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Two copper complex solvatomorphs, namely (3,10-C-meso-3,5,7,7,10,12,14,14-octa­methyl-1,4,8,11-tetra­aza­cyclo­tetradecane)bis­(perchlorato-[kappa]O)copper(II) 1.2-hydrate, [Cu(ClO4)2(C18H40N4)]·1.2H2O, (I), and (3,10-C-meso-3,5,7,7,10,12,14,14-octa­methyl-1,4,8,11-tetra­aza­cyclo­tetradecane)bis­(perchlor­ato-[kappa]O)copper(II), [Cu(ClO4)2(C18H40N4)], (II), are described and compared with each other and with a third, already reported, anhydrous diastereomer, denoted (III). Both compounds present very similar centrosymmetic coordination environments, with the CuII cation lying on an inversion centre in a distorted 4+2 octa­hedral environment, defined by the macrocyclic N4 group in the equatorial sites and two perchlorate groups in trans-axial positions [one of the perchlorate ligands in (I) is partially disordered]. The most significant difference in mol­ecular shape is seen in the orientation of the perchlorate anions, and the influence of this on the intra­molecular hydrogen bonding is discussed. The (partially) hydrated state of (I) favours the formation of chains along [011], while the anhydrous character of (II) and (III) promotes loosely bound structures with low packing indices.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113013711/sk3486sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113013711/sk3486Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113013711/sk3486IIsup3.hkl
Contains datablock II

CCDC references: 956970; 956971

Comment top

Synthetic macrocyclic complexes are important in view of their presence in many biologically significant and naturally occurring metal complexes, such as vitamin B12, haemoglobin and chlorophyll, all of which play vital roles in biological systems (Bernhardt & Lawrance, 1990; Reid & Schroder, 1990). Saturated tetraazamacrocycles have been proven to be versatile macrocyclic ligands capable of forming stable inert complexes with a variety of biomedically important metal ions, the chemistry of which has attracted interest due to their involvement in a variety of catalytic, biochemical and industrial processes (Kimura et al., 1992, 1994). Regarding biological applications, metal complexes of the 14-membered tetraazamacrocyclic ligands directly relevant to the present study have been explored for their use in magnetic resonance imaging (MRI) and radioimmunotherapy (Norman et al., 1995; Konig et al., 1996). They are also useful in terms of their utility in pharmacological (Hollinshead & Smith, 1990), crystal engineering (Suh et al., 2006) and analytical (Singh et al., 1999) endeavours, and they have been found to have antifungal (Roy, Hazari, Dey, Meah et al., 2007), antibacterial (Roy, Hazari, Dey, Miah et al., 2007; Roy, Hazari, Dey, Nath et al., 2007) and (in some cases) potential anticancer properties (Arai et al., 1998; Gao et al., 2010). All the aforementioned potential applications have promoted strong sustained research on the subject, and in this respect we refer the interested reader to a recent review accounting for a 50 year period of research on this type of compound (Curtis, 2012), where a large number of differently N-substituted (viz. methyl, propyl and allyl) macrocyclic ligands complexed to a variety of cations (e.g. Cu, Co, Cr, Zn, Cd and Pd) are analysed.

As continuation of a current research line in our laboratory (Hazari et al., 1999; Roy et al., 2005, 2006), we present herein the crystal structures of the title solvatomorphic variants Cu(ClO4)2(L1).1.2H2O, (I), and Cu(ClO4)2(L1), (II), two mixed CuII complexes having perchlorate as the inorganic balancing anion and L1, an isomeric form of L = 3,5,7,7,10,12,14,14-octamethyl-1,4,8,11-tetraazacyclotetradecane, as the organic ligand.

Even though a large number of analogous CuIIL complexes have been reported with perchlorate as the counter-anion, viz. those presented by Lee et al. (1985) and Hazari et al. (2001), only one has the anion behaving in the coordinated mode observed in (I) and (II), i.e. the anhydrate isomer reported by Lin et al. (2006), hereinafter (III), with which we shall compare our results.

Displacement ellipsoid views of (I) and (II) are shown in Figs. 1(a) and 2(a), respectively, while (III) is shown in Fig. 3. The very similar centrosymmetric coordination environments in (I) and (II) (a distorted 4+2 octahedron) present the macrocycle N4 group occupying the equatorial sites and two axial perchlorate groups in trans axial positions, one in (I) being partially disordered (see Refinement section for details). Coordination distances can be found in Tables 1 and 3. The 14-membered rings have the usual zigzag shape and present four equatorial and four axial methyl groups, the latter ones in pairs, trans to each other due to centrosymmetry. The two independent amine atoms N1 and N2 present their H atoms on the same side of the coordination plane and opposite the neighbouring axial methyl groups (Figs. 1a and 2a). The similarity of both central cores can be envisaged from Fig. 4, which presents a least-squares fit of just the basal coordination planes. It is clearly seen that only the orientations of the pendant perchlorate anions differ substantially. We shall see below the influence this has on intramolecular hydrogen bonding.

Due to coordination, the 14-membered ligand generates four smaller rings, two six-membered rings in chair conformations and two five-membered rings in half-chair forms.

The Cu—Nequatorial bond lengths are similar to each other [2.020 (3) and 2.023 (3) Å in (I); 2.0270 (19) and 2.0295 (19) Å in (II)], while the corresponding bond angles differ from the ideal value of 90° by ±4.25 (12) and 4.66 (7)°, respectively. As expected, the Cu—Oaxial bond lengths for both compounds [2.833 (4) and 2.831 (3) Å] are significantly longer than the latter ones [Which?], and are also longer than the typical axial values for CuN4O2 complexes [mean value = 2.47 (16) Å for 1622 entries in the Cambridge Structural database (CSD, Version 5.3; Allen, 2002)]. The axial coordination is rather tilted, viz. subtending angles with the basal mean plane of 15.32 (2) and 13.74 (3)°, respectively. The structures appear more regular than in the (III) isomer, which shows wider spans [Cu—N = 2.015 (2)–2.048 (2)Å and C—O = 2.570 (3)–2.731 (3)Å; basal angles = 90±5.73 (7)°] but presents more `vertical' apical bonds [angles to the basal mean plane = 9.30 (4) and 5.72 (5)°].

In a centrosymmetric L ligand, there are four independent chiral centres (N1, C4, N2 and C5) and, accordingly, 24 = 16 possible configurations to be expected. The sequence observed for L1 in both (I) and (II) is RRRRSSSS. In conpound (III), the complex we chose for comparison, the isomeric L2 variant is not centrosymmetric and presents a RRRSSRSR distribution of the same sequence of chiral centres. There are two main differences to be noted: (i) a different set-up in what would be the `independent part' [RRRR in (I) and (II) and RRS in (III), viz. different chirality at atom C5]; and (ii) a noncentrosymmetric relationship between sites C4—C4A [RS in (I) and (II), and RR in (III)]. Fig. 5 presents a schematic view of all three configurations, with the critical zones encircled, highlighting the differences between the (I)–(II) pair and (III).

A search of the CSD disclosed, in addition to (I) and (II), 14 other transition metal complexes with an L ligand and the same chiral centres (see Table 5 for some relevant information). Only two of these 16 structures crystallize in a noncentrosymmetric space group. Of the 14 centrosymmetric structures, seven present the central cation lying on a centre of symmetry. An analysis of the distribution of chiral centres suggests the overall distribution to be far from random: there are a total of eight different arrays with quite uneven population structures presenting the RRRRSSSS distribution reported here, referred to as type 1 in Table 5, and these correspond to centrosymmetric molecules. The remaining cases are bunched in a three-membered group (type 2) and a two-membered group (type 3), while the remaining distributions are unique and present no duplication.

These different configurations lead to different orientations between hydrogen-bonding donors and acceptors, either facilitating or hampering some intramolecular interactions. Those in (I) and (II) are presented in Tables 2 (entries 1–7) and 4 (entries 1–4), respectively, and shown in Figs 1(b) and 2(b). For completeness, the interactions in (III) are shown in Fig. 3. The most notable difference is that (II) has both amino H atoms involved in hydrogen bonds with perchlorate O atoms as acceptors. In the case of (I), instead, the R(6) (N1—H1···O2—Cl1—O1—Cu1) ring (Bernstein et al., 1995) opens, making room for the (depleted) O1W water molecule, which thus gives rise to an enlarged R22(8) (N1—H1···O1—H1WA···O2—Cl1—O1—Cu1) loop. In addition, a small R12(4) [check] (H1WA···O1—Cl1—O2···) ring is built up. The presence of this (depleted) water molecule strongly anchored to the molecule gives rise to the second difference concerning intermolecular interactions, viz. the remaining atom H1WB, which is not involved in intramolecular contacts, forms a hydrogen bond to a neighbouring perchlorate ligand (eighth entry in Table 2), defining a (couple of) centrosymmetric hydrogen-bonded R44(12) rings and generating a one-dimensional structure parallel to [011], shown in Fig 6, as well as the rings generated.

A hasty hydrogen-bonding analysis might erroneously lead to the conclusion that the minor-occupancy perchlorate O3' atom `bumps into' water atom H1WA [H1WA···O3' = 1.003 (3) Å]. However, this is only an artifact derived from the fact that both units (the water solvent and the minor part of the perchlorate anion) have incomplete occupancies, allowing for one of the groups to be present while the other is not, and vice versa, so that the apparent interaction is in fact only illusory.

In contrast with (I), the structure of (II) does not show any relevant intermolecular interactions, and the crystal structure can be described as the packing of `spheres', held together by very weak forces of the van der Waals type. Fig. 7 shows a packing view where this set-up is apparent.

Structure (III) shares its anhydrous character with (II), and with this the lack of significant intermolecular interactions. This shows up in the rather low packing indices [66.1% for (II) and 66.2% for (III), calculated using PLATON (Spek, 2009)]. For comparison, the same index for (I) is 69.8% (only the major part of the disordered anion has been considered in the calculation).

Related literature top

For related literature, see: Allen (2002); Arai et al. (1998); Bembi et al. (1989); Bernhardt & Lawrance (1990); Bernstein et al. (1995); Curtis (2012); Curtis et al. (1969); Gao et al. (2010); Hazari et al. (1999, 2001); Hollinshead & Smith (1990); Kimura et al. (1992, 1994); Konig et al. (1996); Lee et al. (1985); Lin et al. (2006); Norman et al. (1995); Reid & Schroder (1990); Roy & Bembi (2005); Roy et al. (2006); Roy, Hazari, Dey, Meah, Rahman, Kim & Park (2007); Roy, Hazari, Dey, Miah, Olbrich & Rehder (2007); Roy, Hazari, Dey, Nath, Anwar, Kim, Kim & Park (2007); Singh et al. (1999); Spek (2009); Suh et al. (2006).

Experimental top

For the synthesis of L, reduction of 3,10-C-meso-Me8[14]diene dihydroperchlorate (Curtis et al., 1969) and resolution of isomeric Me8[14]anes were carried out as described in the literature (Bembi et al., 1989); ligand L in the present work corresponds to Lb in the latter cited paper. Regarding chirality, in the diene ligand there were originally two chiral centres and the reduction process gives rise to two further chiral centres.

For the synthesis of the copper(II) diperchlorate complexes, (I) and (II), copper(II) perchlorate hexahydrate (0.371 g, 1.0 mmol) and L dihydrate (0.320 g, 1.0 mmol) were dissolved separately in hot methanol (50 ml). The colourless ligand solution was added as soon as possible to the copper salt solution while hot. An intense blue solution appeared within a few minutes. The resulting mixture was allowed to evaporate slowly, and dark-blue crystals appeared. These were filtered off and recrystallized from a minimum quantity of aqueous methanol (1:1 v/v). Crystals of both (I) and (II), differentiated by their shape, appeared in the same recrystallization process.

Refinement top

Structure (I) posed some problems due to disorder. Water molecule O1W appeared depleted and refinement of its site-occupancy factor converged to 0.60 (2). The perchlorate anion, in turn, appeared split into two almost `mirror-related' parts with very different occupancies [0.922 (3) and 0.078 (3)]. Three O atoms in the major component (O1, O2 and O4) appear relatively near their O1', O2' and O4' counterparts, and the least-squares plane through the six-membered group corresponds roughly to the `mirror' relating the two components. The Cl units (Cl1 and Cl1') and the fourth O atoms (O3 and O3') lie on both sides, at 0.358 (2) and -0.372 (2), and 1.703 (3) and -1.708 (3) Å from the plane, respectively.

Due to the very small site-occupancy factor for the minor component [0.078 (2)], strong similarity restraints (in both metrics and displacement factors) were introduced in order to link them to the corresponding parameters in the majority component.

C- and N-bound H atoms were found in a difference map, further idealized and finally allowed to ride. Methyl groups were also free to rotate. Water H atoms in (I) were difficult to find, due to depletion, but the hydrogen-bonding donor–acceptor scheme for O1W clearly defined a restrained solid angle for them. The inclusion of an idealized water molecule (O—H = 0.85 Å and H···H = 1.35 Å) resulted in the H atoms lying in slightly positive zones in the difference Fourier map and involved in strong hydrogen bonding. The final positions came from a restrained refinement, with O—H = 0.85 (1) Å and H···H = 1.35 (1) Å. In all cases, H-atom displacement parameters were taken as Uiso(H) = kUeq(host), with C—H = 0.96 Å and k = 1.5 for methyl H atoms, C—H = 0.93 Å and k = 1.2 for aromatic H atoms, N—H = 0.85 Å and k = 1.2, and O—H = 0.85 Å and k = 1.5.

Computing details top

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. (a) Displacement ellipsoid plot of (I), drawn at the 40% probability level. (b) Hydrogen-bonding scheme for (I) (dashed lines). In both, only the major part of the disordered perchlorate anion is drawn. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, -y, -z.]
[Figure 2] Fig. 2. (a) Displacement ellipsoid plot of (II), drawn at the 40% probability level. (b) Hydrogen-bonding scheme for (II) (dashed lines). [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 3] Fig. 3. Ball-and-stick plot of (III), showing its intramolecular hydrogen-bonding scheme (dashed lines).
[Figure 4] Fig. 4. Schematic superposition of (I) (full lines) and (II) (broken lines), where only the CuN4 cores were included in a least-squares match. Note the almost perfect fit displayed by the L ligands and the (rotational) misfit in the pendant perchlorate anions. [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 5] Fig. 5. Schematic representation of the configurations in (I), (II) and (III). Encircled are the critical zones highlighting the differences between the (I)–(II) pair and (III). [Symmetry code: (i) -x + 1, -y + 1, -z + 1.]
[Figure 6] Fig. 6. A packing view of (I), showing the one-dimensional chains running in the [011] direction. Dashed lines indicate hydrogen bonds.
[Figure 7] Fig. 7. A packing view of (II), with molecules drawn with thin lines lying at x = 0 and those drawn with heavy lines lying at x = 1/2.
(I) (3,10-C-meso-3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II) 1.2-hydrate top
Crystal data top
[Cu(ClO4)2(C18H40N4)]·1.2H2OZ = 1
Mr = 596.61F(000) = 315.0
Triclinic, P1Dx = 1.473 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.5783 (10) ÅCell parameters from 2039 reflections
b = 8.7819 (12) Åθ = 3.7–29.0°
c = 10.2156 (13) ŵ = 1.06 mm1
α = 114.835 (13)°T = 294 K
β = 98.036 (10)°Block, red
γ = 98.616 (11)°0.35 × 0.25 × 0.20 mm
V = 672.67 (17) Å3
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
3193 independent reflections
Radiation source: fine-focus sealed tube2285 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
ω scans, thick slicesθmax = 29.1°, θmin = 3.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1111
Tmin = 0.72, Tmax = 0.82k = 1111
9475 measured reflectionsl = 1313
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.170H atoms treated by a mixture of independent and constrained refinement
S = 0.93 w = 1/[σ2(Fo2) + (0.0891P)2 + 0.8414P]
where P = (Fo2 + 2Fc2)/3
3193 reflections(Δ/σ)max = 0.001
183 parametersΔρmax = 0.73 e Å3
97 restraintsΔρmin = 0.49 e Å3
Crystal data top
[Cu(ClO4)2(C18H40N4)]·1.2H2Oγ = 98.616 (11)°
Mr = 596.61V = 672.67 (17) Å3
Triclinic, P1Z = 1
a = 8.5783 (10) ÅMo Kα radiation
b = 8.7819 (12) ŵ = 1.06 mm1
c = 10.2156 (13) ÅT = 294 K
α = 114.835 (13)°0.35 × 0.25 × 0.20 mm
β = 98.036 (10)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
3193 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2285 reflections with I > 2σ(I)
Tmin = 0.72, Tmax = 0.82Rint = 0.057
9475 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05597 restraints
wR(F2) = 0.170H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.73 e Å3
3193 reflectionsΔρmin = 0.49 e Å3
183 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.50000.50000.50000.0396 (2)
N10.4193 (4)0.4998 (4)0.3045 (3)0.0432 (7)
H1N0.48500.44730.24590.052*
N20.3720 (4)0.2576 (4)0.4358 (3)0.0399 (7)
H2N0.43790.19060.38990.048*
C10.4601 (5)0.6810 (5)0.3304 (5)0.0516 (9)
H1A0.38210.74100.37770.062*
H1B0.45570.68530.23670.062*
C20.2487 (5)0.4023 (5)0.2150 (5)0.0518 (10)
C30.2286 (5)0.2165 (5)0.1939 (4)0.0499 (9)
H3A0.13240.14700.11630.060*
H3B0.32010.17500.15740.060*
C40.2151 (4)0.1818 (5)0.3250 (4)0.0435 (8)
H40.13330.23810.37130.052*
C50.3710 (5)0.2314 (5)0.5712 (4)0.0462 (9)
H50.35240.10750.54210.055*
C60.2299 (9)0.3967 (8)0.0608 (6)0.094 (2)
H6A0.32010.36150.02010.141*
H6B0.22650.50920.06940.141*
H6C0.13130.31590.00310.141*
C70.1256 (5)0.4880 (6)0.2930 (7)0.0729 (15)
H7A0.02170.40850.25320.109*
H7B0.11920.58810.27830.109*
H7C0.15790.52180.39690.109*
C80.1590 (5)0.0120 (5)0.2735 (5)0.0593 (11)
H8A0.05480.05460.20640.089*
H8B0.15160.03300.35760.089*
H8C0.23540.07000.22400.089*
C90.2394 (6)0.2996 (6)0.6470 (5)0.0617 (11)
H9A0.24540.41580.66140.093*
H9B0.25390.29790.74130.093*
H9C0.13550.22840.58650.093*
O1W0.5853 (11)0.2881 (8)0.0354 (8)0.094 (3)0.60 (2)
H1WB0.519 (13)0.197 (9)0.031 (10)0.141*0.60 (2)
H1WA0.618 (16)0.263 (14)0.105 (9)0.141*0.60 (2)
Cl10.72465 (13)0.12868 (15)0.28330 (15)0.0532 (4)0.922 (3)
O30.8372 (4)0.1240 (5)0.3979 (4)0.0814 (12)0.922 (3)
O10.6966 (7)0.2981 (5)0.3343 (6)0.0854 (12)0.922 (3)
O20.7911 (5)0.0887 (6)0.1564 (4)0.0908 (14)0.922 (3)
O40.5759 (4)0.0117 (5)0.2537 (5)0.0791 (13)0.922 (3)
Cl1'0.7019 (16)0.1550 (18)0.2246 (19)0.0532 (4)0.078 (3)
O3'0.699 (4)0.191 (5)0.101 (3)0.0814 (12)0.078 (3)
O1'0.684 (6)0.302 (4)0.348 (4)0.0854 (12)0.078 (3)
O2'0.852 (3)0.115 (6)0.261 (4)0.0908 (14)0.078 (3)
O4'0.572 (4)0.012 (5)0.189 (5)0.0791 (13)0.078 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0338 (3)0.0382 (4)0.0424 (4)0.0018 (2)0.0053 (2)0.0174 (3)
N10.0450 (17)0.0383 (16)0.0443 (17)0.0071 (13)0.0103 (13)0.0174 (13)
N20.0370 (15)0.0378 (16)0.0435 (16)0.0080 (12)0.0115 (12)0.0166 (13)
C10.053 (2)0.048 (2)0.051 (2)0.0045 (18)0.0040 (18)0.0253 (19)
C20.048 (2)0.050 (2)0.047 (2)0.0023 (17)0.0038 (17)0.0198 (18)
C30.047 (2)0.045 (2)0.043 (2)0.0026 (16)0.0026 (16)0.0114 (17)
C40.0391 (19)0.0356 (18)0.047 (2)0.0038 (14)0.0083 (15)0.0124 (16)
C50.048 (2)0.0383 (19)0.051 (2)0.0022 (16)0.0088 (17)0.0227 (17)
C60.118 (5)0.083 (4)0.057 (3)0.019 (3)0.022 (3)0.037 (3)
C70.042 (2)0.054 (3)0.106 (4)0.011 (2)0.001 (2)0.026 (3)
C80.050 (2)0.040 (2)0.070 (3)0.0036 (17)0.002 (2)0.017 (2)
C90.063 (3)0.066 (3)0.054 (2)0.002 (2)0.020 (2)0.026 (2)
O1W0.132 (7)0.065 (4)0.076 (5)0.012 (4)0.015 (4)0.030 (4)
Cl10.0441 (6)0.0503 (6)0.0659 (8)0.0112 (4)0.0200 (5)0.0243 (6)
O30.064 (2)0.091 (3)0.087 (3)0.017 (2)0.005 (2)0.042 (2)
O10.081 (3)0.058 (2)0.122 (3)0.0243 (18)0.042 (2)0.037 (2)
O20.094 (3)0.111 (4)0.069 (3)0.035 (3)0.042 (2)0.031 (3)
O40.055 (2)0.071 (2)0.109 (4)0.0029 (17)0.016 (2)0.043 (3)
Cl1'0.0441 (6)0.0503 (6)0.0659 (8)0.0112 (4)0.0200 (5)0.0243 (6)
O3'0.064 (2)0.091 (3)0.087 (3)0.017 (2)0.005 (2)0.042 (2)
O1'0.081 (3)0.058 (2)0.122 (3)0.0243 (18)0.042 (2)0.037 (2)
O2'0.094 (3)0.111 (4)0.069 (3)0.035 (3)0.042 (2)0.031 (3)
O4'0.055 (2)0.071 (2)0.109 (4)0.0029 (17)0.016 (2)0.043 (3)
Geometric parameters (Å, º) top
Cu1—N1i2.020 (3)C5—C1i1.520 (6)
Cu1—N12.020 (3)C5—H50.9800
Cu1—N2i2.023 (3)C6—H6A0.9600
Cu1—N22.023 (3)C6—H6B0.9600
Cu1—O1i2.833 (4)C6—H6C0.9600
Cu1—O12.833 (4)C7—H7A0.9600
N1—C11.476 (5)C7—H7B0.9600
N1—C21.518 (5)C7—H7C0.9600
N1—H1N0.9100C8—H8A0.9600
N2—C41.486 (5)C8—H8B0.9600
N2—C51.496 (5)C8—H8C0.9600
N2—H2N0.9100C9—H9A0.9600
C1—C5i1.520 (6)C9—H9B0.9600
C1—H1A0.9700C9—H9C0.9600
C1—H1B0.9700O1W—H1WB0.850 (10)
C2—C71.511 (7)O1W—H1WA0.851 (10)
C2—C31.532 (6)Cl1—O21.418 (3)
C2—C61.539 (6)Cl1—O31.428 (3)
C3—C41.509 (5)Cl1—O41.419 (3)
C3—H3A0.9700Cl1—O11.427 (3)
C3—H3B0.9700Cl1'—O3'1.422 (4)
C4—C81.528 (5)Cl1'—O4'1.423 (4)
C4—H40.9800Cl1'—O2'1.422 (4)
C5—C91.513 (6)Cl1'—O1'1.423 (4)
N1i—Cu1—N2i94.25 (12)C3—C4—H4108.2
N1—Cu1—N2i85.75 (12)C8—C4—H4108.2
N1i—Cu1—N285.75 (12)N2—C5—C9112.1 (3)
N1—Cu1—N294.25 (12)N2—C5—C1i105.9 (3)
N1i—Cu1—O1i81.43 (14)C9—C5—C1i113.0 (4)
N1—Cu1—O1i98.57 (14)N2—C5—H5108.6
N2i—Cu1—O1i78.20 (13)C9—C5—H5108.6
N2—Cu1—O1i101.80 (13)C1i—C5—H5108.6
N1i—Cu1—O198.57 (14)C2—C6—H6A109.5
N1—Cu1—O181.43 (14)C2—C6—H6B109.5
N2i—Cu1—O1101.80 (13)H6A—C6—H6B109.5
N2—Cu1—O178.20 (13)C2—C6—H6C109.5
C1—N1—C2114.2 (3)H6A—C6—H6C109.5
C1—N1—Cu1106.5 (2)H6B—C6—H6C109.5
C2—N1—Cu1120.1 (2)C2—C7—H7A109.5
C1—N1—H1N104.9C2—C7—H7B109.5
C2—N1—H1N104.9H7A—C7—H7B109.5
Cu1—N1—H1N104.9C2—C7—H7C109.5
C4—N2—C5114.2 (3)H7A—C7—H7C109.5
C4—N2—Cu1122.3 (2)H7B—C7—H7C109.5
C5—N2—Cu1108.0 (2)C4—C8—H8A109.5
C4—N2—H2N103.3C4—C8—H8B109.5
C5—N2—H2N103.3H8A—C8—H8B109.5
Cu1—N2—H2N103.3C4—C8—H8C109.5
N1—C1—C5i109.6 (3)H8A—C8—H8C109.5
N1—C1—H1A109.8H8B—C8—H8C109.5
C5i—C1—H1A109.8C5—C9—H9A109.5
N1—C1—H1B109.8C5—C9—H9B109.5
C5i—C1—H1B109.8H9A—C9—H9B109.5
H1A—C1—H1B108.2C5—C9—H9C109.5
C7—C2—N1110.6 (3)H9A—C9—H9C109.5
C7—C2—C3111.7 (4)H9B—C9—H9C109.5
N1—C2—C3107.4 (3)H1WB—O1W—H1WA105.1 (17)
C7—C2—C6110.4 (5)O2—Cl1—O3109.2 (2)
N1—C2—C6108.9 (4)O2—Cl1—O4112.4 (3)
C3—C2—C6107.7 (4)O3—Cl1—O4108.8 (2)
C4—C3—C2118.7 (3)O2—Cl1—O1109.4 (3)
C4—C3—H3A107.6O3—Cl1—O1108.7 (3)
C2—C3—H3A107.6O4—Cl1—O1108.3 (2)
C4—C3—H3B107.6Cl1—O1—Cu1140.1 (3)
C2—C3—H3B107.6O3'—Cl1'—O4'109.4 (5)
H3A—C3—H3B107.1O3'—Cl1'—O2'109.6 (5)
N2—C4—C3110.0 (3)O4'—Cl1'—O2'109.5 (5)
N2—C4—C8112.1 (3)O3'—Cl1'—O1'109.5 (5)
C3—C4—C8110.0 (3)O4'—Cl1'—O1'109.3 (5)
N2—C4—H4108.2O2'—Cl1'—O1'109.5 (5)
N2i—Cu1—N1—C114.7 (3)C5—N2—C4—C3179.5 (3)
N2—Cu1—N1—C1165.3 (3)Cu1—N2—C4—C346.2 (4)
O1i—Cu1—N1—C162.7 (3)C5—N2—C4—C857.7 (4)
O1—Cu1—N1—C1117.3 (3)Cu1—N2—C4—C8169.0 (3)
N2i—Cu1—N1—C2146.4 (3)C2—C3—C4—N268.5 (4)
N2—Cu1—N1—C233.6 (3)C2—C3—C4—C8167.5 (4)
O1i—Cu1—N1—C269.0 (3)C4—N2—C5—C955.8 (4)
O1—Cu1—N1—C2111.0 (3)Cu1—N2—C5—C983.9 (3)
N1i—Cu1—N2—C4150.3 (3)C4—N2—C5—C1i179.4 (3)
N1—Cu1—N2—C429.7 (3)Cu1—N2—C5—C1i39.8 (3)
O1i—Cu1—N2—C470.0 (3)O2—Cl1—O1—Cu1155.8 (4)
O1—Cu1—N2—C4110.0 (3)O3—Cl1—O1—Cu185.0 (5)
N1i—Cu1—N2—C514.6 (2)O4—Cl1—O1—Cu133.1 (6)
N1—Cu1—N2—C5165.4 (2)N1i—Cu1—O1—Cl162.7 (5)
O1i—Cu1—N2—C565.7 (3)N1—Cu1—O1—Cl1117.3 (5)
O1—Cu1—N2—C5114.3 (3)N2i—Cu1—O1—Cl1158.9 (5)
C2—N1—C1—C5i176.4 (3)N2—Cu1—O1—Cl121.1 (5)
Cu1—N1—C1—C5i41.5 (4)O4'—Cl1'—O3'—O1'119.8 (7)
C1—N1—C2—C759.9 (5)O2'—Cl1'—O3'—O1'120.1 (7)
Cu1—N1—C2—C768.5 (4)O3'—Cl1'—O1'—O4'119.8 (7)
C1—N1—C2—C3178.1 (3)O2'—Cl1'—O1'—O4'120.0 (7)
Cu1—N1—C2—C353.6 (4)O3'—Cl1'—O2'—O1'120.1 (7)
C1—N1—C2—C661.6 (5)O4'—Cl1'—O2'—O1'119.9 (7)
Cu1—N1—C2—C6170.0 (3)O4'—O1'—O2'—Cl1'35.3 (4)
C7—C2—C3—C449.0 (5)O3'—Cl1'—O4'—O1'119.9 (7)
N1—C2—C3—C472.3 (4)O2'—Cl1'—O4'—O1'119.9 (7)
C6—C2—C3—C4170.4 (4)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1W0.912.383.261 (9)163
N2—H2N···O40.912.233.138 (6)173
C7—H7C···O1i0.962.523.437 (7)159
C9—H9A···O1i0.962.473.412 (7)168
O1W—H1WA···O20.85 (1)2.44 (9)3.137 (9)139 (12)
O1W—H1WA···O10.85 (1)2.22 (4)3.029 (9)159 (11)
O1W—H1WB···O4ii0.85 (1)2.17 (6)2.967 (8)155 (12)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z.
(II) (3,10-C-meso-3,5,7,7,10,12,14,14-Octamethyl-1,4,8,11-tetraazacyclotetradecane)bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C18H40N4)]F(000) = 1212
Mr = 574.98Dx = 1.451 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 10594 reflections
a = 9.0206 (2) Åθ = 3.8–28.9°
b = 16.7979 (4) ŵ = 1.08 mm1
c = 17.3754 (5) ÅT = 294 K
V = 2632.84 (11) Å3Prism, blue
Z = 40.35 × 0.30 × 0.23 mm
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
3311 independent reflections
Radiation source: fine-focus sealed tube2614 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
ω scans, thick slicesθmax = 29.0°, θmin = 4.1°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1211
Tmin = 0.69, Tmax = 0.78k = 2222
40587 measured reflectionsl = 2323
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0452P)2 + 2.9167P]
where P = (Fo2 + 2Fc2)/3
3311 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
[Cu(ClO4)2(C18H40N4)]V = 2632.84 (11) Å3
Mr = 574.98Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.0206 (2) ŵ = 1.08 mm1
b = 16.7979 (4) ÅT = 294 K
c = 17.3754 (5) Å0.35 × 0.30 × 0.23 mm
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
3311 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2614 reflections with I > 2σ(I)
Tmin = 0.69, Tmax = 0.78Rint = 0.037
40587 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.07Δρmax = 0.58 e Å3
3311 reflectionsΔρmin = 0.37 e Å3
155 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.03007 (13)
N10.5404 (2)0.52047 (11)0.38696 (11)0.0316 (4)
H1N0.47850.48660.36170.038*
N20.3222 (2)0.57382 (11)0.50517 (10)0.0322 (4)
H2N0.24540.54240.48990.039*
C10.6913 (3)0.48889 (16)0.37144 (15)0.0412 (6)
H1A0.76510.52640.38970.049*
H1B0.70500.48200.31650.049*
C20.5087 (3)0.60077 (15)0.35222 (14)0.0377 (5)
C30.3492 (3)0.62349 (15)0.37188 (14)0.0392 (5)
H3A0.32240.66840.33970.047*
H3B0.28620.57940.35670.047*
C40.3101 (3)0.64493 (14)0.45420 (15)0.0410 (6)
H40.37910.68580.47240.049*
C50.2891 (3)0.58991 (15)0.58827 (14)0.0379 (5)
H50.18490.60590.59270.046*
C60.5180 (4)0.5943 (2)0.26429 (17)0.0628 (9)
H6A0.61700.57970.24960.094*
H6B0.49310.64460.24160.094*
H6C0.44980.55440.24660.094*
C70.6183 (3)0.66191 (16)0.3822 (2)0.0560 (8)
H7A0.62570.65740.43710.084*
H7B0.58480.71440.36890.084*
H7C0.71380.65260.35950.084*
C80.1528 (4)0.6789 (2)0.4556 (2)0.0660 (9)
H8A0.08460.63980.43630.099*
H8B0.14850.72570.42390.099*
H8C0.12650.69260.50750.099*
C90.3847 (3)0.65576 (17)0.62169 (17)0.0516 (7)
H9A0.48700.64540.61010.077*
H9B0.37160.65760.67650.077*
H9C0.35610.70590.59970.077*
Cl10.16768 (7)0.40599 (4)0.38324 (4)0.04963 (19)
O10.2652 (4)0.40146 (17)0.44882 (15)0.0861 (8)
O20.2631 (3)0.42568 (17)0.31962 (14)0.0775 (7)
O30.0934 (4)0.33385 (16)0.3735 (2)0.0996 (10)
O40.0700 (3)0.47002 (17)0.3996 (2)0.1034 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0301 (2)0.0285 (2)0.0316 (2)0.00372 (15)0.00700 (15)0.00055 (15)
N10.0297 (9)0.0321 (9)0.0329 (10)0.0021 (8)0.0048 (8)0.0026 (8)
N20.0294 (9)0.0301 (9)0.0371 (10)0.0012 (8)0.0030 (8)0.0033 (7)
C10.0324 (12)0.0490 (14)0.0423 (13)0.0026 (10)0.0134 (10)0.0010 (11)
C20.0400 (12)0.0371 (12)0.0361 (12)0.0021 (10)0.0014 (10)0.0054 (10)
C30.0397 (13)0.0368 (12)0.0410 (13)0.0034 (10)0.0047 (10)0.0049 (10)
C40.0437 (13)0.0303 (11)0.0489 (14)0.0063 (10)0.0034 (11)0.0010 (10)
C50.0299 (11)0.0416 (13)0.0423 (13)0.0068 (10)0.0096 (10)0.0067 (10)
C60.068 (2)0.083 (2)0.0375 (15)0.0095 (17)0.0067 (14)0.0124 (15)
C70.0481 (15)0.0379 (14)0.082 (2)0.0105 (12)0.0052 (15)0.0052 (14)
C80.064 (2)0.0592 (19)0.075 (2)0.0334 (16)0.0099 (17)0.0083 (16)
C90.0552 (16)0.0449 (14)0.0549 (16)0.0080 (13)0.0023 (13)0.0181 (13)
Cl10.0419 (3)0.0424 (3)0.0646 (4)0.0072 (3)0.0027 (3)0.0043 (3)
O10.100 (2)0.0914 (19)0.0664 (15)0.0083 (16)0.0196 (15)0.0034 (14)
O20.0775 (16)0.0961 (19)0.0589 (13)0.0171 (14)0.0028 (13)0.0070 (13)
O30.093 (2)0.0633 (16)0.143 (3)0.0362 (15)0.0096 (19)0.0193 (17)
O40.0609 (16)0.0619 (15)0.187 (3)0.0083 (14)0.0214 (19)0.003 (2)
Geometric parameters (Å, º) top
Cu1—N12.0270 (19)C4—C81.530 (4)
Cu1—N1i2.0270 (19)C4—H40.9800
Cu1—N22.0295 (19)C5—C1i1.508 (4)
Cu1—N2i2.0295 (19)C5—C91.518 (4)
Cu1—O1i2.831 (3)C5—H50.9800
Cu1—O12.831 (3)C6—H6A0.9600
N1—C11.486 (3)C6—H6B0.9600
N1—C21.505 (3)C6—H6C0.9600
N1—H1N0.9100C7—H7A0.9600
N2—C41.491 (3)C7—H7B0.9600
N2—C51.499 (3)C7—H7C0.9600
N2—H2N0.9100C8—H8A0.9600
C1—C5i1.508 (3)C8—H8B0.9600
C1—H1A0.9700C8—H8C0.9600
C1—H1B0.9700C9—H9A0.9600
C2—C71.517 (4)C9—H9B0.9600
C2—C31.527 (3)C9—H9C0.9600
C2—C61.534 (4)Cl1—O31.395 (2)
C3—C41.517 (3)Cl1—O41.419 (3)
C3—H3A0.9700Cl1—O21.439 (2)
C3—H3B0.9700Cl1—O11.442 (3)
N1—Cu1—N1i180.000 (1)H3A—C3—H3B107.0
N1—Cu1—N294.66 (7)N2—C4—C3110.66 (19)
N1i—Cu1—N285.34 (7)N2—C4—C8111.0 (2)
N1—Cu1—N2i85.34 (7)C3—C4—C8108.7 (2)
N1i—Cu1—N2i94.66 (7)N2—C4—H4108.8
N2—Cu1—N2i180.0C3—C4—H4108.8
N1—Cu1—O1i94.06 (8)C8—C4—H4108.8
N1i—Cu1—O1i85.94 (8)N2—C5—C1i105.40 (18)
N2—Cu1—O1i102.72 (9)N2—C5—C9112.7 (2)
N2i—Cu1—O1i77.28 (9)C1i—C5—C9113.3 (2)
N1—Cu1—O185.94 (8)N2—C5—H5108.4
N1i—Cu1—O194.06 (8)C1i—C5—H5108.4
N2—Cu1—O177.28 (9)C9—C5—H5108.4
N2i—Cu1—O1102.72 (9)C2—C6—H6A109.5
O1i—Cu1—O1180.0C2—C6—H6B109.5
C1—N1—C2114.89 (18)H6A—C6—H6B109.5
C1—N1—Cu1106.25 (15)C2—C6—H6C109.5
C2—N1—Cu1120.44 (14)H6A—C6—H6C109.5
C1—N1—H1N104.5H6B—C6—H6C109.5
C2—N1—H1N104.5C2—C7—H7A109.5
Cu1—N1—H1N104.5C2—C7—H7B109.5
C4—N2—C5114.40 (18)H7A—C7—H7B109.5
C4—N2—Cu1121.41 (15)C2—C7—H7C109.5
C5—N2—Cu1108.07 (14)H7A—C7—H7C109.5
C4—N2—H2N103.6H7B—C7—H7C109.5
C5—N2—H2N103.6C4—C8—H8A109.5
Cu1—N2—H2N103.6C4—C8—H8B109.5
N1—C1—C5i109.66 (19)H8A—C8—H8B109.5
N1—C1—H1A109.7C4—C8—H8C109.5
C5i—C1—H1A109.7H8A—C8—H8C109.5
N1—C1—H1B109.7H8B—C8—H8C109.5
C5i—C1—H1B109.7C5—C9—H9A109.5
H1A—C1—H1B108.2C5—C9—H9B109.5
N1—C2—C7110.2 (2)H9A—C9—H9B109.5
N1—C2—C3108.23 (19)C5—C9—H9C109.5
C7—C2—C3111.6 (2)H9A—C9—H9C109.5
N1—C2—C6109.0 (2)H9B—C9—H9C109.5
C7—C2—C6110.7 (2)O3—Cl1—O4112.60 (19)
C3—C2—C6107.0 (2)O3—Cl1—O2113.16 (18)
C4—C3—C2119.3 (2)O4—Cl1—O2110.55 (18)
C4—C3—H3A107.5O3—Cl1—O1110.10 (19)
C2—C3—H3A107.5O4—Cl1—O1105.1 (2)
C4—C3—H3B107.5O2—Cl1—O1104.72 (17)
C2—C3—H3B107.5Cl1—O1—Cu1132.38 (16)
N2—Cu1—N1—C1165.81 (15)C1—N1—C2—C662.7 (3)
N2i—Cu1—N1—C114.19 (15)Cu1—N1—C2—C6168.19 (19)
O1i—Cu1—N1—C162.68 (16)N1—C2—C3—C470.6 (3)
O1—Cu1—N1—C1117.32 (16)C7—C2—C3—C450.8 (3)
N2—Cu1—N1—C232.98 (17)C6—C2—C3—C4172.1 (2)
N2i—Cu1—N1—C2147.02 (17)C5—N2—C4—C3178.52 (19)
O1i—Cu1—N1—C270.15 (17)Cu1—N2—C4—C346.0 (3)
O1—Cu1—N1—C2109.85 (17)C5—N2—C4—C860.8 (3)
N1—Cu1—N2—C429.46 (18)Cu1—N2—C4—C8166.7 (2)
N1i—Cu1—N2—C4150.54 (18)C2—C3—C4—N267.7 (3)
O1i—Cu1—N2—C465.77 (18)C2—C3—C4—C8170.2 (2)
O1—Cu1—N2—C4114.23 (18)C4—N2—C5—C1i179.7 (2)
N1—Cu1—N2—C5164.56 (15)Cu1—N2—C5—C1i41.1 (2)
N1i—Cu1—N2—C515.44 (15)C4—N2—C5—C955.6 (3)
O1i—Cu1—N2—C569.33 (15)Cu1—N2—C5—C983.0 (2)
O1—Cu1—N2—C5110.67 (15)O3—Cl1—O1—Cu1166.2 (2)
C2—N1—C1—C5i177.8 (2)O4—Cl1—O1—Cu172.3 (3)
Cu1—N1—C1—C5i42.0 (2)O2—Cl1—O1—Cu144.3 (3)
C1—N1—C2—C759.0 (3)N1—Cu1—O1—Cl133.1 (2)
Cu1—N1—C2—C770.1 (2)N1i—Cu1—O1—Cl1146.9 (2)
C1—N1—C2—C3178.7 (2)N2—Cu1—O1—Cl162.6 (2)
Cu1—N1—C2—C352.2 (2)N2i—Cu1—O1—Cl1117.4 (2)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.912.313.188 (3)161
N2—H2N···O40.912.543.403 (3)159
N2—H2N···O10.912.483.099 (3)126
C7—H7A···O1i0.962.423.295 (4)151
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formula[Cu(ClO4)2(C18H40N4)]·1.2H2O[Cu(ClO4)2(C18H40N4)]
Mr596.61574.98
Crystal system, space groupTriclinic, P1Orthorhombic, Pbca
Temperature (K)294294
a, b, c (Å)8.5783 (10), 8.7819 (12), 10.2156 (13)9.0206 (2), 16.7979 (4), 17.3754 (5)
α, β, γ (°)114.835 (13), 98.036 (10), 98.616 (11)90, 90, 90
V3)672.67 (17)2632.84 (11)
Z14
Radiation typeMo KαMo Kα
µ (mm1)1.061.08
Crystal size (mm)0.35 × 0.25 × 0.200.35 × 0.30 × 0.23
Data collection
DiffractometerOxford Gemini S Ultra CCD area-detector
diffractometer
Oxford Gemini S Ultra CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.72, 0.820.69, 0.78
No. of measured, independent and
observed [I > 2σ(I)] reflections
9475, 3193, 2285 40587, 3311, 2614
Rint0.0570.037
(sin θ/λ)max1)0.6830.681
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.170, 0.93 0.044, 0.116, 1.07
No. of reflections31933311
No. of parameters183155
No. of restraints970
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.73, 0.490.58, 0.37

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) for (I) top
Cu1—N12.020 (3)Cu1—O12.833 (4)
Cu1—N22.023 (3)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1W0.912.383.261 (9)163
N2—H2N···O40.912.233.138 (6)173
C7—H7C···O1i0.962.523.437 (7)159
C9—H9A···O1i0.962.473.412 (7)168
O1W—H1WA···O20.851 (10)2.44 (9)3.137 (9)139 (12)
O1W—H1WA···O10.851 (10)2.22 (4)3.029 (9)159 (11)
O1W—H1WB···O4ii0.850 (10)2.17 (6)2.967 (8)155 (12)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z.
Selected bond lengths (Å) for (II) top
Cu1—N12.0270 (19)Cu1—O12.831 (3)
Cu1—N22.0295 (19)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.912.313.188 (3)161
N2—H2N···O40.912.543.403 (3)159
N2—H2N···O10.912.483.099 (3)126
C7—H7A···O1i0.962.423.295 (4)151
Symmetry code: (i) x+1, y+1, z+1.
Comparison of reported structures having the same L ligand and similar chiral sites top
CSD refode (Reference)Space groupCation (symmetry)Sequence (type)
DEFJIH (Lee et al., 1985)P21/cCu (1)RRRR–SSSS (1)
OCMENH (Ferguson et al., 1990)P21/nNi (1)RRRR–SSSS (1)
POTPUJ (Hazari et al., 1997)P21/cCu (1)RRRR–SSSS (1)
QOPJIO (Horn et al., 2001)P1Co (1)RRRR–SSSS (1)
(I) (this work)PbcaCu (1)RRRR–SSSS (1)
(II) (this work)P1Cu (1)RRRR–SSSS (1)
IDAQIP (Roy, Hazari, Barua & Tiekink, 2011)PbcaZn (1)SRRR–SSRS (2)
LIFHAJ (Choi & Suh, 1999)P1Zn (1)SRRR–SSRS (2)
YAVFOS (Roy et al., 2012)C2/cCd (1)SRRR–SSRS (2)
BAQHAC (Choi et al., 1999)P1Ni (1)RSSR–RSSS (3)
MAKPOF (Roy et al., 2010)C2/cCd (1)RSSR–RSSS (3)
ECUREA (Lin et al., 2006)P212121Ni (1)SSSR–SSRS (4)
(III) (Lin et al., 2006)P21/cCu (1)RRRS–SRSR (5)
EQOGIB (Roy, Hazari, Dey et al., 2011)P1Zn (1)RRSR–RSSS (6)
OCMENI (Ito et al., 1981)P43212Ni (1)SSSR–SSSR (7)
VIVSUO (Bembi et al., 1991)P21/cCo (1)SRSR–RSRS (8)
 

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