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The title compound, [Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2O, contains a dinuclear copper(II) complex which lies about a twofold axis at the mid-point of the C-C bond of the ox­amide ligand that bridges the two CuII atoms. The Cu...Cu distance is 5.215 (2) Å and the Cu atoms have distorted octahedral coordination geometry. Intramolecular N-H...O and N-H...N hydrogen bonds and intermolecular C-H...O hydrogen bonds, together with [pi]-[pi] stacking interactions, dominate throughout the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104028367/sq1182sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270104028367/sq1182Isup2.hkl
Contains datablock I

CCDC reference: 263021

Comment top

Bridging oxamidates have played a key role in the design of polynuclear systems, owing to their ability to facilitate strong exchange interactions (Ojima & Nonoyama, 1988). One of the most important properties of these ligands is the very easy cis-trans conformational change affording symmetric and asymmetric oxamidato bridges. N,N'-Disubstituted oxamidates are multifunctional ligands. Coordination complexes of copper(II) with oxamidate are known to act as paramagnetic ligands towards other metal ions (Mathoniere et al., 1993). The crystal structures and magnetic properties of many polynuclear complexes have been previously reported, in which the bridging ligand is the oxamidate group (e.g. Lloret et al., 1992; Zhang et al., 1999). As part of our work in this area, we have designed and synthesized the title novel binuclear complex [Cu2(oxen)(L)2(ClO4)2]·2L, (I) [oxen is N,N'-ethylenediamide-bis(2-aminoethyl) and L is 1,10-N,N-fluorenone], for which we have undertaken the crystal structure determination. \sch

Details of the molecular geometry of (I) are given in Table 1 and the complex is shown in Fig. 1. The structure consists of a [Cu2(oxen)L2(ClO4)2] complex and two free L molecules. The oxen group adopts the trans configuration and acts as a bis-tridentate ligand to connect the two CuII atoms, to form a dinuclear complex with a distance between two Cu atoms of 5.215 (2) Å without direct interactions, slightly shorter than that in [Cu2(oxen)(4-APy)2(ClO4)2] (5.24 Å; Zhang et al., 1999). The two CuII atoms have the same coordination environment, namely a distorted octahedron, the meridional plane of which is composed of atom N1 of L and atoms N5, N6 and O3A of the oxen group. One of the apical positions is occupied by an O atom of the perchlorate group and the other site is weakly linked to atom N2 of L, with typical Jahn-Teller elongated distances comparable with the values reported in [Cu2(oxen)(4-APy)2(ClO4)2].

The angle between the L plane (atoms C1—C11/N1/N2/O1) and the plane of atoms Cu/N5/C25/O3/CuA/N5A/C25A/O3A is 91.20 (7)° [symmetry code: (A) 1 − x, y, 1/2 − z], which shows they are approximately perpendicular. The main structural features of the [Cu2(oxen)L2(ClO4)2] component are similar to the reported complexes [Cu2(oxen)(4-APy)2(ClO4)2] (4-APy = 4-aminopyridine) and [Cu2(oxen)(DAPM)2(Br)2] (DAPM = 4,4'-diaminodiphenylmethane) (Zhang et al., 1999), in that they all contain the oxen group. Their second ligands, however, are different. In [Cu2(oxen)(4-APy)2(ClO4)2] and [Cu2(oxen)(DAPM)2(Br)2], the second ligands are 4-APy and DAPM, respectively, and these are both monodentate, which results in the CuII atoms exhibiting square-pyramidal geometries. Although it may be thought that the CuII atoms in [Cu2(oxen)(4-APy)2(ClO4)2] are in a distorted octahedral environment, the sixth coordinated atom is very weakly linked to the CuII atom [Cu—N4b 3.077 Å; symmetry code: (b) ? Please provide missing symmetry code]. By contrast, in (I), the second ligand is 1,10-N,N-fluorenone and this is bidentate, with the result that the CuII atoms exhibit a Jahn-Teller-distorted octahedral geometry.

Details of the hydrogen-bonding in (I) are listed in Table 2. As illustrated in Fig. 2, the packing has a network of hydrogen bonds. These are mainly formed between atoms O1 and N6 of the [Cu2(oxen)L2(ClO4)2] component, atoms N4 of the free ligands, and atoms O6 of the ClO4 anion.

The ππ stacking interactions in the structure of (I) are also shown in Fig. 2. The [Cu2(oxen)L2(ClO4)2] components are interleaved regularly to form a chain along the c axis via ππ stacking interactions and intermolecular C—H···O hydrogen bonds. Planes 1 and 3 of L are stacked in a parallel fashion, the distance between the two planes being 3.2816 (8) Å. The free ligands insert into the interstices between the [Cu2(oxen)L2(ClO4)2] components along the a axis via ππ stacking interactions and N—H···N hydrogen bonds. The L planes 2 and 4 are also in a parallel arrangement, the distance between the two planes being 3.3040 (8) Å. The L plane 1 in [Cu2(oxen)L2(ClO4)2] and the free ligand L plane 2 are deviate somewhat from being parallel, the angle between them being 12.40 (5)°. The shortest interatomic distance between these planes is 3.3648 (8) Å, while the distance between the centres of the two planes is 3.7720 (8) Å. All these distances, between L planes 1 and 2, L planes 1 and 3 and L planes 2 and 4, are shorter than the distance between neighbouring base pairs in DNA (3.4 Å; Neidle, 1999). Therefore, stacking interactions dominate throughout the crystal structure, stabilizing the crystal packing together with the hydrogen-bonding interactions.

Experimental top

All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company, China, and were used without further purification. [Cu2(oxen)](ClO4)2 was synthesized by the literature method of Zhang et al. (2000). To a methanol solution (30 ml) of Cu(ClO4)2·6H2O (3.71 g, 10 mmol) was added an 80% methanol solution (30 ml) of oxen (Niu et al., 1994) (0.92 g, 5 mmol) with stirring. After a few minutes, a solution of 1M NaOH (10 ml) was added. The mixture was then refluxed for 2 h to obtain a green solid. The solid was filtered, washed with methanol and recrystallized from an 80% methanol solution (yield 77%). To prepare (I), a methanol solution (5 ml) of L (0.36 g, 2 mmol; Henderson et al., 1984) was added to a methanol solution (25 ml) of [Cu2(oxen)](ClO4)2 (0.50 g, 1 mmol) with stirring. The mixture was refluxed for 1 h to obtain a clear blue solution and, after standing at room temperature for three weeks, well shaped blue single crystals of (I) were obtained by slow evaporation.

Refinement top

All H atoms were placed in geometrically idealized positions, with Csp3—H = 0.97, Csp2 = 0.93 and Nsp3—H = 0.90 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity. [Symmetry code: (A) 1 − x, y, 1/2 − z.]
[Figure 2] Fig. 2. The hydrogen-bonding network and ππ stacking interactions of (I). [Symmetry codes: (A) 1 − x, y, 1/2 − z. (B) x, −y, z − 1/2.]
[µ-N,N'-Bis(2-aminoethyl)oxamidato(2-)]bis[(4,5-diazafluoren-9- one)perchloratocopper(II)] 4,5-diazafluoren-9-one disolvate top
Crystal data top
[Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2OF(000) = 2496
Mr = 1226.89Dx = 1.617 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4667 reflections
a = 26.5955 (1) Åθ = 1.9–25.1°
b = 11.4267 (3) ŵ = 1.03 mm1
c = 16.5915 (4) ÅT = 293 K
β = 92.053 (1)°Block, blue
V = 5038.90 (18) Å30.44 × 0.40 × 0.36 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
4441 independent reflections
Radiation source: fine-focus sealed tube3294 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.040
ϕ and ω scansθmax = 25.1°, θmin = 1.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 2531
Tmin = 0.659, Tmax = 0.708k = 1013
8436 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.198H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P]
where P = (Fo2 + 2Fc2)/3
4441 reflections(Δ/σ)max < 0.001
355 parametersΔρmax = 0.82 e Å3
1 restraintΔρmin = 0.58 e Å3
Crystal data top
[Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2OV = 5038.90 (18) Å3
Mr = 1226.89Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.5955 (1) ŵ = 1.03 mm1
b = 11.4267 (3) ÅT = 293 K
c = 16.5915 (4) Å0.44 × 0.40 × 0.36 mm
β = 92.053 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
4441 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
3294 reflections with I > 2σ(I)
Tmin = 0.659, Tmax = 0.708Rint = 0.040
8436 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0691 restraint
wR(F2) = 0.198H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P]
where P = (Fo2 + 2Fc2)/3
4441 reflectionsΔρmax = 0.82 e Å3
355 parametersΔρmin = 0.58 e Å3
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cu0.43625 (2)0.30356 (7)0.36580 (4)0.0443 (3)
Cl0.37123 (7)0.61062 (16)0.37323 (11)0.0655 (5)
O10.4265 (2)0.0072 (6)0.6819 (4)0.1011 (14)
O20.2717 (3)0.0619 (7)0.7278 (3)0.113 (2)
O30.48910 (14)0.3153 (4)0.1440 (2)0.0470 (10)
O40.3665 (3)0.7167 (5)0.3297 (4)0.101 (2)
O50.3762 (3)0.6366 (6)0.4573 (3)0.105 (2)
O60.3285 (2)0.5386 (5)0.3581 (4)0.100 (2)
O70.4150 (2)0.5506 (6)0.3527 (4)0.1011 (14)
N10.43899 (17)0.3101 (5)0.4869 (3)0.0466 (12)
N20.44035 (17)0.0807 (5)0.4022 (3)0.0464 (12)
N30.31471 (19)0.3246 (5)0.5198 (3)0.0532 (13)
N40.31734 (18)0.0762 (5)0.4535 (3)0.0551 (13)
N50.43539 (16)0.3079 (4)0.2505 (3)0.0414 (11)
N60.36123 (16)0.2845 (4)0.3486 (3)0.0453 (11)
H6A0.34940.23230.38390.054*
H6B0.34560.35340.35590.054*
C10.4357 (2)0.2068 (6)0.5227 (3)0.0455 (14)
C20.4407 (2)0.4027 (6)0.5370 (4)0.0580 (16)
H2B0.44320.47720.51500.070*
C30.4389 (3)0.3919 (8)0.6203 (4)0.072 (2)
H3A0.44120.45840.65250.086*
C40.4338 (3)0.2834 (7)0.6555 (4)0.067 (2)
H4A0.43090.27520.71090.081*
C50.4332 (2)0.1879 (6)0.6049 (3)0.0544 (16)
C60.4310 (2)0.0594 (7)0.6178 (3)0.0597 (18)
C70.4354 (2)0.0035 (6)0.5373 (3)0.0502 (15)
C80.4388 (2)0.1093 (6)0.5110 (4)0.0583 (17)
H8A0.43840.17210.54670.070*
C90.4430 (2)0.1259 (6)0.4288 (4)0.0576 (16)
H9A0.44580.20110.40800.069*
C100.4428 (2)0.0311 (7)0.3782 (4)0.0570 (17)
H10A0.44460.04540.32320.068*
C110.4367 (2)0.0935 (5)0.4807 (3)0.0436 (13)
C120.3044 (2)0.2281 (6)0.5596 (4)0.0512 (16)
C130.3112 (2)0.4245 (7)0.5628 (4)0.0653 (19)
H13A0.31870.49450.53730.078*
C140.2972 (3)0.4295 (8)0.6415 (5)0.074 (2)
H14A0.29450.50140.66720.089*
C150.2872 (2)0.3267 (9)0.6825 (4)0.073 (2)
H15A0.27880.32760.73640.088*
C160.2903 (2)0.2235 (7)0.6403 (4)0.063 (2)
C170.2824 (3)0.0996 (8)0.6624 (4)0.074 (2)
C180.2924 (2)0.0308 (7)0.5880 (4)0.0634 (18)
C190.2900 (3)0.0869 (8)0.5719 (6)0.082 (2)
H19A0.28090.14110.61060.099*
C200.3022 (3)0.1205 (8)0.4942 (6)0.082 (2)
H20A0.30150.19930.48020.098*
C210.3149 (3)0.0388 (7)0.4383 (5)0.0672 (19)
H21A0.32230.06460.38690.081*
C220.3058 (2)0.1082 (6)0.5277 (4)0.0518 (15)
C230.3519 (2)0.2427 (7)0.2648 (4)0.0606 (17)
H23A0.31720.25810.24800.073*
H23B0.35740.15890.26240.073*
C240.3866 (2)0.3039 (7)0.2090 (4)0.0578 (17)
H24A0.38860.26110.15870.069*
H24B0.37460.38240.19720.069*
C250.47855 (19)0.3115 (5)0.2183 (3)0.0385 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0404 (4)0.0619 (5)0.0311 (4)0.0001 (3)0.0068 (3)0.0009 (3)
Cl0.0746 (11)0.0564 (10)0.0655 (11)0.0064 (9)0.0022 (8)0.0006 (8)
O10.106 (3)0.115 (4)0.084 (3)0.001 (3)0.014 (2)0.005 (3)
O20.121 (5)0.167 (7)0.051 (3)0.057 (5)0.012 (3)0.031 (4)
O30.037 (2)0.078 (3)0.0266 (18)0.0031 (19)0.0040 (15)0.0026 (18)
O40.147 (6)0.074 (4)0.079 (4)0.027 (4)0.030 (4)0.021 (3)
O50.163 (7)0.089 (4)0.063 (4)0.003 (4)0.002 (4)0.012 (3)
O60.074 (4)0.079 (4)0.146 (6)0.018 (3)0.009 (4)0.013 (4)
O70.106 (3)0.115 (4)0.084 (3)0.001 (3)0.014 (2)0.005 (3)
N10.039 (3)0.063 (3)0.038 (3)0.005 (2)0.0056 (19)0.004 (2)
N20.045 (3)0.062 (3)0.031 (2)0.003 (2)0.0024 (19)0.001 (2)
N30.046 (3)0.067 (4)0.048 (3)0.003 (2)0.008 (2)0.003 (3)
N40.044 (3)0.065 (4)0.056 (3)0.000 (2)0.006 (2)0.000 (3)
N50.032 (2)0.061 (3)0.032 (2)0.001 (2)0.0031 (17)0.000 (2)
N60.036 (2)0.056 (3)0.044 (3)0.005 (2)0.009 (2)0.000 (2)
C10.035 (3)0.072 (4)0.030 (3)0.003 (3)0.004 (2)0.001 (3)
C20.053 (4)0.064 (4)0.057 (4)0.005 (3)0.004 (3)0.014 (3)
C30.077 (5)0.091 (6)0.048 (4)0.016 (4)0.002 (3)0.025 (4)
C40.068 (4)0.099 (6)0.035 (3)0.014 (4)0.002 (3)0.011 (4)
C50.046 (3)0.083 (5)0.034 (3)0.001 (3)0.007 (2)0.006 (3)
C60.060 (4)0.099 (6)0.020 (3)0.002 (4)0.006 (2)0.014 (3)
C70.041 (3)0.068 (4)0.041 (3)0.006 (3)0.001 (2)0.008 (3)
C80.054 (4)0.065 (5)0.055 (4)0.006 (3)0.002 (3)0.014 (3)
C90.050 (4)0.058 (4)0.064 (4)0.006 (3)0.006 (3)0.005 (3)
C100.054 (4)0.079 (5)0.038 (3)0.003 (3)0.005 (3)0.008 (3)
C110.037 (3)0.062 (4)0.032 (3)0.003 (3)0.004 (2)0.002 (3)
C120.034 (3)0.079 (5)0.040 (3)0.002 (3)0.004 (2)0.001 (3)
C130.053 (4)0.080 (5)0.063 (4)0.004 (3)0.006 (3)0.016 (4)
C140.050 (4)0.092 (6)0.079 (5)0.013 (4)0.007 (3)0.032 (5)
C150.039 (3)0.133 (8)0.048 (4)0.010 (4)0.006 (3)0.023 (5)
C160.044 (3)0.107 (6)0.037 (3)0.017 (4)0.005 (3)0.005 (4)
C170.058 (4)0.115 (7)0.048 (4)0.020 (4)0.002 (3)0.018 (4)
C180.053 (4)0.079 (5)0.058 (4)0.007 (3)0.001 (3)0.014 (4)
C190.066 (5)0.087 (6)0.095 (6)0.005 (4)0.006 (4)0.038 (5)
C200.063 (5)0.071 (5)0.111 (7)0.002 (4)0.005 (5)0.004 (5)
C210.055 (4)0.076 (5)0.071 (5)0.000 (4)0.006 (3)0.008 (4)
C220.038 (3)0.075 (5)0.043 (3)0.005 (3)0.007 (2)0.005 (3)
C230.046 (3)0.086 (5)0.050 (4)0.015 (3)0.004 (3)0.009 (3)
C240.040 (3)0.097 (5)0.036 (3)0.001 (3)0.005 (2)0.000 (3)
C250.038 (3)0.044 (3)0.034 (3)0.001 (2)0.003 (2)0.002 (2)
Geometric parameters (Å, º) top
Cu—N51.914 (4)C4—H4A0.9300
Cu—O3i2.002 (4)C5—C61.485 (10)
Cu—N12.009 (5)C6—C71.489 (9)
Cu—N62.017 (4)C7—C81.365 (9)
Cu—N22.619 (5)C7—C111.393 (8)
Cu—O72.885 (7)C8—C91.386 (9)
Cl—O71.404 (6)C8—H8A0.9300
Cl—O41.414 (6)C9—C101.370 (9)
Cl—O61.418 (6)C9—H9A0.9300
Cl—O51.427 (6)C10—H10A0.9300
O1—C61.229 (8)C12—C161.405 (8)
O2—C171.210 (8)C12—C221.469 (10)
O3—C251.274 (6)C13—C141.370 (10)
O3—Cui2.002 (4)C13—H13A0.9300
N1—C11.325 (8)C14—C151.388 (12)
N1—C21.346 (8)C14—H14A0.9300
N2—C111.318 (7)C15—C161.376 (11)
N2—C101.341 (8)C15—H15A0.9300
N3—C121.320 (8)C16—C171.480 (11)
N3—C131.351 (9)C17—C181.496 (11)
N4—C221.331 (8)C18—C191.371 (12)
N4—C211.339 (9)C18—C221.392 (9)
N5—C251.284 (7)C19—C201.394 (12)
N5—C241.448 (7)C19—H19A0.9300
N6—C231.482 (8)C20—C211.367 (11)
N6—H6A0.9000C20—H20A0.9300
N6—H6B0.9000C21—H21A0.9300
C1—C51.384 (8)C23—C241.503 (9)
C1—C111.472 (9)C23—H23A0.9700
C2—C31.390 (9)C23—H23B0.9700
C2—H2B0.9300C24—H24A0.9700
C3—C41.379 (11)C24—H24B0.9700
C3—H3A0.9300C25—C25i1.524 (10)
C4—C51.377 (9)
N5—Cu—O3i83.87 (16)C7—C8—C9116.8 (6)
N5—Cu—N1176.1 (2)C7—C8—H8A121.6
O3i—Cu—N194.49 (17)C9—C8—H8A121.6
N5—Cu—N683.40 (18)C10—C9—C8119.8 (7)
O3i—Cu—N6166.98 (16)C10—C9—H9A120.1
N1—Cu—N698.38 (19)C8—C9—H9A120.1
N5—Cu—N2104.78 (18)N2—C10—C9124.7 (6)
O3i—Cu—N292.89 (16)N2—C10—H10A117.6
N1—Cu—N278.79 (18)C9—C10—H10A117.6
N6—Cu—N287.74 (18)N2—C11—C7126.0 (6)
N5—Cu—O784.49 (19)N2—C11—C1124.7 (5)
O3i—Cu—O796.92 (18)C7—C11—C1109.2 (5)
N1—Cu—O792.23 (19)N3—C12—C16125.2 (7)
N6—Cu—O784.6 (2)N3—C12—C22126.2 (5)
N2—Cu—O7167.20 (16)C16—C12—C22108.7 (6)
O7—Cl—O4110.8 (4)N3—C13—C14124.4 (8)
O7—Cl—O6109.9 (4)N3—C13—H13A117.8
O4—Cl—O6110.6 (4)C14—C13—H13A117.8
O7—Cl—O5106.8 (4)C13—C14—C15119.7 (7)
O4—Cl—O5108.9 (4)C13—C14—H14A120.2
O6—Cl—O5109.8 (4)C15—C14—H14A120.2
C25—O3—Cui109.3 (3)C16—C15—C14117.4 (6)
Cl—O7—Cu128.4 (4)C16—C15—H15A121.3
C1—N1—C2115.1 (5)C14—C15—H15A121.3
C1—N1—Cu114.5 (4)C15—C16—C12118.4 (7)
C2—N1—Cu130.3 (5)C15—C16—C17133.1 (6)
C11—N2—C10113.9 (5)C12—C16—C17108.5 (6)
C11—N2—Cu96.7 (4)O2—C17—C16127.1 (8)
C10—N2—Cu149.3 (4)O2—C17—C18127.4 (9)
C12—N3—C13115.0 (6)C16—C17—C18105.5 (6)
C22—N4—C21115.7 (6)C19—C18—C22119.7 (7)
C25—N5—C24127.1 (5)C19—C18—C17131.9 (7)
C25—N5—Cu116.0 (4)C22—C18—C17108.5 (7)
C24—N5—Cu116.9 (3)C18—C19—C20116.1 (7)
C23—N6—Cu107.4 (3)C18—C19—H19A122.0
C23—N6—H6A110.2C20—C19—H19A122.0
Cu—N6—H6A110.2C21—C20—C19120.7 (8)
C23—N6—H6B110.2C21—C20—H20A119.6
Cu—N6—H6B110.2C19—C20—H20A119.6
H6A—N6—H6B108.5N4—C21—C20123.6 (8)
N1—C1—C5126.0 (6)N4—C21—H21A118.2
N1—C1—C11124.6 (5)C20—C21—H21A118.2
C5—C1—C11109.3 (6)N4—C22—C18124.3 (7)
N1—C2—C3122.9 (7)N4—C22—C12126.9 (6)
N1—C2—H2B118.6C18—C22—C12108.9 (6)
C3—C2—H2B118.6N6—C23—C24110.0 (5)
C4—C3—C2120.6 (7)N6—C23—H23A109.7
C4—C3—H3A119.7C24—C23—H23A109.7
C2—C3—H3A119.7N6—C23—H23B109.7
C5—C4—C3116.9 (6)C24—C23—H23B109.7
C5—C4—H4A121.6H23A—C23—H23B108.2
C3—C4—H4A121.6N5—C24—C23106.4 (5)
C4—C5—C1118.5 (7)N5—C24—H24A110.4
C4—C5—C6134.1 (6)C23—C24—H24A110.4
C1—C5—C6107.4 (6)N5—C24—H24B110.4
O1—C6—C5127.6 (7)C23—C24—H24B110.4
O1—C6—C7125.5 (7)H24A—C24—H24B108.6
C5—C6—C7106.9 (5)O3—C25—N5129.4 (5)
C8—C7—C11118.6 (6)O3—C25—C25i118.9 (6)
C8—C7—C6134.4 (6)N5—C25—C25i111.8 (6)
C11—C7—C6107.0 (6)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6A···N40.902.313.195 (7)169
N6—H6B···O60.902.173.037 (8)163
C10—H10A···O1ii0.932.423.281 (9)155
Symmetry code: (ii) x, y, z1/2.

Experimental details

Crystal data
Chemical formula[Cu2(C6H12N4O2)(ClO4)2(C11H6N2O)2]·2C11H6N2O
Mr1226.89
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)26.5955 (1), 11.4267 (3), 16.5915 (4)
β (°) 92.053 (1)
V3)5038.90 (18)
Z4
Radiation typeMo Kα
µ (mm1)1.03
Crystal size (mm)0.44 × 0.40 × 0.36
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.659, 0.708
No. of measured, independent and
observed [I > 2σ(I)] reflections
8436, 4441, 3294
Rint0.040
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.069, 0.198, 1.09
No. of reflections4441
No. of parameters355
No. of restraints1
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0804P)2 + 32.9042P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.82, 0.58

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97), SHELXL97.

Selected geometric parameters (Å, º) top
Cu—N51.914 (4)Cu—O72.885 (7)
Cu—O3i2.002 (4)Cl—O71.404 (6)
Cu—N12.009 (5)Cl—O41.414 (6)
Cu—N62.017 (4)Cl—O61.418 (6)
Cu—N22.619 (5)Cl—O51.427 (6)
N5—Cu—O3i83.87 (16)N1—Cu—N278.79 (18)
N5—Cu—N1176.1 (2)N6—Cu—N287.74 (18)
O3i—Cu—N194.49 (17)N5—Cu—O784.49 (19)
N5—Cu—N683.40 (18)O3i—Cu—O796.92 (18)
O3i—Cu—N6166.98 (16)N1—Cu—O792.23 (19)
N1—Cu—N698.38 (19)N6—Cu—O784.6 (2)
N5—Cu—N2104.78 (18)N2—Cu—O7167.20 (16)
O3i—Cu—N292.89 (16)
Symmetry code: (i) x+1, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N6—H6A···N40.902.313.195 (7)169
N6—H6B···O60.902.173.037 (8)163
C10—H10A···O1ii0.932.423.281 (9)155
Symmetry code: (ii) x, y, z1/2.
 

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