A new stepped tetra­nuclear copper(II) complex: synthesis, crystal structure and photoluminescence properties

Binuclear and tetra­nuclear copper(II) complexes are of inter­est because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetra­nuclear copper(II) complexes, there are limited reports on the crystal structures and solid-state photoluminescence properties of `stepped' tetra­nuclear copper(II) complexes. A new Cu^II complex, namely bis­{μ₃-3-[(4-meth­oxy-2-oxido­benzyl­idene)amino]­propano­lato}bis­{μ₂-3-[(4-meth­oxy-2-oxido­benzyl­idene)amino]­propano­lato}tetra­copper(II), [Cu₄(C₁₁H₁₃NO₃)₄], has been synthesized and characterized using elemental analysis, FT–IR, solid-state UV–Vis spectroscopy and single-crystal X-ray diffraction. The crystal structure determination shows that the complex is a stepped tetra­nuclear structure con­sisting of two dinuclear [Cu₂(L)₂] units {L is 3-[(4-meth­oxy-2-oxido­benzyl­idene)amino]­propano­late}. The two terminal Cu^II atoms are four-coordinated in square-planar environments, while the two central Cu^II atoms are five-coordinated in square-pyramidal environments. The solid-state photoluminescence properties of both the complex and 3-[(2-hy­droxy-4-meth­oxy­benzyl­idene)amino]­propanol (H₂L) have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H₂L displays a green emission at 515 nm.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2006).

Bis{µ₃-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}bis{µ₂-3-[(4-methoxy-2-oxidobenzylidene)amino]propanolato}tetracopper(II)

Crystal data

[Cu4(C11H13NO3)4]	F(000) = 1112
Mr = 1083.05	Dx = 1.684 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.2592 (3) Å	Cell parameters from 846 reflections
b = 14.2078 (3) Å	θ = 2.6–25.5°
c = 9.2560 (2) Å	µ = 2.03 mm^−1
β = 92.527 (1)°	T = 100 K
V = 2136.13 (8) Å^3	Plate, violet
Z = 2	0.17 × 0.16 × 0.06 mm

Data collection

Bruker APEXII with a CCD area detector diffractometer	5655 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
phi and ω scans	θmax = 33.4°, θmin = 1.3°
Absorption correction: multi-scan (TWINABS; Sheldrick, 2008b)	h = 0→24
Tmin = 0.767, Tmax = 0.885	k = −21→0
8050 measured reflections	l = −14→14
8050 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0276P)^2 + 3.965P] where P = (Fo^2 + 2Fc^2)/3
S = 1.21	(Δ/σ)max = 0.001
8050 reflections	Δρmax = 0.74 e Å^−3
348 parameters	Δρmin = −0.58 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.

Refinement. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.28607 (2)	0.38313 (3)	0.07394 (4)	0.02378 (9)
Cu2	0.47193 (2)	0.39545 (3)	0.07983 (4)	0.02041 (9)
O1	0.37587 (12)	0.39379 (16)	−0.0522 (2)	0.0234 (4)
O2	0.21254 (12)	0.36940 (17)	0.2266 (2)	0.0259 (5)
O3	−0.04308 (14)	0.3618 (2)	0.4600 (3)	0.0395 (6)
O4	0.38181 (12)	0.36959 (15)	0.2028 (2)	0.0212 (4)
O5	0.54848 (12)	0.42022 (15)	−0.0683 (2)	0.0209 (4)
O6	0.80182 (13)	0.38723 (17)	−0.3068 (2)	0.0281 (5)
C1A	0.37454 (19)	0.4003 (3)	−0.2044 (3)	0.0276 (6)	0.498 (10)
H1AA	0.416811	0.357716	−0.241990	0.033*	0.498 (10)
H1AB	0.388372	0.465387	−0.232620	0.033*	0.498 (10)
C2A	0.2896 (4)	0.3737 (6)	−0.2724 (6)	0.0269 (16)	0.498 (10)
H2AA	0.291195	0.377903	−0.378958	0.032*	0.498 (10)
H2AB	0.276681	0.307856	−0.246951	0.032*	0.498 (10)
C3A	0.2224 (4)	0.4381 (6)	−0.2204 (6)	0.0272 (18)	0.498 (10)
H3AA	0.241544	0.504146	−0.223851	0.033*	0.498 (10)
H3AB	0.173068	0.432218	−0.286385	0.033*	0.498 (10)
N1A	0.1998 (5)	0.4155 (6)	−0.0720 (9)	0.0237 (15)	0.498 (10)
C4A	0.1229 (2)	0.3951 (4)	−0.0512 (4)	0.0562 (14)	0.498 (10)
H4A	0.088119	0.385597	−0.135181	0.067*	0.498 (10)
C1B	0.37454 (19)	0.4003 (3)	−0.2044 (3)	0.0276 (6)	0.502 (10)
H1BA	0.387289	0.337842	−0.245317	0.033*	0.502 (10)
H1BB	0.417698	0.444838	−0.233035	0.033*	0.502 (10)
C2B	0.2933 (4)	0.4326 (7)	−0.2652 (7)	0.032 (2)	0.502 (10)
H2BA	0.296411	0.439536	−0.371249	0.039*	0.502 (10)
H2BB	0.281232	0.495365	−0.224827	0.039*	0.502 (10)
C3B	0.2240 (4)	0.3672 (8)	−0.2342 (7)	0.039 (3)	0.502 (10)
H3BA	0.175549	0.382937	−0.298151	0.047*	0.502 (10)
H3BB	0.240552	0.301775	−0.255513	0.047*	0.502 (10)
N1B	0.2012 (5)	0.3740 (7)	−0.0797 (9)	0.0277 (17)	0.502 (10)
C4B	0.1229 (2)	0.3951 (4)	−0.0512 (4)	0.0562 (14)	0.502 (10)
H4B	0.088958	0.418564	−0.129298	0.067*	0.502 (10)
C5	0.0860 (2)	0.3856 (3)	0.0843 (3)	0.0350 (8)
C6	0.13247 (18)	0.3733 (2)	0.2178 (3)	0.0262 (6)
C7	0.08859 (18)	0.3640 (2)	0.3459 (3)	0.0266 (6)
H7	0.117980	0.354849	0.435751	0.032*
C8	0.0033 (2)	0.3682 (3)	0.3419 (4)	0.0314 (7)
C9	−0.0422 (2)	0.3796 (3)	0.2103 (4)	0.0387 (9)
H9	−0.100637	0.381171	0.208214	0.046*
C10	−0.0011 (2)	0.3882 (3)	0.0860 (4)	0.0419 (9)
H10	−0.031936	0.396385	−0.002756	0.050*
C11	−0.0017 (2)	0.3665 (3)	0.5997 (4)	0.0381 (9)
H11A	0.034693	0.311966	0.613042	0.057*
H11B	−0.042486	0.366416	0.674618	0.057*
H11C	0.030915	0.424460	0.607071	0.057*
C12A	0.38366 (19)	0.3635 (2)	0.3554 (3)	0.0243 (6)	0.685 (9)
H12A	0.335667	0.326734	0.385629	0.029*	0.685 (9)
H12B	0.379671	0.427521	0.396816	0.029*	0.685 (9)
C13A	0.4644 (3)	0.3157 (3)	0.4149 (4)	0.0220 (11)	0.685 (9)
H13A	0.461564	0.307797	0.520789	0.026*	0.685 (9)
H13B	0.468442	0.252237	0.371564	0.026*	0.685 (9)
C14A	0.5412 (3)	0.3707 (5)	0.3836 (5)	0.0247 (11)	0.685 (9)
H14A	0.534321	0.436425	0.416470	0.030*	0.685 (9)
H14B	0.588457	0.343250	0.439901	0.030*	0.685 (9)
N2A	0.5596 (5)	0.3712 (5)	0.2307 (9)	0.0200 (12)	0.685 (9)
C15A	0.62992 (19)	0.3384 (3)	0.1943 (3)	0.0295 (7)	0.685 (9)
H15A	0.661471	0.305734	0.267187	0.035*	0.685 (9)
C12B	0.38366 (19)	0.3635 (2)	0.3554 (3)	0.0243 (6)	0.315 (9)
H12C	0.370098	0.298446	0.384172	0.029*	0.315 (9)
H12D	0.341392	0.406034	0.393091	0.029*	0.315 (9)
C13B	0.4644 (6)	0.3892 (7)	0.4192 (9)	0.024 (2)	0.315 (9)
H13C	0.463252	0.386990	0.525997	0.028*	0.315 (9)
H13D	0.478656	0.454041	0.390333	0.028*	0.315 (9)
C14B	0.5283 (7)	0.3209 (11)	0.3675 (10)	0.028 (3)	0.315 (9)
H14C	0.578366	0.324293	0.432046	0.033*	0.315 (9)
H14D	0.506479	0.255901	0.371196	0.033*	0.315 (9)
N2B	0.5494 (11)	0.3433 (11)	0.2190 (19)	0.017 (3)	0.315 (9)
C15B	0.62992 (19)	0.3384 (3)	0.1943 (3)	0.0295 (7)	0.315 (9)
H15B	0.666680	0.328994	0.275680	0.035*	0.315 (9)
C16	0.66532 (17)	0.3459 (2)	0.0556 (3)	0.0220 (5)
C17	0.62523 (17)	0.3916 (2)	−0.0659 (3)	0.0200 (5)
C18	0.67166 (17)	0.4068 (2)	−0.1896 (3)	0.0211 (5)
H18	0.647335	0.438772	−0.270845	0.025*
C19	0.75224 (17)	0.3755 (2)	−0.1934 (3)	0.0215 (5)
C20	0.79026 (19)	0.3267 (2)	−0.0757 (3)	0.0268 (6)
H20	0.844686	0.302990	−0.081051	0.032*
C21	0.74726 (18)	0.3143 (2)	0.0454 (3)	0.0245 (6)
H21	0.773215	0.283350	0.126147	0.029*
C22	0.7697 (2)	0.4359 (3)	−0.4321 (3)	0.0306 (7)
H22A	0.719692	0.404220	−0.469695	0.046*
H22B	0.810852	0.436109	−0.506282	0.046*
H22C	0.756497	0.500918	−0.406097	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01875 (17)	0.0373 (2)	0.01511 (15)	−0.00328 (15)	−0.00174 (12)	0.00247 (14)
Cu2	0.01825 (16)	0.02807 (19)	0.01484 (14)	0.00302 (14)	0.00010 (11)	0.00193 (13)
O1	0.0210 (9)	0.0340 (12)	0.0150 (8)	0.0007 (9)	0.0003 (7)	0.0001 (8)
O2	0.0151 (9)	0.0426 (13)	0.0198 (9)	−0.0014 (9)	−0.0014 (7)	0.0038 (9)
O3	0.0197 (11)	0.0725 (19)	0.0263 (11)	−0.0028 (11)	0.0006 (9)	−0.0019 (12)
O4	0.0196 (9)	0.0286 (11)	0.0153 (8)	0.0004 (8)	−0.0003 (7)	0.0039 (8)
O5	0.0165 (9)	0.0272 (11)	0.0191 (9)	0.0030 (7)	0.0015 (7)	0.0019 (8)
O6	0.0213 (10)	0.0393 (13)	0.0239 (10)	0.0025 (9)	0.0034 (8)	0.0025 (9)
C1A	0.0273 (15)	0.0387 (18)	0.0167 (12)	0.0018 (13)	0.0003 (10)	0.0051 (12)
C2A	0.037 (4)	0.028 (4)	0.016 (2)	−0.002 (3)	−0.005 (2)	−0.001 (2)
C3A	0.031 (3)	0.036 (5)	0.014 (2)	−0.010 (3)	−0.004 (2)	0.007 (2)
N1A	0.026 (3)	0.029 (4)	0.016 (2)	−0.001 (3)	0.000 (2)	0.002 (3)
C4A	0.0244 (16)	0.123 (5)	0.0200 (15)	−0.010 (2)	−0.0071 (13)	0.008 (2)
C1B	0.0273 (15)	0.0387 (18)	0.0167 (12)	0.0018 (13)	0.0003 (10)	0.0051 (12)
C2B	0.033 (4)	0.049 (6)	0.015 (3)	−0.007 (3)	−0.003 (2)	0.006 (3)
C3B	0.024 (3)	0.075 (7)	0.019 (3)	−0.022 (4)	−0.007 (2)	0.007 (3)
N1B	0.026 (3)	0.041 (5)	0.015 (2)	−0.005 (4)	−0.004 (2)	0.000 (4)
C4B	0.0244 (16)	0.123 (5)	0.0200 (15)	−0.010 (2)	−0.0071 (13)	0.008 (2)
C5	0.0222 (14)	0.061 (2)	0.0211 (13)	−0.0102 (15)	−0.0040 (11)	0.0069 (15)
C6	0.0180 (12)	0.0384 (18)	0.0218 (12)	−0.0037 (12)	−0.0029 (10)	0.0003 (12)
C7	0.0190 (13)	0.0402 (18)	0.0205 (12)	−0.0015 (12)	−0.0017 (10)	0.0017 (12)
C8	0.0213 (14)	0.046 (2)	0.0265 (14)	−0.0058 (13)	−0.0023 (11)	0.0015 (14)
C9	0.0196 (14)	0.067 (3)	0.0295 (16)	−0.0015 (16)	−0.0045 (12)	0.0004 (16)
C10	0.0246 (15)	0.071 (3)	0.0291 (16)	−0.0043 (17)	−0.0092 (13)	0.0050 (17)
C11	0.0206 (14)	0.069 (3)	0.0252 (14)	0.0034 (15)	0.0018 (12)	0.0017 (16)
C12A	0.0237 (14)	0.0331 (16)	0.0161 (11)	0.0001 (12)	0.0010 (10)	0.0045 (11)
C13A	0.025 (2)	0.027 (3)	0.0135 (16)	−0.0014 (17)	0.0015 (14)	0.0048 (15)
C14A	0.022 (2)	0.037 (3)	0.0148 (18)	−0.008 (2)	−0.0009 (15)	0.0012 (19)
N2A	0.018 (3)	0.025 (4)	0.017 (2)	−0.006 (2)	−0.0037 (17)	−0.002 (2)
C15A	0.0240 (14)	0.0435 (19)	0.0205 (13)	0.0037 (13)	−0.0043 (11)	0.0085 (13)
C12B	0.0237 (14)	0.0331 (16)	0.0161 (11)	0.0001 (12)	0.0010 (10)	0.0045 (11)
C13B	0.029 (5)	0.026 (6)	0.015 (4)	−0.006 (4)	0.001 (3)	−0.002 (3)
C14B	0.034 (6)	0.041 (7)	0.008 (3)	−0.001 (5)	−0.004 (3)	0.004 (4)
N2B	0.012 (5)	0.025 (8)	0.013 (4)	−0.007 (5)	−0.002 (3)	−0.006 (5)
C15B	0.0240 (14)	0.0435 (19)	0.0205 (13)	0.0037 (13)	−0.0043 (11)	0.0085 (13)
C16	0.0200 (13)	0.0252 (14)	0.0205 (12)	0.0022 (11)	0.0002 (10)	0.0027 (11)
C17	0.0206 (12)	0.0205 (13)	0.0186 (11)	0.0004 (11)	−0.0015 (9)	−0.0024 (10)
C18	0.0201 (12)	0.0241 (14)	0.0189 (11)	0.0024 (10)	0.0008 (10)	0.0006 (10)
C19	0.0183 (12)	0.0247 (14)	0.0220 (12)	−0.0009 (10)	0.0052 (10)	−0.0008 (10)
C20	0.0187 (13)	0.0317 (17)	0.0299 (14)	0.0046 (12)	−0.0012 (11)	−0.0002 (12)
C21	0.0177 (12)	0.0297 (16)	0.0257 (13)	0.0039 (11)	−0.0028 (10)	0.0035 (12)
C22	0.0261 (15)	0.0434 (19)	0.0226 (13)	0.0030 (14)	0.0056 (11)	0.0028 (13)

Geometric parameters (Å, º)

Cu1—O1	1.916 (2)	C5—C10	1.418 (5)
Cu1—O2	1.900 (2)	C6—C7	1.416 (4)
Cu1—O4	1.928 (2)	C7—H7	0.9500
Cu1—N1A	1.959 (8)	C7—C8	1.387 (4)
Cu1—N1B	1.942 (8)	C8—C9	1.406 (5)
Cu2—O1	1.941 (2)	C9—H9	0.9500
Cu2—O4	1.930 (2)	C9—C10	1.361 (5)
Cu2—O5	1.9242 (19)	C10—H10	0.9500
Cu2—O5^i	2.641 (2)	C11—H11A	0.9800
Cu2—N2A	1.982 (9)	C11—H11B	0.9800
Cu2—N2B	1.91 (2)	C11—H11C	0.9800
Cu1—Cu2	3.0251 (5)	C12A—H12A	0.9900
Cu2—Cu2^i	3.459 (5)	C12A—H12B	0.9900
O1—C1A	1.410 (3)	C12A—C13A	1.558 (5)
O1—C1B	1.410 (3)	C13A—H13A	0.9900
O2—C6	1.302 (4)	C13A—H13B	0.9900
O3—C8	1.359 (4)	C13A—C14A	1.511 (7)
O3—C11	1.433 (4)	C14A—H14A	0.9900
O4—C12A	1.414 (3)	C14A—H14B	0.9900
O4—C12B	1.414 (3)	C14A—N2A	1.459 (10)
O5—C17	1.312 (3)	N2A—C15A	1.293 (10)
O6—C19	1.362 (3)	C15A—H15A	0.9500
O6—C22	1.429 (4)	C15A—C16	1.434 (4)
C1A—H1AA	0.9900	C12B—H12C	0.9900
C1A—H1AB	0.9900	C12B—H12D	0.9900
C1A—C2A	1.539 (7)	C12B—C13B	1.462 (10)
C2A—H2AA	0.9900	C13B—H13C	0.9900
C2A—H2AB	0.9900	C13B—H13D	0.9900
C2A—C3A	1.519 (11)	C13B—C14B	1.514 (16)
C3A—H3AA	0.9900	C14B—H14C	0.9900
C3A—H3AB	0.9900	C14B—H14D	0.9900
C3A—N1A	1.473 (10)	C14B—N2B	1.47 (2)
N1A—C4A	1.306 (9)	N2B—C15B	1.341 (18)
C4A—H4A	0.9500	C15B—H15B	0.9500
C4A—C5	1.420 (5)	C15B—C16	1.434 (4)
C1B—H1BA	0.9900	C16—C17	1.430 (4)
C1B—H1BB	0.9900	C16—C21	1.413 (4)
C1B—C2B	1.486 (8)	C17—C18	1.416 (4)
C2B—H2BA	0.9900	C18—H18	0.9500
C2B—H2BB	0.9900	C18—C19	1.385 (4)
C2B—C3B	1.497 (12)	C19—C20	1.410 (4)
C3B—H3BA	0.9900	C20—H20	0.9500
C3B—H3BB	0.9900	C20—C21	1.359 (4)
C3B—N1B	1.497 (10)	C21—H21	0.9500
N1B—C4B	1.345 (10)	C22—H22A	0.9800
C4B—H4B	0.9500	C22—H22B	0.9800
C4B—C5	1.420 (5)	C22—H22C	0.9800
C5—C6	1.430 (4)
O1—Cu1—Cu2	38.62 (6)	O2—C6—C5	123.2 (3)
O1—Cu1—N1A	95.9 (2)	O2—C6—C7	118.9 (3)
O2—Cu1—Cu2	130.78 (6)	C7—C6—C5	117.9 (3)
O2—Cu1—N1A	94.7 (3)	C6—C7—H7	119.5
O4—Cu1—Cu2	38.38 (6)	C8—C7—C6	120.9 (3)
O4—Cu1—N1A	169.7 (3)	C8—C7—H7	119.5
O1—Cu1—N1B	95.5 (3)	O3—C8—C7	124.4 (3)
O2—Cu1—N1B	95.0 (3)	O3—C8—C9	114.5 (3)
O4—Cu1—N1B	167.0 (3)	C7—C8—C9	121.0 (3)
O2—Cu1—O1	169.33 (9)	C8—C9—H9	120.5
O2—Cu1—O4	92.70 (8)	C10—C9—C8	118.9 (3)
O1—Cu1—O4	76.63 (8)	C10—C9—H9	120.5
N1A—Cu1—Cu2	133.1 (2)	C5—C10—H10	118.9
N1B—Cu1—Cu2	134.0 (3)	C9—C10—C5	122.3 (3)
O1—Cu2—Cu1	38.03 (6)	C9—C10—H10	118.9
O1—Cu2—N2A	167.4 (2)	O3—C11—H11A	109.5
O4—Cu2—Cu1	38.35 (6)	O3—C11—H11B	109.5
O4—Cu2—N2A	95.3 (3)	O3—C11—H11C	109.5
O5—Cu2—Cu1	132.43 (6)	H11A—C11—H11B	109.5
O5—Cu2—N2A	93.8 (3)	H11A—C11—H11C	109.5
N2B—Cu2—O1	155.3 (4)	H11B—C11—H11C	109.5
N2B—Cu2—O4	91.4 (5)	O4—C12A—H12A	109.4
N2B—Cu2—O5	97.1 (5)	O4—C12A—H12B	109.4
O4—Cu2—O1	76.01 (8)	O4—C12A—C13A	111.1 (3)
O5—Cu2—O1	94.66 (8)	H12A—C12A—H12B	108.0
O5—Cu2—O4	170.65 (8)	C13A—C12A—H12A	109.4
N2A—Cu2—Cu1	133.6 (3)	C13A—C12A—H12B	109.4
N2B—Cu2—Cu1	128.2 (5)	C12A—C13A—H13A	108.9
Cu1—O1—Cu2	103.34 (9)	C12A—C13A—H13B	108.9
C1A—O1—Cu1	129.45 (18)	H13A—C13A—H13B	107.7
C1A—O1—Cu2	127.20 (18)	C14A—C13A—C12A	113.4 (4)
C1B—O1—Cu1	129.45 (18)	C14A—C13A—H13A	108.9
C1B—O1—Cu2	127.20 (18)	C14A—C13A—H13B	108.9
C6—O2—Cu1	127.56 (19)	C13A—C14A—H14A	108.9
C8—O3—C11	117.9 (3)	C13A—C14A—H14B	108.9
Cu1—O4—Cu2	103.27 (9)	H14A—C14A—H14B	107.7
C12A—O4—Cu1	127.22 (18)	N2A—C14A—C13A	113.3 (4)
C12A—O4—Cu2	128.12 (18)	N2A—C14A—H14A	108.9
C12B—O4—Cu1	127.22 (18)	N2A—C14A—H14B	108.9
C12B—O4—Cu2	128.12 (18)	C14A—N2A—Cu2	120.8 (6)
C17—O5—Cu2	125.17 (18)	C15A—N2A—Cu2	119.7 (6)
C19—O6—C22	118.5 (2)	C15A—N2A—C14A	118.2 (7)
O1—C1A—H1AA	109.3	N2A—C15A—H15A	116.5
O1—C1A—H1AB	109.3	N2A—C15A—C16	126.9 (5)
O1—C1A—C2A	111.5 (3)	C16—C15A—H15A	116.5
H1AA—C1A—H1AB	108.0	O4—C12B—H12C	109.3
C2A—C1A—H1AA	109.3	O4—C12B—H12D	109.3
C2A—C1A—H1AB	109.3	O4—C12B—C13B	111.6 (4)
C1A—C2A—H2AA	109.3	H12C—C12B—H12D	108.0
C1A—C2A—H2AB	109.3	C13B—C12B—H12C	109.3
H2AA—C2A—H2AB	108.0	C13B—C12B—H12D	109.3
C3A—C2A—C1A	111.6 (6)	C12B—C13B—H13C	109.8
C3A—C2A—H2AA	109.3	C12B—C13B—H13D	109.8
C3A—C2A—H2AB	109.3	C12B—C13B—C14B	109.2 (8)
C2A—C3A—H3AA	109.2	H13C—C13B—H13D	108.3
C2A—C3A—H3AB	109.2	C14B—C13B—H13C	109.8
H3AA—C3A—H3AB	107.9	C14B—C13B—H13D	109.8
N1A—C3A—C2A	112.2 (6)	C13B—C14B—H14C	109.6
N1A—C3A—H3AA	109.2	C13B—C14B—H14D	109.6
N1A—C3A—H3AB	109.2	H14C—C14B—H14D	108.1
C3A—N1A—Cu1	119.6 (6)	N2B—C14B—C13B	110.4 (11)
C4A—N1A—Cu1	120.5 (5)	N2B—C14B—H14C	109.6
C4A—N1A—C3A	117.8 (7)	N2B—C14B—H14D	109.6
N1A—C4A—H4A	116.7	C14B—N2B—Cu2	122.8 (12)
N1A—C4A—C5	126.5 (5)	C15B—N2B—Cu2	121.7 (12)
C5—C4A—H4A	116.7	C15B—N2B—C14B	114.8 (14)
O1—C1B—H1BA	109.2	N2B—C15B—H15B	117.2
O1—C1B—H1BB	109.2	N2B—C15B—C16	125.6 (8)
O1—C1B—C2B	111.9 (3)	C16—C15B—H15B	117.2
H1BA—C1B—H1BB	107.9	C17—C16—C15A	123.4 (3)
C2B—C1B—H1BA	109.2	C17—C16—C15B	123.4 (3)
C2B—C1B—H1BB	109.2	C21—C16—C15A	116.9 (3)
C1B—C2B—H2BA	108.9	C21—C16—C15B	116.9 (3)
C1B—C2B—H2BB	108.9	C21—C16—C17	119.3 (3)
C1B—C2B—C3B	113.5 (7)	O5—C17—C16	123.6 (3)
H2BA—C2B—H2BB	107.7	O5—C17—C18	118.7 (2)
C3B—C2B—H2BA	108.9	C18—C17—C16	117.7 (3)
C3B—C2B—H2BB	108.9	C17—C18—H18	119.7
C2B—C3B—H3BA	109.4	C19—C18—C17	120.7 (3)
C2B—C3B—H3BB	109.4	C19—C18—H18	119.7
H3BA—C3B—H3BB	108.0	O6—C19—C18	124.9 (3)
N1B—C3B—C2B	111.3 (6)	O6—C19—C20	113.7 (3)
N1B—C3B—H3BA	109.4	C18—C19—C20	121.4 (3)
N1B—C3B—H3BB	109.4	C19—C20—H20	120.8
C3B—N1B—Cu1	120.4 (6)	C21—C20—C19	118.5 (3)
C4B—N1B—Cu1	119.4 (5)	C21—C20—H20	120.8
C4B—N1B—C3B	118.6 (6)	C16—C21—H21	118.8
N1B—C4B—H4B	116.9	C20—C21—C16	122.4 (3)
N1B—C4B—C5	126.3 (5)	C20—C21—H21	118.8
C5—C4B—H4B	116.9	O6—C22—H22A	109.5
C4A—C5—C6	123.2 (3)	O6—C22—H22B	109.5
C4B—C5—C6	123.2 (3)	O6—C22—H22C	109.5
C10—C5—C4A	117.9 (3)	H22A—C22—H22B	109.5
C10—C5—C4B	117.9 (3)	H22A—C22—H22C	109.5
C10—C5—C6	118.9 (3)	H22B—C22—H22C	109.5

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3B—H3BB···O2^ii	0.99	2.48	3.385 (12)	152
C11—H11B···O6^iii	0.98	2.56	3.359 (4)	138
C12A—H12A···O2	0.99	2.51	2.979 (4)	109
C21—H21···O6^iv	0.95	2.54	3.279 (4)	135
C22—H22C···O2^i	0.98	2.52	3.362 (4)	144

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