[N,N′-Bis­(salicyl­idene)-2,2-di­methyl-1,3-propane­diaminato]­nickel(II) and [N,N′-bis­(salicyl­idene)-2,2-di­methyl-1,3-propane­diaminato]copper(II)

In the title compounds, {2,2′-[2,2-di­methyl-1,3-propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato-κ⁴N,N′,O,O′}nickel(II), [Ni(C₁₉H₂₀N₂O₂)], and {2,2′-[2,2-di­methyl-1,3-propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato-κ⁴N,N′,O,O′}copper(II), [Cu(C₁₉H₂₀N₂O₂)], the Ni^II and Cu^II atoms are coordinated by two iminic N and two phenolic O atoms of the N,N′-bis­(salicyl­idene)-2,2-di­methyl-1,3-propane­diaminate (SALPD²⁻, C₁₇H₁₆N₂O₂²⁻) ligand. The geometry of the coordination sphere is planar in the case of the Ni^II complex and distorted towards tetrahedral for the Cu^II complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20 (6) and 35.13 (7)°, respectively.

S1. Comment

The chemistry of metal complexes with Schiff base ligands and their application has aroused considerable attention mainly because of their preparative accessibility, diversity and structural variability. For example, there has been interest in Cu^II–imine–phenols because of their color isomerism (Yao et al., 1997) and the Ni^II complexes have been used to probe the structural and electronic consequences of small modifications of the ligand skeleton (Gomes et al., 1999). Nickel(II) and copper(II) complexes of diamine Schiff bases generally display square-planar coordination (Akhtar et al., 1981; Radha et al., 1985; Drew et al., 1985). We have synthesized Ni^II[(SALPD)(CH₃)₂], (I), and Cu^II[(SALPD)(CH₃)₂], (II), and report their structures here.

In both compounds, the structure consists of asymmetric monomers (Figs. 1 and 2) which have a monoclinic unit cell containing four molecules. In the structure of (I), the Ni atom has a square-planar coordination involving two O and two N atoms of the tetradentate SALPD^2- ligand. The Ni atom is located 0.013 (3) Å from the best coordination plane consisting of atoms N1, N2, O1 and O2; the dihedral angle between the two Ni/N/O planes is 17.20 (6)°.

Complexes of (N,N'-trimethylenedisalicylideneaminato)nickel(II), [Ni(salpd)], and (N,N'-trimethylenedisalicylideneaminato)copper(II), [Cu(salpd)] (Drew et al., 1985), show a similar structure apart from the methyl groups. Comparison of the Ni—N and Ni—O bond distances, and the O—Ni—O angles of the present work and [Ni(salpd)] show then to be very similar. In the present work, The Ni—N1, Ni—N2, Ni—O1 and Ni—O2 bond distances are 1.8764 (17), 1.8660 (17), 1.8463 (14) and 1.8461 (15) Å, respectively. In [Ni(salpd)], the Ni—N and Ni—O distances are 1.901 (4) and 1.845 (3) Å, respectively. The O1—Ni—O2 angle of 83.91° in (I) is is greater than the value of 78.31 (13)° in [Ni(salpd)].

In the structure of (II), the Cu atom is coordinated in a distorted planar coordination geometry by two N [Cu—N1 1.929 (2) Å and Cu—N2 1.9518 (19) Å] and two O [Cu—O1 1.8967 (17) Å and Cu—O2 1.8956 (17) Å] of the imine–phenol ligand. The tetrahedral distortion between the Cu/N/O planes is 35.13 (7)°. Similar distortions are found in the literature for Cu^II structures. This angle between planes can be compared to the value of 21.0 (1)° for [Cu(salpd)] and 42.7 (1)° for [N,N'-bis(salicylidene)-1,4-diiminobutane]copper(II) (Yao et al., 1997).

The SALPD^2- ligand is not planar. The chelate ring composed of atoms M (Ni or Cu), N1, C8, C9, C10 and N2 has a distorted boat conformation. The distances of the two para-positioned boat atoms, M and C9, from the best plane of the six atoms are 0.0001 (3) and 0.06 (2) Å for Cu, and 0.0036 (3) and 0.155 (2) Å for Ni, respectively.

S2. Experimental

N,N'-Bis(salicylidene)-2,2-dimethyl-1,3-propanediamine (0.620 g, 0.002 mol) was dissolved in a hot dioxane–MeOH mixture (1:1, 50 ml). To this solution were added triethylamine (1 ml) and a solution of NiCl₂·6H₂O (0.476 g, 0.002 mol) in hot MeOH (30 ml) for the Ni complex and a solution of CuCl₂·2H₂O (0.340 g, 0.002 mol) in hot MeOH (30 ml) for the Cu complex. The mixture was set aside for 2 d and the dark-brown crystals of the nickel(II) complex and dark-green crystals of the copper(II) complex which formed were filtered off and dried in an oven at 373 K.

S3. Refinement

H atoms bonded to C atoms were placed geometrically. All H atoms were refined as riding with U_eq(H) = 1.2U_iso(C).

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1993); cell refinement: SHELXL97 (Sheldrick, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. PLATON (Spek, 2000) drawing of [Ni(C19H20N2O2)]. H atoms are shown as small circles with arbitrary radii and ellipsoids are shown at the 50% probability level. The Cu^II molecule is essentially identical to the Ni^II molecule.

(I)

Crystal data

[Ni(C19H20N2O2)]	Z = 4
Mr = 367.08	Dx = 1.406 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 9.9329 (12) Å	θ = 4.9–74.2°
b = 15.8778 (11) Å	µ = 1.72 mm^−1
c = 11.8793 (10) Å	T = 301 K
β = 112.200 (3)°	Prism, dark brown
V = 1734.6 (3) Å^3	0.35 × 0.30 × 0.25 mm

Data collection

CAD-4 EXPRESS diffractometer	Rint = 0.036
ω/2θ scans	θmax = 74.2°
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990)	h = −12→0
Tmin = 0.585, Tmax = 0.673	k = −19→0
3704 measured reflections	l = −13→14
3503 independent reflections	3 standard reflections every 120 min
3058 reflections with I > 2σ(I)	intensity decay: 2.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0548P)^2 + 0.6415P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
3503 reflections	Δρmax = 0.29 e Å^−3
218 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: Larson (1970), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0072 (4)

Special details

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
Ni	0.08080 (3)	0.84458 (2)	0.03050 (3)	0.04271 (14)
O1	−0.03878 (16)	0.86878 (10)	−0.12785 (13)	0.0533 (4)
O2	−0.06158 (18)	0.76706 (12)	0.02109 (14)	0.0661 (5)
N1	0.19661 (16)	0.94094 (11)	0.04913 (15)	0.0435 (4)
N2	0.21126 (16)	0.79860 (11)	0.17515 (15)	0.0457 (4)
C1	−0.0227 (2)	0.92728 (13)	−0.19938 (17)	0.0449 (4)
C2	−0.1143 (2)	0.92654 (16)	−0.32386 (19)	0.0541 (5)
C3	−0.1071 (3)	0.98985 (17)	−0.4003 (2)	0.0613 (6)
C4	−0.0095 (3)	1.05648 (17)	−0.3573 (2)	0.0634 (6)
C5	0.0805 (2)	1.05831 (15)	−0.2384 (2)	0.0564 (5)
C6	0.0791 (2)	0.99361 (13)	−0.15711 (19)	0.0456 (4)
C7	0.1773 (2)	0.99832 (13)	−0.0332 (2)	0.0468 (4)
C8	0.2948 (2)	0.96133 (14)	0.17390 (19)	0.0510 (5)
C9	0.4209 (2)	0.89987 (16)	0.2274 (2)	0.0557 (5)
C10	0.3666 (2)	0.80918 (16)	0.1963 (2)	0.0563 (5)
C11	0.5389 (3)	0.9152 (2)	0.1765 (3)	0.0858 (9)
C12	0.4821 (3)	0.9131 (2)	0.3656 (3)	0.0906 (10)
C13	0.1777 (2)	0.75188 (13)	0.24973 (19)	0.0492 (5)
C14	0.0331 (2)	0.72554 (13)	0.23033 (18)	0.0459 (4)
C15	0.0031 (3)	0.68684 (17)	0.3251 (2)	0.0630 (6)
C16	−0.1313 (3)	0.65550 (19)	0.3073 (3)	0.0761 (8)
C17	−0.2391 (3)	0.6585 (2)	0.1920 (3)	0.0792 (8)
C18	−0.2124 (3)	0.69404 (19)	0.0979 (2)	0.0724 (8)
C19	−0.0785 (2)	0.73099 (14)	0.11370 (19)	0.0515 (5)
H2	−0.1817	0.8818	−0.3550	0.065*
H3	−0.1694	0.9882	−0.4837	0.074*
H4	−0.0062	1.1002	−0.4107	0.076*
H5	0.1460	1.1041	−0.2091	0.068*
H7	0.2338	1.0482	−0.0088	0.056*
H8A	0.2379	0.9623	0.2266	0.061*
H8B	0.3346	1.0186	0.1746	0.061*
H10A	0.3826	0.7913	0.1224	0.068*
H10B	0.4250	0.7717	0.2637	0.068*
H11A	0.6181	0.8746	0.2123	0.129*
H11B	0.5768	0.9725	0.1965	0.129*
H11C	0.4975	0.9081	0.0880	0.129*
H12A	0.5639	0.8745	0.4037	0.136*
H12B	0.4059	0.9017	0.3972	0.136*
H12C	0.5157	0.9713	0.3842	0.136*
H13	0.2541	0.7339	0.3221	0.059*
H15	0.0784	0.6825	0.4033	0.076*
H16	−0.1507	0.6319	0.3732	0.091*
H17	−0.3324	0.6356	0.1782	0.095*
H18	−0.2871	0.6937	0.0190	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.03443 (19)	0.0535 (2)	0.0356 (2)	−0.00042 (14)	0.00791 (14)	−0.00660 (13)
O1	0.0494 (8)	0.0631 (9)	0.0385 (7)	0.0025 (6)	0.0065 (6)	−0.0155 (7)
O2	0.0581 (9)	0.0876 (12)	0.0383 (7)	0.0096 (7)	0.0020 (7)	−0.0319 (8)
N1	0.0335 (7)	0.0513 (9)	0.0435 (8)	−0.0049 (7)	0.0119 (6)	−0.0008 (6)
N2	0.0324 (8)	0.0538 (10)	0.0461 (9)	−0.0013 (7)	0.0094 (7)	−0.0013 (7)
C1	0.0406 (9)	0.0555 (11)	0.0405 (9)	0.0023 (8)	0.0174 (8)	0.0023 (8)
C2	0.0516 (11)	0.0660 (14)	0.0425 (10)	0.0013 (9)	0.0155 (9)	0.0033 (10)
C3	0.0597 (13)	0.0827 (17)	0.0440 (11)	0.0118 (11)	0.0224 (10)	0.0156 (12)
C4	0.0630 (14)	0.0734 (16)	0.0621 (14)	0.0225 (12)	0.0332 (12)	0.0150 (12)
C5	0.0482 (11)	0.0602 (13)	0.0668 (14)	0.0102 (11)	0.0287 (10)	0.0045 (10)
C6	0.0377 (9)	0.0527 (11)	0.0501 (11)	0.0040 (9)	0.0210 (8)	0.0047 (8)
C7	0.0362 (9)	0.0496 (11)	0.0569 (12)	−0.0034 (9)	0.0203 (8)	−0.0030 (8)
C8	0.0412 (10)	0.0586 (12)	0.0469 (11)	−0.0103 (9)	0.0096 (8)	−0.0053 (9)
C9	0.0327 (9)	0.0677 (14)	0.0578 (12)	−0.0058 (10)	0.0071 (9)	−0.0046 (9)
C10	0.0326 (9)	0.0648 (14)	0.0666 (14)	0.0008 (11)	0.0134 (9)	0.0042 (9)
C11	0.0465 (13)	0.091 (2)	0.124 (3)	−0.0004 (19)	0.0368 (16)	−0.0065 (13)
C12	0.0733 (18)	0.106 (2)	0.0601 (16)	−0.0091 (16)	−0.0117 (14)	−0.0009 (17)
C13	0.0415 (10)	0.0542 (12)	0.0431 (10)	0.0028 (9)	0.0061 (8)	0.0041 (9)
C14	0.0460 (10)	0.0477 (11)	0.0401 (10)	0.0036 (8)	0.0117 (8)	−0.0002 (8)
C15	0.0685 (15)	0.0708 (15)	0.0446 (11)	0.0097 (11)	0.0155 (11)	−0.0054 (12)
C16	0.0839 (19)	0.087 (2)	0.0640 (16)	0.0126 (14)	0.0355 (15)	−0.0196 (15)
C17	0.0615 (15)	0.094 (2)	0.0799 (18)	0.0191 (15)	0.0246 (14)	−0.0229 (14)
C18	0.0537 (13)	0.0895 (19)	0.0603 (14)	0.0183 (13)	0.0060 (11)	−0.0246 (13)
C19	0.0466 (11)	0.0586 (12)	0.0427 (10)	0.0052 (9)	0.0094 (8)	−0.0117 (9)

Geometric parameters (Å, º)

C1—O1	1.309 (2)	C11—H11A	0.98
C1—C2	1.414 (3)	C11—H11B	0.98
C1—C6	1.414 (3)	C11—H11C	0.98
C2—C3	1.375 (3)	C12—H12A	0.98
C2—H2	0.95	C12—H12B	0.98
C3—C4	1.394 (4)	C12—H12C	0.98
C3—H3	0.95	C13—N2	1.292 (3)
C4—C5	1.357 (3)	C13—C14	1.429 (3)
C4—H4	0.95	C13—H13	0.95
C5—C6	1.414 (3)	C14—C15	1.410 (3)
C5—H5	0.95	C14—C19	1.413 (3)
C6—C7	1.428 (3)	C15—C16	1.364 (4)
C7—N1	1.297 (3)	C15—H15	0.95
C7—H7	0.95	C16—C17	1.385 (4)
C8—N1	1.470 (2)	C16—H16	0.95
C8—C9	1.524 (3)	C17—C18	1.365 (4)
C8—H8A	0.99	C17—H17	0.95
C8—H8B	0.99	C18—C19	1.399 (3)
C9—C11	1.528 (3)	C18—H18	0.95
C9—C12	1.534 (4)	C19—O2	1.306 (3)
C9—C10	1.533 (3)	Ni—N1	1.8764 (17)
C10—N2	1.477 (2)	Ni—N2	1.8660 (17)
C10—H10A	0.99	Ni—O2	1.8461 (15)
C10—H10B	0.99	Ni—O1	1.8463 (14)
O1—C1—C2	119.00 (19)	H11A—C11—H11C	109.5
O1—C1—C6	122.98 (18)	H11B—C11—H11C	109.5
C2—C1—C6	117.98 (19)	C9—C12—H12A	109.5
C3—C2—C1	120.7 (2)	C9—C12—H12B	109.5
C3—C2—H2	119.6	H12A—C12—H12B	109.5
C1—C2—H2	119.6	C9—C12—H12C	109.5
C2—C3—C4	121.0 (2)	H12A—C12—H12C	109.5
C2—C3—H3	119.5	H12B—C12—H12C	109.5
C4—C3—H3	119.5	N2—C13—C14	124.16 (18)
C5—C4—C3	119.4 (2)	N2—C13—H13	117.9
C5—C4—H4	120.3	C14—C13—H13	117.9
C3—C4—H4	120.3	C15—C14—C19	119.1 (2)
C4—C5—C6	121.5 (2)	C15—C14—C13	120.12 (19)
C4—C5—H5	119.2	C19—C14—C13	120.58 (18)
C6—C5—H5	119.2	C16—C15—C14	121.7 (2)
C5—C6—C1	119.27 (19)	C16—C15—H15	119.2
C5—C6—C7	119.1 (2)	C14—C15—H15	119.2
C1—C6—C7	121.57 (18)	C15—C16—C17	119.1 (2)
N1—C7—C6	126.12 (19)	C15—C16—H16	120.5
N1—C7—H7	116.9	C17—C16—H16	120.5
C6—C7—H7	116.9	C18—C17—C16	120.5 (2)
N1—C8—C9	114.02 (18)	C18—C17—H17	119.7
N1—C8—H8A	108.7	C16—C17—H17	119.7
C9—C8—H8A	108.7	C17—C18—C19	122.2 (2)
N1—C8—H8B	108.7	C17—C18—H18	118.9
C9—C8—H8B	108.7	C19—C18—H18	118.9
H8A—C8—H8B	107.6	O2—C19—C18	119.3 (2)
C8—C9—C11	111.4 (2)	O2—C19—C14	123.36 (19)
C8—C9—C12	106.8 (2)	C18—C19—C14	117.4 (2)
C11—C9—C12	110.4 (2)	C7—N1—C8	117.30 (18)
C8—C9—C10	110.00 (16)	C7—N1—Ni	125.06 (14)
C11—C9—C10	107.8 (2)	C8—N1—Ni	116.24 (14)
C12—C9—C10	110.3 (2)	C13—N2—C10	118.20 (18)
N2—C10—C9	113.42 (18)	C13—N2—Ni	125.93 (13)
N2—C10—H10A	108.9	C10—N2—Ni	115.43 (14)
C9—C10—H10A	108.9	O2—Ni—O1	83.91 (7)
N2—C10—H10B	108.9	O2—Ni—N2	92.55 (7)
C9—C10—H10B	108.9	O1—Ni—N2	167.22 (8)
H10A—C10—H10B	107.7	O2—Ni—N1	166.48 (8)
C9—C11—H11A	109.5	O1—Ni—N1	94.60 (7)
C9—C11—H11B	109.5	N2—Ni—N1	91.66 (7)
H11A—C11—H11B	109.5	C1—O1—Ni	128.30 (13)
C9—C11—H11C	109.5	C19—O2—Ni	125.50 (14)
O1—C1—C2—C3	175.9 (2)	C9—C10—N2—C13	−115.2 (2)
C4—C5—C6—C7	179.3 (2)	C9—C10—N2—Ni	71.9 (2)
O1—C1—C6—C5	−174.39 (19)	C13—N2—Ni—O2	−20.54 (19)
C2—C1—C6—C7	−178.95 (18)	C10—N2—Ni—O2	151.73 (16)
C5—C6—C7—N1	−174.19 (19)	C13—N2—Ni—O1	−94.0 (3)
C1—C6—C7—N1	7.9 (3)	C10—N2—Ni—O1	78.2 (4)
N1—C8—C9—C11	76.6 (3)	C13—N2—Ni—N1	146.61 (19)
N1—C8—C9—C12	−162.7 (2)	C10—N2—Ni—N1	−41.12 (16)
N1—C8—C9—C10	−42.9 (3)	C7—N1—Ni—O2	−81.7 (3)
C8—C9—C10—N2	−25.9 (3)	C8—N1—Ni—O2	84.3 (3)
C11—C9—C10—N2	−147.7 (2)	C8—N1—Ni—O1	167.38 (14)
C12—C9—C10—N2	91.7 (2)	C7—N1—Ni—N2	170.17 (17)
N2—C13—C14—C15	−169.3 (2)	C8—N1—Ni—N2	−23.77 (14)
N2—C13—C14—C19	16.4 (3)	C2—C1—O1—Ni	169.90 (15)
C13—C14—C15—C16	−175.2 (3)	C6—C1—O1—Ni	−12.6 (3)
C17—C18—C19—O2	−177.2 (3)	O2—Ni—O1—C1	175.94 (19)
C15—C14—C19—O2	178.7 (2)	N2—Ni—O1—C1	−109.6 (3)
C13—C14—C19—O2	−6.9 (4)	N1—Ni—O1—C1	9.43 (19)
C13—C14—C19—C18	171.8 (2)	C18—C19—O2—Ni	160.9 (2)
C6—C7—N1—C8	−175.18 (18)	C14—C19—O2—Ni	−20.4 (4)
C6—C7—N1—Ni	−9.3 (3)	O1—Ni—O2—C19	−162.7 (2)
C9—C8—N1—C7	−123.0 (2)	N2—Ni—O2—C19	29.6 (2)
C9—C8—N1—Ni	69.8 (2)	N1—Ni—O2—C19	−78.4 (4)
C14—C13—N2—C10	−169.9 (2)

(II)

Crystal data

[Cu(C19H20N2O2)]	Z = 4
Mr = 371.91	Dx = 1.407 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2yn	Cell parameters from 15 reflections
a = 9.7452 (12) Å	θ = 5.0–74.2°
b = 17.2276 (14) Å	µ = 1.86 mm^−1
c = 11.3606 (10) Å	T = 301 K
β = 112.981 (3)°	Prism, dark green
V = 1755.9 (3) Å^3	0.30 × 0.20 × 0.20 mm

Data collection

CAD-4 EXPRESS diffractometer	Rint = 0.036
ω/2θ scans	θmax = 74.2°
Absorption correction: ψ scan empirical (using intensity measurements) via ψ scans (Fair, 1990)	h = −11→12
Tmin = 0.606, Tmax = 0.707	k = 0→21
3591 measured reflections	l = −14→0
3419 independent reflections	3 standard reflections every 120 min
2982 reflections with I > 2σ(I)	intensity decay: 1.3%

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.106	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0581P)^2 + 0.8826P] where P = (Fo^2 + 2Fc^2)/3
3419 reflections	(Δ/σ)max = 0.001
218 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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	0.54580 (3)	0.85029 (2)	0.50685 (3)	0.04307 (14)
O1	0.37681 (18)	0.79780 (10)	0.51132 (17)	0.0512 (4)
O2	0.4367 (2)	0.87954 (11)	0.33448 (17)	0.0554 (5)
N1	0.6881 (2)	0.78903 (12)	0.6416 (2)	0.0484 (5)
N2	0.6845 (2)	0.93727 (11)	0.54226 (19)	0.0424 (4)
C1	0.3761 (3)	0.74868 (14)	0.5991 (2)	0.0451 (5)
C2	0.2376 (3)	0.72296 (17)	0.5969 (3)	0.0591 (7)
C3	0.2291 (4)	0.6712 (2)	0.6858 (3)	0.0718 (8)
C4	0.3569 (4)	0.6419 (2)	0.7811 (3)	0.0761 (9)
C5	0.4924 (4)	0.66565 (18)	0.7862 (3)	0.0654 (8)
C6	0.5069 (3)	0.71909 (14)	0.6973 (2)	0.0481 (6)
C7	0.6554 (3)	0.73841 (15)	0.7104 (2)	0.0517 (6)
C8	0.8451 (3)	0.80062 (16)	0.6600 (3)	0.0558 (7)
C9	0.9083 (3)	0.87958 (17)	0.7201 (3)	0.0533 (6)
C10	0.7883 (3)	0.94358 (15)	0.6758 (2)	0.0484 (6)
C11	0.9638 (4)	0.8752 (2)	0.8661 (3)	0.0808 (10)
C12	1.0369 (3)	0.8997 (2)	0.6805 (4)	0.0786 (10)
C13	0.6724 (2)	0.99340 (14)	0.4645 (2)	0.0436 (5)
C14	0.5688 (2)	0.99732 (14)	0.3333 (2)	0.0435 (5)
C15	0.5763 (3)	1.06304 (16)	0.2616 (3)	0.0546 (6)
C16	0.4832 (4)	1.07150 (19)	0.1362 (3)	0.0670 (8)
C17	0.3784 (3)	1.01392 (19)	0.0769 (3)	0.0641 (7)
C18	0.3667 (3)	0.94992 (18)	0.1440 (2)	0.0556 (6)
C19	0.4589 (3)	0.93972 (14)	0.2746 (2)	0.0442 (5)
H2	0.1482	0.7419	0.5326	0.071*
H3	0.1341	0.6551	0.6819	0.086*
H4	0.3500	0.6058	0.8419	0.091*
H5	0.5799	0.6457	0.8515	0.078*
H7	0.7356	0.7120	0.7743	0.062*
H8A	0.8535	0.7963	0.5762	0.067*
H8B	0.9062	0.7588	0.7157	0.067*
H10A	0.7307	0.9420	0.7308	0.058*
H10B	0.8385	0.9947	0.6885	0.058*
H11A	0.8804	0.8623	0.8903	0.121*
H11B	1.0058	0.9255	0.9031	0.121*
H11C	1.0408	0.8351	0.8982	0.121*
H12A	1.0797	0.9498	0.7176	0.118*
H12B	0.9999	0.9027	0.5871	0.118*
H12C	1.1137	0.8594	0.7115	0.118*
H13	0.7378	1.0363	0.4965	0.052*
H15	0.6479	1.1023	0.3016	0.065*
H16	0.4898	1.1162	0.0898	0.080*
H17	0.3146	1.0191	−0.0107	0.077*
H18	0.2946	0.9114	0.1016	0.067*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03387 (19)	0.0422 (2)	0.0458 (2)	0.00270 (14)	0.00764 (14)	−0.00282 (13)
O1	0.0374 (8)	0.0556 (10)	0.0509 (9)	0.0077 (8)	0.0068 (7)	−0.0054 (7)
O2	0.0524 (10)	0.0524 (10)	0.0472 (9)	0.0043 (8)	0.0040 (8)	−0.0125 (8)
N1	0.0345 (9)	0.0455 (11)	0.0563 (12)	0.0013 (9)	0.0081 (9)	0.0017 (8)
N2	0.0323 (9)	0.0431 (10)	0.0473 (10)	−0.0035 (8)	0.0106 (8)	0.0000 (8)
C1	0.0427 (12)	0.0428 (12)	0.0455 (12)	−0.0026 (10)	0.0125 (10)	−0.0049 (10)
C2	0.0477 (14)	0.0601 (16)	0.0650 (17)	0.0014 (13)	0.0172 (12)	−0.0118 (12)
C3	0.0666 (19)	0.077 (2)	0.075 (2)	0.0009 (17)	0.0310 (16)	−0.0243 (16)
C4	0.090 (2)	0.072 (2)	0.0672 (19)	0.0125 (16)	0.0315 (18)	−0.0235 (18)
C5	0.0700 (18)	0.0584 (17)	0.0580 (16)	0.0125 (13)	0.0143 (14)	−0.0063 (14)
C6	0.0489 (13)	0.0415 (12)	0.0478 (13)	0.0023 (10)	0.0123 (11)	−0.0039 (10)
C7	0.0441 (12)	0.0442 (13)	0.0531 (14)	0.0069 (11)	0.0043 (11)	0.0048 (10)
C8	0.0339 (12)	0.0548 (15)	0.0726 (17)	0.0042 (13)	0.0143 (11)	0.0069 (10)
C9	0.0313 (11)	0.0603 (15)	0.0604 (15)	0.0011 (13)	0.0094 (10)	0.0010 (10)
C10	0.0388 (12)	0.0517 (14)	0.0473 (13)	−0.0065 (11)	0.0088 (10)	−0.0030 (10)
C11	0.0649 (19)	0.089 (2)	0.0622 (19)	0.0051 (17)	−0.0038 (15)	0.0028 (17)
C12	0.0436 (15)	0.078 (2)	0.115 (3)	−0.006 (2)	0.0312 (17)	−0.0061 (14)
C13	0.0351 (10)	0.0421 (12)	0.0549 (14)	−0.0045 (10)	0.0190 (10)	−0.0028 (9)
C14	0.0394 (11)	0.0444 (12)	0.0506 (13)	0.0007 (10)	0.0219 (10)	0.0030 (9)
C15	0.0514 (14)	0.0532 (15)	0.0659 (16)	0.0079 (13)	0.0303 (13)	0.0007 (11)
C16	0.0744 (19)	0.0695 (19)	0.0664 (18)	0.0230 (15)	0.0378 (16)	0.0100 (16)
C17	0.0702 (18)	0.075 (2)	0.0474 (14)	0.0093 (14)	0.0230 (13)	0.0129 (16)
C18	0.0540 (14)	0.0623 (16)	0.0466 (13)	−0.0011 (12)	0.0153 (11)	0.0030 (12)
C19	0.0413 (12)	0.0449 (12)	0.0453 (12)	0.0001 (10)	0.0158 (10)	0.0036 (9)

Geometric parameters (Å, º)

C1—O1	1.310 (3)	C11—H11A	0.98
C1—C2	1.412 (3)	C11—H11B	0.98
C1—C6	1.421 (3)	C11—H11C	0.98
C2—C3	1.374 (4)	C12—H12A	0.98
C2—H2	0.95	C12—H12B	0.98
C3—C4	1.388 (5)	C12—H12C	0.98
C3—H3	0.95	C13—N2	1.284 (3)
C4—C5	1.362 (5)	C13—C14	1.439 (3)
C4—H4	0.95	C13—H13	0.95
C5—C6	1.414 (4)	C14—C15	1.413 (3)
C5—H5	0.95	C14—C19	1.421 (3)
C6—C7	1.435 (4)	C15—C16	1.365 (4)
C7—N1	1.291 (3)	C15—H15	0.95
C7—H7	0.95	C16—C17	1.394 (4)
C8—N1	1.475 (3)	C16—H16	0.95
C8—C9	1.538 (4)	C17—C18	1.370 (4)
C8—H8A	0.99	C17—H17	0.95
C8—H8B	0.99	C18—C19	1.414 (3)
C9—C12	1.528 (4)	C18—H18	0.95
C9—C11	1.532 (4)	C19—O2	1.304 (3)
C9—C10	1.542 (3)	Cu—O2	1.8956 (17)
C10—N2	1.463 (3)	Cu—O1	1.8967 (17)
C10—H10A	0.99	Cu—N1	1.929 (2)
C10—H10B	0.99	Cu—N2	1.9518 (19)
O1—C1—C2	118.6 (2)	H11A—C11—H11C	109.5
O1—C1—C6	124.0 (2)	H11B—C11—H11C	109.5
C2—C1—C6	117.4 (2)	C9—C12—H12A	109.5
C3—C2—C1	121.5 (3)	C9—C12—H12B	109.5
C3—C2—H2	119.3	H12A—C12—H12B	109.5
C1—C2—H2	119.3	C9—C12—H12C	109.5
C2—C3—C4	121.1 (3)	H12A—C12—H12C	109.5
C2—C3—H3	119.5	H12B—C12—H12C	109.5
C4—C3—H3	119.5	N2—C13—C14	125.9 (2)
C5—C4—C3	118.9 (3)	N2—C13—H13	117.0
C5—C4—H4	120.5	C14—C13—H13	117.0
C3—C4—H4	120.5	C15—C14—C19	119.3 (2)
C4—C5—C6	122.1 (3)	C15—C14—C13	117.5 (2)
C4—C5—H5	119.0	C19—C14—C13	123.3 (2)
C6—C5—H5	119.0	C16—C15—C14	121.6 (3)
C5—C6—C1	119.0 (2)	C16—C15—H15	119.2
C5—C6—C7	117.1 (2)	C14—C15—H15	119.2
C1—C6—C7	123.9 (2)	C15—C16—C17	119.4 (3)
N1—C7—C6	124.8 (2)	C15—C16—H16	120.3
N1—C7—H7	117.6	C17—C16—H16	120.3
C6—C7—H7	117.6	C18—C17—C16	120.6 (3)
N1—C8—C9	113.3 (2)	C18—C17—H17	119.7
N1—C8—H8A	108.9	C16—C17—H17	119.7
C9—C8—H8A	108.9	C17—C18—C19	121.8 (3)
N1—C8—H8B	108.9	C17—C18—H18	119.1
C9—C8—H8B	108.9	C19—C18—H18	119.1
H8A—C8—H8B	107.7	O2—C19—C18	118.6 (2)
C12—C9—C11	110.2 (2)	O2—C19—C14	124.0 (2)
C12—C9—C8	107.6 (2)	C18—C19—C14	117.3 (2)
C11—C9—C8	110.4 (3)	O2—Cu—O1	90.67 (8)
C12—C9—C10	110.3 (2)	O2—Cu—N1	154.76 (9)
C11—C9—C10	106.9 (2)	O1—Cu—N1	94.61 (8)
C8—C9—C10	111.51 (19)	O2—Cu—N2	94.18 (8)
N2—C10—C9	114.5 (2)	O1—Cu—N2	154.05 (9)
N2—C10—H10A	108.6	N1—Cu—N2	91.78 (8)
C9—C10—H10A	108.6	C7—N1—C8	119.5 (2)
N2—C10—H10B	108.6	C7—N1—Cu	125.40 (17)
C9—C10—H10B	108.6	C8—N1—Cu	115.03 (17)
H10A—C10—H10B	107.6	C13—N2—C10	119.9 (2)
C9—C11—H11A	109.5	C13—N2—Cu	124.49 (16)
C9—C11—H11B	109.5	C10—N2—Cu	114.44 (16)
H11A—C11—H11B	109.5	C1—O1—Cu	126.24 (15)
C9—C11—H11C	109.5	C19—O2—Cu	127.58 (16)
O1—C1—C2—C3	179.6 (3)	N2—Cu—N1—C7	147.9 (2)
C4—C5—C6—C7	−178.6 (3)	O2—Cu—N1—C8	68.8 (3)
O1—C1—C6—C5	−179.4 (3)	O1—Cu—N1—C8	170.30 (18)
C2—C1—C6—C7	178.6 (3)	N2—Cu—N1—C8	−34.88 (19)
C5—C6—C7—N1	−176.2 (3)	C14—C13—N2—C10	−175.8 (2)
C1—C6—C7—N1	5.7 (4)	C14—C13—N2—Cu	−8.9 (3)
N1—C8—C9—C12	−155.2 (2)	C9—C10—N2—C13	−121.4 (2)
N1—C8—C9—C11	84.5 (3)	C9—C10—N2—Cu	70.4 (2)
N1—C8—C9—C10	−34.1 (3)	O2—Cu—N2—C13	6.9 (2)
C12—C9—C10—N2	82.1 (3)	O1—Cu—N2—C13	−93.3 (3)
C11—C9—C10—N2	−158.1 (2)	N1—Cu—N2—C13	162.3 (2)
C8—C9—C10—N2	−37.4 (3)	O2—Cu—N2—C10	174.41 (16)
N2—C13—C14—C15	−177.8 (2)	O1—Cu—N2—C10	74.2 (2)
N2—C13—C14—C19	3.7 (4)	N1—Cu—N2—C10	−30.13 (17)
C13—C14—C15—C16	179.5 (2)	C2—C1—O1—Cu	171.53 (19)
C17—C18—C19—O2	176.4 (3)	C6—C1—O1—Cu	−8.6 (4)
C15—C14—C19—O2	−175.6 (2)	O2—Cu—O1—C1	166.3 (2)
C13—C14—C19—C18	−178.5 (2)	N1—Cu—O1—C1	11.0 (2)
C6—C7—N1—C8	−176.8 (3)	N2—Cu—O1—C1	−92.7 (3)
C9—C8—N1—C7	−110.8 (3)	C18—C19—O2—Cu	178.28 (18)
C9—C8—N1—Cu	71.8 (3)	C14—C19—O2—Cu	−3.2 (4)
O2—Cu—N1—C7	−108.4 (3)	O1—Cu—O2—C19	153.4 (2)
O1—Cu—N1—C7	−6.9 (2)	N1—Cu—O2—C19	−104.2 (3)