supplementary materials


vm2190 scheme

Acta Cryst. (2013). E69, m231    [ doi:10.1107/S1600536813006831 ]

catena-Poly[[copper(I)-[mu]-2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine] hexafluoridophosphate acetonitrile monosolvate] from single-crystal synchrotron data

L. Xiao, M. Bhadbhade and A. T. Baker

Abstract top

The title complex, {[Cu(C21H13N5S2)]PF6·CH3CN}n, was formed immediately on adding together a methanol solution containing copper(I) ions and a methanol solution of 2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine. Crystallographic studies of the complex reveal a coordination polymer with the ligand acting as a bis(bidentate) ligand with the pyridine N atom not coordinating a metal centre. The CuI atom is four-coordinate with approximately tetrahedral stereochemistry: the N4 donor set is provided by bipyridine-like moieties of the two heterocyclic ligands. Parallel chains of the coordination polymer run along the b-axis direction with the disordered (0.50:0.50 occupancy ratio) PF6- anions and acetonitrile solvent molecules located between the chains.

Comment top

We have prepared and studied many analogues of 2,2'-bipyridine and 2,2':6',2"-terpyridine (Baker and Matthews, 1999 and references therein) and have extended this work to the preparation of ligands analogous to quinquepyridine. For metal complexes of these quinquepyridine analogues, a number of features have been observed. The interpolation of a five-membered heterocycle appears to reduce the capacity of the ligands to employ all five donor atoms and we have seen several examples where the ligands act in a bis(bidentate) mode [2 + 2]. In such cases the ligands bridge between metal centres in binuclear complexes. Herein we report a coordination polymer shown in Scheme 1, again where the ligand binds in [2 + 2] mode. A thermal ellipsoid plot is shown in Fig. 1. Each copper centre has approximately tetrahedral stereochemistry as shown in Fig. 1. The principal cause of distortion being the bite angles of the bidentate ligand N2B—Cu1—N1B (82.47 (8)°) and N2Ai—Cu1—N1Ai (82.95 (8)°) (symmetry code: (i) -x + 1, y + 1/2, -z + 1/2) are considerably less than the ideal tetrahedral angle. Two 'thiazolylpyridine' moieties coordinate each copper(I) centre with the relevant bond lengths being Cu—N1Ai 2.098 (2) Å, Cu—N1B 2.050 (2) Å, Cu—N2A 1.992 (2) Å and Cu—N2B 2.024 (2) Å. The Cu—N bond lengths are similar but the Cu—Npyridinyl bonds are slightly shorter than the Cu—Nthiazolyl bonds. This indicates a slightly stronger interaction of the metal atom with the pyridinyl moiety, in line with base strength. A single chain of the coordination polymer, thus created, is depicted in Fig. 2 and packing of these chains that include PF6- anions and solvent molecules of acetonitriles are shown in Fig. 3.

Related literature top

For a related complex, see: Baker & Matthews (1999).

Experimental top

The quinquedentate ligand 2,6-bis(4-(pyridin-2-yl)thiazol-2-yl)pyridine was prepared by adding a solution of 2-(bromoacetyl)pyridinium hydrobromide (5.6 g, 20 mmol) in hot ethanol (50 ml) to a solution of 2,6-di(thioamido)pyridine (2.0 g, 10 mmol) in hot ethanol (50 ml). The solution was heated for 5 min, a yellow precipitate of 2,6-bis(4-(pyridin-2-yl)thiazol-2-yl)pyridinium hydrobromide separated soon. The mixture was allowed to stand for 30 min s and the yellow precipitate was filtered and washed with sodium bicarbonate (5%) until effervescence ceased. Yield: 75%. The complex was prepared as follows: Tetrakis(acetonitrile)copper(I) hexafluorophosphate (200 mg, 0.54 mmol) in hot methanol (20 ml) was added to a solution of the ligand (214 mg, 0.54 mmol) in hot methanol (20 ml). The reaction mixture was heated on the water bath for 1 h. An orange solid formed during this time and once cooled the solid was collected, washed with cooled methanol and stored over silica gel (yield 164 mg, 50%). Crystals were grown by vapour diffusion of diethyl ether into a concentrated acetonitrile solution of the complex.

Refinement top

All the H-atoms were fixed stereochemically and included in the refinement using riding model option in SHELXL97. The PF6 anion was found to exhibit orientational disorder, which was modelled over two positions.

H atoms were positioned geometrically with C—H = 0.93 - 0.96 Å. Uiso(H) values were set at 1.2Ueq (aromatic) or 1.5Ueq of the parent atom (methyl group).

Computing details top

Data collection: BLU-ICE (McPhillips et al., 2002); cell refinement: XDS (Kabsch, 1993); data reduction: XDS (Kabsch, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoids plot (40% probability) of the part of the coordination polymer showing the geometry around Cu(I) ion. Hydrogen atoms, the PF6 anion and the solvent acetonitrile molecule are omitted for clarity. Symmetry code: (i) -x + 1, y + 1/2, -z + 1/2.
[Figure 2] Fig. 2. A single chain showing the construction of the coordination polymer formed with the ligand.
[Figure 3] Fig. 3. Packing of coordination polymers viewed down c axis that includes PF6 anions (disorder omitted for clarity) and solvent molecules (acetonitrile).
catena-Poly[[copper(I)-µ-2,6-bis[4-(pyridin-2-yl)thiazol-2-yl]pyridine] hexafluoridophosphate acetonitrile monosolvate] top
Crystal data top
[Cu(C21H13N5S2)]PF6·C2H3NF(000) = 1304
Mr = 649.05Dx = 1.702 Mg m3
Monoclinic, P21/cSynchrotron radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9980 reflections
a = 12.525 (3) Åθ = 2.5–22.5°
b = 13.950 (3) ŵ = 1.16 mm1
c = 14.626 (3) ÅT = 100 K
β = 97.72 (3)°Thin plates, blue
V = 2532.4 (9) Å30.03 × 0.02 × 0.01 mm
Z = 4
Data collection top
3-BM1 Australian Synchrotron
diffractometer
3641 reflections with I > 2σ(I)
Radiation source: Synchrotron BMRint = 0.024
Si<111> monochromatorθmax = 23.8°, θmin = 1.6°
φ scansh = 1414
28022 measured reflectionsk = 1515
3890 independent reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0359P)2 + 3.8973P],P = (Fo2 + 2Fc2)/3
3890 reflections(Δ/σ)max = 0.001
389 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.57 e Å3
Crystal data top
[Cu(C21H13N5S2)]PF6·C2H3NV = 2532.4 (9) Å3
Mr = 649.05Z = 4
Monoclinic, P21/cSynchrotron radiation, λ = 0.71073 Å
a = 12.525 (3) ŵ = 1.16 mm1
b = 13.950 (3) ÅT = 100 K
c = 14.626 (3) Å0.03 × 0.02 × 0.01 mm
β = 97.72 (3)°
Data collection top
3-BM1 Australian Synchrotron
diffractometer
Rint = 0.024
28022 measured reflectionsθmax = 23.8°
3890 independent reflectionsStandard reflections: 0
3641 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.078Δρmax = 0.30 e Å3
S = 1.08Δρmin = 0.57 e Å3
3890 reflectionsAbsolute structure: ?
389 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.

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
xyzUiso*/UeqOcc. (<1)
Cu10.70815 (2)1.19154 (2)0.36895 (2)0.01965 (11)
N10.40269 (16)0.95445 (14)0.35587 (13)0.0159 (4)
C10.5696 (2)0.89759 (19)0.25992 (17)0.0211 (6)
H10.62570.87840.22850.025*
C20.4814 (2)0.83892 (18)0.26281 (17)0.0197 (5)
H20.47730.77940.23390.024*
C30.3990 (2)0.87086 (17)0.30999 (16)0.0165 (5)
C40.48924 (19)1.00992 (17)0.35293 (16)0.0162 (5)
C50.5735 (2)0.98545 (18)0.30444 (17)0.0197 (5)
H50.63111.02700.30200.024*
S1A0.21354 (5)0.84000 (5)0.39190 (4)0.02002 (16)
N1A0.27744 (16)0.73513 (14)0.26615 (14)0.0163 (4)
N2A0.17898 (16)0.59744 (15)0.15433 (14)0.0180 (4)
C1A0.3024 (2)0.81261 (17)0.31486 (16)0.0160 (5)
C2A0.18499 (19)0.69316 (17)0.28980 (17)0.0173 (5)
C3A0.1400 (2)0.74016 (19)0.35688 (17)0.0207 (5)
H3A0.07810.72070.38030.025*
C4A0.14469 (19)0.60735 (18)0.23785 (17)0.0173 (5)
C5A0.0784 (2)0.5404 (2)0.27187 (18)0.0239 (6)
H5A0.05740.54840.33000.029*
C6A0.0438 (2)0.4617 (2)0.21859 (19)0.0276 (6)
H6A0.00010.41570.24050.033*
C7A0.0757 (2)0.4527 (2)0.13181 (19)0.0275 (6)
H7A0.05200.40150.09370.033*
C8A0.1432 (2)0.52119 (18)0.10326 (18)0.0232 (6)
H8A0.16520.51420.04540.028*
S1B0.37811 (5)1.12599 (5)0.46088 (4)0.02089 (16)
N1B0.56301 (16)1.16578 (14)0.41446 (13)0.0154 (4)
N2B0.69867 (17)1.31538 (14)0.43946 (14)0.0193 (5)
C1B0.48752 (19)1.09985 (18)0.40534 (16)0.0165 (5)
C2B0.5353 (2)1.24125 (18)0.46810 (16)0.0173 (5)
C3B0.4376 (2)1.23154 (18)0.49859 (17)0.0207 (5)
H4B0.40761.27620.53490.025*
C4B0.6105 (2)1.32303 (18)0.48297 (17)0.0190 (5)
C5B0.5930 (2)1.40191 (19)0.53706 (18)0.0248 (6)
H5B0.53301.40470.56820.030*
C6B0.6670 (2)1.47623 (19)0.54353 (19)0.0290 (6)
H6B0.65661.53030.57850.035*
C7B0.7559 (2)1.46972 (19)0.49804 (18)0.0263 (6)
H7B0.80591.51930.50130.032*
C8B0.7696 (2)1.38795 (19)0.44740 (18)0.0239 (6)
H8B0.83051.38310.41760.029*
P10.91781 (5)0.77051 (5)0.06197 (5)0.02250 (17)
F11.02028 (15)0.72763 (13)0.02232 (14)0.0467 (5)
F20.9637 (5)0.7561 (5)0.1692 (5)0.0320 (13)0.50
F30.8706 (11)0.6650 (9)0.0595 (7)0.034 (2)0.50
F40.8738 (5)0.7876 (5)0.0432 (4)0.0503 (15)0.50
F50.9640 (8)0.8778 (6)0.0694 (4)0.0348 (15)0.50
F2'1.0012 (6)0.7796 (6)0.1511 (5)0.064 (2)0.50
F3'0.8878 (13)0.6654 (11)0.0896 (8)0.063 (4)0.50
F4'0.8345 (5)0.7575 (6)0.0299 (5)0.063 (2)0.50
F5'0.9533 (8)0.8721 (7)0.0272 (6)0.080 (3)0.50
F60.81523 (16)0.81302 (15)0.10063 (17)0.0572 (6)
C1AN0.1934 (3)0.1022 (3)0.2238 (2)0.0507 (9)
H1A10.14680.07720.17180.076*
H1A20.16370.16060.24420.076*
H1A30.20010.05620.27300.076*
C2AN0.2998 (3)0.1214 (2)0.19694 (19)0.0297 (7)
N1AN0.3824 (2)0.13309 (19)0.17597 (18)0.0368 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02253 (19)0.01556 (18)0.02245 (18)0.00197 (12)0.00884 (13)0.00093 (12)
N10.0184 (11)0.0143 (10)0.0151 (10)0.0000 (8)0.0026 (8)0.0017 (8)
C10.0218 (13)0.0219 (14)0.0209 (13)0.0003 (11)0.0083 (10)0.0021 (11)
C20.0243 (14)0.0154 (13)0.0195 (13)0.0016 (10)0.0031 (10)0.0016 (10)
C30.0198 (13)0.0146 (12)0.0146 (12)0.0000 (10)0.0012 (10)0.0032 (10)
C40.0214 (13)0.0130 (12)0.0137 (12)0.0013 (10)0.0000 (10)0.0016 (10)
C50.0195 (13)0.0194 (13)0.0210 (13)0.0038 (10)0.0058 (10)0.0006 (10)
S1A0.0198 (3)0.0213 (3)0.0196 (3)0.0006 (3)0.0054 (2)0.0028 (3)
N1A0.0173 (10)0.0145 (11)0.0172 (10)0.0002 (8)0.0024 (8)0.0026 (9)
N2A0.0174 (10)0.0165 (11)0.0199 (11)0.0017 (9)0.0022 (8)0.0025 (9)
C1A0.0179 (12)0.0151 (13)0.0150 (12)0.0023 (10)0.0025 (10)0.0023 (10)
C2A0.0157 (12)0.0173 (13)0.0188 (12)0.0003 (10)0.0016 (10)0.0047 (10)
C3A0.0173 (13)0.0243 (14)0.0211 (13)0.0019 (11)0.0046 (10)0.0023 (11)
C4A0.0148 (12)0.0160 (13)0.0207 (13)0.0019 (10)0.0009 (10)0.0041 (10)
C5A0.0221 (14)0.0262 (14)0.0233 (13)0.0032 (11)0.0029 (11)0.0052 (11)
C6A0.0258 (14)0.0227 (14)0.0337 (15)0.0093 (11)0.0023 (12)0.0069 (12)
C7A0.0317 (15)0.0188 (14)0.0310 (15)0.0073 (12)0.0004 (12)0.0022 (12)
C8A0.0272 (14)0.0199 (14)0.0226 (13)0.0005 (11)0.0036 (11)0.0002 (11)
S1B0.0197 (3)0.0201 (3)0.0244 (3)0.0023 (3)0.0085 (3)0.0034 (3)
N1B0.0189 (11)0.0132 (10)0.0146 (10)0.0000 (8)0.0038 (8)0.0009 (8)
N2B0.0225 (11)0.0152 (11)0.0197 (11)0.0005 (9)0.0010 (9)0.0010 (9)
C1B0.0181 (12)0.0178 (13)0.0141 (12)0.0018 (10)0.0039 (10)0.0021 (10)
C2B0.0230 (13)0.0148 (12)0.0142 (12)0.0020 (10)0.0025 (10)0.0001 (10)
C3B0.0231 (14)0.0186 (13)0.0212 (13)0.0005 (11)0.0059 (10)0.0051 (11)
C4B0.0229 (13)0.0166 (13)0.0172 (12)0.0019 (10)0.0013 (10)0.0019 (10)
C5B0.0294 (15)0.0196 (14)0.0253 (14)0.0035 (11)0.0037 (11)0.0033 (11)
C6B0.0404 (17)0.0173 (14)0.0288 (15)0.0022 (12)0.0022 (13)0.0060 (11)
C7B0.0336 (16)0.0153 (13)0.0283 (15)0.0057 (11)0.0021 (12)0.0008 (11)
C8B0.0236 (14)0.0212 (14)0.0269 (14)0.0031 (11)0.0030 (11)0.0038 (11)
P10.0214 (4)0.0218 (4)0.0244 (4)0.0027 (3)0.0035 (3)0.0035 (3)
F10.0402 (11)0.0389 (11)0.0688 (13)0.0088 (8)0.0354 (10)0.0116 (9)
F20.046 (4)0.029 (2)0.021 (2)0.009 (2)0.003 (2)0.0040 (16)
F30.033 (4)0.020 (4)0.051 (5)0.010 (3)0.016 (3)0.016 (4)
F40.064 (5)0.061 (4)0.023 (2)0.018 (3)0.008 (3)0.011 (2)
F50.046 (3)0.017 (2)0.046 (3)0.001 (2)0.024 (3)0.002 (3)
F2'0.053 (5)0.092 (6)0.039 (4)0.035 (4)0.018 (3)0.038 (4)
F3'0.051 (6)0.043 (5)0.103 (10)0.004 (4)0.037 (6)0.032 (6)
F4'0.031 (3)0.113 (6)0.041 (3)0.001 (3)0.010 (2)0.001 (3)
F5'0.038 (3)0.030 (4)0.176 (9)0.006 (3)0.027 (6)0.054 (6)
F60.0392 (11)0.0510 (13)0.0864 (16)0.0157 (9)0.0267 (11)0.0079 (11)
C1AN0.0362 (19)0.077 (3)0.0421 (19)0.0020 (18)0.0159 (15)0.0064 (19)
C2AN0.0368 (18)0.0305 (16)0.0215 (14)0.0006 (13)0.0026 (13)0.0061 (12)
N1AN0.0347 (16)0.0418 (16)0.0340 (14)0.0042 (12)0.0049 (12)0.0149 (12)
Geometric parameters (Å, º) top
Cu1—N2Ai1.992 (2)C8A—H8A0.9300
Cu1—N2B2.024 (2)S1B—C3B1.708 (3)
Cu1—N1B2.050 (2)S1B—C1B1.723 (2)
Cu1—N1Ai2.098 (2)N1B—C1B1.313 (3)
N1—C41.337 (3)N1B—C2B1.385 (3)
N1—C31.343 (3)N2B—C8B1.342 (3)
C1—C21.380 (4)N2B—C4B1.351 (3)
C1—C51.386 (4)C2B—C3B1.364 (4)
C1—H10.9300C2B—C4B1.476 (4)
C2—C31.390 (4)C3B—H4B0.9300
C2—H20.9300C4B—C5B1.390 (4)
C3—C1A1.467 (3)C5B—C6B1.385 (4)
C4—C51.391 (4)C5B—H5B0.9300
C4—C1B1.472 (3)C6B—C7B1.375 (4)
C5—H50.9300C6B—H6B0.9300
S1A—C3A1.710 (3)C7B—C8B1.383 (4)
S1A—C1A1.730 (2)C7B—H7B0.9300
N1A—C1A1.309 (3)C8B—H8B0.9300
N1A—C2A1.382 (3)P1—F2'1.562 (7)
N1A—Cu1ii2.098 (2)P1—F3'1.580 (16)
N2A—C8A1.342 (3)P1—F41.581 (6)
N2A—C4A1.355 (3)P1—F31.585 (13)
N2A—Cu1ii1.992 (2)P1—F61.587 (2)
C2A—C3A1.363 (4)P1—F5'1.589 (9)
C2A—C4A1.470 (4)P1—F11.5941 (18)
C3A—H3A0.9300P1—F4'1.597 (7)
C4A—C5A1.385 (4)P1—F51.603 (9)
C5A—C6A1.382 (4)P1—F21.609 (7)
C5A—H5A0.9300C1AN—C2AN1.464 (4)
C6A—C7A1.387 (4)C1AN—H1A10.9600
C6A—H6A0.9300C1AN—H1A20.9600
C7A—C8A1.377 (4)C1AN—H1A30.9600
C7A—H7A0.9300C2AN—N1AN1.130 (4)
N2Ai—Cu1—N2B137.85 (9)S1B—C3B—H4B124.7
N2Ai—Cu1—N1B128.37 (8)N2B—C4B—C5B122.1 (2)
N2B—Cu1—N1B82.47 (8)N2B—C4B—C2B114.5 (2)
N2Ai—Cu1—N1Ai82.95 (8)C5B—C4B—C2B123.3 (2)
N2B—Cu1—N1Ai104.53 (8)C6B—C5B—C4B118.5 (3)
N1B—Cu1—N1Ai123.28 (8)C6B—C5B—H5B120.8
C4—N1—C3117.4 (2)C4B—C5B—H5B120.8
C2—C1—C5119.2 (2)C7B—C6B—C5B119.7 (3)
C2—C1—H1120.4C7B—C6B—H6B120.1
C5—C1—H1120.4C5B—C6B—H6B120.1
C1—C2—C3118.4 (2)C6B—C7B—C8B118.7 (3)
C1—C2—H2120.8C6B—C7B—H7B120.7
C3—C2—H2120.8C8B—C7B—H7B120.7
N1—C3—C2123.3 (2)N2B—C8B—C7B122.7 (3)
N1—C3—C1A115.5 (2)N2B—C8B—H8B118.6
C2—C3—C1A121.3 (2)C7B—C8B—H8B118.6
N1—C4—C5123.3 (2)F2'—P1—F3'91.0 (5)
N1—C4—C1B114.1 (2)F2'—P1—F4155.0 (4)
C5—C4—C1B122.7 (2)F3'—P1—F4109.0 (5)
C1—C5—C4118.4 (2)F2'—P1—F3107.4 (5)
C1—C5—H5120.8F3'—P1—F316.8 (6)
C4—C5—H5120.8F4—P1—F392.2 (5)
C3A—S1A—C1A89.57 (12)F2'—P1—F698.9 (3)
C1A—N1A—C2A111.1 (2)F3'—P1—F691.4 (6)
C1A—N1A—Cu1ii135.01 (17)F4—P1—F695.6 (3)
C2A—N1A—Cu1ii107.09 (15)F3—P1—F692.2 (5)
C8A—N2A—C4A117.4 (2)F2'—P1—F5'90.6 (5)
C8A—N2A—Cu1ii128.23 (18)F3'—P1—F5'174.9 (7)
C4A—N2A—Cu1ii113.89 (16)F4—P1—F5'68.3 (4)
N1A—C1A—C3124.7 (2)F3—P1—F5'160.2 (5)
N1A—C1A—S1A114.16 (18)F6—P1—F5'93.2 (3)
C3—C1A—S1A121.09 (18)F2'—P1—F181.6 (3)
C3A—C2A—N1A114.7 (2)F3'—P1—F188.6 (6)
C3A—C2A—C4A128.1 (2)F4—P1—F184.0 (3)
N1A—C2A—C4A117.2 (2)F3—P1—F187.7 (5)
C2A—C3A—S1A110.47 (19)F6—P1—F1179.52 (13)
C2A—C3A—H3A124.8F5'—P1—F186.8 (3)
S1A—C3A—H3A124.8F2'—P1—F4'177.9 (4)
N2A—C4A—C5A122.2 (2)F3'—P1—F4'87.6 (5)
N2A—C4A—C2A114.9 (2)F4—P1—F4'25.2 (2)
C5A—C4A—C2A122.9 (2)F3—P1—F4'71.1 (5)
C6A—C5A—C4A119.4 (2)F6—P1—F4'82.8 (3)
C6A—C5A—H5A120.3F5'—P1—F4'90.7 (4)
C4A—C5A—H5A120.3F1—P1—F4'96.8 (3)
C5A—C6A—C7A118.8 (2)F2'—P1—F570.9 (4)
C5A—C6A—H6A120.6F3'—P1—F5161.0 (4)
C7A—C6A—H6A120.6F4—P1—F590.0 (3)
C8A—C7A—C6A118.6 (3)F3—P1—F5177.2 (5)
C8A—C7A—H7A120.7F6—P1—F586.0 (3)
C6A—C7A—H7A120.7F5'—P1—F522.4 (4)
N2A—C8A—C7A123.6 (2)F1—P1—F594.2 (3)
N2A—C8A—H8A118.2F4'—P1—F5110.7 (4)
C7A—C8A—H8A118.2F2'—P1—F223.9 (3)
C3B—S1B—C1B89.68 (12)F3'—P1—F272.6 (4)
C1B—N1B—C2B111.0 (2)F4—P1—F2178.4 (3)
C1B—N1B—Cu1138.40 (17)F3—P1—F289.4 (4)
C2B—N1B—Cu1110.56 (16)F6—P1—F284.2 (2)
C8B—N2B—C4B118.3 (2)F5'—P1—F2110.2 (4)
C8B—N2B—Cu1127.22 (18)F1—P1—F296.2 (2)
C4B—N2B—Cu1114.53 (17)F4'—P1—F2156.0 (3)
N1B—C1B—C4126.1 (2)F5—P1—F288.4 (3)
N1B—C1B—S1B114.28 (18)C2AN—C1AN—H1A1109.5
C4—C1B—S1B119.61 (18)C2AN—C1AN—H1A2109.5
C3B—C2B—N1B114.4 (2)H1A1—C1AN—H1A2109.5
C3B—C2B—C4B127.6 (2)C2AN—C1AN—H1A3109.5
N1B—C2B—C4B117.9 (2)H1A1—C1AN—H1A3109.5
C2B—C3B—S1B110.60 (19)H1A2—C1AN—H1A3109.5
C2B—C3B—H4B124.7N1AN—C2AN—C1AN177.8 (4)
C5—C1—C2—C30.5 (4)N2B—Cu1—N1B—C1B176.7 (3)
C4—N1—C3—C22.0 (3)N1Ai—Cu1—N1B—C1B74.2 (3)
C4—N1—C3—C1A179.8 (2)N2Ai—Cu1—N1B—C2B147.28 (15)
C1—C2—C3—N12.6 (4)N2B—Cu1—N1B—C2B0.84 (16)
C1—C2—C3—C1A179.3 (2)N1Ai—Cu1—N1B—C2B103.31 (16)
C3—N1—C4—C50.6 (3)N2Ai—Cu1—N2B—C8B39.4 (3)
C3—N1—C4—C1B179.6 (2)N1B—Cu1—N2B—C8B178.7 (2)
C2—C1—C5—C41.9 (4)N1Ai—Cu1—N2B—C8B56.2 (2)
N1—C4—C5—C12.6 (4)N2Ai—Cu1—N2B—C4B140.17 (17)
C1B—C4—C5—C1177.7 (2)N1B—Cu1—N2B—C4B1.73 (17)
C2A—N1A—C1A—C3176.6 (2)N1Ai—Cu1—N2B—C4B124.25 (17)
Cu1ii—N1A—C1A—C337.1 (4)C2B—N1B—C1B—C4179.8 (2)
C2A—N1A—C1A—S1A0.7 (3)Cu1—N1B—C1B—C42.3 (4)
Cu1ii—N1A—C1A—S1A145.62 (16)C2B—N1B—C1B—S1B0.3 (3)
N1—C3—C1A—N1A171.2 (2)Cu1—N1B—C1B—S1B177.16 (14)
C2—C3—C1A—N1A10.5 (4)N1—C4—C1B—N1B179.0 (2)
N1—C3—C1A—S1A11.7 (3)C5—C4—C1B—N1B1.2 (4)
C2—C3—C1A—S1A166.63 (19)N1—C4—C1B—S1B1.5 (3)
C3A—S1A—C1A—N1A0.76 (19)C5—C4—C1B—S1B178.24 (19)
C3A—S1A—C1A—C3176.6 (2)C3B—S1B—C1B—N1B0.1 (2)
C1A—N1A—C2A—C3A0.2 (3)C3B—S1B—C1B—C4179.6 (2)
Cu1ii—N1A—C2A—C3A155.55 (18)C1B—N1B—C2B—C3B0.5 (3)
C1A—N1A—C2A—C4A177.6 (2)Cu1—N1B—C2B—C3B177.75 (17)
Cu1ii—N1A—C2A—C4A21.8 (2)C1B—N1B—C2B—C4B178.3 (2)
N1A—C2A—C3A—S1A0.3 (3)Cu1—N1B—C2B—C4B0.1 (3)
C4A—C2A—C3A—S1A176.7 (2)N1B—C2B—C3B—S1B0.4 (3)
C1A—S1A—C3A—C2A0.6 (2)C4B—C2B—C3B—S1B178.0 (2)
C8A—N2A—C4A—C5A2.3 (3)C1B—S1B—C3B—C2B0.2 (2)
Cu1ii—N2A—C4A—C5A170.47 (19)C8B—N2B—C4B—C5B1.8 (4)
C8A—N2A—C4A—C2A178.9 (2)Cu1—N2B—C4B—C5B177.81 (19)
Cu1ii—N2A—C4A—C2A8.3 (3)C8B—N2B—C4B—C2B178.2 (2)
C3A—C2A—C4A—N2A155.6 (2)Cu1—N2B—C4B—C2B2.2 (3)
N1A—C2A—C4A—N2A21.4 (3)C3B—C2B—C4B—N2B176.0 (2)
C3A—C2A—C4A—C5A25.6 (4)N1B—C2B—C4B—N2B1.5 (3)
N1A—C2A—C4A—C5A157.4 (2)C3B—C2B—C4B—C5B4.0 (4)
N2A—C4A—C5A—C6A1.4 (4)N1B—C2B—C4B—C5B178.5 (2)
C2A—C4A—C5A—C6A179.9 (2)N2B—C4B—C5B—C6B2.3 (4)
C4A—C5A—C6A—C7A0.7 (4)C2B—C4B—C5B—C6B177.7 (2)
C5A—C6A—C7A—C8A1.8 (4)C4B—C5B—C6B—C7B1.0 (4)
C4A—N2A—C8A—C7A1.1 (4)C5B—C6B—C7B—C8B0.6 (4)
Cu1ii—N2A—C8A—C7A170.5 (2)C4B—N2B—C8B—C7B0.0 (4)
C6A—C7A—C8A—N2A1.0 (4)Cu1—N2B—C8B—C7B179.53 (19)
N2Ai—Cu1—N1B—C1B35.2 (3)C6B—C7B—C8B—N2B1.2 (4)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
Acknowledgements top

The authors thank the Australain Synchrotron Facility, Melbourne, for the X-ray data.

references
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