Tracking the dissolution–recrystallization structural transformation (DRST) of copper(II) com­plexes: a combined crystallographic, mass spectrometric and DFT study

Methanol- and temperature-induced dissolution–recrystallization structural transformation (DRST) was observed among two novel Cu^II com­plexes. This is first time that the combination of X-ray crystallography, mass spectrometry and density functional theory (DFT) theoretical calculations has been used to describe the fragmentation and recombination of a mononuclear Cu^II com­plex at 60 °C in methanol to obtain a binuclear copper(II) com­plex. Combining time-dependent high-resolution electrospray mass spectrometry, we propose a possible mechanism for the conversion of bis­(8-meth­oxy­quinoline-κ²N,O)bis­(thio­cyanato-κN)copper(II), [Cu(NCS)₂(C₁₀H₉NO)₂], Cu1, to di-μ-methano­l­ato-κ⁴O:O-bis­[(8-meth­oxy­quinoline-κ²N,O)(thio­cyanato-κN)copper(II)], [Cu₂(CH₃O)₂(NCS)₂(C₁₀H₉NO)₂], Cu2, viz. [Cu(SCN)₂(L)₂] (Cu1) → [Cu(L)₂] → [Cu(L)]/L → [Cu₂(CH₃O)₂(NCS)₂(L)₂] (Cu2). We screened the anti­tumour activities of L (8-meth­oxy­quinoline), Cu1 and Cu2 and found that the anti­proliferative effect of Cu2 on some tumour cells was much greater than that of L and Cu1.

Computing details

For both structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis(8-methoxyquinoline-κ²N,O)bis(thiocyanato-κN)copper(II) (Cu1)

Crystal data

[Cu(NCS)2(C10H9NO)2]	Dx = 1.503 Mg m^−3
Mr = 498.06	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3221	Cell parameters from 1978 reflections
a = 9.7940 (3) Å	θ = 3.9–23.9°
c = 19.8673 (8) Å	µ = 1.21 mm^−1
V = 1650.40 (10) Å^3	T = 293 K
Z = 3	Block, green
F(000) = 765	0.05 × 0.03 × 0.03 mm

Data collection

Rigaku SuperNova Single Source diffractometer with an Eos detector	1937 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source	1685 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.036
Detector resolution: 15.9784 pixels mm^-1	θmax = 25.0°, θmin = 3.9°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD 2015)	k = −11→11
Tmin = 0.812, Tmax = 1.000	l = −23→22
7518 measured reflections

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.149	w = 1/[σ^2(Fo^2) + (0.0663P)^2 + 2.3337P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
1937 reflections	Δρmax = 0.77 e Å^−3
142 parameters	Δρmin = −0.43 e Å^−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: dual	Absolute structure parameter: 0.32 (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 > 2sigma(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.

Diffraction data for these complexes were collected on a Rigaku Oxford Diffraction (Mo-Kα radiation and λ = 0.71073 Å) in Φ and ω scan modes. The structures were solved by direct methods followed by difference Fourier syntheses, and then refined by full-matrix least-squares techniques on F² using SHELXL (Sheldrick, 2015). All other non-hydrogen atoms were refined with anisotropic thermal parameters.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	1.0000	0.56436 (10)	0.3333	0.0441 (3)
S1	0.6161 (3)	0.0593 (3)	0.26515 (12)	0.0835 (7)
O1	0.8579 (5)	0.5224 (5)	0.4387 (2)	0.0562 (12)
N2	1.1163 (5)	0.7683 (5)	0.3867 (2)	0.0429 (10)
C11	0.7492 (8)	0.2376 (9)	0.2879 (3)	0.0538 (16)
C7	1.0685 (6)	0.7794 (7)	0.4510 (3)	0.0414 (13)
C6	1.1538 (7)	0.9182 (7)	0.4888 (3)	0.0511 (15)
N1	0.8560 (8)	0.3562 (7)	0.2996 (3)	0.079 (2)
C5	1.1037 (9)	0.9244 (10)	0.5550 (4)	0.072 (2)
H5	1.1581	1.0154	0.5808	0.087*
C9	1.3276 (8)	1.0289 (9)	0.3973 (3)	0.0653 (19)
H9	1.4139	1.1137	0.3770	0.078*
C10	1.2426 (7)	0.8887 (7)	0.3623 (3)	0.0519 (16)
H10	1.2770	0.8803	0.3197	0.062*
C2	0.9323 (7)	0.6492 (7)	0.4793 (3)	0.0455 (14)
C4	0.9746 (10)	0.7952 (10)	0.5803 (4)	0.077 (2)
H4	0.9441	0.7980	0.6244	0.092*
C8	1.2865 (8)	1.0435 (8)	0.4600 (3)	0.0599 (17)
H8	1.3462	1.1364	0.4840	0.072*
C3	0.8876 (8)	0.6606 (9)	0.5428 (3)	0.0654 (16)
H3	0.7973	0.5766	0.5611	0.078*
C1	0.7280 (8)	0.3808 (8)	0.4657 (4)	0.070 (2)
H1A	0.6387	0.3954	0.4714	0.104*
H1B	0.7573	0.3577	0.5085	0.104*
H1C	0.7011	0.2948	0.4353	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0366 (5)	0.0413 (4)	0.0530 (6)	0.0183 (3)	−0.0053 (5)	−0.0026 (2)
S1	0.0744 (14)	0.0687 (13)	0.0966 (15)	0.0277 (11)	−0.0044 (11)	−0.0115 (11)
O1	0.046 (2)	0.049 (2)	0.055 (2)	0.010 (2)	0.007 (2)	0.007 (2)
N2	0.036 (2)	0.041 (2)	0.046 (2)	0.015 (2)	−0.002 (2)	0.008 (2)
C11	0.047 (4)	0.071 (5)	0.049 (3)	0.034 (4)	0.006 (3)	0.013 (3)
C7	0.036 (3)	0.047 (3)	0.043 (3)	0.023 (2)	−0.005 (2)	0.003 (2)
C6	0.046 (4)	0.051 (4)	0.051 (3)	0.020 (3)	−0.002 (3)	−0.001 (3)
N1	0.076 (5)	0.049 (3)	0.099 (5)	0.022 (3)	−0.034 (4)	−0.019 (3)
C5	0.066 (5)	0.077 (5)	0.060 (4)	0.026 (4)	−0.002 (4)	−0.021 (4)
C9	0.051 (4)	0.058 (4)	0.063 (4)	0.010 (3)	0.006 (3)	0.010 (4)
C10	0.044 (3)	0.044 (3)	0.051 (3)	0.009 (3)	0.002 (3)	0.005 (3)
C2	0.038 (3)	0.048 (4)	0.046 (3)	0.017 (2)	−0.004 (3)	0.001 (3)
C4	0.072 (5)	0.097 (6)	0.055 (4)	0.038 (5)	0.012 (4)	−0.007 (4)
C8	0.053 (4)	0.047 (4)	0.064 (4)	0.013 (3)	−0.005 (3)	−0.007 (3)
C3	0.051 (4)	0.068 (4)	0.058 (3)	0.014 (3)	0.006 (3)	0.004 (4)
C1	0.048 (4)	0.048 (4)	0.092 (5)	0.008 (3)	0.012 (4)	0.013 (4)

Geometric parameters (Å, º)

Cu1—O1	2.432 (4)	C6—C8	1.389 (9)
Cu1—O1^i	2.432 (4)	C5—H5	0.9300
Cu1—N2^i	2.034 (5)	C5—C4	1.361 (11)
Cu1—N2	2.034 (5)	C9—H9	0.9300
Cu1—N1^i	1.928 (6)	C9—C10	1.385 (9)
Cu1—N1	1.928 (6)	C9—C8	1.339 (9)
S1—C11	1.636 (8)	C10—H10	0.9300
O1—C2	1.349 (7)	C2—C3	1.357 (8)
O1—C1	1.437 (7)	C4—H4	0.9300
N2—C7	1.384 (7)	C4—C3	1.377 (10)
N2—C10	1.303 (7)	C8—H8	0.9300
C11—N1	1.132 (8)	C3—H3	0.9300
C7—C6	1.405 (8)	C1—H1A	0.9600
C7—C2	1.422 (8)	C1—H1B	0.9600
C6—C5	1.415 (9)	C1—H1C	0.9600
O1^i—Cu1—O1	166.6 (2)	C11—N1—Cu1	165.4 (7)
N2—Cu1—O1	73.11 (15)	C6—C5—H5	120.5
N2^i—Cu1—O1^i	73.11 (15)	C4—C5—C6	118.9 (7)
N2—Cu1—O1^i	97.25 (16)	C4—C5—H5	120.5
N2^i—Cu1—O1	97.25 (16)	C10—C9—H9	119.7
N2^i—Cu1—N2	90.8 (3)	C8—C9—H9	119.7
N1^i—Cu1—O1^i	93.8 (2)	C8—C9—C10	120.6 (6)
N1^i—Cu1—O1	95.5 (2)	N2—C10—C9	122.6 (6)
N1—Cu1—O1^i	95.5 (2)	N2—C10—H10	118.7
N1—Cu1—O1	93.8 (2)	C9—C10—H10	118.7
N1^i—Cu1—N2	89.8 (2)	O1—C2—C7	114.9 (5)
N1^i—Cu1—N2^i	166.8 (2)	O1—C2—C3	125.7 (6)
N1—Cu1—N2^i	89.8 (2)	C3—C2—C7	119.3 (6)
N1—Cu1—N2	166.8 (2)	C5—C4—H4	118.9
N1—Cu1—N1^i	92.5 (4)	C5—C4—C3	122.2 (7)
C2—O1—Cu1	111.1 (3)	C3—C4—H4	118.9
C2—O1—C1	118.3 (5)	C6—C8—H8	120.4
C1—O1—Cu1	129.8 (4)	C9—C8—C6	119.1 (6)
C7—N2—Cu1	120.9 (3)	C9—C8—H8	120.4
C10—N2—Cu1	120.5 (4)	C2—C3—C4	120.8 (7)
C10—N2—C7	118.5 (5)	C2—C3—H3	119.6
N1—C11—S1	170.4 (7)	C4—C3—H3	119.6
N2—C7—C6	120.6 (5)	O1—C1—H1A	109.5
N2—C7—C2	119.8 (5)	O1—C1—H1B	109.5
C6—C7—C2	119.6 (5)	O1—C1—H1C	109.5
C7—C6—C5	119.2 (6)	H1A—C1—H1B	109.5
C8—C6—C7	118.4 (5)	H1A—C1—H1C	109.5
C8—C6—C5	122.4 (6)	H1B—C1—H1C	109.5
Cu1—O1—C2—C7	3.4 (5)	C7—N2—C10—C9	−2.2 (9)
Cu1—O1—C2—C3	−176.7 (5)	C7—C6—C5—C4	0.4 (11)
Cu1—N2—C7—C6	177.0 (4)	C7—C6—C8—C9	0.8 (10)
Cu1—N2—C7—C2	−2.7 (6)	C7—C2—C3—C4	−1.5 (10)
Cu1—N2—C10—C9	−178.7 (5)	C6—C7—C2—O1	179.3 (5)
S1—C11—N1—Cu1	−170 (2)	C6—C7—C2—C3	−0.6 (8)
O1^i—Cu1—O1—C2	−49.0 (3)	C6—C5—C4—C3	−2.5 (13)
O1^i—Cu1—O1—C1	141.5 (5)	N1^i—Cu1—O1—C2	84.5 (4)
O1^i—Cu1—N2—C7	173.7 (4)	N1—Cu1—O1—C2	177.4 (4)
O1—Cu1—N2—C7	3.3 (4)	N1^i—Cu1—O1—C1	−85.0 (5)
O1—Cu1—N2—C10	179.7 (5)	N1—Cu1—O1—C1	7.9 (6)
O1^i—Cu1—N2—C10	−9.9 (5)	N1—Cu1—N2—C7	7.8 (13)
O1—Cu1—N1—C11	30 (3)	N1^i—Cu1—N2—C7	−92.6 (4)
O1^i—Cu1—N1—C11	−140 (2)	N1—Cu1—N2—C10	−175.8 (10)
O1—C2—C3—C4	178.7 (7)	N1^i—Cu1—N2—C10	83.9 (5)
N2—Cu1—O1—C2	−3.6 (3)	N1^i—Cu1—N1—C11	126 (3)
N2^i—Cu1—O1—C2	−92.3 (4)	C5—C6—C8—C9	179.6 (7)
N2—Cu1—O1—C1	−173.2 (6)	C5—C4—C3—C2	3.1 (13)
N2^i—Cu1—O1—C1	98.2 (5)	C10—N2—C7—C6	0.5 (8)
N2^i—Cu1—N2—C7	100.6 (4)	C10—N2—C7—C2	−179.2 (5)
N2^i—Cu1—N2—C10	−83.0 (5)	C10—C9—C8—C6	−2.5 (11)
N2^i—Cu1—N1—C11	−67 (3)	C2—C7—C6—C5	1.1 (9)
N2—Cu1—N1—C11	26 (3)	C2—C7—C6—C8	179.9 (6)
N2—C7—C6—C5	−178.6 (6)	C8—C6—C5—C4	−178.3 (8)
N2—C7—C6—C8	0.2 (8)	C8—C9—C10—N2	3.2 (11)
N2—C7—C2—O1	−1.0 (7)	C1—O1—C2—C7	174.3 (5)
N2—C7—C2—C3	179.1 (5)	C1—O1—C2—C3	−5.8 (9)

Symmetry code: (i) −x+2, −x+y+1, −z+2/3.

Di-µ-methanolato-κ⁴O:O-bis[(8-methoxyquinoline-κ²N,O)(thiocyanato-κN)copper(II)] (Cu2)

Crystal data

[Cu2(CH3O)2(NCS)2(C10H9NO)2]	Z = 1
Mr = 623.67	F(000) = 318
Triclinic, P1	Dx = 1.575 Mg m^−3
a = 7.5050 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9967 (7) Å	Cell parameters from 1310 reflections
c = 11.9102 (19) Å	θ = 3.5–22.2°
α = 76.112 (10)°	µ = 1.81 mm^−1
β = 71.827 (14)°	T = 293 K
γ = 82.057 (9)°	Block, blue
V = 657.73 (15) Å^3	0.08 × 0.06 × 0.04 mm

Data collection

Rigaku SuperNova Single Source diffractometer with an Eos detector	2588 independent reflections
Radiation source: fine-focus sealed tube	1548 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.099
Detector resolution: 15.9784 pixels mm^-1	θmax = 26.0°, θmin = 3.5°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD 2015)	k = −9→9
Tmin = 0.784, Tmax = 1.000	l = −14→14
8594 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.272	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0999P)^2 + 2.0616P] where P = (Fo^2 + 2Fc^2)/3
2588 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.73 e Å^−3
0 restraints	Δρmin = −0.62 e Å^−3

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 > 2sigma(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	0.46152 (12)	0.57333 (11)	0.88048 (8)	0.0504 (3)
S1	−0.0147 (3)	0.9640 (3)	0.7692 (2)	0.0688 (7)
O1	0.6627 (7)	0.4724 (7)	0.9488 (5)	0.0605 (15)
O2	0.4171 (8)	0.3172 (6)	0.8267 (5)	0.0682 (17)
N2	0.6150 (8)	0.5851 (7)	0.7094 (5)	0.0485 (15)
N1	0.2642 (9)	0.7331 (9)	0.8329 (6)	0.066 (2)
C10	0.6192 (9)	0.4606 (8)	0.6483 (7)	0.0455 (18)
C11	0.1494 (11)	0.8269 (9)	0.8072 (7)	0.053 (2)
C6	0.7245 (10)	0.4732 (9)	0.5265 (7)	0.0489 (18)
C9	0.7131 (10)	0.7211 (9)	0.6486 (7)	0.056 (2)
H9	0.7102	0.8065	0.6903	0.067*
C1	0.3331 (12)	0.1671 (10)	0.9000 (8)	0.071 (3)
H1A	0.4276	0.0733	0.9024	0.106*
H1B	0.2415	0.1394	0.8675	0.106*
H1C	0.2728	0.1857	0.9803	0.106*
C2	0.5144 (10)	0.3129 (9)	0.7107 (7)	0.0516 (19)
C5	0.7257 (10)	0.3361 (11)	0.4685 (8)	0.064 (2)
H5	0.7935	0.3418	0.3878	0.076*
C8	0.8187 (10)	0.7468 (9)	0.5291 (8)	0.058 (2)
H8	0.8844	0.8454	0.4915	0.070*
C7	0.8226 (10)	0.6218 (10)	0.4687 (7)	0.059 (2)
H7	0.8915	0.6349	0.3877	0.071*
C3	0.5245 (11)	0.1847 (9)	0.6535 (7)	0.057 (2)
H3	0.4619	0.0857	0.6958	0.068*
C0AA	0.8453 (11)	0.4199 (13)	0.8903 (8)	0.078 (3)
H0AA	0.8495	0.3031	0.8814	0.118*
H0AB	0.9269	0.4263	0.9370	0.118*
H0AC	0.8861	0.4940	0.8120	0.118*
C4	0.6250 (12)	0.1958 (10)	0.5337 (8)	0.067 (2)
H4	0.6246	0.1063	0.4963	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0578 (5)	0.0515 (5)	0.0453 (5)	−0.0031 (4)	−0.0145 (4)	−0.0172 (4)
S1	0.0663 (12)	0.0612 (12)	0.0762 (16)	−0.0026 (10)	−0.0225 (11)	−0.0081 (11)
O1	0.052 (3)	0.076 (3)	0.050 (3)	0.007 (2)	−0.012 (2)	−0.017 (3)
O2	0.084 (3)	0.058 (3)	0.062 (4)	−0.030 (3)	−0.004 (3)	−0.021 (3)
N2	0.057 (3)	0.045 (3)	0.052 (3)	−0.008 (3)	−0.019 (3)	−0.017 (3)
N1	0.065 (4)	0.072 (4)	0.055 (4)	0.010 (3)	−0.017 (3)	−0.012 (3)
C10	0.049 (4)	0.041 (3)	0.050 (4)	0.002 (3)	−0.016 (3)	−0.015 (3)
C11	0.061 (4)	0.055 (4)	0.039 (4)	−0.017 (3)	−0.002 (3)	−0.010 (3)
C6	0.052 (4)	0.050 (4)	0.047 (4)	0.003 (3)	−0.014 (3)	−0.018 (3)
C9	0.064 (4)	0.046 (4)	0.064 (5)	−0.008 (3)	−0.026 (4)	−0.009 (3)
C1	0.090 (5)	0.053 (4)	0.067 (6)	−0.024 (4)	−0.021 (5)	0.001 (4)
C2	0.051 (4)	0.050 (4)	0.059 (5)	−0.010 (3)	−0.014 (3)	−0.018 (3)
C5	0.048 (4)	0.086 (5)	0.065 (5)	0.003 (4)	−0.015 (4)	−0.037 (4)
C8	0.059 (4)	0.045 (4)	0.066 (5)	−0.015 (3)	−0.015 (4)	−0.002 (4)
C7	0.048 (4)	0.072 (5)	0.046 (5)	−0.004 (4)	−0.003 (3)	−0.004 (4)
C3	0.068 (4)	0.046 (4)	0.066 (5)	−0.007 (3)	−0.022 (4)	−0.024 (3)
C0AA	0.046 (4)	0.106 (7)	0.060 (6)	0.022 (4)	−0.003 (4)	−0.005 (5)
C4	0.075 (5)	0.062 (4)	0.081 (5)	0.011 (4)	−0.031 (4)	−0.046 (4)

Geometric parameters (Å, º)

Cu1—Cu1^i	3.0083 (19)	C9—H9	0.9300
Cu1—O1^i	1.922 (5)	C9—C8	1.378 (11)
Cu1—O1	1.925 (5)	C1—H1A	0.9600
Cu1—O2	2.381 (5)	C1—H1B	0.9600
Cu1—N2	1.990 (6)	C1—H1C	0.9600
Cu1—N1	1.949 (7)	C2—C3	1.343 (11)
S1—C11	1.631 (8)	C5—H5	0.9300
O1—Cu1^i	1.922 (5)	C5—C4	1.372 (11)
O1—C0AA	1.388 (9)	C8—H8	0.9300
O2—C1	1.401 (9)	C8—C7	1.358 (12)
O2—C2	1.352 (9)	C7—H7	0.9300
N2—C10	1.358 (9)	C3—H3	0.9300
N2—C9	1.327 (9)	C3—C4	1.378 (11)
N1—C11	1.129 (10)	C0AA—H0AA	0.9600
C10—C6	1.405 (10)	C0AA—H0AB	0.9600
C10—C2	1.428 (9)	C0AA—H0AC	0.9600
C6—C5	1.427 (11)	C4—H4	0.9300
C6—C7	1.400 (10)
O1^i—Cu1—Cu1^i	38.61 (15)	N2—C9—C8	125.6 (8)
O1—Cu1—Cu1^i	38.52 (15)	C8—C9—H9	117.2
O1^i—Cu1—O1	77.1 (2)	O2—C1—H1A	109.5
O1^i—Cu1—O2	101.7 (2)	O2—C1—H1B	109.5
O1—Cu1—O2	95.3 (2)	O2—C1—H1C	109.5
O1^i—Cu1—N2	170.7 (2)	H1A—C1—H1B	109.5
O1—Cu1—N2	95.3 (2)	H1A—C1—H1C	109.5
O1^i—Cu1—N1	96.6 (2)	H1B—C1—H1C	109.5
O1—Cu1—N1	162.5 (3)	O2—C2—C10	113.9 (6)
O2—Cu1—Cu1^i	100.90 (15)	C3—C2—O2	126.8 (7)
N2—Cu1—Cu1^i	133.64 (18)	C3—C2—C10	119.3 (7)
N2—Cu1—O2	73.2 (2)	C6—C5—H5	120.6
N1—Cu1—Cu1^i	133.2 (2)	C4—C5—C6	118.9 (8)
N1—Cu1—O2	102.0 (3)	C4—C5—H5	120.6
N1—Cu1—N2	92.2 (3)	C9—C8—H8	121.5
Cu1^i—O1—Cu1	102.9 (2)	C7—C8—C9	117.0 (7)
C0AA—O1—Cu1^i	127.6 (5)	C7—C8—H8	121.5
C0AA—O1—Cu1	128.8 (5)	C6—C7—H7	119.5
C1—O2—Cu1	129.8 (5)	C8—C7—C6	121.0 (7)
C2—O2—Cu1	111.7 (4)	C8—C7—H7	119.5
C2—O2—C1	117.7 (6)	C2—C3—H3	119.1
C10—N2—Cu1	122.6 (4)	C2—C3—C4	121.8 (7)
C9—N2—Cu1	120.3 (5)	C4—C3—H3	119.1
C9—N2—C10	117.1 (6)	O1—C0AA—H0AA	109.5
C11—N1—Cu1	178.7 (7)	O1—C0AA—H0AB	109.5
N2—C10—C6	121.9 (6)	O1—C0AA—H0AC	109.5
N2—C10—C2	118.6 (6)	H0AA—C0AA—H0AB	109.5
C6—C10—C2	119.6 (7)	H0AA—C0AA—H0AC	109.5
N1—C11—S1	179.4 (8)	H0AB—C0AA—H0AC	109.5
C10—C6—C5	118.9 (6)	C5—C4—C3	121.4 (8)
C10—C6—C7	117.5 (7)	C5—C4—H4	119.3
C7—C6—C5	123.6 (7)	C3—C4—H4	119.3
N2—C9—H9	117.2
Cu1^i—Cu1—O1—C0AA	170.9 (8)	N2—Cu1—O2—C1	168.4 (7)
Cu1^i—Cu1—O2—C1	35.9 (7)	N2—Cu1—O2—C2	−0.7 (5)
Cu1^i—Cu1—O2—C2	−133.2 (5)	N2—Cu1—N1—C11	−144 (30)
Cu1^i—Cu1—N2—C10	90.7 (6)	N2—C10—C6—C5	178.8 (7)
Cu1^i—Cu1—N2—C9	−91.9 (6)	N2—C10—C6—C7	−1.4 (10)
Cu1^i—Cu1—N1—C11	26 (30)	N2—C10—C2—O2	1.3 (10)
Cu1—O2—C2—C10	−0.1 (8)	N2—C10—C2—C3	−176.7 (7)
Cu1—O2—C2—C3	177.8 (7)	N2—C9—C8—C7	−0.1 (12)
Cu1—N2—C10—C6	178.3 (5)	N1—Cu1—O1—Cu1^i	70.5 (9)
Cu1—N2—C10—C2	−2.2 (9)	N1—Cu1—O1—C0AA	−118.6 (10)
Cu1—N2—C9—C8	−177.6 (6)	N1—Cu1—O2—C1	−102.9 (7)
Cu1—N1—C11—S1	91 (80)	N1—Cu1—O2—C2	87.9 (5)
O1^i—Cu1—O1—Cu1^i	0.0	N1—Cu1—N2—C10	−100.3 (6)
O1^i—Cu1—O1—C0AA	170.9 (8)	N1—Cu1—N2—C9	77.0 (6)
O1—Cu1—O2—C1	74.4 (7)	C10—N2—C9—C8	0.0 (11)
O1^i—Cu1—O2—C1	−3.5 (7)	C10—C6—C5—C4	−0.5 (11)
O1^i—Cu1—O2—C2	−172.6 (5)	C10—C6—C7—C8	1.3 (11)
O1—Cu1—O2—C2	−94.7 (5)	C10—C2—C3—C4	−3.7 (12)
O1^i—Cu1—N2—C10	59.8 (17)	C6—C10—C2—O2	−179.1 (6)
O1—Cu1—N2—C10	95.4 (6)	C6—C10—C2—C3	2.8 (11)
O1^i—Cu1—N2—C9	−122.8 (14)	C6—C5—C4—C3	−0.3 (12)
O1—Cu1—N2—C9	−87.2 (6)	C9—N2—C10—C6	0.8 (10)
O1^i—Cu1—N1—C11	40 (30)	C9—N2—C10—C2	−179.6 (6)
O1—Cu1—N1—C11	−28 (30)	C9—C8—C7—C6	−0.6 (12)
O2—Cu1—O1—Cu1^i	−100.9 (2)	C1—O2—C2—C10	−170.7 (7)
O2—Cu1—O1—C0AA	70.0 (7)	C1—O2—C2—C3	7.2 (12)
O2—Cu1—N2—C10	1.5 (5)	C2—C10—C6—C5	−0.8 (10)
O2—Cu1—N2—C9	178.9 (6)	C2—C10—C6—C7	179.0 (7)
O2—Cu1—N1—C11	143 (29)	C2—C3—C4—C5	2.5 (13)
O2—C2—C3—C4	178.5 (8)	C5—C6—C7—C8	−178.9 (7)
N2—Cu1—O1—Cu1^i	−174.5 (2)	C7—C6—C5—C4	179.7 (7)
N2—Cu1—O1—C0AA	−3.6 (7)

Symmetry code: (i) −x+1, −y+1, −z+2.