(2,9-Dimethyl-1,10-phenanthroline-κ²N,N′)(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)copper(II) trihydrate

The copper(II) centre in the mononuclear title complex, [Cu(C₇H₃NO₄)(C₁₄H₁₂N₂)]·3H₂O, is surrounded by one bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and one tridentate pyridine-2,6-dicarboxylate ligand, and exhibits a distorted square-pyramidal geometry. The crystal packing involves both hydrogen-bonding and π–π inter­actions. The solvent water mol­ecules link monomers to one another through hydrogen-bonding inter­actions, forming ladder-like chains in the bc plane. Face-to-face and slipped π–π inter­actions also occur between dmphen rings of neighboring mol­ecules and are responsible for inter­chain packing.

S1. Comment

Pyridine-2,6-dicarboxylic acid (dipicolinic acid) is regarded as the key component for the high heat resistance of bacterial spores, owing to its ability to build stabilizing structures with divalent metals (Chung et al., 1971). Metal complexes of this ligand have been studied extensively because of its ability to form stable chelates (Ducommun et al., 1989) with different coordination modes, such as bidentate (Zhou & Kostic, 1988) or bridging (Sengupta et al., 1983). Since rare-earth metals are known to have antitumor activity (Zhou et al., 2001), a series of isomorphous dipicolinate complexes with these metals were synthesized and the structures were reported (Chen et al., 2002; Okabe et al., 2002). To clarify further the coordination modes of chelates of pyridine-2,6-dicarboxylic acid with biologically important transition metal ions, we report here the synthesis and crystal structure of a mononuclear copper dipicolinate (dpc) compound with 2,9-dimethyl-1,10-phenanthroline (dmphen).

The structure of the title compound, (I) (Fig. 1), consists of a neutral [Cu(dpc)(dmphen)] unit and three solvent water molecules. The dpc anion with its two carboxylate groups in ortho-positions with respect to the pyridine N atom is potentially tridentate. The copper ion is bonded to the pyridine N atom [Cu1—N3 = 1.904 (2) Å] as well as to one O atom of each carboxylate group [Cu1—O1 = 2.0343 (18) Å and Cu1—O2 = 2.019 (2) Å]. The dmphen ligand chelates the copper center [Cu1—N1 = 1.987 (2) and Cu1—N2 = 2.228 (2) Å]. These bond distances are comparable to those found in other copper–dipicolinate complexes (Okabe & Oya, 2000; Altin et al., 2004; Chaigneau et al., 2004). The degree of trigonality τ = 0.1 indicates that the Cu^II ion lies in a distorted square-pyramidal environment. [As defined by Addison et al. (1984), τ is 0 for the regular square-pyramidal (SQP) structure and increases to 1 for the trigonal-bipyramidal (TBP) structure.] The dmphen atom N2 occupies the axial position, while the base is formed by the two carboxylate O atoms, one pyridine N atom from the dpc anion and one N atom from the dmphen ligand. The Cu atom lies 0.1681 (18) Å out of the basal plane, which is distorted from a square by the double chelate formed by dpc and which, furthermore, is not completly planar [maximum atomic deviation 0.0512 (12) Å].

The fact that the Cu1—N3 distance is significantly shorter than the two Cu—N(dmphen) distances indicates that atom N3 is the strongest donor site, since the two carboxylate groups in ortho positions enhance the basicity of atom N3. The dpc chelate angles are 79.71 (8) and 80.33 (8)°, which are comparable to those found in other Cu–dipicolinate complexes (Okabe & Oya, 2000; Chaigneau et al., 2004). The internal geometry of the dmphen ligand is similar to that established in previous studies (Kon et al., 1987; Kovalevsky et al., 2003). All atoms in the dpc anion are also nearly coplanar, with a maximum deviation of 0.0648 (17) Å for atom O1. The dihedral angle between the dmphen and dpc planes is 80.29 (4)°.

Both intermolecular hydrogen-bonding and π–π interactions combine to stabilize the extended structure (Fig. 2). The uncoordinated water molecules link molecules of the complex, acting as hydrogen-bond donors to the unligated carboxylate O atoms (Table 2). These interactions mediate the formation of ladder-type chains in the bc plane (Fig. 2). Adjacent chains are linked by π–π interactions, which are either face-to-face interactions [CgA···CgA^v = 3.6307 (15) Å; CgA is the center of the C4–C7/C11/C12 ring; symmetry code: (v) 1 − x, −y, −z] or slipped interactions [CgB···CgC^vi = 3.7184 (15) Å; CgB is the center of the C1–C4/C12/N1 ring and CgC is the center of the C7–C10/N2/C11; symmetry code: (vi) 1 − x, −1/2 + y, 1/2 − z]. Ring A is oriented in such a way that the perpendicular distance from A to A^v is 3.428 Å, the closest interatomic distance being C12···C7^v [3.451 (4) Å]. The perpendicular distance from ring B to ring C^vi is 3.281 Å, the closest interatomic distance being C12···C9^vi [3.392 (4) Å]; the dihedral angle between these rings is 14.99 (6)°.

S2. Experimental

To an EtOH/H₂O solution (30 ml, ca 1:1 v/v) containing CuCl₂·4H₂O (1 mmol) and disodium dipicolinate (1 mmol), 2,9-dimethyl-1,10-phenanthroline (1 mmol) was added slowly with continuous stirring. The resulting solution was refluxed for 1 h and then filtered. The blue filtrate was allowed to stand for 21 d at room temperature, after which time blue crystals of (I) suitable for X-ray difraction analysis were harvested.

S3. Refinement

H atoms attached to C atoms were placed at calculated positions (C—H = 0.93 and 0.96 Å) and were allowed to ride on their parent atoms [U_iso(H) = 1.2_eq(C) and 1.5_eq(C_methyl)]. The water H atoms were located in a difference map and refined with O—H and H_water···H_water distances restrained to 0.85 (3) and 1.35 (3) Å, and with U_iso(H)=1.5U_eq(O).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. : A view of the title compound, showing the atom labelling scheme and 40% probability displacement ellipsoids. The water molecules have been omitted for clarity.
	Fig. 2. : A partial view of the packing, showing hydrogen-bond and π–π interactions as dashed lines. H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (v) 1 − x, −y, −z; (vi) 1 − x, −1/2 + y, 1/2 − z.]

(2,9-Dimethyl-1,10-phenanthroline-κ²,N·N')(dipicolinato- κ³O²,N,O⁶)copper(II) trihydrate

Crystal data

[Cu(C7H3NO4)(C14H12N2)]·3H2O	F(000) = 1012
Mr = 490.96	Dx = 1.595 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4580 reflections
a = 14.6634 (12) Å	θ = 1.8–24.9°
b = 10.8960 (6) Å	µ = 1.12 mm^−1
c = 13.6985 (11) Å	T = 297 K
β = 110.866 (6)°	Prism, blue
V = 2045.1 (3) Å^3	0.3 × 0.2 × 0.1 mm
Z = 4

Data collection

STOE IPDS-II diffractometer	4848 independent reflections
Radiation source: fine-focus sealed tube	3555 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
Detector resolution: 6.67 pixels mm^-1	θmax = 27.9°, θmin = 2.4°
ω scans	h = −19→19
Absorption correction: integration (X-RED32, Stoe & Cie, 2002)	k = −14→14
Tmin = 0.95, Tmax = 0.98	l = −17→17
17419 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0533P)^2] where P = (Fo^2 + 2Fc^2)/3
4848 reflections	(Δ/σ)max = 0.041
309 parameters	Δρmax = 0.40 e Å^−3
9 restraints	Δρmin = −0.74 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.27607 (2)	−0.01166 (3)	0.09910 (2)	0.03404 (10)
C1	0.3511 (2)	−0.2549 (2)	0.0686 (2)	0.0392 (6)
C2	0.4248 (2)	−0.3380 (2)	0.0715 (2)	0.0477 (7)
H2	0.4093	−0.4203	0.0564	0.057*
C3	0.5183 (2)	−0.3001 (3)	0.0961 (2)	0.0490 (7)
H3	0.5670	−0.3566	0.0996	0.059*
C4	0.5416 (2)	−0.1751 (3)	0.1163 (2)	0.0414 (6)
C5	0.6372 (2)	−0.1258 (3)	0.1399 (2)	0.0517 (7)
H5	0.6881	−0.1779	0.1422	0.062*
C6	0.6549 (2)	−0.0050 (3)	0.1590 (2)	0.0534 (8)
H6	0.7182	0.0246	0.1763	0.064*
C7	0.5780 (2)	0.0777 (3)	0.1529 (2)	0.0450 (6)
C8	0.5912 (3)	0.2058 (3)	0.1682 (2)	0.0537 (8)
H8	0.6533	0.2400	0.1874	0.064*
C9	0.5124 (3)	0.2784 (3)	0.1546 (2)	0.0500 (7)
H9	0.5206	0.3628	0.1636	0.060*
C10	0.4189 (2)	0.2278 (2)	0.1272 (2)	0.0416 (6)
C11	0.48273 (19)	0.0337 (2)	0.12848 (18)	0.0349 (5)
C12	0.46411 (19)	−0.0961 (2)	0.11107 (19)	0.0341 (5)
C13	0.2476 (3)	−0.2945 (3)	0.0418 (3)	0.0587 (8)
H13A	0.2203	−0.2545	0.0875	0.088*
H13B	0.2452	−0.3818	0.0500	0.088*
H13C	0.2108	−0.2726	−0.0292	0.088*
C14	0.3310 (3)	0.3059 (3)	0.1060 (2)	0.0539 (8)
H14A	0.2930	0.3041	0.0326	0.081*
H14B	0.3506	0.3887	0.1270	0.081*
H14C	0.2925	0.2753	0.1445	0.081*
C15	0.16382 (19)	0.0903 (2)	0.20701 (19)	0.0337 (5)
C16	0.0902 (2)	0.1587 (2)	0.2187 (2)	0.0430 (6)
H16	0.0889	0.1750	0.2848	0.052*
C17	0.0177 (2)	0.2031 (3)	0.1305 (2)	0.0463 (7)
H17	−0.0329	0.2495	0.1373	0.056*
C18	0.0198 (2)	0.1790 (2)	0.0321 (2)	0.0425 (6)
H18	−0.0289	0.2084	−0.0276	0.051*
C19	0.09610 (19)	0.1102 (2)	0.02527 (19)	0.0333 (5)
C20	0.2518 (2)	0.0333 (2)	0.2907 (2)	0.0363 (5)
C21	0.1148 (2)	0.0702 (2)	−0.0717 (2)	0.0365 (5)
N1	0.37136 (16)	−0.13601 (17)	0.08878 (16)	0.0327 (4)
N2	0.40487 (16)	0.10646 (18)	0.11619 (16)	0.0346 (4)
N3	0.16602 (15)	0.07023 (17)	0.11152 (16)	0.0320 (4)
O1	0.31235 (14)	−0.01866 (16)	0.25682 (14)	0.0403 (4)
O2	0.19180 (15)	0.00595 (18)	−0.05317 (15)	0.0453 (4)
O3	0.26026 (16)	0.04276 (19)	0.38309 (15)	0.0492 (5)
O4	0.05724 (16)	0.09917 (18)	−0.15889 (15)	0.0480 (5)
O5	0.1347 (2)	0.7793 (3)	0.2328 (3)	0.0855 (8)
H5A	0.117 (4)	0.700 (2)	0.217 (4)	0.128*
H5B	0.079 (3)	0.817 (4)	0.203 (4)	0.128*
O6	0.1103 (2)	0.0615 (3)	0.4778 (2)	0.0787 (8)
H6A	0.058 (2)	0.041 (5)	0.440 (4)	0.118*
H6B	0.154 (3)	0.049 (5)	0.454 (4)	0.118*
O7	0.0826 (2)	0.5276 (2)	0.1669 (2)	0.0702 (7)
H7A	0.098 (4)	0.489 (4)	0.127 (3)	0.105*
H7B	0.072 (4)	0.487 (4)	0.212 (3)	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02848 (16)	0.04103 (17)	0.03474 (16)	0.00414 (13)	0.01386 (12)	−0.00220 (12)
C1	0.0437 (15)	0.0369 (12)	0.0413 (14)	0.0019 (11)	0.0204 (12)	−0.0042 (10)
C2	0.0586 (19)	0.0404 (13)	0.0484 (16)	0.0108 (13)	0.0243 (14)	0.0009 (11)
C3	0.0513 (18)	0.0555 (16)	0.0439 (16)	0.0242 (14)	0.0213 (14)	0.0066 (12)
C4	0.0332 (14)	0.0629 (16)	0.0299 (12)	0.0133 (12)	0.0134 (11)	0.0025 (11)
C5	0.0313 (14)	0.087 (2)	0.0393 (14)	0.0143 (14)	0.0151 (12)	0.0027 (14)
C6	0.0290 (13)	0.094 (2)	0.0380 (14)	−0.0046 (15)	0.0127 (11)	0.0020 (15)
C7	0.0371 (14)	0.0693 (17)	0.0294 (13)	−0.0122 (13)	0.0129 (11)	−0.0007 (11)
C8	0.0554 (19)	0.0713 (19)	0.0367 (15)	−0.0310 (16)	0.0193 (14)	−0.0045 (13)
C9	0.066 (2)	0.0495 (14)	0.0355 (14)	−0.0205 (15)	0.0201 (14)	−0.0037 (11)
C10	0.0552 (18)	0.0403 (12)	0.0308 (12)	−0.0092 (12)	0.0172 (12)	−0.0005 (10)
C11	0.0321 (12)	0.0471 (13)	0.0266 (11)	−0.0046 (10)	0.0118 (10)	−0.0014 (9)
C12	0.0302 (12)	0.0452 (12)	0.0294 (11)	0.0031 (10)	0.0137 (10)	0.0003 (9)
C13	0.0504 (19)	0.0460 (15)	0.085 (2)	−0.0077 (13)	0.0298 (18)	−0.0155 (15)
C14	0.071 (2)	0.0399 (14)	0.0494 (17)	0.0040 (14)	0.0190 (16)	0.0012 (12)
C15	0.0358 (13)	0.0324 (11)	0.0353 (12)	−0.0036 (10)	0.0159 (11)	−0.0035 (9)
C16	0.0444 (16)	0.0461 (13)	0.0436 (14)	0.0055 (12)	0.0221 (13)	−0.0032 (11)
C17	0.0408 (15)	0.0496 (14)	0.0524 (17)	0.0146 (12)	0.0215 (14)	−0.0010 (12)
C18	0.0370 (15)	0.0465 (13)	0.0431 (14)	0.0080 (12)	0.0133 (12)	0.0051 (11)
C19	0.0312 (12)	0.0345 (11)	0.0360 (12)	−0.0023 (9)	0.0140 (10)	0.0005 (9)
C20	0.0363 (13)	0.0384 (12)	0.0350 (12)	−0.0003 (10)	0.0136 (11)	0.0002 (9)
C21	0.0357 (13)	0.0412 (12)	0.0344 (12)	−0.0027 (11)	0.0147 (11)	0.0004 (10)
N1	0.0315 (11)	0.0362 (9)	0.0327 (10)	0.0016 (8)	0.0143 (9)	−0.0017 (8)
N2	0.0368 (12)	0.0379 (10)	0.0301 (10)	−0.0023 (8)	0.0133 (9)	−0.0012 (8)
N3	0.0307 (10)	0.0335 (9)	0.0337 (10)	−0.0001 (8)	0.0137 (8)	−0.0010 (8)
O1	0.0367 (10)	0.0494 (9)	0.0358 (9)	0.0091 (8)	0.0141 (8)	0.0026 (7)
O2	0.0383 (10)	0.0643 (11)	0.0369 (9)	0.0104 (9)	0.0178 (8)	−0.0021 (8)
O3	0.0496 (12)	0.0664 (12)	0.0334 (10)	0.0041 (10)	0.0169 (9)	−0.0005 (8)
O4	0.0501 (12)	0.0562 (11)	0.0352 (10)	0.0059 (9)	0.0123 (9)	0.0043 (8)
O5	0.0615 (18)	0.0929 (19)	0.098 (2)	−0.0085 (16)	0.0237 (17)	0.0039 (18)
O6	0.0603 (17)	0.107 (2)	0.0774 (19)	0.0086 (17)	0.0352 (15)	0.0035 (16)
O7	0.0786 (19)	0.0784 (16)	0.0571 (15)	−0.0038 (14)	0.0286 (14)	0.0036 (12)

Geometric parameters (Å, º)

Cu1—N2	2.228 (2)	C12—N1	1.355 (3)
Cu1—N3	1.904 (2)	C13—H13A	0.9600
Cu1—N1	1.987 (2)	C13—H13B	0.9600
Cu1—O1	2.0343 (18)	C13—H13C	0.9600
Cu1—O2	2.019 (2)	C14—H14A	0.9600
C1—N1	1.336 (3)	C14—H14B	0.9600
C1—C2	1.398 (4)	C14—H14C	0.9600
C1—C13	1.493 (4)	C15—N3	1.338 (3)
C2—C3	1.355 (5)	C15—C16	1.368 (4)
C2—H2	0.9300	C15—C20	1.520 (4)
C3—C4	1.407 (4)	C16—C17	1.381 (4)
C3—H3	0.9300	C16—H16	0.9300
C4—C12	1.407 (4)	C17—C18	1.384 (4)
C4—C5	1.426 (4)	C17—H17	0.9300
C5—C6	1.350 (5)	C18—C19	1.378 (4)
C5—H5	0.9300	C18—H18	0.9300
C6—C7	1.423 (4)	C19—N3	1.332 (3)
C6—H6	0.9300	C19—C21	1.513 (3)
C7—C11	1.400 (4)	C20—O3	1.231 (3)
C7—C8	1.415 (4)	C20—O1	1.272 (3)
C8—C9	1.357 (5)	C21—O4	1.233 (3)
C8—H8	0.9300	C21—O2	1.275 (3)
C9—C10	1.399 (4)	O5—H5A	0.91 (3)
C9—H9	0.9300	O5—H5B	0.88 (3)
C10—N2	1.338 (3)	O6—H6A	0.79 (3)
C10—C14	1.485 (4)	O6—H6B	0.82 (3)
C11—N2	1.350 (3)	O7—H7A	0.78 (2)
C11—C12	1.444 (3)	O7—H7B	0.83 (2)
N3—Cu1—N1	164.96 (8)	C1—C13—H13B	109.5
N3—Cu1—O2	79.71 (8)	H13A—C13—H13B	109.5
N1—Cu1—O2	100.28 (8)	C1—C13—H13C	109.5
N3—Cu1—O1	80.33 (8)	H13A—C13—H13C	109.5
N1—Cu1—O1	97.21 (8)	H13B—C13—H13C	109.5
O2—Cu1—O1	158.89 (8)	C10—C14—H14A	109.5
N3—Cu1—N2	115.70 (8)	C10—C14—H14B	109.5
N1—Cu1—N2	79.06 (8)	H14A—C14—H14B	109.5
O2—Cu1—N2	103.75 (8)	C10—C14—H14C	109.5
O1—Cu1—N2	91.08 (8)	H14A—C14—H14C	109.5
N1—C1—C2	120.6 (3)	H14B—C14—H14C	109.5
N1—C1—C13	117.5 (2)	N3—C15—C16	119.9 (2)
C2—C1—C13	121.8 (2)	N3—C15—C20	111.2 (2)
C3—C2—C1	120.9 (3)	C16—C15—C20	128.9 (2)
C3—C2—H2	119.6	C15—C16—C17	118.8 (3)
C1—C2—H2	119.6	C15—C16—H16	120.6
C2—C3—C4	119.7 (3)	C17—C16—H16	120.6
C2—C3—H3	120.1	C16—C17—C18	120.6 (3)
C4—C3—H3	120.1	C16—C17—H17	119.7
C12—C4—C3	116.6 (3)	C18—C17—H17	119.7
C12—C4—C5	119.4 (3)	C19—C18—C17	118.0 (3)
C3—C4—C5	124.0 (3)	C19—C18—H18	121.0
C6—C5—C4	121.2 (3)	C17—C18—H18	121.0
C6—C5—H5	119.4	N3—C19—C18	120.3 (2)
C4—C5—H5	119.4	N3—C19—C21	111.2 (2)
C5—C6—C7	120.8 (3)	C18—C19—C21	128.4 (2)
C5—C6—H6	119.6	O3—C20—O1	125.8 (2)
C7—C6—H6	119.6	O3—C20—C15	119.3 (2)
C11—C7—C8	116.4 (3)	O1—C20—C15	115.0 (2)
C11—C7—C6	120.0 (3)	O4—C21—O2	125.8 (2)
C8—C7—C6	123.5 (3)	O4—C21—C19	120.1 (2)
C9—C8—C7	119.3 (3)	O2—C21—C19	114.1 (2)
C9—C8—H8	120.3	C1—N1—C12	119.3 (2)
C7—C8—H8	120.3	C1—N1—Cu1	124.49 (19)
C8—C9—C10	120.8 (3)	C12—N1—Cu1	116.08 (15)
C8—C9—H9	119.6	C10—N2—C11	118.4 (2)
C10—C9—H9	119.6	C10—N2—Cu1	132.33 (19)
N2—C10—C9	121.1 (3)	C11—N2—Cu1	108.77 (15)
N2—C10—C14	117.1 (3)	C19—N3—C15	122.3 (2)
C9—C10—C14	121.7 (3)	C19—N3—Cu1	118.89 (16)
N2—C11—C7	123.8 (2)	C15—N3—Cu1	118.70 (18)
N2—C11—C12	116.9 (2)	C20—O1—Cu1	114.73 (16)
C7—C11—C12	119.2 (2)	C21—O2—Cu1	115.49 (16)
N1—C12—C4	122.8 (2)	H5A—O5—H5B	102 (3)
N1—C12—C11	117.9 (2)	H6A—O6—H6B	114 (4)
C4—C12—C11	119.3 (2)	H7A—O7—H7B	114 (4)
C1—C13—H13A	109.5
N1—C1—C2—C3	0.8 (4)	O1—Cu1—N1—C1	94.7 (2)
C13—C1—C2—C3	−179.9 (3)	N2—Cu1—N1—C1	−175.6 (2)
C1—C2—C3—C4	−1.7 (4)	N3—Cu1—N1—C12	−160.2 (3)
C2—C3—C4—C12	1.0 (4)	O2—Cu1—N1—C12	111.20 (18)
C2—C3—C4—C5	−178.2 (3)	O1—Cu1—N1—C12	−80.69 (18)
C12—C4—C5—C6	1.1 (4)	N2—Cu1—N1—C12	9.02 (17)
C3—C4—C5—C6	−179.8 (3)	C9—C10—N2—C11	−2.3 (4)
C4—C5—C6—C7	−2.0 (4)	C14—C10—N2—C11	175.8 (2)
C5—C6—C7—C11	1.0 (4)	C9—C10—N2—Cu1	168.81 (19)
C5—C6—C7—C8	−177.6 (3)	C14—C10—N2—Cu1	−13.1 (4)
C11—C7—C8—C9	−2.7 (4)	C7—C11—N2—C10	0.4 (4)
C6—C7—C8—C9	176.0 (3)	C12—C11—N2—C10	−177.1 (2)
C7—C8—C9—C10	1.0 (4)	C7—C11—N2—Cu1	−172.6 (2)
C8—C9—C10—N2	1.6 (4)	C12—C11—N2—Cu1	9.8 (3)
C8—C9—C10—C14	−176.4 (3)	N3—Cu1—N2—C10	−5.0 (3)
C8—C7—C11—N2	2.0 (4)	N1—Cu1—N2—C10	178.1 (2)
C6—C7—C11—N2	−176.7 (2)	O2—Cu1—N2—C10	80.0 (2)
C8—C7—C11—C12	179.5 (2)	O1—Cu1—N2—C10	−84.8 (2)
C6—C7—C11—C12	0.8 (4)	N3—Cu1—N2—C11	166.74 (15)
C3—C4—C12—N1	0.6 (4)	N1—Cu1—N2—C11	−10.17 (15)
C5—C4—C12—N1	179.8 (2)	O2—Cu1—N2—C11	−108.20 (16)
C3—C4—C12—C11	−178.5 (2)	O1—Cu1—N2—C11	86.96 (16)
C5—C4—C12—C11	0.7 (4)	C18—C19—N3—C15	2.7 (4)
N2—C11—C12—N1	−3.1 (3)	C21—C19—N3—C15	−177.6 (2)
C7—C11—C12—N1	179.2 (2)	C18—C19—N3—Cu1	−174.35 (19)
N2—C11—C12—C4	176.0 (2)	C21—C19—N3—Cu1	5.4 (3)
C7—C11—C12—C4	−1.6 (3)	C16—C15—N3—C19	−3.0 (4)
N3—C15—C16—C17	1.7 (4)	C20—C15—N3—C19	179.2 (2)
C20—C15—C16—C17	179.0 (3)	C16—C15—N3—Cu1	173.99 (19)
C15—C16—C17—C18	−0.2 (4)	C20—C15—N3—Cu1	−3.8 (3)
C16—C17—C18—C19	−0.2 (4)	N1—Cu1—N3—C19	−98.1 (4)
C17—C18—C19—N3	−1.0 (4)	O2—Cu1—N3—C19	−6.71 (18)
C17—C18—C19—C21	179.3 (3)	O1—Cu1—N3—C19	−179.78 (19)
N3—C15—C20—O3	−179.5 (2)	N2—Cu1—N3—C19	93.70 (18)
C16—C15—C20—O3	3.0 (4)	N1—Cu1—N3—C15	84.8 (4)
N3—C15—C20—O1	2.2 (3)	O2—Cu1—N3—C15	176.17 (19)
C16—C15—C20—O1	−175.3 (3)	O1—Cu1—N3—C15	3.09 (17)
N3—C19—C21—O4	180.0 (2)	N2—Cu1—N3—C15	−83.42 (18)
C18—C19—C21—O4	−0.3 (4)	O3—C20—O1—Cu1	−178.0 (2)
N3—C19—C21—O2	0.7 (3)	C15—C20—O1—Cu1	0.1 (3)
C18—C19—C21—O2	−179.5 (3)	N3—Cu1—O1—C20	−1.66 (17)
C2—C1—N1—C12	0.8 (4)	N1—Cu1—O1—C20	−166.65 (18)
C13—C1—N1—C12	−178.5 (3)	O2—Cu1—O1—C20	−20.9 (3)
C2—C1—N1—Cu1	−174.50 (19)	N2—Cu1—O1—C20	114.24 (18)
C13—C1—N1—Cu1	6.2 (4)	O4—C21—O2—Cu1	174.8 (2)
C4—C12—N1—C1	−1.5 (4)	C19—C21—O2—Cu1	−6.0 (3)
C11—C12—N1—C1	177.6 (2)	N3—Cu1—O2—C21	7.00 (18)
C4—C12—N1—Cu1	174.20 (18)	N1—Cu1—O2—C21	171.71 (19)
C11—C12—N1—Cu1	−6.7 (3)	O1—Cu1—O2—C21	26.3 (3)
N3—Cu1—N1—C1	15.2 (5)	N2—Cu1—O2—C21	−107.16 (19)
O2—Cu1—N1—C1	−73.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O7	0.91 (3)	2.00 (3)	2.902 (4)	173 (5)
O5—H5B···O4^i	0.88 (3)	2.08 (3)	2.945 (4)	169 (6)
O6—H6A···O7^ii	0.79 (3)	2.06 (3)	2.841 (5)	168 (6)
O6—H6B···O3	0.82 (3)	2.12 (3)	2.932 (4)	172 (6)
O7—H7A···O6^iii	0.78 (2)	2.19 (3)	2.927 (4)	158 (5)
O7—H7B···O4^iv	0.83 (2)	2.07 (3)	2.894 (3)	172 (5)

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