (11)0.0268 (11)0.0197 (10)0.0042 (9)0.0103 (8)0.0067 (8)
C2150.0323 (11)0.0214 (11)0.0338 (12)0.0083 (9)0.0142 (9)0.0013 (9)
C2160.0258 (10)0.0150 (9)0.0253 (10)0.0041 (8)0.0049 (8)0.0005 (8)
C2210.0153 (8)0.0129 (9)0.0197 (9)0.0024 (7)0.0007 (7)0.0022 (7)
C2220.0188 (9)0.0181 (10)0.0278 (11)0.0018 (8)0.0018 (8)0.0034 (8)
C2230.0175 (9)0.0226 (11)0.0441 (13)0.0038 (8)0.0080 (9)0.0001 (9)
C2240.0145 (9)0.0202 (10)0.0429 (13)0.0040 (8)0.0076 (8)0.0083 (9)
C2250.0301 (11)0.0255 (11)0.0249 (11)0.0083 (9)0.0057 (9)0.0002 (8)
C2260.0248 (10)0.0229 (11)0.0212 (10)0.0030 (8)0.0021 (8)0.0011 (8)
C2310.0146 (8)0.0160 (9)0.0162 (9)0.0052 (7)0.0026 (7)0.0002 (7)
C2320.0187 (8)0.0163 (9)0.0204 (9)0.0068 (7)0.0009 (7)0.0014 (7)
C2330.0231 (9)0.0255 (11)0.0241 (10)0.0110 (8)0.0043 (8)0.0044 (8)
C2340.0273 (10)0.0337 (12)0.0169 (10)0.0189 (9)0.0003 (8)0.0031 (8)
C2350.0235 (9)0.0238 (11)0.0344 (12)0.0089 (8)0.0054 (8)0.0143 (9)
C2360.0167 (9)0.0191 (10)0.0305 (11)0.0021 (7)0.0020 (8)0.0073 (8)
C3110.0144 (8)0.0148 (9)0.0121 (8)0.0030 (7)0.0020 (6)0.0013 (6)
C3120.0154 (8)0.0153 (9)0.0196 (9)0.0040 (7)0.0021 (7)0.0003 (7)
C3130.0146 (8)0.0218 (10)0.0266 (10)0.0028 (7)0.0005 (7)0.0012 (8)
C3140.0225 (9)0.0176 (10)0.0202 (10)0.0013 (8)0.0009 (7)0.0039 (7)
C3150.0290 (10)0.0154 (9)0.0242 (10)0.0087 (8)0.0022 (8)0.0028 (7)
C3160.0199 (9)0.0174 (9)0.0214 (10)0.0077 (7)0.0023 (7)0.0005 (7)
C3210.0147 (8)0.0135 (8)0.0164 (9)0.0067 (7)0.0028 (6)0.0019 (7)
C3220.0167 (8)0.0159 (9)0.0213 (10)0.0052 (7)0.0024 (7)0.0015 (7)
C3230.0131 (8)0.0223 (10)0.0379 (12)0.0049 (8)0.0032 (8)0.0008 (8)
C3240.0190 (9)0.0205 (10)0.0358 (12)0.0108 (8)0.0165 (8)0.0094 (8)
C3250.0312 (10)0.0270 (11)0.0207 (10)0.0155 (9)0.0107 (8)0.0048 (8)
C3260.0200 (9)0.0232 (10)0.0177 (9)0.0098 (8)0.0030 (7)0.0020 (7)
C3310.0133 (8)0.0128 (8)0.0152 (9)0.0039 (7)0.0030 (6)0.0024 (6)
C3320.0233 (9)0.0187 (10)0.0199 (10)0.0087 (8)0.0051 (7)0.0013 (7)
C3330.0300 (10)0.0178 (10)0.0191 (10)0.0063 (8)0.0041 (8)0.0051 (7)
C3340.0224 (9)0.0125 (9)0.0225 (10)0.0066 (7)0.0099 (7)0.0033 (7)
C3350.0178 (9)0.0188 (10)0.0290 (11)0.0086 (8)0.0003 (7)0.0044 (8)
C3360.0155 (8)0.0170 (9)0.0226 (10)0.0049 (7)0.0034 (7)0.0003 (7)
N10.0156 (7)0.0231 (9)0.0315 (10)0.0032 (7)0.0046 (7)0.0089 (7)
O10.0144 (6)0.0267 (7)0.0269 (7)0.0059 (6)0.0067 (5)0.0062 (6)
O20.0338 (8)0.0245 (8)0.0250 (8)0.0007 (6)0.0099 (6)0.0000 (6)
O30.0131 (7)0.0582 (11)0.0545 (11)0.0075 (7)0.0034 (7)0.0180 (9)
F110.0277 (6)0.0272 (7)0.0392 (7)0.0039 (5)0.0192 (5)0.0091 (5)
F120.0462 (8)0.0346 (8)0.0653 (10)0.0196 (6)0.0318 (7)0.0038 (7)
F130.0361 (7)0.0334 (7)0.0298 (7)0.0134 (6)0.0123 (5)0.0017 (5)
F210.0517 (8)0.0537 (9)0.0229 (7)0.0095 (7)0.0156 (6)0.0076 (6)
F220.0165 (6)0.0341 (8)0.0685 (10)0.0086 (5)0.0121 (6)0.0083 (7)
F230.0444 (7)0.0440 (8)0.0280 (7)0.0263 (6)0.0070 (6)0.0078 (6)
F310.0287 (6)0.0238 (6)0.0409 (7)0.0006 (5)0.0087 (5)0.0140 (5)
F320.0242 (6)0.0418 (8)0.0470 (8)0.0159 (6)0.0236 (5)0.0143 (6)
F330.0366 (6)0.0156 (6)0.0289 (6)0.0135 (5)0.0089 (5)0.0020 (5)
P10.0130 (2)0.0125 (2)0.0160 (2)0.00207 (17)0.00181 (16)0.00245 (17)
P20.0129 (2)0.0121 (2)0.0153 (2)0.00204 (17)0.00006 (16)0.00020 (17)
P30.01112 (19)0.0127 (2)0.0135 (2)0.00410 (17)0.00106 (16)0.00032 (16)
Cu10.01211 (10)0.01249 (11)0.01381 (11)0.00253 (8)0.00091 (8)0.00025 (8)
Geometric parameters (Å, º) top
C111—C1161.394 (2)C225—H2250.95
C111—C1121.397 (3)C226—H2260.95
C111—P11.8372 (18)C231—C2361.391 (2)
C112—C1131.384 (3)C231—C2321.392 (2)
C112—H1120.95C231—P21.8209 (18)
C113—C1141.375 (3)C232—C2331.383 (3)
C113—H1130.95C232—H2320.95
C114—F111.359 (2)C233—C2341.375 (3)
C114—C1151.369 (3)C233—H2330.95
C115—C1161.391 (3)C234—F231.359 (2)
C115—H1150.95C234—C2351.370 (3)
C116—H1160.95C235—C2361.392 (3)
C121—C1261.386 (3)C235—H2350.95
C121—C1221.392 (2)C236—H2360.95
C121—P11.8249 (17)C311—C3121.395 (2)
C122—C1231.389 (3)C311—C3161.396 (2)
C122—H1220.95C311—P31.8340 (18)
C123—C1241.370 (3)C312—C3131.388 (3)
C123—H1230.95C312—H3120.95
C124—F121.359 (2)C313—C3141.374 (3)
C124—C1251.371 (3)C313—H3130.95
C125—C1261.390 (3)C314—F311.355 (2)
C125—H1250.95C314—C3151.375 (3)
C126—H1260.95C315—C3161.391 (3)
C131—C1321.391 (2)C315—H3150.95
C131—C1361.401 (2)C316—H3160.95
C131—P11.8263 (18)C321—C3221.392 (2)
C132—C1331.389 (3)C321—C3261.398 (2)
C132—H1320.95C321—P31.8236 (17)
C133—C1341.371 (3)C322—C3231.391 (2)
C133—H1330.95C322—H3220.95
C134—F131.360 (2)C323—C3241.370 (3)
C134—C1351.379 (3)C323—H3230.95
C135—C1361.385 (2)C324—F321.363 (2)
C135—H1350.95C324—C3251.371 (3)
C136—H1360.95C325—C3261.392 (2)
C211—C2161.389 (2)C325—H3250.95
C211—C2121.397 (3)C326—H3260.95
C211—P21.8166 (18)C331—C3321.392 (2)
C212—C2131.385 (3)C331—C3361.394 (2)
C212—H2120.95C331—P31.8385 (17)
C213—C2141.376 (3)C332—C3331.390 (2)
C213—H2130.95C332—H3320.95
C214—F211.357 (2)C333—C3341.368 (3)
C214—C2151.367 (3)C333—H3330.95
C215—C2161.396 (3)C334—F331.3624 (19)
C215—H2150.95C334—C3351.372 (3)
C216—H2160.95C335—C3361.388 (2)
C221—C2261.393 (3)C335—H3350.95
C221—C2221.393 (2)C336—H3360.95
C221—P21.8199 (18)N1—O31.234 (2)
C222—C2231.383 (3)N1—O21.249 (2)
C222—H2220.95N1—O11.2757 (19)
C223—C2241.364 (3)O1—Cu12.1182 (12)
C223—H2230.95P1—Cu12.2901 (5)
C224—F221.364 (2)P2—Cu12.2840 (5)
C224—C2251.370 (3)P3—Cu12.3256 (5)
C225—C2261.387 (3)
C116—C111—C112118.43 (16)C231—C232—H232119.3
C116—C111—P1123.28 (14)C234—C233—C232117.67 (18)
C112—C111—P1118.20 (13)C234—C233—H233121.2
C113—C112—C111121.34 (17)C232—C233—H233121.2
C113—C112—H112119.3F23—C234—C235118.14 (18)
C111—C112—H112119.3F23—C234—C233118.74 (18)
C114—C113—C112118.08 (18)C235—C234—C233123.11 (17)
C114—C113—H113121C234—C235—C236118.50 (18)
C112—C113—H113121C234—C235—H235120.8
F11—C114—C115118.73 (17)C236—C235—H235120.8
F11—C114—C113118.43 (17)C231—C236—C235120.30 (18)
C115—C114—C113122.83 (17)C231—C236—H236119.8
C114—C115—C116118.59 (17)C235—C236—H236119.8
C114—C115—H115120.7C312—C311—C316118.70 (16)
C116—C115—H115120.7C312—C311—P3121.87 (13)
C115—C116—C111120.70 (18)C316—C311—P3119.29 (13)
C115—C116—H116119.7C313—C312—C311120.86 (16)
C111—C116—H116119.7C313—C312—H312119.6
C126—C121—C122119.30 (16)C311—C312—H312119.6
C126—C121—P1122.57 (13)C314—C313—C312118.43 (16)
C122—C121—P1118.08 (14)C314—C313—H313120.8
C123—C122—C121120.47 (18)C312—C313—H313120.8
C123—C122—H122119.8F31—C314—C313118.77 (16)
C121—C122—H122119.8F31—C314—C315118.34 (17)
C124—C123—C122118.28 (18)C313—C314—C315122.88 (17)
C124—C123—H123120.9C314—C315—C316118.14 (17)
C122—C123—H123120.9C314—C315—H315120.9
F12—C124—C123118.94 (18)C316—C315—H315120.9
F12—C124—C125117.93 (19)C315—C316—C311120.98 (16)
C123—C124—C125123.13 (18)C315—C316—H316119.5
C124—C125—C126118.07 (19)C311—C316—H316119.5
C124—C125—H125121C322—C321—C326119.14 (16)
C126—C125—H125121C322—C321—P3118.73 (13)
C121—C126—C125120.75 (18)C326—C321—P3122.01 (13)
C121—C126—H126119.6C323—C322—C321120.44 (17)
C125—C126—H126119.6C323—C322—H322119.8
C132—C131—C136118.98 (16)C321—C322—H322119.8
C132—C131—P1123.15 (13)C324—C323—C322118.23 (17)
C136—C131—P1117.86 (13)C324—C323—H323120.9
C133—C132—C131120.39 (16)C322—C323—H323120.9
C133—C132—H132119.8F32—C324—C323118.35 (18)
C131—C132—H132119.8F32—C324—C325117.95 (18)
C134—C133—C132118.55 (17)C323—C324—C325123.70 (17)
C134—C133—H133120.7C324—C325—C326117.62 (18)
C132—C133—H133120.7C324—C325—H325121.2
F13—C134—C133118.11 (17)C326—C325—H325121.2
F13—C134—C135118.56 (16)C325—C326—C321120.84 (17)
C133—C134—C135123.33 (17)C325—C326—H326119.6
C134—C135—C136117.47 (16)C321—C326—H326119.6
C134—C135—H135121.3C332—C331—C336118.71 (16)
C136—C135—H135121.3C332—C331—P3122.55 (13)
C135—C136—C131121.24 (17)C336—C331—P3118.56 (13)
C135—C136—H136119.4C333—C332—C331121.02 (16)
C131—C136—H136119.4C333—C332—H332119.5
C216—C211—C212119.37 (17)C331—C332—H332119.5
C216—C211—P2123.31 (14)C334—C333—C332118.15 (17)
C212—C211—P2117.31 (13)C334—C333—H333120.9
C213—C212—C211120.73 (18)C332—C333—H333120.9
C213—C212—H212119.6F33—C334—C333118.72 (17)
C211—C212—H212119.6F33—C334—C335118.29 (16)
C214—C213—C212117.87 (19)C333—C334—C335122.97 (17)
C214—C213—H213121.1C334—C335—C336118.45 (17)
C212—C213—H213121.1C334—C335—H335120.8
F21—C214—C215118.41 (19)C336—C335—H335120.8
F21—C214—C213118.1 (2)C335—C336—C331120.68 (17)
C215—C214—C213123.51 (18)C335—C336—H336119.7
C214—C215—C216118.15 (19)C331—C336—H336119.7
C214—C215—H215120.9O3—N1—O2121.54 (17)
C216—C215—H215120.9O3—N1—O1118.99 (17)
C211—C216—C215120.35 (19)O2—N1—O1119.45 (15)
C211—C216—H216119.8N1—O1—Cu1129.87 (11)
C215—C216—H216119.8C121—P1—C131103.52 (8)
C226—C221—C222118.76 (17)C121—P1—C111102.89 (8)
C226—C221—P2122.63 (14)C131—P1—C111101.99 (8)
C222—C221—P2118.38 (14)C121—P1—Cu1115.18 (6)
C223—C222—C221120.54 (18)C131—P1—Cu1116.00 (6)
C223—C222—H222119.7C111—P1—Cu1115.38 (6)
C221—C222—H222119.7C211—P2—C221102.44 (8)
C224—C223—C222118.67 (18)C211—P2—C231103.80 (8)
C224—C223—H223120.7C221—P2—C231104.60 (8)
C222—C223—H223120.7C211—P2—Cu1117.00 (6)
F22—C224—C223118.50 (18)C221—P2—Cu1114.73 (6)
F22—C224—C225118.46 (19)C231—P2—Cu1112.79 (6)
C223—C224—C225123.04 (18)C321—P3—C311102.69 (8)
C224—C225—C226118.02 (19)C321—P3—C331101.81 (8)
C224—C225—H225121C311—P3—C331103.93 (8)
C226—C225—H225121C321—P3—Cu1119.88 (6)
C225—C226—C221120.88 (18)C311—P3—Cu1113.47 (6)
C225—C226—H226119.6C331—P3—Cu1113.18 (6)
C221—C226—H226119.6O1—Cu1—P2103.96 (4)
C236—C231—C232118.97 (16)O1—Cu1—P1112.11 (4)
C236—C231—P2123.58 (14)P2—Cu1—P1119.537 (18)
C232—C231—P2117.38 (13)O1—Cu1—P387.93 (4)
C233—C232—C231121.42 (18)P2—Cu1—P3112.289 (18)
C233—C232—H232119.3P1—Cu1—P3115.765 (18)
C116—C111—C112—C1131.6 (3)C332—C331—C336—C3350.4 (3)
P1—C111—C112—C113174.93 (14)P3—C331—C336—C335175.65 (14)
C111—C112—C113—C1140.3 (3)O3—N1—O1—Cu1168.52 (13)
C112—C113—C114—F11178.64 (16)O2—N1—O1—Cu110.1 (2)
C112—C113—C114—C1151.4 (3)C126—C121—P1—C13186.16 (17)
F11—C114—C115—C116178.39 (16)C122—C121—P1—C13191.29 (16)
C113—C114—C115—C1161.6 (3)C126—C121—P1—C11119.76 (18)
C114—C115—C116—C1110.2 (3)C122—C121—P1—C111162.80 (15)
C112—C111—C116—C1151.4 (3)C126—C121—P1—Cu1146.16 (15)
P1—C111—C116—C115175.00 (14)C122—C121—P1—Cu136.39 (17)
C126—C121—C122—C1230.2 (3)C132—C131—P1—C1212.17 (17)
P1—C121—C122—C123177.78 (16)C136—C131—P1—C121178.98 (14)
C121—C122—C123—C1240.1 (3)C132—C131—P1—C111104.43 (15)
C122—C123—C124—F12179.89 (19)C136—C131—P1—C11174.42 (15)
C122—C123—C124—C1250.6 (4)C132—C131—P1—Cu1129.34 (14)
F12—C124—C125—C126179.9 (2)C136—C131—P1—Cu151.81 (15)
C123—C124—C125—C1260.6 (4)C116—C111—P1—C121115.02 (15)
C122—C121—C126—C1250.2 (3)C112—C111—P1—C12168.61 (15)
P1—C121—C126—C125177.63 (17)C116—C111—P1—C1317.93 (17)
C124—C125—C126—C1210.2 (3)C112—C111—P1—C131175.70 (14)
C136—C131—C132—C1330.5 (3)C116—C111—P1—Cu1118.70 (14)
P1—C131—C132—C133178.38 (14)C112—C111—P1—Cu157.67 (15)
C131—C132—C133—C1341.1 (3)C216—C211—P2—C221104.51 (16)
C132—C133—C134—F13178.86 (16)C212—C211—P2—C22175.32 (15)
C132—C133—C134—C1351.2 (3)C216—C211—P2—C2314.16 (18)
F13—C134—C135—C136179.62 (16)C212—C211—P2—C231176.01 (14)
C133—C134—C135—C1360.4 (3)C216—C211—P2—Cu1129.11 (14)
C134—C135—C136—C1312.0 (3)C212—C211—P2—Cu151.06 (15)
C132—C131—C136—C1352.0 (3)C226—C221—P2—C2116.02 (17)
P1—C131—C136—C135176.86 (14)C222—C221—P2—C211168.41 (14)
C216—C211—C212—C2131.3 (3)C226—C221—P2—C231102.03 (16)
P2—C211—C212—C213178.51 (14)C222—C221—P2—C23183.53 (15)
C211—C212—C213—C2140.6 (3)C226—C221—P2—Cu1133.86 (14)
C212—C213—C214—F21179.82 (17)C222—C221—P2—Cu140.58 (16)
C212—C213—C214—C2150.3 (3)C236—C231—P2—C21194.43 (16)
F21—C214—C215—C216179.91 (17)C232—C231—P2—C21188.54 (14)
C213—C214—C215—C2160.4 (3)C236—C231—P2—C22112.62 (17)
C212—C211—C216—C2151.2 (3)C232—C231—P2—C221164.42 (13)
P2—C211—C216—C215178.61 (15)C236—C231—P2—Cu1137.95 (14)
C214—C215—C216—C2110.4 (3)C232—C231—P2—Cu139.08 (15)
C226—C221—C222—C2232.1 (3)C322—C321—P3—C311155.05 (14)
P2—C221—C222—C223172.58 (15)C326—C321—P3—C31128.92 (16)
C221—C222—C223—C2240.5 (3)C322—C321—P3—C33197.54 (14)
C222—C223—C224—F22176.99 (17)C326—C321—P3—C33178.49 (16)
C222—C223—C224—C2252.9 (3)C322—C321—P3—Cu128.18 (16)
F22—C224—C225—C226177.41 (18)C326—C321—P3—Cu1155.80 (12)
C223—C224—C225—C2262.5 (3)C312—C311—P3—C321135.09 (15)
C224—C225—C226—C2210.3 (3)C316—C311—P3—C32149.29 (16)
C222—C221—C226—C2252.5 (3)C312—C311—P3—C33129.31 (16)
P2—C221—C226—C225171.92 (16)C316—C311—P3—C331155.07 (14)
C236—C231—C232—C2331.5 (3)C312—C311—P3—Cu194.04 (14)
P2—C231—C232—C233175.64 (14)C316—C311—P3—Cu181.58 (15)
C231—C232—C233—C2340.6 (3)C332—C331—P3—C32110.69 (17)
C232—C233—C234—F23179.96 (16)C336—C331—P3—C321164.33 (14)
C232—C233—C234—C2351.0 (3)C332—C331—P3—C31195.75 (16)
F23—C234—C235—C236179.45 (17)C336—C331—P3—C31189.23 (15)
C233—C234—C235—C2361.6 (3)C332—C331—P3—Cu1140.71 (14)
C232—C231—C236—C2350.9 (3)C336—C331—P3—Cu134.31 (15)
P2—C231—C236—C235176.07 (15)N1—O1—Cu1—P247.17 (15)
C234—C235—C236—C2310.6 (3)N1—O1—Cu1—P183.31 (15)
C316—C311—C312—C3131.7 (3)N1—O1—Cu1—P3159.63 (15)
P3—C311—C312—C313177.38 (14)C211—P2—Cu1—O1115.58 (8)
C311—C312—C313—C3141.1 (3)C221—P2—Cu1—O14.47 (8)
C312—C313—C314—F31179.49 (16)C231—P2—Cu1—O1124.11 (7)
C312—C313—C314—C3150.2 (3)C211—P2—Cu1—P110.33 (7)
F31—C314—C315—C316178.93 (17)C221—P2—Cu1—P1130.38 (6)
C313—C314—C315—C3160.7 (3)C231—P2—Cu1—P1109.98 (6)
C314—C315—C316—C3110.0 (3)C211—P2—Cu1—P3150.88 (7)
C312—C311—C316—C3151.2 (3)C221—P2—Cu1—P389.07 (7)
P3—C311—C316—C315176.91 (14)C231—P2—Cu1—P330.58 (6)
C326—C321—C322—C3231.5 (3)C121—P1—Cu1—O13.63 (8)
P3—C321—C322—C323174.63 (14)C131—P1—Cu1—O1124.75 (7)
C321—C322—C323—C3240.1 (3)C111—P1—Cu1—O1116.10 (7)
C322—C323—C324—F32179.21 (16)C121—P1—Cu1—P2118.34 (7)
C322—C323—C324—C3251.5 (3)C131—P1—Cu1—P22.78 (7)
F32—C324—C325—C326179.20 (16)C111—P1—Cu1—P2121.93 (6)
C323—C324—C325—C3261.5 (3)C121—P1—Cu1—P3102.42 (7)
C324—C325—C326—C3210.0 (3)C131—P1—Cu1—P3136.47 (6)
C322—C321—C326—C3251.5 (3)C111—P1—Cu1—P317.32 (6)
P3—C321—C326—C325174.51 (14)C321—P3—Cu1—O1179.52 (8)
C336—C331—C332—C3330.6 (3)C311—P3—Cu1—O158.78 (7)
P3—C331—C332—C333174.43 (14)C331—P3—Cu1—O159.34 (7)
C331—C332—C333—C3341.2 (3)C321—P3—Cu1—P276.24 (7)
C332—C333—C334—F33179.35 (16)C311—P3—Cu1—P245.46 (6)
C332—C333—C334—C3350.7 (3)C331—P3—Cu1—P2163.59 (6)
F33—C334—C335—C336178.36 (15)C321—P3—Cu1—P165.89 (7)
C333—C334—C335—C3360.2 (3)C311—P3—Cu1—P1172.40 (6)
C334—C335—C336—C3310.8 (3)C331—P3—Cu1—P154.28 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C122—H122···O20.952.303.224 (2)163
C336—H336···O10.952.173.037 (2)151
C126—H126···F22i0.952.403.281 (2)154
C136—H136···O3ii0.952.533.223 (2)130
C215—H215···F13iii0.952.513.301 (2)141
C315—H315···F33iv0.952.503.403 (2)159
C332—H332···F32v0.952.483.131 (2)125
C326—H326···F33vi0.952.363.150 (2)141
Symmetry codes: (i) x1, y+1, z; (ii) x1, y, z; (iii) x+1, y+1, z+1; (iv) x, y1, z; (v) x+1, y+2, z; (vi) x+2, y+2, z.
Selected geometric parameters (Å, º) top
O1—Cu12.1182 (12)P2—Cu12.2840 (5)
P1—Cu12.2901 (5)P3—Cu12.3256 (5)
N1—O1—Cu1129.87 (11)O1—Cu1—P387.93 (4)
O1—Cu1—P2103.96 (4)P2—Cu1—P3112.289 (18)
O1—Cu1—P1112.11 (4)P1—Cu1—P3115.765 (18)
P2—Cu1—P1119.537 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C122—H122···O20.952.303.224 (2)163
C336—H336···O10.952.173.037 (2)151
C126—H126···F22i0.952.403.281 (2)154
C136—H136···O3ii0.952.533.223 (2)130
C215—H215···F13iii0.952.513.301 (2)141
C315—H315···F33iv0.952.503.403 (2)159
C332—H332···F32v0.952.483.131 (2)125
C326—H326···F33vi0.952.363.150 (2)141
Symmetry codes: (i) x1, y+1, z; (ii) x1, y, z; (iii) x+1, y+1, z+1; (iv) x, y1, z; (v) x+1, y+2, z; (vi) x+2, y+2, z.
Acknowledgements top

Financial assistance from the University of the Free State is gratefully acknowledged. We also express our gratitude towards SASOL and the South African National Research Foundation (SA-NRF/THRIP) for financial support of this project. Part of this material is based on work supported by the SA-NRF/THRIP under grant No. GUN 2068915. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the SA-NRF.

references
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