(12,17-Dieth-oxy-carbonyl-11,18-dimethyl-2,3:6,7-dibutano-corrphycenato)copper(II)-12,17-dieth-oxy-carbonyl-11,18-dimethyl-2:3,6:7-dibutano-corrphycene (3/97).

The corrphycene mol-ecule of the title compound, [Cu(C(36)H(36)N(4)O(4))](0.034).0.966C(36)H(38)N(4)O(4), has an essentially planar macrocyclic framwork with a slightly distorted trapezoidal N(4) core; the r.m.s. deviation of the peripheral 20 C atoms and four N atoms is 0.054 (3) Å. The surface area within the N(4)-coordinating core (8.358 Å(2)) is significantly smaller than that (8.503 Å(2)) of the corresponding free-base porphyrin. Two intra-molecular N-H⋯N hydrogen bonds are observed. Detailed structure analysis clarified that the co-crystallization of the free-base corrphycene together with a quite minor component (ca 3%) of corrphycenato-Cu(II) occurred in the recrystallization process.

Related literature

For the first synthesis of free-base corrphycene, see: Sessler et al. (1994 ▶). For some related metal corrphycene compounds, see: Sessler et al. (2000 ▶). For related porphyrin analogues such as porphycene, N-confused porphyrins, corroles etc. see: Chmielewski et al. (1994 ▶); Erben et al. (2000 ▶); Furuta et al. (1994 ▶); Gross et al. (2000 ▶). For structures of five-coordinated halide-ligated iron(III) porphyrin, porphycene and corrphycene complexes, see: Ohgo, Neya, Funasaki et al. (2001 ▶); Ohgo, Neya, Ikeue et al. (2001 ▶); Ohgo et al. (2002 ▶). For the synthesis of the starting materials, see: Neya et al. (1998 ▶); Hombrecher & Horter (1992 ▶). For the structure of the corresponding porphyrin free-base, see: Lauher & Ibers (1973 ▶).

Experimental

Crystal data

[Cu(C36H36N4O4)]0.034·0.966C36H38N4O4

M = 592.80

Triclinic,

a = 8.8759 (5) Å

b = 13.2493 (8) Å

c = 13.2891 (7) Å

α = 108.496 (2)°

β = 90.708 (2)°

γ = 98.142 (2)°

V = 1464.4 (1) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.31 × 0.25 × 0.10 mm

Data collection

Rigaku RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.788, T max = 0.923

14734 measured reflections

6677 independent reflections

3707 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.072

wR(F 2) = 0.246

S = 1.15

6677 reflections

412 parameters

H-atom parameters constrained

Δρmax = 1.69 e Å−3

Δρmin = −0.58 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-2000; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052214/is5019sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052214/is5019Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811052214/is5019Isup4.cdx

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

[Cu(C36H36N4O4)]0.034·0.966C36H38N4O4	Z = 2
Mr = 592.80	F(000) = 630.8
Triclinic, P1	Dx = 1.344 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8759 (5) Å	Cell parameters from 9696 reflections
b = 13.2493 (8) Å	θ = 3.0–27.5°
c = 13.2891 (7) Å	µ = 0.11 mm−1
α = 108.496 (2)°	T = 296 K
β = 90.708 (2)°	Block, purple
γ = 98.142 (2)°	0.31 × 0.25 × 0.10 mm
V = 1464.4 (1) Å3

Rigaku RAPID diffractometer	6677 independent reflections
Radiation source: fine-focus sealed tube	3707 reflections with I > 2σ(I)
graphite	Rint = 0.044
Detector resolution: 10 pixels mm-1	θmax = 27.5°, θmin = 3.0°
ω–scan	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
Tmin = 0.788, Tmax = 0.923	l = −17→17
14734 measured reflections

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.246	H-atom parameters constrained
S = 1.15	w = 1/[σ2(Fo2) + (0.1301P)2] where P = (Fo2 + 2Fc2)/3
6677 reflections	(Δ/σ)max < 0.001
412 parameters	Δρmax = 1.69 e Å−3
0 restraints	Δρmin = −0.58 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	Occ. (<1)
Cu	0.0199 (11)	−0.0170 (8)	0.6898 (8)	0.023 (4)*	0.0342 (17)
H1	−0.0579	−0.0371	0.7551	0.066 (14)*	0.9658 (17)
H3	0.1166	0.0014	0.6183	0.090 (18)*	0.9658 (17)
O1	0.5049 (3)	0.24582 (18)	0.5059 (2)	0.0473 (6)
O2	0.5345 (2)	0.10428 (16)	0.36605 (17)	0.0342 (5)
O3	0.2084 (4)	0.46877 (19)	0.9008 (2)	0.0608 (8)
O4	0.2074 (3)	0.45953 (18)	1.06523 (19)	0.0498 (7)
N1	−0.1223 (3)	−0.0788 (2)	0.7810 (2)	0.0307 (6)
N2	−0.0363 (3)	−0.16368 (19)	0.5921 (2)	0.0301 (6)
N3	0.1672 (3)	0.00372 (19)	0.5646 (2)	0.0285 (5)
N4	0.0455 (3)	0.12471 (19)	0.82171 (19)	0.0294 (6)
C1	−0.1757 (3)	−0.0399 (2)	0.8790 (2)	0.0300 (6)
C2	−0.2824 (3)	−0.1250 (2)	0.8933 (2)	0.0309 (7)
C3	−0.2908 (3)	−0.2135 (2)	0.8016 (2)	0.0288 (6)
C4	−0.1868 (3)	−0.1822 (2)	0.7303 (2)	0.0293 (6)
C5	−0.1381 (3)	−0.2301 (2)	0.6262 (2)	0.0278 (6)
C6	−0.1705 (3)	−0.3366 (2)	0.5470 (2)	0.0299 (6)
C7	−0.0859 (4)	−0.3315 (2)	0.4628 (2)	0.0316 (7)
C8	−0.0022 (3)	−0.2228 (2)	0.4921 (2)	0.0295 (6)
C9	0.0992 (3)	−0.1786 (2)	0.4340 (2)	0.0306 (7)
H9	0.1155	−0.2226	0.3663	0.037*
C10	0.1798 (3)	−0.0737 (2)	0.4675 (2)	0.0301 (6)
C11	0.2930 (3)	−0.0293 (2)	0.4121 (2)	0.0295 (6)
C12	0.3471 (3)	0.0748 (2)	0.4781 (2)	0.0291 (6)
C13	0.2670 (3)	0.0956 (2)	0.5738 (2)	0.0276 (6)
C14	0.2903 (3)	0.1949 (2)	0.6577 (2)	0.0311 (7)
H14	0.3664	0.2425	0.6418	0.037*
C15	0.2366 (3)	0.2440 (2)	0.7553 (2)	0.0312 (7)
H15	0.2841	0.3151	0.7830	0.037*
C16	0.1310 (3)	0.2192 (2)	0.8265 (2)	0.0300 (6)
C17	0.1087 (3)	0.3021 (2)	0.9271 (2)	0.0310 (7)
C18	0.0115 (3)	0.2540 (2)	0.9838 (2)	0.0300 (6)
C19	−0.0280 (3)	0.1427 (2)	0.9157 (2)	0.0299 (6)
C20	−0.1292 (3)	0.0661 (2)	0.9425 (2)	0.0301 (6)
H20	−0.1691	0.0880	1.0090	0.036*
C21	−0.3712 (4)	−0.1235 (3)	0.9887 (3)	0.0351 (7)
H21A	−0.4455	−0.0750	0.9958	0.042*
H21B	−0.3024	−0.0962	1.0519	0.042*
C22	−0.4532 (4)	−0.2350 (3)	0.9811 (3)	0.0443 (8)
H22A	−0.3830	−0.2734	1.0054	0.053*
H22B	−0.5367	−0.2272	1.0280	0.053*
C23	−0.5151 (4)	−0.3006 (3)	0.8697 (3)	0.0419 (8)
H23A	−0.5915	−0.2650	0.8478	0.050*
H23B	−0.5650	−0.3705	0.8701	0.050*
C24	−0.3943 (4)	−0.3170 (2)	0.7888 (3)	0.0348 (7)
H24A	−0.3347	−0.3699	0.7978	0.042*
H24B	−0.4431	−0.3445	0.7177	0.042*
C25	−0.2743 (4)	−0.4357 (2)	0.5472 (3)	0.0379 (7)
H25A	−0.3795	−0.4250	0.5411	0.045*
H25B	−0.2580	−0.4490	0.6139	0.045*
C26	−0.2449 (4)	−0.5331 (3)	0.4549 (3)	0.0474 (9)
H26A	−0.1542	−0.5583	0.4730	0.057*
H26B	−0.3301	−0.5908	0.4444	0.057*
C27	−0.2240 (5)	−0.5075 (3)	0.3518 (3)	0.0485 (9)
H27A	−0.2122	−0.5727	0.2950	0.058*
H27B	−0.3142	−0.4817	0.3336	0.058*
C28	−0.0856 (4)	−0.4230 (2)	0.3618 (3)	0.0354 (7)
H28A	0.0065	−0.4547	0.3616	0.042*
H28B	−0.0869	−0.3966	0.3016	0.042*
C29	0.3370 (4)	−0.0890 (3)	0.3028 (2)	0.0345 (7)
H29A	0.3439	−0.0425	0.2600	0.052*
H29B	0.2612	−0.1509	0.2707	0.052*
H29C	0.4339	−0.1118	0.3080	0.052*
C30	0.4677 (3)	0.1519 (2)	0.4546 (2)	0.0303 (6)
C31	0.6546 (4)	0.1722 (2)	0.3344 (2)	0.0335 (7)
H31A	0.7376	0.1991	0.3888	0.040*
H31B	0.6159	0.2331	0.3235	0.040*
C32	0.7086 (4)	0.1028 (3)	0.2324 (3)	0.0411 (8)
H32A	0.7390	0.0401	0.2431	0.062*
H32B	0.7938	0.1429	0.2111	0.062*
H32C	0.6274	0.0813	0.1780	0.062*
C33	0.1799 (4)	0.4170 (2)	0.9603 (3)	0.0366 (7)
C34	0.2742 (6)	0.5728 (3)	1.1055 (3)	0.0632 (12)
H34A	0.3510	0.5880	1.0588	0.076*
H34B	0.1958	0.6171	1.1067	0.076*
C35	0.3420 (6)	0.5982 (3)	1.2102 (4)	0.0796 (16)
H35A	0.2674	0.5788	1.2552	0.119*
H35B	0.3787	0.6741	1.2381	0.119*
H35C	0.4256	0.5589	1.2079	0.119*
C36	−0.0458 (4)	0.3008 (2)	1.0907 (3)	0.0354 (7)
H36A	0.0165	0.2874	1.1432	0.053*
H36B	−0.1493	0.2683	1.0917	0.053*
H36C	−0.0416	0.3771	1.1063	0.053*

	U11	U22	U33	U12	U13	U23
O1	0.0499 (14)	0.0317 (12)	0.0501 (15)	−0.0069 (11)	0.0205 (12)	0.0036 (11)
O2	0.0380 (12)	0.0289 (11)	0.0339 (12)	−0.0020 (9)	0.0101 (9)	0.0104 (9)
O3	0.109 (2)	0.0311 (13)	0.0394 (15)	−0.0042 (14)	0.0083 (15)	0.0134 (11)
O4	0.0808 (19)	0.0276 (11)	0.0339 (14)	−0.0099 (12)	−0.0029 (12)	0.0081 (10)
N1	0.0306 (13)	0.0276 (12)	0.0311 (14)	−0.0015 (11)	0.0012 (11)	0.0081 (11)
N2	0.0295 (13)	0.0264 (12)	0.0327 (14)	−0.0010 (11)	0.0008 (10)	0.0095 (10)
N3	0.0313 (13)	0.0253 (12)	0.0275 (13)	0.0016 (11)	0.0036 (10)	0.0077 (10)
N4	0.0296 (13)	0.0288 (13)	0.0291 (14)	0.0026 (11)	0.0027 (10)	0.0090 (10)
C1	0.0307 (15)	0.0285 (15)	0.0310 (16)	0.0009 (13)	0.0029 (12)	0.0116 (12)
C2	0.0319 (15)	0.0304 (15)	0.0301 (16)	0.0045 (13)	0.0031 (12)	0.0095 (12)
C3	0.0258 (14)	0.0254 (14)	0.0360 (17)	0.0005 (12)	0.0016 (12)	0.0124 (12)
C4	0.0266 (15)	0.0275 (14)	0.0330 (17)	0.0009 (12)	−0.0020 (12)	0.0102 (12)
C5	0.0246 (14)	0.0239 (14)	0.0353 (17)	0.0008 (12)	0.0015 (12)	0.0113 (12)
C6	0.0279 (15)	0.0263 (14)	0.0347 (17)	0.0023 (12)	0.0003 (12)	0.0096 (12)
C7	0.0349 (16)	0.0278 (15)	0.0306 (17)	0.0028 (13)	0.0001 (12)	0.0081 (12)
C8	0.0264 (14)	0.0288 (14)	0.0318 (16)	−0.0001 (12)	0.0027 (12)	0.0096 (12)
C9	0.0327 (16)	0.0288 (15)	0.0273 (16)	0.0013 (13)	−0.0007 (12)	0.0066 (12)
C10	0.0285 (15)	0.0299 (15)	0.0321 (16)	0.0036 (13)	0.0011 (12)	0.0105 (12)
C11	0.0306 (15)	0.0273 (14)	0.0304 (16)	0.0006 (13)	0.0010 (12)	0.0109 (12)
C12	0.0281 (15)	0.0285 (15)	0.0318 (16)	0.0035 (13)	0.0015 (12)	0.0117 (12)
C13	0.0256 (14)	0.0291 (15)	0.0303 (16)	0.0015 (12)	0.0046 (11)	0.0136 (12)
C14	0.0316 (15)	0.0288 (15)	0.0328 (17)	−0.0016 (13)	0.0022 (12)	0.0124 (13)
C15	0.0321 (16)	0.0270 (14)	0.0321 (17)	−0.0025 (13)	0.0002 (12)	0.0090 (12)
C16	0.0321 (16)	0.0253 (14)	0.0319 (16)	−0.0007 (13)	0.0020 (12)	0.0103 (12)
C17	0.0333 (16)	0.0235 (14)	0.0344 (17)	−0.0013 (13)	−0.0011 (13)	0.0094 (12)
C18	0.0304 (15)	0.0304 (15)	0.0287 (16)	0.0003 (13)	0.0015 (12)	0.0106 (12)
C19	0.0299 (15)	0.0308 (15)	0.0288 (16)	0.0032 (13)	0.0016 (12)	0.0098 (12)
C20	0.0307 (15)	0.0278 (15)	0.0301 (16)	0.0003 (13)	0.0025 (12)	0.0087 (12)
C21	0.0390 (17)	0.0330 (16)	0.0344 (17)	0.0068 (14)	0.0044 (13)	0.0119 (13)
C22	0.0430 (19)	0.0433 (19)	0.045 (2)	−0.0026 (16)	0.0066 (16)	0.0165 (16)
C23	0.046 (2)	0.0388 (18)	0.042 (2)	0.0018 (16)	0.0080 (15)	0.0163 (15)
C24	0.0376 (17)	0.0303 (16)	0.0367 (18)	0.0006 (14)	0.0011 (13)	0.0132 (13)
C25	0.0377 (17)	0.0311 (16)	0.0420 (19)	−0.0014 (14)	0.0079 (14)	0.0103 (14)
C26	0.050 (2)	0.0319 (17)	0.050 (2)	−0.0057 (16)	0.0081 (17)	0.0044 (15)
C27	0.056 (2)	0.0370 (18)	0.042 (2)	−0.0061 (17)	0.0051 (17)	0.0036 (15)
C28	0.0391 (17)	0.0273 (15)	0.0368 (18)	0.0016 (13)	0.0012 (13)	0.0078 (13)
C29	0.0354 (16)	0.0348 (16)	0.0324 (17)	0.0022 (14)	0.0048 (13)	0.0109 (13)
C30	0.0288 (15)	0.0292 (15)	0.0323 (17)	−0.0022 (13)	0.0024 (12)	0.0117 (13)
C31	0.0320 (16)	0.0337 (16)	0.0344 (17)	−0.0034 (14)	0.0035 (13)	0.0142 (13)
C32	0.048 (2)	0.0457 (19)	0.0343 (18)	0.0087 (17)	0.0110 (15)	0.0183 (15)
C33	0.0456 (19)	0.0280 (15)	0.0357 (18)	0.0050 (14)	0.0023 (14)	0.0101 (13)
C34	0.111 (4)	0.0269 (17)	0.044 (2)	−0.013 (2)	−0.007 (2)	0.0112 (16)
C35	0.086 (3)	0.034 (2)	0.103 (4)	−0.006 (2)	−0.032 (3)	0.007 (2)
C36	0.0399 (17)	0.0287 (15)	0.0365 (18)	0.0033 (14)	0.0080 (14)	0.0099 (13)

Cu—N2	1.954 (10)	C17—C18	1.373 (4)
Cu—N1	2.026 (10)	C17—C33	1.485 (4)
Cu—N4	2.105 (10)	C18—C19	1.453 (4)
Cu—N3	2.189 (10)	C18—C36	1.487 (4)
O1—C30	1.209 (4)	C19—C20	1.394 (4)
O2—C30	1.337 (4)	C20—H20	0.9300
O2—C31	1.450 (4)	C21—C22	1.523 (5)
O3—C33	1.208 (4)	C21—H21A	0.9700
O4—C33	1.332 (4)	C21—H21B	0.9700
O4—C34	1.456 (4)	C22—C23	1.510 (5)
N1—C4	1.357 (4)	C22—H22A	0.9700
N1—C1	1.358 (4)	C22—H22B	0.9700
N1—H1	0.886	C23—C24	1.516 (5)
N2—C5	1.355 (4)	C23—H23A	0.9700
N2—C8	1.374 (4)	C23—H23B	0.9700
N3—C13	1.371 (4)	C24—H24A	0.9700
N3—C10	1.388 (4)	C24—H24B	0.9700
N3—H3	0.854	C25—C26	1.528 (4)
N4—C16	1.351 (4)	C25—H25A	0.9700
N4—C19	1.385 (4)	C25—H25B	0.9700
C1—C20	1.390 (4)	C26—C27	1.519 (5)
C1—C2	1.429 (4)	C26—H26A	0.9700
C2—C3	1.390 (4)	C26—H26B	0.9700
C2—C21	1.497 (4)	C27—C28	1.515 (5)
C3—C4	1.444 (4)	C27—H27A	0.9700
C3—C24	1.498 (4)	C27—H27B	0.9700
C4—C5	1.427 (4)	C28—H28A	0.9700
C5—C6	1.456 (4)	C28—H28B	0.9700
C6—C7	1.369 (4)	C29—H29A	0.9600
C6—C25	1.494 (4)	C29—H29B	0.9600
C7—C8	1.453 (4)	C29—H29C	0.9600
C7—C28	1.497 (4)	C31—C32	1.504 (4)
C8—C9	1.379 (4)	C31—H31A	0.9700
C9—C10	1.400 (4)	C31—H31B	0.9700
C9—H9	0.9300	C32—H32A	0.9600
C10—C11	1.423 (4)	C32—H32B	0.9600
C11—C12	1.392 (4)	C32—H32C	0.9600
C11—C29	1.503 (4)	C34—C35	1.427 (6)
C12—C13	1.433 (4)	C34—H34A	0.9700
C12—C30	1.479 (4)	C34—H34B	0.9700
C13—C14	1.416 (4)	C35—H35A	0.9600
C14—C15	1.379 (4)	C35—H35B	0.9600
C14—H14	0.9300	C35—H35C	0.9600
C15—C16	1.419 (4)	C36—H36A	0.9600
C15—H15	0.9300	C36—H36B	0.9600
C16—C17	1.473 (4)	C36—H36C	0.9600
N2—Cu—N1	80.7 (4)	C22—C21—H21B	109.2
N2—Cu—N4	165.0 (6)	H21A—C21—H21B	107.9
N1—Cu—N4	84.3 (4)	C23—C22—C21	112.9 (3)
N2—Cu—N3	83.9 (4)	C23—C22—H22A	109.0
N1—Cu—N3	164.4 (5)	C21—C22—H22A	109.0
N4—Cu—N3	110.9 (4)	C23—C22—H22B	109.0
C30—O2—C31	116.0 (2)	C21—C22—H22B	109.0
C33—O4—C34	116.5 (3)	H22A—C22—H22B	107.8
C4—N1—C1	111.7 (3)	C22—C23—C24	113.7 (3)
C4—N1—Cu	112.8 (3)	C22—C23—H23A	108.8
C1—N1—Cu	135.4 (3)	C24—C23—H23A	108.8
C4—N1—H1	127.1	C22—C23—H23B	108.8
C5—N2—C8	106.3 (2)	C24—C23—H23B	108.8
C5—N2—Cu	116.1 (3)	H23A—C23—H23B	107.7
C8—N2—Cu	137.5 (4)	C3—C24—C23	111.0 (3)
C13—N3—C10	109.8 (2)	C3—C24—H24A	109.4
C13—N3—Cu	124.0 (3)	C23—C24—H24A	109.4
C10—N3—Cu	126.1 (3)	C3—C24—H24B	109.4
C13—N3—H3	117.9	C23—C24—H24B	109.4
C10—N3—H3	132.0	H24A—C24—H24B	108.0
C16—N4—C19	106.7 (2)	C6—C25—C26	110.7 (3)
C16—N4—Cu	125.3 (3)	C6—C25—H25A	109.5
C19—N4—Cu	127.9 (3)	C26—C25—H25A	109.5
N1—C1—C20	121.0 (3)	C6—C25—H25B	109.5
N1—C1—C2	106.8 (3)	C26—C25—H25B	109.5
C20—C1—C2	132.2 (3)	H25A—C25—H25B	108.1
C3—C2—C1	107.9 (3)	C27—C26—C25	112.6 (3)
C3—C2—C21	124.3 (3)	C27—C26—H26A	109.1
C1—C2—C21	127.8 (3)	C25—C26—H26A	109.1
C2—C3—C4	106.8 (3)	C27—C26—H26B	109.1
C2—C3—C24	122.2 (3)	C25—C26—H26B	109.1
C4—C3—C24	131.0 (3)	H26A—C26—H26B	107.8
N1—C4—C5	115.8 (3)	C28—C27—C26	111.2 (3)
N1—C4—C3	106.8 (3)	C28—C27—H27A	109.4
C5—C4—C3	137.4 (3)	C26—C27—H27A	109.4
N2—C5—C4	114.4 (3)	C28—C27—H27B	109.4
N2—C5—C6	111.0 (3)	C26—C27—H27B	109.4
C4—C5—C6	134.5 (3)	H27A—C27—H27B	108.0
C7—C6—C5	105.9 (3)	C7—C28—C27	109.9 (3)
C7—C6—C25	123.0 (3)	C7—C28—H28A	109.7
C5—C6—C25	131.1 (3)	C27—C28—H28A	109.7
C6—C7—C8	106.6 (3)	C7—C28—H28B	109.7
C6—C7—C28	124.5 (3)	C27—C28—H28B	109.7
C8—C7—C28	128.8 (3)	H28A—C28—H28B	108.2
N2—C8—C9	121.3 (3)	C11—C29—H29A	109.5
N2—C8—C7	110.1 (3)	C11—C29—H29B	109.5
C9—C8—C7	128.6 (3)	H29A—C29—H29B	109.5
C8—C9—C10	126.1 (3)	C11—C29—H29C	109.5
C8—C9—H9	117.0	H29A—C29—H29C	109.5
C10—C9—H9	117.0	H29B—C29—H29C	109.5
N3—C10—C9	125.0 (3)	O1—C30—O2	122.4 (3)
N3—C10—C11	108.1 (3)	O1—C30—C12	126.7 (3)
C9—C10—C11	126.9 (3)	O2—C30—C12	110.9 (2)
C12—C11—C10	106.5 (3)	O2—C31—C32	106.4 (3)
C12—C11—C29	129.9 (3)	O2—C31—H31A	110.4
C10—C11—C29	123.6 (3)	C32—C31—H31A	110.4
C11—C12—C13	108.8 (3)	O2—C31—H31B	110.4
C11—C12—C30	126.1 (3)	C32—C31—H31B	110.4
C13—C12—C30	125.1 (3)	H31A—C31—H31B	108.6
N3—C13—C14	129.2 (3)	C31—C32—H32A	109.5
N3—C13—C12	106.8 (2)	C31—C32—H32B	109.5
C14—C13—C12	124.0 (3)	H32A—C32—H32B	109.5
C15—C14—C13	140.4 (3)	C31—C32—H32C	109.5
C15—C14—H14	109.8	H32A—C32—H32C	109.5
C13—C14—H14	109.8	H32B—C32—H32C	109.5
C14—C15—C16	139.4 (3)	O3—C33—O4	122.4 (3)
C14—C15—H15	110.3	O3—C33—C17	125.0 (3)
C16—C15—H15	110.3	O4—C33—C17	112.6 (3)
N4—C16—C15	130.2 (3)	C35—C34—O4	110.2 (3)
N4—C16—C17	109.5 (3)	C35—C34—H34A	109.6
C15—C16—C17	120.2 (3)	O4—C34—H34A	109.6
C18—C17—C16	107.7 (3)	C35—C34—H34B	109.6
C18—C17—C33	126.6 (3)	O4—C34—H34B	109.6
C16—C17—C33	125.6 (3)	H34A—C34—H34B	108.1
C17—C18—C19	104.9 (3)	C34—C35—H35A	109.5
C17—C18—C36	129.6 (3)	C34—C35—H35B	109.5
C19—C18—C36	125.5 (3)	H35A—C35—H35B	109.5
N4—C19—C20	125.4 (3)	C34—C35—H35C	109.5
N4—C19—C18	111.2 (3)	H35A—C35—H35C	109.5
C20—C19—C18	123.5 (3)	H35B—C35—H35C	109.5
C1—C20—C19	125.9 (3)	C18—C36—H36A	109.5
C1—C20—H20	117.0	C18—C36—H36B	109.5
C19—C20—H20	117.0	H36A—C36—H36B	109.5
C2—C21—C22	112.1 (3)	C18—C36—H36C	109.5
C2—C21—H21A	109.2	H36A—C36—H36C	109.5
C22—C21—H21A	109.2	H36B—C36—H36C	109.5
C2—C21—H21B	109.2
N2—Cu—N1—C4	−2.9 (4)	C8—C9—C10—C11	175.0 (3)
N4—Cu—N1—C4	178.1 (2)	N3—C10—C11—C12	0.4 (3)
N3—Cu—N1—C4	−13.5 (19)	C9—C10—C11—C12	−176.7 (3)
N2—Cu—N1—C1	−178.4 (3)	N3—C10—C11—C29	−179.1 (3)
N4—Cu—N1—C1	2.6 (5)	C9—C10—C11—C29	3.8 (5)
N3—Cu—N1—C1	171.0 (16)	C10—C11—C12—C13	−0.6 (3)
N1—Cu—N2—C5	2.1 (4)	C29—C11—C12—C13	178.8 (3)
N4—Cu—N2—C5	6(2)	C10—C11—C12—C30	179.2 (3)
N3—Cu—N2—C5	179.3 (2)	C29—C11—C12—C30	−1.4 (5)
N1—Cu—N2—C8	−178.9 (3)	C10—N3—C13—C14	178.4 (3)
N4—Cu—N2—C8	−175.1 (17)	Cu—N3—C13—C14	−4.3 (5)
N3—Cu—N2—C8	−1.8 (6)	C10—N3—C13—C12	−0.4 (3)
N2—Cu—N3—C13	−175.6 (2)	Cu—N3—C13—C12	176.9 (3)
N1—Cu—N3—C13	−165.1 (17)	C11—C12—C13—N3	0.7 (3)
N4—Cu—N3—C13	2.6 (5)	C30—C12—C13—N3	−179.2 (2)
N2—Cu—N3—C10	1.2 (5)	C11—C12—C13—C14	−178.3 (3)
N1—Cu—N3—C10	12 (2)	C30—C12—C13—C14	1.9 (4)
N4—Cu—N3—C10	179.4 (3)	N3—C13—C14—C15	−0.4 (6)
N2—Cu—N4—C16	178.0 (18)	C12—C13—C14—C15	178.2 (3)
N1—Cu—N4—C16	−178.2 (2)	C13—C14—C15—C16	2.9 (7)
N3—Cu—N4—C16	5.1 (6)	C19—N4—C16—C15	175.0 (3)
N2—Cu—N4—C19	−7(2)	Cu—N4—C16—C15	−9.2 (5)
N1—Cu—N4—C19	−3.3 (5)	C19—N4—C16—C17	−1.4 (3)
N3—Cu—N4—C19	−180.0 (3)	Cu—N4—C16—C17	174.4 (3)
C4—N1—C1—C20	−177.3 (3)	C14—C15—C16—N4	4.7 (6)
Cu—N1—C1—C20	−1.7 (6)	C14—C15—C16—C17	−179.2 (3)
C4—N1—C1—C2	0.5 (3)	N4—C16—C17—C18	2.0 (3)
Cu—N1—C1—C2	176.0 (4)	C15—C16—C17—C18	−174.8 (3)
N1—C1—C2—C3	−0.5 (3)	N4—C16—C17—C33	−178.3 (3)
C20—C1—C2—C3	176.8 (3)	C15—C16—C17—C33	4.9 (4)
N1—C1—C2—C21	179.1 (3)	C16—C17—C18—C19	−1.7 (3)
C20—C1—C2—C21	−3.6 (5)	C33—C17—C18—C19	178.6 (3)
C1—C2—C3—C4	0.4 (3)	C16—C17—C18—C36	178.8 (3)
C21—C2—C3—C4	−179.2 (3)	C33—C17—C18—C36	−1.0 (5)
C1—C2—C3—C24	−179.1 (2)	C16—N4—C19—C20	179.2 (3)
C21—C2—C3—C24	1.3 (4)	Cu—N4—C19—C20	3.6 (5)
C1—N1—C4—C5	179.8 (2)	C16—N4—C19—C18	0.3 (3)
Cu—N1—C4—C5	3.2 (4)	Cu—N4—C19—C18	−175.3 (4)
C1—N1—C4—C3	−0.2 (3)	C17—C18—C19—N4	0.9 (3)
Cu—N1—C4—C3	−176.8 (3)	C36—C18—C19—N4	−179.5 (3)
C2—C3—C4—N1	−0.1 (3)	C17—C18—C19—C20	−178.0 (3)
C24—C3—C4—N1	179.3 (3)	C36—C18—C19—C20	1.6 (5)
C2—C3—C4—C5	179.9 (3)	N1—C1—C20—C19	0.4 (4)
C24—C3—C4—C5	−0.6 (5)	C2—C1—C20—C19	−176.7 (3)
C8—N2—C5—C4	179.7 (2)	N4—C19—C20—C1	−1.5 (5)
Cu—N2—C5—C4	−1.1 (4)	C18—C19—C20—C1	177.3 (3)
C8—N2—C5—C6	0.9 (3)	C3—C2—C21—C22	8.9 (4)
Cu—N2—C5—C6	−179.9 (3)	C1—C2—C21—C22	−170.6 (3)
N1—C4—C5—N2	−1.5 (4)	C2—C21—C22—C23	−37.3 (4)
C3—C4—C5—N2	178.5 (3)	C21—C22—C23—C24	58.1 (4)
N1—C4—C5—C6	177.0 (3)	C2—C3—C24—C23	16.9 (4)
C3—C4—C5—C6	−3.0 (6)	C4—C3—C24—C23	−162.5 (3)
N2—C5—C6—C7	−1.0 (3)	C22—C23—C24—C3	−45.9 (4)
C4—C5—C6—C7	−179.5 (3)	C7—C6—C25—C26	12.8 (4)
N2—C5—C6—C25	−179.5 (3)	C5—C6—C25—C26	−168.9 (3)
C4—C5—C6—C25	2.0 (5)	C6—C25—C26—C27	−43.0 (4)
C5—C6—C7—C8	0.6 (3)	C25—C26—C27—C28	62.6 (4)
C25—C6—C7—C8	179.3 (3)	C6—C7—C28—C27	17.6 (4)
C5—C6—C7—C28	−179.0 (3)	C8—C7—C28—C27	−162.0 (3)
C25—C6—C7—C28	−0.4 (5)	C26—C27—C28—C7	−46.9 (4)
C5—N2—C8—C9	179.9 (3)	C31—O2—C30—O1	−0.2 (4)
Cu—N2—C8—C9	1.0 (6)	C31—O2—C30—C12	179.7 (2)
C5—N2—C8—C7	−0.5 (3)	C11—C12—C30—O1	171.8 (3)
Cu—N2—C8—C7	−179.4 (4)	C13—C12—C30—O1	−8.4 (5)
C6—C7—C8—N2	−0.1 (3)	C11—C12—C30—O2	−8.2 (4)
C28—C7—C8—N2	179.5 (3)	C13—C12—C30—O2	171.6 (2)
C6—C7—C8—C9	179.4 (3)	C30—O2—C31—C32	−178.4 (2)
C28—C7—C8—C9	−1.0 (5)	C34—O4—C33—O3	0.1 (5)
N2—C8—C9—C10	1.3 (5)	C34—O4—C33—C17	−178.7 (3)
C7—C8—C9—C10	−178.3 (3)	C18—C17—C33—O3	−146.8 (4)
C13—N3—C10—C9	177.2 (3)	C16—C17—C33—O3	33.5 (5)
Cu—N3—C10—C9	0.0 (5)	C18—C17—C33—O4	31.9 (4)
C13—N3—C10—C11	0.0 (3)	C16—C17—C33—O4	−147.8 (3)
Cu—N3—C10—C11	−177.2 (3)	C33—O4—C34—C35	−161.3 (4)
C8—C9—C10—N3	−1.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N2	0.85	2.33	2.777 (4)	113
N1—H1···N4	0.89	2.11	2.774 (4)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N2	0.85	2.33	2.777 (4)	113
N1—H1⋯N4	0.89	2.11	2.774 (4)	131