Solvent-mediated structural transformations of copper(II) coordination polymers induced by different short-chain alcohols

A three-dimensional copper(II) coordination polymer (CP), {Cu(L-F)(N₃)}_n (1), was synthesized by reacting Cu(NO₃)₂ with 5-fluoro­nicotinic acid (HL-F) and NaN₃ in a water medium. Complex (1) shows a 3D network, in which the 1D [Cu₂(COO)N₃]_n chains are interconnected via L-F ligands. By immersing (1) into different short-chain alcohols (CH₃OH, C₂H₅OH and HOC₂H₄OH), three different CPs were isolated, including {Cu₃(L-F)₄(N₃)₂(CH₃OH)₂}_n (2), {Cu₃(L-F)₄(N₃)₂(C₂H₅OH)₂}_n (3) and {Cu_2.5(L-F)₃(N₃)₂(HOC₂H₄OH)_0.5}_n (4). CPs (2) and (3) display a similar structure, in which trinuclear subunit [Cu₃(COO)₂(N₃)₂(solvent)₂] is generated. Furthermore, such entities are interconnected via L-F ligands to give rise to a 3D network. As for (4), there are trinuclear [Cu₃(COO)₂(N₃)₂] and binuclear [Cu₂(COO)N₃] units, which are interconnected by L-F ligands to generate a 3D network. Notably, in (2) and (3), the coordination modes of CH₃OH and C₂H₅OH solvents are monodentate; whereas for (4), the HOC₂H₄OH solvent adopts a bridging mode to link two Cu atoms. Of further interest, these processes are solvent-mediated structural transformations, with obvious colour changes in the crystals. Structural changes and mechanisms of transformation are discussed in detail.

Computing details

Data collection: Bruker SMART for (2), (3), (4). Cell refinement: Bruker SMART for (2), (3), (4). Data reduction: Bruker SAINT for (2), (3), (4). Program(s) used to solve structure: Bruker SHELXTL for (2), (3), (4). Program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016) for (1); SHELXL2018/3 (Sheldrick, 2018) for (2), (3), (4). Molecular graphics: Bruker SHELXTL for (2), (3), (4). Software used to prepare material for publication: Bruker SHELXTL for (2), (3), (4).

(1)

Crystal data

C6H3CuFN4O2	Dx = 2.089 Mg m^−3
Mr = 245.66	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 3648 reflections
a = 6.6235 (3) Å	θ = 2.7–28.2°
b = 9.4208 (4) Å	µ = 2.79 mm^−1
c = 12.5188 (5) Å	T = 173 K
V = 781.16 (6) Å^3	Block, green
Z = 4	0.22 × 0.21 × 0.18 mm
F(000) = 484

Data collection

CCD area detector diffractometer	1877 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.023
Absorption correction: multi-scan SADABS	θmax = 28.2°, θmin = 2.7°
Tmin = 0.579, Tmax = 0.634	h = −8→8
5780 measured reflections	k = −12→11
1928 independent reflections	l = −16→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.018	w = 1/[σ^2(Fo^2) + (0.0204P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.044	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.33 e Å^−3
1928 reflections	Δρmin = −0.34 e Å^−3
128 parameters	Absolute structure: Refined as an inversion twin.
0 restraints	Absolute structure parameter: 0.069 (16)

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. Refined as a 2-component inversion twin

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

	x	y	z	Uiso*/Ueq
Cu1	0.71245 (4)	0.70968 (3)	0.49248 (2)	0.00710 (8)
F1	0.6605 (2)	0.85152 (18)	−0.03596 (12)	0.0196 (4)
O1	0.7954 (3)	0.79528 (18)	0.35456 (12)	0.0112 (3)
O2	1.1220 (3)	0.86214 (18)	0.36899 (13)	0.0110 (4)
N1	1.1145 (3)	1.0146 (2)	0.05896 (17)	0.0106 (4)
N2	0.9361 (3)	0.8107 (2)	0.56858 (16)	0.0088 (4)
N3	0.9219 (3)	0.8315 (2)	0.66477 (18)	0.0106 (5)
N4	0.9065 (4)	0.8542 (3)	0.75352 (18)	0.0189 (5)
C1	0.9577 (4)	0.8458 (3)	0.31993 (19)	0.0082 (5)
C2	0.9570 (4)	0.8892 (2)	0.2036 (2)	0.0086 (5)
C3	1.1108 (4)	0.9722 (3)	0.1617 (2)	0.0104 (5)
H3	1.218196	1.000235	0.207375	0.012*
C4	0.7992 (4)	0.8474 (2)	0.13746 (19)	0.0110 (5)
H4	0.689350	0.792785	0.163811	0.013*
C5	0.8093 (4)	0.8886 (3)	0.0318 (2)	0.0117 (5)
C6	0.9662 (3)	0.9715 (2)	−0.0055 (2)	0.0103 (5)
H6	0.968643	0.998339	−0.078639	0.012*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00638 (13)	0.01107 (13)	0.00386 (13)	−0.00025 (11)	0.00002 (11)	0.00098 (12)
F1	0.0201 (9)	0.0286 (8)	0.0101 (7)	−0.0114 (7)	−0.0066 (6)	0.0027 (7)
O1	0.0109 (8)	0.0162 (8)	0.0066 (7)	−0.0028 (9)	−0.0008 (7)	0.0023 (7)
O2	0.0090 (9)	0.0168 (8)	0.0072 (8)	0.0006 (8)	−0.0007 (7)	0.0028 (7)
N1	0.0113 (11)	0.0124 (10)	0.0082 (10)	−0.0007 (9)	0.0014 (9)	0.0018 (8)
N2	0.0073 (10)	0.0148 (11)	0.0044 (9)	0.0000 (9)	−0.0003 (7)	−0.0017 (8)
N3	0.0059 (10)	0.0133 (11)	0.0126 (11)	0.0018 (8)	0.0000 (9)	−0.0001 (9)
N4	0.0162 (12)	0.0315 (13)	0.0091 (11)	0.0028 (11)	−0.0014 (9)	−0.0069 (11)
C1	0.0114 (12)	0.0075 (11)	0.0058 (11)	0.0017 (10)	−0.0001 (10)	0.0004 (9)
C2	0.0112 (13)	0.0078 (11)	0.0069 (11)	0.0018 (10)	0.0005 (10)	0.0015 (10)
C3	0.0104 (12)	0.0135 (11)	0.0073 (11)	−0.0006 (10)	−0.0022 (10)	0.0004 (10)
C4	0.0115 (12)	0.0110 (10)	0.0105 (11)	−0.0026 (10)	0.0018 (11)	0.0019 (9)
C5	0.0128 (13)	0.0118 (11)	0.0103 (11)	−0.0004 (10)	−0.0044 (10)	−0.0028 (9)
C6	0.0152 (12)	0.0103 (9)	0.0054 (11)	0.0012 (9)	0.0016 (11)	−0.0017 (11)

Geometric parameters (Å, º)

Cu1—O2^i	1.9556 (17)	N2—N3	1.224 (3)
Cu1—O1	1.9833 (16)	N3—N4	1.136 (3)
Cu1—N2^i	1.993 (2)	C1—C2	1.513 (3)
Cu1—N2	2.002 (2)	C2—C3	1.387 (3)
Cu1—N1^ii	2.259 (2)	C2—C4	1.391 (4)
F1—C5	1.347 (3)	C3—H3	0.9500
O1—C1	1.253 (3)	C4—C5	1.380 (3)
O2—C1	1.259 (3)	C4—H4	0.9500
N1—C6	1.335 (3)	C5—C6	1.381 (3)
N1—C3	1.347 (3)	C6—H6	0.9500
O2^i—Cu1—O1	176.03 (7)	O1—C1—O2	128.3 (2)
O2^i—Cu1—N2^i	91.46 (8)	O1—C1—C2	115.7 (2)
O1—Cu1—N2^i	87.69 (8)	O2—C1—C2	116.0 (2)
O2^i—Cu1—N2	88.23 (8)	C3—C2—C4	119.1 (2)
O1—Cu1—N2	90.92 (8)	C3—C2—C1	121.0 (2)
N2^i—Cu1—N2	155.22 (5)	C4—C2—C1	119.9 (2)
O2^i—Cu1—N1^ii	97.28 (7)	N1—C3—C2	122.8 (2)
O1—Cu1—N1^ii	86.67 (8)	N1—C3—H3	118.6
N2^i—Cu1—N1^ii	106.16 (8)	C2—C3—H3	118.6
N2—Cu1—N1^ii	98.44 (8)	C5—C4—C2	117.0 (2)
C1—O1—Cu1	133.89 (16)	C5—C4—H4	121.5
C1—O2—Cu1^iii	130.92 (17)	C2—C4—H4	121.5
C6—N1—C3	118.3 (2)	F1—C5—C4	119.7 (2)
C6—N1—Cu1^iv	116.66 (16)	F1—C5—C6	118.9 (2)
C3—N1—Cu1^iv	121.52 (17)	C4—C5—C6	121.3 (2)
N3—N2—Cu1^iii	117.61 (18)	N1—C6—C5	121.4 (2)
N3—N2—Cu1	119.17 (18)	N1—C6—H6	119.3
Cu1^iii—N2—Cu1	116.83 (10)	C5—C6—H6	119.3
N4—N3—N2	178.2 (3)
Cu1—O1—C1—O2	−3.5 (4)	C4—C2—C3—N1	0.1 (4)
Cu1—O1—C1—C2	174.90 (15)	C1—C2—C3—N1	−179.1 (2)
Cu1^iii—O2—C1—O1	11.7 (4)	C3—C2—C4—C5	1.8 (3)
Cu1^iii—O2—C1—C2	−166.70 (15)	C1—C2—C4—C5	−179.0 (2)
O1—C1—C2—C3	166.7 (2)	C2—C4—C5—F1	−179.8 (2)
O2—C1—C2—C3	−14.7 (4)	C2—C4—C5—C6	−1.9 (4)
O1—C1—C2—C4	−12.5 (3)	C3—N1—C6—C5	1.7 (4)
O2—C1—C2—C4	166.1 (2)	Cu1^iv—N1—C6—C5	−157.37 (18)
C6—N1—C3—C2	−1.9 (4)	F1—C5—C6—N1	178.0 (2)
Cu1^iv—N1—C3—C2	156.15 (19)	C4—C5—C6—N1	0.2 (4)

Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+2, y−1/2, −z+1/2; (iii) x+1/2, −y+3/2, −z+1; (iv) −x+2, y+1/2, −z+1/2.

(2)

Crystal data

C26H20Cu3F4N10O10	F(000) = 898
Mr = 899.14	Dx = 1.826 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.441 (2) Å	Cell parameters from 3510 reflections
b = 8.0580 (16) Å	θ = 2.7–28.2°
c = 19.542 (4) Å	µ = 2.03 mm^−1
β = 95.92 (3)°	T = 173 K
V = 1635.4 (6) Å^3	Block, green
Z = 2	0.22 × 0.21 × 0.18 mm

Data collection

CCD area detector diffractometer	2692 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.033
Absorption correction: multi-scan SADABS	θmax = 26.0°, θmin = 2.1°
	h = −12→10
9799 measured reflections	k = −8→9
3210 independent reflections	l = −24→21

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.7657P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3210 reflections	Δρmax = 0.48 e Å^−3
242 parameters	Δρmin = −0.41 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.74524 (3)	0.89225 (4)	0.89693 (2)	0.00954 (10)
Cu2	1.000000	1.000000	1.000000	0.01023 (12)
F1	0.69131 (15)	1.0564 (3)	1.28503 (8)	0.0365 (5)
F2	1.11884 (14)	0.9534 (2)	0.57559 (8)	0.0198 (4)
O1	0.69081 (16)	0.8807 (2)	0.98990 (9)	0.0115 (4)
O2	0.86926 (15)	0.9363 (2)	1.06127 (9)	0.0135 (4)
O3	0.78292 (16)	0.9223 (2)	0.80220 (9)	0.0117 (4)
O4	0.97633 (17)	0.7985 (2)	0.80659 (9)	0.0181 (4)
O5	0.99748 (17)	0.7318 (2)	0.94373 (10)	0.0206 (4)
H5A	0.984421	0.747637	0.900574	0.031*
N1	0.86279 (19)	1.0757 (3)	0.92785 (11)	0.0117 (5)
N2	0.88729 (19)	1.1817 (3)	0.88673 (11)	0.0143 (5)
N3	0.9096 (2)	1.2830 (3)	0.84896 (13)	0.0290 (6)
N4	0.45713 (19)	0.9852 (3)	1.14099 (11)	0.0112 (5)
N5	0.84423 (19)	1.1714 (3)	0.62591 (11)	0.0108 (4)
C1	0.7504 (2)	0.9177 (3)	1.04737 (13)	0.0100 (5)
C2	0.6692 (2)	0.9465 (3)	1.10554 (13)	0.0098 (5)
C3	0.5354 (2)	0.9455 (3)	1.09326 (13)	0.0095 (5)
H3	0.498361	0.915766	1.049662	0.011*
C4	0.5103 (2)	1.0207 (3)	1.20435 (13)	0.0127 (6)
H4	0.457712	1.046440	1.238481	0.015*
C5	0.6427 (2)	1.0196 (4)	1.21994 (14)	0.0191 (6)
C6	0.7248 (2)	0.9862 (4)	1.17123 (14)	0.0174 (6)
H6	0.813645	0.989980	1.181672	0.021*
C7	0.8901 (2)	0.8868 (3)	0.77868 (13)	0.0107 (5)
C8	0.9081 (2)	0.9644 (3)	0.71038 (13)	0.0098 (5)
C9	1.0106 (2)	0.9170 (3)	0.67493 (13)	0.0117 (5)
H9	1.068356	0.835185	0.691712	0.014*
C10	1.0228 (2)	0.9972 (3)	0.61367 (13)	0.0121 (6)
C11	0.9417 (2)	1.1228 (3)	0.58960 (13)	0.0123 (6)
H11	0.953490	1.174925	0.548251	0.015*
C12	0.8270 (2)	1.0896 (3)	0.68376 (13)	0.0104 (5)
H12	0.757074	1.118171	0.707227	0.012*
C13	1.1081 (4)	0.6252 (5)	0.95611 (19)	0.0413 (9)
H13A	1.184291	0.685598	0.947831	0.062*
H13B	1.098276	0.531329	0.925786	0.062*
H13C	1.115624	0.587644	1.002973	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00850 (16)	0.01488 (19)	0.00592 (16)	−0.00190 (12)	0.00400 (11)	−0.00081 (12)
Cu2	0.0047 (2)	0.0202 (3)	0.0060 (2)	−0.00057 (17)	0.00205 (16)	0.00161 (18)
F1	0.0136 (8)	0.0844 (15)	0.0114 (9)	−0.0051 (9)	0.0007 (7)	−0.0181 (9)
F2	0.0193 (8)	0.0261 (9)	0.0166 (8)	0.0074 (7)	0.0151 (6)	0.0032 (7)
O1	0.0090 (8)	0.0194 (10)	0.0066 (9)	−0.0031 (7)	0.0031 (7)	−0.0004 (7)
O2	0.0057 (8)	0.0268 (11)	0.0084 (9)	−0.0005 (8)	0.0020 (7)	0.0022 (8)
O3	0.0115 (9)	0.0158 (10)	0.0085 (9)	−0.0014 (7)	0.0037 (7)	−0.0006 (7)
O4	0.0182 (9)	0.0259 (11)	0.0108 (10)	0.0089 (9)	0.0039 (7)	0.0052 (9)
O5	0.0254 (10)	0.0239 (11)	0.0130 (10)	0.0012 (9)	0.0045 (8)	0.0007 (8)
N1	0.0085 (10)	0.0182 (13)	0.0087 (11)	−0.0015 (9)	0.0022 (8)	0.0032 (9)
N2	0.0105 (10)	0.0212 (13)	0.0103 (11)	−0.0022 (10)	−0.0025 (9)	−0.0015 (11)
N3	0.0325 (14)	0.0327 (16)	0.0205 (14)	−0.0116 (13)	−0.0034 (11)	0.0104 (13)
N4	0.0099 (10)	0.0144 (12)	0.0096 (11)	−0.0001 (9)	0.0024 (8)	−0.0004 (9)
N5	0.0099 (10)	0.0140 (12)	0.0089 (11)	−0.0006 (9)	0.0029 (8)	−0.0008 (9)
C1	0.0097 (12)	0.0107 (14)	0.0099 (13)	0.0000 (10)	0.0028 (10)	0.0016 (10)
C2	0.0080 (11)	0.0121 (13)	0.0096 (13)	−0.0001 (10)	0.0025 (9)	0.0026 (10)
C3	0.0103 (12)	0.0118 (13)	0.0063 (12)	−0.0009 (10)	0.0010 (9)	0.0003 (10)
C4	0.0122 (12)	0.0178 (15)	0.0091 (13)	0.0003 (11)	0.0049 (10)	−0.0022 (11)
C5	0.0128 (13)	0.0369 (19)	0.0072 (13)	−0.0032 (12)	−0.0003 (10)	−0.0051 (12)
C6	0.0081 (12)	0.0323 (18)	0.0120 (14)	−0.0017 (11)	0.0012 (10)	−0.0017 (12)
C7	0.0127 (12)	0.0120 (14)	0.0078 (13)	−0.0027 (10)	0.0039 (10)	−0.0031 (10)
C8	0.0106 (12)	0.0113 (14)	0.0077 (12)	−0.0032 (10)	0.0021 (9)	−0.0032 (10)
C9	0.0097 (12)	0.0134 (14)	0.0121 (13)	0.0013 (10)	0.0020 (10)	−0.0012 (11)
C10	0.0114 (12)	0.0168 (15)	0.0093 (13)	0.0005 (11)	0.0068 (10)	−0.0043 (11)
C11	0.0151 (13)	0.0168 (15)	0.0058 (12)	−0.0022 (11)	0.0056 (10)	0.0012 (11)
C12	0.0069 (11)	0.0169 (15)	0.0079 (12)	−0.0014 (10)	0.0039 (9)	−0.0012 (10)
C13	0.057 (2)	0.033 (2)	0.031 (2)	0.0188 (18)	−0.0101 (17)	−0.0064 (16)

Geometric parameters (Å, º)

Cu1—O3	1.9470 (18)	N4—C3	1.340 (3)
Cu1—O1	1.9610 (17)	N5—C12	1.337 (3)
Cu1—N1	1.976 (2)	N5—C11	1.356 (3)
Cu1—N5^i	2.038 (2)	C1—C2	1.504 (3)
Cu1—N4^ii	2.380 (2)	C2—C6	1.390 (4)
Cu2—O2^iii	1.9743 (17)	C2—C3	1.394 (3)
Cu2—O2	1.9743 (17)	C3—H3	0.9300
Cu2—N1	1.999 (2)	C4—C5	1.385 (4)
Cu2—N1^iii	1.999 (2)	C4—H4	0.9300
Cu2—O5^iii	2.423 (2)	C5—C6	1.371 (4)
Cu2—O5	2.423 (2)	C6—H6	0.9300
F1—C5	1.353 (3)	C7—C8	1.503 (3)
F2—C10	1.356 (3)	C8—C12	1.383 (4)
O1—C1	1.262 (3)	C8—C9	1.388 (3)
O2—C1	1.251 (3)	C9—C10	1.378 (4)
O3—C7	1.285 (3)	C9—H9	0.9300
O4—C7	1.230 (3)	C10—C11	1.372 (4)
O5—C13	1.440 (4)	C11—H11	0.9300
O5—H5A	0.8499	C12—H12	0.9300
N1—N2	1.218 (3)	C13—H13A	0.9600
N2—N3	1.140 (3)	C13—H13B	0.9600
N4—C4	1.335 (3)	C13—H13C	0.9600
O3—Cu1—O1	173.27 (7)	O2—C1—C2	116.2 (2)
O3—Cu1—N1	91.01 (8)	O1—C1—C2	116.4 (2)
O1—Cu1—N1	88.99 (8)	C6—C2—C3	118.4 (2)
O3—Cu1—N5^i	91.92 (8)	C6—C2—C1	121.3 (2)
O1—Cu1—N5^i	89.50 (8)	C3—C2—C1	120.2 (2)
N1—Cu1—N5^i	167.57 (9)	N4—C3—C2	123.4 (2)
O3—Cu1—N4^ii	84.97 (8)	N4—C3—H3	118.3
O1—Cu1—N4^ii	88.59 (8)	C2—C3—H3	118.3
N1—Cu1—N4^ii	106.76 (8)	N4—C4—C5	120.9 (2)
N5^i—Cu1—N4^ii	85.53 (8)	N4—C4—H4	119.6
O2^iii—Cu2—O2	180.0	C5—C4—H4	119.6
O2^iii—Cu2—N1	89.03 (8)	F1—C5—C6	119.7 (2)
O2—Cu2—N1	90.97 (8)	F1—C5—C4	118.3 (2)
O2^iii—Cu2—N1^iii	90.98 (8)	C6—C5—C4	122.0 (3)
O2—Cu2—N1^iii	89.02 (8)	C5—C6—C2	117.1 (2)
N1—Cu2—N1^iii	180.00 (8)	C5—C6—H6	121.5
O2^iii—Cu2—O5^iii	93.87 (7)	C2—C6—H6	121.5
O2—Cu2—O5^iii	86.13 (7)	O4—C7—O3	126.5 (2)
N1—Cu2—O5^iii	91.23 (8)	O4—C7—C8	118.8 (2)
N1^iii—Cu2—O5^iii	88.77 (8)	O3—C7—C8	114.7 (2)
O2^iii—Cu2—O5	86.13 (7)	C12—C8—C9	119.1 (2)
O2—Cu2—O5	93.87 (7)	C12—C8—C7	120.6 (2)
N1—Cu2—O5	88.77 (8)	C9—C8—C7	120.1 (2)
N1^iii—Cu2—O5	91.23 (8)	C10—C9—C8	116.7 (2)
O5^iii—Cu2—O5	180.0	C10—C9—H9	121.6
C1—O1—Cu1	130.51 (16)	C8—C9—H9	121.6
C1—O2—Cu2	129.16 (16)	F2—C10—C11	118.0 (2)
C7—O3—Cu1	125.53 (16)	F2—C10—C9	119.6 (2)
C13—O5—Cu2	119.00 (19)	C11—C10—C9	122.4 (2)
C13—O5—H5A	107.4	N5—C11—C10	120.2 (2)
Cu2—O5—H5A	108.1	N5—C11—H11	119.9
N2—N1—Cu1	119.29 (17)	C10—C11—H11	119.9
N2—N1—Cu2	119.69 (16)	N5—C12—C8	123.1 (2)
Cu1—N1—Cu2	111.41 (11)	N5—C12—H12	118.4
N3—N2—N1	178.9 (3)	C8—C12—H12	118.4
C4—N4—C3	118.1 (2)	O5—C13—H13A	109.5
C4—N4—Cu1^ii	118.09 (16)	O5—C13—H13B	109.5
C3—N4—Cu1^ii	117.86 (17)	H13A—C13—H13B	109.5
C12—N5—C11	118.3 (2)	O5—C13—H13C	109.5
C12—N5—Cu1^iv	121.13 (17)	H13A—C13—H13C	109.5
C11—N5—Cu1^iv	119.26 (17)	H13B—C13—H13C	109.5
O2—C1—O1	127.5 (2)
Cu2—O2—C1—O1	25.8 (4)	C1—C2—C6—C5	176.3 (3)
Cu2—O2—C1—C2	−152.70 (18)	Cu1—O3—C7—O4	16.0 (4)
Cu1—O1—C1—O2	−17.6 (4)	Cu1—O3—C7—C8	−163.56 (16)
Cu1—O1—C1—C2	160.95 (17)	O4—C7—C8—C12	−166.9 (2)
O2—C1—C2—C6	−2.0 (4)	O3—C7—C8—C12	12.6 (3)
O1—C1—C2—C6	179.3 (2)	O4—C7—C8—C9	9.7 (4)
O2—C1—C2—C3	173.4 (2)	O3—C7—C8—C9	−170.7 (2)
O1—C1—C2—C3	−5.3 (4)	C12—C8—C9—C10	−1.5 (4)
C4—N4—C3—C2	−2.9 (4)	C7—C8—C9—C10	−178.2 (2)
Cu1^ii—N4—C3—C2	149.5 (2)	C8—C9—C10—F2	−178.2 (2)
C6—C2—C3—N4	1.9 (4)	C8—C9—C10—C11	2.7 (4)
C1—C2—C3—N4	−173.6 (2)	C12—N5—C11—C10	−2.5 (4)
C3—N4—C4—C5	1.2 (4)	Cu1^iv—N5—C11—C10	164.5 (2)
Cu1^ii—N4—C4—C5	−151.2 (2)	F2—C10—C11—N5	−179.8 (2)
N4—C4—C5—F1	−179.9 (3)	C9—C10—C11—N5	−0.8 (4)
N4—C4—C5—C6	1.5 (5)	C11—N5—C12—C8	3.9 (4)
F1—C5—C6—C2	178.9 (3)	Cu1^iv—N5—C12—C8	−162.96 (19)
C4—C5—C6—C2	−2.5 (5)	C9—C8—C12—N5	−1.8 (4)
C3—C2—C6—C5	0.9 (4)	C7—C8—C12—N5	174.9 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+2; (iii) −x+2, −y+2, −z+2; (iv) −x+3/2, y+1/2, −z+3/2.

(3)

Crystal data

C28H24Cu3F4N10O10	F(000) = 930
Mr = 927.19	Dx = 1.779 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.3405 (15) Å	Cell parameters from 4369 reflections
b = 8.6279 (13) Å	θ = 2.6–28.4°
c = 19.594 (3) Å	µ = 1.92 mm^−1
β = 98.153 (3)°	T = 173 K
V = 1730.4 (4) Å^3	Block, green
Z = 2	0.22 × 0.21 × 0.18 mm

Data collection

CCD area detector diffractometer	2561 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.029
Absorption correction: multi-scan SADABS	θmax = 25.0°, θmin = 2.1°
Tmin = 0.678, Tmax = 0.724	h = −12→7
9290 measured reflections	k = −9→10
3046 independent reflections	l = −23→23

Refinement

Refinement on F^2	144 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.0727P)^2 + 4.2264P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.001
3046 reflections	Δρmax = 1.23 e Å^−3
282 parameters	Δρmin = −1.70 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.24042 (5)	0.59799 (6)	0.89516 (2)	0.01991 (19)
Cu2	0.500000	0.500000	1.000000	0.0216 (2)
F1	0.5806 (4)	0.5568 (4)	0.56944 (16)	0.0563 (10)
F2A	0.2101 (8)	0.3916 (13)	1.2767 (4)	0.0405 (10)	0.358 (6)
F2B	0.2167 (4)	0.4882 (7)	1.2883 (2)	0.0405 (10)	0.642 (6)
O1	0.2722 (3)	0.5581 (4)	0.80055 (15)	0.0249 (7)
O2	0.4606 (3)	0.6865 (4)	0.80102 (16)	0.0306 (7)
O3	0.1888 (3)	0.6141 (3)	0.98823 (15)	0.0212 (6)
O4	0.3742 (3)	0.5698 (5)	1.05996 (16)	0.0370 (9)
O5A	0.4615 (6)	0.7238 (6)	0.9337 (3)	0.0460 (11)	0.693 (7)
H5A	0.422859	0.711600	0.887033	0.069*	0.693 (7)
O5B	0.5293 (13)	0.7370 (16)	0.9394 (7)	0.0460 (11)	0.307 (7)
H5B	0.455128	0.785553	0.914020	0.069*	0.307 (7)
N1	0.3427 (3)	0.3095 (4)	0.62896 (17)	0.0190 (7)
N2A	−0.0343 (10)	0.513 (5)	1.1392 (11)	0.0176 (8)	0.358 (6)
N2B	−0.0313 (6)	0.518 (3)	1.1422 (6)	0.0176 (8)	0.642 (6)
N3	0.3556 (3)	0.4214 (5)	0.92965 (19)	0.0259 (8)
N4	0.3773 (3)	0.3212 (5)	0.8890 (2)	0.0287 (9)
N5	0.3966 (4)	0.2247 (5)	0.8518 (2)	0.0402 (10)
C1	0.3751 (4)	0.5952 (5)	0.7753 (2)	0.0220 (9)
C2	0.3238 (4)	0.3864 (5)	0.6864 (2)	0.0200 (9)
H2	0.260741	0.347811	0.712903	0.024*
C3	0.3919 (4)	0.5192 (5)	0.7086 (2)	0.0211 (9)
C4	0.4812 (4)	0.5792 (5)	0.6695 (2)	0.0259 (10)
H4	0.529892	0.670098	0.683165	0.031*
C5	0.4963 (5)	0.5020 (6)	0.6103 (2)	0.0338 (11)
C6	0.4278 (4)	0.3684 (5)	0.5904 (2)	0.0255 (9)
H6	0.441260	0.317672	0.548921	0.031*
C7	0.2537 (4)	0.5839 (6)	1.0462 (2)	0.0247 (10)
C8A	0.0418 (9)	0.5507 (19)	1.0918 (4)	0.0172 (8)	0.642 (6)
H8A	−0.000311	0.561739	1.045670	0.021*	0.642 (6)
C8B	0.0432 (15)	0.562 (3)	1.0926 (8)	0.0172 (8)	0.358 (6)
H8B	0.005118	0.615832	1.052337	0.021*	0.358 (6)
C9A	0.1760 (14)	0.5359 (17)	1.1035 (6)	0.0193 (9)	0.358 (6)
C9B	0.1759 (8)	0.5681 (9)	1.1055 (3)	0.0193 (9)	0.642 (6)
C10A	0.2333 (9)	0.4791 (16)	1.1665 (5)	0.0219 (9)	0.358 (6)
H10A	0.325304	0.465645	1.175831	0.026*	0.358 (6)
C10B	0.2378 (5)	0.5463 (9)	1.1721 (3)	0.0219 (9)	0.642 (6)
H10B	0.330017	0.555084	1.182723	0.026*	0.642 (6)
C11A	0.1560 (10)	0.4426 (17)	1.2153 (5)	0.0235 (9)	0.358 (6)
C11B	0.1632 (6)	0.5116 (10)	1.2226 (3)	0.0235 (9)	0.642 (6)
C12A	0.0227 (10)	0.4640 (17)	1.2024 (7)	0.0201 (9)	0.358 (6)
H12A	−0.029381	0.444686	1.237726	0.024*	0.358 (6)
C12B	0.0290 (6)	0.4973 (9)	1.2072 (4)	0.0201 (9)	0.642 (6)
H12B	−0.021152	0.472431	1.242703	0.024*	0.642 (6)
C13A	0.4905 (8)	0.8754 (9)	0.9569 (5)	0.0513 (12)	0.693 (7)
H13A	0.478329	0.887335	1.005866	0.062*	0.693 (7)
H13B	0.435076	0.951988	0.928777	0.062*	0.693 (7)
C13B	0.6552 (15)	0.808 (2)	0.9402 (11)	0.0513 (12)	0.307 (7)
H13C	0.679510	0.822481	0.893503	0.062*	0.307 (7)
H13D	0.725650	0.753721	0.970371	0.062*	0.307 (7)
C14A	0.613 (2)	0.959 (2)	0.9716 (13)	0.0656 (17)	0.307 (7)
H14A	0.520983	0.977792	0.954527	0.098*	0.307 (7)
H14B	0.665993	1.045232	0.958277	0.098*	0.307 (7)
H14C	0.625253	0.949642	1.021917	0.098*	0.307 (7)
C14B	0.6362 (9)	0.8944 (15)	0.9478 (6)	0.0656 (17)	0.693 (7)
H14D	0.686506	0.805015	0.967769	0.098*	0.693 (7)
H14E	0.670746	0.989275	0.971079	0.098*	0.693 (7)
H14F	0.643326	0.901475	0.898519	0.098*	0.693 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0182 (3)	0.0248 (3)	0.0194 (3)	−0.00189 (19)	0.0117 (2)	0.0001 (2)
Cu2	0.0071 (3)	0.0400 (5)	0.0187 (4)	0.0007 (3)	0.0048 (3)	0.0055 (3)
F1	0.073 (2)	0.073 (2)	0.0304 (17)	−0.0447 (19)	0.0328 (16)	−0.0096 (16)
F2A	0.0298 (16)	0.066 (2)	0.0246 (17)	0.008 (2)	−0.0007 (13)	0.0021 (19)
F2B	0.0298 (16)	0.066 (2)	0.0246 (17)	0.008 (2)	−0.0007 (13)	0.0021 (19)
O1	0.0283 (16)	0.0264 (15)	0.0229 (16)	0.0000 (13)	0.0136 (13)	−0.0004 (13)
O2	0.0291 (17)	0.0367 (18)	0.0271 (17)	−0.0045 (15)	0.0071 (13)	−0.0020 (14)
O3	0.0145 (14)	0.0320 (16)	0.0184 (15)	−0.0017 (12)	0.0067 (11)	−0.0015 (12)
O4	0.0094 (14)	0.079 (3)	0.0238 (17)	−0.0027 (15)	0.0060 (12)	−0.0045 (17)
O5A	0.047 (2)	0.0499 (17)	0.0413 (17)	−0.0085 (17)	0.0058 (17)	0.0093 (15)
O5B	0.047 (2)	0.0499 (17)	0.0413 (17)	−0.0085 (17)	0.0058 (17)	0.0093 (15)
N1	0.0159 (16)	0.0246 (18)	0.0176 (17)	0.0037 (14)	0.0063 (13)	0.0039 (14)
N2A	0.0149 (12)	0.0231 (18)	0.0158 (14)	−0.0019 (11)	0.0053 (11)	−0.0017 (14)
N2B	0.0149 (12)	0.0231 (18)	0.0158 (14)	−0.0019 (11)	0.0053 (11)	−0.0017 (14)
N3	0.0119 (17)	0.042 (2)	0.024 (2)	0.0056 (16)	0.0054 (14)	−0.0041 (17)
N4	0.0131 (17)	0.041 (2)	0.032 (2)	0.0040 (16)	0.0029 (15)	0.005 (2)
N5	0.038 (2)	0.040 (3)	0.041 (3)	0.013 (2)	0.0012 (19)	−0.005 (2)
C1	0.023 (2)	0.022 (2)	0.022 (2)	0.0020 (17)	0.0058 (17)	0.0068 (17)
C2	0.0163 (19)	0.023 (2)	0.023 (2)	0.0036 (16)	0.0093 (16)	0.0044 (17)
C3	0.018 (2)	0.025 (2)	0.022 (2)	0.0064 (16)	0.0057 (16)	0.0062 (17)
C4	0.028 (2)	0.029 (2)	0.021 (2)	−0.0064 (18)	0.0052 (18)	0.0047 (18)
C5	0.035 (3)	0.048 (3)	0.021 (2)	−0.012 (2)	0.014 (2)	0.010 (2)
C6	0.027 (2)	0.033 (2)	0.018 (2)	−0.0035 (19)	0.0086 (17)	0.0005 (18)
C7	0.014 (2)	0.042 (3)	0.019 (2)	−0.0044 (18)	0.0052 (16)	−0.0039 (19)
C8A	0.0144 (13)	0.0213 (19)	0.0167 (14)	0.0001 (12)	0.0051 (11)	−0.0021 (13)
C8B	0.0144 (13)	0.0213 (19)	0.0167 (14)	0.0001 (12)	0.0051 (11)	−0.0021 (13)
C9A	0.0145 (13)	0.024 (2)	0.0201 (14)	0.0012 (15)	0.0047 (12)	−0.0032 (15)
C9B	0.0145 (13)	0.024 (2)	0.0201 (14)	0.0012 (15)	0.0047 (12)	−0.0032 (15)
C10A	0.0179 (12)	0.0261 (17)	0.0219 (13)	0.0014 (13)	0.0029 (11)	−0.0028 (13)
C10B	0.0179 (12)	0.0261 (17)	0.0219 (13)	0.0014 (13)	0.0029 (11)	−0.0028 (13)
C11A	0.0210 (12)	0.0289 (16)	0.0205 (13)	0.0012 (13)	0.0023 (11)	−0.0010 (13)
C11B	0.0210 (12)	0.0289 (16)	0.0205 (13)	0.0012 (13)	0.0023 (11)	−0.0010 (13)
C12A	0.0186 (14)	0.025 (2)	0.0171 (15)	−0.0007 (14)	0.0046 (12)	−0.0009 (15)
C12B	0.0186 (14)	0.025 (2)	0.0171 (15)	−0.0007 (14)	0.0046 (12)	−0.0009 (15)
C13A	0.0518 (17)	0.0525 (16)	0.0490 (15)	−0.0059 (12)	0.0050 (12)	0.0050 (12)
C13B	0.0518 (17)	0.0525 (16)	0.0490 (15)	−0.0059 (12)	0.0050 (12)	0.0050 (12)
C14A	0.065 (2)	0.066 (2)	0.065 (2)	−0.006 (2)	0.007 (2)	0.000 (2)
C14B	0.065 (2)	0.066 (2)	0.065 (2)	−0.006 (2)	0.007 (2)	0.000 (2)

Geometric parameters (Å, º)

Cu1—O1	1.959 (3)	C2—H2	0.9500
Cu1—O3	1.976 (3)	C3—C4	1.381 (6)
Cu1—N3	1.992 (4)	C4—C5	1.365 (7)
Cu1—N1^i	2.044 (4)	C4—H4	0.9500
Cu1—N2A^ii	2.35 (2)	C5—C6	1.380 (7)
Cu2—O4	1.967 (3)	C6—H6	0.9500
Cu2—O4^iii	1.967 (3)	C7—C9B	1.510 (8)
Cu2—N3^iii	2.001 (4)	C7—C9A	1.529 (11)
Cu2—N3	2.001 (4)	C8A—C9B	1.383 (7)
Cu2—O5A^iii	2.330 (6)	C8A—H8A	0.9500
Cu2—O5A	2.330 (6)	C8B—C9A	1.379 (8)
Cu2—O5B^iii	2.405 (13)	C8B—H8B	0.9500
Cu2—O5B	2.405 (13)	C9A—C10A	1.381 (8)
F1—C5	1.350 (5)	C9B—C10B	1.383 (7)
F2A—C11A	1.329 (8)	C10A—C11A	1.367 (8)
F2B—C11B	1.341 (6)	C10A—H10A	0.9500
O1—C1	1.276 (5)	C10B—C11B	1.371 (6)
O2—C1	1.237 (5)	C10B—H10B	0.9500
O3—C7	1.261 (5)	C11A—C12A	1.377 (8)
O4—C7	1.242 (5)	C11B—C12B	1.383 (6)
O5A—C13A	1.403 (8)	C12A—H12A	0.9500
O5A—H5A	0.9500	C12B—H12B	0.9500
O5B—C13B	1.438 (10)	C13A—C14B	1.551 (8)
O5B—H5B	0.9499	C13A—H13A	0.9900
N1—C6	1.339 (5)	C13A—H13B	0.9900
N1—C2	1.344 (5)	C13B—C14A	1.525 (10)
N2A—C12A	1.360 (8)	C13B—H13C	0.9900
N2A—C8B	1.366 (8)	C13B—H13D	0.9900
N2B—C12B	1.347 (7)	C14A—H14A	0.9801
N2B—C8A	1.356 (6)	C14A—H14B	0.9800
N3—N4	1.218 (6)	C14A—H14C	0.9801
N4—N5	1.142 (6)	C14B—H14D	0.9800
C1—C3	1.494 (6)	C14B—H14E	0.9800
C2—C3	1.382 (6)	C14B—H14F	0.9800
O1—Cu1—O3	171.61 (12)	F1—C5—C4	119.6 (4)
O1—Cu1—N3	90.81 (14)	F1—C5—C6	118.2 (4)
O3—Cu1—N3	88.14 (14)	C4—C5—C6	122.2 (4)
O1—Cu1—N1^i	93.42 (13)	N1—C6—C5	120.6 (4)
O3—Cu1—N1^i	89.47 (13)	N1—C6—H6	119.7
N3—Cu1—N1^i	166.64 (15)	C5—C6—H6	119.7
O1—Cu1—N2A^ii	85.7 (6)	O4—C7—O3	127.2 (4)
O3—Cu1—N2A^ii	86.6 (6)	O4—C7—C9B	116.8 (5)
N3—Cu1—N2A^ii	105.2 (9)	O3—C7—C9B	115.9 (4)
N1^i—Cu1—N2A^ii	87.8 (9)	O4—C7—C9A	115.4 (6)
O4—Cu2—O4^iii	180.0	O3—C7—C9A	116.7 (6)
O4—Cu2—N3^iii	88.68 (14)	N2B—C8A—C9B	121.9 (5)
O4^iii—Cu2—N3^iii	91.32 (14)	N2B—C8A—H8A	119.1
O4—Cu2—N3	91.32 (14)	C9B—C8A—H8A	119.1
O4^iii—Cu2—N3	88.68 (14)	N2A—C8B—C9A	120.6 (7)
N3^iii—Cu2—N3	180.0	N2A—C8B—H8B	119.7
O4—Cu2—O5A^iii	89.75 (19)	C9A—C8B—H8B	119.7
O4^iii—Cu2—O5A^iii	90.25 (19)	C8B—C9A—C10A	119.3 (5)
N3^iii—Cu2—O5A^iii	81.08 (19)	C8B—C9A—C7	117.2 (9)
N3—Cu2—O5A^iii	98.92 (19)	C10A—C9A—C7	123.3 (9)
O4—Cu2—O5A	90.25 (19)	C8A—C9B—C10B	119.0 (4)
O4^iii—Cu2—O5A	89.75 (19)	C8A—C9B—C7	119.3 (6)
N3^iii—Cu2—O5A	98.92 (19)	C10B—C9B—C7	120.9 (6)
N3—Cu2—O5A	81.08 (19)	C11A—C10A—C9A	119.2 (5)
O5A^iii—Cu2—O5A	180.0	C11A—C10A—H10A	120.4
O4—Cu2—O5B^iii	79.9 (4)	C9A—C10A—H10A	120.4
O4^iii—Cu2—O5B^iii	100.1 (4)	C11B—C10B—C9B	118.6 (4)
N3^iii—Cu2—O5B^iii	94.7 (3)	C11B—C10B—H10B	120.7
N3—Cu2—O5B^iii	85.3 (4)	C9B—C10B—H10B	120.7
O4—Cu2—O5B	100.1 (4)	F2A—C11A—C10A	119.8 (8)
O4^iii—Cu2—O5B	79.9 (4)	F2A—C11A—C12A	119.5 (9)
N3^iii—Cu2—O5B	85.3 (4)	C10A—C11A—C12A	120.7 (5)
N3—Cu2—O5B	94.7 (3)	F2B—C11B—C10B	121.8 (5)
O5B^iii—Cu2—O5B	180.0	F2B—C11B—C12B	117.5 (5)
C1—O1—Cu1	125.7 (3)	C10B—C11B—C12B	120.7 (4)
C7—O3—Cu1	129.6 (3)	N2A—C12A—C11A	120.1 (5)
C7—O4—Cu2	128.9 (3)	N2A—C12A—H12A	120.0
C13A—O5A—Cu2	125.4 (5)	C11A—C12A—H12A	120.0
C13A—O5A—H5A	117.2	N2B—C12B—C11B	120.7 (4)
Cu2—O5A—H5A	117.4	N2B—C12B—H12B	119.6
C13B—O5B—Cu2	122.4 (12)	C11B—C12B—H12B	119.6
C13B—O5B—H5B	118.6	O5A—C13A—C14B	103.1 (8)
Cu2—O5B—H5B	119.0	O5A—C13A—H13A	111.1
C6—N1—C2	118.1 (4)	C14B—C13A—H13A	111.1
C6—N1—Cu1^iv	119.8 (3)	O5A—C13A—H13B	111.1
C2—N1—Cu1^iv	121.9 (3)	C14B—C13A—H13B	111.1
C12A—N2A—C8B	119.1 (6)	H13A—C13A—H13B	109.1
C12A—N2A—Cu1^ii	113.3 (13)	O5B—C13B—C14A	93.4 (14)
C8B—N2A—Cu1^ii	122.1 (17)	O5B—C13B—H13C	113.0
C12B—N2B—C8A	119.0 (4)	C14A—C13B—H13C	113.0
N4—N3—Cu1	118.5 (3)	O5B—C13B—H13D	113.0
N4—N3—Cu2	120.2 (3)	C14A—C13B—H13D	113.0
Cu1—N3—Cu2	109.05 (18)	H13C—C13B—H13D	110.4
N5—N4—N3	178.4 (5)	C13B—C14A—H14A	108.9
O2—C1—O1	126.1 (4)	C13B—C14A—H14B	109.9
O2—C1—C3	118.1 (4)	H14A—C14A—H14B	109.5
O1—C1—C3	115.9 (4)	C13B—C14A—H14C	109.6
N1—C2—C3	123.0 (4)	H14A—C14A—H14C	109.5
N1—C2—H2	118.5	H14B—C14A—H14C	109.5
C3—C2—H2	118.5	C13A—C14B—H14D	109.9
C4—C3—C2	119.1 (4)	C13A—C14B—H14E	109.3
C4—C3—C1	119.4 (4)	H14D—C14B—H14E	109.5
C2—C3—C1	121.5 (4)	C13A—C14B—H14F	109.3
C5—C4—C3	117.0 (4)	H14D—C14B—H14F	109.5
C5—C4—H4	121.5	H14E—C14B—H14F	109.5
C3—C4—H4	121.5
Cu1—O1—C1—O2	−14.5 (6)	N2A—C8B—C9A—C7	175 (3)
Cu1—O1—C1—C3	165.2 (3)	O4—C7—C9A—C8B	174.5 (18)
C6—N1—C2—C3	−2.7 (6)	O3—C7—C9A—C8B	−14 (2)
Cu1^iv—N1—C2—C3	171.3 (3)	O4—C7—C9A—C10A	−0.6 (16)
N1—C2—C3—C4	1.8 (6)	O3—C7—C9A—C10A	170.9 (11)
N1—C2—C3—C1	−175.6 (4)	N2B—C8A—C9B—C10B	2 (3)
O2—C1—C3—C4	−16.0 (6)	N2B—C8A—C9B—C7	172.3 (16)
O1—C1—C3—C4	164.3 (4)	O4—C7—C9B—C8A	−166.8 (10)
O2—C1—C3—C2	161.4 (4)	O3—C7—C9B—C8A	15.0 (12)
O1—C1—C3—C2	−18.3 (6)	O4—C7—C9B—C10B	2.9 (10)
C2—C3—C4—C5	0.1 (6)	O3—C7—C9B—C10B	−175.3 (6)
C1—C3—C4—C5	177.6 (4)	C8B—C9A—C10A—C11A	4 (3)
C3—C4—C5—F1	178.9 (4)	C7—C9A—C10A—C11A	178.5 (12)
C3—C4—C5—C6	−1.1 (7)	C8A—C9B—C10B—C11B	−1.5 (14)
C2—N1—C6—C5	1.7 (6)	C7—C9B—C10B—C11B	−171.2 (7)
Cu1^iv—N1—C6—C5	−172.5 (4)	C9A—C10A—C11A—F2A	−178.3 (13)
F1—C5—C6—N1	−179.8 (4)	C9A—C10A—C11A—C12A	−1 (2)
C4—C5—C6—N1	0.2 (8)	C9B—C10B—C11B—F2B	179.7 (7)
Cu2—O4—C7—O3	−29.1 (8)	C9B—C10B—C11B—C12B	0.6 (12)
Cu2—O4—C7—C9B	152.9 (4)	C8B—N2A—C12A—C11A	−10 (5)
Cu2—O4—C7—C9A	141.2 (7)	Cu1^ii—N2A—C12A—C11A	144.2 (14)
Cu1—O3—C7—O4	17.6 (7)	F2A—C11A—C12A—N2A	−178 (2)
Cu1—O3—C7—C9B	−164.5 (4)	C10A—C11A—C12A—N2A	4 (3)
Cu1—O3—C7—C9A	−152.7 (7)	C8A—N2B—C12B—C11B	1 (3)
C12B—N2B—C8A—C9B	−2 (3)	Cu1^ii—N2B—C12B—C11B	155.9 (8)
Cu1^ii—N2B—C8A—C9B	−158.1 (11)	F2B—C11B—C12B—N2B	−179.7 (13)
C12A—N2A—C8B—C9A	13 (6)	C10B—C11B—C12B—N2B	−0.5 (15)
Cu1^ii—N2A—C8B—C9A	−139.1 (19)	Cu2—O5A—C13A—C14B	84.8 (8)
N2A—C8B—C9A—C10A	−10 (5)	Cu2—O5B—C13B—C14A	−120.7 (15)

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x+1/2, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12B^b—H12B^b···O1^ii	0.95	2.63	3.134 (7)	114
C8A^b—H8A^b···O3^ii	0.95	2.49	3.018 (11)	115
C12A^a—H12A^a···O1^ii	0.95	2.52	3.048 (10)	116
C10A^a—H10A^a···O2^iii	0.95	2.56	3.448 (10)	156
C6—H6···F1^v	0.95	2.54	3.187 (5)	125
C6—H6···O3^iv	0.95	2.27	2.848 (6)	119
C2—H2···O2^iv	0.95	2.66	3.449 (5)	141
C2—H2···O1^iv	0.95	2.53	3.025 (5)	113
C14B^b—H14F^b···F2B^b^vi	0.98	2.57	3.496 (12)	157
O5A^b—H5A^b···O2	0.95	1.80	2.618 (7)	143
O5A^b—H5A^b···O1	0.95	2.51	3.352 (7)	148
C13B^a—H13D^a···N3^iii	0.99	2.70	3.24 (2)	115

Symmetry codes: (ii) −x, −y+1, −z+2; (iii) −x+1, −y+1, −z+2; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) x+1/2, −y+3/2, z−1/2.

(4)

Crystal data

C38H24Cu5F6N18O14	Z = 1
Mr = 1388.45	F(000) = 689
Triclinic, P1	Dx = 1.982 Mg m^−3
a = 7.2091 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.3296 (13) Å	Cell parameters from 3896 reflections
c = 13.5573 (14) Å	θ = 2.9–28.4°
α = 99.680 (2)°	µ = 2.36 mm^−1
β = 101.459 (2)°	T = 173 K
γ = 90.199 (2)°	Block, green
V = 1163.4 (2) Å^3	0.22 × 0.21 × 0.18 mm

Data collection

CCD area detector diffractometer	4998 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.019
Absorption correction: multi-scan SADABS	θmax = 28.4°, θmin = 1.7°
Tmin = 0.625, Tmax = 0.676	h = −9→9
8692 measured reflections	k = −10→16
5780 independent reflections	l = −18→16

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 0.7399P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5780 reflections	Δρmax = 0.73 e Å^−3
370 parameters	Δρmin = −0.73 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.21427 (4)	−0.02306 (2)	0.22407 (2)	0.00780 (7)
Cu2	0.000000	0.000000	0.000000	0.00774 (9)
Cu3	0.000000	0.500000	0.500000	0.00644 (8)
Cu4	0.500000	0.500000	0.500000	0.00714 (8)
O1	0.0275 (2)	0.14915 (12)	0.08114 (12)	0.0125 (3)
O2	0.1285 (2)	0.12868 (12)	0.24534 (12)	0.0107 (3)
O3	0.2679 (2)	−0.17385 (12)	0.23879 (12)	0.0104 (3)
O4	0.3113 (2)	−0.23397 (13)	0.07933 (13)	0.0150 (3)
O5	0.1338 (2)	0.66793 (12)	0.48808 (12)	0.0094 (3)
O6	0.4417 (2)	0.64934 (12)	0.55460 (12)	0.0089 (3)
O7	0.3192 (2)	−0.02612 (12)	0.07145 (12)	0.0107 (3)
H7	0.326988	−0.095321	0.068485	0.016*
F1	0.4699 (2)	−0.62924 (11)	0.08496 (11)	0.0227 (3)
F2	−0.1499 (2)	0.54116 (11)	0.10886 (11)	0.0239 (3)
F3	0.05237 (18)	1.06668 (10)	0.63791 (11)	0.0159 (3)
N1	0.3812 (3)	−0.47811 (15)	0.31985 (15)	0.0103 (4)
N2	−0.0265 (2)	0.44335 (14)	0.34608 (14)	0.0079 (3)
N3	0.5262 (3)	0.97133 (14)	0.68695 (14)	0.0092 (4)
N4	−0.0300 (3)	−0.06119 (15)	0.12456 (14)	0.0092 (4)
N5	−0.1179 (3)	−0.14782 (16)	0.11940 (16)	0.0152 (4)
N6	−0.2056 (4)	−0.2254 (2)	0.1165 (2)	0.0332 (6)
N7	0.2558 (2)	0.43294 (14)	0.52474 (15)	0.0089 (4)
N8	0.2671 (3)	0.33979 (15)	0.54387 (14)	0.0101 (4)
N9	0.2806 (3)	0.25191 (16)	0.56125 (18)	0.0188 (4)
C1	0.3030 (3)	−0.24742 (17)	0.16660 (17)	0.0099 (4)
C2	0.3418 (3)	−0.36002 (17)	0.19383 (18)	0.0107 (4)
C3	0.3393 (3)	−0.38085 (17)	0.29116 (17)	0.0103 (4)
H3	0.306233	−0.323211	0.339783	0.012*
C4	0.3866 (3)	−0.44365 (18)	0.12119 (18)	0.0123 (4)
H4	0.390391	−0.432380	0.053984	0.015*
C5	0.4255 (3)	−0.54404 (18)	0.15138 (18)	0.0132 (5)
C6	0.4243 (3)	−0.55923 (17)	0.24944 (17)	0.0108 (4)
H6	0.454709	−0.628977	0.267932	0.013*
C7	0.0560 (3)	0.18142 (17)	0.17547 (17)	0.0085 (4)
C8	0.0037 (3)	0.29750 (17)	0.20960 (17)	0.0095 (4)
C9	0.0164 (3)	0.33976 (17)	0.31232 (17)	0.0087 (4)
H9	0.057285	0.293213	0.360968	0.010*
C10	−0.0555 (3)	0.36499 (18)	0.13782 (17)	0.0125 (4)
H10	−0.067844	0.338811	0.066711	0.015*
C11	−0.0952 (3)	0.47142 (18)	0.17449 (18)	0.0132 (5)
C12	−0.0812 (3)	0.50936 (17)	0.27707 (18)	0.0116 (4)
H12	−0.110529	0.583318	0.299515	0.014*
C13	0.2915 (3)	0.70292 (17)	0.53801 (16)	0.0080 (4)
C14	0.3162 (3)	0.82302 (17)	0.58752 (17)	0.0087 (4)
C15	0.1619 (3)	0.89092 (17)	0.58508 (17)	0.0090 (4)
H15	0.038111	0.864778	0.550197	0.011*
C16	0.1974 (3)	0.99773 (17)	0.63567 (17)	0.0104 (4)
C17	0.3769 (3)	1.03748 (17)	0.68496 (17)	0.0115 (4)
H17	0.395730	1.112170	0.717865	0.014*
C18	0.4942 (3)	0.86615 (17)	0.63828 (17)	0.0096 (4)
H18	0.598613	0.819340	0.638805	0.012*
C19	0.4843 (3)	0.02365 (19)	0.05221 (18)	0.0127 (4)
H19A	0.595898	0.010990	0.104168	0.015*
H19B	0.469571	0.104101	0.057564	0.015*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.00958 (13)	0.00355 (12)	0.00842 (14)	0.00193 (9)	−0.00115 (10)	−0.00067 (9)
Cu2	0.01120 (18)	0.00402 (16)	0.00634 (18)	0.00199 (13)	−0.00028 (14)	−0.00139 (13)
Cu3	0.00686 (17)	0.00354 (16)	0.00757 (18)	0.00233 (12)	0.00008 (13)	−0.00126 (13)
Cu4	0.00682 (17)	0.00236 (16)	0.01125 (19)	0.00147 (12)	0.00117 (14)	−0.00092 (13)
O1	0.0206 (8)	0.0062 (7)	0.0097 (8)	0.0039 (6)	0.0017 (6)	−0.0004 (6)
O2	0.0138 (8)	0.0055 (7)	0.0104 (8)	0.0041 (6)	−0.0017 (6)	−0.0006 (6)
O3	0.0133 (8)	0.0051 (7)	0.0109 (8)	0.0024 (6)	−0.0005 (6)	−0.0003 (6)
O4	0.0240 (9)	0.0095 (8)	0.0120 (8)	0.0051 (6)	0.0043 (7)	0.0027 (6)
O5	0.0080 (7)	0.0074 (7)	0.0113 (8)	0.0000 (6)	−0.0007 (6)	0.0005 (6)
O6	0.0097 (7)	0.0038 (7)	0.0114 (8)	0.0025 (5)	0.0004 (6)	−0.0013 (6)
O7	0.0116 (7)	0.0078 (7)	0.0131 (8)	0.0024 (6)	0.0033 (6)	0.0021 (6)
F1	0.0437 (9)	0.0102 (7)	0.0144 (7)	0.0124 (6)	0.0086 (7)	−0.0009 (5)
F2	0.0459 (10)	0.0105 (7)	0.0132 (7)	0.0116 (6)	−0.0013 (7)	0.0045 (5)
F3	0.0136 (7)	0.0085 (6)	0.0231 (8)	0.0075 (5)	0.0000 (6)	−0.0007 (5)
N1	0.0098 (9)	0.0095 (9)	0.0112 (9)	0.0012 (7)	0.0005 (7)	0.0023 (7)
N2	0.0067 (8)	0.0057 (8)	0.0095 (9)	0.0010 (6)	−0.0002 (7)	−0.0012 (7)
N3	0.0112 (9)	0.0052 (8)	0.0094 (9)	0.0016 (7)	−0.0010 (7)	0.0000 (7)
N4	0.0100 (9)	0.0064 (8)	0.0092 (9)	−0.0007 (7)	−0.0014 (7)	−0.0006 (7)
N5	0.0140 (10)	0.0123 (9)	0.0168 (10)	0.0019 (7)	−0.0034 (8)	0.0030 (8)
N6	0.0313 (14)	0.0193 (12)	0.0436 (16)	−0.0106 (10)	−0.0082 (12)	0.0096 (11)
N7	0.0066 (8)	0.0051 (8)	0.0147 (10)	0.0021 (6)	0.0011 (7)	0.0015 (7)
N8	0.0068 (8)	0.0112 (9)	0.0119 (9)	0.0025 (7)	0.0016 (7)	0.0009 (7)
N9	0.0159 (10)	0.0106 (10)	0.0323 (13)	0.0040 (8)	0.0055 (9)	0.0100 (9)
C1	0.0082 (10)	0.0073 (10)	0.0124 (11)	0.0009 (7)	−0.0009 (8)	0.0002 (8)
C2	0.0100 (10)	0.0063 (9)	0.0147 (11)	0.0009 (8)	−0.0008 (8)	0.0020 (8)
C3	0.0092 (10)	0.0072 (10)	0.0132 (11)	0.0019 (8)	0.0006 (8)	0.0003 (8)
C4	0.0150 (11)	0.0107 (10)	0.0102 (11)	0.0027 (8)	0.0009 (9)	0.0011 (8)
C5	0.0158 (11)	0.0073 (10)	0.0143 (12)	0.0016 (8)	0.0003 (9)	−0.0013 (8)
C6	0.0116 (10)	0.0064 (9)	0.0129 (11)	0.0008 (8)	−0.0014 (8)	0.0021 (8)
C7	0.0089 (10)	0.0059 (9)	0.0097 (10)	0.0004 (7)	0.0016 (8)	−0.0017 (8)
C8	0.0091 (10)	0.0062 (9)	0.0111 (11)	0.0013 (7)	−0.0004 (8)	−0.0017 (8)
C9	0.0073 (9)	0.0045 (9)	0.0130 (11)	0.0023 (7)	0.0005 (8)	−0.0001 (8)
C10	0.0188 (11)	0.0080 (10)	0.0083 (11)	0.0027 (8)	−0.0004 (9)	−0.0017 (8)
C11	0.0158 (11)	0.0095 (10)	0.0131 (11)	0.0055 (8)	−0.0013 (9)	0.0030 (9)
C12	0.0125 (10)	0.0047 (9)	0.0161 (12)	0.0039 (8)	0.0015 (9)	−0.0007 (8)
C13	0.0108 (10)	0.0052 (9)	0.0086 (10)	0.0035 (7)	0.0037 (8)	0.0014 (8)
C14	0.0118 (10)	0.0053 (9)	0.0088 (10)	0.0017 (8)	0.0016 (8)	0.0009 (8)
C15	0.0094 (10)	0.0073 (9)	0.0097 (10)	0.0026 (8)	−0.0002 (8)	0.0020 (8)
C16	0.0121 (10)	0.0070 (10)	0.0120 (11)	0.0067 (8)	0.0012 (8)	0.0026 (8)
C17	0.0145 (11)	0.0057 (9)	0.0126 (11)	0.0040 (8)	0.0005 (9)	−0.0004 (8)
C18	0.0125 (10)	0.0043 (9)	0.0108 (11)	0.0032 (8)	0.0005 (8)	0.0001 (8)
C19	0.0106 (10)	0.0121 (10)	0.0147 (12)	0.0006 (8)	0.0017 (9)	0.0015 (9)

Geometric parameters (Å, º)

Cu1—O3	1.9352 (15)	N2—C12	1.343 (3)
Cu1—O2	1.9655 (15)	N3—C18	1.349 (3)
Cu1—N4	1.9948 (18)	N3—C17	1.351 (3)
Cu1—N3^i	2.0493 (18)	N4—N5	1.225 (3)
Cu1—O7	2.3346 (16)	N5—N6	1.136 (3)
Cu2—O1^ii	1.9650 (15)	N7—N8	1.219 (3)
Cu2—O1	1.9651 (15)	N8—N9	1.147 (3)
Cu2—N4^ii	2.0099 (19)	C1—C2	1.509 (3)
Cu2—N4	2.0099 (19)	C2—C4	1.387 (3)
Cu2—O7	2.3582 (15)	C2—C3	1.389 (3)
Cu2—O7^ii	2.3582 (15)	C3—H3	0.9500
Cu3—N7	2.0138 (18)	C4—C5	1.380 (3)
Cu3—N7^iii	2.0138 (18)	C4—H4	0.9500
Cu3—N2	2.0566 (19)	C5—C6	1.375 (3)
Cu3—N2^iii	2.0566 (19)	C6—H6	0.9500
Cu3—O5	2.3248 (15)	C7—C8	1.502 (3)
Cu3—O5^iii	2.3248 (15)	C8—C9	1.387 (3)
Cu4—O6^i	1.9456 (14)	C8—C10	1.390 (3)
Cu4—O6	1.9457 (15)	C9—H9	0.9500
Cu4—N7^i	2.0525 (18)	C10—C11	1.375 (3)
Cu4—N7	2.0525 (18)	C10—H10	0.9500
O1—C7	1.249 (3)	C11—C12	1.374 (3)
O2—C7	1.267 (3)	C12—H12	0.9500
O3—C1	1.283 (3)	C13—C14	1.514 (3)
O4—C1	1.235 (3)	C14—C18	1.387 (3)
O5—C13	1.237 (3)	C14—C15	1.393 (3)
O6—C13	1.272 (2)	C15—C16	1.376 (3)
O7—C19	1.426 (3)	C15—H15	0.9500
O7—H7	0.8500	C16—C17	1.379 (3)
F1—C5	1.347 (3)	C17—H17	0.9500
F2—C11	1.344 (3)	C18—H18	0.9500
F3—C16	1.352 (2)	C19—C19^iv	1.498 (5)
N1—C3	1.339 (3)	C19—H19A	0.9900
N1—C6	1.344 (3)	C19—H19B	0.9900
N2—C9	1.341 (3)
O3—Cu1—O2	162.96 (7)	Cu1—N4—Cu2	105.22 (8)
O3—Cu1—N4	94.74 (7)	N6—N5—N4	176.8 (3)
O2—Cu1—N4	86.88 (7)	N8—N7—Cu3	119.14 (15)
O3—Cu1—N3^i	90.31 (7)	N8—N7—Cu4	115.38 (15)
O2—Cu1—N3^i	89.95 (7)	Cu3—N7—Cu4	124.86 (9)
N4—Cu1—N3^i	172.40 (8)	N9—N8—N7	178.8 (2)
O3—Cu1—O7	97.15 (6)	O4—C1—O3	126.4 (2)
O2—Cu1—O7	99.85 (6)	O4—C1—C2	118.0 (2)
N4—Cu1—O7	80.29 (7)	O3—C1—C2	115.5 (2)
N3^i—Cu1—O7	93.46 (7)	C4—C2—C3	119.3 (2)
O1^ii—Cu2—O1	180.00 (11)	C4—C2—C1	119.4 (2)
O1^ii—Cu2—N4^ii	89.60 (7)	C3—C2—C1	121.4 (2)
O1—Cu2—N4^ii	90.40 (7)	N1—C3—C2	123.3 (2)
O1^ii—Cu2—N4	90.40 (7)	N1—C3—H3	118.4
O1—Cu2—N4	89.60 (7)	C2—C3—H3	118.4
N4^ii—Cu2—N4	180.0	C5—C4—C2	116.7 (2)
O1^ii—Cu2—O7	91.66 (6)	C5—C4—H4	121.6
O1—Cu2—O7	88.34 (6)	C2—C4—H4	121.6
N4^ii—Cu2—O7	100.59 (6)	F1—C5—C6	118.4 (2)
N4—Cu2—O7	79.41 (6)	F1—C5—C4	120.1 (2)
O1^ii—Cu2—O7^ii	88.34 (6)	C6—C5—C4	121.4 (2)
O1—Cu2—O7^ii	91.66 (6)	N1—C6—C5	121.8 (2)
N4^ii—Cu2—O7^ii	79.41 (6)	N1—C6—H6	119.1
N4—Cu2—O7^ii	100.59 (6)	C5—C6—H6	119.1
O7—Cu2—O7^ii	180.0	O1—C7—O2	127.6 (2)
N7—Cu3—N7^iii	180.0	O1—C7—C8	115.97 (19)
N7—Cu3—N2	89.23 (7)	O2—C7—C8	116.44 (19)
N7^iii—Cu3—N2	90.77 (7)	C9—C8—C10	119.0 (2)
N7—Cu3—N2^iii	90.77 (7)	C9—C8—C7	121.11 (19)
N7^iii—Cu3—N2^iii	89.23 (7)	C10—C8—C7	119.9 (2)
N2—Cu3—N2^iii	180.0	N2—C9—C8	123.0 (2)
N7—Cu3—O5	91.74 (6)	N2—C9—H9	118.5
N7^iii—Cu3—O5	88.26 (6)	C8—C9—H9	118.5
N2—Cu3—O5	92.25 (6)	C11—C10—C8	116.9 (2)
N2^iii—Cu3—O5	87.75 (6)	C11—C10—H10	121.5
N7—Cu3—O5^iii	88.26 (6)	C8—C10—H10	121.5
N7^iii—Cu3—O5^iii	91.74 (6)	F2—C11—C12	118.4 (2)
N2—Cu3—O5^iii	87.75 (6)	F2—C11—C10	119.6 (2)
N2^iii—Cu3—O5^iii	92.25 (6)	C12—C11—C10	121.9 (2)
O5—Cu3—O5^iii	180.0	N2—C12—C11	120.9 (2)
O6^i—Cu4—O6	180.0	N2—C12—H12	119.5
O6^i—Cu4—N7^i	93.42 (7)	C11—C12—H12	119.5
O6—Cu4—N7^i	86.58 (7)	O5—C13—O6	127.7 (2)
O6^i—Cu4—N7	86.58 (7)	O5—C13—C14	118.63 (18)
O6—Cu4—N7	93.42 (7)	O6—C13—C14	113.68 (18)
N7^i—Cu4—N7	180.0	C18—C14—C15	119.1 (2)
C7—O1—Cu2	131.10 (14)	C18—C14—C13	119.83 (19)
C7—O2—Cu1	125.64 (14)	C15—C14—C13	121.04 (19)
C1—O3—Cu1	123.81 (14)	C16—C15—C14	116.7 (2)
C13—O5—Cu3	122.71 (13)	C16—C15—H15	121.6
C13—O6—Cu4	131.53 (14)	C14—C15—H15	121.6
C19—O7—Cu1	130.35 (13)	F3—C16—C15	119.36 (19)
C19—O7—Cu2	127.80 (13)	F3—C16—C17	118.34 (19)
Cu1—O7—Cu2	85.38 (5)	C15—C16—C17	122.3 (2)
C19—O7—H7	112.5	N3—C17—C16	120.7 (2)
Cu1—O7—H7	86.9	N3—C17—H17	119.6
Cu2—O7—H7	104.9	C16—C17—H17	119.6
C3—N1—C6	117.5 (2)	N3—C18—C14	123.2 (2)
C9—N2—C12	118.24 (19)	N3—C18—H18	118.4
C9—N2—Cu3	120.43 (15)	C14—C18—H18	118.4
C12—N2—Cu3	121.30 (15)	O7—C19—C19^iv	110.5 (2)
C18—N3—C17	117.91 (19)	O7—C19—H19A	109.5
C18—N3—Cu1^i	120.70 (15)	C19^iv—C19—H19A	109.5
C17—N3—Cu1^i	120.94 (15)	O7—C19—H19B	109.5
N5—N4—Cu1	121.11 (15)	C19^iv—C19—H19B	109.5
N5—N4—Cu2	122.60 (15)	H19A—C19—H19B	108.1
Cu1—O3—C1—O4	1.4 (3)	C7—C8—C10—C11	−177.9 (2)
Cu1—O3—C1—C2	179.84 (13)	C8—C10—C11—F2	178.8 (2)
O4—C1—C2—C4	0.5 (3)	C8—C10—C11—C12	−1.3 (4)
O3—C1—C2—C4	−178.08 (19)	C9—N2—C12—C11	0.8 (3)
O4—C1—C2—C3	178.5 (2)	Cu3—N2—C12—C11	178.82 (17)
O3—C1—C2—C3	−0.1 (3)	F2—C11—C12—N2	−179.7 (2)
C6—N1—C3—C2	−1.2 (3)	C10—C11—C12—N2	0.4 (4)
C4—C2—C3—N1	1.1 (3)	Cu3—O5—C13—O6	42.7 (3)
C1—C2—C3—N1	−176.9 (2)	Cu3—O5—C13—C14	−136.84 (16)
C3—C2—C4—C5	0.3 (3)	Cu4—O6—C13—O5	7.7 (4)
C1—C2—C4—C5	178.4 (2)	Cu4—O6—C13—C14	−172.74 (14)
C2—C4—C5—F1	179.9 (2)	O5—C13—C14—C18	−175.8 (2)
C2—C4—C5—C6	−1.6 (3)	O6—C13—C14—C18	4.6 (3)
C3—N1—C6—C5	−0.1 (3)	O5—C13—C14—C15	5.7 (3)
F1—C5—C6—N1	−179.9 (2)	O6—C13—C14—C15	−173.9 (2)
C4—C5—C6—N1	1.5 (3)	C18—C14—C15—C16	−1.0 (3)
Cu2—O1—C7—O2	22.4 (3)	C13—C14—C15—C16	177.5 (2)
Cu2—O1—C7—C8	−159.65 (15)	C14—C15—C16—F3	−178.47 (19)
Cu1—O2—C7—O1	−1.1 (3)	C14—C15—C16—C17	1.3 (3)
Cu1—O2—C7—C8	−179.00 (13)	C18—N3—C17—C16	0.8 (3)
O1—C7—C8—C9	175.4 (2)	Cu1^i—N3—C17—C16	−171.56 (17)
O2—C7—C8—C9	−6.4 (3)	F3—C16—C17—N3	178.5 (2)
O1—C7—C8—C10	−5.8 (3)	C15—C16—C17—N3	−1.2 (4)
O2—C7—C8—C10	172.4 (2)	C17—N3—C18—C14	−0.6 (3)
C12—N2—C9—C8	−1.1 (3)	Cu1^i—N3—C18—C14	171.81 (17)
Cu3—N2—C9—C8	−179.12 (16)	C15—C14—C18—N3	0.7 (3)
C10—C8—C9—N2	0.2 (3)	C13—C14—C18—N3	−177.8 (2)
C7—C8—C9—N2	179.07 (19)	Cu1—O7—C19—C19^iv	166.04 (17)
C9—C8—C10—C11	1.0 (3)	Cu2—O7—C19—C19^iv	−72.3 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O2^i	0.95	2.27	2.856 (3)	119
C17—H17···O3^i	0.95	2.46	2.964 (3)	113
C12—H12···N8^iii	0.95	2.64	3.308 (3)	128
C10—H10···O4^ii	0.95	2.53	3.302 (3)	138
C9—H9···N8	0.95	2.61	3.296 (3)	130
C6—H6···O6^v	0.95	2.43	3.034 (3)	121
C4—H4···F1^vi	0.95	2.52	3.417 (3)	157
C3—H3···O5^vii	0.95	2.58	3.274 (3)	130
O7—H7···O4	0.85	1.75	2.584 (2)	168

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