Synthesis, structure and magnetic properties of tetrakis-μ-carboxylato-bis(dodecylnicotinato)dicopper(II) complexes; crystal and molecular structure of the decyl carboxylate derivative

Dodecylnicotinate bis-adducts of binuclear copper carboxy­lates, of the general formula Cu₂(O₂CC_{n − 1}H_{2n − 1})₄(C₅H₄N­COOC₁₂H₂₅)₂, were synthesized for n = 10, 12, 14, 16, 18 and 20, and their crystal structure, thermal behavior and magnetic properties studied. The molecular structure of the decyl derivative has been determined from single-crystal X-ray diffraction data. The dimer is centrosymmetric with the Cu^II ions in a square-pyramidal coordination with four O-alkyl O atoms [average d(Cu—O) 1.960 (6) Å] in the basal plane and the nicotine N atom at apical positions [d(Cu—N) 2.183 (3)  Å]. The copper ions, 2.615 (1) Å apart, are bridged by four O-alkyl carboxylate groups. Both the n = 20 and n  =  18 homologues exhibit lamellar phases, which can be related to the supramolecular arrangement found in the n = 10 derivative. The magnetic behavior of the decyl and octadecyl dimers was studied in the 2–300 K temperature range. They exhibit a strong intramolecular antiferromagnetic interaction (Cu–Cu superexchange coupling constant J  = −347 cm⁻¹ for the decyl derivative), which can be attributed to a large overlap of the metal 3d orbitals and the oxygen lone pair orbitals of the linking carboxylate groups.

Computing details

Data collection: Enraf-Nonius CAD4; cell refinement: Enraf-Nonius CAD4; data reduction: SDP (Frenz, 1983); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).

Tetrakis-µ-decylcarboxylato-bis(dodecylnicotinato)-dicopper (II)

Crystal data

[Cu(C10H19O2)4(C18H29NO2)2]	F(000) = 758
Mr = 1394.93	Dx = 1.132 Mg m^−3 Dm = 1.12 Mg m^−3 Dm measured by immersion
Triclinic, P1	Melting point: 42 K
a = 10.231 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.878 (4) Å	Cell parameters from 23 reflections
c = 16.804 (2) Å	θ = 9.8–15.7°
α = 92.39 (2)°	µ = 0.57 mm^−1
β = 104.31 (2)°	T = 293 K
γ = 106.17 (3)°	Plate, blue-green
V = 2045.8 (9) Å^3	0.44 × 0.40 × 0.16 mm
Z = 1

Data collection

Enraf-Nonius CAD4 diffractometer	4529 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
Graphite monochromator	θmax = 25.0°, θmin = 1.3°
ω–2θ scans	h = −12→11
Absorption correction: numerical Busing & Levy, 1957)	k = −15→15
Tmin = 0.793, Tmax = 0.916	l = 0→19
7627 measured reflections	1 standard reflections every 30 min
6369 independent reflections	intensity decay: 1.5%

Refinement

Refinement on F^2	Primary atom site location: Patterson
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H-atom parameters constrained
S = 1.05	Calculated w = 1/[σ^2(Fo^2) + (0.0878P)^2 + 0.2591P] where P = (Fo^2 + 2Fc^2)/3
6369 reflections	(Δ/σ)max = −0.006
423 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.29 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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > 2σ(F²) is used only for calculating R factor obs 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	0.10395 (4)	0.45719 (3)	0.01842 (2)	0.0564 (2)
O11	0.2103 (2)	0.6037 (2)	0.0749 (2)	0.0755 (7)
O12	0.0340 (3)	0.6753 (2)	0.0450 (2)	0.0738 (7)
C11	0.1594 (4)	0.6801 (3)	0.0795 (2)	0.0635 (9)
C12	0.2546 (5)	0.7861 (3)	0.1286 (3)	0.0900 (13)
H12A	0.3035 (5)	0.8291 (3)	0.0927 (3)	0.197 (8)*
H12B	0.1965 (5)	0.8260 (3)	0.1456 (3)	0.197 (8)*
C13	0.3620 (6)	0.7753 (4)	0.2037 (3)	0.119 (2)
H13A	0.4265 (6)	0.8471 (4)	0.2263 (3)	0.197 (8)*
H13B	0.4165 (6)	0.7317 (4)	0.1872 (3)	0.197 (8)*
C14	0.3002 (5)	0.7241 (4)	0.2708 (3)	0.1032 (15)
H14A	0.2378 (5)	0.7633 (4)	0.2831 (3)	0.197 (8)*
H14B	0.2434 (5)	0.6497 (4)	0.2498 (3)	0.197 (8)*
C15	0.4061 (8)	0.7233 (5)	0.3483 (4)	0.149 (3)
H15A	0.4688 (8)	0.6856 (5)	0.3343 (4)	0.197 (8)*
H15B	0.4623 (8)	0.7982 (5)	0.3678 (4)	0.197 (8)*
C16	0.3615 (7)	0.6762 (5)	0.4168 (4)	0.125 (2)
H16A	0.3068 (7)	0.6008 (5)	0.3980 (4)	0.197 (8)*
H16B	0.2980 (7)	0.7131 (5)	0.4308 (4)	0.197 (8)*
C17	0.4698 (9)	0.6783 (6)	0.4930 (4)	0.156 (3)
H17A	0.5344 (9)	0.6439 (6)	0.4774 (4)	0.197 (8)*
H17B	0.5227 (9)	0.7543 (6)	0.5111 (4)	0.197 (8)*
C18	0.4390 (8)	0.6327 (6)	0.5634 (4)	0.150 (2)
H18A	0.3862 (8)	0.5566 (6)	0.5458 (4)	0.197 (8)*
H18B	0.3750 (8)	0.6673 (6)	0.5796 (4)	0.197 (8)*
C19	0.5486 (11)	0.6364 (7)	0.6368 (5)	0.193 (4)
H19A	0.6106 (11)	0.6005 (7)	0.6196 (5)	0.197 (8)*
H19B	0.6027 (11)	0.7126 (7)	0.6521 (5)	0.197 (8)*
C110	0.5294 (12)	0.5972 (8)	0.7081 (6)	0.243 (5)
H11A	0.505 (9)	0.649 (3)	0.740 (2)	0.312 (19)*
H11B	0.615 (3)	0.586 (6)	0.740 (3)	0.312 (19)*
H11C	0.455 (6)	0.530 (4)	0.6955 (6)	0.312 (19)*
O21	0.1358 (2)	0.5074 (2)	−0.08604 (14)	0.0690 (6)
O22	−0.0400 (3)	0.5803 (2)	−0.1173 (2)	0.0776 (7)
C21	0.0622 (4)	0.5559 (3)	−0.1319 (2)	0.0652 (9)
C22	0.1020 (5)	0.5869 (5)	−0.2092 (3)	0.107 (2)
H22A	0.1787 (5)	0.6545 (5)	−0.1949 (3)	0.225 (10)*
H22B	0.1391 (5)	0.5316 (5)	−0.2280 (3)	0.225 (10)*
C23	−0.0062 (4)	0.6012 (4)	−0.2789 (2)	0.0834 (12)
H23A	−0.0416 (4)	0.6580 (4)	−0.2609 (2)	0.225 (10)*
H23B	−0.0841 (4)	0.5343 (4)	−0.2927 (2)	0.225 (10)*
C24	0.0357 (5)	0.6294 (4)	−0.3555 (2)	0.0963 (14)
H24A	0.1132 (5)	0.6965 (4)	−0.3414 (2)	0.225 (10)*
H24B	0.0724 (5)	0.5730 (4)	−0.3728 (2)	0.225 (10)*
C25	−0.0698 (5)	0.6432 (5)	−0.4265 (3)	0.111 (2)
H25A	−0.1060 (5)	0.6997 (5)	−0.4089 (3)	0.225 (10)*
H25B	−0.1475 (5)	0.5762 (5)	−0.4398 (3)	0.225 (10)*
C26	−0.0331 (6)	0.6702 (4)	−0.5030 (3)	0.1043 (15)
H26A	0.0022 (6)	0.6134 (4)	−0.5212 (3)	0.225 (10)*
H26B	0.0450 (6)	0.7370 (4)	−0.4898 (3)	0.225 (10)*
C27	−0.1412 (7)	0.6847 (6)	−0.5740 (3)	0.136 (2)
H27A	−0.2201 (7)	0.6186 (6)	−0.5857 (3)	0.225 (10)*
H27B	−0.1746 (7)	0.7426 (6)	−0.5558 (3)	0.225 (10)*
C28	−0.1105 (7)	0.7088 (5)	−0.6513 (3)	0.132 (2)
H28A	−0.0763 (7)	0.6514 (5)	−0.6695 (3)	0.225 (10)*
H28B	−0.0325 (7)	0.7755 (5)	−0.6400 (3)	0.225 (10)*
C29	−0.2204 (9)	0.7217 (8)	−0.7215 (4)	0.195 (4)
H29A	−0.2980 (9)	0.6547 (8)	−0.7322 (4)	0.225 (10)*
H29B	−0.2548 (9)	0.7785 (8)	−0.7026 (4)	0.225 (10)*
C210	−0.1972 (10)	0.7449 (7)	−0.7960 (4)	0.206 (4)
H21A	−0.139 (8)	0.819 (2)	−0.7909 (13)	0.312 (19)*
H21B	−0.2858 (13)	0.736 (7)	−0.8361 (13)	0.312 (19)*
H21C	−0.150 (8)	0.697 (5)	−0.814 (2)	0.312 (19)*
N3	0.2843 (3)	0.3929 (3)	0.0471 (2)	0.0620 (7)
C31	0.2706 (4)	0.2926 (3)	0.0172 (2)	0.0650 (9)
H31	0.1807 (4)	0.2451 (3)	−0.0067 (2)	0.091 (7)*
C32	0.3890 (4)	0.2567 (3)	0.0207 (2)	0.0731 (10)
C33	0.5196 (4)	0.3283 (4)	0.0548 (3)	0.0857 (13)
H33	0.5999 (4)	0.3074 (4)	0.0556 (3)	0.091 (7)*
C34	0.5326 (4)	0.4298 (4)	0.0875 (3)	0.0880 (13)
H34	0.6212 (4)	0.4781 (4)	0.1132 (3)	0.091 (7)*
C35	0.4130 (4)	0.4599 (4)	0.0821 (2)	0.0749 (11)
H35	0.4221 (4)	0.5300 (4)	0.1036 (2)	0.091 (7)*
C36	0.3746 (5)	0.1470 (4)	−0.0151 (3)	0.0896 (13)
O31	0.4702 (4)	0.1206 (3)	−0.0311 (3)	0.1292 (13)
O32	0.2456 (4)	0.0796 (2)	−0.0285 (2)	0.0933 (9)
C37	0.2233 (7)	−0.0308 (4)	−0.0645 (4)	0.123 (2)
H37A	0.2844 (7)	−0.0650 (4)	−0.0283 (4)	0.186 (6)*
H37B	0.2450 (7)	−0.0297 (4)	−0.1176 (4)	0.186 (6)*
C38	0.0733 (8)	−0.0924 (4)	−0.0752 (4)	0.132 (2)
H38A	0.0534 (8)	−0.0885 (4)	−0.0218 (4)	0.186 (6)*
H38B	0.0604 (8)	−0.1682 (4)	−0.0923 (4)	0.186 (6)*
C39	−0.0347 (7)	−0.0551 (5)	−0.1366 (4)	0.128 (2)
H39A	−0.1277 (7)	−0.0921 (5)	−0.1307 (4)	0.186 (6)*
H39B	−0.0170 (7)	0.0223 (5)	−0.1223 (4)	0.186 (6)*
C310	−0.0369 (8)	−0.0738 (5)	−0.2247 (5)	0.144 (2)
H31A	0.0570 (8)	−0.0387 (5)	−0.2301 (5)	0.186 (6)*
H31B	−0.0572 (8)	−0.1514 (5)	−0.2393 (5)	0.186 (6)*
C311	−0.1377 (7)	−0.0354 (6)	−0.2844 (5)	0.149 (2)
H31C	−0.1214 (7)	0.0408 (6)	−0.2665 (5)	0.186 (6)*
H31D	−0.2315 (7)	−0.0743 (6)	−0.2807 (5)	0.186 (6)*
C312	−0.1397 (8)	−0.0449 (6)	−0.3740 (5)	0.145 (2)
H31E	−0.0445 (8)	−0.0105 (6)	−0.3777 (5)	0.186 (6)*
H31F	−0.1633 (8)	−0.1216 (6)	−0.3933 (5)	0.186 (6)*
C313	−0.2330 (8)	0.0001 (6)	−0.4301 (5)	0.157 (3)
H31G	−0.2119 (8)	0.0759 (6)	−0.4089 (5)	0.186 (6)*
H31H	−0.3283 (8)	−0.0365 (6)	−0.4275 (5)	0.186 (6)*
C314	−0.2346 (8)	−0.0035 (5)	−0.5189 (5)	0.144 (2)
H31I	−0.1393 (8)	0.0324 (5)	−0.5219 (5)	0.186 (6)*
H31J	−0.2578 (8)	−0.0792 (5)	−0.5408 (5)	0.186 (6)*
C315	−0.3294 (8)	0.0446 (6)	−0.5730 (5)	0.161 (3)
H31K	−0.3081 (8)	0.1193 (6)	−0.5492 (5)	0.186 (6)*
H31L	−0.4245 (8)	0.0069 (6)	−0.5707 (5)	0.186 (6)*
C316	−0.3324 (8)	0.0469 (5)	−0.6608 (5)	0.139 (2)
H31M	−0.3522 (8)	−0.0274 (5)	−0.6850 (5)	0.186 (6)*
H31N	−0.2385 (8)	0.0866 (5)	−0.6638 (5)	0.186 (6)*
C317	−0.4337 (11)	0.0948 (8)	−0.7127 (6)	0.201 (4)
H31O	−0.5268 (11)	0.0545 (8)	−0.7087 (6)	0.186 (6)*
H31P	−0.4138 (11)	0.1684 (8)	−0.6871 (6)	0.186 (6)*
C318	−0.4441 (11)	0.1012 (7)	−0.7969 (6)	0.198 (4)
H31Q	−0.360 (4)	0.152 (5)	−0.8031 (6)	0.312 (19)*
H31R	−0.524 (5)	0.125 (7)	−0.8215 (13)	0.312 (19)*
H31S	−0.455 (9)	0.0308 (17)	−0.8238 (11)	0.312 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0438 (2)	0.0714 (3)	0.0595 (3)	0.0268 (2)	0.0123 (2)	0.0128 (2)
O11	0.0576 (14)	0.077 (2)	0.083 (2)	0.0239 (13)	0.0014 (12)	−0.0027 (14)
O12	0.060 (2)	0.070 (2)	0.088 (2)	0.0222 (12)	0.0107 (13)	0.0037 (13)
C11	0.061 (2)	0.064 (2)	0.063 (2)	0.015 (2)	0.016 (2)	0.008 (2)
C12	0.081 (3)	0.076 (3)	0.089 (3)	0.006 (2)	−0.001 (2)	0.002 (2)
C13	0.118 (4)	0.102 (4)	0.099 (4)	0.001 (3)	0.000 (3)	−0.007 (3)
C14	0.102 (4)	0.107 (4)	0.087 (3)	0.016 (3)	0.019 (3)	0.007 (3)
C15	0.175 (7)	0.132 (5)	0.103 (4)	0.008 (5)	0.017 (4)	0.005 (4)
C16	0.146 (5)	0.118 (4)	0.102 (4)	0.023 (4)	0.033 (4)	0.014 (3)
C17	0.194 (7)	0.153 (6)	0.096 (4)	0.035 (5)	0.014 (5)	0.003 (4)
C18	0.200 (7)	0.150 (6)	0.101 (4)	0.053 (5)	0.043 (5)	0.022 (4)
C19	0.261 (10)	0.215 (9)	0.104 (5)	0.088 (8)	0.030 (6)	0.036 (6)
C110	0.336 (15)	0.272 (12)	0.152 (8)	0.122 (11)	0.082 (9)	0.066 (8)
O21	0.0535 (13)	0.101 (2)	0.0644 (14)	0.0353 (13)	0.0203 (11)	0.0233 (13)
O22	0.066 (2)	0.115 (2)	0.072 (2)	0.0473 (15)	0.0284 (13)	0.0356 (15)
C21	0.050 (2)	0.088 (3)	0.057 (2)	0.020 (2)	0.013 (2)	0.014 (2)
C22	0.073 (3)	0.190 (5)	0.076 (3)	0.054 (3)	0.030 (2)	0.055 (3)
C23	0.081 (3)	0.115 (3)	0.063 (2)	0.037 (2)	0.021 (2)	0.026 (2)
C24	0.090 (3)	0.139 (4)	0.066 (3)	0.038 (3)	0.025 (2)	0.032 (3)
C25	0.110 (4)	0.164 (5)	0.072 (3)	0.055 (4)	0.028 (3)	0.043 (3)
C26	0.115 (4)	0.130 (4)	0.069 (3)	0.036 (3)	0.025 (3)	0.031 (3)
C27	0.141 (5)	0.205 (7)	0.083 (3)	0.077 (5)	0.032 (3)	0.059 (4)
C28	0.164 (6)	0.152 (5)	0.075 (3)	0.044 (4)	0.025 (3)	0.035 (3)
C29	0.208 (8)	0.318 (11)	0.095 (4)	0.128 (8)	0.037 (5)	0.085 (6)
C210	0.296 (12)	0.217 (8)	0.086 (4)	0.074 (8)	0.017 (6)	0.044 (5)
N3	0.049 (2)	0.083 (2)	0.062 (2)	0.0293 (15)	0.0163 (13)	0.021 (2)
C31	0.059 (2)	0.082 (3)	0.067 (2)	0.038 (2)	0.020 (2)	0.019 (2)
C32	0.068 (3)	0.098 (3)	0.074 (2)	0.052 (2)	0.026 (2)	0.028 (2)
C33	0.058 (2)	0.124 (4)	0.097 (3)	0.054 (3)	0.024 (2)	0.040 (3)
C34	0.049 (2)	0.116 (4)	0.099 (3)	0.033 (2)	0.008 (2)	0.025 (3)
C35	0.051 (2)	0.094 (3)	0.079 (3)	0.027 (2)	0.008 (2)	0.016 (2)
C36	0.091 (3)	0.109 (4)	0.098 (3)	0.065 (3)	0.035 (3)	0.035 (3)
O31	0.118 (3)	0.139 (3)	0.179 (4)	0.089 (2)	0.067 (3)	0.030 (3)
O32	0.103 (2)	0.089 (2)	0.110 (2)	0.056 (2)	0.037 (2)	0.017 (2)
C37	0.144 (5)	0.094 (4)	0.156 (5)	0.068 (4)	0.049 (4)	0.021 (3)
C38	0.164 (6)	0.084 (4)	0.172 (6)	0.049 (4)	0.071 (5)	0.026 (4)
C39	0.135 (5)	0.122 (5)	0.141 (5)	0.040 (4)	0.058 (4)	0.006 (4)
C310	0.175 (7)	0.123 (5)	0.158 (6)	0.059 (5)	0.070 (5)	0.011 (4)
C311	0.119 (5)	0.163 (6)	0.147 (6)	0.037 (5)	0.018 (4)	−0.018 (5)
C312	0.152 (6)	0.127 (5)	0.149 (6)	0.035 (5)	0.037 (5)	−0.004 (4)
C313	0.124 (5)	0.175 (7)	0.153 (7)	0.039 (5)	0.016 (5)	−0.023 (5)
C314	0.134 (6)	0.124 (5)	0.157 (6)	0.024 (4)	0.031 (5)	−0.009 (5)
C315	0.137 (6)	0.159 (6)	0.170 (7)	0.044 (5)	0.017 (6)	−0.022 (6)
C316	0.136 (6)	0.119 (5)	0.155 (6)	0.026 (4)	0.042 (5)	−0.001 (5)
C317	0.222 (10)	0.186 (8)	0.196 (9)	0.093 (8)	0.029 (8)	−0.010 (7)
C318	0.308 (12)	0.186 (8)	0.143 (7)	0.093 (8)	0.112 (8)	0.037 (6)

Geometric parameters (Å, º)

Cu—O12^i	1.950 (3)	C26—C27	1.470 (7)
Cu—O11	1.960 (3)	C27—C28	1.436 (6)
Cu—O22^i	1.962 (2)	C28—C29	1.466 (8)
Cu—O21	1.966 (2)	C29—C210	1.360 (8)
Cu—N3	2.183 (3)	N3—C31	1.323 (4)
Cu—Cu^i	2.6146 (10)	N3—C35	1.329 (4)
O11—C11	1.242 (4)	C31—C32	1.401 (5)
O12—C11	1.254 (4)	C32—C33	1.362 (6)
O12—Cu^i	1.950 (3)	C32—C36	1.466 (6)
C11—C12	1.504 (5)	C33—C34	1.356 (6)
C12—C13	1.495 (6)	C34—C35	1.366 (5)
C13—C14	1.513 (7)	C36—O31	1.206 (5)
C14—C15	1.476 (7)	C36—O32	1.321 (5)
C15—C16	1.437 (7)	O32—C37	1.457 (6)
C16—C17	1.465 (8)	C37—C38	1.480 (8)
C17—C18	1.408 (8)	C38—C39	1.513 (8)
C18—C19	1.437 (9)	C39—C310	1.482 (7)
C19—C110	1.358 (9)	C310—C311	1.458 (9)
O21—C21	1.252 (4)	C311—C312	1.501 (8)
O22—C21	1.247 (4)	C312—C313	1.429 (9)
O22—Cu^i	1.962 (2)	C313—C314	1.486 (8)
C21—C22	1.493 (5)	C314—C315	1.449 (9)
C22—C23	1.456 (5)	C315—C316	1.470 (8)
C23—C24	1.482 (5)	C316—C317	1.473 (10)
C24—C25	1.451 (6)	C317—C318	1.399 (9)
C25—C26	1.456 (6)
O12^i—Cu—O11	168.03 (9)	C23—C22—C21	118.6 (3)
O12^i—Cu—O22^i	90.31 (12)	C22—C23—C24	117.3 (4)
O11—Cu—O22^i	89.42 (12)	C25—C24—C23	118.8 (4)
O12^i—Cu—O21	88.59 (11)	C24—C25—C26	120.5 (5)
O11—Cu—O21	89.27 (11)	C25—C26—C27	119.6 (5)
O22^i—Cu—O21	168.33 (9)	C28—C27—C26	121.5 (6)
O12^i—Cu—N3	96.76 (11)	C27—C28—C29	120.5 (7)
O11—Cu—N3	95.15 (11)	C210—C29—C28	123.0 (8)
O22^i—Cu—N3	97.00 (10)	C31—N3—C35	119.0 (3)
O21—Cu—N3	94.66 (10)	C31—N3—Cu	120.2 (2)
O12^i—Cu—Cu^i	85.15 (8)	C35—N3—Cu	119.7 (3)
O11—Cu—Cu^i	82.90 (8)	N3—C31—C32	121.2 (4)
O22^i—Cu—Cu^i	85.18 (7)	C33—C32—C31	118.3 (4)
O21—Cu—Cu^i	83.16 (7)	C33—C32—C36	120.2 (4)
N3—Cu—Cu^i	177.08 (8)	C31—C32—C36	121.4 (4)
C11—O11—Cu	125.0 (2)	C34—C33—C32	120.0 (3)
C11—O12—Cu^i	122.5 (2)	C33—C34—C35	118.7 (4)
O11—C11—O12	124.4 (3)	N3—C35—C34	122.6 (4)
O11—C11—C12	118.1 (3)	O31—C36—O32	123.2 (5)
O12—C11—C12	117.5 (3)	O31—C36—C32	123.7 (5)
C13—C12—C11	114.9 (4)	O32—C36—C32	113.1 (4)
C12—C13—C14	114.3 (5)	C36—O32—C37	116.1 (4)
C15—C14—C13	114.5 (5)	O32—C37—C38	107.7 (4)
C16—C15—C14	120.2 (6)	C37—C38—C39	116.2 (5)
C15—C16—C17	118.5 (6)	C310—C39—C38	115.8 (6)
C18—C17—C16	123.5 (7)	C311—C310—C39	116.3 (6)
C17—C18—C19	121.6 (8)	C310—C311—C312	119.5 (7)
C110—C19—C18	126.0 (10)	C313—C312—C311	118.1 (7)
C21—O21—Cu	124.4 (2)	C312—C313—C314	120.0 (7)
C21—O22—Cu^i	122.3 (2)	C315—C314—C313	118.0 (7)
O22—C21—O21	124.9 (3)	C314—C315—C316	120.5 (7)
O22—C21—C22	118.4 (3)	C315—C316—C317	117.7 (7)
O21—C21—C22	116.7 (3)	C318—C317—C316	122.0 (9)

Symmetry code: (i) −x, −y+1, −z.