Two coordination modes of Cu(II) in a binuclear complex with N-(pyridin-2-yl-carbon-yl)pyridine-2-carboxamidate ligands.

In the title dinuclear complex, (acetonitrile-1κN)[μ-N-(pyri-din-2-ylcarbonyl)pyridine-2-carboxamidato-1:2κ(5)N,N',N'':O,O'][N-(pyridin-2-ylcarbonyl)pyridine-2-carboxamidato-2κ(3)N,N',N'']bis(trifluoromethanesulfonato-1κO)dicopper(II), [Cu(2)(C(12)H(8)N(3)O(2))(2)(CF(3)O(3)S)(2)(CH(3)CN)], one of the Cu(II) ions is five-coordinated in a distorted square-pyramidal N(3)O(2) environment provided by two N-(pyridin-2-ylcarbon-yl)pyridine-2-carboxamidate (bpca) ligands, while the second Cu(II) ion is six-coordinated in a distorted octa-hedral N(4)O(2) environment provided by one bpca ligand, two trifluoro-methansulfonate ligands and one acetonitrile mol-ecule. Weak inter-molecular C-H⋯O and C-H⋯F hydrogen bonds and π-π stacking inter-actions with centroid-centroid distances of 3.6799 (15) and 3.8520 (16) Å stabilize the crystal packing and lead to a three-dimensional network.

Related literature

For complexes of divalent metal ions with the N-(pyridin-2-ylcarbon­yl)pyridine-2-carboxamidate (bpca) ligand, see: Chowdhury et al. (2007 ▶); Folgado et al. (1988 ▶); Ha (2010 ▶, 2011 ▶); Halder et al. (2010 ▶); Miguel et al. (2009 ▶). For complexes of trivalent metal ions with the bpca ligand, see: Li et al. (2011 ▶); Sugimoto et al. (2002 ▶); Wocadlo et al. (1993 ▶). For electrochemical and magnetic studies for example complexes of Cu(II), see: Cangussu de Castro Gomes et al. (2008 ▶); Kajiwara et al. (2002 ▶). For the synthesis of the ligand, see: Larter et al. (1998 ▶).

Experimental

Crystal data

[Cu2(C12H8N3O2)2(CF3O3S)2(C2H3N)]

M = 918.70

Triclinic,

a = 8.9726 (7) Å

b = 10.0569 (8) Å

c = 18.3689 (15) Å

α = 82.573 (1)°

β = 83.802 (1)°

γ = 82.222 (1)°

V = 1621.6 (2) Å3

Z = 2

Mo Kα radiation

μ = 1.55 mm−1

T = 100 K

0.32 × 0.24 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.638, T max = 0.768

15254 measured reflections

5686 independent reflections

5292 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.087

S = 1.04

5686 reflections

497 parameters

H-atom parameters constrained

Δρmax = 0.83 e Å−3

Δρmin = −0.50 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812038330/wm2669sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812038330/wm2669Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2(C12H8N3O2)2(CF3SO3)2(C2H3N)]	Z = 2
Mr = 918.70	F(000) = 920
Triclinic, P1	Dx = 1.882 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9726 (7) Å	Cell parameters from 6358 reflections
b = 10.0569 (8) Å	θ = 2.2–28.3°
c = 18.3689 (15) Å	µ = 1.55 mm−1
α = 82.573 (1)°	T = 100 K
β = 83.802 (1)°	Rectangular prism, green
γ = 82.222 (1)°	0.32 × 0.24 × 0.18 mm
V = 1621.6 (2) Å3

Bruker SMART CCD area-detector diffractometer	5686 independent reflections
Radiation source: fine-focus sealed tube	5292 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
phi and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
Tmin = 0.638, Tmax = 0.768	k = −11→11
15254 measured reflections	l = −21→21

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0451P)2 + 2.0646P] where P = (Fo2 + 2Fc2)/3
5686 reflections	(Δ/σ)max = 0.008
497 parameters	Δρmax = 0.83 e Å−3
0 restraints	Δρmin = −0.50 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.84461 (3)	0.49089 (3)	0.586455 (16)	0.01596 (10)
Cu2	0.71274 (4)	0.65971 (3)	0.851929 (17)	0.02035 (10)
S1	0.90238 (8)	0.33964 (7)	0.90897 (4)	0.02539 (16)
S2	0.55073 (7)	0.99281 (7)	0.74959 (4)	0.02062 (15)
F1	0.7268 (3)	0.1888 (2)	0.99513 (11)	0.0517 (6)
F2	0.8668 (3)	0.08502 (19)	0.91195 (12)	0.0532 (6)
F3	0.6749 (2)	0.2241 (2)	0.88165 (13)	0.0564 (6)
F4	0.8208 (2)	1.0523 (2)	0.76493 (11)	0.0508 (5)
F5	0.7233 (2)	1.15490 (17)	0.66873 (11)	0.0381 (4)
F6	0.8107 (2)	0.94594 (19)	0.67342 (11)	0.0416 (5)
N1	0.9880 (2)	0.3263 (2)	0.60772 (11)	0.0176 (4)
N2	0.8212 (2)	0.4073 (2)	0.50069 (11)	0.0170 (4)
N3	0.6971 (2)	0.6358 (2)	0.54179 (11)	0.0175 (4)
N4	0.5243 (2)	0.5723 (2)	0.85181 (12)	0.0197 (5)
N5	0.7535 (2)	0.5968 (2)	0.75566 (12)	0.0201 (5)
N6	0.9188 (2)	0.7201 (2)	0.82471 (12)	0.0191 (5)
N7	0.6692 (3)	0.7400 (2)	0.94561 (12)	0.0237 (5)
O1	0.8791 (2)	0.20122 (18)	0.45319 (10)	0.0241 (4)
O2	0.6910 (2)	0.44173 (19)	0.39529 (10)	0.0236 (4)
O3	0.6675 (2)	0.45898 (18)	0.68097 (9)	0.0202 (4)
O4	0.9287 (2)	0.59552 (18)	0.65287 (10)	0.0200 (4)
O5	0.7980 (2)	0.4528 (2)	0.92880 (11)	0.0309 (5)
O6	1.0187 (2)	0.2967 (2)	0.95778 (12)	0.0374 (5)
O7	0.9513 (2)	0.3449 (2)	0.83152 (11)	0.0367 (5)
O8	0.5841 (3)	0.8840 (2)	0.80548 (13)	0.0442 (6)
O9	0.4725 (2)	1.1139 (2)	0.77653 (12)	0.0339 (5)
O10	0.4920 (2)	0.9585 (2)	0.68607 (12)	0.0342 (5)
C1	1.0716 (3)	0.2935 (3)	0.66516 (15)	0.0228 (6)
H1	1.0666	0.3552	0.7006	0.027*
C2	1.1649 (3)	0.1725 (3)	0.67427 (16)	0.0264 (6)
H2	1.2239	0.1514	0.7152	0.032*
C3	1.1708 (3)	0.0831 (3)	0.62301 (15)	0.0246 (6)
H3	1.2344	−0.0005	0.6281	0.030*
C4	1.0842 (3)	0.1154 (3)	0.56420 (15)	0.0211 (6)
H4	1.0867	0.0546	0.5284	0.025*
C5	0.9936 (3)	0.2380 (3)	0.55840 (14)	0.0176 (5)
C6	0.8920 (3)	0.2789 (2)	0.49648 (14)	0.0175 (5)
C7	0.7229 (3)	0.4747 (3)	0.45235 (14)	0.0181 (5)
C8	0.6495 (3)	0.6052 (3)	0.47920 (13)	0.0171 (5)
C9	0.5377 (3)	0.6875 (3)	0.44324 (14)	0.0201 (5)
H9	0.5069	0.6650	0.3989	0.024*
C10	0.4715 (3)	0.8028 (3)	0.47282 (15)	0.0228 (6)
H10	0.3949	0.8616	0.4489	0.027*
C11	0.5179 (3)	0.8319 (3)	0.53755 (15)	0.0223 (6)
H11	0.4716	0.9097	0.5594	0.027*
C12	0.6315 (3)	0.7474 (3)	0.57013 (14)	0.0207 (6)
H12	0.6645	0.7690	0.6141	0.025*
C13	0.4100 (3)	0.5647 (3)	0.90416 (15)	0.0232 (6)
H13	0.4128	0.6060	0.9476	0.028*
C14	0.2871 (3)	0.4986 (3)	0.89746 (15)	0.0243 (6)
H14	0.2068	0.4951	0.9356	0.029*
C15	0.2829 (3)	0.4384 (3)	0.83506 (15)	0.0258 (6)
H15	0.1990	0.3937	0.8291	0.031*
C16	0.4027 (3)	0.4434 (3)	0.78055 (15)	0.0230 (6)
H16	0.4031	0.4012	0.7371	0.028*
C17	0.5205 (3)	0.5109 (3)	0.79105 (14)	0.0187 (5)
C18	0.6545 (3)	0.5187 (3)	0.73564 (14)	0.0187 (5)
C19	0.8827 (3)	0.6220 (2)	0.71644 (13)	0.0166 (5)
C20	0.9778 (3)	0.6941 (2)	0.75634 (14)	0.0176 (5)
C21	1.1151 (3)	0.7301 (3)	0.72523 (14)	0.0201 (5)
H21	1.1531	0.7101	0.6770	0.024*
C22	1.1966 (3)	0.7964 (3)	0.76622 (15)	0.0232 (6)
H22	1.2918	0.8230	0.7466	0.028*
C23	1.1370 (3)	0.8229 (3)	0.83589 (15)	0.0252 (6)
H23	1.1909	0.8681	0.8649	0.030*
C24	0.9979 (3)	0.7832 (3)	0.86351 (15)	0.0233 (6)
H24	0.9579	0.8018	0.9117	0.028*
C25	0.6605 (3)	0.7991 (3)	0.99484 (16)	0.0266 (6)
C26	0.6546 (4)	0.8740 (3)	1.05813 (17)	0.0329 (7)
H26A	0.7570	0.8726	1.0724	0.049*
H26B	0.5919	0.8321	1.0995	0.049*
H26C	0.6110	0.9677	1.0451	0.049*
C27	0.7879 (4)	0.2023 (3)	0.92485 (18)	0.0374 (7)
C28	0.7356 (3)	1.0402 (3)	0.71278 (16)	0.0254 (6)

	U11	U22	U33	U12	U13	U23
Cu1	0.01840 (17)	0.01472 (17)	0.01487 (17)	−0.00005 (12)	−0.00226 (12)	−0.00360 (12)
Cu2	0.02125 (18)	0.02642 (19)	0.01445 (17)	−0.00578 (14)	−0.00002 (12)	−0.00476 (13)
S1	0.0219 (3)	0.0308 (4)	0.0235 (4)	−0.0026 (3)	−0.0030 (3)	−0.0034 (3)
S2	0.0196 (3)	0.0222 (3)	0.0200 (3)	−0.0035 (3)	−0.0015 (3)	−0.0011 (3)
F1	0.0657 (14)	0.0437 (12)	0.0441 (12)	−0.0192 (10)	0.0183 (10)	−0.0058 (9)
F2	0.0772 (16)	0.0270 (10)	0.0535 (13)	0.0020 (10)	−0.0004 (11)	−0.0113 (9)
F3	0.0441 (12)	0.0621 (14)	0.0711 (15)	−0.0188 (11)	−0.0180 (11)	−0.0151 (12)
F4	0.0324 (11)	0.0827 (16)	0.0427 (11)	−0.0211 (10)	−0.0145 (9)	−0.0035 (11)
F5	0.0342 (10)	0.0265 (9)	0.0497 (11)	−0.0080 (8)	0.0021 (8)	0.0093 (8)
F6	0.0282 (10)	0.0393 (11)	0.0543 (12)	−0.0005 (8)	0.0117 (8)	−0.0110 (9)
N1	0.0170 (11)	0.0177 (11)	0.0173 (11)	−0.0013 (9)	−0.0005 (8)	−0.0009 (9)
N2	0.0201 (11)	0.0147 (11)	0.0160 (10)	0.0000 (9)	−0.0023 (8)	−0.0034 (8)
N3	0.0207 (11)	0.0159 (11)	0.0153 (10)	−0.0013 (9)	0.0000 (8)	−0.0012 (8)
N4	0.0212 (11)	0.0215 (11)	0.0160 (11)	−0.0038 (9)	−0.0004 (9)	−0.0003 (9)
N5	0.0198 (11)	0.0267 (12)	0.0150 (11)	−0.0057 (9)	0.0001 (9)	−0.0051 (9)
N6	0.0200 (11)	0.0203 (11)	0.0168 (11)	−0.0011 (9)	−0.0036 (9)	−0.0017 (9)
N7	0.0284 (13)	0.0250 (12)	0.0177 (12)	−0.0045 (10)	0.0005 (9)	−0.0036 (10)
O1	0.0318 (11)	0.0180 (9)	0.0230 (10)	0.0017 (8)	−0.0063 (8)	−0.0066 (8)
O2	0.0283 (10)	0.0242 (10)	0.0186 (10)	0.0030 (8)	−0.0063 (8)	−0.0070 (8)
O3	0.0218 (9)	0.0218 (9)	0.0180 (9)	−0.0059 (8)	0.0003 (7)	−0.0037 (8)
O4	0.0204 (9)	0.0214 (9)	0.0194 (9)	−0.0044 (7)	0.0000 (7)	−0.0066 (7)
O5	0.0397 (12)	0.0265 (11)	0.0255 (11)	−0.0026 (9)	−0.0018 (9)	−0.0025 (8)
O6	0.0278 (11)	0.0557 (15)	0.0284 (11)	−0.0046 (10)	−0.0080 (9)	0.0005 (10)
O7	0.0315 (12)	0.0515 (14)	0.0247 (11)	−0.0044 (10)	0.0033 (9)	−0.0016 (10)
O8	0.0366 (13)	0.0437 (14)	0.0445 (14)	−0.0016 (11)	−0.0006 (10)	0.0184 (11)
O9	0.0334 (12)	0.0347 (12)	0.0344 (12)	−0.0005 (9)	0.0019 (9)	−0.0150 (9)
O10	0.0265 (11)	0.0491 (13)	0.0312 (11)	−0.0105 (10)	0.0000 (9)	−0.0169 (10)
C1	0.0234 (14)	0.0253 (14)	0.0195 (13)	−0.0017 (11)	−0.0030 (11)	−0.0023 (11)
C2	0.0222 (14)	0.0305 (16)	0.0252 (14)	0.0008 (12)	−0.0060 (11)	0.0009 (12)
C3	0.0209 (14)	0.0205 (14)	0.0289 (15)	0.0035 (11)	−0.0001 (11)	0.0024 (11)
C4	0.0194 (13)	0.0186 (13)	0.0242 (14)	−0.0009 (10)	0.0007 (11)	−0.0022 (11)
C5	0.0172 (13)	0.0169 (12)	0.0178 (13)	−0.0043 (10)	0.0023 (10)	0.0006 (10)
C6	0.0190 (13)	0.0161 (13)	0.0167 (12)	−0.0018 (10)	0.0008 (10)	−0.0017 (10)
C7	0.0180 (13)	0.0180 (13)	0.0171 (13)	−0.0025 (10)	0.0018 (10)	−0.0004 (10)
C8	0.0194 (13)	0.0164 (13)	0.0150 (12)	−0.0027 (10)	−0.0003 (10)	−0.0005 (10)
C9	0.0206 (13)	0.0205 (13)	0.0183 (13)	−0.0024 (11)	−0.0005 (10)	−0.0002 (10)
C10	0.0219 (14)	0.0209 (14)	0.0224 (14)	0.0013 (11)	0.0005 (11)	0.0027 (11)
C11	0.0262 (14)	0.0150 (13)	0.0229 (14)	0.0010 (11)	0.0046 (11)	−0.0013 (10)
C12	0.0267 (14)	0.0173 (13)	0.0182 (13)	−0.0008 (11)	−0.0017 (11)	−0.0047 (10)
C13	0.0265 (14)	0.0235 (14)	0.0178 (13)	−0.0005 (11)	0.0014 (11)	−0.0011 (11)
C14	0.0231 (14)	0.0257 (14)	0.0215 (14)	−0.0013 (11)	0.0031 (11)	0.0012 (11)
C15	0.0226 (14)	0.0289 (15)	0.0258 (15)	−0.0089 (12)	0.0003 (11)	0.0017 (12)
C16	0.0258 (14)	0.0237 (14)	0.0196 (13)	−0.0045 (11)	−0.0020 (11)	−0.0015 (11)
C17	0.0203 (13)	0.0180 (13)	0.0169 (13)	−0.0009 (10)	−0.0016 (10)	0.0004 (10)
C18	0.0203 (13)	0.0182 (13)	0.0169 (13)	−0.0008 (10)	−0.0038 (10)	0.0010 (10)
C19	0.0197 (13)	0.0141 (12)	0.0152 (12)	0.0006 (10)	−0.0024 (10)	−0.0010 (10)
C20	0.0211 (13)	0.0147 (12)	0.0162 (12)	0.0015 (10)	−0.0040 (10)	−0.0007 (10)
C21	0.0212 (13)	0.0194 (13)	0.0192 (13)	−0.0004 (10)	−0.0031 (10)	−0.0019 (10)
C22	0.0208 (14)	0.0225 (14)	0.0266 (14)	−0.0054 (11)	−0.0036 (11)	0.0000 (11)
C23	0.0303 (15)	0.0233 (14)	0.0245 (14)	−0.0070 (12)	−0.0085 (12)	−0.0028 (11)
C24	0.0273 (15)	0.0250 (14)	0.0191 (13)	−0.0046 (11)	−0.0056 (11)	−0.0035 (11)
C25	0.0262 (15)	0.0247 (15)	0.0270 (16)	−0.0023 (12)	0.0002 (12)	0.0009 (13)
C26	0.0398 (18)	0.0337 (17)	0.0271 (16)	−0.0023 (14)	−0.0038 (13)	−0.0124 (13)
C27	0.0411 (19)	0.0339 (18)	0.0372 (18)	−0.0062 (14)	0.0011 (15)	−0.0063 (14)
C28	0.0231 (14)	0.0252 (15)	0.0277 (15)	−0.0035 (12)	−0.0039 (11)	−0.0002 (12)

Cu1—N2	1.922 (2)	C1—C2	1.382 (4)
Cu1—O4	1.9772 (18)	C1—H1	0.9500
Cu1—N1	1.978 (2)	C2—C3	1.376 (4)
Cu1—N3	1.988 (2)	C2—H2	0.9500
Cu1—O3	2.2452 (18)	C3—C4	1.378 (4)
Cu2—N5	1.936 (2)	C3—H3	0.9500
Cu2—N7	1.973 (2)	C4—C5	1.381 (4)
Cu2—N4	2.008 (2)	C4—H4	0.9500
Cu2—N6	2.016 (2)	C5—C6	1.515 (4)
Cu2—O5	2.439 (2)	C7—C8	1.505 (3)
S1—O5	1.432 (2)	C8—C9	1.380 (4)
S1—O6	1.435 (2)	C9—C10	1.378 (4)
S1—O7	1.439 (2)	C9—H9	0.9500
S1—C27	1.807 (3)	C10—C11	1.379 (4)
S2—O8	1.424 (2)	C10—H10	0.9500
S2—O10	1.430 (2)	C11—C12	1.373 (4)
S2—O9	1.439 (2)	C11—H11	0.9500
S2—C28	1.823 (3)	C12—H12	0.9500
F1—C27	1.344 (4)	C13—C14	1.387 (4)
F2—C27	1.326 (4)	C13—H13	0.9500
F3—C27	1.332 (4)	C14—C15	1.370 (4)
F4—C28	1.316 (3)	C14—H14	0.9500
F5—C28	1.320 (3)	C15—C16	1.389 (4)
F6—C28	1.332 (3)	C15—H15	0.9500
N1—C5	1.341 (3)	C16—C17	1.374 (4)
N1—C1	1.341 (3)	C16—H16	0.9500
N2—C6	1.367 (3)	C17—C18	1.493 (4)
N2—C7	1.371 (3)	C19—C20	1.493 (4)
N3—C12	1.335 (3)	C20—C21	1.375 (4)
N3—C8	1.354 (3)	C21—C22	1.388 (4)
N4—C13	1.331 (4)	C21—H21	0.9500
N4—C17	1.349 (3)	C22—C23	1.377 (4)
N5—C19	1.333 (3)	C22—H22	0.9500
N5—C18	1.370 (3)	C23—C24	1.385 (4)
N6—C24	1.327 (3)	C23—H23	0.9500
N6—C20	1.353 (3)	C24—H24	0.9500
N7—C25	1.135 (4)	C25—C26	1.457 (4)
O1—C6	1.209 (3)	C26—H26A	0.9800
O2—C7	1.213 (3)	C26—H26B	0.9800
O3—C18	1.222 (3)	C26—H26C	0.9800
O4—C19	1.246 (3)
N2—Cu1—O4	160.54 (8)	O2—C7—C8	120.4 (2)
N2—Cu1—N1	82.83 (9)	N2—C7—C8	110.6 (2)
O4—Cu1—N1	94.22 (8)	N3—C8—C9	121.9 (2)
N2—Cu1—N3	82.65 (9)	N3—C8—C7	116.0 (2)
O4—Cu1—N3	99.18 (8)	C9—C8—C7	122.1 (2)
N1—Cu1—N3	165.44 (9)	C10—C9—C8	118.7 (2)
N2—Cu1—O3	115.15 (8)	C10—C9—H9	120.6
O4—Cu1—O3	84.30 (7)	C8—C9—H9	120.6
N1—Cu1—O3	99.70 (8)	C9—C10—C11	119.2 (2)
N3—Cu1—O3	87.33 (8)	C9—C10—H10	120.4
N5—Cu2—N7	175.01 (10)	C11—C10—H10	120.4
N5—Cu2—N4	81.63 (9)	C12—C11—C10	119.4 (2)
N7—Cu2—N4	100.19 (9)	C12—C11—H11	120.3
N5—Cu2—N6	81.49 (9)	C10—C11—H11	120.3
N7—Cu2—N6	96.84 (9)	N3—C12—C11	122.0 (2)
N4—Cu2—N6	162.92 (9)	N3—C12—H12	119.0
N5—Cu2—O5	99.74 (8)	C11—C12—H12	119.0
N7—Cu2—O5	85.09 (8)	N4—C13—C14	122.3 (3)
N4—Cu2—O5	84.15 (8)	N4—C13—H13	118.9
N6—Cu2—O5	96.16 (8)	C14—C13—H13	118.9
O5—S1—O6	114.89 (13)	C15—C14—C13	119.1 (3)
O5—S1—O7	114.47 (13)	C15—C14—H14	120.5
O6—S1—O7	115.54 (13)	C13—C14—H14	120.5
O5—S1—C27	102.93 (14)	C14—C15—C16	119.3 (3)
O6—S1—C27	103.22 (15)	C14—C15—H15	120.3
O7—S1—C27	103.38 (15)	C16—C15—H15	120.3
O8—S2—O10	115.97 (15)	C17—C16—C15	118.3 (3)
O8—S2—O9	114.56 (14)	C17—C16—H16	120.9
O10—S2—O9	113.69 (13)	C15—C16—H16	120.9
O8—S2—C28	103.89 (13)	N4—C17—C16	122.8 (2)
O10—S2—C28	102.71 (13)	N4—C17—C18	115.7 (2)
O9—S2—C28	103.82 (13)	C16—C17—C18	121.5 (2)
C5—N1—C1	118.9 (2)	O3—C18—N5	127.5 (2)
C5—N1—Cu1	113.08 (17)	O3—C18—C17	121.2 (2)
C1—N1—Cu1	128.01 (18)	N5—C18—C17	111.3 (2)
C6—N2—C7	124.7 (2)	O4—C19—N5	128.4 (2)
C6—N2—Cu1	117.27 (17)	O4—C19—C20	118.8 (2)
C7—N2—Cu1	117.67 (17)	N5—C19—C20	112.7 (2)
C12—N3—C8	118.8 (2)	N6—C20—C21	123.2 (2)
C12—N3—Cu1	127.81 (18)	N6—C20—C19	115.0 (2)
C8—N3—Cu1	112.95 (17)	C21—C20—C19	121.8 (2)
C13—N4—C17	118.3 (2)	C20—C21—C22	118.1 (2)
C13—N4—Cu2	128.22 (19)	C20—C21—H21	120.9
C17—N4—Cu2	113.47 (17)	C22—C21—H21	120.9
C19—N5—C18	124.5 (2)	C23—C22—C21	118.8 (3)
C19—N5—Cu2	117.75 (17)	C23—C22—H22	120.6
C18—N5—Cu2	117.49 (17)	C21—C22—H22	120.6
C24—N6—C20	118.2 (2)	C22—C23—C24	119.7 (3)
C24—N6—Cu2	128.81 (19)	C22—C23—H23	120.2
C20—N6—Cu2	112.96 (17)	C24—C23—H23	120.2
C25—N7—Cu2	169.2 (2)	N6—C24—C23	122.0 (3)
C18—O3—Cu1	123.40 (17)	N6—C24—H24	119.0
C19—O4—Cu1	130.64 (17)	C23—C24—H24	119.0
S1—O5—Cu2	128.85 (12)	N7—C25—C26	178.2 (3)
N1—C1—C2	121.9 (3)	C25—C26—H26A	109.5
N1—C1—H1	119.0	C25—C26—H26B	109.5
C2—C1—H1	119.0	H26A—C26—H26B	109.5
C3—C2—C1	118.7 (3)	C25—C26—H26C	109.5
C3—C2—H2	120.6	H26A—C26—H26C	109.5
C1—C2—H2	120.6	H26B—C26—H26C	109.5
C2—C3—C4	119.8 (3)	F2—C27—F3	107.4 (3)
C2—C3—H3	120.1	F2—C27—F1	107.6 (3)
C4—C3—H3	120.1	F3—C27—F1	107.6 (3)
C3—C4—C5	118.5 (3)	F2—C27—S1	112.3 (2)
C3—C4—H4	120.7	F3—C27—S1	111.2 (2)
C5—C4—H4	120.7	F1—C27—S1	110.5 (2)
N1—C5—C4	122.2 (2)	F4—C28—F5	108.4 (2)
N1—C5—C6	116.2 (2)	F4—C28—F6	106.6 (2)
C4—C5—C6	121.6 (2)	F5—C28—F6	107.3 (2)
O1—C6—N2	128.9 (2)	F4—C28—S2	112.5 (2)
O1—C6—C5	121.0 (2)	F5—C28—S2	111.41 (19)
N2—C6—C5	110.1 (2)	F6—C28—S2	110.37 (19)
O2—C7—N2	129.0 (2)
N2—Cu1—N1—C5	−3.42 (18)	N1—C5—C6—N2	4.8 (3)
O4—Cu1—N1—C5	−164.09 (17)	C4—C5—C6—N2	−176.5 (2)
N3—Cu1—N1—C5	−7.1 (4)	C6—N2—C7—O2	−7.3 (4)
O3—Cu1—N1—C5	110.98 (17)	Cu1—N2—C7—O2	179.8 (2)
N2—Cu1—N1—C1	179.3 (2)	C6—N2—C7—C8	172.0 (2)
O4—Cu1—N1—C1	18.6 (2)	Cu1—N2—C7—C8	−0.9 (3)
N3—Cu1—N1—C1	175.6 (3)	C12—N3—C8—C9	1.4 (4)
O3—Cu1—N1—C1	−66.4 (2)	Cu1—N3—C8—C9	174.49 (19)
O4—Cu1—N2—C6	88.9 (3)	C12—N3—C8—C7	−177.1 (2)
N1—Cu1—N2—C6	6.56 (18)	Cu1—N3—C8—C7	−4.1 (3)
N3—Cu1—N2—C6	−174.4 (2)	O2—C7—C8—N3	−177.3 (2)
O3—Cu1—N2—C6	−90.82 (19)	N2—C7—C8—N3	3.3 (3)
O4—Cu1—N2—C7	−97.7 (3)	O2—C7—C8—C9	4.1 (4)
N1—Cu1—N2—C7	179.96 (19)	N2—C7—C8—C9	−175.3 (2)
N3—Cu1—N2—C7	−0.96 (18)	N3—C8—C9—C10	−1.0 (4)
O3—Cu1—N2—C7	82.58 (19)	C7—C8—C9—C10	177.4 (2)
N2—Cu1—N3—C12	175.1 (2)	C8—C9—C10—C11	−0.5 (4)
O4—Cu1—N3—C12	−24.5 (2)	C9—C10—C11—C12	1.7 (4)
N1—Cu1—N3—C12	178.7 (3)	C8—N3—C12—C11	−0.2 (4)
O3—Cu1—N3—C12	59.3 (2)	Cu1—N3—C12—C11	−172.1 (2)
N2—Cu1—N3—C8	2.79 (17)	C10—C11—C12—N3	−1.3 (4)
O4—Cu1—N3—C8	163.21 (17)	C17—N4—C13—C14	−1.4 (4)
N1—Cu1—N3—C8	6.4 (4)	Cu2—N4—C13—C14	−178.7 (2)
O3—Cu1—N3—C8	−113.00 (17)	N4—C13—C14—C15	0.3 (4)
N5—Cu2—N4—C13	−179.7 (2)	C13—C14—C15—C16	0.9 (4)
N7—Cu2—N4—C13	−4.4 (2)	C14—C15—C16—C17	−1.0 (4)
N6—Cu2—N4—C13	171.5 (3)	C13—N4—C17—C16	1.3 (4)
O5—Cu2—N4—C13	79.6 (2)	Cu2—N4—C17—C16	179.0 (2)
N5—Cu2—N4—C17	2.86 (18)	C13—N4—C17—C18	−177.8 (2)
N7—Cu2—N4—C17	178.15 (18)	Cu2—N4—C17—C18	−0.1 (3)
N6—Cu2—N4—C17	−6.0 (4)	C15—C16—C17—N4	−0.1 (4)
O5—Cu2—N4—C17	−97.92 (18)	C15—C16—C17—C18	178.9 (2)
N4—Cu2—N5—C19	−179.5 (2)	Cu1—O3—C18—N5	−10.9 (4)
N6—Cu2—N5—C19	−2.17 (19)	Cu1—O3—C18—C17	169.94 (17)
O5—Cu2—N5—C19	−97.01 (19)	C19—N5—C18—O3	1.1 (4)
N4—Cu2—N5—C18	−5.51 (19)	Cu2—N5—C18—O3	−172.5 (2)
N6—Cu2—N5—C18	171.9 (2)	C19—N5—C18—C17	−179.7 (2)
O5—Cu2—N5—C18	77.03 (19)	Cu2—N5—C18—C17	6.7 (3)
N5—Cu2—N6—C24	−179.7 (2)	N4—C17—C18—O3	175.1 (2)
N7—Cu2—N6—C24	5.0 (2)	C16—C17—C18—O3	−4.0 (4)
N4—Cu2—N6—C24	−170.9 (3)	N4—C17—C18—N5	−4.2 (3)
O5—Cu2—N6—C24	−80.8 (2)	C16—C17—C18—N5	176.7 (2)
N5—Cu2—N6—C20	2.40 (17)	Cu1—O4—C19—N5	−6.8 (4)
N7—Cu2—N6—C20	−172.86 (18)	Cu1—O4—C19—C20	174.63 (16)
N4—Cu2—N6—C20	11.3 (4)	C18—N5—C19—O4	9.3 (4)
O5—Cu2—N6—C20	101.37 (17)	Cu2—N5—C19—O4	−177.1 (2)
N4—Cu2—N7—C25	−158.9 (13)	C18—N5—C19—C20	−172.1 (2)
N6—Cu2—N7—C25	22.3 (13)	Cu2—N5—C19—C20	1.5 (3)
O5—Cu2—N7—C25	117.9 (13)	C24—N6—C20—C21	−0.1 (4)
N2—Cu1—O3—C18	−170.46 (19)	Cu2—N6—C20—C21	178.0 (2)
O4—Cu1—O3—C18	9.6 (2)	C24—N6—C20—C19	179.6 (2)
N1—Cu1—O3—C18	103.0 (2)	Cu2—N6—C20—C19	−2.3 (3)
N3—Cu1—O3—C18	−89.9 (2)	O4—C19—C20—N6	179.4 (2)
N2—Cu1—O4—C19	178.8 (2)	N5—C19—C20—N6	0.6 (3)
N1—Cu1—O4—C19	−100.9 (2)	O4—C19—C20—C21	−0.9 (4)
N3—Cu1—O4—C19	84.8 (2)	N5—C19—C20—C21	−179.7 (2)
O3—Cu1—O4—C19	−1.5 (2)	N6—C20—C21—C22	−0.1 (4)
O6—S1—O5—Cu2	130.69 (15)	C19—C20—C21—C22	−179.8 (2)
O7—S1—O5—Cu2	−6.5 (2)	C20—C21—C22—C23	0.1 (4)
C27—S1—O5—Cu2	−117.89 (17)	C21—C22—C23—C24	0.0 (4)
N5—Cu2—O5—S1	22.78 (18)	C20—N6—C24—C23	0.2 (4)
N7—Cu2—O5—S1	−155.98 (17)	Cu2—N6—C24—C23	−177.5 (2)
N4—Cu2—O5—S1	103.22 (17)	C22—C23—C24—N6	−0.2 (4)
N6—Cu2—O5—S1	−59.61 (17)	O5—S1—C27—F2	−177.7 (2)
C5—N1—C1—C2	1.0 (4)	O6—S1—C27—F2	−57.9 (3)
Cu1—N1—C1—C2	178.2 (2)	O7—S1—C27—F2	62.9 (3)
N1—C1—C2—C3	−0.5 (4)	O5—S1—C27—F3	61.9 (3)
C1—C2—C3—C4	−0.2 (4)	O6—S1—C27—F3	−178.2 (2)
C2—C3—C4—C5	0.2 (4)	O7—S1—C27—F3	−57.5 (3)
C1—N1—C5—C4	−0.9 (4)	O5—S1—C27—F1	−57.5 (3)
Cu1—N1—C5—C4	−178.5 (2)	O6—S1—C27—F1	62.3 (3)
C1—N1—C5—C6	177.7 (2)	O7—S1—C27—F1	−176.9 (2)
Cu1—N1—C5—C6	0.1 (3)	O8—S2—C28—F4	−47.3 (2)
C3—C4—C5—N1	0.3 (4)	O10—S2—C28—F4	−168.5 (2)
C3—C4—C5—C6	−178.3 (2)	O9—S2—C28—F4	72.8 (2)
C7—N2—C6—O1	−2.7 (4)	O8—S2—C28—F5	−169.3 (2)
Cu1—N2—C6—O1	170.2 (2)	O10—S2—C28—F5	69.5 (2)
C7—N2—C6—C5	179.3 (2)	O9—S2—C28—F5	−49.2 (2)
Cu1—N2—C6—C5	−7.8 (3)	O8—S2—C28—F6	71.6 (2)
N1—C5—C6—O1	−173.4 (2)	O10—S2—C28—F6	−49.6 (2)
C4—C5—C6—O1	5.3 (4)	O9—S2—C28—F6	−168.27 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O9i	0.95	2.57	3.448 (3)	154
C4—H4···O1ii	0.95	2.53	3.210 (4)	128
C10—H10···F5iii	0.95	2.54	3.239 (3)	130
C21—H21···O1iv	0.95	2.48	3.257 (3)	140
C21—H21···O2iv	0.95	2.37	3.203 (3)	147
C22—H22···O10v	0.95	2.48	3.400 (3)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O9i	0.95	2.57	3.448 (3)	154
C4—H4⋯O1ii	0.95	2.53	3.210 (4)	128
C10—H10⋯F5iii	0.95	2.54	3.239 (3)	130
C21—H21⋯O1iv	0.95	2.48	3.257 (3)	140
C21—H21⋯O2iv	0.95	2.37	3.203 (3)	147
C22—H22⋯O10v	0.95	2.48	3.400 (3)	163

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .