catena-Poly[copper(II)-di-μ-acetyl­acetonato-copper(II)-bis(μ-4-hydroxy-3-methoxybenzaldehyde picoloyl­hydrazonato)] and (acetyl­acetonato)(4-meth­oxy­benzaldehyde picoloyl­hydrazonato)copper(II)

In the two title copper(II) complexes, [CuL(C₅H₇O₂)]_n, (I), and [CuL′(C₅H₇O₂)], (II), respectively, where HL is 4-hy­­droxy-3-meth­oxy­benzaldehyde picoloylhydrazone, C₁₄H₁₂N₃O₃, and HL′ is 4-meth­oxy­benzaldehyde picoloylhydrazone, C₁₄H₁₂N₃O₂, the Cu^II ions display a highly Jahn–Teller-distorted octa­hedral and a square-planar coordination geom­etry, respectively. In complex (I), two neighbouring Cu^II atoms are bridged by L⁻ and acetyl­acetonate, alternately, giving rise to a one-dimensional chain of CuN₂O₄ octa­hedra inter­connected by these two ligands along the a axis. In addition, the hydroxy H atom of the vanillin group connects to the carboxyl O atom of the adjacent chain via an O—H...O hydrogen bond, giving rise to a three-dimensional supra­molecular assembly. Complex (II) displays a discrete structure.

S1. Comment

Studies of acylhydrazone Schiff base and construction of complexes of transition metals are of great interest, not only because of their intriguing structural motifs but also because of their important potential applications (Pickart et al., 1983; Sreekanth et al., 2004) such as catalytic materials (Duda et al., 2003) and magnetochemistry (Lin et al., 2008). The use of carefully selected multidentate ligands and metal ions has allowed the construction of polymers with defined geometries and special properties. From the structural point of view, picoloylhydrazone and its derivatives have been extensively used as blocking ligands as they have potential N,O-donor sites, which give rise to different coordination modes (Domiano et al., 1980; Wu & Liu, 2003). As part of continuing investigations of these types of Schiff base ligands, this work presents the syntheses and structural characterization of two copper(II) complexes, [CuL(C₅H₇O₂)]_n, (I), and [CuL'(C₅H₇O₂)], (II), where HL and HL' are 4-hydroxy-3-methoxybenzaldehyde picoloylhydrazone and 4-methoxybenzaldehyde picoloylhydrazone, respectively. To the best of the author's knowledge, the title complexes represent the first examples of structurally characterized CuL and CuL' complexes.

Structural views of (I) and (II) are shown in Figs. 1 and 2, respectively, and selected bond lengths and angles are given in Tables 1 and 3. In complex (I), the Cu^II ion displays a highly Jahn–Teller distorted CuN₂O₄ octahedron, with the equatorial plane defined by the two N atoms [N1(pyridyl) and N2(hydrazine)] of the L^- ligand and atoms O4 and O5 of the acetylacetonate ligand. The Cu1—N1(pyridyl) and Cu1—N2(hydrazine) distances are similar to the values reported for other copper complexes involving N-donor ligands (Table 4). The Cu1—O4 and Cu1—O5 bond lengths correspond to the distances observed in other Cu acetylacetonate complexes (Heinze & Reinhart, 2006). There is no significant deviation of the metal centre from the N₂O₂ equatorial plane, which shows a small but significant tetrahedral distortion. The maximum displacements from the least-squares plane through atoms N1, N2, O4 and O5 are -0.0798 (15) and 0.0824 (15) Å for atoms N2 and N1, respectively; Cu1 is 0.0339 (16) Å below this plane. The two axial positions are occupied by carbonyl atom O5A of an acetylacetonate ligand [symmetry code: (A) 1 - x, 1 - y, 1 - z] and carboxyl atom O1B of an L^- ligand [symmetry code: (B) - x, 1 - y, 1 - z], with two weak coordination bonds of 2.8466 (30) and 2.8935 (32) Å, respectively (Das & Pal, 2005; Heinze & Reinhart, 2006).

The tridentate hydrazone ligand L^- is a bridging ligand to coordinate to two neighbouring Cu^II ions through its donors carboxyl atom O2, hydrazine atom N2 and phenolic atom O1. In addition, atom O5 of acetylacetonate acts as a bridging atom linking Cu1 and Cu1A [symmetry code: (A) 1 - x, 1 - y, 1 - z]. Therefore, a one-dimensional chain is built up, consisting of CuN₂O₄ octahedra connected by two ligands along the a axis, shown in Fig. 3.

The planes through acetylacetonate (O4/C15–C19/O5) and picoloylhydrazone (C1–C5/N1/C6/O1/N2/N3) make dihedral angles of 17.40 (18) and 8.60 (18)°, respectively, with the equatorial N₂O₄ plane. More buckling of the acetylacetonate than picoloylhydrazone allows for a closer approach of atom O5 towards Cu1A [symmetry code: (A) 1 - x, 1 - y, 1 - z] and simultaneously reduces the steric interaction between the two ligands (Bhadbhade & Srinivas, 1993) (Fig. 3). The O—H function of the vanillin group connects to the carboxyl O atom of the adjacent chain via an O3—H3B···O1A hydrogen bond [symmetry code: (A) x, 1/2 - y, -1/2 + z], giving rise to a three-dimensional supramolecular assembly, as shown in Fig. 4.

In complex (II), atom Cu1 displays a square-planar coordination geometry (Fig. 2). The Cu1—N and Cu1—O bond lengths in the N₂O₄ plane are comparable with those found in (I) (Table 3). However, unlike (I), (II) does not form chains but is rather a simple discrete complex. The closest distance between a Cu^II ion and an O atom from a neighbouring molecule is 3.334 (4) Å for Cu1—O3A [symmetry code: (A) - x, 1 - y, 1 - z], indicating that no intermolecular bonding interactions are present. Just as in (I), there is no significant deviation of the metal centre from the N₂O₄ coordination plane and the distortion of this plane is even smaller. The maximum displacements from the least-squares plane through atoms N1, N2, O3 and O4 are -0.0422 (20) and 0.0432 (20) Å for atoms N2 and N1, respectively; Cu1 is 0.0054 (19) Å below this plane. It is worth noting that the acetylacetonate (C15–C19/O3/O4) and picoloylhydrazone (C1–C5/N1/C6/O1/N2/N3) planes make dihedral angles of 7.97 (18) and 6.43 (15)°, respectively, with the N₂O₄ plane. The approximately planar conformation of the Cu^II ion in complex (II) could be due to the absence of the Cu1—O3A interaction, which reduces the steric interaction between the ligands and a second molecule compared with (I).

S2. Experimental

The ligand HL was prepared by the reaction of picoloylhydrazide and 4-hydroxy-3-methoxybenzaldehyde in a molar ratio of 1:1 under reflux in ethanol for 3 h. The yellow product obtained on cooling was washed with anhydrous ethanol. The ligand HL' was obtained by a similar procedure to that for HL, but using 4-methoxybenzaldehyde in place of 4-hydroxy-3-methoxybenzaldehyde.

Both complexes were prepared using the same method. Complex (I) was synthesized by adding Cu(acac)₂ (16.2 mg, 0.10 mmol) to a solution of HL (27.1 mg, 0.10 mmol) in methanol (15 ml). The resulting mixture was stirred for 3 h at room temperature to afford a green solution. The solution was allowed to stand at room temperature for about two weeks, during which time dark-green crystals of (I) were produced at the bottom of the vessel on slow evaporation of the methanol [yield 56.0% (based on Cu)].

Complex (II) was obtained by using HL' in place of HL. After two weeks, dark-green crystals of complex (II) appeared [yield 49.0% (based on Cu)].

S3. Refinement

In both complexes, H atoms bonded to C atoms were positioned geometrically and refined using a riding model, with Csp²—H = 0.93 Å, C_methyl—H = 0.96 Å, and U_iso(H) = 1.2U_eq(C_sp²) or 1.5U_eq(C_methyl). The H atom bonded to the phenolate O atom in (I) was located in a difference Fourier map and subesquently refined with the help of an O—H distance restraint of 0.82(s.u.?) Å [0.79 (3) given in CIF tables - please clarify], and with U_iso(H) = 1.2U_eq(O).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The one-dimensional chain structure in (I). [Symmetry codes: (A) 1 - x, 1 - y, 1 - z; (B) - x, 1 - y, 1 - z.]
	Fig. 4. The three-dimensional structure of (I). [Symmetry code: (A) x, 1/2 - y, - 1/2 + z.]

(I) catena-Poly[copper(II)-di-µ-acetylacetonato-copper(II)-bis(µ-4- hydroxy-3-methoxybenzaldehyde picoloylhydrazonato)]

Crystal data

[Cu(C14H12N3O3)(C5H7O2)]	F(000) = 892
Mr = 432.91	Dx = 1.502 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2831 reflections
a = 8.4719 (15) Å	θ = 3.0–27.5°
b = 23.586 (3) Å	µ = 1.18 mm^−1
c = 9.8635 (14) Å	T = 293 K
β = 103.683 (6)°	Prism, green
V = 1915.0 (5) Å^3	0.42 × 0.31 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD area detector diffractometer	4358 independent reflections
Radiation source: fine-focus sealed tube	2831 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
ϕ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.652, Tmax = 0.809	k = −30→30
18642 measured reflections	l = −12→12

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0553P)^2 + 1.1925P] where P = (Fo^2 + 2Fc^2)/3
4358 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.47 e Å^−3
1 restraint	Δρmin = −0.63 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	0.27797 (6)	0.488508 (18)	0.44863 (5)	0.03741 (17)
N1	0.2710 (4)	0.54082 (11)	0.6040 (3)	0.0343 (7)
N2	0.1482 (4)	0.43977 (11)	0.5474 (3)	0.0330 (7)
N3	0.0740 (4)	0.38704 (11)	0.5137 (3)	0.0358 (7)
O1	−0.0036 (4)	0.44891 (10)	0.7130 (3)	0.0499 (8)
O2	−0.2864 (4)	0.21111 (11)	0.4284 (3)	0.0546 (8)
O3	−0.1439 (4)	0.14071 (13)	0.2930 (4)	0.0683 (10)
H3B	−0.079 (6)	0.123 (2)	0.266 (6)	0.082*
O4	0.2557 (4)	0.43982 (11)	0.2915 (3)	0.0529 (8)
O5	0.4142 (4)	0.54076 (11)	0.3774 (3)	0.0462 (7)
C1	0.1758 (5)	0.52238 (14)	0.6851 (4)	0.0349 (8)
C2	0.1525 (6)	0.55332 (15)	0.7969 (4)	0.0426 (10)
H2A	0.0840	0.5399	0.8508	0.051*
C3	0.2317 (6)	0.60469 (16)	0.8287 (5)	0.0518 (12)
H3A	0.2191	0.6260	0.9046	0.062*
C4	0.3285 (6)	0.62304 (16)	0.7457 (5)	0.0510 (11)
H4A	0.3831	0.6574	0.7648	0.061*
C5	0.3459 (5)	0.59081 (15)	0.6332 (4)	0.0459 (10)
H5A	0.4112	0.6042	0.5765	0.055*
C6	0.0950 (5)	0.46569 (14)	0.6477 (4)	0.0338 (8)
C7	0.1491 (5)	0.35102 (14)	0.4553 (4)	0.0407 (9)
H7A	0.2496	0.3601	0.4383	0.049*
C8	0.0762 (5)	0.29536 (14)	0.4152 (4)	0.0388 (9)
C9	−0.0694 (5)	0.28020 (14)	0.4464 (4)	0.0375 (9)
H9A	−0.1195	0.3053	0.4957	0.045*
C10	−0.1411 (5)	0.22865 (15)	0.4057 (4)	0.0396 (9)
C11	−0.0640 (6)	0.19020 (15)	0.3322 (4)	0.0442 (10)
C12	0.0820 (6)	0.20446 (16)	0.3037 (4)	0.0471 (10)
H12A	0.1343	0.1789	0.2573	0.056*
C13	0.1518 (5)	0.25694 (15)	0.3441 (4)	0.0456 (10)
H13A	0.2501	0.2665	0.3235	0.055*
C14	−0.3631 (6)	0.24627 (18)	0.5081 (5)	0.0590 (12)
H14A	−0.4624	0.2288	0.5175	0.089*
H14B	−0.3868	0.2823	0.4625	0.089*
H14C	−0.2926	0.2517	0.5989	0.089*
C15	0.2242 (8)	0.4112 (3)	0.0586 (6)	0.0821 (17)
H15A	0.1180	0.3979	0.0617	0.123*
H15B	0.2980	0.3797	0.0702	0.123*
H15C	0.2194	0.4290	−0.0297	0.123*
C16	0.2830 (6)	0.4538 (2)	0.1754 (5)	0.0551 (12)
C17	0.3582 (6)	0.5033 (2)	0.1499 (5)	0.0616 (13)
H17A	0.3678	0.5097	0.0592	0.074*
C18	0.4199 (6)	0.54383 (18)	0.2487 (5)	0.0497 (11)
C19	0.5032 (6)	0.5954 (2)	0.2104 (6)	0.0677 (15)
H19A	0.4464	0.6288	0.2282	0.102*
H19B	0.5034	0.5939	0.1132	0.102*
H19C	0.6130	0.5966	0.2652	0.102*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0440 (3)	0.0347 (3)	0.0372 (3)	−0.0028 (2)	0.0169 (2)	−0.00061 (18)
N1	0.0340 (19)	0.0286 (15)	0.0394 (18)	0.0000 (12)	0.0067 (14)	0.0016 (12)
N2	0.040 (2)	0.0237 (15)	0.0354 (18)	−0.0014 (12)	0.0095 (14)	−0.0008 (11)
N3	0.043 (2)	0.0268 (15)	0.0379 (18)	−0.0025 (12)	0.0101 (15)	0.0012 (11)
O1	0.066 (2)	0.0358 (15)	0.0590 (19)	−0.0089 (13)	0.0376 (17)	−0.0047 (12)
O2	0.054 (2)	0.0400 (16)	0.075 (2)	−0.0074 (13)	0.0261 (17)	−0.0105 (13)
O3	0.055 (2)	0.0420 (18)	0.112 (3)	−0.0058 (14)	0.028 (2)	−0.0298 (17)
O4	0.070 (2)	0.0514 (17)	0.0426 (18)	−0.0026 (14)	0.0239 (16)	−0.0044 (12)
O5	0.0499 (19)	0.0469 (15)	0.0454 (17)	0.0002 (13)	0.0186 (14)	0.0121 (12)
C1	0.034 (2)	0.0320 (19)	0.036 (2)	0.0039 (14)	0.0023 (17)	0.0002 (13)
C2	0.054 (3)	0.038 (2)	0.037 (2)	0.0070 (17)	0.0120 (19)	−0.0014 (15)
C3	0.068 (3)	0.041 (2)	0.043 (3)	0.003 (2)	0.007 (2)	−0.0113 (17)
C4	0.061 (3)	0.030 (2)	0.057 (3)	−0.0049 (18)	0.005 (2)	−0.0061 (17)
C5	0.050 (3)	0.036 (2)	0.051 (3)	−0.0036 (17)	0.011 (2)	0.0002 (16)
C6	0.037 (2)	0.0304 (18)	0.035 (2)	0.0022 (15)	0.0095 (17)	0.0018 (14)
C7	0.043 (3)	0.033 (2)	0.048 (2)	0.0010 (16)	0.013 (2)	−0.0025 (15)
C8	0.048 (3)	0.0299 (19)	0.038 (2)	−0.0011 (15)	0.0082 (19)	−0.0044 (14)
C9	0.048 (3)	0.0263 (18)	0.040 (2)	0.0026 (15)	0.0145 (19)	−0.0050 (14)
C10	0.044 (3)	0.0321 (19)	0.040 (2)	0.0014 (16)	0.0060 (18)	−0.0023 (14)
C11	0.055 (3)	0.0260 (19)	0.049 (2)	0.0024 (17)	0.007 (2)	−0.0097 (16)
C12	0.054 (3)	0.038 (2)	0.051 (3)	0.0052 (18)	0.016 (2)	−0.0131 (17)
C13	0.049 (3)	0.038 (2)	0.053 (3)	−0.0027 (17)	0.016 (2)	−0.0079 (17)
C14	0.061 (3)	0.049 (3)	0.074 (3)	−0.002 (2)	0.031 (3)	−0.001 (2)
C15	0.090 (5)	0.111 (4)	0.049 (3)	0.003 (3)	0.023 (3)	−0.023 (3)
C16	0.050 (3)	0.081 (3)	0.037 (3)	0.015 (2)	0.015 (2)	0.001 (2)
C17	0.062 (3)	0.089 (4)	0.038 (3)	0.011 (3)	0.021 (2)	0.016 (2)
C18	0.042 (3)	0.060 (3)	0.051 (3)	0.014 (2)	0.019 (2)	0.023 (2)
C19	0.052 (3)	0.078 (3)	0.078 (4)	0.006 (2)	0.024 (3)	0.041 (3)

Geometric parameters (Å, º)

Cu1—O4	1.902 (3)	C7—C8	1.465 (5)
Cu1—O5	1.931 (3)	C7—H7A	0.9300
Cu1—N1	1.979 (3)	C8—C9	1.387 (6)
Cu1—N2	1.996 (3)	C8—C13	1.391 (5)
N1—C1	1.336 (5)	C9—C10	1.376 (5)
N1—C5	1.338 (5)	C9—H9A	0.9300
N2—C6	1.329 (4)	C10—C11	1.414 (5)
N2—N3	1.398 (4)	C11—C12	1.374 (6)
N3—C7	1.278 (5)	C12—C13	1.389 (5)
O1—C6	1.234 (4)	C12—H12A	0.9300
O2—C10	1.367 (5)	C13—H13A	0.9300
O2—C14	1.404 (5)	C14—H14A	0.9600
O3—C11	1.359 (5)	C14—H14B	0.9600
O3—H3B	0.79 (3)	C14—H14C	0.9600
O4—C16	1.265 (5)	C15—C16	1.521 (7)
O5—C18	1.284 (5)	C15—H15A	0.9600
C1—C2	1.375 (5)	C15—H15B	0.9600
C1—C6	1.507 (5)	C15—H15C	0.9600
C2—C3	1.385 (6)	C16—C17	1.381 (7)
C2—H2A	0.9300	C17—C18	1.378 (7)
C3—C4	1.358 (6)	C17—H17A	0.9300
C3—H3A	0.9300	C18—C19	1.499 (6)
C4—C5	1.382 (6)	C19—H19A	0.9600
C4—H4A	0.9300	C19—H19B	0.9600
C5—H5A	0.9300	C19—H19C	0.9600
O4—Cu1—O5	92.40 (12)	C10—C9—H9A	119.4
O4—Cu1—N1	172.69 (14)	C8—C9—H9A	119.4
O5—Cu1—N1	90.77 (12)	O2—C10—C9	124.9 (4)
O4—Cu1—N2	95.14 (12)	O2—C10—C11	115.7 (3)
O5—Cu1—N2	172.15 (12)	C9—C10—C11	119.4 (4)
N1—Cu1—N2	81.99 (12)	O3—C11—C12	124.3 (4)
C1—N1—C5	118.7 (3)	O3—C11—C10	116.0 (4)
C1—N1—Cu1	113.2 (2)	C12—C11—C10	119.7 (3)
C5—N1—Cu1	128.1 (3)	C11—C12—C13	120.2 (4)
C6—N2—N3	111.9 (3)	C11—C12—H12A	119.9
C6—N2—Cu1	114.9 (2)	C13—C12—H12A	119.9
N3—N2—Cu1	131.7 (2)	C12—C13—C8	120.6 (4)
C7—N3—N2	117.0 (3)	C12—C13—H13A	119.7
C10—O2—C14	117.9 (3)	C8—C13—H13A	119.7
C11—O3—H3B	102 (4)	O2—C14—H14A	109.5
C16—O4—Cu1	125.2 (3)	O2—C14—H14B	109.5
C18—O5—Cu1	124.1 (3)	H14A—C14—H14B	109.5
N1—C1—C2	121.9 (3)	O2—C14—H14C	109.5
N1—C1—C6	116.5 (3)	H14A—C14—H14C	109.5
C2—C1—C6	121.6 (4)	H14B—C14—H14C	109.5
C1—C2—C3	119.5 (4)	C16—C15—H15A	109.5
C1—C2—H2A	120.3	C16—C15—H15B	109.5
C3—C2—H2A	120.3	H15A—C15—H15B	109.5
C4—C3—C2	118.2 (4)	C16—C15—H15C	109.5
C4—C3—H3A	120.9	H15A—C15—H15C	109.5
C2—C3—H3A	120.9	H15B—C15—H15C	109.5
C3—C4—C5	120.2 (4)	O4—C16—C17	125.2 (4)
C3—C4—H4A	119.9	O4—C16—C15	114.6 (5)
C5—C4—H4A	119.9	C17—C16—C15	120.2 (4)
N1—C5—C4	121.5 (4)	C18—C17—C16	124.9 (4)
N1—C5—H5A	119.3	C18—C17—H17A	117.5
C4—C5—H5A	119.3	C16—C17—H17A	117.5
O1—C6—N2	129.2 (3)	O5—C18—C17	124.3 (4)
O1—C6—C1	118.7 (3)	O5—C18—C19	115.1 (4)
N2—C6—C1	112.1 (3)	C17—C18—C19	120.5 (4)
N3—C7—C8	119.6 (4)	C18—C19—H19A	109.5
N3—C7—H7A	120.2	C18—C19—H19B	109.5
C8—C7—H7A	120.2	H19A—C19—H19B	109.5
C9—C8—C13	118.9 (3)	C18—C19—H19C	109.5
C9—C8—C7	120.8 (3)	H19A—C19—H19C	109.5
C13—C8—C7	120.3 (4)	H19B—C19—H19C	109.5
C10—C9—C8	121.2 (3)
O4—Cu1—N1—C1	61.0 (10)	N3—N2—C6—C1	179.6 (3)
O5—Cu1—N1—C1	176.7 (3)	Cu1—N2—C6—C1	−12.6 (4)
N2—Cu1—N1—C1	−6.3 (2)	N1—C1—C6—O1	−174.6 (3)
O4—Cu1—N1—C5	−117.7 (9)	C2—C1—C6—O1	5.5 (6)
O5—Cu1—N1—C5	−2.0 (3)	N1—C1—C6—N2	7.5 (5)
N2—Cu1—N1—C5	175.0 (3)	C2—C1—C6—N2	−172.4 (3)
O4—Cu1—N2—C6	−162.3 (3)	N2—N3—C7—C8	−178.9 (3)
O5—Cu1—N2—C6	34.0 (10)	N3—C7—C8—C9	−3.4 (6)
N1—Cu1—N2—C6	10.9 (3)	N3—C7—C8—C13	176.2 (4)
O4—Cu1—N2—N3	2.5 (3)	C13—C8—C9—C10	−1.4 (6)
O5—Cu1—N2—N3	−161.2 (7)	C7—C8—C9—C10	178.2 (4)
N1—Cu1—N2—N3	175.7 (3)	C14—O2—C10—C9	−5.0 (6)
C6—N2—N3—C7	−157.7 (3)	C14—O2—C10—C11	176.3 (4)
Cu1—N2—N3—C7	37.2 (5)	C8—C9—C10—O2	−177.9 (4)
O5—Cu1—O4—C16	−18.8 (4)	C8—C9—C10—C11	0.7 (6)
N1—Cu1—O4—C16	96.9 (10)	O2—C10—C11—O3	0.1 (6)
N2—Cu1—O4—C16	163.4 (4)	C9—C10—C11—O3	−178.7 (4)
O4—Cu1—O5—C18	20.4 (3)	O2—C10—C11—C12	179.5 (4)
N1—Cu1—O5—C18	−153.1 (3)	C9—C10—C11—C12	0.7 (6)
N2—Cu1—O5—C18	−175.9 (8)	O3—C11—C12—C13	177.9 (4)
C5—N1—C1—C2	0.2 (5)	C10—C11—C12—C13	−1.5 (7)
Cu1—N1—C1—C2	−178.7 (3)	C11—C12—C13—C8	0.8 (7)
C5—N1—C1—C6	−179.7 (3)	C9—C8—C13—C12	0.7 (6)
Cu1—N1—C1—C6	1.4 (4)	C7—C8—C13—C12	−178.9 (4)
N1—C1—C2—C3	−1.1 (6)	Cu1—O4—C16—C17	11.1 (7)
C6—C1—C2—C3	178.8 (4)	Cu1—O4—C16—C15	−168.3 (4)
C1—C2—C3—C4	1.0 (6)	O4—C16—C17—C18	2.5 (8)
C2—C3—C4—C5	0.0 (7)	C15—C16—C17—C18	−178.1 (5)
C1—N1—C5—C4	0.9 (6)	Cu1—O5—C18—C17	−14.5 (6)
Cu1—N1—C5—C4	179.5 (3)	Cu1—O5—C18—C19	166.6 (3)
C3—C4—C5—N1	−1.0 (7)	C16—C17—C18—O5	−0.4 (8)
N3—N2—C6—O1	1.9 (6)	C16—C17—C18—C19	178.4 (4)
Cu1—N2—C6—O1	169.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1^i	0.79 (3)	1.93 (4)	2.636 (4)	149 (6)

Symmetry code: (i) x, −y+1/2, z−1/2.

(II) (acetylacetonato)(4-methoxybenzaldehyde picoloylhydrazone)copper(II)

Crystal data

[Cu(C14H12N3O2)(C5H7O2)]	F(000) = 860
Mr = 416.91	Dx = 1.570 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1904 reflections
a = 7.4198 (15) Å	θ = 3.0–27.5°
b = 14.969 (3) Å	µ = 1.27 mm^−1
c = 15.885 (3) Å	T = 293 K
β = 91.78 (3)°	Prism, green
V = 1763.4 (6) Å^3	0.39 × 0.26 × 0.17 mm
Z = 4

Data collection

Bruker APEXII CCD area detector diffractometer	4005 independent reflections
Radiation source: fine-focus sealed tube	1904 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.125
ϕ and ω scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
Tmin = 0.680, Tmax = 0.806	k = −19→19
16505 measured reflections	l = −20→20

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0677P)^2] where P = (Fo^2 + 2Fc^2)/3
4005 reflections	(Δ/σ)max < 0.001
247 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.51 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	0.24285 (8)	0.56946 (3)	0.50749 (3)	0.0421 (2)
N1	0.3473 (5)	0.4815 (2)	0.5885 (2)	0.0393 (9)
N2	0.3357 (6)	0.6542 (2)	0.5925 (2)	0.0410 (10)
N3	0.3051 (6)	0.7470 (2)	0.5978 (2)	0.0440 (10)
O1	0.4486 (6)	0.6567 (2)	0.7300 (2)	0.0646 (11)
O2	0.1997 (6)	1.1571 (2)	0.5092 (3)	0.0654 (11)
O3	0.1728 (5)	0.4759 (2)	0.4311 (2)	0.0531 (10)
O4	0.1361 (5)	0.6575 (2)	0.4366 (2)	0.0528 (9)
C1	0.4082 (6)	0.5176 (3)	0.6605 (3)	0.0385 (11)
C2	0.4723 (7)	0.4689 (3)	0.7257 (3)	0.0480 (13)
H2A	0.5130	0.4967	0.7751	0.058*
C3	0.4772 (7)	0.3757 (3)	0.7184 (3)	0.0509 (13)
H3B	0.5216	0.3402	0.7623	0.061*
C4	0.4146 (7)	0.3387 (3)	0.6444 (4)	0.0495 (14)
H4A	0.4157	0.2770	0.6377	0.059*
C5	0.3500 (7)	0.3920 (3)	0.5800 (3)	0.0480 (13)
H5A	0.3076	0.3661	0.5300	0.058*
C6	0.3994 (7)	0.6193 (3)	0.6645 (3)	0.0425 (12)
C7	0.3257 (7)	0.7900 (3)	0.5298 (3)	0.0432 (11)
H7A	0.3651	0.7595	0.4828	0.052*
C8	0.2895 (6)	0.8855 (3)	0.5230 (3)	0.0394 (11)
C9	0.3057 (7)	0.9292 (3)	0.4477 (3)	0.0445 (11)
H9A	0.3385	0.8967	0.4007	0.053*
C10	0.2750 (7)	1.0194 (3)	0.4395 (3)	0.0477 (13)
H10A	0.2856	1.0474	0.3876	0.057*
C11	0.2287 (7)	1.0674 (3)	0.5090 (3)	0.0459 (11)
C12	0.2118 (7)	1.0254 (3)	0.5850 (3)	0.0490 (13)
H12A	0.1821	1.0585	0.6322	0.059*
C13	0.2384 (7)	0.9348 (3)	0.5923 (3)	0.0446 (11)
H13A	0.2220	0.9066	0.6436	0.054*
C14	0.1839 (9)	1.2024 (3)	0.4313 (4)	0.0703 (18)
H14A	0.1495	1.2633	0.4409	0.105*
H14B	0.0937	1.1738	0.3961	0.105*
H14C	0.2975	1.2010	0.4041	0.105*
C15	0.0746 (8)	0.4017 (3)	0.3083 (3)	0.0520 (14)
H15A	0.0066	0.3601	0.3405	0.078*
H15B	0.1892	0.3760	0.2958	0.078*
H15C	0.0095	0.4152	0.2567	0.078*
C16	0.1035 (7)	0.4856 (3)	0.3579 (3)	0.0415 (12)
C17	0.0572 (7)	0.5661 (3)	0.3220 (3)	0.0456 (12)
H17A	0.0081	0.5655	0.2675	0.055*
C18	0.0786 (7)	0.6484 (3)	0.3615 (3)	0.0417 (12)
C19	0.0328 (9)	0.7324 (3)	0.3156 (4)	0.0637 (16)
H19A	−0.0146	0.7752	0.3541	0.096*
H19B	−0.0558	0.7201	0.2718	0.096*
H19C	0.1394	0.7562	0.2911	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0585 (4)	0.0362 (3)	0.0311 (3)	0.0018 (3)	−0.0044 (3)	−0.0006 (3)
N1	0.049 (3)	0.039 (2)	0.030 (2)	0.0017 (17)	0.0011 (19)	0.0027 (16)
N2	0.056 (3)	0.033 (2)	0.033 (2)	0.0054 (17)	−0.003 (2)	0.0009 (15)
N3	0.056 (3)	0.035 (2)	0.041 (3)	−0.0029 (18)	−0.003 (2)	−0.0040 (17)
O1	0.100 (3)	0.048 (2)	0.044 (2)	0.0039 (19)	−0.025 (2)	−0.0072 (16)
O2	0.092 (3)	0.038 (2)	0.066 (3)	0.0090 (18)	−0.004 (2)	0.0013 (17)
O3	0.085 (3)	0.0400 (18)	0.034 (2)	0.0044 (17)	−0.0089 (18)	0.0003 (14)
O4	0.070 (3)	0.0401 (18)	0.047 (2)	0.0009 (16)	−0.0129 (19)	−0.0018 (15)
C1	0.040 (3)	0.042 (3)	0.033 (3)	0.001 (2)	0.000 (2)	0.0013 (19)
C2	0.055 (4)	0.047 (3)	0.040 (3)	0.007 (2)	−0.007 (3)	0.004 (2)
C3	0.056 (4)	0.055 (3)	0.042 (3)	0.013 (3)	0.003 (3)	0.012 (2)
C4	0.057 (4)	0.037 (3)	0.055 (4)	0.010 (2)	0.011 (3)	0.007 (2)
C5	0.065 (4)	0.036 (3)	0.044 (3)	0.003 (2)	0.003 (3)	−0.004 (2)
C6	0.045 (3)	0.045 (3)	0.037 (3)	0.002 (2)	0.002 (2)	−0.004 (2)
C7	0.050 (3)	0.039 (3)	0.041 (3)	−0.003 (2)	0.004 (2)	−0.004 (2)
C8	0.041 (3)	0.039 (3)	0.038 (3)	−0.004 (2)	−0.003 (2)	−0.0003 (19)
C9	0.057 (3)	0.041 (3)	0.035 (3)	−0.003 (2)	0.005 (2)	−0.002 (2)
C10	0.060 (4)	0.046 (3)	0.037 (3)	−0.005 (2)	−0.004 (2)	0.004 (2)
C11	0.051 (3)	0.041 (3)	0.046 (3)	0.003 (2)	−0.006 (2)	0.001 (2)
C12	0.063 (4)	0.045 (3)	0.039 (3)	0.006 (2)	0.001 (3)	−0.008 (2)
C13	0.058 (3)	0.045 (3)	0.030 (2)	−0.002 (2)	0.001 (2)	−0.003 (2)
C14	0.091 (5)	0.041 (3)	0.077 (4)	0.003 (3)	−0.023 (4)	0.017 (3)
C15	0.068 (4)	0.049 (3)	0.039 (3)	−0.002 (2)	0.000 (3)	−0.005 (2)
C16	0.045 (3)	0.049 (3)	0.031 (3)	−0.007 (2)	0.006 (2)	0.000 (2)
C17	0.048 (3)	0.058 (3)	0.031 (3)	−0.006 (2)	−0.005 (2)	0.003 (2)
C18	0.041 (3)	0.044 (3)	0.040 (3)	−0.001 (2)	−0.009 (2)	0.005 (2)
C19	0.080 (5)	0.052 (3)	0.058 (4)	0.001 (3)	−0.015 (3)	0.012 (3)

Geometric parameters (Å, º)

Cu1—O4	1.892 (3)	C8—C9	1.371 (6)
Cu1—O3	1.914 (3)	C8—C13	1.388 (6)
Cu1—N2	1.962 (4)	C9—C10	1.376 (6)
Cu1—N1	1.982 (4)	C9—H9A	0.9300
N1—C1	1.331 (6)	C10—C11	1.370 (7)
N1—C5	1.347 (5)	C10—H10A	0.9300
N2—C6	1.331 (6)	C11—C12	1.371 (7)
N2—N3	1.412 (5)	C12—C13	1.374 (6)
N3—C7	1.271 (6)	C12—H12A	0.9300
O1—C6	1.227 (6)	C13—H13A	0.9300
O2—C11	1.359 (5)	C14—H14A	0.9600
O2—C14	1.414 (6)	C14—H14B	0.9600
O3—C16	1.265 (6)	C14—H14C	0.9600
O4—C18	1.261 (6)	C15—C16	1.495 (6)
C1—C2	1.342 (6)	C15—H15A	0.9600
C1—C6	1.524 (6)	C15—H15B	0.9600
C2—C3	1.401 (7)	C15—H15C	0.9600
C2—H2A	0.9300	C16—C17	1.371 (6)
C3—C4	1.367 (7)	C17—C18	1.389 (6)
C3—H3B	0.9300	C17—H17A	0.9300
C4—C5	1.372 (7)	C18—C19	1.488 (6)
C4—H4A	0.9300	C19—H19A	0.9600
C5—H5A	0.9300	C19—H19B	0.9600
C7—C8	1.458 (6)	C19—H19C	0.9600
C7—H7A	0.9300
O4—Cu1—O3	91.81 (14)	C8—C9—H9A	118.9
O4—Cu1—N2	95.25 (15)	C10—C9—H9A	118.9
O3—Cu1—N2	172.67 (16)	C11—C10—C9	118.9 (5)
O4—Cu1—N1	176.03 (16)	C11—C10—H10A	120.5
O3—Cu1—N1	91.08 (15)	C9—C10—H10A	120.5
N2—Cu1—N1	81.97 (15)	O2—C11—C10	124.3 (5)
C1—N1—C5	119.0 (4)	O2—C11—C12	115.6 (4)
C1—N1—Cu1	113.8 (3)	C10—C11—C12	120.0 (4)
C5—N1—Cu1	127.0 (4)	C11—C12—C13	120.7 (5)
C6—N2—N3	112.9 (4)	C11—C12—H12A	119.7
C6—N2—Cu1	116.5 (3)	C13—C12—H12A	119.7
N3—N2—Cu1	128.6 (3)	C12—C13—C8	120.0 (5)
C7—N3—N2	115.0 (4)	C12—C13—H13A	120.0
C11—O2—C14	118.8 (4)	C8—C13—H13A	120.0
C16—O3—Cu1	126.4 (3)	O2—C14—H14A	109.5
C18—O4—Cu1	127.7 (3)	O2—C14—H14B	109.5
N1—C1—C2	123.1 (4)	H14A—C14—H14B	109.5
N1—C1—C6	115.3 (4)	O2—C14—H14C	109.5
C2—C1—C6	121.6 (5)	H14A—C14—H14C	109.5
C1—C2—C3	119.1 (5)	H14B—C14—H14C	109.5
C1—C2—H2A	120.5	C16—C15—H15A	109.5
C3—C2—H2A	120.5	C16—C15—H15B	109.5
C4—C3—C2	117.8 (5)	H15A—C15—H15B	109.5
C4—C3—H3B	121.1	C16—C15—H15C	109.5
C2—C3—H3B	121.1	H15A—C15—H15C	109.5
C3—C4—C5	120.4 (5)	H15B—C15—H15C	109.5
C3—C4—H4A	119.8	O3—C16—C17	124.9 (4)
C5—C4—H4A	119.8	O3—C16—C15	115.8 (4)
N1—C5—C4	120.6 (5)	C17—C16—C15	119.3 (5)
N1—C5—H5A	119.7	C16—C17—C18	124.6 (4)
C4—C5—H5A	119.7	C16—C17—H17A	117.7
O1—C6—N2	129.6 (4)	C18—C17—H17A	117.7
O1—C6—C1	118.7 (5)	O4—C18—C17	123.6 (4)
N2—C6—C1	111.7 (4)	O4—C18—C19	116.0 (4)
N3—C7—C8	122.1 (4)	C17—C18—C19	120.5 (5)
N3—C7—H7A	118.9	C18—C19—H19A	109.5
C8—C7—H7A	118.9	C18—C19—H19B	109.5
C9—C8—C13	118.1 (4)	H19A—C19—H19B	109.5
C9—C8—C7	120.7 (4)	C18—C19—H19C	109.5
C13—C8—C7	121.2 (4)	H19A—C19—H19C	109.5
C8—C9—C10	122.2 (4)	H19B—C19—H19C	109.5
O4—Cu1—N1—C1	−39 (2)	N3—N2—C6—O1	−7.2 (8)
O3—Cu1—N1—C1	−175.8 (3)	Cu1—N2—C6—O1	−172.4 (5)
N2—Cu1—N1—C1	6.6 (3)	N3—N2—C6—C1	172.6 (4)
O4—Cu1—N1—C5	136 (2)	Cu1—N2—C6—C1	7.5 (5)
O3—Cu1—N1—C5	−0.8 (4)	N1—C1—C6—O1	178.0 (5)
N2—Cu1—N1—C5	−178.5 (4)	C2—C1—C6—O1	−1.7 (8)
O4—Cu1—N2—C6	169.2 (4)	N1—C1—C6—N2	−1.9 (6)
O3—Cu1—N2—C6	−26.5 (15)	C2—C1—C6—N2	178.4 (4)
N1—Cu1—N2—C6	−8.0 (3)	N2—N3—C7—C8	176.5 (4)
O4—Cu1—N2—N3	6.8 (4)	N3—C7—C8—C9	−177.2 (5)
O3—Cu1—N2—N3	171.1 (11)	N3—C7—C8—C13	2.9 (8)
N1—Cu1—N2—N3	−170.4 (4)	C13—C8—C9—C10	0.8 (8)
C6—N2—N3—C7	149.1 (5)	C7—C8—C9—C10	−179.1 (5)
Cu1—N2—N3—C7	−48.0 (6)	C8—C9—C10—C11	0.7 (8)
O4—Cu1—O3—C16	7.9 (4)	C14—O2—C11—C10	11.9 (8)
N2—Cu1—O3—C16	−156.5 (11)	C14—O2—C11—C12	−169.2 (5)
N1—Cu1—O3—C16	−174.8 (4)	C9—C10—C11—O2	178.2 (5)
O3—Cu1—O4—C18	−11.7 (4)	C9—C10—C11—C12	−0.6 (8)
N2—Cu1—O4—C18	166.3 (4)	O2—C11—C12—C13	−179.9 (5)
N1—Cu1—O4—C18	−148 (2)	C10—C11—C12—C13	−1.0 (8)
C5—N1—C1—C2	−0.1 (7)	C11—C12—C13—C8	2.5 (8)
Cu1—N1—C1—C2	175.2 (4)	C9—C8—C13—C12	−2.4 (7)
C5—N1—C1—C6	−179.8 (4)	C7—C8—C13—C12	177.5 (5)
Cu1—N1—C1—C6	−4.4 (5)	Cu1—O3—C16—C17	−3.7 (7)
N1—C1—C2—C3	0.4 (8)	Cu1—O3—C16—C15	175.3 (3)
C6—C1—C2—C3	−180.0 (5)	O3—C16—C17—C18	−0.6 (8)
C1—C2—C3—C4	−0.4 (8)	C15—C16—C17—C18	−179.6 (5)
C2—C3—C4—C5	0.2 (8)	Cu1—O4—C18—C17	11.2 (7)
C1—N1—C5—C4	−0.1 (7)	Cu1—O4—C18—C19	−168.9 (4)
Cu1—N1—C5—C4	−174.8 (4)	C16—C17—C18—O4	−3.2 (8)
C3—C4—C5—N1	0.1 (8)	C16—C17—C18—C19	176.8 (5)