A new mixed-valence Cu^I/Cu^II three-dimensional coordination polymer constructed with an N,O-donor ligand generated via solvothermal synthesis: structural features and magnetic properties

A new mixed-valence Cu^I/Cu^II three-dimensional coordination polymer, poly[[di­aqua­bis­[μ₄-2-(pyra­zin-2-yl)quinoline-4-carboxyl­ato]dicopper(I)copper(II)] bis­(tetra­fluorido­borate)], {[Cu₃(C₁₄H₈N₃O₂)₂(H₂O)₂](BF₄)₂}_n, was synthesized and characterized, with 2-(pyra­zin-2-yl)quinoline-4-carb­oxy­lic acid being em­ployed as a linker ligand. The ligand was isolated as its hydro­chloride salt, 4-carb­oxy-2-(pyra­zin-2-yl)quinolin-1-ium chloride dihydrate, C₁₄H₁₀N₃O₂⁺·Cl⁻·2H₂O. The compounds show luminescence at 550 nm for the ligand and at 565 nm for the polymer at 297 K. The ligand structure was rationalized by means of quantum-chemical calculations, which led to a similar conformation to that determined from X-ray diffraction studies.

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: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2016 (Sheldrick, 2015b).

4-Carboxy-2-(pyrazin-2-yl)quinolin-1-ium chloride dihydrate (II)

Crystal data

C14H10N3O2^+·Cl^−·2H2O	Dx = 1.520 Mg m^−3
Mr = 323.73	Cu Kα radiation, λ = 1.5418 Å
Orthorhombic, Pca21	Cell parameters from 2129 reflections
a = 23.7648 (5) Å	θ = 3.7–67.7°
b = 8.5785 (2) Å	µ = 2.61 mm^−1
c = 6.9373 (2) Å	T = 100 K
V = 1414.28 (6) Å^3	Block, colorless
Z = 4	0.35 × 0.25 × 0.20 mm
F(000) = 672

Data collection

Rigaku Xcalibur Gemini Ultra diffractometer	2018 reflections with I > 2σ(I)
CCD scans	Rint = 0.024
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	θmax = 68.0°, θmin = 3.7°
Tmin = 0.678, Tmax = 0.789	h = −18→28
4162 measured reflections	k = −6→10
2129 independent reflections	l = −8→8

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0246P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.064	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.26 e Å^−3
2129 reflections	Δρmin = −0.16 e Å^−3
205 parameters	Absolute structure: Flack x determined using 662 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.019 (11)

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. Both studied crystal structures were solved with direct methods in SHELXTL software suite. They were refined using the full-matrix method in SHELXL (Sheldrick, 2008; Sheldrick, 2015).

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

	x	y	z	Uiso*/Ueq
Cl1	0.57021 (3)	−0.02306 (7)	0.58883 (12)	0.01968 (16)
O1	0.20340 (8)	0.5778 (2)	0.4474 (3)	0.0213 (5)
H1O	0.173346	0.628146	0.423968	0.065 (15)*
O2	0.15808 (8)	0.3614 (2)	0.3561 (3)	0.0203 (5)
O1W	0.11188 (8)	0.7174 (2)	0.3812 (4)	0.0232 (5)
H1W	0.099691	0.795537	0.443882	0.055 (14)*
H2W	0.083778	0.656959	0.368369	0.050 (13)*
O2W	0.44705 (8)	0.0708 (2)	0.6426 (3)	0.0234 (5)
H3W	0.480646	0.041213	0.621884	0.028 (9)*
H4W	0.442609	0.065082	0.763959	0.036 (12)*
N1	0.36031 (9)	0.2092 (3)	0.4718 (3)	0.0147 (5)
H1N	0.391915	0.168100	0.498390	0.025 (10)*
N2	0.51044 (10)	0.4540 (3)	0.3605 (4)	0.0190 (6)
N3	0.40649 (10)	0.6021 (3)	0.4078 (4)	0.0193 (6)
C1	0.25663 (11)	0.3459 (3)	0.4331 (4)	0.0143 (6)
C2	0.30491 (11)	0.4296 (3)	0.4009 (4)	0.0158 (6)
H2	0.302547	0.536313	0.365072	0.019*
C3	0.35785 (11)	0.3584 (3)	0.4207 (4)	0.0144 (6)
C4	0.31372 (11)	0.1190 (3)	0.5047 (4)	0.0146 (6)
C5	0.32126 (12)	−0.0371 (3)	0.5603 (4)	0.0168 (6)
H5	0.357955	−0.080287	0.570615	0.020*
C6	0.27472 (11)	−0.1259 (3)	0.5993 (5)	0.0173 (6)
H6	0.279056	−0.232004	0.635811	0.021*
C7	0.22053 (11)	−0.0608 (3)	0.5856 (5)	0.0175 (6)
H7	0.188770	−0.123487	0.615776	0.021*
C8	0.21244 (11)	0.0903 (3)	0.5299 (4)	0.0159 (6)
H8	0.175378	0.130999	0.520286	0.019*
C9	0.25940 (11)	0.1866 (3)	0.4862 (4)	0.0147 (6)
C10	0.41089 (12)	0.4462 (3)	0.3966 (4)	0.0165 (6)
C11	0.46230 (11)	0.3725 (3)	0.3666 (5)	0.0178 (6)
H11	0.463333	0.262561	0.350101	0.021*
C12	0.50659 (12)	0.6079 (3)	0.3794 (5)	0.0200 (7)
H12	0.539991	0.668705	0.380945	0.024*
C13	0.45439 (11)	0.6822 (3)	0.3969 (5)	0.0204 (7)
H13	0.453103	0.792789	0.401174	0.024*
C14	0.20016 (11)	0.4280 (3)	0.4083 (4)	0.0149 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0146 (3)	0.0177 (3)	0.0268 (4)	0.0011 (3)	0.0013 (3)	0.0013 (4)
O1	0.0162 (10)	0.0121 (10)	0.0357 (14)	0.0026 (8)	−0.0030 (9)	−0.0026 (10)
O2	0.0145 (9)	0.0167 (11)	0.0296 (12)	−0.0005 (9)	−0.0027 (10)	−0.0019 (10)
O1W	0.0146 (10)	0.0156 (10)	0.0394 (13)	0.0012 (9)	0.0005 (10)	−0.0037 (11)
O2W	0.0140 (9)	0.0310 (12)	0.0251 (13)	0.0052 (9)	−0.0006 (9)	0.0042 (10)
N1	0.0112 (11)	0.0149 (12)	0.0181 (13)	0.0010 (10)	0.0000 (10)	−0.0013 (11)
N2	0.0162 (13)	0.0177 (13)	0.0231 (13)	−0.0026 (10)	0.0007 (11)	0.0028 (12)
N3	0.0190 (12)	0.0148 (12)	0.0239 (15)	0.0006 (10)	0.0005 (11)	0.0013 (12)
C1	0.0137 (13)	0.0166 (14)	0.0128 (14)	0.0012 (11)	−0.0030 (12)	−0.0036 (12)
C2	0.0159 (14)	0.0145 (13)	0.0172 (17)	0.0013 (11)	0.0001 (12)	−0.0003 (13)
C3	0.0167 (13)	0.0123 (14)	0.0142 (14)	0.0007 (11)	0.0012 (12)	−0.0014 (12)
C4	0.0142 (13)	0.0141 (14)	0.0154 (13)	−0.0026 (11)	0.0006 (12)	−0.0021 (12)
C5	0.0175 (12)	0.0141 (14)	0.0187 (17)	0.0021 (11)	−0.0010 (13)	−0.0027 (13)
C6	0.0218 (13)	0.0119 (12)	0.0181 (15)	−0.0024 (10)	−0.0024 (15)	−0.0011 (14)
C7	0.0177 (12)	0.0171 (13)	0.0176 (14)	−0.0051 (10)	0.0021 (15)	−0.0041 (15)
C8	0.0135 (13)	0.0181 (14)	0.0161 (16)	−0.0006 (12)	0.0002 (11)	−0.0037 (12)
C9	0.0152 (13)	0.0162 (14)	0.0127 (14)	−0.0005 (12)	−0.0018 (11)	−0.0026 (12)
C10	0.0194 (14)	0.0147 (14)	0.0155 (16)	−0.0005 (11)	−0.0005 (12)	0.0014 (13)
C11	0.0180 (13)	0.0136 (14)	0.0219 (14)	−0.0010 (12)	−0.0008 (14)	0.0001 (14)
C12	0.0179 (14)	0.0173 (15)	0.0248 (18)	−0.0046 (12)	0.0005 (14)	0.0023 (14)
C13	0.0211 (14)	0.0116 (13)	0.0283 (19)	−0.0026 (12)	−0.0009 (13)	0.0017 (13)
C14	0.0134 (14)	0.0137 (13)	0.0176 (17)	0.0006 (11)	0.0020 (12)	0.0005 (12)

Geometric parameters (Å, º)

O1—C14	1.316 (3)	C2—H2	0.9500
O1—H1O	0.8501	C3—C10	1.478 (4)
O2—C14	1.207 (3)	C4—C5	1.405 (4)
O1W—H1W	0.8500	C4—C9	1.421 (4)
O1W—H2W	0.8499	C5—C6	1.370 (4)
O2W—H3W	0.8499	C5—H5	0.9500
O2W—H4W	0.8501	C6—C7	1.407 (4)
N1—C3	1.329 (4)	C6—H6	0.9500
N1—C4	1.370 (3)	C7—C8	1.366 (4)
N1—H1N	0.8501	C7—H7	0.9500
N2—C12	1.329 (4)	C8—C9	1.421 (4)
N2—C11	1.342 (4)	C8—H8	0.9500
N3—C13	1.331 (4)	C10—C11	1.391 (4)
N3—C10	1.344 (4)	C11—H11	0.9500
C1—C2	1.372 (4)	C12—C13	1.400 (4)
C1—C9	1.417 (4)	C12—H12	0.9500
C1—C14	1.525 (4)	C13—H13	0.9500
C2—C3	1.405 (4)
C14—O1—H1O	114.0	C7—C6—H6	119.8
H1W—O1W—H2W	105.5	C8—C7—C6	121.6 (2)
H3W—O2W—H4W	105.5	C8—C7—H7	119.2
C3—N1—C4	123.6 (2)	C6—C7—H7	119.2
C3—N1—H1N	119.8	C7—C8—C9	120.1 (3)
C4—N1—H1N	116.3	C7—C8—H8	119.9
C12—N2—C11	117.1 (2)	C9—C8—H8	119.9
C13—N3—C10	116.3 (2)	C1—C9—C4	117.4 (2)
C2—C1—C9	120.5 (2)	C1—C9—C8	125.4 (3)
C2—C1—C14	118.4 (2)	C4—C9—C8	117.2 (3)
C9—C1—C14	121.0 (2)	N3—C10—C11	122.0 (3)
C1—C2—C3	120.4 (3)	N3—C10—C3	115.7 (2)
C1—C2—H2	119.8	C11—C10—C3	122.3 (3)
C3—C2—H2	119.8	N2—C11—C10	121.1 (3)
N1—C3—C2	118.9 (3)	N2—C11—H11	119.5
N1—C3—C10	118.9 (2)	C10—C11—H11	119.5
C2—C3—C10	122.1 (3)	N2—C12—C13	121.4 (3)
N1—C4—C5	118.8 (2)	N2—C12—H12	119.3
N1—C4—C9	119.2 (3)	C13—C12—H12	119.3
C5—C4—C9	122.0 (3)	N3—C13—C12	121.8 (3)
C6—C5—C4	118.8 (3)	N3—C13—H13	119.1
C6—C5—H5	120.6	C12—C13—H13	119.1
C4—C5—H5	120.6	O2—C14—O1	124.9 (3)
C5—C6—C7	120.3 (3)	O2—C14—C1	123.0 (3)
C5—C6—H6	119.8	O1—C14—C1	112.1 (2)
C9—C1—C2—C3	−0.2 (5)	C5—C4—C9—C8	1.1 (4)
C14—C1—C2—C3	−179.5 (3)	C7—C8—C9—C1	−177.8 (3)
C4—N1—C3—C2	0.7 (4)	C7—C8—C9—C4	−0.5 (4)
C4—N1—C3—C10	177.6 (3)	C13—N3—C10—C11	−2.8 (5)
C1—C2—C3—N1	−0.3 (4)	C13—N3—C10—C3	176.4 (3)
C1—C2—C3—C10	−177.0 (3)	N1—C3—C10—N3	−159.1 (3)
C3—N1—C4—C5	−179.3 (3)	C2—C3—C10—N3	17.7 (4)
C3—N1—C4—C9	−0.7 (4)	N1—C3—C10—C11	20.2 (5)
N1—C4—C5—C6	177.9 (3)	C2—C3—C10—C11	−163.1 (3)
C9—C4—C5—C6	−0.6 (5)	C12—N2—C11—C10	−1.7 (5)
C4—C5—C6—C7	−0.6 (5)	N3—C10—C11—N2	4.6 (5)
C5—C6—C7—C8	1.3 (5)	C3—C10—C11—N2	−174.6 (3)
C6—C7—C8—C9	−0.7 (5)	C11—N2—C12—C13	−2.5 (5)
C2—C1—C9—C4	0.2 (4)	C10—N3—C13—C12	−1.4 (5)
C14—C1—C9—C4	179.5 (3)	N2—C12—C13—N3	4.3 (5)
C2—C1—C9—C8	177.5 (3)	C2—C1—C14—O2	149.1 (3)
C14—C1—C9—C8	−3.1 (5)	C9—C1—C14—O2	−30.3 (5)
N1—C4—C9—C1	0.2 (4)	C2—C1—C14—O1	−30.0 (4)
C5—C4—C9—C1	178.7 (3)	C9—C1—C14—O1	150.6 (3)
N1—C4—C9—C8	−177.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2W	0.85	1.85	2.658 (3)	159
O1—H1O···O1W	0.85	1.68	2.525 (3)	176
O1W—H1W···Cl1^i	0.85	2.30	3.151 (2)	174
O1W—H2W···N2^i	0.85	1.99	2.827 (3)	170
O2W—H3W···Cl1	0.85	2.21	3.058 (2)	175
O2W—H4W···Cl1^ii	0.85	2.30	3.149 (2)	174
C5—H5···O2W	0.95	2.53	3.181 (3)	126
C8—H8···O2	0.95	2.32	2.921 (3)	121
C8—H8···Cl1^iii	0.95	2.71	3.453 (3)	136

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

Poly[[diaquabis[µ₄-2-(pyrazin-2-yl)quinoline-4-carboxylato]dicopper(I)copper(II)] bis(tetrafluoridoborate)] (I)

Crystal data

[Cu3(C14H8N3O2)2(H2O)2](BF4)2	Dx = 1.895 Mg m^−3
Mr = 900.74	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbcn	Cell parameters from 2839 reflections
a = 21.9637 (8) Å	θ = 4.0–67.5°
b = 12.4106 (3) Å	µ = 3.28 mm^−1
c = 11.5844 (4) Å	T = 100 K
V = 3157.71 (18) Å^3	Prism, light green
Z = 4	0.20 × 0.20 × 0.19 mm
F(000) = 1788

Data collection

Rigaku Xcalibur Gemini Ultra diffractometer	2565 reflections with I > 2σ(I)
CCD scans	Rint = 0.032
Absorption correction: analytical (CrysAlis PRO; Rigaku OD, 2015)	θmax = 67.5°, θmin = 4.0°
Tmin = 0.897, Tmax = 0.970	h = −26→26
13656 measured reflections	k = −14→14
2839 independent reflections	l = −11→13

Refinement

Refinement on F^2	51 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 2.3063P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
2839 reflections	Δρmax = 0.45 e Å^−3
256 parameters	Δρmin = −0.60 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. Both studied crystal structures were solved with direct methods in SHELXTL software suite. They were refined using the full-matrix method in SHELXL (Sheldrick, 2008; Sheldrick, 2015).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.000000	0.74536 (3)	−0.250000	0.01528 (14)
Cu2	0.19245 (2)	0.65799 (2)	−0.23617 (3)	0.01571 (13)
O1	0.10315 (7)	0.69880 (12)	−0.17283 (13)	0.0181 (3)
O2	0.01259 (7)	0.63081 (13)	−0.13388 (14)	0.0204 (3)
O3W	0.00091 (7)	0.85819 (14)	−0.36894 (15)	0.0221 (4)
H1W	−0.031223	0.878391	−0.403625	0.047 (10)*
H2W	0.019334	0.916484	−0.352749	0.048 (10)*
N1	0.15991 (8)	0.41714 (14)	0.11511 (15)	0.0154 (4)
N2	0.22414 (8)	0.49183 (14)	0.29452 (16)	0.0155 (4)
N3	0.27101 (9)	0.70098 (14)	0.28718 (16)	0.0163 (4)
C1	0.09924 (9)	0.55395 (17)	−0.04000 (19)	0.0163 (4)
C2	0.13321 (10)	0.59515 (17)	0.04871 (19)	0.0168 (4)
H2	0.136147	0.670830	0.059720	0.020*
C3	0.16378 (10)	0.52364 (17)	0.12356 (18)	0.0154 (4)
C4	0.12735 (9)	0.37494 (17)	0.02503 (18)	0.0165 (4)
C5	0.12736 (11)	0.26115 (17)	0.0108 (2)	0.0204 (5)
H5	0.146516	0.216513	0.066641	0.024*
C6	0.09978 (10)	0.21597 (19)	−0.0834 (2)	0.0218 (5)
H6	0.100427	0.139997	−0.093291	0.026*
C7	0.07027 (11)	0.28172 (19)	−0.1661 (2)	0.0223 (5)
H7	0.051960	0.249556	−0.231958	0.027*
C8	0.06788 (10)	0.39095 (19)	−0.1522 (2)	0.0198 (5)
H8	0.046994	0.433918	−0.207372	0.024*
C9	0.09622 (10)	0.44048 (17)	−0.05653 (19)	0.0170 (4)
C10	0.06988 (10)	0.63278 (17)	−0.12175 (18)	0.0157 (4)
C11	0.20558 (10)	0.56378 (17)	0.21402 (18)	0.0152 (4)
C12	0.22827 (10)	0.66791 (16)	0.21289 (19)	0.0159 (4)
H12	0.212987	0.717484	0.157531	0.019*
C13	0.28982 (10)	0.62874 (18)	0.36614 (19)	0.0179 (4)
H13	0.320250	0.648854	0.420292	0.021*
C14	0.26566 (10)	0.52536 (17)	0.37010 (19)	0.0177 (4)
H14	0.279167	0.477184	0.428457	0.021*
F1	0.07315 (7)	0.02535 (12)	0.69342 (13)	0.0344 (4)
F2A	0.16332 (7)	−0.02487 (12)	0.61020 (14)	0.0285 (4)	0.933 (4)
F3A	0.14104 (8)	0.15184 (12)	0.63147 (15)	0.0309 (5)	0.933 (4)
F4A	0.08928 (7)	0.05038 (13)	0.50054 (13)	0.0319 (5)	0.933 (4)
F2B	0.0863 (9)	0.1354 (16)	0.5440 (17)	0.047 (8)*	0.067 (4)
F3B	0.1331 (12)	−0.0271 (15)	0.543 (2)	0.074 (11)*	0.067 (4)
F4B	0.1640 (10)	0.107 (2)	0.6651 (19)	0.096 (15)*	0.070 (4)
B1	0.11668 (12)	0.0520 (2)	0.6110 (2)	0.0211 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0180 (3)	0.0088 (2)	0.0191 (2)	0.000	−0.00242 (17)	0.000
Cu2	0.0191 (2)	0.00685 (19)	0.0212 (2)	−0.00066 (12)	0.00091 (12)	−0.00235 (11)
O1	0.0192 (7)	0.0120 (8)	0.0230 (8)	0.0007 (6)	0.0021 (6)	0.0032 (6)
O2	0.0186 (7)	0.0163 (8)	0.0262 (8)	−0.0007 (6)	−0.0029 (6)	0.0052 (6)
O3W	0.0253 (9)	0.0155 (8)	0.0255 (8)	−0.0033 (7)	−0.0037 (7)	0.0041 (6)
N1	0.0190 (9)	0.0098 (8)	0.0173 (8)	−0.0007 (7)	−0.0004 (7)	0.0009 (7)
N2	0.0176 (8)	0.0099 (8)	0.0190 (9)	0.0010 (7)	0.0004 (7)	0.0024 (7)
N3	0.0191 (9)	0.0102 (9)	0.0196 (9)	0.0004 (7)	−0.0004 (7)	0.0014 (7)
C1	0.0163 (10)	0.0125 (11)	0.0200 (11)	0.0010 (8)	0.0023 (8)	0.0008 (8)
C2	0.0193 (10)	0.0075 (9)	0.0234 (11)	0.0000 (8)	−0.0002 (9)	0.0010 (8)
C3	0.0168 (10)	0.0103 (10)	0.0192 (10)	−0.0002 (8)	0.0018 (8)	0.0008 (8)
C4	0.0174 (10)	0.0132 (10)	0.0190 (10)	−0.0011 (8)	0.0025 (8)	0.0009 (8)
C5	0.0257 (11)	0.0107 (10)	0.0248 (11)	0.0005 (9)	−0.0006 (10)	0.0012 (9)
C6	0.0257 (12)	0.0124 (10)	0.0272 (12)	−0.0007 (9)	−0.0002 (9)	−0.0033 (9)
C7	0.0242 (11)	0.0197 (11)	0.0229 (11)	−0.0007 (10)	−0.0015 (9)	−0.0044 (10)
C8	0.0197 (10)	0.0177 (11)	0.0219 (11)	0.0008 (9)	0.0000 (9)	0.0014 (9)
C9	0.0171 (10)	0.0129 (11)	0.0209 (11)	−0.0009 (8)	0.0018 (8)	0.0003 (9)
C10	0.0198 (10)	0.0102 (10)	0.0170 (10)	0.0025 (9)	0.0002 (8)	−0.0027 (8)
C11	0.0189 (10)	0.0096 (10)	0.0173 (10)	0.0018 (8)	0.0024 (8)	0.0008 (8)
C12	0.0201 (11)	0.0084 (10)	0.0192 (10)	0.0019 (8)	−0.0011 (9)	0.0027 (8)
C13	0.0208 (10)	0.0139 (10)	0.0190 (10)	−0.0012 (9)	−0.0019 (9)	0.0015 (9)
C14	0.0226 (11)	0.0120 (10)	0.0186 (10)	0.0011 (9)	−0.0019 (9)	0.0029 (8)
F1	0.0392 (9)	0.0310 (8)	0.0331 (8)	−0.0154 (7)	0.0104 (7)	−0.0038 (7)
F2A	0.0349 (9)	0.0179 (8)	0.0326 (9)	0.0038 (6)	−0.0038 (7)	−0.0018 (6)
F3A	0.0363 (9)	0.0143 (8)	0.0421 (10)	−0.0089 (7)	0.0076 (7)	−0.0053 (7)
F4A	0.0340 (8)	0.0332 (10)	0.0284 (9)	−0.0005 (7)	−0.0082 (7)	0.0043 (7)
B1	0.0249 (13)	0.0150 (12)	0.0235 (13)	−0.0036 (10)	−0.0012 (10)	0.0009 (10)

Geometric parameters (Å, º)

Cu1—O3W	1.9646 (17)	C3—C11	1.480 (3)
Cu1—O3W^i	1.9647 (17)	C4—C5	1.422 (3)
Cu1—O2^i	1.9766 (16)	C4—C9	1.422 (3)
Cu1—O2	1.9766 (16)	C5—C6	1.368 (3)
Cu2—N3^ii	1.9444 (18)	C5—H5	0.9500
Cu2—N2^iii	2.0169 (18)	C6—C7	1.416 (3)
Cu2—N1^iii	2.0853 (18)	C6—H6	0.9500
Cu2—O1	2.1545 (15)	C7—C8	1.366 (3)
O1—C10	1.247 (3)	C7—H7	0.9500
O2—C10	1.266 (3)	C8—C9	1.412 (3)
O3W—H1W	0.8499	C8—H8	0.9500
O3W—H2W	0.8499	C11—C12	1.385 (3)
N1—C3	1.328 (3)	C12—H12	0.9500
N1—C4	1.369 (3)	C13—C14	1.389 (3)
N2—C14	1.331 (3)	C13—H13	0.9500
N2—C11	1.354 (3)	C14—H14	0.9500
N3—C12	1.338 (3)	F1—B1	1.391 (3)
N3—C13	1.346 (3)	F2A—B1	1.399 (3)
C1—C2	1.369 (3)	F3A—B1	1.371 (3)
C1—C9	1.423 (3)	F4A—B1	1.414 (3)
C1—C10	1.507 (3)	F2B—B1	1.455 (13)
C2—C3	1.411 (3)	F3B—B1	1.311 (14)
C2—H2	0.9500	F4B—B1	1.391 (14)
O3W—Cu1—O3W^i	89.08 (10)	C4—C5—H5	120.0
O3W—Cu1—O2^i	92.11 (7)	C5—C6—C7	120.4 (2)
O3W^i—Cu1—O2^i	171.31 (7)	C5—C6—H6	119.8
O3W—Cu1—O2	171.31 (7)	C7—C6—H6	119.8
O3W^i—Cu1—O2	92.11 (7)	C8—C7—C6	120.6 (2)
O2^i—Cu1—O2	88.02 (10)	C8—C7—H7	119.7
N3^ii—Cu2—N2^iii	131.52 (8)	C6—C7—H7	119.7
N3^ii—Cu2—N1^iii	131.22 (8)	C7—C8—C9	120.5 (2)
N2^iii—Cu2—N1^iii	81.48 (7)	C7—C8—H8	119.8
N3^ii—Cu2—O1	96.70 (7)	C9—C8—H8	119.8
N2^iii—Cu2—O1	118.08 (6)	C8—C9—C4	119.0 (2)
N1^iii—Cu2—O1	94.27 (7)	C8—C9—C1	123.8 (2)
C10—O1—Cu2	122.72 (13)	C4—C9—C1	117.02 (19)
C10—O2—Cu1	101.57 (13)	O1—C10—O2	122.8 (2)
Cu1—O3W—H1W	122.2	O1—C10—C1	118.29 (18)
Cu1—O3W—H2W	117.2	O2—C10—C1	118.85 (19)
H1W—O3W—H2W	104.4	N2—C11—C12	120.9 (2)
C3—N1—C4	118.06 (19)	N2—C11—C3	116.91 (19)
C3—N1—Cu2^iv	111.23 (14)	C12—C11—C3	122.1 (2)
C4—N1—Cu2^iv	129.62 (14)	N3—C12—C11	122.2 (2)
C14—N2—C11	116.95 (18)	N3—C12—H12	118.9
C14—N2—Cu2^iv	129.84 (15)	C11—C12—H12	118.9
C11—N2—Cu2^iv	112.50 (15)	N3—C13—C14	121.4 (2)
C12—N3—C13	116.63 (19)	N3—C13—H13	119.3
C12—N3—Cu2^v	118.44 (15)	C14—C13—H13	119.3
C13—N3—Cu2^v	124.58 (15)	N2—C14—C13	121.9 (2)
C2—C1—C9	119.7 (2)	N2—C14—H14	119.0
C2—C1—C10	117.55 (19)	C13—C14—H14	119.0
C9—C1—C10	122.56 (19)	F3B—B1—F4B	115.6 (11)
C1—C2—C3	119.06 (19)	F3B—B1—F1	115.2 (10)
C1—C2—H2	120.5	F3A—B1—F1	111.3 (2)
C3—C2—H2	120.5	F4B—B1—F1	108.6 (10)
N1—C3—C2	123.4 (2)	F3A—B1—F2A	109.4 (2)
N1—C3—C11	115.28 (19)	F1—B1—F2A	110.22 (19)
C2—C3—C11	121.25 (19)	F3A—B1—F4A	109.6 (2)
N1—C4—C5	117.9 (2)	F1—B1—F4A	109.0 (2)
N1—C4—C9	122.60 (19)	F2A—B1—F4A	107.25 (19)
C5—C4—C9	119.4 (2)	F3B—B1—F2B	109.7 (10)
C6—C5—C4	120.0 (2)	F4B—B1—F2B	103.6 (10)
C6—C5—H5	120.0	F1—B1—F2B	102.7 (8)
C9—C1—C2—C3	−1.1 (3)	C10—C1—C9—C4	178.21 (19)
C10—C1—C2—C3	−176.94 (19)	Cu2—O1—C10—O2	−143.62 (17)
C4—N1—C3—C2	3.9 (3)	Cu2—O1—C10—C1	37.9 (3)
Cu2^iv—N1—C3—C2	−165.33 (17)	Cu1—O2—C10—O1	2.7 (2)
C4—N1—C3—C11	−172.87 (18)	Cu1—O2—C10—C1	−178.81 (16)
Cu2^iv—N1—C3—C11	17.9 (2)	C2—C1—C10—O1	56.8 (3)
C1—C2—C3—N1	−2.3 (3)	C9—C1—C10—O1	−118.9 (2)
C1—C2—C3—C11	174.29 (19)	C2—C1—C10—O2	−121.8 (2)
C3—N1—C4—C5	175.0 (2)	C9—C1—C10—O2	62.6 (3)
Cu2^iv—N1—C4—C5	−18.1 (3)	C14—N2—C11—C12	−1.3 (3)
C3—N1—C4—C9	−2.2 (3)	Cu2^iv—N2—C11—C12	−172.55 (17)
Cu2^iv—N1—C4—C9	164.73 (15)	C14—N2—C11—C3	174.51 (18)
N1—C4—C5—C6	−174.5 (2)	Cu2^iv—N2—C11—C3	3.2 (2)
C9—C4—C5—C6	2.7 (3)	N1—C3—C11—N2	−14.8 (3)
C4—C5—C6—C7	−1.0 (3)	C2—C3—C11—N2	168.4 (2)
C5—C6—C7—C8	−1.2 (4)	N1—C3—C11—C12	160.9 (2)
C6—C7—C8—C9	1.7 (3)	C2—C3—C11—C12	−15.9 (3)
C7—C8—C9—C4	0.1 (3)	C13—N3—C12—C11	−2.0 (3)
C7—C8—C9—C1	175.7 (2)	Cu2^v—N3—C12—C11	171.48 (17)
N1—C4—C9—C8	174.8 (2)	N2—C11—C12—N3	2.9 (3)
C5—C4—C9—C8	−2.3 (3)	C3—C11—C12—N3	−172.7 (2)
N1—C4—C9—C1	−1.0 (3)	C12—N3—C13—C14	−0.3 (3)
C5—C4—C9—C1	−178.2 (2)	Cu2^v—N3—C13—C14	−173.30 (16)
C2—C1—C9—C8	−173.0 (2)	C11—N2—C14—C13	−1.0 (3)
C10—C1—C9—C8	2.6 (3)	Cu2^iv—N2—C14—C13	168.51 (16)
C2—C1—C9—C4	2.6 (3)	N3—C13—C14—N2	1.8 (3)

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