(5-tert-Butyl­porphyrinato)copper(II), a nonplanar porphyrin with only one sterically demanding meso residue

The title compound, [Cu(C₂₄H₂₀N₄)], is a rare example of a porphyrin carrying only one substituent. Its crystal structure exhibits two molecules in the asymmetric unit. The bulky meso tert-butyl residue gives rise to a nonplanar macrocycle with significant ruf and sad distortions. As a result of the position of the substituent, the conformational effects are unsymmetric and to a significant extent localized in the affected quadrant of the macrocycle. In line with results for highly substituted nonplanar porphyrins, comparison with a free base and a nickel(II) complex shows that the conformation of the macro­cycle is modulated via additional metal effects.

S1. Comment

Porphyrins are conformationally very flexible compounds and, depending on steric strain, packing or metal effects, can have a wide range of different macrocycle conformations (Hoard, 1973; Scheidt & Lee, 1987; Senge, 2006). Especially highly substituted porphyrins, where peripheral peri interactions give rise to nonplanar conformations, have elicited wide interest (Senge, 2006). They exhibit photophysical and chemical properties quite distinct from planar porphyrins and they have served as models for the modulation of porphyrin cofactors in vivo through apoprotein–chromophore interactions (Barkigia et al., 1988, 2004; Senge, 1992). Nevertheless, these studies have almost exclusively addressed the structure and conformation of sterically `overloaded' porphyrins, e.g. dodeca-substituted porphyrins (Barkigia et al., 1990; Senge et al., 2000) where numerous peripheral steric interactions give rise to very nonplanar tetrapyrroles.

Much less attention has been given to sterically strained porphyrins with as few substituents as possible (Senge et al., 1996; Song, Jaquinod et al., 1998). The most simple and interesting systems would be porphyrins with only one sterically demanding residue and no other meso or β substituents. The first such structure, (II), was obtained from a low-yield condensation some time ago (Song, Jentzen et al., 1998). However, a general entry into these systems has only recently become available through new synthetic developments and now allows more detailed structural comparisons (Wiehe et al., 2002; Ryppa et al., 2005). Here we describe the conformation of the related copper(II) complex, (III), which carries one tert-butyl residue in a meso position of the porphyrin ring system. Only few structures of tert-butyl porphyrins have been reported (Ema et al., 1994; Senge et al., 1995; Song et al., 1996).

The stucture of the title compound, (III), is shown below (Fig. 1). Dimensions are available in the archived CIF. The compound was prepared via standard insertion of copper(II) into the corresponding free base, (I). The porphyrin crystallized with two crystallographically independent molecules in the unit cell. Fig. 1 shows a thermal ellipsoid plot of molecule 1 in (I) [(III)?]. The two molecules form π-stacked dimers with the tert-butyl groups pointing in opposite directions (Fig. 2). This is in line with the general characteristics for the crystal packing of unsymmetrical porphyrins (Senge et al., 1993). According to the definitions given by Scheidt & Lee (1987) these aggregates are characterized by a mean-plane separation of 3.396 Å, a centre-to-centre distance of 4.969 Å and a slip angle of 134.4°, giving a lateral shift of 3.55 Å. These `dimers' in turn form slightly closer packed, edge-to-edge stacked dimers, with a mean-plane separation of the two 4 N-planes of 3.329 Å, a centre-to-centre distance of 4.461 Å, a slip angle of 43.3° and a lateral shift of 3.059 Å. Both types of dimers belong to group `I' (Scheidt & Lee, 1987). Thus, the packing is characterized by the formation of tetrameric units (Cu1···Cu2···Cu2···Cu1) through edge-to-edge contacts.

Table 1 compiles selected structural data for the three, now available, mono-tert-butylporphyrins. These include the free base, (I) (Ryppa et al., 2005), the nickel(II) complex, (II) (Song, Jentzen et al., 1998) and the copper(II) complex, (III). In addition, we include the structure of the related (5,15-di-tert-butylporphyinato)copper(II), (IV) (Song, Jaquinod et al., 1998). Visual inspection of the crystal structure reveals a `folded' macrocycle conformation with a localized influence of the tert-butyl substituents, as indicated in the skeletal deviation plot shown in Fig. 3. Clearly, the deformation is more pronounced in the two quadrants involving the substituent than the others. For example the tilt angles of individual pyrrole rings against the 24-atom plane are 17.9, 14.3, 7.6, and 8.4° for pyrrole rings with N21, N22, N23 and N24 in molecule 1, respectively. This localized effect of the bulky residue is also evidenced in the displacements of the individual meso carbon atoms from the 4 N-plane and the widening of the respective C_a—C_m—C_a angles. In (III) the substituted position is displaced by about 0.6 Å compared to 0.21–0.34 Å for the unsubstituted meso positions. The 5,15-disubstituted derivative, (IV), exhibits similar trends along the 5,15-axis, albeit in a much more symmetrical fashion.

Metal effects established for other nonplanar porphyrins are retained in this series. Thus, the core size of the free base, (I), is larger and that of the nickel(II) complex, (II), is smaller compared to (III). As expected, no significant in-plane distortion is evident from the core size elongation parameter in (III). The overall degree of nonplanarity (Δ24) is significantly larger (~0.19 Å) compared to the free base (0.14 Å) but smaller than in the nickel(II) complex (0.34 Å).

A normal-coordinate structural decomposition analysis as developed by Shelnutt and coworkers (Jentzen et al., 1997) gives further details on the mix of distortion modes present in this type of porphyrin. This method classifies the distortions in terms of equivalent displacements along the normal coordinates. As shown in Fig. 4, the main contributors to the out-of-plane distortions are ruf (B_1u), dom (A_2u), wav(x) (E_GX) and wav(y) (E_gy) and a minor contribution of sad (B_2u) distortion, which differs significantly in the two independent molecules. For the in-plane distortions the main contributors are m-str (B_{2 g}) and A_{1 g}. The nickel(II) complex clearly shows a significantly larger ruf distortion, as a result of M—N bond shortening. For the in-plane distortions m-str is larger in the free base and the disubstituted copper(II) complex while the A_{1 g} contribution is larger in the nickel(II) complex and in compound (IV). Thus, the central metal exerts a significant influence on the overall conformation and the mix of individual distortion modes, and can mask the steric influence of the individual meso substituent to some extent.

Related literature

For related literature, see: Barkigia et al. (1988, 1990, 2004); Ema et al. (1994); Hoard (1973); Hope (1994); Jentzen et al. (1997); Ryppa et al. (2005); Scheidt & Lee (1987); Senge (1992, 2006); Senge et al. (1993, 1995, 1996, 2000); Song et al. (1996); Song, Jaquinod et al. (1998); Song, Jentzen et al. (1998); Wiehe et al. (2002).

S2. Experimental

Compound (III) was prepared via metallation of the respective free base porphyrin, (I). 5-(tert-Butyl)porphyrin (58 mg, 0.16 mmol) was dissolved in 50 ml DMF [dimethylformamide?] and heated to reflux with copper(II) acetate (10 equiv.) for 10 h. The residue was dissolved in CH₂Cl₂ and the mixture filtered through silica gel, eluting with CH₂Cl₂. Finally, the solvent was removed under reduced pressure and the product recrystallized from CH₂Cl₂/MeOH. Yield: 49 mg (0.11 mmol, 72%) of purple crystals. M.p. 547 K. R_f 0.73 (CH₂Cl₂: n-hexane = 2:1, v/v, silica gel, 6 × 3 cm). UV/vis (CH₂Cl₂) [λ _max, nm (lg ε)]: 404 (5.44), 534 (4.00), 575 (3.65). MS (EI, 493 K, 70 eV) m/z: 427 (89%, [M]⁺), 412 (100%, [M –CH₃]⁺), 397 (18%, [M – C₂H₆]⁺), 371 (69%, [C₂₀H₁₂N₄Cu]⁺), 214 (6%, [M]²⁺). HRMS (EI): m/z = 427.0977 (427.0984 for C₂₄H₂₀N₄Cu).

The compound was crystallized via liquid diffusion of methanol into a solution of the porphyrin in methylene chloride. Crystals were handled as described by Hope (1994).

S3. Refinement

Hydrogen atoms were located in difference maps and refined using a standard riding model. The largest residual electron-density peak is located in the tert-butyl residue at C25.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: XPREP (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP within SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the molecular structure of one of the two independent moleculues of (III) in the crystal. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity.
	Fig. 2. A view of the π-stacks formed in the crystal structure of (III). H atoms have been omitted for clarity.
	Fig. 3. A skeletal deviation plot with respect to the plane of the 24 macrocycle atoms for (III); the tert-butyl-substituted meso C atom is highlighted; the x axis is not to scale; the sequence of pyrrole rings follows the IUPAC nomenclature from left to right (N21, N22, N23, N24).
	Fig. 4. A graphical representation of the displacements along the lowest-frequency coordinates that best simulate the structures.

(5-tert-Butylporphyrinato)copper(II)

Crystal data

[Cu(C24H20N4)]	F(000) = 1768
Mr = 427.98	Dx = 1.518 Mg m^−3
Monoclinic, P21/c	Melting point: 274 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.6765 (10) Å	Cell parameters from 950 reflections
b = 12.4744 (8) Å	θ = 2.2–20°
c = 26.024 (2) Å	µ = 1.19 mm^−1
β = 98.892 (7)°	T = 213 K
V = 3745.1 (5) Å^3	Block, red
Z = 8	0.38 × 0.27 × 0.21 mm

Data collection

CCD area detector diffractometer	6481 independent reflections
Radiation source: sealed tube	4741 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −13→13
Tmin = 0.662, Tmax = 0.789	k = −14→14
23765 measured reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0823P)^2] where P = (Fo^2 + 2Fc^2)/3
6481 reflections	(Δ/σ)max = 0.001
529 parameters	Δρmax = 1.82 e Å^−3
0 restraints	Δρmin = −0.66 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 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. Residual electron density located in tBu group.

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

	x	y	z	Uiso*/Ueq
Cu1	0.69223 (4)	0.66664 (3)	0.213967 (17)	0.02554 (13)
N21	0.6227 (3)	0.7697 (2)	0.25808 (12)	0.0276 (7)
N22	0.5447 (2)	0.6702 (2)	0.16456 (11)	0.0262 (6)
N23	0.7622 (2)	0.5672 (2)	0.16781 (12)	0.0300 (7)
N24	0.8388 (3)	0.6623 (2)	0.26507 (13)	0.0306 (7)
C1	0.6851 (3)	0.8313 (3)	0.29663 (14)	0.0304 (8)
C2	0.6123 (3)	0.9144 (3)	0.31171 (15)	0.0353 (9)
H2	0.6355	0.9695	0.3357	0.042*
C3	0.5057 (3)	0.8996 (3)	0.28562 (15)	0.0343 (9)
H3	0.4401	0.9415	0.2885	0.041*
C4	0.5097 (3)	0.8074 (3)	0.25213 (14)	0.0286 (8)
C5	0.4173 (3)	0.7671 (3)	0.21655 (15)	0.0289 (8)
C6	0.4400 (3)	0.7154 (3)	0.17111 (14)	0.0272 (8)
C7	0.3624 (3)	0.7108 (3)	0.12212 (15)	0.0310 (8)
H7	0.2859	0.7368	0.1158	0.037*
C8	0.4189 (3)	0.6627 (3)	0.08718 (15)	0.0343 (9)
H8	0.3903	0.6503	0.0519	0.041*
C9	0.5314 (3)	0.6340 (3)	0.11410 (14)	0.0291 (8)
C10	0.6098 (3)	0.5727 (3)	0.09268 (15)	0.0338 (8)
H10	0.5891	0.5520	0.0577	0.041*
C11	0.7160 (3)	0.5388 (3)	0.11796 (15)	0.0333 (8)
C12	0.7958 (4)	0.4697 (3)	0.09678 (18)	0.0429 (10)
H12	0.7850	0.4395	0.0633	0.051*
C13	0.8883 (4)	0.4565 (3)	0.13366 (18)	0.0433 (10)
H13	0.9540	0.4147	0.1309	0.052*
C14	0.8688 (3)	0.5177 (3)	0.17802 (17)	0.0360 (9)
C15	0.9462 (3)	0.5287 (3)	0.22348 (17)	0.0392 (9)
H15	1.0138	0.4867	0.2271	0.047*
C16	0.9324 (3)	0.5967 (3)	0.26442 (16)	0.0357 (9)
C17	1.0169 (4)	0.6145 (3)	0.30945 (18)	0.0440 (10)
H17	1.0873	0.5776	0.3185	0.053*
C18	0.9761 (3)	0.6945 (3)	0.33645 (17)	0.0420 (10)
H18	1.0132	0.7247	0.3677	0.050*
C19	0.8652 (3)	0.7247 (3)	0.30835 (15)	0.0331 (9)
C20	0.7961 (3)	0.8075 (3)	0.32096 (15)	0.0362 (9)
H20	0.8275	0.8520	0.3488	0.043*
C51	0.2906 (3)	0.7810 (3)	0.22655 (16)	0.0340 (9)
C52	0.2827 (4)	0.7849 (4)	0.28523 (17)	0.0447 (10)
H52A	0.2024	0.7768	0.2901	0.067*
H52B	0.3122	0.8531	0.2995	0.067*
H52C	0.3284	0.7271	0.3029	0.067*
C53	0.2265 (5)	0.8809 (3)	0.19857 (17)	0.0570 (14)
H53A	0.1435	0.8725	0.1972	0.085*
H53B	0.2445	0.8863	0.1635	0.085*
H53C	0.2519	0.9455	0.2178	0.085*
C54	0.2165 (3)	0.6823 (3)	0.20714 (18)	0.0442 (10)
H54A	0.2527	0.6180	0.2232	0.066*
H54B	0.2108	0.6768	0.1697	0.066*
H54C	0.1396	0.6900	0.2164	0.066*
Cu2	0.56849 (4)	0.85815 (3)	0.047195 (18)	0.03169 (14)
N25	0.6372 (3)	0.7521 (2)	0.00411 (12)	0.0315 (7)
N26	0.7146 (3)	0.8497 (2)	0.09758 (12)	0.0364 (8)
N27	0.4990 (3)	0.9594 (3)	0.09239 (14)	0.0444 (9)
N28	0.4222 (3)	0.8612 (2)	−0.00326 (13)	0.0361 (7)
C21	0.5746 (3)	0.6927 (3)	−0.03523 (15)	0.0333 (8)
C22	0.6483 (4)	0.6125 (3)	−0.05204 (16)	0.0403 (9)
H22	0.6258	0.5590	−0.0770	0.048*
C23	0.7544 (4)	0.6274 (3)	−0.02598 (17)	0.0411 (10)
H23	0.8206	0.5871	−0.0297	0.049*
C24	0.7500 (3)	0.7160 (3)	0.00889 (15)	0.0335 (8)
C25	0.8428 (3)	0.7556 (3)	0.04508 (16)	0.0366 (9)
C26	0.8191 (3)	0.8048 (3)	0.09083 (15)	0.0355 (9)
C27	0.8977 (4)	0.8087 (3)	0.14043 (17)	0.0455 (11)
H27	0.9742	0.7828	0.1470	0.055*
C28	0.8399 (4)	0.8559 (3)	0.17435 (18)	0.0507 (13)
H28	0.8681	0.8678	0.2097	0.061*
C29	0.7270 (4)	0.8858 (3)	0.14795 (15)	0.0427 (11)
C30	0.6491 (5)	0.9494 (3)	0.16828 (17)	0.0509 (12)
H30	0.6683	0.9685	0.2035	0.061*
C31	0.5466 (5)	0.9878 (3)	0.14244 (19)	0.0485 (12)
C32	0.4702 (6)	1.0647 (4)	0.1621 (2)	0.0697 (17)
H32	0.4818	1.0963	0.1953	0.084*
C33	0.3789 (6)	1.0827 (4)	0.1238 (3)	0.0685 (17)
H33	0.3167	1.1298	0.1253	0.082*
C34	0.3961 (4)	1.0153 (3)	0.0804 (2)	0.0509 (12)
C35	0.3194 (4)	1.0028 (3)	0.0353 (2)	0.0523 (12)
H35	0.2541	1.0478	0.0306	0.063*
C36	0.3292 (4)	0.9298 (3)	−0.00386 (19)	0.0443 (10)
C37	0.2431 (4)	0.9085 (4)	−0.0485 (2)	0.0505 (12)
H37	0.1731	0.9458	−0.0582	0.061*
C38	0.2815 (4)	0.8258 (4)	−0.0736 (2)	0.0494 (11)
H38	0.2427	0.7929	−0.1039	0.059*
C39	0.3933 (4)	0.7961 (3)	−0.04576 (16)	0.0385 (9)
C40	0.4628 (3)	0.7145 (3)	−0.05862 (16)	0.0383 (9)
H40	0.4310	0.6691	−0.0860	0.046*
C251	0.9699 (4)	0.7450 (4)	0.03403 (18)	0.0462 (11)
C252	0.9771 (5)	0.7462 (5)	−0.0245 (2)	0.0694 (15)
H25A	1.0566	0.7589	−0.0295	0.104*
H25B	0.9279	0.8028	−0.0413	0.104*
H25C	0.9513	0.6777	−0.0397	0.104*
C253	1.0299 (4)	0.6454 (4)	0.0543 (3)	0.091 (3)
H25D	0.9784	0.5847	0.0462	0.136*
H25E	1.0517	0.6511	0.0917	0.136*
H25F	1.0988	0.6353	0.0383	0.136*
C254	1.0426 (4)	0.8441 (4)	0.0551 (2)	0.0619 (14)
H25G	1.0449	0.8489	0.0925	0.093*
H25H	1.0074	0.9085	0.0388	0.093*
H25I	1.1208	0.8369	0.0473	0.093*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0263 (2)	0.0228 (2)	0.0282 (3)	−0.00314 (15)	0.00610 (18)	−0.00073 (16)
N21	0.0312 (16)	0.0249 (14)	0.0267 (17)	−0.0044 (11)	0.0049 (13)	0.0017 (11)
N22	0.0303 (15)	0.0225 (13)	0.0265 (16)	−0.0037 (11)	0.0065 (13)	−0.0013 (11)
N23	0.0283 (15)	0.0283 (15)	0.0346 (18)	−0.0012 (12)	0.0091 (14)	−0.0005 (12)
N24	0.0280 (15)	0.0278 (15)	0.0358 (18)	−0.0025 (12)	0.0041 (14)	0.0027 (12)
C1	0.036 (2)	0.0289 (17)	0.0264 (19)	−0.0054 (14)	0.0043 (16)	0.0014 (14)
C2	0.046 (2)	0.0294 (18)	0.031 (2)	−0.0038 (15)	0.0092 (18)	−0.0036 (15)
C3	0.041 (2)	0.0314 (18)	0.031 (2)	0.0029 (15)	0.0098 (18)	−0.0044 (15)
C4	0.0342 (19)	0.0259 (16)	0.0271 (19)	0.0000 (14)	0.0097 (16)	0.0029 (14)
C5	0.0311 (19)	0.0219 (16)	0.035 (2)	0.0011 (13)	0.0090 (16)	0.0028 (14)
C6	0.0276 (18)	0.0236 (16)	0.031 (2)	−0.0027 (13)	0.0060 (15)	0.0020 (13)
C7	0.0291 (18)	0.0272 (17)	0.036 (2)	−0.0019 (14)	0.0017 (16)	0.0001 (15)
C8	0.043 (2)	0.0275 (18)	0.030 (2)	−0.0060 (15)	−0.0007 (17)	0.0024 (15)
C9	0.036 (2)	0.0223 (16)	0.029 (2)	−0.0078 (14)	0.0062 (16)	0.0006 (14)
C10	0.045 (2)	0.0285 (18)	0.030 (2)	−0.0054 (15)	0.0128 (18)	−0.0026 (15)
C11	0.040 (2)	0.0285 (17)	0.035 (2)	−0.0070 (15)	0.0147 (18)	−0.0057 (15)
C12	0.051 (3)	0.037 (2)	0.046 (3)	−0.0041 (18)	0.022 (2)	−0.0089 (18)
C13	0.040 (2)	0.036 (2)	0.058 (3)	0.0052 (17)	0.022 (2)	−0.0046 (19)
C14	0.033 (2)	0.0267 (18)	0.050 (3)	0.0006 (14)	0.0123 (18)	0.0002 (16)
C15	0.031 (2)	0.0329 (19)	0.055 (3)	0.0033 (15)	0.0114 (19)	0.0024 (18)
C16	0.0280 (19)	0.0324 (19)	0.046 (2)	−0.0012 (14)	0.0029 (18)	0.0081 (16)
C17	0.032 (2)	0.040 (2)	0.057 (3)	0.0000 (16)	−0.002 (2)	0.0077 (19)
C18	0.035 (2)	0.043 (2)	0.045 (3)	−0.0084 (17)	−0.0053 (19)	0.0046 (18)
C19	0.031 (2)	0.0318 (19)	0.035 (2)	−0.0072 (15)	0.0016 (17)	0.0035 (15)
C20	0.043 (2)	0.0342 (19)	0.031 (2)	−0.0094 (16)	0.0029 (18)	−0.0009 (16)
C51	0.0275 (19)	0.0316 (19)	0.043 (2)	0.0033 (14)	0.0059 (17)	0.0016 (16)
C52	0.043 (2)	0.052 (2)	0.043 (3)	0.0034 (18)	0.018 (2)	−0.0001 (19)
C53	0.113 (4)	0.029 (2)	0.034 (2)	0.035 (2)	0.029 (3)	0.0109 (17)
C54	0.033 (2)	0.046 (2)	0.055 (3)	−0.0038 (17)	0.010 (2)	0.002 (2)
Cu2	0.0409 (3)	0.0274 (2)	0.0284 (3)	−0.00868 (17)	0.0106 (2)	−0.00208 (17)
N25	0.0367 (17)	0.0315 (15)	0.0257 (17)	−0.0069 (12)	0.0034 (14)	−0.0010 (12)
N26	0.053 (2)	0.0303 (15)	0.0253 (17)	−0.0166 (14)	0.0052 (15)	−0.0014 (12)
N27	0.062 (2)	0.0302 (16)	0.047 (2)	−0.0116 (15)	0.0276 (19)	−0.0029 (15)
N28	0.0373 (18)	0.0329 (16)	0.040 (2)	−0.0042 (13)	0.0124 (15)	0.0060 (14)
C21	0.040 (2)	0.0321 (18)	0.027 (2)	−0.0088 (15)	0.0045 (17)	0.0005 (15)
C22	0.050 (2)	0.042 (2)	0.030 (2)	−0.0070 (17)	0.0068 (19)	−0.0075 (16)
C23	0.046 (2)	0.041 (2)	0.038 (2)	−0.0023 (17)	0.011 (2)	−0.0035 (17)
C24	0.036 (2)	0.0371 (19)	0.028 (2)	−0.0066 (15)	0.0080 (17)	0.0019 (15)
C25	0.039 (2)	0.0344 (19)	0.035 (2)	−0.0110 (16)	0.0006 (18)	0.0043 (16)
C26	0.040 (2)	0.0345 (19)	0.031 (2)	−0.0122 (16)	0.0025 (17)	0.0033 (15)
C27	0.054 (3)	0.043 (2)	0.035 (2)	−0.0197 (19)	−0.006 (2)	0.0062 (19)
C28	0.077 (3)	0.040 (2)	0.031 (2)	−0.031 (2)	−0.003 (2)	0.0038 (18)
C29	0.073 (3)	0.0310 (19)	0.024 (2)	−0.0279 (19)	0.008 (2)	−0.0016 (15)
C30	0.088 (4)	0.039 (2)	0.030 (2)	−0.031 (2)	0.020 (2)	−0.0100 (18)
C31	0.074 (3)	0.033 (2)	0.047 (3)	−0.023 (2)	0.034 (2)	−0.0129 (18)
C32	0.111 (5)	0.042 (3)	0.072 (4)	−0.023 (3)	0.063 (4)	−0.018 (2)
C33	0.084 (4)	0.039 (2)	0.098 (5)	−0.007 (2)	0.061 (4)	−0.013 (3)
C34	0.063 (3)	0.031 (2)	0.068 (3)	−0.0112 (19)	0.040 (3)	−0.006 (2)
C35	0.050 (3)	0.035 (2)	0.079 (4)	−0.0002 (18)	0.033 (3)	0.008 (2)
C36	0.039 (2)	0.036 (2)	0.062 (3)	−0.0057 (17)	0.020 (2)	0.0121 (19)
C37	0.036 (2)	0.049 (2)	0.068 (3)	−0.0007 (19)	0.011 (2)	0.022 (2)
C38	0.037 (2)	0.058 (3)	0.053 (3)	−0.010 (2)	0.005 (2)	0.016 (2)
C39	0.039 (2)	0.041 (2)	0.036 (2)	−0.0100 (17)	0.0056 (18)	0.0109 (17)
C40	0.040 (2)	0.043 (2)	0.030 (2)	−0.0139 (17)	0.0004 (18)	−0.0022 (16)
C251	0.037 (2)	0.056 (3)	0.044 (3)	−0.0086 (18)	0.000 (2)	0.0063 (19)
C252	0.047 (3)	0.105 (4)	0.059 (4)	−0.016 (3)	0.020 (3)	0.004 (3)
C253	0.024 (2)	0.046 (3)	0.190 (8)	0.0045 (19)	−0.019 (3)	−0.027 (3)
C254	0.038 (2)	0.069 (3)	0.077 (4)	−0.019 (2)	0.005 (2)	0.014 (3)

Geometric parameters (Å, º)

Cu1—N21	1.980 (3)	Cu2—N25	1.983 (3)
Cu1—N22	1.984 (3)	Cu2—N27	1.983 (4)
Cu1—N23	1.988 (3)	Cu2—N26	1.988 (3)
Cu1—N24	2.000 (3)	Cu2—N28	1.988 (3)
N21—C1	1.378 (4)	N25—C21	1.379 (5)
N21—C4	1.387 (5)	N25—C24	1.379 (5)
N22—C9	1.374 (5)	N26—C29	1.372 (5)
N22—C6	1.381 (5)	N26—C26	1.378 (5)
N23—C11	1.373 (5)	N27—C31	1.381 (6)
N23—C14	1.378 (5)	N27—C34	1.382 (6)
N24—C19	1.365 (5)	N28—C39	1.372 (5)
N24—C16	1.367 (5)	N28—C36	1.380 (5)
C1—C20	1.384 (5)	C21—C40	1.380 (5)
C1—C2	1.433 (5)	C21—C22	1.432 (6)
C2—C3	1.335 (5)	C22—C23	1.330 (6)
C2—H2	0.9400	C22—H22	0.9400
C3—C4	1.448 (5)	C23—C24	1.436 (6)
C3—H3	0.9400	C23—H23	0.9400
C4—C5	1.402 (5)	C24—C25	1.410 (5)
C5—C6	1.408 (5)	C25—C26	1.405 (6)
C5—C51	1.550 (5)	C25—C251	1.560 (6)
C6—C7	1.447 (5)	C26—C27	1.465 (5)
C7—C8	1.344 (6)	C27—C28	1.329 (7)
C7—H7	0.9400	C27—H27	0.9400
C8—C9	1.435 (5)	C28—C29	1.438 (7)
C8—H8	0.9400	C28—H28	0.9400
C9—C10	1.376 (5)	C29—C30	1.373 (7)
C10—C11	1.377 (5)	C30—C31	1.366 (7)
C10—H10	0.9400	C30—H30	0.9400
C11—C12	1.440 (6)	C31—C32	1.456 (7)
C12—C13	1.339 (6)	C32—C33	1.360 (8)
C12—H12	0.9400	C32—H32	0.9400
C13—C14	1.431 (6)	C33—C34	1.448 (7)
C13—H13	0.9400	C33—H33	0.9400
C14—C15	1.380 (6)	C34—C35	1.370 (7)
C15—C16	1.390 (6)	C35—C36	1.385 (7)
C15—H15	0.9400	C35—H35	0.9400
C16—C17	1.428 (6)	C36—C37	1.440 (7)
C17—C18	1.349 (6)	C37—C38	1.334 (7)
C17—H17	0.9400	C37—H37	0.9400
C18—C19	1.436 (5)	C38—C39	1.439 (6)
C18—H18	0.9400	C38—H38	0.9400
C19—C20	1.381 (6)	C39—C40	1.375 (6)
C20—H20	0.9400	C40—H40	0.9400
C51—C52	1.545 (6)	C251—C253	1.483 (7)
C51—C54	1.545 (5)	C251—C252	1.539 (7)
C51—C53	1.573 (5)	C251—C254	1.551 (6)
C52—H52A	0.9700	C252—H25A	0.9700
C52—H52B	0.9700	C252—H25B	0.9700
C52—H52C	0.9700	C252—H25C	0.9700
C53—H53A	0.9700	C253—H25D	0.9700
C53—H53B	0.9700	C253—H25E	0.9700
C53—H53C	0.9700	C253—H25F	0.9700
C54—H54A	0.9700	C254—H25G	0.9700
C54—H54B	0.9700	C254—H25H	0.9700
C54—H54C	0.9700	C254—H25I	0.9700
N21—Cu1—N22	88.21 (12)	N25—Cu2—N27	177.60 (13)
N21—Cu1—N23	177.95 (12)	N25—Cu2—N26	87.51 (13)
N22—Cu1—N23	91.09 (12)	N27—Cu2—N26	91.75 (15)
N21—Cu1—N24	91.00 (12)	N25—Cu2—N28	91.20 (13)
N22—Cu1—N24	178.69 (13)	N27—Cu2—N28	89.48 (15)
N23—Cu1—N24	89.73 (13)	N26—Cu2—N28	178.06 (12)
C1—N21—C4	106.2 (3)	C21—N25—C24	106.4 (3)
C1—N21—Cu1	124.5 (2)	C21—N25—Cu2	124.3 (3)
C4—N21—Cu1	128.6 (2)	C24—N25—Cu2	129.1 (2)
C9—N22—C6	106.3 (3)	C29—N26—C26	106.9 (3)
C9—N22—Cu1	124.8 (2)	C29—N26—Cu2	124.5 (3)
C6—N22—Cu1	128.7 (2)	C26—N26—Cu2	128.6 (3)
C11—N23—C14	106.2 (3)	C31—N27—C34	107.0 (4)
C11—N23—Cu1	126.4 (2)	C31—N27—Cu2	125.5 (3)
C14—N23—Cu1	127.4 (3)	C34—N27—Cu2	127.4 (3)
C19—N24—C16	105.9 (3)	C39—N28—C36	105.2 (3)
C19—N24—Cu1	126.4 (2)	C39—N28—Cu2	126.9 (3)
C16—N24—Cu1	127.7 (3)	C36—N28—Cu2	127.8 (3)
N21—C1—C20	124.5 (3)	N25—C21—C40	125.4 (4)
N21—C1—C2	109.4 (3)	N25—C21—C22	109.1 (3)
C20—C1—C2	125.7 (3)	C40—C21—C22	125.2 (4)
C3—C2—C1	107.8 (3)	C23—C22—C21	107.7 (3)
C3—C2—H2	126.1	C23—C22—H22	126.2
C1—C2—H2	126.1	C21—C22—H22	126.2
C2—C3—C4	107.6 (3)	C22—C23—C24	108.0 (4)
C2—C3—H3	126.2	C22—C23—H23	126.0
C4—C3—H3	126.2	C24—C23—H23	126.0
N21—C4—C5	125.1 (3)	N25—C24—C25	124.8 (4)
N21—C4—C3	108.7 (3)	N25—C24—C23	108.7 (3)
C5—C4—C3	126.1 (3)	C25—C24—C23	126.4 (4)
C4—C5—C6	119.6 (3)	C26—C25—C24	119.2 (4)
C4—C5—C51	120.4 (3)	C26—C25—C251	120.7 (3)
C6—C5—C51	120.0 (3)	C24—C25—C251	120.1 (4)
N22—C6—C5	125.2 (3)	N26—C26—C25	125.4 (3)
N22—C6—C7	108.7 (3)	N26—C26—C27	108.7 (4)
C5—C6—C7	125.8 (3)	C25—C26—C27	125.6 (4)
C8—C7—C6	107.9 (3)	C28—C27—C26	106.6 (4)
C8—C7—H7	126.0	C28—C27—H27	126.7
C6—C7—H7	126.0	C26—C27—H27	126.7
C7—C8—C9	106.8 (3)	C27—C28—C29	108.6 (4)
C7—C8—H8	126.6	C27—C28—H28	125.7
C9—C8—H8	126.6	C29—C28—H28	125.7
N22—C9—C10	125.8 (3)	N26—C29—C30	125.4 (4)
N22—C9—C8	110.2 (3)	N26—C29—C28	109.0 (4)
C10—C9—C8	123.9 (3)	C30—C29—C28	125.3 (4)
C9—C10—C11	125.7 (4)	C31—C30—C29	126.5 (4)
C9—C10—H10	117.2	C31—C30—H30	116.7
C11—C10—H10	117.2	C29—C30—H30	116.7
N23—C11—C10	124.5 (4)	C30—C31—N27	124.6 (4)
N23—C11—C12	109.4 (3)	C30—C31—C32	126.6 (5)
C10—C11—C12	126.1 (4)	N27—C31—C32	108.7 (5)
C13—C12—C11	107.3 (4)	C33—C32—C31	107.8 (5)
C13—C12—H12	126.4	C33—C32—H32	126.1
C11—C12—H12	126.4	C31—C32—H32	126.1
C12—C13—C14	107.5 (4)	C32—C33—C34	106.8 (5)
C12—C13—H13	126.2	C32—C33—H33	126.6
C14—C13—H13	126.2	C34—C33—H33	126.6
N23—C14—C15	124.9 (4)	C35—C34—N27	124.5 (4)
N23—C14—C13	109.6 (3)	C35—C34—C33	125.7 (5)
C15—C14—C13	125.5 (4)	N27—C34—C33	109.7 (5)
C14—C15—C16	125.4 (4)	C34—C35—C36	125.9 (4)
C14—C15—H15	117.3	C34—C35—H35	117.0
C16—C15—H15	117.3	C36—C35—H35	117.0
N24—C16—C15	124.2 (3)	N28—C36—C35	123.7 (4)
N24—C16—C17	110.4 (4)	N28—C36—C37	110.2 (4)
C15—C16—C17	125.2 (4)	C35—C36—C37	126.1 (4)
C18—C17—C16	106.7 (4)	C38—C37—C36	106.9 (4)
C18—C17—H17	126.6	C38—C37—H37	126.5
C16—C17—H17	126.6	C36—C37—H37	126.5
C17—C18—C19	107.0 (4)	C37—C38—C39	107.5 (4)
C17—C18—H18	126.5	C37—C38—H38	126.3
C19—C18—H18	126.5	C39—C38—H38	126.3
N24—C19—C20	123.9 (3)	N28—C39—C40	123.6 (4)
N24—C19—C18	109.9 (3)	N28—C39—C38	110.1 (4)
C20—C19—C18	126.1 (4)	C40—C39—C38	126.3 (4)
C19—C20—C1	126.3 (3)	C39—C40—C21	126.3 (4)
C19—C20—H20	116.9	C39—C40—H40	116.8
C1—C20—H20	116.9	C21—C40—H40	116.8
C52—C51—C54	103.4 (3)	C253—C251—C252	105.4 (5)
C52—C51—C5	112.0 (3)	C253—C251—C254	109.8 (4)
C54—C51—C5	110.9 (3)	C252—C251—C254	103.4 (4)
C52—C51—C53	109.6 (3)	C253—C251—C25	114.6 (4)
C54—C51—C53	106.1 (3)	C252—C251—C25	112.4 (4)
C5—C51—C53	114.2 (3)	C254—C251—C25	110.6 (4)
C51—C52—H52A	109.5	C251—C252—H25A	109.5
C51—C52—H52B	109.5	C251—C252—H25B	109.5
H52A—C52—H52B	109.5	H25A—C252—H25B	109.5
C51—C52—H52C	109.5	C251—C252—H25C	109.5
H52A—C52—H52C	109.5	H25A—C252—H25C	109.5
H52B—C52—H52C	109.5	H25B—C252—H25C	109.5
C51—C53—H53A	109.5	C251—C253—H25D	109.5
C51—C53—H53B	109.5	C251—C253—H25E	109.5
H53A—C53—H53B	109.5	H25D—C253—H25E	109.5
C51—C53—H53C	109.5	C251—C253—H25F	109.5
H53A—C53—H53C	109.5	H25D—C253—H25F	109.5
H53B—C53—H53C	109.5	H25E—C253—H25F	109.5
C51—C54—H54A	109.5	C251—C254—H25G	109.5
C51—C54—H54B	109.5	C251—C254—H25H	109.5
H54A—C54—H54B	109.5	H25G—C254—H25H	109.5
C51—C54—H54C	109.5	C251—C254—H25I	109.5
H54A—C54—H54C	109.5	H25G—C254—H25I	109.5
H54B—C54—H54C	109.5	H25H—C254—H25I	109.5