(Piperidine-κN)[N-(salicyl­idene)­phenyl­alaninato-κ³O,N,O′]copper(II)

The tridentate Schiff base ligand derived from the condens­ation of salicyl­aldehyde and L-phenyl­alanine, in the presence of piperidine, when reacted with copper sulfate pentahydrate, forms a polymeric square pyramidal five-coord­inate copper complex, [Cu(C₁₇H₁₄O₃)(C₄H₁₀N₂)]. The axial position of the square pyramid is occupied by the carboxyl O atoms of a neighboring mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.082
• Data-to-parameter ratio = 14.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N(2)   -   H(2A)             ?

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      2
                   O2  -CU  -O1  -C2      9.80  1.20   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      4
                   O1  -CU  -O2  -C9     19.80  1.20   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #      9
                   N2  -CU  -N1  -C7   -161.50  1.50   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     12
                   N2  -CU  -N1  -C8     31.10  1.80   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     14
                   N1  -CU  -N2  -C25   -25.00  1.80   1.555   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #     17
                   N1  -CU  -N2  -C21   105.80  1.60   1.555   1.555   1.555   1.555

PLAT_711  Alert C BOND    Unknown or Inconsistent Label ........       O3A
                           CU     O3A

PLAT_712  Alert C ANGLE   Unknown or Inconsistent Label ........       O3A
                           O3A    CU     O1

PLAT_712  Alert C ANGLE   Unknown or Inconsistent Label ........       O3A
                           O3A    CU     O2

PLAT_712  Alert C ANGLE   Unknown or Inconsistent Label ........       O3A
                           O3A    CU     N1

PLAT_712  Alert C ANGLE   Unknown or Inconsistent Label ........       O3A
                           O3A    CU     N2

General Notes



ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      1.663
          Tmax scaled      0.790 Tmin scaled      0.562

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           32.50
         From the CIF: _reflns_number_total               3609
         Count of symmetry unique reflns         3429
         Completeness (_total/calc)            105.25%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       180
         Fraction of Friedel pairs measured     0.052
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 12 Alert Level C = Please check

---

S1. Comment

Galactose oxidase is a type II copper protein that catalyzes the oxidation of primary alcohols to aldehydes with a concomitant reduction of molecular oxygen (Whittaker, 1994). Its crystal structure (Ito et al., 1994) reveals a unique mononuclear Cu site with two N donors (from histidine imidazole groups), two O donors (one axial and one equatorial tyrosine group), and an exogenous water or acetate molecule, all arranged in a distorted square-pyramidal coordination. Several different theories have been proposed to explain how galactose oxidase, which contains a single Cu atom, can catalyze a two-electron redox reaction. The currently accepted theory (Whittaker & Whittaker, 2001) suggests that the `inactive' form of galactose oxidase is oxidized by the loss of one electron to produce the `active' form which contains a tyrosine (tyrosine 272) free radical ion coupled to the Cu^II ion. The active form is then reduced to the Cu^I species and the alcohol oxidized to the corresponding aldehyde.

There has been considerable interest in the study of model compounds of galactose oxidase in recent years (Butcher et al., 2003a,b; Kruse et al., 2002; Shimazaki et al., 2002; Thomas et al., 2002). One group of compounds that have attracted considerable interest consist of five-coordinate copper complexes with tridentate Schiff base ligands derived from the condensation of amino acids with substituted salicylaldehydes. In this type of complex, the Cu coordination sphere also contains a monodentate Lewis base. With two exceptions (Plesch et al., 1997; Sivy et al., 1994), X-ray crystallographic studies have shown that these Cu^II compounds contain Cu^II in a distorted square-pyramidal environment and fit into three main types:

(i) monomeric with a water molecule occupying the fifth coordination site (Butcher et al., 2003a; Dawes et al., 1982; Fujimaki et al., 1971; Garcia-Raso et al., 1996; Korhonen & Hamalainen, 1979; Ueki et al., 1969; Warda et al., 1996; Warda, 1997 g; Warda, 1998a,d,e,f);

(ii) dimeric with an adjacent phenolic O atom occupying the fifth coordination site (Butcher et al., 2003b; Davies, 1984; Hamalainen et al., 1978; Hill & Warda, 1999; Warda, 1997b,e; Warda, 1998b,c,e,g; Warda, 1999; Warda et al., 1998);

(iii) polymeric with the fifth coordination site occupied by an adjacent carboxyl O atom (Ukei et al., 1967; Kettman et al., 1993; Korhonen et al., 1984; Plesch et al., 1998; Warda et al., 1997; Warda, 1997a,b,c,d,f; Sivy et al., 1990).

The tridentate Schiff base ligand derived from the condensation of salicylaldehyde and l-phenylalanine, in the presence of piperidine, forms a square-pyramidal five-coordinate Cu complex of type iii. In this complex, the carboxyl O from an adjacent molecule occupies the apical site, at a distance of 2.674 (2) Å, forming a polymeric zigzag chain in the c direction. Unlike other square-pyramidal five-coordinate analogs, in this example, the Cu is only slightly displaced [0.012 (1) Å] from the basal plane formed by atoms O1, O2, N1, and N2, due to the comparatively weak out-of-plane bond to a neighboring carbonyl O donor. Neither the Cu—O1, Cu—O2, and Cu—N1 bond distances [1.918 (2), 1.964 (2), and 1.935 (2) Å, respectively] nor the Cu—N2 bond distance [2.002 (3) Å] differ significantly from those of similar type iii polymeric compounds mentioned above.

S2. Experimental

The title complex was synthesized in two stages. In the first stage, 10 g of l-phenylalanine (phenala) and an equimolar amount of sodium hydroxide were dissolved in 300 ml of hot water. To this solution was added an equimolar quantity of copper sulfate pentahydrate dissolved in 100 ml of water. The blue–purple [Cu(phenala)₂].nH₂O compound precipitated on cooling the solution. 6 g of this compound, two mole equivalents of salicylaldehyde, triethylamine (10 ml) and piperidine (10 ml) were refluxed in methanol for 1 h. The hot solution was filtered and allowed to stand until the dark-green product precipitated from solution. X-ray quality crystals were grown by slow evaporation from a methanol–acetonitrile solution.

S3. Refinement

All H atoms were included in calculated positions with C—H distances ranging from 0.93 to 0.98 Å and N—H distances of 0.91 Å. The H atoms were then included in the refinement using a riding-motion approximation, with U_iso = 1.2U_eq of the carrier atom.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the coordination sphere of the Cu, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms are represented by circles of arbitrary size.
	Fig. 2. The molecular packing viewed along the a axis, showing the zigzag chain of complexes in the c direction, linked through the carboxyl O atoms.

(Piperidine-κN)[N-(salicylidene)phenylalaninato-κ³O,N,O']copper(II)

Crystal data

[Cu(C17H14O3)(C4H10N2)]	F(000) = 868
Mr = 415.96	Dx = 1.462 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 8.7002 (9) Å	Cell parameters from 72 reflections
b = 22.6624 (15) Å	θ = 5.3–14.0°
c = 9.9711 (8) Å	µ = 1.18 mm^−1
β = 106.010 (7)°	T = 293 K
V = 1889.7 (3) Å^3	Chunk, dark green
Z = 4	0.58 × 0.28 × 0.20 mm

Data collection

Siemens P4S diffractometer	2912 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 32.5°, θmin = 2.8°
ω scans	h = −13→0
Absorption correction: empirical (using intensity measurements) (North et al., 1968)	k = 0→34
Tmin = 0.338, Tmax = 0.475	l = −14→15
3692 measured reflections	3 standard reflections every 97 reflections
3609 independent reflections	intensity decay: 1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0338P)^2 + 0.1576P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.082	(Δ/σ)max = 0.002
S = 1.02	Δρmax = 0.21 e Å^−3
3609 reflections	Δρmin = −0.21 e Å^−3
245 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0019 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.001 (13)

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.

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

	x	y	z	Uiso*/Ueq
Cu	0.17566 (3)	0.913602 (14)	0.10216 (3)	0.03518 (10)
O1	0.0359 (3)	0.88176 (11)	−0.0657 (2)	0.0458 (5)
O2	0.2992 (3)	0.95101 (10)	0.2762 (2)	0.0421 (5)
O3	0.2759 (3)	1.00042 (11)	0.4630 (2)	0.0505 (6)
N1	−0.0040 (3)	0.94124 (11)	0.1639 (2)	0.0341 (5)
N2	0.3710 (3)	0.88281 (13)	0.0524 (3)	0.0421 (6)
H2A	0.3907	0.9101	−0.0077	0.051*
C1	−0.2022 (3)	0.93480 (13)	−0.0599 (3)	0.0349 (5)
C2	−0.1095 (4)	0.89996 (12)	−0.1268 (3)	0.0376 (6)
C3	−0.1813 (5)	0.88563 (15)	−0.2689 (3)	0.0485 (8)
H3A	−0.1264	0.8615	−0.3155	0.058*
C4	−0.3304 (5)	0.90656 (16)	−0.3396 (4)	0.0580 (10)
H4A	−0.3725	0.8970	−0.4332	0.070*
C5	−0.4193 (4)	0.94164 (18)	−0.2741 (4)	0.0543 (9)
H5A	−0.5192	0.9558	−0.3235	0.065*
C6	−0.3571 (4)	0.95504 (15)	−0.1351 (4)	0.0454 (7)
H6A	−0.4168	0.9776	−0.0897	0.054*
C7	−0.1458 (3)	0.95207 (12)	0.0847 (3)	0.0351 (6)
H7A	−0.2162	0.9723	0.1234	0.042*
C8	0.0384 (4)	0.96191 (13)	0.3086 (3)	0.0392 (6)
H8A	−0.0165	0.9993	0.3127	0.047*
C81	−0.0095 (4)	0.91695 (17)	0.4063 (4)	0.0494 (8)
H81A	−0.0014	0.9360	0.4951	0.059*
H81B	−0.1206	0.9061	0.3662	0.059*
C82	0.0897 (4)	0.86149 (15)	0.4325 (3)	0.0429 (7)
C83	0.2191 (5)	0.85677 (18)	0.5497 (4)	0.0582 (9)
H83A	0.2412	0.8874	0.6142	0.070*
C84	0.3160 (5)	0.8072 (2)	0.5724 (4)	0.0676 (11)
H84A	0.4021	0.8051	0.6520	0.081*
C85	0.2869 (6)	0.76152 (19)	0.4795 (5)	0.0656 (11)
H85A	0.3538	0.7287	0.4945	0.079*
C86	0.1574 (6)	0.76452 (18)	0.3632 (4)	0.0607 (10)
H86A	0.1353	0.7333	0.3003	0.073*
C87	0.0600 (4)	0.81386 (17)	0.3398 (4)	0.0517 (8)
H87A	−0.0269	0.8154	0.2608	0.062*
C9	0.2186 (4)	0.97250 (12)	0.3537 (3)	0.0379 (6)
C21	0.3506 (5)	0.82616 (19)	−0.0273 (4)	0.0564 (10)
H21A	0.4412	0.8200	−0.0646	0.068*
H21B	0.2546	0.8280	−0.1048	0.068*
C22	0.3383 (6)	0.77587 (17)	0.0666 (4)	0.0631 (10)
H22A	0.3284	0.7392	0.0147	0.076*
H22B	0.2426	0.7806	0.0975	0.076*
C23	0.4818 (5)	0.77236 (16)	0.1921 (4)	0.0581 (10)
H23A	0.5748	0.7608	0.1626	0.070*
H23B	0.4636	0.7425	0.2557	0.070*
C24	0.5134 (4)	0.83102 (15)	0.2666 (4)	0.0472 (7)
H24A	0.4292	0.8391	0.3106	0.057*
H24C	0.6138	0.8290	0.3392	0.057*
C25	0.5209 (4)	0.88044 (16)	0.1679 (4)	0.0471 (8)
H25C	0.5363	0.9176	0.2179	0.056*
H25A	0.6111	0.8744	0.1300	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.02850 (13)	0.03775 (16)	0.03588 (15)	0.00512 (17)	0.00315 (10)	−0.00671 (17)
O1	0.0381 (11)	0.0491 (13)	0.0445 (12)	0.0069 (10)	0.0018 (9)	−0.0146 (10)
O2	0.0329 (10)	0.0505 (12)	0.0396 (11)	−0.0027 (9)	0.0043 (9)	−0.0074 (10)
O3	0.0571 (15)	0.0456 (12)	0.0405 (12)	−0.0065 (11)	−0.0004 (11)	−0.0125 (10)
N1	0.0310 (11)	0.0370 (12)	0.0322 (11)	0.0024 (9)	0.0049 (9)	−0.0062 (10)
N2	0.0419 (14)	0.0442 (14)	0.0433 (14)	0.0141 (11)	0.0171 (11)	0.0128 (11)
C1	0.0262 (11)	0.0371 (13)	0.0380 (13)	−0.0034 (11)	0.0032 (10)	0.0043 (11)
C2	0.0353 (14)	0.0325 (13)	0.0404 (14)	−0.0070 (11)	0.0028 (12)	−0.0023 (11)
C3	0.058 (2)	0.0408 (17)	0.0410 (16)	−0.0094 (15)	0.0034 (15)	−0.0088 (13)
C4	0.064 (2)	0.054 (2)	0.0414 (15)	−0.0158 (17)	−0.0099 (16)	0.0020 (15)
C5	0.0406 (17)	0.058 (2)	0.0510 (19)	−0.0048 (16)	−0.0099 (15)	0.0103 (16)
C6	0.0324 (14)	0.0481 (17)	0.0489 (17)	−0.0033 (12)	−0.0001 (12)	0.0073 (14)
C7	0.0290 (12)	0.0352 (13)	0.0404 (14)	0.0025 (10)	0.0083 (11)	0.0007 (11)
C8	0.0389 (14)	0.0412 (15)	0.0357 (14)	0.0048 (12)	0.0073 (11)	−0.0104 (12)
C81	0.0462 (17)	0.066 (2)	0.0387 (15)	−0.0062 (15)	0.0159 (13)	−0.0098 (15)
C82	0.0431 (15)	0.0517 (17)	0.0353 (14)	−0.0121 (14)	0.0134 (12)	0.0013 (13)
C83	0.070 (2)	0.060 (2)	0.0381 (16)	−0.0173 (19)	0.0047 (17)	−0.0010 (15)
C84	0.060 (2)	0.075 (3)	0.057 (2)	−0.009 (2)	−0.0023 (19)	0.024 (2)
C85	0.074 (3)	0.055 (2)	0.073 (3)	0.001 (2)	0.028 (2)	0.022 (2)
C86	0.074 (3)	0.053 (2)	0.062 (2)	−0.0191 (19)	0.031 (2)	−0.0062 (17)
C87	0.0488 (18)	0.061 (2)	0.0443 (17)	−0.0162 (16)	0.0104 (14)	−0.0085 (15)
C9	0.0436 (15)	0.0311 (13)	0.0332 (13)	−0.0022 (12)	0.0010 (12)	−0.0021 (10)
C21	0.056 (2)	0.071 (2)	0.0428 (17)	0.0259 (18)	0.0151 (15)	−0.0067 (16)
C22	0.076 (3)	0.0453 (19)	0.069 (3)	0.0050 (18)	0.022 (2)	−0.0146 (17)
C23	0.075 (3)	0.0408 (18)	0.065 (2)	0.0163 (17)	0.029 (2)	0.0098 (16)
C24	0.0449 (16)	0.0517 (18)	0.0418 (16)	0.0076 (14)	0.0064 (13)	0.0078 (14)
C25	0.0294 (14)	0.0455 (17)	0.065 (2)	0.0024 (13)	0.0109 (14)	0.0056 (15)

Geometric parameters (Å, º)

Cu—O1	1.918 (2)	C81—C82	1.506 (5)
Cu—N1	1.935 (2)	C81—H81A	0.9700
Cu—O2	1.964 (2)	C81—H81B	0.9700
Cu—N2	2.022 (3)	C82—C83	1.385 (5)
Cu—O3A	2.674 (2)	C82—C87	1.398 (5)
O1—C2	1.310 (4)	C83—C84	1.384 (6)
O2—C9	1.274 (4)	C83—H83A	0.9300
O3—C9	1.240 (3)	C84—C85	1.366 (7)
N1—C7	1.292 (3)	C84—H84A	0.9300
N1—C8	1.464 (4)	C85—C86	1.378 (6)
N2—C25	1.484 (4)	C85—H85A	0.9300
N2—C21	1.494 (5)	C86—C87	1.383 (6)
N2—H2A	0.9100	C86—H86A	0.9300
C1—C2	1.420 (4)	C87—H87A	0.9300
C1—C6	1.425 (4)	C21—C22	1.497 (6)
C1—C7	1.443 (4)	C21—H21A	0.9700
C2—C3	1.420 (4)	C21—H21B	0.9700
C3—C4	1.378 (6)	C22—C23	1.506 (6)
C3—H3A	0.9300	C22—H22A	0.9700
C4—C5	1.391 (7)	C22—H22B	0.9700
C4—H4A	0.9300	C23—C24	1.511 (5)
C5—C6	1.376 (5)	C23—H23A	0.9700
C5—H5A	0.9300	C23—H23B	0.9700
C6—H6A	0.9300	C24—C25	1.504 (5)
C7—H7A	0.9300	C24—H24A	0.9700
C8—C9	1.526 (4)	C24—H24C	0.9700
C8—C81	1.545 (5)	C25—H25C	0.9700
C8—H8A	0.9800	C25—H25A	0.9700
O1—Cu—N1	91.49 (10)	H81A—C81—H81B	107.6
O1—Cu—O2	173.91 (10)	C83—C82—C87	117.2 (4)
N1—Cu—O2	82.65 (10)	C83—C82—C81	120.3 (3)
O1—Cu—N2	91.69 (11)	C87—C82—C81	122.5 (3)
N1—Cu—N2	175.76 (11)	C84—C83—C82	121.2 (4)
O2—Cu—N2	94.24 (11)	C84—C83—H83A	119.4
O3A—Cu—O1	92.3 (1)	C82—C83—H83A	119.4
O3A—Cu—O2	88.1 (1)	C85—C84—C83	120.9 (4)
O3A—Cu—N1	109.7 (1)	C85—C84—H84A	119.6
O3A—Cu—N2	73.0 (1)	C83—C84—H84A	119.6
C2—O1—Cu	125.9 (2)	C84—C85—C86	119.3 (4)
C9—O2—Cu	116.25 (19)	C84—C85—H85A	120.4
C7—N1—C8	118.7 (2)	C86—C85—H85A	120.4
C7—N1—Cu	125.9 (2)	C85—C86—C87	120.2 (4)
C8—N1—Cu	114.27 (18)	C85—C86—H86A	119.9
C25—N2—C21	109.4 (3)	C87—C86—H86A	119.9
C25—N2—Cu	116.1 (2)	C86—C87—C82	121.3 (4)
C21—N2—Cu	116.3 (2)	C86—C87—H87A	119.3
C25—N2—H2A	104.5	C82—C87—H87A	119.3
C21—N2—H2A	104.5	O3—C9—O2	124.9 (3)
Cu—N2—H2A	104.5	O3—C9—C8	118.1 (3)
C2—C1—C6	120.6 (3)	O2—C9—C8	117.0 (2)
C2—C1—C7	122.7 (3)	N2—C21—C22	109.9 (3)
C6—C1—C7	116.7 (3)	N2—C21—H21A	109.7
O1—C2—C1	123.9 (3)	C22—C21—H21A	109.7
O1—C2—C3	119.7 (3)	N2—C21—H21B	109.7
C1—C2—C3	116.5 (3)	C22—C21—H21B	109.7
C4—C3—C2	121.6 (4)	H21A—C21—H21B	108.2
C4—C3—H3A	119.2	C21—C22—C23	111.9 (4)
C2—C3—H3A	119.2	C21—C22—H22A	109.2
C3—C4—C5	121.6 (3)	C23—C22—H22A	109.2
C3—C4—H4A	119.2	C21—C22—H22B	109.2
C5—C4—H4A	119.2	C23—C22—H22B	109.2
C6—C5—C4	118.9 (3)	H22A—C22—H22B	107.9
C6—C5—H5A	120.5	C22—C23—C24	111.0 (3)
C4—C5—H5A	120.5	C22—C23—H23A	109.4
C5—C6—C1	120.8 (3)	C24—C23—H23A	109.4
C5—C6—H6A	119.6	C22—C23—H23B	109.4
C1—C6—H6A	119.6	C24—C23—H23B	109.4
N1—C7—C1	124.3 (3)	H23A—C23—H23B	108.0
N1—C7—H7A	117.9	C25—C24—C23	111.6 (3)
C1—C7—H7A	117.9	C25—C24—H24A	109.3
N1—C8—C9	107.5 (2)	C23—C24—H24A	109.3
N1—C8—C81	111.9 (3)	C25—C24—H24C	109.3
C9—C8—C81	110.6 (3)	C23—C24—H24C	109.3
N1—C8—H8A	109.0	H24A—C24—H24C	108.0
C9—C8—H8A	109.0	N2—C25—C24	110.3 (3)
C81—C8—H8A	109.0	N2—C25—H25C	109.6
C82—C81—C8	114.7 (3)	C24—C25—H25C	109.6
C82—C81—H81A	108.6	N2—C25—H25A	109.6
C8—C81—H81A	108.6	C24—C25—H25A	109.6
C82—C81—H81B	108.6	H25C—C25—H25A	108.1
C8—C81—H81B	108.6
N1—Cu—O1—C2	25.7 (3)	C2—C1—C7—N1	4.8 (5)
O2—Cu—O1—C2	9.8 (12)	C6—C1—C7—N1	−174.4 (3)
N2—Cu—O1—C2	−157.1 (3)	C7—N1—C8—C9	−151.7 (3)
O1—Cu—O2—C9	19.8 (12)	Cu—N1—C8—C9	16.7 (3)
N1—Cu—O2—C9	3.8 (2)	C7—N1—C8—C81	86.7 (3)
N2—Cu—O2—C9	−173.3 (2)	Cu—N1—C8—C81	−104.8 (3)
O1—Cu—N1—C7	−22.9 (3)	N1—C8—C81—C82	70.9 (4)
O2—Cu—N1—C7	155.4 (3)	C9—C8—C81—C82	−48.8 (3)
N2—Cu—N1—C7	−161.5 (15)	C8—C81—C82—C83	95.4 (4)
O1—Cu—N1—C8	169.6 (2)	C8—C81—C82—C87	−82.5 (4)
O2—Cu—N1—C8	−12.1 (2)	C87—C82—C83—C84	1.0 (5)
N2—Cu—N1—C8	31.1 (18)	C81—C82—C83—C84	−177.1 (4)
O1—Cu—N2—C25	−163.6 (2)	C82—C83—C84—C85	0.1 (6)
N1—Cu—N2—C25	−25.0 (18)	C83—C84—C85—C86	−1.3 (6)
O2—Cu—N2—C25	17.8 (2)	C84—C85—C86—C87	1.3 (6)
O1—Cu—N2—C21	−32.8 (2)	C85—C86—C87—C82	−0.2 (6)
N1—Cu—N2—C21	105.8 (16)	C83—C82—C87—C86	−0.9 (5)
O2—Cu—N2—C21	148.6 (2)	C81—C82—C87—C86	177.0 (3)
Cu—O1—C2—C1	−17.9 (4)	Cu—O2—C9—O3	−175.8 (2)
Cu—O1—C2—C3	161.0 (2)	Cu—O2—C9—C8	5.2 (3)
C6—C1—C2—O1	177.3 (3)	N1—C8—C9—O3	166.8 (3)
C7—C1—C2—O1	−2.0 (5)	C81—C8—C9—O3	−70.9 (3)
C6—C1—C2—C3	−1.6 (4)	N1—C8—C9—O2	−14.2 (4)
C7—C1—C2—C3	179.1 (3)	C81—C8—C9—O2	108.2 (3)
O1—C2—C3—C4	−176.3 (3)	C25—N2—C21—C22	61.3 (4)
C1—C2—C3—C4	2.6 (5)	Cu—N2—C21—C22	−72.6 (3)
C2—C3—C4—C5	−1.5 (6)	N2—C21—C22—C23	−57.2 (4)
C3—C4—C5—C6	−0.8 (6)	C21—C22—C23—C24	52.2 (4)
C4—C5—C6—C1	1.7 (5)	C22—C23—C24—C25	−51.6 (4)
C2—C1—C6—C5	−0.5 (5)	C21—N2—C25—C24	−61.1 (4)
C7—C1—C6—C5	178.8 (3)	Cu—N2—C25—C24	72.9 (3)
C8—N1—C7—C1	179.3 (3)	C23—C24—C25—N2	56.6 (4)
Cu—N1—C7—C1	12.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O3^i	0.91	2.24	2.841 (4)	123

Symmetry code: (i) x, −y+2, z−1/2.