A copper(II)–oxalate compound resulting from the fixation of carbon dioxide: μ-oxalato-bis­[bis­(1-benzyl-1H-pyrazole)(trifluoro­methane­sulfonato)copper(II)]

Reductive coupling of adventitious CO₂ by Cu^I has afforded the title compound, μ-oxalato-1κ²O¹,O²:2κ²O^1′,O^2′-bis­[bis­(1-benzyl-1H-pyrazole-κN²)(trifluoro­methane­sulfonato-κO)copper(II)], [Cu₂(CF₃O₃S)₂(C₂O₄)(C₁₀H₁₀N₂)₄], which contains centrosymmetric mol­ecules in which the Cu^II ions, bridged by a planar oxalate ligand, exhibit a distorted square-pyramidal N₂(pyrazole)O₂(oxalato)O(trifluoro­methane­sulf­on­ate) coordination geometry, with the trifluoro­methane­sulfonate ligand coordinated axially. The mol­ecule exhibits five intra­molecular C—H...O,F hydrogen bonds per asymmetric unit, which help to stabilize the mol­ecule and to orient the benzyl and trifluoro­methane­sulfonate groups. Inter­molecular C—H...O hydrogen bonds link the mol­ecules to form two-dimensional layers.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.033
• wR factor = 0.111
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.98 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu     -   O11     ..       5.48 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C11    -   C11_a  ...       1.53 Ang.

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

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

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S1. Comment

As part of our continuing interest in the chemistry of Cu-containing complexes (Stibrany, Fikar et al., 2002; Stibrany et al., 2003, 2004), we attempted to prepare a tris(N-benzylpyrazole) complex of Cu^I and obtained instead the oxalate-containing title compound, (I), in which the oxalate ion appears to have been formed by the reductive coupling of adventitious CO₂. Reductive coupling of CO₂, induced by metal complexes, to afford oxalate is rare, and we are aware of only one such example, the salt µ-oxalato-1κ²O,O':2κ²O'',O'''-bis(triallyl-1,4,7- triazacyclononane)copper(II) bis(tetraphenylborate), (II), in which a Cu^I complex served as the reducing agent (Farrugia et al., 2001). In that case also, the product was originally obtained serendipitously.

Crystals of (I) (Fig. 1) contain discrete neutral centrosymmetric molecules in which each Cu^II ion is five-coordinate and is bonded to two O atoms from a bridging oxalate group, the imine N atoms of two N-benzylpyrazole ligands, and one O atom from a trifluoromethanesulfonate anion. Five-coordinate copper(II) complexes typically have geometries ranging from trigonal–bipyramidal to square-pyramidal. Energetically, the limiting trigonal–bipyramidal and square-pyramidal forms are often almost equally favorable, with a low activation barrier to interconversion. In the present instance, the observed geometry is best described as distorted square-pyramidal, with atom O1 apical, as indicated by the geometric parameters in Table 1 and by the calculated value of the distortion parameter τ (Addison et al., 1984) of 0.19, which is closer to the ideal value of τ = 0 for a perfect square-pyramidal symmetry than to the ideal value of 1 for an ideal trigonal–bipyramidal geometry.

Structurally characterized examples of species with Cu^II—O(trifluoromethanesulfonate) bonds are uncommon. The Cambridge Structural Database (CSD, version 5.26; Allen, 2002) lists only a single example, CSD refcode RORFIN (van Albada et al., 1997), a binuclear square-pyramidal dication (two per asymmetric unit), each of which contains a bridging axially bonded trifluoromethanesulfonate ligand. Axial copper(II)—O bond lengths in these cations range from 2.408 (5) to 2.437 (6) Å, all significantly longer than the value of 2.3626 (17) Å for the corresponding bond in (I). The equatorial metal–ligand bond lengths in (I) agree well with those reported for other comparable systems. In particular, the Cu—O(oxalate) bond lengths in Table 1 lie within the range of 1.960 (2)–2.041 (3) Å reported for several distorted square-pyramidal Cu^II–oxalate complexes (refcodes FEYXUC, HOSTAK, IMIHAN, JOFKEU, QEJQOL, WURYEN and XUFZON), while the Cu—N(pyrazole) linkages are similarly within the range of 1.938 (5)–2.024 (3) Å observed for equatorial Cu—N(pyrazole) linkages in a variety of square-pyramidal complexes (refcodes BENDED, ESIKIA, FAYTOO02, PIBXIO, POWJAM, QOTJAK, REDLER, REDLER01 and RIHYAI).

Molecule (I) exhibits five intramolecular C—H···O,F hydrogen bonds per asymmetric unit (Table 2), one of which is trifurcated (Fig. 2). These hydrogen bonds, which involve the methylene C atoms of the benzyl fragments and a C atom of one of the phenyl rings, help to stabilize the molecule, while serving also to orient the benzyl and trifluoromethanesulfonate groups.

Two unique intermolecular C—H···O hydrogen bonds (Table 2) link the pyrazole and phenyl rings of one ligand to the O atoms of the oxalate and trifluoromethanesulfonate fragments, respectively, to form a two-dimensional network along the a and b unit-cell directions (Fig. 3). When translated along the c unit-cell direction, the resulting layers complete the structure, in which a variety of C—H···F,O and C—H···π interactions complement the ubiquitous van der Waals interactions to complete the packing. There is little, if any, evidence of π–π interactions among the pyrazole and phenyl rings.

S2. Experimental

A colorless solution containing CuI(CH₃CN)₄(trifluoromethanesulfonate) (154 mg, 0.41 mmol), N-benzylpyrazole (194 mg, 1.23 mmol), acetonitrile (8 ml) and triethylorthoformate (1 ml) was prepared in a 50 ml flask. The flask was placed in a jar containing some liquid diethyl ether and diethyl ether vapor was diffused into the solution. Although the jar was closed, no special effort was made to exclude air. After approximately two weeks, blue rhomboids of (I) began to deposit.

S3. Refinement

H atoms were included in the riding-model approximation, with C—H = 0.93 Å (aromatic H) and 0.97 Å (methylene H), and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. A view of (I), showing 25% probability displacement ellipsoids and the atom-numbering scheme. [Symmetry code: (i) 2 − x, 1 − y, −z.]
	Fig. 2. A view of (I), showing the intramolecular hydrogen-bonding scheme (dashed lines). [Symmetry code: (i) 2 − x, 1 − y, −z.]
	Fig. 3. A view of the structure of (I) approximately normal to (001). Dashed lines indicate C—H···O hydrogen bonds.

µ-oxalato-1κ²O¹,O²:2κ²O^1',O^2'-bis[bis(1-benzyl-1H-pyrazole- κN²)(trifluoromethanesulfonato-κO)copper(II)]

Crystal data

[Cu2(CF3O3S)2(C2O4)(C10H10N2)4]	Z = 1
Mr = 1146.05	F(000) = 584
Triclinic, P1	Dx = 1.576 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.8432 (5) Å	Cell parameters from 978 reflections
b = 11.0190 (5) Å	θ = 3.5–25.0°
c = 11.4895 (5) Å	µ = 1.06 mm^−1
α = 87.389 (4)°	T = 298 K
β = 75.577 (4)°	Rhomboid, blue
γ = 65.539 (4)°	0.51 × 0.41 × 0.28 mm
V = 1207.60 (11) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	4166 independent reflections
Radiation source: fine-focus sealed tube	3841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −12→12
Tmin = 0.552, Tmax = 0.744	k = −12→13
12405 measured reflections	l = −13→13

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0818P)^2 + 0.5052P] where P = (Fo^2 + 2Fc^2)/3
4166 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu	0.87628 (3)	0.66336 (3)	0.18987 (2)	0.03501 (13)
S	0.94478 (6)	0.34381 (6)	0.29384 (5)	0.03783 (17)
F1	1.1663 (2)	0.12834 (18)	0.3042 (2)	0.0849 (6)
F2	1.1277 (2)	0.2934 (2)	0.42237 (19)	0.0823 (6)
F3	1.21141 (18)	0.2921 (2)	0.2332 (2)	0.0746 (5)
O1	0.91087 (19)	0.48368 (17)	0.31679 (16)	0.0457 (4)
O11	0.82342 (16)	0.58593 (16)	0.06792 (14)	0.0385 (4)
O12	1.06845 (17)	0.56675 (17)	0.08787 (14)	0.0392 (4)
O2	0.8657 (2)	0.29151 (19)	0.38333 (18)	0.0554 (5)
O3	0.9633 (2)	0.3058 (2)	0.17093 (17)	0.0565 (5)
N11	0.9346 (2)	0.7739 (2)	0.27735 (18)	0.0404 (5)
N12	1.0489 (2)	0.7376 (2)	0.32118 (18)	0.0405 (5)
N31	0.6780 (2)	0.7552 (2)	0.28507 (18)	0.0398 (5)
N32	0.5597 (2)	0.8206 (2)	0.2480 (2)	0.0490 (5)
C1	1.1211 (3)	0.2601 (3)	0.3153 (3)	0.0528 (7)
C11	1.0707 (2)	0.4946 (2)	0.0058 (2)	0.0339 (5)
C13	1.0562 (3)	0.8459 (3)	0.3621 (3)	0.0547 (7)
H13	1.1247	0.8459	0.3973	0.066*
C14	0.9455 (3)	0.9561 (3)	0.3431 (3)	0.0573 (7)
H14	0.9237	1.0450	0.3618	0.069*
C15	0.8730 (3)	0.9071 (3)	0.2903 (3)	0.0517 (6)
H15	0.7919	0.9599	0.2667	0.062*
C21	1.3528 (3)	0.5934 (3)	0.1795 (3)	0.0541 (7)
H21	1.2978	0.6316	0.1258	0.065*
C22	1.4941 (3)	0.5621 (3)	0.1445 (3)	0.0593 (7)
H22	1.5336	0.5804	0.0680	0.071*
C23	1.5769 (3)	0.5042 (3)	0.2220 (3)	0.0583 (7)
H23	1.6724	0.4828	0.1979	0.070*
C24	1.5189 (3)	0.4781 (3)	0.3344 (3)	0.0580 (7)
H24	1.5751	0.4381	0.3869	0.070*
C25	1.3765 (3)	0.5112 (3)	0.3706 (2)	0.0488 (6)
H25	1.3376	0.4943	0.4480	0.059*
C26	1.2918 (3)	0.5686 (2)	0.2938 (2)	0.0399 (5)
C27	1.1380 (3)	0.5980 (2)	0.3325 (2)	0.0420 (5)
H27A	1.1192	0.5414	0.2835	0.050*
H27B	1.1148	0.5766	0.4157	0.050*
C33	0.4481 (3)	0.8550 (3)	0.3418 (4)	0.0718 (10)
H33	0.3554	0.9019	0.3388	0.086*
C34	0.4921 (4)	0.8102 (4)	0.4422 (3)	0.0750 (10)
H34	0.4371	0.8189	0.5204	0.090*
C35	0.6363 (3)	0.7488 (3)	0.4036 (3)	0.0548 (7)
H35	0.6960	0.7086	0.4533	0.066*
C41	0.7551 (3)	0.9249 (3)	0.0121 (3)	0.0612 (8)
H41	0.8004	0.8407	−0.0281	0.073*
C42	0.8153 (5)	1.0140 (5)	−0.0117 (4)	0.0862 (12)
H42	0.9013	0.9903	−0.0676	0.103*
C43	0.7466 (6)	1.1404 (5)	0.0487 (5)	0.1004 (15)
H43	0.7868	1.2013	0.0338	0.121*
C44	0.6189 (6)	1.1745 (4)	0.1304 (4)	0.0908 (13)
H44	0.5721	1.2590	0.1701	0.109*
C45	0.5611 (4)	1.0847 (3)	0.1530 (3)	0.0691 (9)
H45	0.4750	1.1083	0.2087	0.083*
C46	0.6285 (3)	0.9591 (3)	0.0946 (2)	0.0487 (6)
C47	0.5646 (3)	0.8599 (3)	0.1238 (3)	0.0549 (7)
H47A	0.4704	0.8989	0.1127	0.066*
H47B	0.6192	0.7812	0.0687	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03158 (19)	0.03487 (19)	0.03713 (19)	−0.01049 (13)	−0.01124 (12)	−0.00256 (12)
S	0.0340 (3)	0.0324 (3)	0.0424 (3)	−0.0086 (2)	−0.0109 (2)	0.0029 (2)
F1	0.0659 (12)	0.0408 (9)	0.1328 (18)	0.0004 (8)	−0.0401 (12)	0.0125 (10)
F2	0.0679 (12)	0.1021 (16)	0.0754 (12)	−0.0206 (11)	−0.0413 (10)	0.0037 (11)
F3	0.0375 (9)	0.0739 (12)	0.0964 (14)	−0.0148 (8)	−0.0038 (9)	0.0016 (10)
O1	0.0467 (10)	0.0328 (9)	0.0533 (10)	−0.0119 (7)	−0.0135 (8)	0.0034 (7)
O11	0.0312 (8)	0.0427 (9)	0.0386 (8)	−0.0123 (7)	−0.0079 (7)	−0.0039 (7)
O12	0.0339 (8)	0.0457 (9)	0.0395 (9)	−0.0167 (7)	−0.0102 (7)	−0.0053 (7)
O2	0.0545 (11)	0.0471 (10)	0.0625 (12)	−0.0234 (9)	−0.0085 (9)	0.0105 (9)
O3	0.0611 (12)	0.0510 (11)	0.0494 (10)	−0.0126 (9)	−0.0178 (9)	−0.0041 (8)
N11	0.0386 (11)	0.0355 (10)	0.0469 (11)	−0.0117 (9)	−0.0161 (9)	−0.0023 (9)
N12	0.0399 (11)	0.0409 (11)	0.0468 (11)	−0.0187 (9)	−0.0176 (9)	0.0018 (9)
N31	0.0354 (10)	0.0355 (10)	0.0441 (11)	−0.0083 (8)	−0.0136 (9)	0.0005 (8)
N32	0.0336 (11)	0.0426 (12)	0.0645 (14)	−0.0078 (9)	−0.0170 (10)	0.0086 (10)
C1	0.0442 (15)	0.0441 (15)	0.0631 (17)	−0.0082 (12)	−0.0201 (13)	0.0040 (12)
C11	0.0343 (12)	0.0348 (11)	0.0336 (11)	−0.0145 (9)	−0.0105 (9)	0.0053 (9)
C13	0.0593 (17)	0.0528 (16)	0.0645 (17)	−0.0313 (14)	−0.0221 (14)	−0.0026 (13)
C14	0.0706 (19)	0.0393 (14)	0.0658 (18)	−0.0257 (14)	−0.0176 (15)	−0.0039 (13)
C15	0.0547 (16)	0.0374 (13)	0.0591 (16)	−0.0117 (12)	−0.0200 (13)	−0.0025 (11)
C21	0.0542 (16)	0.0634 (17)	0.0479 (15)	−0.0263 (14)	−0.0164 (12)	0.0096 (13)
C22	0.0599 (18)	0.0651 (18)	0.0542 (16)	−0.0344 (15)	−0.0012 (14)	0.0013 (14)
C23	0.0410 (15)	0.0556 (17)	0.076 (2)	−0.0223 (13)	−0.0061 (14)	−0.0076 (14)
C24	0.0413 (15)	0.0668 (18)	0.0694 (18)	−0.0194 (14)	−0.0251 (14)	0.0018 (15)
C25	0.0458 (14)	0.0574 (16)	0.0442 (13)	−0.0203 (12)	−0.0150 (11)	0.0037 (12)
C26	0.0408 (13)	0.0413 (13)	0.0422 (12)	−0.0187 (11)	−0.0153 (10)	0.0003 (10)
C27	0.0407 (13)	0.0406 (13)	0.0498 (14)	−0.0186 (11)	−0.0173 (11)	0.0056 (10)
C33	0.0348 (15)	0.0578 (18)	0.098 (3)	−0.0033 (13)	−0.0045 (16)	0.0112 (17)
C34	0.0545 (19)	0.068 (2)	0.068 (2)	−0.0067 (16)	0.0109 (16)	0.0061 (17)
C35	0.0555 (16)	0.0507 (16)	0.0453 (14)	−0.0133 (13)	−0.0054 (12)	0.0005 (12)
C41	0.0645 (19)	0.0611 (18)	0.0498 (15)	−0.0176 (15)	−0.0158 (14)	0.0046 (13)
C42	0.088 (3)	0.104 (3)	0.072 (2)	−0.049 (2)	−0.017 (2)	0.028 (2)
C43	0.145 (5)	0.085 (3)	0.115 (4)	−0.076 (3)	−0.065 (3)	0.051 (3)
C44	0.123 (4)	0.0448 (19)	0.106 (3)	−0.027 (2)	−0.046 (3)	0.0111 (19)
C45	0.070 (2)	0.0401 (16)	0.077 (2)	−0.0032 (14)	−0.0194 (17)	0.0013 (14)
C46	0.0517 (15)	0.0404 (14)	0.0491 (14)	−0.0076 (12)	−0.0257 (12)	0.0078 (11)
C47	0.0524 (16)	0.0494 (15)	0.0648 (17)	−0.0137 (13)	−0.0328 (14)	0.0107 (13)

Geometric parameters (Å, º)

Cu—O12	1.9771 (16)	C21—H21	0.9300
Cu—O11	1.9834 (16)	C22—C23	1.370 (5)
Cu—N11	1.990 (2)	C22—H22	0.9300
Cu—N31	1.992 (2)	C23—C24	1.363 (5)
Cu—O1	2.3626 (17)	C23—H23	0.9300
S—O2	1.428 (2)	C24—C25	1.385 (4)
S—O3	1.433 (2)	C24—H24	0.9300
S—O1	1.4490 (18)	C25—C26	1.377 (4)
S—C1	1.822 (3)	C25—H25	0.9300
F1—C1	1.327 (3)	C26—C27	1.511 (3)
F2—C1	1.327 (4)	C27—H27A	0.9700
F3—C1	1.330 (4)	C27—H27B	0.9700
O11—C11^i	1.250 (3)	C33—C34	1.352 (5)
O12—C11	1.250 (3)	C33—H33	0.9300
N11—C15	1.335 (3)	C34—C35	1.381 (4)
N11—N12	1.353 (3)	C34—H34	0.9300
N12—C13	1.342 (3)	C35—H35	0.9300
N12—C27	1.459 (3)	C41—C46	1.372 (4)
N31—C35	1.332 (4)	C41—C42	1.372 (6)
N31—N32	1.351 (3)	C41—H41	0.9300
N32—C33	1.333 (4)	C42—C43	1.396 (7)
N32—C47	1.467 (4)	C42—H42	0.9300
C11—O11^i	1.250 (3)	C43—C44	1.376 (7)
C11—C11^i	1.527 (4)	C43—H43	0.9300
C13—C14	1.365 (4)	C44—C45	1.360 (6)
C13—H13	0.9300	C44—H44	0.9300
C14—C15	1.377 (4)	C45—C46	1.380 (4)
C14—H14	0.9300	C45—H45	0.9300
C15—H15	0.9300	C46—C47	1.505 (4)
C21—C22	1.377 (4)	C47—H47A	0.9700
C21—C26	1.387 (4)	C47—H47B	0.9700
O12—Cu—O11	83.76 (6)	C23—C22—H22	119.8
O12—Cu—N11	92.34 (8)	C21—C22—H22	119.8
O11—Cu—N11	164.51 (8)	C24—C23—C22	119.8 (3)
O12—Cu—N31	176.05 (7)	C24—C23—H23	120.1
O11—Cu—N31	92.30 (7)	C22—C23—H23	120.1
N11—Cu—N31	91.52 (8)	C23—C24—C25	120.1 (3)
O12—Cu—O1	90.13 (7)	C23—C24—H24	120.0
O11—Cu—O1	96.14 (7)	C25—C24—H24	120.0
N11—Cu—O1	98.86 (8)	C26—C25—C24	120.9 (3)
N31—Cu—O1	90.07 (7)	C26—C25—H25	119.5
O2—S—O3	116.45 (13)	C24—C25—H25	119.5
O2—S—O1	114.14 (12)	C25—C26—C21	118.2 (2)
O3—S—O1	114.53 (11)	C25—C26—C27	120.3 (2)
O2—S—C1	103.23 (13)	C21—C26—C27	121.5 (2)
O3—S—C1	103.09 (13)	N12—C27—C26	112.3 (2)
O1—S—C1	102.91 (12)	N12—C27—H27A	109.1
S—O1—Cu	132.08 (11)	C26—C27—H27A	109.1
C11^i—O11—Cu	111.29 (14)	N12—C27—H27B	109.1
C11—O12—Cu	111.28 (14)	C26—C27—H27B	109.1
C15—N11—N12	105.6 (2)	H27A—C27—H27B	107.9
C15—N11—Cu	124.21 (18)	N32—C33—C34	108.7 (3)
N12—N11—Cu	129.73 (15)	N32—C33—H33	125.6
C13—N12—N11	110.3 (2)	C34—C33—H33	125.6
C13—N12—C27	127.1 (2)	C33—C34—C35	105.1 (3)
N11—N12—C27	122.21 (19)	C33—C34—H34	127.5
C35—N31—N32	105.8 (2)	C35—C34—H34	127.5
C35—N31—Cu	123.64 (18)	N31—C35—C34	110.5 (3)
N32—N31—Cu	130.18 (17)	N31—C35—H35	124.8
C33—N32—N31	110.0 (2)	C34—C35—H35	124.8
C33—N32—C47	128.1 (2)	C46—C41—C42	120.6 (3)
N31—N32—C47	121.4 (2)	C46—C41—H41	119.7
F2—C1—F1	108.5 (2)	C42—C41—H41	119.7
F2—C1—F3	106.9 (3)	C41—C42—C43	119.5 (4)
F1—C1—F3	107.0 (2)	C41—C42—H42	120.3
F2—C1—S	112.1 (2)	C43—C42—H42	120.3
F1—C1—S	111.0 (2)	C44—C43—C42	119.7 (4)
F3—C1—S	111.2 (2)	C44—C43—H43	120.2
O11^i—C11—O12	126.9 (2)	C42—C43—H43	120.2
O11^i—C11—C11^i	116.3 (2)	C45—C44—C43	120.0 (4)
O12—C11—C11^i	116.7 (2)	C45—C44—H44	120.0
N12—C13—C14	108.0 (2)	C43—C44—H44	120.0
N12—C13—H13	126.0	C44—C45—C46	120.9 (4)
C14—C13—H13	126.0	C44—C45—H45	119.6
C13—C14—C15	105.2 (2)	C46—C45—H45	119.6
C13—C14—H14	127.4	C41—C46—C45	119.4 (3)
C15—C14—H14	127.4	C41—C46—C47	120.6 (3)
N11—C15—C14	110.9 (3)	C45—C46—C47	120.0 (3)
N11—C15—H15	124.5	N32—C47—C46	111.4 (2)
C14—C15—H15	124.5	N32—C47—H47A	109.3
C22—C21—C26	120.7 (3)	C46—C47—H47A	109.3
C22—C21—H21	119.7	N32—C47—H47B	109.3
C26—C21—H21	119.7	C46—C47—H47B	109.3
C23—C22—C21	120.3 (3)	H47A—C47—H47B	108.0
O2—S—O1—Cu	−136.62 (14)	O2—S—C1—F3	176.4 (2)
O3—S—O1—Cu	1.19 (19)	O3—S—C1—F3	54.7 (2)
C1—S—O1—Cu	112.29 (16)	O1—S—C1—F3	−64.6 (2)
O12—Cu—O1—S	−59.49 (15)	Cu—O12—C11—O11^i	−174.42 (19)
O11—Cu—O1—S	24.25 (15)	Cu—O12—C11—C11^i	5.4 (3)
N11—Cu—O1—S	−151.88 (15)	N11—N12—C13—C14	−1.0 (3)
N31—Cu—O1—S	116.57 (15)	C27—N12—C13—C14	−174.1 (2)
O12—Cu—O11—C11^i	6.67 (15)	N12—C13—C14—C15	0.4 (4)
N11—Cu—O11—C11^i	82.8 (3)	N12—N11—C15—C14	−0.8 (3)
N31—Cu—O11—C11^i	−173.11 (16)	Cu—N11—C15—C14	−173.3 (2)
O1—Cu—O11—C11^i	−82.79 (16)	C13—C14—C15—N11	0.2 (4)
O11—Cu—O12—C11	−6.57 (15)	C26—C21—C22—C23	0.9 (5)
N11—Cu—O12—C11	−171.54 (16)	C21—C22—C23—C24	−0.3 (5)
O12—Cu—N11—C15	127.3 (2)	C22—C23—C24—C25	−0.6 (5)
O11—Cu—N11—C15	52.3 (4)	C23—C24—C25—C26	1.0 (4)
N31—Cu—N11—C15	−51.9 (2)	C24—C25—C26—C21	−0.5 (4)
O1—Cu—N11—C15	−142.2 (2)	C24—C25—C26—C27	177.1 (3)
O12—Cu—N11—N12	−43.4 (2)	C22—C21—C26—C25	−0.4 (4)
O11—Cu—N11—N12	−118.4 (3)	C22—C21—C26—C27	−178.0 (3)
N31—Cu—N11—N12	137.4 (2)	C13—N12—C27—C26	−49.6 (3)
O1—Cu—N11—N12	47.1 (2)	N11—N12—C27—C26	138.0 (2)
C15—N11—N12—C13	1.1 (3)	C25—C26—C27—N12	125.4 (3)
Cu—N11—N12—C13	173.07 (19)	C21—C26—C27—N12	−57.1 (3)
C15—N11—N12—C27	174.6 (2)	N31—N32—C33—C34	−1.0 (4)
Cu—N11—N12—C27	−13.4 (3)	C47—N32—C33—C34	−172.7 (3)
O11—Cu—N31—C35	130.9 (2)	N32—C33—C34—C35	0.8 (4)
N11—Cu—N31—C35	−64.2 (2)	N32—N31—C35—C34	−0.2 (3)
O1—Cu—N31—C35	34.7 (2)	Cu—N31—C35—C34	−173.6 (2)
O11—Cu—N31—N32	−40.8 (2)	C33—C34—C35—N31	−0.4 (4)
N11—Cu—N31—N32	124.2 (2)	C46—C41—C42—C43	−0.2 (6)
O1—Cu—N31—N32	−137.0 (2)	C41—C42—C43—C44	−0.5 (6)
C35—N31—N32—C33	0.8 (3)	C42—C43—C44—C45	0.8 (7)
Cu—N31—N32—C33	173.6 (2)	C43—C44—C45—C46	−0.3 (6)
C35—N31—N32—C47	173.1 (2)	C42—C41—C46—C45	0.7 (5)
Cu—N31—N32—C47	−14.1 (4)	C42—C41—C46—C47	−178.0 (3)
O2—S—C1—F2	−64.0 (2)	C44—C45—C46—C41	−0.4 (5)
O3—S—C1—F2	174.3 (2)	C44—C45—C46—C47	178.2 (3)
O1—S—C1—F2	55.0 (2)	C33—N32—C47—C46	107.3 (4)
O2—S—C1—F1	57.4 (2)	N31—N32—C47—C46	−63.6 (3)
O3—S—C1—F1	−64.2 (2)	C41—C46—C47—N32	113.1 (3)
O1—S—C1—F1	176.4 (2)	C45—C46—C47—N32	−65.5 (3)

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C27—H27A···F3	0.97	2.54	3.313 (3)	136
C27—H27A···O1	0.97	2.53	3.240 (4)	130
C27—H27A···O12	0.97	2.42	3.154 (3)	132
C41—H41···O3^i	0.93	2.57	3.327 (4)	139
C47—H47B···O11	0.97	2.36	3.109 (4)	133
C14—H14···O2^ii	0.93	2.53	3.454 (4)	172
C23—H23···O11^iii	0.93	2.52	3.253 (4)	135

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