Four- and five-coordinate copper(II) complexes with N-(4,4-diphenyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)­glycine

The two title mononuclear compounds are four-coordinate bis­[N-(5-oxo-4,4-diphenyl-4,5-dihydro-1H-imidazolidin-2-ylidene)glycinato]copper(II) dimethyl­formamide disolvate, [Cu(C₁₇H₁₄N₃O₃)₂]·2C₃H₇NO, (I), and five-coordinate aqua­bis[N-(5-oxo-4,4-diphenyl-4,5-dihydro-1H-imidazolidin-2-ylidene)glycinato]copper(II) dimethyl­formamide disolvate, [Cu(C₁₇H₁₄N₃O₃)₂(H₂O)]·2C₃H₇NO, (II). In (I), the Cu^II ion lies on an inversion centre with one-half of the complex mol­ecule in the asymmetric unit, while in (II) there are two independent ligand mol­ecules in the asymmetric unit, with the Cu^II ion and coordinated water mol­ecule located on a general position. In both crystal structures, the complex mol­ecules assemble in ribbons via N—H...O hydrogen-bond networks.

S1. Comment

In our previous research, diphenyl- and arylidene-imidazoline-4-one amino acids have been studied from the viewpoint of their binding to ionotropic (iGluRs) (Kieć-Kononowicz et al., 1998) and/or metabotropic (iGluRs) receptors (Karolak-Wojciechowska & Kieć-Kononowicz, in preparation). From information based on the model of ligand-receptor interactions with iGluRs (Karolak-Wojciechowska et al., 2000), it was postulated that the presence of COO^- ions in the amino acids studied was indispensable for binding (Karolak-Wojciechowska et al., 2001). For this reason, we are currently focusing our attention on interactions between such amino acids and metals. As a first example, we obtained an interesting six-coordinate potassium polymeric complex with o-Cl-benzylidene-imidazoline-4-one β-alanine and water molecules (Mrozek et al., 2003). Recently, we obtained the two title Cu^II complexes, (I) and (II), with 5,5-diphenyl-4-oxo-imidazolidinyl glycine, and present their crystal structures here.

The molecular structures of (I) and (II) are shown in Figs. 1 and 2, respectively. In (I), the four-coordinate Cu^II ion lies on a crystallographic inversion centre and forms a square-planar CuN₂O₂ unit (Table 1). The O,N-bidentate unit, belonging to the 5,5-diphenyl-4-oxo-imidazolidinyl-glycine (hereinafter abbreviated as DPGly) ligand, forms a planar five-membered ring. Even though the coordination numbers in structures (I) and (II) are not the same, in both compounds the Cu^II atom is coordinated by two O,N-bidentate units, with atoms O9 and N6 [and O49 and N46 in (II)] in a trans geometry. An increase in the coordination number of Cu^II from four in (I) to five in (II) is caused by the presence of a water molecule. This results not only in bond-length elongation in the coordination environment (Tables 1 and 3), but also in a shift of the Cu atom from the basal plane towards the apical atom O1 (water molecule) in (II) [0.052 (5) Å for (I) and 0.1646 (11) Å for (II)]. Furthermore, the structure of (II) loses the centre of symmetry, with the space group changng from P2₁/n in (I) to P2₁ in (II). The distortion from ideal five-coordinate geometries can be best described by the degree of trigonality τ (Addison et al., 1984). For a regular square-pyramidal (SQP) geometry, the trigonality parameter is 0, and for a trigonal–bipyramidal (TBP) structure it increases to 1. In (II), τ = 0.114, indicating a slightly distorted SQP coordination geometry around Cu^II.

The bond valences around Cu^II atoms in both structures were computed according to Brown (1994) and O'Keeffe & Brese (1991) as ν_ij = exp[(R_ij- d_ij)/0.37], where R_ij is the bond-valence parameter (in the formal sense, it is the single-bond length between the i and j atoms) and d_ij is the observed bond length. In the present structures, the application of this correlation allows one to compare the relative importance of Cu—L bonds of Cu polyhedra, and to check the valence-sum rule for the Cu^II atom (Brown, 2002). According to Shields et al. (2000), R_Cu—N and R_Cu—O were taken as 1.716 and 1.657 Å for (I), respectively, and 1.705 and 1.652 Å for (II), respectively. The estimated bond valences of the Cu^II atom show that, in both structures, the equatorial Cu—N bonds are distinctly stronger than the equatorial Cu—O ones [ν_Cu—N = 0.530 and ν_Cu—O = 0.489 v.u. in (I), and ν_{Cu—N(average)} = 0.485 and ν_{Cu–O(average)} = 0.439 v.u. in (II)]. The valence of the axial Cu–O1 bond in structure (II) amounts to 0.155 v.u. Finally, the valences of the four- and five-coordinate Cu atoms are consistent with the valence-sum rule (V_i = Σν_ij), which gives here V_Cu = 2.037 for (I) and 2.003 for (II).

The dihedral angles between the planes of the five-membered imidazole ring and the respective phenyl rings located on atoms C5 and C45 in (II) are not equal [76.76 (13)° for the C11–C16 ring, 57.34 (10)° for C21–C26, 67.04 (9)° for C51–C56 and 64.72 (11)° for C61–C66], while in (I) they are equal to within experimental error [68.78 (14) and 69.26 (14)° for the corresponding C11–C16 and C21–C26 rings, respectively].

In the structure of (I), intramolecular N3—H3···O9(-x, -y, -z) hydrogen bonds join two DPGly ligand molecules. This bond generates an S(6) graph-set motif (Etter et al., 1990) in the plane of the O,N-bidentate units. The complex molecules are connected together by N1—H1···O10(1 - x, -y, -z) hydrogen bonds, forming rings of graph-set R₂²(14). These rings construct ribbons running along the a axis which are slightly inclined with respect to the ac plane (Fig. 3 and Table 2). The distance between two parallel ribbons is equal to the b axis value [14.075 (6) Å], but at 0.5b another ribbon, oppositely inclined to the ac plane, is present. Between these two ribbons there is enough space for the location of all the phenyl rings from the DPGly molecules and the respective number of dimethylformamide (DMF) solvent molecules. The DMF molecules bridge successive ribbons through non-covalent interactions in the crystal of (I). Therefore, from one site, DMF atom O31 is involved in a weak C71—H71···O31(-x + 1/2, y - 1/2, -z + 1/2) interaction with the glycine atom C7 of one ribbon, while the other imidazolidinone carbonyl O atom from the second ribbon participates in a weak C34–H342···O4(-x, -y, 1 - z) interaction with a DMF C atom [3.514 (8) Å].

Analogous intra- and intermolecular N—H···O hydrogen bonds are also recognized in the structure of (II) (Fig. 4 and Table 4), with the final ribbons running along the c axis and with the distance between parallel ribbons amounting to the a axis value [8.7305 (3) Å]. The space between them contains not only the phenyl rings from the DPGly molecules and the respective number of DMF solvent molecules, but also a ligand water molecule. The solvent DMF molecules in (II) are differently anchored than in (I). Both DMF molecules are hydrogen-bonded to the coordinated water via relevant O1—H1W···O31 and O1—H2W···O41(x, y, z + 1) interactions. Additionally, weak hydrogen-bond C7—H7B···O71(x - 1, y, z) interactions involving one DMF molecule maintain the parallel ribbons. It is worth mentioning that one of the two imidazolidinone carbonyl O atoms in (II) (O44) is involved in an intermolecular interaction, creating a relatively strong C24—H24···O44(-x, 1/2 + y, 1 - z) hydrogen bond to a neighbouring ribbon at an angle of 170°. Due to this extended interaction, parallel ribbons form a helix down the b axis.

Related literature

For related literature, see: Addison et al. (1984); Brown (1994, 2002); Bruker (2003); Dziemidowicz-Borys (2006); Etter et al. (1990); Karolak-Wojciechowska, Kieć-Kononowicz & Mrozek (2001); Karolak-Wojciechowska, Mrozek & Kieć-Kononowicz (2000); Kieć-Kononowicz, Karolak-Wojciechowska & Handzlik (1998); Kieć-Kononowicz, Karolak-Wojciechowska, Mrozek & Poseł (1995); Mrozek et al. (2003); O'Keeffe & Brese (1991); Shields et al. (2000).

S2. Experimental

To obtain crystals of these complexes, the method described by Dziemidowicz-Borys (2006) was adapted for our compounds. Locally synthesized N-[(5,5-diphenyl)-4-oxo-imidazolidinyl]glycine (Kieć-Kononowicz et al., 1995) was used as the ligand for complex formation. A solution of CuCl₂·2H₂O (9 mg, 0.052 mmol) in DMF (2 ml) was added to N-[(5,5-diphenyl)-4-oxo-imidazolidinyl]glycine (16 mg, 0.052 mmol) dissolved in warmed DMF (2 ml). The resulting green–blue solution was left at room temperature for a couple of days with limited air contact. After two weeks, violet crystals [Of (I)?] appeared, which were carefully filtered out. From the filtrate left in contact with air, a few blue crystals [Of (II)?] were obtained after a further two weeks. [Was the air thus the source of the coordinated water in (II)?]

S3. Refinement

In (I), the H atoms attached to atoms N1 and N3 were located in a difference Fourier map and their positions and displacement parameters were refined freely. In (II), H atoms attached to N atoms were placed in idealized positions and constrained to ride on their parent atoms, with N—H = 0.86 Å and with U_iso(H) = 1.2U_eq(N). For both compounds, phenylene and methylene H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 and 0.97 Å and U_iso(H) = 1.2U_eq(C). The methyl H atoms in the DMF molecules were found in a difference Fourier map and were included using an AFIX 137 command (SHELXTL; Bruker, 2003), with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C). One of the DMF molecules in (II) showed disorder; the occupancies of the disordered positions were initially refined, and later fixed at 0.65 and 0.35.

Computing details

Data collection: SMART (Bruker, 2002) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). Cell refinement: SAINT-Plus (Bruker, 2003) for (I); CrysAlis RED (Oxford Diffraction, 2006) for (II). Data reduction: SAINT-Plus (Bruker, 2003) for (I); CrysAlis RED (Oxford Diffraction, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. View of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as spheres of arbitrary radii. Unlabelled atoms are related to the corresponding labelled atoms by the symmetry code (-x, -y, -z).
	Fig. 2. View of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are depicted as spheres of arbitrary radii. For clarity, only the major component of the disordered atoms is shown.
	Fig. 3. Hydrogen-bonded polymeric ribbons in (I), running along the [100] direction and viewed down the [010] direction. Hydrogen bonds are drawn as dashed lines. DMF molecules have been omitted for clarity.
	Fig. 4. Hydrogen-bonded polymeric ribbons in (II), running along the [001] direction. Hydrogen bonds are drawn as dashed lines. DMF molecules have been omitted for clarity.

(I) bis[N-(4,4-diphenyl-5-oxo-4,5-dihydro-1H-imidazol-2- yl)glycinato]copper(II) dimethylformamide disolvate

Crystal data

[Cu(C17H14N3O3)2]·2C3H7NO	F(000) = 862
Mr = 826.37	Dx = 1.346 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1580 reflections
a = 8.987 (4) Å	θ = 2.5–21.5°
b = 14.075 (6) Å	µ = 0.60 mm^−1
c = 16.208 (7) Å	T = 291 K
β = 95.913 (6)°	Prism, violet
V = 2039.3 (15) Å^3	0.2 × 0.1 × 0.05 mm
Z = 2

Data collection

Bruker SMART APEXII CCD diffractometer	3590 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2815 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.924, Tmax = 0.979	k = −16→16
28748 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 1.7037P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
3590 reflections	Δρmax = 0.67 e Å^−3
269 parameters	Δρmin = −0.27 e Å^−3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.00000	0.00000	0.00000	0.0299 (2)
O4	0.1398 (3)	0.0524 (2)	0.33959 (14)	0.0562 (9)
O9	0.1134 (2)	−0.02151 (17)	−0.09254 (13)	0.0419 (8)
O10	0.3414 (3)	−0.0211 (2)	−0.13303 (14)	0.0528 (9)
N1	0.3722 (3)	0.0238 (2)	0.18148 (16)	0.0352 (9)
N3	0.1325 (3)	0.0316 (2)	0.19893 (16)	0.0360 (9)
N6	0.1959 (3)	0.01488 (18)	0.06272 (15)	0.0332 (8)
C2	0.2349 (3)	0.0228 (2)	0.14118 (18)	0.0287 (9)
C4	0.2010 (4)	0.0403 (2)	0.2778 (2)	0.0380 (10)
C5	0.3714 (3)	0.0298 (2)	0.27167 (18)	0.0335 (10)
C7	0.3184 (3)	0.0053 (2)	0.00944 (18)	0.0353 (10)
C8	0.2571 (3)	−0.0141 (2)	−0.07912 (19)	0.0343 (10)
C11	0.4220 (4)	−0.0635 (2)	0.3153 (2)	0.0381 (11)
C12	0.4645 (5)	−0.1423 (3)	0.2728 (2)	0.0551 (14)
C13	0.5081 (6)	−0.2244 (3)	0.3161 (3)	0.0751 (18)
C14	0.5078 (6)	−0.2292 (3)	0.4003 (3)	0.081 (2)
C15	0.4644 (6)	−0.1517 (3)	0.4425 (3)	0.0722 (18)
C16	0.4225 (5)	−0.0689 (3)	0.4012 (2)	0.0528 (14)
C21	0.4634 (4)	0.1150 (2)	0.30572 (19)	0.0367 (10)
C22	0.6178 (4)	0.1068 (3)	0.3171 (2)	0.0485 (12)
C23	0.7063 (5)	0.1836 (3)	0.3428 (3)	0.0671 (17)
C24	0.6425 (7)	0.2681 (4)	0.3579 (3)	0.0803 (19)
C25	0.4910 (7)	0.2778 (3)	0.3476 (3)	0.079 (2)
C26	0.3995 (5)	0.2015 (3)	0.3208 (2)	0.0548 (14)
O31	0.0365 (6)	0.2951 (3)	0.4520 (3)	0.1166 (19)
N32	0.0603 (5)	0.1811 (3)	0.5500 (2)	0.0734 (17)
C31	0.0867 (7)	0.2210 (4)	0.4799 (4)	0.090 (3)
C33	−0.0323 (12)	0.2286 (6)	0.6028 (5)	0.180 (5)
C34	0.1268 (8)	0.0929 (5)	0.5783 (5)	0.135 (3)
H1	0.442 (4)	0.019 (2)	0.157 (2)	0.038 (10)*
H3	0.042 (4)	0.033 (2)	0.182 (2)	0.031 (9)*
H71	0.38370	−0.04640	0.02960	0.0420*
H72	0.37700	0.06330	0.01190	0.0420*
H12	0.46390	−0.14030	0.21550	0.0660*
H13	0.53810	−0.27710	0.28740	0.0900*
H14	0.53680	−0.28470	0.42860	0.0970*
H15	0.46310	−0.15480	0.49980	0.0870*
H16	0.39440	−0.01630	0.43070	0.0640*
H22	0.66230	0.04880	0.30740	0.0580*
H23	0.80980	0.17720	0.34980	0.0810*
H24	0.70240	0.31970	0.37530	0.0970*
H25	0.44810	0.33600	0.35860	0.0950*
H26	0.29610	0.20880	0.31320	0.0660*
H31	0.15110	0.18870	0.44840	0.1070*
H331	−0.01800	0.29600	0.59880	0.2710*
H332	−0.00640	0.20860	0.65900	0.2710*
H333	−0.13520	0.21340	0.58620	0.2710*
H341	0.20050	0.07440	0.54250	0.2020*
H342	0.05090	0.04480	0.57740	0.2020*
H343	0.17370	0.10030	0.63380	0.2020*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0176 (3)	0.0453 (3)	0.0269 (3)	−0.0004 (2)	0.0022 (2)	−0.0033 (2)
O4	0.0419 (15)	0.097 (2)	0.0316 (13)	−0.0012 (14)	0.0135 (11)	−0.0108 (13)
O9	0.0184 (11)	0.0754 (17)	0.0321 (11)	−0.0024 (10)	0.0031 (9)	−0.0093 (11)
O10	0.0246 (12)	0.102 (2)	0.0327 (12)	−0.0028 (12)	0.0070 (10)	−0.0106 (12)
N1	0.0223 (14)	0.0595 (19)	0.0238 (13)	−0.0013 (12)	0.0023 (11)	−0.0031 (11)
N3	0.0204 (14)	0.0571 (18)	0.0309 (14)	−0.0004 (12)	0.0043 (11)	−0.0054 (12)
N6	0.0200 (12)	0.0514 (17)	0.0280 (13)	0.0002 (11)	0.0018 (10)	−0.0026 (11)
C2	0.0226 (15)	0.0368 (18)	0.0267 (15)	−0.0006 (12)	0.0032 (12)	−0.0026 (12)
C4	0.0327 (18)	0.0499 (19)	0.0319 (17)	−0.0004 (15)	0.0059 (14)	−0.0007 (14)
C5	0.0296 (17)	0.0469 (19)	0.0242 (15)	−0.0027 (13)	0.0034 (12)	−0.0040 (13)
C7	0.0270 (16)	0.0505 (19)	0.0277 (15)	0.0000 (15)	−0.0005 (12)	−0.0023 (15)
C8	0.0247 (16)	0.049 (2)	0.0296 (15)	0.0016 (14)	0.0042 (12)	−0.0018 (14)
C11	0.0321 (18)	0.047 (2)	0.0342 (17)	−0.0075 (15)	−0.0010 (14)	−0.0013 (14)
C12	0.067 (3)	0.051 (2)	0.047 (2)	−0.0025 (19)	0.0052 (19)	−0.0105 (18)
C13	0.103 (4)	0.044 (2)	0.080 (3)	0.008 (2)	0.018 (3)	−0.005 (2)
C14	0.109 (4)	0.052 (3)	0.082 (4)	0.001 (3)	0.004 (3)	0.019 (2)
C15	0.099 (4)	0.071 (3)	0.046 (2)	−0.001 (3)	0.004 (2)	0.017 (2)
C16	0.067 (3)	0.056 (2)	0.0346 (19)	0.0009 (19)	0.0011 (18)	−0.0001 (16)
C21	0.041 (2)	0.0450 (19)	0.0239 (15)	−0.0073 (15)	0.0020 (14)	0.0017 (13)
C22	0.038 (2)	0.061 (2)	0.046 (2)	−0.0099 (17)	0.0014 (16)	−0.0052 (17)
C23	0.060 (3)	0.082 (3)	0.058 (3)	−0.032 (2)	0.000 (2)	−0.006 (2)
C24	0.101 (4)	0.066 (3)	0.071 (3)	−0.039 (3)	−0.005 (3)	−0.002 (2)
C25	0.119 (5)	0.042 (2)	0.073 (3)	−0.003 (3)	−0.003 (3)	−0.005 (2)
C26	0.061 (3)	0.049 (2)	0.052 (2)	0.0059 (19)	−0.0059 (19)	−0.0006 (17)
O31	0.165 (4)	0.083 (3)	0.097 (3)	−0.011 (3)	−0.009 (3)	0.011 (2)
N32	0.077 (3)	0.073 (3)	0.072 (3)	−0.002 (2)	0.016 (2)	0.001 (2)
C31	0.116 (5)	0.075 (4)	0.079 (4)	−0.007 (3)	0.017 (3)	−0.013 (3)
C33	0.270 (12)	0.139 (7)	0.154 (7)	0.056 (7)	0.128 (8)	0.011 (6)
C34	0.115 (6)	0.113 (5)	0.180 (7)	0.017 (4)	0.030 (5)	0.058 (5)

Geometric parameters (Å, º)

Cu1—O9	1.922 (2)	C15—C16	1.377 (6)
Cu1—N6	1.951 (3)	C21—C26	1.379 (5)
O4—C4	1.203 (4)	C21—C22	1.386 (5)
O9—C8	1.292 (3)	C22—C23	1.381 (6)
O10—C8	1.218 (4)	C23—C24	1.354 (7)
O31—C31	1.206 (7)	C24—C25	1.361 (9)
N1—C2	1.335 (4)	C25—C26	1.395 (7)
N1—C5	1.465 (4)	C7—H72	0.97
N3—C4	1.366 (4)	C7—H71	0.97
N3—C2	1.384 (4)	C12—H12	0.93
N6—C2	1.289 (4)	C13—H13	0.93
N6—C7	1.474 (4)	C14—H14	0.93
N1—H1	0.78 (4)	C15—H15	0.93
N3—H3	0.83 (4)	C16—H16	0.93
N32—C34	1.433 (8)	C22—H22	0.93
N32—C31	1.311 (7)	C23—H23	0.93
N32—C33	1.421 (10)	C24—H24	0.93
C4—C5	1.552 (5)	C25—H25	0.93
C5—C11	1.538 (4)	C26—H26	0.93
C5—C21	1.527 (4)	C31—H31	0.93
C7—C8	1.509 (4)	C33—H331	0.96
C11—C12	1.380 (5)	C33—H332	0.96
C11—C16	1.394 (5)	C33—H333	0.96
C12—C13	1.387 (6)	C34—H341	0.96
C13—C14	1.367 (7)	C34—H342	0.96
C14—C15	1.366 (6)	C34—H343	0.96
O9—Cu1—N6	84.32 (9)	C23—C24—C25	120.2 (5)
O9—Cu1—N6^i	95.68 (9)	C24—C25—C26	120.7 (5)
Cu1—O9—C8	117.21 (19)	C21—C26—C25	119.5 (4)
C2—N1—C5	112.9 (2)	N6—C7—H71	109
C2—N3—C4	112.0 (3)	N6—C7—H72	110
Cu1—N6—C2	131.5 (2)	C8—C7—H71	109
Cu1—N6—C7	111.92 (18)	C8—C7—H72	110
C2—N6—C7	116.3 (3)	H71—C7—H72	108
C2—N1—H1	120 (2)	C13—C12—H12	120
C5—N1—H1	127 (2)	C11—C12—H12	120
C2—N3—H3	118 (2)	C12—C13—H13	120
C4—N3—H3	130 (2)	C14—C13—H13	119
C33—N32—C34	117.8 (5)	C13—C14—H14	120
C31—N32—C33	119.3 (5)	C15—C14—H14	120
C31—N32—C34	122.8 (5)	C16—C15—H15	120
N1—C2—N6	128.9 (3)	C14—C15—H15	120
N1—C2—N3	108.3 (3)	C15—C16—H16	120
N3—C2—N6	122.9 (3)	C11—C16—H16	120
O4—C4—C5	127.3 (3)	C21—C22—H22	120
O4—C4—N3	126.2 (3)	C23—C22—H22	120
N3—C4—C5	106.5 (3)	C22—C23—H23	120
N1—C5—C11	112.2 (2)	C24—C23—H23	120
C4—C5—C21	113.8 (2)	C25—C24—H24	120
N1—C5—C21	110.4 (2)	C23—C24—H24	120
N1—C5—C4	100.1 (2)	C24—C25—H25	120
C11—C5—C21	112.4 (2)	C26—C25—H25	120
C4—C5—C11	107.4 (2)	C21—C26—H26	120
N6—C7—C8	110.6 (2)	C25—C26—H26	120
O9—C8—C7	115.8 (2)	O31—C31—N32	127.0 (6)
O9—C8—O10	123.9 (3)	O31—C31—H31	117
O10—C8—C7	120.3 (3)	N32—C31—H31	116
C5—C11—C12	122.7 (3)	N32—C33—H331	109
C5—C11—C16	118.4 (3)	N32—C33—H332	110
C12—C11—C16	118.8 (3)	N32—C33—H333	109
C11—C12—C13	119.7 (3)	H331—C33—H332	109
C12—C13—C14	121.1 (4)	H331—C33—H333	109
C13—C14—C15	119.4 (4)	H332—C33—H333	109
C14—C15—C16	120.7 (4)	N32—C34—H341	109
C11—C16—C15	120.3 (4)	N32—C34—H342	110
C5—C21—C26	122.5 (3)	N32—C34—H343	110
C22—C21—C26	118.7 (3)	H341—C34—H342	109
C5—C21—C22	118.7 (3)	H341—C34—H343	109
C21—C22—C23	120.9 (4)	H342—C34—H343	109
C22—C23—C24	120.1 (4)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O10^ii	0.78 (4)	2.02 (4)	2.768 (4)	160 (3)
N3—H3···O9^i	0.83 (4)	1.91 (3)	2.663 (3)	149 (3)
C7—H71···O31^iii	0.97	2.35	3.268 (5)	157

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

(II) aquabis[N-(4,4-diphenyl-5-oxo-4,5-dihydro-1H-imidazol-2- yl)glycinato]copper(II) dimethylformamide disolvate

Crystal data

[Cu(C20H21N4O4)2(H2O)]·2C3H7NO	F(000) = 882
Mr = 844.38	Dx = 1.341 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 14141 reflections
a = 8.7305 (3) Å	θ = 2.7–28.0°
b = 30.0213 (5) Å	µ = 0.59 mm^−1
c = 9.0447 (2) Å	T = 293 K
β = 118.102 (4)°	Prism, blue
V = 2091.15 (12) Å^3	0.30 × 0.25 × 0.22 mm
Z = 2

Data collection

Kuma KM-4 CCD diffractometer	7171 independent reflections
Radiation source: CX-Mo12x0.4-S Seifert Mo tube	6447 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
Detector resolution: 8.2356 pixels mm^-1	θmax = 25.0°, θmin = 2.6°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −35→35
Tmin = 0.825, Tmax = 0.882	l = −10→10
21287 measured reflections

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0437P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.026	(Δ/σ)max = 0.001
wR(F^2) = 0.066	Δρmax = 0.20 e Å^−3
S = 1.00	Δρmin = −0.17 e Å^−3
7171 reflections	Extinction correction: SHELXTL (Bruker, 2003), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
545 parameters	Extinction coefficient: 0.0024 (5)
0 restraints	Absolute structure: Flack (1983), with 1462 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (1)
Hydrogen site location: inferred from neighbouring sites

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	Occ. (<1)
Cu1	0.23376 (4)	0.73110 (1)	0.96070 (3)	0.0410 (1)
O1	0.5298 (3)	0.71475 (8)	1.0725 (3)	0.0800 (8)
O4	0.4293 (2)	0.90778 (5)	0.9854 (2)	0.0514 (6)
O9	0.1622 (3)	0.68377 (5)	0.79326 (19)	0.0537 (6)
O10	0.1085 (3)	0.66750 (5)	0.5345 (2)	0.0633 (7)
O44	0.0452 (2)	0.55349 (5)	0.94614 (19)	0.0517 (6)
O49	0.2791 (2)	0.78043 (5)	1.11801 (18)	0.0492 (5)
O50	0.3073 (3)	0.79813 (5)	1.3663 (2)	0.0606 (6)
N1	0.3273 (2)	0.82801 (5)	0.6714 (2)	0.0384 (5)
N3	0.3387 (2)	0.83549 (5)	0.9181 (2)	0.0394 (5)
N6	0.2350 (2)	0.76765 (6)	0.7797 (2)	0.0393 (6)
N41	0.0931 (2)	0.63795 (5)	1.2317 (2)	0.0383 (6)
N43	0.1086 (2)	0.62767 (5)	0.9974 (2)	0.0381 (5)
N46	0.1770 (3)	0.69893 (6)	1.1186 (2)	0.0420 (6)
C2	0.2965 (3)	0.80705 (6)	0.7852 (2)	0.0337 (6)
C4	0.3932 (3)	0.87584 (7)	0.8932 (3)	0.0364 (7)
C5	0.4032 (3)	0.87201 (6)	0.7283 (2)	0.0330 (6)
C7	0.1964 (3)	0.74098 (7)	0.6300 (2)	0.0446 (7)
C8	0.1523 (3)	0.69381 (8)	0.6523 (3)	0.0444 (7)
C11	0.5969 (3)	0.87405 (8)	0.7785 (3)	0.0433 (7)
C12	0.6920 (3)	0.83617 (11)	0.7925 (3)	0.0693 (10)
C13	0.8748 (5)	0.84057 (17)	0.8500 (5)	0.1082 (18)
C14	0.9483 (5)	0.88226 (19)	0.8873 (5)	0.1075 (18)
C15	0.8551 (4)	0.91867 (15)	0.8749 (5)	0.0957 (15)
C16	0.6799 (3)	0.91488 (10)	0.8198 (3)	0.0641 (10)
C21	0.3020 (3)	0.90749 (7)	0.5964 (3)	0.0402 (7)
C22	0.3055 (3)	0.90600 (9)	0.4442 (3)	0.0549 (8)
C23	0.2139 (5)	0.93693 (11)	0.3226 (3)	0.0793 (10)
C24	0.1245 (5)	0.96959 (11)	0.3485 (5)	0.1063 (14)
C25	0.1212 (5)	0.97158 (12)	0.4960 (5)	0.1120 (16)
C26	0.2088 (4)	0.94048 (9)	0.6234 (4)	0.0760 (11)
C42	0.1288 (3)	0.65827 (7)	1.1198 (2)	0.0342 (6)
C44	0.0665 (3)	0.58626 (7)	1.0298 (2)	0.0365 (6)
C45	0.0474 (3)	0.59098 (7)	1.1910 (2)	0.0352 (6)
C47	0.1962 (3)	0.72663 (8)	1.2590 (2)	0.0468 (7)
C48	0.2657 (3)	0.77214 (7)	1.2508 (3)	0.0421 (7)
C51	−0.1418 (3)	0.58053 (7)	1.1470 (2)	0.0376 (7)
C52	−0.2528 (3)	0.61316 (9)	1.1457 (3)	0.0555 (8)
C53	−0.4240 (4)	0.60250 (11)	1.1013 (4)	0.0721 (11)
C54	−0.4832 (4)	0.55945 (12)	1.0574 (4)	0.0692 (10)
C55	−0.3729 (4)	0.52759 (10)	1.0605 (3)	0.0640 (9)
C56	−0.2025 (3)	0.53757 (8)	1.1055 (3)	0.0519 (8)
C61	0.1750 (3)	0.56119 (7)	1.3347 (3)	0.0390 (7)
C62	0.1678 (4)	0.56138 (9)	1.4826 (3)	0.0587 (9)
C63	0.2828 (4)	0.53717 (12)	1.6178 (4)	0.0775 (11)
C64	0.4050 (5)	0.51109 (11)	1.6046 (4)	0.0914 (13)
C65	0.4139 (6)	0.51080 (15)	1.4600 (4)	0.1214 (16)
C66	0.2965 (4)	0.53544 (12)	1.3241 (4)	0.0868 (15)
O31	0.6205 (7)	0.71035 (17)	0.8111 (6)	0.196 (3)
N32	0.6511 (4)	0.66366 (13)	0.6355 (4)	0.1047 (14)
C31A	0.6041 (9)	0.6702 (3)	0.7518 (8)	0.115 (3)	0.650
C33A	0.6699 (14)	0.6199 (3)	0.5799 (12)	0.189 (6)	0.650
C34A	0.6876 (10)	0.6985 (3)	0.5494 (11)	0.155 (5)	0.650
C31B	0.6802 (17)	0.7036 (3)	0.7054 (17)	0.119 (4)*	0.350
C33B	0.680 (3)	0.6558 (7)	0.4947 (17)	0.163 (7)*	0.350
C34B	0.5725 (14)	0.6344 (4)	0.7057 (15)	0.100 (3)*	0.350
O71	0.7665 (5)	0.76973 (13)	0.3193 (6)	0.200 (2)
N72	0.7741 (3)	0.84430 (11)	0.3386 (3)	0.0828 (10)
C71	0.7215 (7)	0.8061 (2)	0.3681 (7)	0.144 (3)
C73	0.7303 (8)	0.88511 (19)	0.3974 (7)	0.164 (3)
C74	0.8666 (6)	0.8464 (2)	0.2544 (6)	0.167 (3)
H1	0.30490	0.81680	0.57580	0.0460*
H1W	0.560 (4)	0.7134 (11)	0.997 (4)	0.084 (12)*
H2W	0.597 (5)	0.7355 (16)	1.141 (5)	0.137 (17)*
H3	0.33150	0.82850	1.00680	0.0470*
H7A	0.29640	0.74100	0.61020	0.0540*
H7B	0.09950	0.75410	0.53320	0.0540*
H12	0.63870	0.80840	0.76520	0.0830*
H13	0.94260	0.81560	0.86200	0.1290*
H14	1.06640	0.88520	0.92210	0.1290*
H15	0.90870	0.94640	0.90350	0.1150*
H16	0.61540	0.94040	0.81010	0.0770*
H22	0.36960	0.88420	0.42510	0.0660*
H23	0.21380	0.93520	0.21980	0.0950*
H24	0.06540	0.99070	0.26560	0.1280*
H25	0.05900	0.99430	0.51330	0.1340*
H26	0.20420	0.94210	0.72390	0.0910*
H41	0.09660	0.65100	1.31790	0.0460*
H43	0.12120	0.63400	0.91100	0.0460*
H47A	0.27500	0.71230	1.36360	0.0560*
H47B	0.08450	0.72980	1.25650	0.0560*
H52	−0.21350	0.64230	1.17450	0.0670*
H53	−0.49900	0.62450	1.10110	0.0860*
H54	−0.59820	0.55250	1.02600	0.0830*
H55	−0.41240	0.49850	1.03180	0.0770*
H56	−0.12790	0.51510	1.10790	0.0620*
H62	0.08320	0.57830	1.49150	0.0700*
H63	0.27810	0.53840	1.71840	0.0930*
H64	0.48100	0.49380	1.69480	0.1100*
H65	0.49890	0.49400	1.45120	0.1450*
H66	0.30140	0.53420	1.22360	0.1040*
H33C	0.58560	0.61600	0.46450	0.2270*	0.650
H34A	0.62440	0.69340	0.43080	0.1860*	0.650
H34B	0.80980	0.69910	0.58420	0.1860*	0.650
H34C	0.65300	0.72660	0.57530	0.1860*	0.650
H31A	0.56090	0.64710	0.79010	0.1380*	0.650
H33A	0.65210	0.59770	0.64680	0.2270*	0.650
H33B	0.78450	0.61680	0.59160	0.2270*	0.650
H31B	0.73980	0.72550	0.68060	0.1420*	0.350
H33D	0.70790	0.68350	0.45930	0.1960*	0.350
H33E	0.57710	0.64350	0.40440	0.1960*	0.350
H33F	0.77480	0.63540	0.52580	0.1960*	0.350
H34D	0.60740	0.64300	0.81930	0.1200*	0.350
H34E	0.60910	0.60440	0.70350	0.1200*	0.350
H34F	0.44840	0.63630	0.64110	0.1200*	0.350
H71	0.65390	0.80480	0.42240	0.1740*
H73A	0.63610	0.87940	0.42140	0.1970*
H73B	0.69640	0.90760	0.31230	0.1970*
H73C	0.82960	0.89520	0.49730	0.1970*
H74A	0.98820	0.84720	0.33270	0.2000*
H74B	0.83530	0.87290	0.18670	0.2000*
H74C	0.84210	0.82070	0.18370	0.2000*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0781 (2)	0.0272 (1)	0.0321 (1)	−0.0105 (1)	0.0379 (1)	−0.0062 (1)
O1	0.0912 (15)	0.0761 (15)	0.0757 (14)	0.0113 (12)	0.0417 (13)	−0.0035 (12)
O4	0.0815 (11)	0.0337 (9)	0.0460 (9)	−0.0115 (8)	0.0359 (8)	−0.0115 (7)
O9	0.1097 (13)	0.0320 (8)	0.0404 (8)	−0.0187 (8)	0.0527 (9)	−0.0093 (6)
O10	0.1257 (16)	0.0407 (9)	0.0455 (9)	−0.0273 (9)	0.0584 (10)	−0.0177 (8)
O44	0.0831 (12)	0.0355 (9)	0.0478 (9)	−0.0116 (8)	0.0401 (9)	−0.0151 (7)
O49	0.0979 (12)	0.0286 (8)	0.0398 (8)	−0.0129 (8)	0.0480 (8)	−0.0076 (6)
O50	0.1205 (14)	0.0384 (9)	0.0470 (9)	−0.0277 (9)	0.0594 (10)	−0.0192 (8)
N1	0.0666 (11)	0.0261 (9)	0.0307 (8)	−0.0085 (8)	0.0296 (8)	−0.0034 (7)
N3	0.0673 (11)	0.0303 (9)	0.0320 (8)	−0.0048 (8)	0.0327 (8)	−0.0035 (7)
N6	0.0732 (12)	0.0265 (9)	0.0303 (8)	−0.0077 (8)	0.0345 (8)	−0.0048 (7)
N41	0.0671 (11)	0.0274 (9)	0.0350 (9)	−0.0085 (8)	0.0361 (9)	−0.0059 (7)
N43	0.0645 (11)	0.0302 (9)	0.0326 (8)	−0.0098 (8)	0.0337 (8)	−0.0057 (7)
N46	0.0764 (12)	0.0284 (10)	0.0351 (9)	−0.0136 (9)	0.0377 (9)	−0.0093 (7)
C2	0.0505 (11)	0.0259 (11)	0.0300 (9)	0.0009 (9)	0.0233 (9)	−0.0014 (8)
C4	0.0481 (12)	0.0297 (11)	0.0352 (11)	−0.0018 (9)	0.0227 (10)	−0.0017 (9)
C5	0.0441 (11)	0.0272 (10)	0.0321 (10)	−0.0036 (9)	0.0215 (9)	−0.0016 (8)
C7	0.0786 (14)	0.0376 (15)	0.0292 (9)	−0.0102 (10)	0.0349 (10)	−0.0061 (9)
C8	0.0759 (15)	0.0331 (11)	0.0386 (12)	−0.0136 (11)	0.0388 (11)	−0.0103 (10)
C11	0.0463 (12)	0.0513 (13)	0.0339 (11)	0.0024 (10)	0.0203 (10)	0.0026 (10)
C12	0.0627 (17)	0.0790 (19)	0.0685 (17)	0.0161 (15)	0.0328 (14)	−0.0077 (15)
C13	0.073 (2)	0.148 (4)	0.103 (3)	0.041 (3)	0.041 (2)	−0.016 (3)
C14	0.058 (2)	0.159 (4)	0.107 (3)	−0.011 (3)	0.040 (2)	−0.028 (3)
C15	0.0561 (19)	0.117 (3)	0.109 (3)	−0.027 (2)	0.0347 (18)	−0.019 (2)
C16	0.0508 (15)	0.0731 (19)	0.0654 (16)	−0.0125 (13)	0.0248 (13)	−0.0026 (14)
C21	0.0469 (12)	0.0285 (11)	0.0376 (12)	−0.0052 (10)	0.0136 (9)	0.0021 (9)
C22	0.0661 (16)	0.0513 (15)	0.0399 (13)	−0.0117 (12)	0.0189 (12)	0.0047 (11)
C23	0.102 (2)	0.0614 (19)	0.0422 (14)	−0.0271 (18)	0.0073 (15)	0.0167 (14)
C24	0.122 (3)	0.056 (2)	0.074 (2)	0.004 (2)	−0.009 (2)	0.0303 (17)
C25	0.132 (3)	0.062 (2)	0.101 (3)	0.050 (2)	0.021 (2)	0.019 (2)
C26	0.085 (2)	0.0554 (17)	0.0666 (18)	0.0255 (15)	0.0184 (15)	0.0017 (14)
C42	0.0492 (11)	0.0327 (11)	0.0274 (9)	−0.0053 (9)	0.0237 (9)	−0.0040 (8)
C44	0.0488 (12)	0.0308 (11)	0.0344 (10)	−0.0045 (9)	0.0233 (9)	−0.0055 (9)
C45	0.0525 (12)	0.0262 (10)	0.0329 (10)	−0.0062 (9)	0.0250 (9)	−0.0031 (8)
C47	0.0847 (14)	0.0375 (12)	0.0366 (9)	−0.0175 (13)	0.0438 (10)	−0.0091 (10)
C48	0.0743 (15)	0.0303 (11)	0.0364 (11)	−0.0070 (10)	0.0382 (11)	−0.0052 (9)
C51	0.0484 (12)	0.0360 (12)	0.0329 (10)	−0.0004 (9)	0.0229 (9)	0.0043 (8)
C52	0.0595 (15)	0.0490 (14)	0.0629 (15)	−0.0009 (12)	0.0329 (12)	−0.0014 (12)
C53	0.0624 (17)	0.078 (2)	0.084 (2)	0.0096 (15)	0.0411 (15)	−0.0057 (16)
C54	0.0541 (16)	0.092 (2)	0.0640 (17)	−0.0164 (16)	0.0300 (14)	−0.0016 (16)
C55	0.0653 (17)	0.0629 (17)	0.0580 (15)	−0.0232 (14)	0.0242 (13)	−0.0039 (12)
C56	0.0564 (15)	0.0380 (13)	0.0596 (14)	−0.0087 (11)	0.0260 (11)	−0.0018 (11)
C61	0.0471 (12)	0.0305 (11)	0.0396 (12)	−0.0063 (9)	0.0206 (10)	−0.0033 (9)
C62	0.0666 (16)	0.0686 (17)	0.0397 (13)	0.0045 (14)	0.0241 (13)	0.0062 (12)
C63	0.089 (2)	0.096 (2)	0.0395 (15)	0.002 (2)	0.0237 (15)	0.0117 (16)
C64	0.106 (3)	0.075 (2)	0.0586 (18)	0.0315 (19)	0.0103 (17)	0.0112 (16)
C65	0.137 (3)	0.133 (3)	0.072 (2)	0.086 (3)	0.031 (2)	0.012 (2)
C66	0.106 (3)	0.109 (3)	0.0491 (16)	0.059 (2)	0.0397 (17)	0.0129 (16)
O31	0.261 (5)	0.220 (5)	0.170 (4)	0.088 (4)	0.154 (4)	0.013 (3)
N32	0.088 (2)	0.146 (3)	0.081 (2)	−0.007 (2)	0.0406 (17)	−0.015 (2)
C31A	0.133 (5)	0.137 (6)	0.087 (4)	−0.006 (5)	0.062 (4)	0.029 (4)
C33A	0.232 (11)	0.196 (11)	0.106 (6)	0.002 (9)	0.053 (7)	−0.026 (7)
C34A	0.137 (6)	0.228 (10)	0.148 (7)	0.015 (6)	0.107 (6)	0.056 (7)
O71	0.152 (3)	0.125 (3)	0.223 (5)	−0.020 (3)	0.007 (3)	−0.050 (3)
N72	0.0697 (15)	0.100 (2)	0.0762 (17)	−0.0162 (15)	0.0323 (13)	−0.0059 (15)
C71	0.131 (4)	0.168 (5)	0.147 (4)	−0.055 (4)	0.076 (3)	−0.033 (4)
C73	0.185 (6)	0.152 (5)	0.121 (4)	0.020 (4)	0.043 (4)	−0.024 (4)
C74	0.109 (3)	0.311 (9)	0.098 (3)	0.021 (4)	0.063 (3)	0.036 (4)

Geometric parameters (Å, º)

Cu1—O1	2.341 (3)	C45—C61	1.538 (3)
Cu1—O9	1.9523 (15)	C47—C48	1.511 (3)
Cu1—O49	1.9606 (15)	C51—C56	1.378 (3)
Cu1—N6	1.9751 (17)	C51—C52	1.374 (4)
Cu1—N46	1.971 (2)	C52—C53	1.390 (5)
O4—C4	1.211 (3)	C53—C54	1.379 (5)
O9—C8	1.273 (3)	C54—C55	1.348 (5)
O10—C8	1.234 (3)	C55—C56	1.378 (5)
O44—C44	1.201 (2)	C61—C66	1.352 (5)
O49—C48	1.285 (3)	C61—C62	1.369 (4)
O50—C48	1.214 (3)	C62—C63	1.369 (4)
O1—H2W	0.88 (5)	C63—C64	1.373 (6)
O1—H1W	0.84 (4)	C64—C65	1.346 (5)
O31—C31A	1.300 (10)	C65—C66	1.386 (5)
O31—C31B	1.302 (16)	C7—H7A	0.97
O71—C71	1.306 (7)	C7—H7B	0.97
N1—C5	1.459 (2)	C12—H12	0.93
N1—C2	1.337 (3)	C13—H13	0.93
N3—C4	1.359 (3)	C14—H14	0.93
N3—C2	1.376 (2)	C15—H15	0.93
N6—C7	1.469 (2)	C16—H16	0.93
N6—C2	1.290 (3)	C22—H22	0.93
N41—C42	1.338 (3)	C23—H23	0.93
N41—C45	1.465 (3)	C24—H24	0.93
N43—C42	1.384 (2)	C25—H25	0.93
N43—C44	1.367 (3)	C26—H26	0.93
N46—C42	1.293 (3)	C47—H47A	0.97
N46—C47	1.460 (3)	C47—H47B	0.97
N1—H1	0.86	C52—H52	0.93
N3—H3	0.86	C53—H53	0.93
N41—H41	0.86	C54—H54	0.93
N43—H43	0.86	C55—H55	0.93
N32—C33B	1.43 (2)	C56—H56	0.93
N32—C31A	1.312 (8)	C62—H62	0.93
N32—C33A	1.443 (10)	C63—H63	0.93
N32—C34A	1.427 (10)	C64—H64	0.93
N32—C31B	1.323 (11)	C65—H65	0.93
N32—C34B	1.434 (13)	C66—H66	0.93
N72—C73	1.457 (7)	C31A—H31A	0.93
N72—C74	1.347 (6)	C31B—H31B	0.93
N72—C71	1.309 (7)	C33A—H33C	0.96
C4—C5	1.539 (3)	C33A—H33A	0.96
C5—C11	1.532 (4)	C33A—H33B	0.96
C5—C21	1.532 (3)	C33B—H33D	0.96
C7—C8	1.506 (3)	C33B—H33E	0.96
C11—C16	1.383 (4)	C33B—H33F	0.96
C11—C12	1.378 (4)	C34A—H34C	0.96
C12—C13	1.433 (6)	C34A—H34A	0.96
C13—C14	1.374 (7)	C34A—H34B	0.96
C14—C15	1.336 (7)	C34B—H34E	0.96
C15—C16	1.372 (5)	C34B—H34F	0.96
C21—C22	1.392 (4)	C34B—H34D	0.96
C21—C26	1.375 (4)	C71—H71	0.93
C22—C23	1.372 (4)	C73—H73A	0.96
C23—C24	1.341 (6)	C73—H73B	0.96
C24—C25	1.349 (6)	C73—H73C	0.96
C25—C26	1.398 (5)	C74—H74A	0.96
C44—C45	1.550 (3)	C74—H74B	0.96
C45—C51	1.538 (4)	C74—H74C	0.96
O1—Cu1—O9	93.86 (10)	C61—C62—C63	121.3 (3)
O1—Cu1—O49	92.32 (8)	C62—C63—C64	119.9 (3)
O1—Cu1—N6	92.21 (8)	C63—C64—C65	119.4 (3)
O1—Cu1—N46	100.81 (9)	C64—C65—C66	120.1 (4)
O9—Cu1—O49	173.81 (9)	C61—C66—C65	121.3 (3)
O9—Cu1—N6	83.46 (7)	C8—C7—H7A	110.00
O9—Cu1—N46	96.18 (8)	N6—C7—H7A	110.00
O49—Cu1—N6	95.96 (7)	N6—C7—H7B	110.00
O49—Cu1—N46	82.99 (7)	H7A—C7—H7B	108.00
N6—Cu1—N46	166.97 (9)	C8—C7—H7B	109.00
Cu1—O9—C8	116.78 (15)	C11—C12—H12	121.00
Cu1—O49—C48	117.13 (14)	C13—C12—H12	121.00
H1W—O1—H2W	104 (4)	C12—C13—H13	120.00
Cu1—O1—H1W	111 (2)	C14—C13—H13	121.00
Cu1—O1—H2W	113 (3)	C13—C14—H14	119.00
C2—N1—C5	112.16 (15)	C15—C14—H14	119.00
C2—N3—C4	112.28 (18)	C16—C15—H15	120.00
Cu1—N6—C2	129.94 (13)	C14—C15—H15	120.00
Cu1—N6—C7	111.88 (13)	C15—C16—H16	119.00
C2—N6—C7	116.48 (17)	C11—C16—H16	119.00
C42—N41—C45	112.44 (16)	C21—C22—H22	120.00
C42—N43—C44	112.21 (17)	C23—C22—H22	120.00
Cu1—N46—C42	131.50 (15)	C22—C23—H23	119.00
Cu1—N46—C47	112.71 (15)	C24—C23—H23	119.00
C42—N46—C47	115.8 (2)	C23—C24—H24	120.00
C2—N1—H1	124.00	C25—C24—H24	120.00
C5—N1—H1	124.00	C24—C25—H25	119.00
C4—N3—H3	124.00	C26—C25—H25	119.00
C2—N3—H3	124.00	C21—C26—H26	121.00
C42—N41—H41	124.00	C25—C26—H26	121.00
C45—N41—H41	124.00	C48—C47—H47A	109.00
C42—N43—H43	124.00	C48—C47—H47B	109.00
C44—N43—H43	124.00	H47A—C47—H47B	108.00
C33A—N32—C34A	112.7 (6)	N46—C47—H47B	109.00
C31B—N32—C34B	111.6 (8)	N46—C47—H47A	110.00
C33B—N32—C34B	128.0 (10)	C53—C52—H52	120.00
C31A—N32—C34A	124.2 (6)	C51—C52—H52	120.00
C31B—N32—C33B	120.0 (11)	C52—C53—H53	120.00
C31A—N32—C33A	123.1 (7)	C54—C53—H53	120.00
C73—N72—C74	119.8 (4)	C53—C54—H54	120.00
C71—N72—C74	121.2 (4)	C55—C54—H54	120.00
C71—N72—C73	119.0 (4)	C54—C55—H55	120.00
N3—C2—N6	122.55 (19)	C56—C55—H55	120.00
N1—C2—N6	129.24 (17)	C55—C56—H56	120.00
N1—C2—N3	108.20 (16)	C51—C56—H56	120.00
N3—C4—C5	106.16 (17)	C61—C62—H62	119.00
O4—C4—N3	126.1 (2)	C63—C62—H62	119.00
O4—C4—C5	127.7 (2)	C64—C63—H63	120.00
C4—C5—C21	115.32 (19)	C62—C63—H63	120.00
C4—C5—C11	105.57 (17)	C63—C64—H64	120.00
C11—C5—C21	110.8 (2)	C65—C64—H64	120.00
N1—C5—C4	100.71 (17)	C64—C65—H65	120.00
N1—C5—C21	110.82 (16)	C66—C65—H65	120.00
N1—C5—C11	113.29 (18)	C65—C66—H66	119.00
N6—C7—C8	110.56 (17)	C61—C66—H66	119.00
O9—C8—C7	117.1 (2)	O31—C31A—N32	117.0 (7)
O10—C8—C7	118.8 (2)	O31—C31B—N32	116.0 (10)
O9—C8—O10	124.1 (2)	O31—C31A—H31A	122.00
C12—C11—C16	119.4 (3)	N32—C31A—H31A	121.00
C5—C11—C16	118.7 (2)	N32—C31B—H31B	122.00
C5—C11—C12	121.8 (2)	O31—C31B—H31B	122.00
C11—C12—C13	118.5 (3)	N32—C33A—H33C	110.00
C12—C13—C14	119.0 (4)	H33A—C33A—H33B	109.00
C13—C14—C15	122.0 (4)	N32—C33A—H33B	109.00
C14—C15—C16	119.6 (4)	H33A—C33A—H33C	109.00
C11—C16—C15	121.6 (3)	H33B—C33A—H33C	109.00
C22—C21—C26	119.3 (2)	N32—C33A—H33A	109.00
C5—C21—C26	122.4 (2)	N32—C33B—H33E	110.00
C5—C21—C22	118.3 (2)	N32—C33B—H33F	110.00
C21—C22—C23	119.7 (3)	H33D—C33B—H33E	109.00
C22—C23—C24	121.5 (3)	N32—C33B—H33D	109.00
C23—C24—C25	119.4 (3)	H33D—C33B—H33F	109.00
C24—C25—C26	121.8 (4)	H33E—C33B—H33F	110.00
C21—C26—C25	118.3 (3)	H34A—C34A—H34C	109.00
N41—C42—N43	108.36 (18)	N32—C34A—H34C	109.00
N41—C42—N46	129.01 (18)	H34A—C34A—H34B	110.00
N43—C42—N46	122.63 (19)	N32—C34A—H34A	110.00
N43—C44—C45	106.11 (16)	N32—C34A—H34B	110.00
O44—C44—N43	125.98 (19)	H34B—C34A—H34C	109.00
O44—C44—C45	127.9 (2)	N32—C34B—H34F	109.00
C51—C45—C61	111.23 (19)	H34D—C34B—H34F	109.00
C44—C45—C51	108.43 (16)	H34E—C34B—H34F	110.00
N41—C45—C61	110.14 (16)	H34D—C34B—H34E	110.00
C44—C45—C61	112.7 (2)	N32—C34B—H34D	109.00
N41—C45—C44	100.79 (17)	N32—C34B—H34E	109.00
N41—C45—C51	113.18 (19)	O71—C71—N72	118.3 (6)
N46—C47—C48	110.89 (19)	O71—C71—H71	121.00
O49—C48—C47	115.89 (19)	N72—C71—H71	121.00
O49—C48—O50	123.9 (2)	N72—C73—H73A	109.00
O50—C48—C47	120.2 (2)	N72—C73—H73B	109.00
C52—C51—C56	119.1 (3)	N72—C73—H73C	109.00
C45—C51—C56	119.3 (2)	H73A—C73—H73B	109.00
C45—C51—C52	121.6 (2)	H73A—C73—H73C	109.00
C51—C52—C53	119.8 (3)	H73B—C73—H73C	109.00
C52—C53—C54	120.3 (3)	N72—C74—H74A	109.00
C53—C54—C55	119.5 (3)	N72—C74—H74B	109.00
C54—C55—C56	120.9 (3)	N72—C74—H74C	110.00
C51—C56—C55	120.5 (3)	H74A—C74—H74B	109.00
C62—C61—C66	118.1 (3)	H74A—C74—H74C	109.00
C45—C61—C66	123.6 (2)	H74B—C74—H74C	109.00
C45—C61—C62	118.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O50^i	0.86	1.99	2.828 (2)	166
N41—H41···O10^ii	0.86	1.98	2.821 (2)	167
O1—H1W···O31	0.84 (4)	1.99 (4)	2.828 (6)	178 (4)
O1—H2W···O71^ii	0.88 (5)	1.90 (4)	2.763 (5)	168 (4)
N3—H3···O49	0.86	1.93	2.676 (2)	144
N43—H43···O9	0.86	1.96	2.698 (3)	143
C24—H24···O44^iii	0.93	2.53	3.453 (4)	170

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