Di-μ-cyanato-bis[(cyanato-κN)(tetramethylethylenediamine-κ²N,N′)copper(II)] and catena-poly[[μ₃-cyanato-κ³O:N:N-bis[(cyanato-κN)(1,3-diaminopropane-κ²N,N′)copper(II)]]-μ₃-cyanato-κ³N:N:O]

The two title Cu^II complexes, [Cu₂(NCO)₄(tmeda)₂] (tmeda is tetra­methyl­ethyl­enedi­amine, C₆H₁₆N₂), (I), and [Cu(NCO)₂(pn)]_n (pn is 1,3-di­amino­propane, C₃H₁₀N₂), (II), have been synthesized and their crystal structures determined. In (I), which lies about an inversion centre, each Cu centre possesses a distorted tetragonal–pyramidal geometry with four basal N atoms from two cyanate anions [Cu—N = 1.945 (2) and 1.948 (3) Å] and one tmeda mol­ecule [Cu—N = 2.053 (2) and 2.071 (2) Å], and one axial O atom [Cu—O = 2.737 (3) Å] from another cyanate anion. The two neighbouring Cu atoms in (I) are joined by a pair of cyanates in an end-to-end fashion, forming a dimer. In (II), each Cu centre adopts a distorted square-bipyramidal geometry, with four equatorial N atoms from two cyanates [Cu—N = 1.988 (2) and 2.007 (3) Å] and a pn ligand [Cu—N = 1.996 (3) and 2.011 (3) Å], and one apical N atom [Cu—N = 2.437 (3) Å] and an apical O atom [Cu—O = 2.900 (3) Å] from two cyanates. In contrast with (I), the two neighbouring Cu atoms in (II) are bridged by two cyanates in an end-on fashion, to form a centrosymmetric dimeric unit. These units are further crosslinked, forming a two-dimensional network structure, via weak interactions between the bridging cyanate O atom and a neighbouring Cu atom, plus interactions of the amine H atoms with the cyanate O atoms and the terminal cyanate N atom.

S1. Comment

The synthesis of cyanate complexes continues to be the subject of much interest, and intensive investigations have resulted from their diverse structures and potential applications in magnetic materials (Diaz et al., 2001; Grove et al., 2001; Hernández et al., 2001). It is noteworthy that, in most dinuclear Cu-cyanate complexes for which structural and magnetic data are available, two Cu atoms are linked together by different bridging ligands (Boillot et al., 1985; Mallah et al., 1986; Kahn et al., 1989), while known homocyanate-bridged Cu₂ complexes with aliphatic amine co-ligands, such as substituted ethylenediamine (Mauro et al., 1990; Zukerman-Schpector et al., 1991), substituted diethylenetriamine (Escuer et al., 1999) and azacryptate (Harding et al., 1996), are scarce. To date, no two-dimensional structure linked by homocyanate-bridged Cu₂ moieties with aliphatic amine co-ligands has been reported. To gain a deeper insight into the structures and properties of homocyanate-bridged Cu₂ complexes, we report herein the syntheses and crystal structures of two new copper cyanate complexes with tetramethylethylenediamine (tmeda) and 1,3-diaminopropane (pn) as co-ligands, [Cu(tmeda)(N₂C₂O₂)]₂, (I), and [Cu₂(pn)₂(N₂C₂O₂)₂]_n, (II). \sch

Complex (I) (Fig. 1) is a centrosymmetric dinuclear structure with two end-to-end cyanate bridges, in which each Cu^II ion is pentacoordinated to three cyanate anions and one tmeda ligand to give a distorted tetragonal-pyramidal geometry. For atom Cu1, the basal plane is formed by one terminal cyanate atom (N1), one bridged cyanate atom (N2) and two atoms (N3 and N4) of the tmeda ligand, the apical site being occupied by one atom (O2ⁱ) of another bridged cyanate [symmetry code: (i) 2 − x, 2 − y, 2 − z Correct?]. In each dimer, the Cu···Cu distance is 5.4330 (12) Å [the closest Cu···Cu separation is 4.9814 (14) Å].

In (II), the atom Cu1 is bonded to one terminal cyanate atom (N3), one bridged cyanate atom (N4ⁱ) and two atoms (N1 and N2) of one pn ligand in the basal plane, along with one bridged cyanate N atom (N4) and another bridged cyanate O atom (O2ⁱⁱ) in the apical sites, to form a distorted tetragonal-bipyramidal geometry [symmetry codes: (i) 2 − x, 2 − y, −z; (ii) x, y − 1, z Correct?]. Two Cu atoms are linked by two cyanates in a end-on bonding mode to define a dimer (Fig. 2). These dimeric units are linked together to form a one-dimensional chain (Fig. 3) via weak interactions [Cu···O 2.900 (3) Å]. These chains are then crosslinked via hydrogen bonds (Table 3) involving the terminal cyanate N atom [N···N 3.188 (4) Å], the bridging cyanate O atom [N···O 3.034 (4) Å] and the terminal cyanate O atoms [N···O 3.120 (4) and 3.162 (4) Å], thus forming a two-dimensional network (Fig. 4). To our knowledge, such two-dimensional networks are rare in Cu-cyanate complexes. In (II), the cyanates exhibit two types of coordination mode, one of which is end-on within the dimer, while the second cyanate is end-to-end between dimers. The Cu···Cu distance within the dimers in (II) is 3.2137 (9) Å, and 5.375 (2) Å between neighbouring units.

Interestingly, by replacing tmeda with pn as the co-ligand, the title Cu complexes change from a simple dimer to a two-dimensional structure, and the bonding model of the bridging cyanate also changes. This may be attributed to the steric difference between the two aliphatic amine ligands. As tmeda is more sterically crowded than pn, in (I) the bridging cyanates adopt an end-to-end bonding fashion to reduce the steric repulsion between two tmeda ligands. In contrast with (I), the metal ion would be sterically unsaturated if (II) had a similar structure to (I). As a result, the smaller pn ligand allows the bonding model of the bridged cyanate to change from end-to-end to end-on and forces the Cu atom to coordinate further to the neighbouring O atom, thus forming a one-dimensional infinite chain with a higher coordination number.

In (I), the Cu—N(tmeda) bond lengths [2.053 (2)–2.071 (2) Å] are longer than the Cu—N(cyanate) distances [1.945 (2)–1.948 (3) Å; Table 1]. The data are similar to the corresponding distances in [{CuL(NCO)}_n][ClO₄]_n (L is N,N,N',N'',N''-pentamethyl-3-azapentane-1,5-diamine; Vicente et al., 1994). In contrast with (I), the Cu—N bond lengths in the basal plane of (II) [1.988 (2)–2.011 (3) Å; Table 2] show no distinct differences and are comparable with the corresponding distances in [Cu₂(N₂C₂O₂)(medien)₂][ClO₄]₂ (medien is 4-methyldiethylenetriamine; Escuer et al., 1999). The apical Cu—N(cyanate) [2.437 (3) Å] or Cu—O(cyanate) distances [2.900 (3) Å] in (II) are longer than the Cu—N distances in the basal plane. A similar situation is also seen in (I). The N—Cu—N angles (two neighbouring N atoms) are in the range 85.35 (8)–94.16 (12)° for (I) and 84.56 (11)–97.19 (11)° for (II). Both ranges deviate from the ideal value of 90°, but the N(basal)-Cu—O(apical) angles in (I) [87.20 (8)–98.81 (10)°] deviate less than those in (II) [74.01 (10)–100.84 (9)°], indicating that the geometry of (II) is more distorted than that of (I).

In (I) and (II), the geometric parameters for the tmeda [1.480 (4)–1.505 (4) Å and 107.9 (2)–111.6 (2)°] and pn [1.460 (5)–1.466 (4) Å and 113.9 (3)–119.2 (3)°] ligands are normal for aliphatic amine-containing complexes (Kovbasyuk et al., 1997; Zukerman-Schpector et al., 1991). The cyanates are almost linear, with N—C and C—O bond lengths in the ranges 1.146 (3)–1.169 (4) Å and 1.188 (3)–1.211 (3) Å, respectively. The N—C—O angles [177.8 (3)–178.8 (3)°] are similar to those in other cyanate complexes (Rojo et al., 1989; Real et al., 1993; Otieno et al., 1993).

Table 3. Hydrogen-bonding and contact geometry of II (Å, °).

S2. Experimental

To a solution of copper acetate (0.60 mmol, 119.79 mg) in ethanol (4 ml) was added tmeda (0.60 mmol, 69.73 mg) in ethanol (4 ml). After stirring for 5 min, an aqueous solution of sodium cyanate (2 ml; 0.60 mmol, 39.01 mg) was added and the mixture stirred for a further 5 min. The solution was filtered and the filtrate slowly evaporated in air. After one week, blue block crystals of (I) were isolated in 67% yield. Analysis calculated for C₁₆H₃₂N₈O₄Cu₂: C 36.43, H 6.11, N 21.24%; found: C 36.02, H 5.82, N 21.38%. Crystals of (II) were prepared in a similar manner, using the pn ligand as a starting material, resulting in an 11% yield. Analysis calculated for C₁₀H₂₀N₈O₄Cu₂: C 27.09, H 4.55, N 25.27%; found: C 26.32, H 4.61, N 24.73%.

S3. Refinement

In (I), all the H atoms were constrained to an ideal geometry, with C3—H and C4—H distances of 0.97 Å and all other C—H distances of 0.96 Å. In (II), the amine H atoms were found from a difference Fourier map and refined freely, with all other H atoms placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97 Å.

Computing details

For both compounds, data collection: SMART APEX (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity [symmetry code: (i) 2 − x, 2 − y, 2 − z].
	Fig. 2. A view of the Cu^II coordination environment of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity [symmetry codes: (i) 2 − x, 2 − y, −z; (ii) x, y − 1, z; (iii) 1 − x, 2 − y, −z].
	Fig. 3. The one-dimensional chain structure of (II) linked via the weak interactions, with a view of the unit cell.
	Fig. 4. The two-dimensional network of (II) crosslinked via the hydrogen-bond interactions, viewed along the c axis [symmetry codes: (i) 2 − x, 1 − y, −z; (ii) 1 − x, 2 − y, −z; (iii) 1 − x, 1 − y, −z; (iv) x, y − 1, z; (v) 2 − x, 2 − y, −z]. Please clarify - the figure does not show any symmetry codes. Do you wish to add them?

(I) Di-µ-cyanato-bis[(cyanato-κN)(tetramethylethylenediamine- κ²N,N')copper(II)]

Crystal data

[Cu2(NCO)4(C6H16N2)2]	Z = 1
Mr = 527.58	F(000) = 274
Triclinic, P1	Dx = 1.496 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.656 (2) Å	Cell parameters from 2262 reflections
b = 8.613 (2) Å	θ = 2.4–27.0°
c = 9.671 (2) Å	µ = 1.85 mm^−1
α = 78.893 (3)°	T = 293 K
β = 71.433 (3)°	Block, blue
γ = 77.984 (3)°	0.50 × 0.45 × 0.45 mm
V = 585.8 (2) Å^3

Data collection

Make Model CCD area-detector diffractometer	2033 independent reflections
Radiation source: fine-focus sealed tube	1883 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.406, Tmax = 0.434	k = −10→9
2462 measured reflections	l = −11→9

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0519P)^2 + 0.0912P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2033 reflections	Δρmax = 0.53 e Å^−3
141 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.066 (5)

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	1.00792 (4)	0.88494 (3)	0.75517 (3)	0.03709 (16)
N1	1.2201 (4)	0.9915 (3)	0.6402 (3)	0.0609 (7)
N2	0.8773 (4)	1.0650 (3)	0.8619 (3)	0.0586 (6)
N4	0.7675 (3)	0.7819 (3)	0.8246 (2)	0.0432 (5)
N3	1.1333 (3)	0.6811 (2)	0.6598 (2)	0.0385 (5)
O1	1.3371 (4)	1.2275 (3)	0.6181 (4)	0.0974 (10)
O2	0.8645 (4)	1.2593 (3)	1.0096 (3)	0.0770 (7)
C1	1.2758 (4)	1.1078 (3)	0.6317 (3)	0.0451 (6)
C2	0.8728 (4)	1.1601 (3)	0.9334 (3)	0.0480 (7)
C3	1.0076 (4)	0.5602 (3)	0.7336 (4)	0.0548 (7)
H3A	1.0229	0.5175	0.8302	0.066*
H3B	1.0395	0.4723	0.6761	0.066*
C4	0.8083 (4)	0.6374 (3)	0.7487 (4)	0.0573 (8)
H4A	0.7889	0.6682	0.6522	0.069*
H4B	0.7249	0.5621	0.8054	0.069*
C5	1.1575 (5)	0.7140 (4)	0.4994 (3)	0.0582 (7)
H5A	1.2083	0.6165	0.4569	0.087*
H5B	1.2411	0.7907	0.4550	0.087*
H5C	1.0387	0.7564	0.4823	0.087*
C6	1.3197 (4)	0.6162 (3)	0.6818 (3)	0.0474 (6)
H6A	1.3657	0.5153	0.6445	0.071*
H6B	1.3093	0.6012	0.7849	0.071*
H6C	1.4046	0.6902	0.6301	0.071*
C7	0.6116 (4)	0.8944 (4)	0.7820 (4)	0.0563 (7)
H7A	0.6441	0.9194	0.6767	0.085*
H7B	0.5891	0.9910	0.8248	0.085*
H7C	0.5010	0.8454	0.8169	0.085*
C8	0.7118 (5)	0.7393 (5)	0.9868 (3)	0.0708 (9)
H8A	0.5936	0.7020	1.0189	0.106*
H8B	0.7015	0.8319	1.0321	0.106*
H8C	0.8043	0.6562	1.0146	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0381 (2)	0.0310 (2)	0.0435 (2)	−0.00335 (13)	−0.01160 (14)	−0.01097 (13)
N1	0.0551 (15)	0.0414 (13)	0.0825 (19)	−0.0158 (11)	−0.0078 (13)	−0.0116 (12)
N2	0.0652 (16)	0.0491 (14)	0.0660 (16)	0.0049 (12)	−0.0231 (13)	−0.0270 (13)
N4	0.0353 (11)	0.0436 (12)	0.0473 (12)	−0.0039 (9)	−0.0086 (10)	−0.0064 (10)
N3	0.0379 (11)	0.0349 (11)	0.0435 (11)	−0.0064 (9)	−0.0093 (9)	−0.0111 (9)
O1	0.0867 (18)	0.0533 (14)	0.142 (3)	−0.0355 (13)	0.0077 (17)	−0.0326 (15)
O2	0.0954 (18)	0.0581 (13)	0.0776 (15)	−0.0191 (12)	−0.0055 (13)	−0.0353 (12)
C1	0.0375 (13)	0.0378 (15)	0.0535 (16)	−0.0021 (11)	−0.0057 (12)	−0.0083 (11)
C2	0.0498 (15)	0.0407 (15)	0.0468 (15)	−0.0059 (12)	−0.0026 (12)	−0.0112 (13)
C3	0.0456 (15)	0.0347 (13)	0.082 (2)	−0.0090 (11)	−0.0110 (15)	−0.0131 (13)
C4	0.0446 (16)	0.0462 (16)	0.082 (2)	−0.0127 (13)	−0.0127 (15)	−0.0150 (15)
C5	0.0691 (19)	0.0621 (18)	0.0470 (16)	−0.0057 (15)	−0.0184 (14)	−0.0181 (14)
C6	0.0399 (14)	0.0441 (14)	0.0579 (16)	0.0008 (11)	−0.0132 (12)	−0.0163 (12)
C7	0.0412 (14)	0.0634 (18)	0.0638 (18)	0.0010 (13)	−0.0180 (13)	−0.0125 (15)
C8	0.0578 (19)	0.090 (2)	0.0513 (18)	−0.0139 (17)	−0.0070 (15)	0.0094 (17)

Geometric parameters (Å, º)

Cu1—N2	1.945 (2)	C3—H3A	0.9700
Cu1—N1	1.948 (3)	C3—H3B	0.9700
Cu1—N3	2.053 (2)	C4—H4A	0.9700
Cu1—N4	2.071 (2)	C4—H4B	0.9700
Cu1—O2^i	2.737 (3)	C5—H5A	0.9600
Cu1—Cu1^i	5.4330 (12)	C5—H5B	0.9600
N1—C1	1.146 (3)	C5—H5C	0.9600
N2—C2	1.159 (4)	C6—H6A	0.9600
N4—C8	1.481 (4)	C6—H6B	0.9600
N4—C7	1.487 (3)	C6—H6C	0.9600
N4—C4	1.493 (4)	C7—H7A	0.9600
N3—C5	1.480 (4)	C7—H7B	0.9600
N3—C6	1.487 (3)	C7—H7C	0.9600
N3—C3	1.487 (3)	C8—H8A	0.9600
O1—C1	1.188 (3)	C8—H8B	0.9600
O2—C2	1.211 (3)	C8—H8C	0.9600
C3—C4	1.505 (4)
N2—Cu1—N1	94.16 (12)	N3—C3—H3B	109.8
N2—Cu1—N3	174.55 (10)	C4—C3—H3B	109.8
N1—Cu1—N3	90.61 (10)	H3A—C3—H3B	108.2
N2—Cu1—N4	90.68 (10)	N4—C4—C3	109.0 (2)
N1—Cu1—N4	164.90 (11)	N4—C4—H4A	109.9
N3—Cu1—N4	85.35 (8)	C3—C4—H4A	109.9
N2—Cu1—O2^i	89.48 (9)	N4—C4—H4B	109.9
N1—Cu1—O2^i	98.81 (10)	C3—C4—H4B	109.9
N3—Cu1—O2^i	87.20 (8)	H4A—C4—H4B	108.3
N4—Cu1—O2^i	95.52 (8)	N3—C5—H5A	109.5
N2—Cu1—Cu1^i	41.69 (8)	N3—C5—H5B	109.5
N1—Cu1—Cu1^i	90.47 (9)	H5A—C5—H5B	109.5
N3—Cu1—Cu1^i	135.79 (6)	N3—C5—H5C	109.5
N4—Cu1—Cu1^i	102.56 (6)	H5A—C5—H5C	109.5
O2^i—Cu1—Cu1^i	49.05 (5)	H5B—C5—H5C	109.5
C1—N1—Cu1	139.6 (2)	N3—C6—H6A	109.5
C2—N2—Cu1	151.3 (3)	N3—C6—H6B	109.5
C8—N4—C7	108.7 (2)	H6A—C6—H6B	109.5
C8—N4—C4	111.5 (2)	N3—C6—H6C	109.5
C7—N4—C4	108.5 (2)	H6A—C6—H6C	109.5
C8—N4—Cu1	110.1 (2)	H6B—C6—H6C	109.5
C7—N4—Cu1	110.7 (2)	N4—C7—H7A	109.5
C4—N4—Cu1	107.3 (2)	N4—C7—H7B	109.5
C5—N3—C6	107.9 (2)	H7A—C7—H7B	109.5
C5—N3—C3	111.6 (2)	N4—C7—H7C	109.5
C6—N3—C3	108.4 (2)	H7A—C7—H7C	109.5
C5—N3—Cu1	110.1 (2)	H7B—C7—H7C	109.5
C6—N3—Cu1	113.05 (15)	N4—C8—H8A	109.5
C3—N3—Cu1	105.8 (2)	N4—C8—H8B	109.5
N1—C1—O1	177.8 (3)	H8A—C8—H8B	109.5
N2—C2—O2	178.8 (3)	N4—C8—H8C	109.5
N3—C3—C4	109.5 (2)	H8A—C8—H8C	109.5
N3—C3—H3A	109.8	H8B—C8—H8C	109.5
C4—C3—H3A	109.8

Symmetry code: (i) −x+2, −y+2, −z+2.

(II) catena-poly[[[µ₂-cyanato-κ²N:N-bis[(cyanato-κN)(1,3-diaminopropane- κ²N,N')copper(II)]]-µ₃-cyanato-κ³N:N:O]

Crystal data

[Cu(NCO)2(C3H10N2)]	F(000) = 452
Mr = 221.72	Dx = 1.746 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 2190 reflections
a = 6.711 (2) Å	θ = 3.1–26.8°
b = 6.636 (2) Å	µ = 2.56 mm^−1
c = 19.230 (6) Å	T = 298 K
β = 100.049 (3)°	Block, blue
V = 843.3 (4) Å^3	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection

Make Model CCD area-detector diffractometer	1859 independent reflections
Radiation source: fine-focus sealed tube	1517 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 27.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.629, Tmax = 0.784	k = −8→7
4002 measured reflections	l = −17→24

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0497P)^2] where P = (Fo^2 + 2Fc^2)/3
1859 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.38 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	0.87202 (5)	0.84257 (5)	0.037997 (15)	0.03450 (14)
N1	1.0906 (4)	0.8645 (4)	0.12368 (14)	0.0413 (6)
N2	0.6455 (4)	0.8605 (5)	0.09258 (14)	0.0388 (6)
N3	0.6693 (4)	0.7830 (4)	−0.04791 (13)	0.0461 (6)
N4	0.8975 (4)	1.2015 (4)	0.01424 (14)	0.0425 (6)
O1	0.6221 (4)	0.5063 (4)	−0.12689 (11)	0.0585 (6)
O2	0.8364 (4)	1.4451 (4)	0.09735 (14)	0.0762 (8)
C1	1.0528 (5)	0.9377 (6)	0.19213 (16)	0.0618 (10)
H1C	1.1622	0.8930	0.2287	0.074*
H1D	1.0543	1.0838	0.1918	0.074*
C2	0.8609 (5)	0.8695 (7)	0.20994 (16)	0.0662 (11)
H2C	0.8633	0.7233	0.2107	0.079*
H2D	0.8565	0.9140	0.2577	0.079*
C3	0.6717 (5)	0.9314 (6)	0.16555 (15)	0.0562 (9)
H3A	0.6651	1.0775	0.1653	0.067*
H3B	0.5598	0.8821	0.1866	0.067*
C4	0.6481 (4)	0.6458 (5)	−0.08637 (15)	0.0396 (7)
C5	0.8691 (4)	1.3239 (4)	0.05517 (16)	0.0408 (7)
H1A	1.155 (4)	0.752 (5)	0.1306 (15)	0.041 (9)*
H2A	0.570 (5)	0.917 (5)	0.0717 (15)	0.035 (10)*
H2B	0.598 (5)	0.748 (6)	0.0910 (15)	0.040 (9)*
H1B	1.179 (6)	0.925 (7)	0.1057 (19)	0.078 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0400 (2)	0.0316 (2)	0.0324 (2)	0.00045 (14)	0.00756 (14)	−0.00441 (13)
N1	0.0457 (14)	0.0396 (15)	0.0382 (14)	0.0041 (13)	0.0062 (11)	−0.0013 (11)
N2	0.0429 (14)	0.0358 (16)	0.0374 (14)	−0.0020 (13)	0.0067 (12)	0.0001 (12)
N3	0.0496 (14)	0.0440 (15)	0.0430 (15)	−0.0037 (12)	0.0029 (11)	−0.0115 (12)
N4	0.0531 (14)	0.0330 (14)	0.0441 (14)	0.0020 (11)	0.0164 (11)	−0.0013 (11)
O1	0.0660 (14)	0.0493 (15)	0.0554 (14)	0.0053 (11)	−0.0023 (11)	−0.0169 (11)
O2	0.0925 (19)	0.0489 (16)	0.094 (2)	0.0036 (14)	0.0336 (16)	−0.0315 (14)
C1	0.0583 (19)	0.084 (3)	0.0410 (18)	−0.0029 (19)	0.0022 (15)	−0.0135 (18)
C2	0.068 (2)	0.100 (3)	0.0317 (17)	0.005 (2)	0.0112 (16)	−0.0027 (17)
C3	0.0558 (18)	0.074 (3)	0.0415 (18)	0.0011 (18)	0.0152 (14)	−0.0152 (17)
C4	0.0356 (13)	0.0446 (18)	0.0368 (15)	0.0027 (13)	0.0016 (11)	0.0049 (13)
C5	0.0430 (15)	0.0276 (15)	0.0538 (18)	−0.0002 (12)	0.0135 (13)	0.0033 (14)

Geometric parameters (Å, º)

Cu1—N1	2.011 (3)	N2—H2B	0.81 (4)
Cu1—N2	1.996 (3)	N3—C4	1.166 (4)
Cu1—N3	1.988 (2)	N4—C5	1.169 (4)
Cu1—N4^i	2.007 (3)	O1—C4	1.203 (4)
Cu1—N4	2.437 (3)	O2—C5	1.190 (4)
Cu1—O2^ii	2.900 (3)	C1—C2	1.461 (5)
Cu1—Cu1^i	3.2137 (9)	C1—H1C	0.9700
Cu1—Cu1^iii	5.375 (2)	C1—H1D	0.9700
N1—C1	1.466 (4)	C2—C3	1.460 (5)
N1—H1A	0.86 (3)	C2—H2C	0.9700
N1—H1B	0.84 (4)	C2—H2D	0.9700
N2—C3	1.461 (4)	C3—H3A	0.9700
N2—H2A	0.70 (3)	C3—H3B	0.9700
N3—Cu1—N2	88.59 (11)	H2A—N2—H2B	103 (3)
N3—Cu1—N4^i	91.74 (11)	C4—N3—Cu1	132.3 (2)
N2—Cu1—N4^i	174.85 (12)	C5—N4—Cu1^i	131.9 (2)
N3—Cu1—N1	172.23 (12)	C5—N4—Cu1	121.8 (2)
N2—Cu1—N1	94.50 (12)	Cu1^i—N4—Cu1	92.11 (10)
N4^i—Cu1—N1	84.56 (11)	C2—C1—N1	113.9 (3)
N3—Cu1—N4	95.68 (11)	C2—C1—H1C	108.8
N2—Cu1—N4	97.19 (11)	N1—C1—H1C	108.8
N4^i—Cu1—N4	87.89 (10)	C2—C1—H1D	108.8
N1—Cu1—N4	91.02 (11)	N1—C1—H1D	108.8
N3—Cu1—O2^ii	93.13 (10)	H1C—C1—H1D	107.7
N2—Cu1—O2^ii	74.01 (10)	C3—C2—C1	119.2 (3)
N4^i—Cu1—O2^ii	100.84 (9)	C3—C2—H2C	107.5
N1—Cu1—O2^ii	80.90 (10)	C1—C2—H2C	107.5
N4—Cu1—O2^ii	167.40 (8)	C3—C2—H2D	107.5
C1—N1—Cu1	123.0 (2)	C1—C2—H2D	107.5
C1—N1—H1A	108 (2)	H2C—C2—H2D	107.0
Cu1—N1—H1A	110 (2)	C2—C3—N2	114.7 (3)
C1—N1—H1B	117 (3)	C2—C3—H3A	108.6
Cu1—N1—H1B	99 (3)	N2—C3—H3A	108.6
H1A—N1—H1B	96 (3)	C2—C3—H3B	108.6
C3—N2—Cu1	123.3 (2)	N2—C3—H3B	108.6
C3—N2—H2A	109 (3)	H3A—C3—H3B	107.6
Cu1—N2—H2A	106 (2)	N3—C4—O1	178.5 (3)
C3—N2—H2B	108 (2)	N4—C5—O2	178.2 (4)
Cu1—N2—H2B	105 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^iv	0.86 (3)	2.28 (3)	3.120 (4)	163 (3)
N2—H2A···N3^iii	0.70 (3)	2.55 (3)	3.188 (4)	153 (3)
N2—H2B···O1^v	0.81 (4)	2.42 (4)	3.162 (4)	153 (3)
N2—H2B···O2^ii	0.81 (4)	2.56 (3)	3.034 (4)	119 (3)
N1—H1B···N3^i	0.84 (4)	2.53 (4)	3.318 (4)	156 (4)

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