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The three transition-metal complexes, (meso-5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetra­azacyclo­tetra­decane-[kappa]4N)bis­(perchlorato-[kappa]O)copper(II), [Cu(ClO4)2(C18H40N4)], (I), (meso-5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetra­azacyclo­tetra­decane-[kappa]4N)bis­(nitrato-[kappa]O)zinc(II), [Zn(NO3)2(C18H40N4)], (II), and aqua­chlorido­(meso-5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetraazacyclo­tetra­decane-[kappa]4N)copper(II) chloride, [CuCl(C18H40N4)(H2O)]Cl, (III), are described. The mol­ecules display a very similarly distorted 4+2 octa­hedral environment for the cation [located at an inversion centre in (I) and (II)], defined by the macrocycle N4 group in the equatorial sites and two further ligands in trans-axial positions [two O-ClO3 ligands in (I), two O-NO2 ligands in (II) and one chloride and one aqua ligand in (III)]. The most significant difference in mol­ecular shape resides in these axial ligands, the effect of which on the intra- and inter­molecular hydrogen bonding is discussed. In the case of (I), all strong hydrogen-bond donors are saturated in intra­molecular inter­actions, while weak inter­molecular C-H...O contacts result in a three-dimensional network. In (II) and (III), instead, there are N-H and O-H donors left over for inter­molecular inter­actions, giving rise to the formation of strongly linked but weakly inter­acting chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113018465/sk3501sup1.cif
Contains datablocks I, II, III, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501IIIsup4.hkl
Contains datablock III

CCDC references: 962900; 962901; 962902

Introduction top

The importance of synthetic macrocyclic complexes is due to their presence in many naturally occurring metal complexes of biological significance, such as haemoglobin, vitamin B12, chloro­phyll etc., which play vital roles in biology (Reid & Schroder, 1990; Bernhardt & Lawrance, 1990) Among the most versatile macrocyclic ligands synthesized, saturated tetra­aza­macrocycles have a key role, since they are capable of producing inert stable complexes with a number of different metal ions of biomedical importance, a fact which has attracted the inter­est of chemists due to their impact in various industrial, biochemical and catalytic processes (Kimura et al., 1992, 1994). Metal complexes of the 14-membered tetra­aza­macrocyclic ligands, such as the ones reported here, have been studied in radioimmunotherapy and magnetic resonance imaging (Konig et al., 1996; Norman et al., 1995), in pharmacological endeavours (Hollinshead & Smith, 1990) and in crystal engineering (Suh et al., 2006). Among their biologically relevant properties, 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 are to be mentioned (Arai et al., 1998; Gao et al., 2010).

The strong sustained research on this subject over the last 50 years has been summarized in a recent review (Curtis, 2012), where a large number of different N-substituted (N-methyl, N-propyl or N-allyl) macrocyclic ligands complexed to a variety of cations (e.g. Cu, Co, Cr, Zn, Cd and Pd) were analysed.

As part of our inter­est in macrocyclic complexes, we have recently discussed the slight molecular distortions taking place, and the rather large hydrogen-bonding changes they give rise to, in three CuII complexes having different isomers of 3,5,7,7,10,12,14,14-o­cta­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane, viz. the centrosymmetric L1, with an RRRRSSSS chiral centre distribution, and the non-centrosymmetric L2 with an RRRSSRSR one. These complexes had in common two axially coordinated ClO4 counter-anions (Nath et al., 2013).

We discuss now a different but somewhat related issue: three transition metal (Tr) complexes with one (and the same) hexa­methyl­ated ligand closely related to L1, viz. meso-5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane (L), but now having different axial ligands, namely [CuII(ClO4)2(L)], (I), [ZnII(NO3)2(L)], (II), and [CuIICl(L)(H2O)]Cl, (III), and the effect which these latter ligands have on both the intra- and inter­molecular hydrogen-bonding inter­actions.

At this stage it should be mentioned that some closely related structures to the ones presented here have already been reported in the literature, though without the detailed hydrogen-bonding analysis mentioned above and which is the main scope of this paper. Among the most relevant we will mention two relatives of (I), an isomorph with CoII instead of CuII and the same 5,7,7,12,14,14-hexa­methyl L ligand (Bakac & Espenson, 1990), and an isostructural variant having the same CuII cation but bound to a 5,5,7,12,12,14-hexa­methyl isomer of L (Kalita et al., 2011). There is also an isostructural variant of (III), reported by Temple et al. (1984), having CrIII (instead of CuII) as the central cation and NO3- (instead of Cl-) as the counter-anion.

Experimental top

Synthesis and crystallization top

For the synthesis of [Cu(ClO4)2(L)], (I), copper(II) perchlorate hexahydrate (0.479 g, 1.0 mmol) and meso-5,7,7,12,14,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane dihydrate (L.H2O [dihydrate = 2H2O?]; 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 blue salt solution while hot. The resulting mixture was allowed to evaporate slowly and dark-blue [Red in CIF tables - please clarify] crystals of (I) separated. These were filtered off and recrystallized from a minimum qu­antity of aqueous methanol (1:1 v/v) (yield 0.12 g). The product was again treated with di­bromo­pyridine to prepare the N-substituted ligand. However, the final product gave an identical IR spectrum to the initial diperchlorate complex, showing that no N-substitution had taken place.

For the synthesis of [Zn(NO3)2(L)], (II), L.H2O [dihydrate = 2H2O?] (0.320 g, 1.0 mmol) and zinc(II) nitrate hexahydrate (0.297 g, 1.0 mmol) were dissolved separately in hot methanol (20 ml) and mixed while hot. The solution was heated in a steam bath and the volume of the solution reduced to 10 ml. The solution was allowed to cool and the white [Red in CIF tables - please clarify] product, (II), was separated from the solution, washed with methanol followed by di­ethyl ether, and dried in a vacuum desiccator over silica gel.

For the synthesis of [CuCl(L)(H2O)]Cl, (III), (I) (0.541 g, 1.0 mmol) was added to hot methanol (50 ml) and, after dissolution by heating, a blue [From red crystals?] solution was obtained. A similar procedure was performed with potassium chloride (0.224 g, 3.0 mmol), KCl, resulting in a colourless solution. A mixture of both solutions gave a blue–violet solution, which was further heated for 30 min on a water bath and filtered to remove potassium perchlorate as a white solid. The resulting filtrate was dried to give a blue–violet [Red in CIF tables - please clarify] product, (III), and cooled to room temperature. After cooling, chloro­form (100 ml) was added and stirred. The light-blue–violet chloro­form extract was evaporated off to give the stable blue–violet final product, which was cooled and stored in a desiccator over silica gel.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All three macrocycles present the same SRS(SRS) chiral centre distribution, in an N1–N2–C4 sequence. 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 (III) posed some problems due to the large displacement parameter for atom O1W; they were not clearly seen in the difference map, 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 = 1.30 Å) ended up with the H atoms lying on clearly positive zones in the difference Fourier map and involved in strong hydrogen bonding, so this treatment of the water molecule as a rigid group was considered adequate. In all cases, H-atom displacement parameters were taken as Uiso(H) = xUeq(parent) [methyl C—H = 0.96 Å and x = 1.5; aromatic C—H = 0.93 Å and x = 1.2; N—H = 0.85 Å and x = 1.2; O—H = 0.85 Å and x = 1.5]. Some unresolved disorder as high as 0.8 e Å3 was found near the C2—C3 bond in (III).

Results and discussion top

Displacement ellipsoid plots for (I), (II), (III) are shown in Figs. 1, 2 and 3, respectively. They present a distorted o­cta­hedral disposition around the cation, which in (I) and (II) lie on a centre of symmetry, thus rendering only half of the molecule independent. In spite of the cation differences, the chlathrate (L)Tr nuclei (Tr = Cu or Zn) are geometrically similar, with a basal span of Tr—N distances and N—Tr—N angles of, respectively, 2.025 (2)–2.040 (2) Å and 90±4.38 (10)° for (I), 2.078 (2)–2.104 (2) Å and 90±4.42 (9)° for (II), and 2.0106 (17)–2.0555 (18) Å and 90±5.60 (7)° for (III).

Since one of the cations involved is CuII, the main differences are obviously found in the (Jahn–Teller-elongated) axial bonds, viz. 2.589 (3) and 2.8143 (6)–2.861 (2) Å for the CuII-containing complexes (I) and (III), respectively, versus 2.349 (2) Å for the ZnII-containing complex (II). Tables 2, 4 and 6 present the full coordination distances in all three compounds, while Fig. 4 presents a least-squares fit of the basal coordination planes, confirming that the molecular differences reside mainly in the orientation and bonding distances of the axial ligands. We shall see below the impact this has on the hydrogen-bonding schemes.

The 14-membered rings have the usual zigzag shape and present four equatorial and two axial methyl groups, the latter being trans to each other. Amine atoms N1 and N2 [and N1' and N2' in (III)] present their H atoms on the same side of the coordination plane and opposite to the neighbouring axial methyl group. Due to coordination, the 14-membered ligand generates four smaller rings, two six-membered ones in chair conformations and two five-membered ones in half-chair forms. There are six chiral centres in the L ligand (N1/N1', C4/C4' and N2/N2'), in an SRRSSR configuration.

In the same way, different characteristics and orientations of the axial ligands lead to different orientations between hydrogen-bonding donors and acceptors, either facilitating or hampering intra­molecular inter­actions.

In the case of (I), the perchlorate ligand coordinates to the cation through one of its O atoms (O2), leaving three potentially good acceptors ready for hydrogen bonding. The anionic group, which pivots on atom O2 and leans towards L, facilitates a double hydrogen-bonding inter­action involving amine atoms N1 and N2 (Table 3, first and second entries), defining two R(6) rings (A and B in Fig. 1; for details on graph-set notation, see Bernstein et al., 1995), and a weaker C—H···O inter­action (third entry), all of which have the double effect of strongly binding the anion to the molecule while cancelling any possibility of strong inter­molecular hydrogen bonds due to saturation of all suitable N—H donors. The result is a weak three-dimensional supra­molecular structure sustained by weak hydrogen bonds involving two different C—H groups and free atom O4 (Table 3, fourth and fifth entries). The first of these describes the inter­action defining broad (100) planes (Fig. 5a), while the second corresponds to the hydrogen bond which links planes together along [010] (Fig. 5b) to form the final three-dimensional structure. A very similar effect has been observed in the o­cta­methyl­ated counterpart of (I), [CuII(ClO4)2(L1)] (Nath et al., 2013).

In (II), the ligand is the planar nitrate anion which binds the ZnII cation through atom O1, thus leaving only two possible inter­active O atoms. Of these, atom O2 appears in a favourable position for an intra­molecular hydrogen bond with amine atom N1i [symmetry code: (i) -x + 1/2, -y + 1/2, -z + 1; Table 5, first entry], generating the usual R(6) ring (A in Fig. 2). There is in addition a weak C—H···O bond (Table 5, second entry) completing the scheme of intra­molecular contacts. As a consequence, amine atom N2 remains free to act as a donor and atom O3 as an acceptor for a single significant inter­molecular inter­action (Table 5, third entry) defining [101] chains. Fig. 6 shows details of this one-dimensional structure, which embeds inversion centres at the cation sites, and perpendicular twofold axes at the centres of the R22(12) loops (B in Fig. 6).

Finally, structure (III) presents a disrupting variant. The molecule is not centrosymmetric and there are two different axial ligands, one chloride anion (Cl1) and one neutral aqua ligand, which provides two efficient hydrogen-bond donors (H1WA and H1WB). There is, in addition, a second (noncoordinating) chloride counter-anion (Cl2). The intra­molecular scheme is rather similar to that in (II), with amine atom N1 making a hydrogen bond to one axial ligand (Table 7, first entry), defining a tight R(4) ring A (Fig. 3), and two weaker C—H..X bonds (X = Cl or O; Table 7, second and third entries) completing the intra­molecular scheme. This leaves amine atoms N2, N1' and N2' (now all independent) free to act as inter­molecular hydrogen-bonding donors in conjunction with the aqua H atoms, while having the chloride anions as acceptors. As a result, a number of linking hydrogen-bonding rings appear (B to E in Fig. 7), giving raise to the strongly connected [100] chain shown in Fig. 7.

The present discussion shows that the most significant difference in the hydrogen-bonding schemes in these three examples resides in the stronger (or weaker) acceptor character of the axial ligand(s) involved. In the case of (I), with its three available acceptor sites, all strong hydrogen-bonding donors in the macrocycle are saturated in intra­molecular inter­actions, with the weak inter­molecular contacts evenly distributed, and this provides for a smooth three-dimensional linkage. In (II) and (III), instead, there are N—H (and O—H) donors left over for inter­molecular inter­actions, giving rise to the formation of strongly linked, though weakly inter­acting, chains.

Related literature top

For related literature, see: Arai et al. (1998); Bakac & Espenson (1990); Bernhardt & Lawrance (1990); Bernstein et al. (1995); Curtis (2012); Gao et al. (2010); Hollinshead & Smith (1990); Kalita et al. (2011); Kimura et al. (1992, 1994); Konig et al. (1996); Nath et al. (2013); Norman et al. (1995); Reid & Schroder (1990); Roy, Hazari, Dey, Meah, Rahman, Kim & Park (2007); Roy, Hazari, Dey, Miah, Olbrich & Rehder (2007); Roy, Hazari, Dey, Nath, Anwar, Kim, Kim & Park (2007); Suh et al. (2006); Temple et al. (1984).

Computing details top

For all 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 30% probability level, showing the atom-numbering scheme. Full (empty) ellipsoids represent independent (symmetry-related) atoms. Double (single) broken lines denote conventional (non-conventional) hydrogen bonds. Labels A and B correspond to the R(6) rings defined by the intramolecular N—H···O hydrogen bonds. [Symmetry code: (i) ? Please complete.]
[Figure 2] Fig. 2. A displacement ellipsoid plot of (II), drawn at the 30% probability level, showing the atom-numbering scheme. Full (empty) ellipsoids represent independent (symmetry-related) atoms. Double (single) broken lines denote conventional (non-conventional) hydrogen bonds. Label A corresponds to the R(6) ring defined by the intramolecular N—H···O hydrogen bond. [Symmetry codes: (i) ?; (ii) ? Please complete.]
[Figure 3] Fig. 3. A displacement ellipsoid plot of (III), drawn at the 30% probability level, showing the atom-numbering scheme. Double (single) broken lines denote conventional (non-conventional) hydrogen bonds. Label A corresponds to the R(4) ring defined by the intramolecular N—H···O hydrogen bond. [Symmetry codes: (i) ?; (ii) ? Please complete.]
[Figure 4] Fig. 4. A schematic superposition of (I), (II) and (III), with only the CuN4 cores included in the least-squares match.
[Figure 5] Fig. 5. Packing views of (I), (a) along [100], showing the broad (100) plane determined by the C3—H32···O4ii hydrogen bond, and (b) along [010], with planes (connected by the C5—H52···O4iii hydrogen bond) shown sideways. One of the planes has been highlighted for clarity. [Symmetry codes: (ii) -x + 1/2, y - 1/2, -z + 1/2; (iii) x + 1, y, z.]
[Figure 6] Fig. 6. A packing view of (II), showing the one-dimensional chain running in the [101] direction. Double (single) broken lines denote conventional (non-conventional) hydrogen bonds. Label B corresponds to the R22(12) ring defined by the intermolecular N—H···O hydrogen bond. [Symmetry codes: (i) ?; (ii) ? Please complete.]
[Figure 7] Fig. 7. A packing view of (III), showing the one-dimensional chain running in the [100] direction. Double (single) broken lines denote conventional (non-conventional) hydrogen bonds. Label B corresponds to the R42(8) ring defined by the intermolecular O—H···Cl hydrogen bonds. [Symmetry codes: (i) ?; (ii) ? Please complete.]
(I) (meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C18H40N4)]Z = 2
Mr = 546.93F(000) = 574
Monoclinic, P21/nDx = 1.527 Mg m3
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71069 Å
a = 8.460 (5) ŵ = 1.19 mm1
b = 9.162 (5) ÅT = 295 K
c = 15.506 (5) ÅBlock, dark blue
β = 98.097 (5)°0.22 × 0.20 × 0.16 mm
V = 1189.9 (10) Å3
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
2878 independent reflections
Radiation source: fine-focus sealed tube2167 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scans, thick slicesθmax = 29.0°, θmin = 3.7°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1010
Tmin = 0.72, Tmax = 0.82k = 1212
15029 measured reflectionsl = 2019
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0523P)2 + 0.964P]
where P = (Fo2 + 2Fc2)/3
2878 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.51 e Å3
21 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Cu(ClO4)2(C18H40N4)]V = 1189.9 (10) Å3
Mr = 546.93Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.460 (5) ŵ = 1.19 mm1
b = 9.162 (5) ÅT = 295 K
c = 15.506 (5) Å0.22 × 0.20 × 0.16 mm
β = 98.097 (5)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
2878 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
2167 reflections with I > 2σ(I)
Tmin = 0.72, Tmax = 0.82Rint = 0.043
15029 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04321 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.08Δρmax = 0.51 e Å3
2878 reflectionsΔρmin = 0.43 e Å3
145 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.02898 (16)
N10.4505 (3)0.2941 (2)0.45378 (15)0.0317 (5)
H1N0.54190.24400.47200.038*
N20.6097 (3)0.5614 (3)0.39787 (15)0.0307 (5)
H2N0.71230.52940.40970.037*
C10.3340 (4)0.2316 (3)0.5067 (2)0.0427 (7)
H110.33350.12590.50250.051*
H120.22740.26700.48580.051*
C20.4173 (4)0.2601 (3)0.35834 (19)0.0394 (7)
C30.5438 (4)0.3370 (3)0.3131 (2)0.0425 (7)
H310.64770.30540.34140.051*
H320.53250.30200.25350.051*
C40.5448 (4)0.5016 (3)0.31030 (19)0.0380 (7)
H40.43450.53560.29530.046*
C50.6170 (4)0.7222 (3)0.4003 (2)0.0389 (7)
H510.51330.76300.37820.047*
H520.69390.75710.36420.047*
C60.4368 (6)0.0957 (4)0.3448 (3)0.0674 (12)
H610.35500.04400.36930.101*
H620.53970.06500.37300.101*
H630.42780.07510.28360.101*
C70.2503 (4)0.3076 (5)0.3206 (2)0.0593 (10)
H710.23180.40520.33940.089*
H720.17370.24280.34040.089*
H730.23940.30500.25820.089*
C80.6409 (5)0.5541 (5)0.2400 (2)0.0665 (11)
H810.63980.65880.23800.100*
H820.59430.51610.18450.100*
H830.74910.52040.25320.100*
Cl10.12730 (10)0.71769 (11)0.45681 (6)0.0578 (3)
O10.2075 (6)0.8512 (4)0.4664 (4)0.194 (3)
O20.2372 (3)0.6183 (4)0.4265 (2)0.1006 (12)
O30.0985 (4)0.6695 (5)0.5393 (2)0.1091 (13)
O40.0135 (3)0.7212 (6)0.4002 (2)0.136 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0318 (3)0.0265 (2)0.0293 (3)0.00251 (19)0.00673 (18)0.00051 (18)
N10.0339 (12)0.0264 (11)0.0348 (13)0.0001 (9)0.0051 (10)0.0004 (9)
N20.0289 (11)0.0320 (12)0.0315 (12)0.0007 (10)0.0054 (9)0.0012 (10)
C10.0465 (17)0.0379 (16)0.0447 (18)0.0152 (14)0.0103 (14)0.0030 (13)
C20.0470 (17)0.0364 (15)0.0339 (16)0.0046 (13)0.0022 (13)0.0065 (12)
C30.0499 (18)0.0444 (17)0.0343 (16)0.0010 (14)0.0103 (13)0.0086 (13)
C40.0420 (16)0.0433 (16)0.0292 (15)0.0008 (13)0.0073 (12)0.0009 (12)
C50.0408 (16)0.0344 (15)0.0427 (17)0.0056 (13)0.0100 (13)0.0061 (13)
C60.106 (3)0.0377 (18)0.061 (2)0.011 (2)0.021 (2)0.0166 (17)
C70.048 (2)0.072 (3)0.053 (2)0.0143 (18)0.0087 (16)0.0025 (19)
C80.089 (3)0.075 (3)0.041 (2)0.020 (2)0.026 (2)0.0010 (19)
Cl10.0399 (4)0.0706 (6)0.0644 (6)0.0109 (4)0.0122 (4)0.0171 (5)
O10.154 (5)0.062 (3)0.380 (10)0.007 (3)0.088 (6)0.025 (4)
O20.0576 (18)0.139 (3)0.101 (3)0.037 (2)0.0036 (17)0.032 (2)
O30.086 (2)0.178 (4)0.063 (2)0.012 (3)0.0095 (18)0.027 (2)
O40.0468 (17)0.287 (6)0.074 (2)0.047 (3)0.0024 (16)0.062 (3)
Geometric parameters (Å, º) top
Cu1—N22.025 (2)C3—H320.9700
Cu1—N2i2.025 (2)C4—C81.527 (4)
Cu1—N12.040 (2)C4—H40.9800
Cu1—N1i2.040 (2)C5—C1i1.504 (4)
Cu1—O2i2.589 (3)C5—H510.9700
Cu1—O22.589 (3)C5—H520.9700
N1—C11.484 (4)C6—H610.9600
N1—C21.500 (4)C6—H620.9600
N1—H1N0.9100C6—H630.9600
N2—C51.475 (4)C7—H710.9600
N2—C41.495 (4)C7—H720.9600
N2—H2N0.9100C7—H730.9600
C1—C5i1.504 (4)C8—H810.9600
C1—H110.9700C8—H820.9600
C1—H120.9700C8—H830.9600
C2—C71.516 (5)Cl1—O41.377 (3)
C2—C31.531 (4)Cl1—O11.397 (4)
C2—C61.533 (5)Cl1—O31.407 (3)
C3—C41.509 (4)Cl1—O21.427 (3)
C3—H310.9700
N2—Cu1—N2i180.000 (1)C2—C3—H31107.6
N2—Cu1—N194.38 (10)C4—C3—H32107.6
N2i—Cu1—N185.62 (10)C2—C3—H32107.6
N2—Cu1—N1i85.62 (10)H31—C3—H32107.1
N2i—Cu1—N1i94.38 (10)N2—C4—C3110.1 (2)
N1—Cu1—N1i180.0N2—C4—C8111.7 (3)
N2—Cu1—O2i90.05 (11)C3—C4—C8110.0 (3)
N2i—Cu1—O2i89.95 (11)N2—C4—H4108.4
N1—Cu1—O2i83.60 (11)C3—C4—H4108.4
N1i—Cu1—O2i96.40 (11)C8—C4—H4108.4
N2—Cu1—O289.95 (11)N2—C5—C1i108.1 (2)
N2i—Cu1—O290.05 (11)N2—C5—H51110.1
N1—Cu1—O296.40 (11)C1i—C5—H51110.1
N1i—Cu1—O283.60 (11)N2—C5—H52110.1
O2i—Cu1—O2180.000 (1)C1i—C5—H52110.1
C1—N1—C2114.8 (2)H51—C5—H52108.4
C1—N1—Cu1106.40 (17)C2—C6—H61109.5
C2—N1—Cu1122.66 (18)C2—C6—H62109.5
C1—N1—H1N103.6H61—C6—H62109.5
C2—N1—H1N103.6C2—C6—H63109.5
Cu1—N1—H1N103.6H61—C6—H63109.5
C5—N2—C4113.4 (2)H62—C6—H63109.5
C5—N2—Cu1106.27 (17)C2—C7—H71109.5
C4—N2—Cu1117.28 (18)C2—C7—H72109.5
C5—N2—H2N106.4H71—C7—H72109.5
C4—N2—H2N106.4C2—C7—H73109.5
Cu1—N2—H2N106.4H71—C7—H73109.5
N1—C1—C5i107.9 (2)H72—C7—H73109.5
N1—C1—H11110.1C4—C8—H81109.5
C5i—C1—H11110.1C4—C8—H82109.5
N1—C1—H12110.1H81—C8—H82109.5
C5i—C1—H12110.1C4—C8—H83109.5
H11—C1—H12108.4H81—C8—H83109.5
N1—C2—C7110.8 (3)H82—C8—H83109.5
N1—C2—C3108.1 (2)O4—Cl1—O1114.2 (3)
C7—C2—C3111.4 (3)O4—Cl1—O3110.0 (2)
N1—C2—C6109.3 (3)O1—Cl1—O3108.8 (3)
C7—C2—C6110.0 (3)O4—Cl1—O2110.5 (2)
C3—C2—C6107.1 (3)O1—Cl1—O2105.3 (3)
C4—C3—C2118.7 (3)O3—Cl1—O2107.6 (2)
C4—C3—H31107.6Cl1—O2—Cu1132.95 (19)
N2—Cu1—N1—C1166.96 (19)Cu1—N1—C2—C346.1 (3)
N2i—Cu1—N1—C113.04 (19)C1—N1—C2—C665.9 (4)
O2i—Cu1—N1—C1103.5 (2)Cu1—N1—C2—C6162.4 (2)
O2—Cu1—N1—C176.5 (2)N1—C2—C3—C466.7 (4)
N2—Cu1—N1—C231.9 (2)C7—C2—C3—C455.3 (4)
N2i—Cu1—N1—C2148.1 (2)C6—C2—C3—C4175.6 (3)
O2i—Cu1—N1—C2121.5 (2)C5—N2—C4—C3179.1 (2)
O2—Cu1—N1—C258.5 (2)Cu1—N2—C4—C356.3 (3)
N1—Cu1—N2—C5163.30 (18)C5—N2—C4—C856.7 (4)
N1i—Cu1—N2—C516.70 (18)Cu1—N2—C4—C8178.7 (2)
O2i—Cu1—N2—C5113.11 (19)C2—C3—C4—N274.4 (4)
O2—Cu1—N2—C566.89 (19)C2—C3—C4—C8162.2 (3)
N1—Cu1—N2—C435.2 (2)C4—N2—C5—C1i173.7 (2)
N1i—Cu1—N2—C4144.8 (2)Cu1—N2—C5—C1i43.4 (3)
O2i—Cu1—N2—C4118.8 (2)O4—Cl1—O2—Cu1165.5 (3)
O2—Cu1—N2—C461.2 (2)O1—Cl1—O2—Cu170.6 (4)
C2—N1—C1—C5i179.1 (2)O3—Cl1—O2—Cu145.3 (4)
Cu1—N1—C1—C5i40.1 (3)N2—Cu1—O2—Cl1130.2 (3)
C1—N1—C2—C755.5 (3)N2i—Cu1—O2—Cl149.8 (3)
Cu1—N1—C2—C776.2 (3)N1—Cu1—O2—Cl1135.4 (3)
C1—N1—C2—C3177.8 (2)N1i—Cu1—O2—Cl144.6 (3)
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···O1i0.912.373.266 (6)170
N2—H2N···O3i0.912.483.293 (5)149
C7—H71···O20.962.373.296 (6)162
C3—H32···O4ii0.972.483.448 (5)177
C5—H52···O4iii0.972.483.126 (5)124
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y, z.
(II) (meso-5,7,7,12,14,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)bis(nitrato-κO)zinc(II) top
Crystal data top
[Zn(NO3)2(C18H40N4)]Z = 4
Mr = 473.88F(000) = 1008
Monoclinic, C2/cDx = 1.449 Mg m3
Hall symbol: -C 2ycMo Kα radiation, λ = 0.71073 Å
a = 12.9252 (9) ŵ = 1.17 mm1
b = 11.7664 (5) ÅT = 295 K
c = 15.5628 (10) ÅBlock, white
β = 113.352 (8)°0.42 × 0.18 × 0.18 mm
V = 2173.0 (2) Å3
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
2475 independent reflections
Radiation source: fine-focus sealed tube1687 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω scans, thick slicesθmax = 29.0°, θmin = 3.8°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1712
Tmin = 0.72, Tmax = 0.82k = 1415
4791 measured reflectionsl = 2119
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0519P)2 + 1.6552P]
where P = (Fo2 + 2Fc2)/3
2475 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Zn(NO3)2(C18H40N4)]V = 2173.0 (2) Å3
Mr = 473.88Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.9252 (9) ŵ = 1.17 mm1
b = 11.7664 (5) ÅT = 295 K
c = 15.5628 (10) Å0.42 × 0.18 × 0.18 mm
β = 113.352 (8)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
2475 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
1687 reflections with I > 2σ(I)
Tmin = 0.72, Tmax = 0.82Rint = 0.032
4791 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 1.04Δρmax = 0.46 e Å3
2475 reflectionsΔρmin = 0.35 e Å3
136 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.25000.25000.50000.0412 (2)
N10.1962 (2)0.4203 (2)0.48729 (17)0.0354 (6)
H1N0.12210.41580.44820.042*
N20.2863 (2)0.25408 (19)0.38136 (16)0.0326 (5)
H2N0.22010.24470.33090.039*
C10.1925 (3)0.4475 (3)0.5787 (2)0.0464 (8)
H110.14580.51400.57270.056*
H120.26790.46430.62410.056*
C20.2408 (2)0.5102 (3)0.4429 (2)0.0384 (7)
C30.2513 (3)0.4596 (3)0.3561 (2)0.0413 (7)
H310.26990.52110.32320.050*
H320.17760.43160.31530.050*
C40.3363 (2)0.3636 (3)0.3686 (2)0.0384 (7)
H40.40360.37880.42540.046*
C50.3551 (3)0.1524 (3)0.3883 (2)0.0445 (8)
H510.43200.16630.43200.053*
H520.35610.13550.32770.053*
C60.1564 (3)0.6092 (3)0.4103 (3)0.0649 (11)
H610.14390.63920.46270.097*
H620.08640.58240.36390.097*
H630.18630.66790.38380.097*
C70.3531 (3)0.5563 (3)0.5121 (3)0.0520 (9)
H710.40380.49420.53930.078*
H720.34140.59800.56050.078*
H730.38500.60570.47990.078*
C80.3707 (3)0.3609 (3)0.2856 (3)0.0603 (10)
H810.42530.30190.29480.090*
H820.40280.43280.28040.090*
H830.30560.34620.22930.090*
N30.5248 (2)0.2577 (3)0.64525 (19)0.0452 (7)
O10.43588 (19)0.3035 (2)0.59374 (18)0.0608 (7)
O20.5319 (3)0.1550 (3)0.6448 (3)0.1232 (16)
O30.6044 (2)0.3154 (3)0.6959 (2)0.0821 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0579 (4)0.0316 (3)0.0469 (3)0.0046 (2)0.0342 (3)0.0012 (2)
N10.0316 (12)0.0328 (14)0.0405 (14)0.0015 (11)0.0131 (11)0.0020 (11)
N20.0299 (12)0.0397 (15)0.0275 (12)0.0029 (10)0.0107 (10)0.0027 (11)
C10.058 (2)0.0361 (18)0.051 (2)0.0042 (15)0.0275 (17)0.0102 (15)
C20.0337 (15)0.0292 (16)0.0479 (18)0.0001 (12)0.0116 (14)0.0038 (14)
C30.0375 (16)0.0435 (19)0.0368 (17)0.0053 (14)0.0083 (14)0.0082 (14)
C40.0331 (15)0.0475 (19)0.0347 (15)0.0093 (14)0.0136 (13)0.0007 (14)
C50.0470 (18)0.050 (2)0.0462 (18)0.0042 (16)0.0287 (16)0.0053 (16)
C60.068 (2)0.044 (2)0.082 (3)0.0154 (18)0.029 (2)0.016 (2)
C70.053 (2)0.044 (2)0.058 (2)0.0114 (16)0.0204 (18)0.0083 (17)
C80.069 (2)0.068 (3)0.058 (2)0.007 (2)0.040 (2)0.004 (2)
N30.0314 (14)0.057 (2)0.0388 (15)0.0074 (14)0.0047 (12)0.0091 (14)
O10.0375 (13)0.0563 (16)0.0648 (16)0.0029 (12)0.0050 (12)0.0074 (13)
O20.068 (2)0.070 (2)0.160 (4)0.0120 (17)0.031 (2)0.004 (2)
O30.0571 (16)0.086 (2)0.0676 (19)0.0298 (16)0.0128 (14)0.0190 (16)
Geometric parameters (Å, º) top
Zn1—N22.078 (2)C3—H310.9700
Zn1—N2i2.078 (2)C3—H320.9700
Zn1—N12.104 (2)C4—C81.524 (4)
Zn1—N1i2.104 (2)C4—H40.9800
Zn1—O12.349 (2)C5—C1i1.508 (4)
Zn1—O1i2.349 (2)C5—H510.9700
N1—C11.477 (4)C5—H520.9700
N1—C21.498 (4)C6—H610.9600
N1—H1N0.9100C6—H620.9600
N2—C51.469 (4)C6—H630.9600
N2—C41.490 (4)C7—H710.9600
N2—H2N0.9100C7—H720.9600
C1—C5i1.508 (4)C7—H730.9600
C1—H110.9700C8—H810.9600
C1—H120.9700C8—H820.9600
C2—C71.524 (4)C8—H830.9600
C2—C31.532 (4)N3—O21.212 (4)
C2—C61.538 (4)N3—O31.224 (4)
C3—C41.533 (4)N3—O11.235 (3)
N2i—Zn1—N2180.0C2—C3—H31107.6
N2i—Zn1—N185.58 (9)C4—C3—H31107.6
N2—Zn1—N194.42 (9)C2—C3—H32107.6
N2i—Zn1—N1i94.42 (9)C4—C3—H32107.6
N2—Zn1—N1i85.58 (9)H31—C3—H32107.0
N1—Zn1—N1i180.0N2—C4—C8112.5 (3)
N2i—Zn1—O189.41 (10)N2—C4—C3109.1 (2)
N2—Zn1—O190.59 (10)C8—C4—C3110.0 (3)
N1—Zn1—O191.23 (9)N2—C4—H4108.4
N1i—Zn1—O188.77 (9)C8—C4—H4108.4
N2i—Zn1—O1i90.59 (10)C3—C4—H4108.4
N2—Zn1—O1i89.41 (10)N2—C5—C1i110.1 (2)
N1—Zn1—O1i88.77 (9)N2—C5—H51109.6
N1i—Zn1—O1i91.23 (9)C1i—C5—H51109.6
O1—Zn1—O1i180.00 (7)N2—C5—H52109.6
C1—N1—C2117.1 (2)C1i—C5—H52109.6
C1—N1—Zn1104.59 (18)H51—C5—H52108.2
C2—N1—Zn1122.88 (18)C2—C6—H61109.5
C1—N1—H1N103.2C2—C6—H62109.5
C2—N1—H1N103.2H61—C6—H62109.5
Zn1—N1—H1N103.2C2—C6—H63109.5
C5—N2—C4115.6 (2)H61—C6—H63109.5
C5—N2—Zn1105.00 (18)H62—C6—H63109.5
C4—N2—Zn1113.65 (17)C2—C7—H71109.5
C5—N2—H2N107.4C2—C7—H72109.5
C4—N2—H2N107.4H71—C7—H72109.5
Zn1—N2—H2N107.4C2—C7—H73109.5
N1—C1—C5i109.4 (2)H71—C7—H73109.5
N1—C1—H11109.8H72—C7—H73109.5
C5i—C1—H11109.8C4—C8—H81109.5
N1—C1—H12109.8C4—C8—H82109.5
C5i—C1—H12109.8H81—C8—H82109.5
H11—C1—H12108.2C4—C8—H83109.5
N1—C2—C7111.0 (3)H81—C8—H83109.5
N1—C2—C3108.5 (2)H82—C8—H83109.5
C7—C2—C3111.6 (3)O2—N3—O3120.7 (3)
N1—C2—C6109.6 (3)O2—N3—O1119.0 (3)
C7—C2—C6108.4 (3)O3—N3—O1120.3 (3)
C3—C2—C6107.6 (3)N3—O1—Zn1138.2 (2)
C2—C3—C4119.0 (3)
N2i—Zn1—N1—C114.07 (19)Zn1—N1—C2—C341.0 (3)
N2—Zn1—N1—C1165.93 (19)C1—N1—C2—C669.9 (3)
O1—Zn1—N1—C175.25 (19)Zn1—N1—C2—C6158.2 (2)
O1i—Zn1—N1—C1104.75 (19)N1—C2—C3—C465.4 (3)
N2i—Zn1—N1—C2150.8 (2)C7—C2—C3—C457.2 (4)
N2—Zn1—N1—C229.2 (2)C6—C2—C3—C4176.1 (3)
O1—Zn1—N1—C261.5 (2)C5—N2—C4—C853.9 (4)
O1i—Zn1—N1—C2118.5 (2)Zn1—N2—C4—C8175.4 (2)
N1—Zn1—N2—C5165.03 (19)C5—N2—C4—C3176.3 (2)
N1i—Zn1—N2—C514.97 (19)Zn1—N2—C4—C362.2 (3)
O1—Zn1—N2—C573.75 (19)C2—C3—C4—N280.6 (3)
O1i—Zn1—N2—C5106.25 (19)C2—C3—C4—C8155.5 (3)
N1—Zn1—N2—C437.7 (2)C4—N2—C5—C1i168.0 (2)
N1i—Zn1—N2—C4142.3 (2)Zn1—N2—C5—C1i41.9 (3)
O1—Zn1—N2—C453.53 (19)O2—N3—O1—Zn111.2 (6)
O1i—Zn1—N2—C4126.47 (19)O3—N3—O1—Zn1168.8 (3)
C2—N1—C1—C5i179.7 (2)N2i—Zn1—O1—N381.4 (3)
Zn1—N1—C1—C5i40.6 (3)N2—Zn1—O1—N398.6 (3)
C1—N1—C2—C749.9 (4)N1—Zn1—O1—N3167.0 (3)
Zn1—N1—C2—C782.0 (3)N1i—Zn1—O1—N313.0 (3)
C1—N1—C2—C3172.9 (2)
Symmetry code: (i) x+1/2, y+1/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.912.112.983 (5)159
C7—H71···O10.962.383.245 (4)150
N2—H2N···O3ii0.912.163.024 (4)159
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x1/2, y+1/2, z1/2.
(III) Aquachlorido(meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N)copper(II) chloride top
Crystal data top
[CuCl(C18H40N4)(H2O)]ClZ = 4
Mr = 436.94F(000) = 932
Monoclinic, P21/cDx = 1.381 Mg m3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 14.0350 (4) ŵ = 1.31 mm1
b = 11.6288 (2) ÅT = 295 K
c = 13.8132 (4) ÅBlock, blue–violet
β = 111.255 (3)°0.32 × 0.18 × 0.12 mm
V = 2101.10 (9) Å3
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
5230 independent reflections
Radiation source: fine-focus sealed tube4195 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
ω scans, thick slicesθmax = 29.1°, θmin = 3.5°
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
h = 1818
Tmin = 0.72, Tmax = 0.82k = 1515
45230 measured reflectionsl = 1818
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0375P)2 + 1.6364P]
where P = (Fo2 + 2Fc2)/3
5230 reflections(Δ/σ)max = 0.001
235 parametersΔρmax = 0.86 e Å3
3 restraintsΔρmin = 0.34 e Å3
Crystal data top
[CuCl(C18H40N4)(H2O)]ClV = 2101.10 (9) Å3
Mr = 436.94Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.0350 (4) ŵ = 1.31 mm1
b = 11.6288 (2) ÅT = 295 K
c = 13.8132 (4) Å0.32 × 0.18 × 0.12 mm
β = 111.255 (3)°
Data collection top
Oxford Gemini S Ultra CCD area-detector
diffractometer
5230 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
4195 reflections with I > 2σ(I)
Tmin = 0.72, Tmax = 0.82Rint = 0.045
45230 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0393 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.86 e Å3
5230 reflectionsΔρmin = 0.34 e Å3
235 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.25910 (2)0.57454 (2)0.455119 (19)0.03022 (9)
N10.27191 (14)0.74432 (15)0.42025 (15)0.0326 (4)
H1N0.31710.74110.38690.064 (9)*
N20.37329 (13)0.57811 (15)0.59458 (13)0.0298 (4)
H2N0.43090.55570.58400.036 (7)*
C10.17558 (19)0.7735 (2)0.33555 (18)0.0399 (5)
H110.18440.84250.30020.048*
H120.12230.78770.36330.048*
C20.31681 (19)0.83539 (19)0.4997 (2)0.0394 (5)
C30.4118 (2)0.7847 (2)0.5834 (2)0.0501 (6)
H310.45620.75550.54920.060*
H320.44800.84720.62820.060*
C40.3978 (2)0.6907 (2)0.65141 (19)0.0444 (6)
H40.34010.71160.67190.053*
C50.35013 (17)0.4874 (2)0.65651 (17)0.0368 (5)
H510.29580.51240.67940.044*
H520.41020.47090.71740.044*
C60.3551 (3)0.9363 (2)0.4506 (3)0.0675 (9)
H610.40500.90860.42370.101*
H620.38550.99390.50240.101*
H630.29850.96910.39510.101*
C70.2386 (2)0.8806 (2)0.5418 (2)0.0506 (7)
H710.19070.92890.49070.076*
H720.27240.92440.60370.076*
H730.20290.81730.55780.076*
C80.4935 (2)0.6806 (3)0.7503 (2)0.0572 (8)
H810.55150.66300.73180.086*
H820.48380.62040.79340.086*
H830.50490.75210.78750.086*
Cl10.40429 (4)0.56190 (5)0.35862 (5)0.04264 (15)
Cl20.08968 (5)0.40873 (7)0.65903 (6)0.0604 (2)
N1'0.23177 (13)0.41166 (14)0.49404 (14)0.0284 (4)
H1N'0.17710.41940.51420.035 (7)*
N2'0.14008 (13)0.56947 (14)0.31823 (13)0.0286 (4)
H2N'0.08200.57480.33280.042 (7)*
C1'0.31760 (18)0.3817 (2)0.59060 (19)0.0408 (5)
H11'0.37440.35200.57390.049*
H12'0.29630.32270.62810.049*
C2'0.20114 (17)0.31713 (18)0.41408 (18)0.0334 (5)
C3'0.11245 (17)0.36088 (19)0.31913 (18)0.0356 (5)
H31'0.08770.29690.27160.043*
H32'0.05740.38320.34200.043*
C4'0.13266 (17)0.4612 (2)0.25817 (17)0.0346 (5)
H4'0.19820.44810.24960.042*
C5'0.14629 (19)0.6745 (2)0.26105 (17)0.0386 (5)
H51'0.08070.68950.20660.046*
H52'0.19690.66450.22910.046*
C6'0.1624 (2)0.2126 (2)0.4567 (2)0.0508 (7)
H61'0.21650.18310.51650.076*
H62'0.14040.15410.40420.076*
H6C'0.10600.23520.47610.076*
C7'0.29152 (19)0.2815 (2)0.3843 (2)0.0465 (6)
H71'0.32520.34890.37240.070*
H72'0.26750.23590.32220.070*
H73'0.33880.23730.43970.070*
C8'0.0485 (2)0.4669 (3)0.1507 (2)0.0514 (7)
H81'0.01550.48430.15780.077*
H82'0.04360.39410.11640.077*
H83'0.06460.52590.11050.077*
O1W0.11027 (19)0.6332 (2)0.5439 (2)0.0669 (6)
H1WA0.104 (2)0.581 (2)0.5840 (18)0.060 (10)*
H1WB0.0525 (13)0.638 (3)0.4959 (17)0.066 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.03170 (15)0.02389 (14)0.02826 (14)0.00177 (10)0.00272 (11)0.00005 (10)
N10.0353 (10)0.0273 (9)0.0379 (10)0.0000 (7)0.0164 (8)0.0027 (7)
N20.0252 (9)0.0325 (9)0.0285 (9)0.0021 (7)0.0060 (7)0.0032 (7)
C10.0452 (13)0.0298 (11)0.0427 (13)0.0060 (10)0.0135 (11)0.0062 (10)
C20.0443 (13)0.0270 (11)0.0492 (14)0.0040 (10)0.0196 (11)0.0068 (10)
C30.0413 (14)0.0452 (14)0.0638 (17)0.0123 (11)0.0191 (13)0.0175 (13)
C40.0423 (14)0.0424 (13)0.0413 (13)0.0035 (11)0.0064 (11)0.0135 (11)
C50.0326 (11)0.0450 (13)0.0279 (11)0.0004 (10)0.0049 (9)0.0047 (9)
C60.082 (2)0.0450 (16)0.090 (2)0.0228 (15)0.049 (2)0.0089 (16)
C70.0584 (17)0.0447 (14)0.0569 (16)0.0008 (12)0.0306 (14)0.0136 (12)
C80.0488 (16)0.0580 (17)0.0476 (15)0.0002 (13)0.0033 (12)0.0205 (13)
Cl10.0353 (3)0.0472 (3)0.0505 (3)0.0073 (2)0.0215 (3)0.0000 (3)
Cl20.0458 (4)0.0725 (5)0.0706 (5)0.0156 (3)0.0304 (3)0.0313 (4)
N1'0.0242 (8)0.0269 (8)0.0328 (9)0.0005 (7)0.0090 (7)0.0006 (7)
N2'0.0265 (9)0.0301 (9)0.0282 (9)0.0017 (7)0.0089 (7)0.0011 (7)
C1'0.0357 (12)0.0350 (12)0.0428 (13)0.0027 (10)0.0034 (10)0.0105 (10)
C2'0.0325 (11)0.0234 (10)0.0438 (12)0.0009 (8)0.0133 (10)0.0019 (9)
C3'0.0302 (11)0.0324 (11)0.0413 (12)0.0064 (9)0.0097 (10)0.0103 (9)
C4'0.0336 (11)0.0374 (11)0.0314 (11)0.0009 (9)0.0100 (9)0.0070 (9)
C5'0.0428 (13)0.0380 (12)0.0306 (11)0.0032 (10)0.0081 (10)0.0073 (9)
C6'0.0558 (16)0.0308 (12)0.0658 (17)0.0101 (11)0.0221 (14)0.0009 (12)
C7'0.0418 (13)0.0389 (13)0.0629 (16)0.0070 (11)0.0239 (12)0.0058 (12)
C8'0.0513 (16)0.0575 (16)0.0358 (13)0.0064 (13)0.0042 (12)0.0083 (12)
O1W0.0698 (16)0.0588 (14)0.0749 (16)0.0134 (12)0.0296 (14)0.0034 (12)
Geometric parameters (Å, º) top
Cu1—N22.0106 (17)C8—H810.9600
Cu1—N2'2.0197 (17)C8—H820.9600
Cu1—N1'2.0429 (17)C8—H830.9600
Cu1—N12.0555 (18)N1'—C1'1.479 (3)
Cu1—Cl12.8143 (6)N1'—C2'1.506 (3)
Cu1—O1W2.861 (2)N1'—H1N'0.9100
N1—C11.471 (3)N2'—C5'1.474 (3)
N1—C21.490 (3)N2'—C4'1.491 (3)
N1—H1N0.9100N2'—H2N'0.9100
N2—C51.467 (3)C1'—H11'0.9700
N2—C41.501 (3)C1'—H12'0.9700
N2—H2N0.9100C2'—C7'1.526 (3)
C1—C5'1.500 (3)C2'—C3'1.531 (3)
C1—H110.9700C2'—C6'1.534 (3)
C1—H120.9700C3'—C4'1.524 (3)
C2—C71.511 (3)C3'—H31'0.9700
C2—C31.532 (4)C3'—H32'0.9700
C2—C61.546 (4)C4'—C8'1.527 (3)
C3—C41.499 (4)C4'—H4'0.9800
C3—H310.9700C5'—H51'0.9700
C3—H320.9700C5'—H52'0.9700
C4—C81.533 (3)C6'—H61'0.9600
C4—H40.9800C6'—H62'0.9600
C5—C1'1.499 (3)C6'—H6C'0.9600
C5—H510.9700C7'—H71'0.9600
C5—H520.9700C7'—H72'0.9600
C6—H610.9600C7'—H73'0.9600
C6—H620.9600C8'—H81'0.9600
C6—H630.9600C8'—H82'0.9600
C7—H710.9600C8'—H83'0.9600
C7—H720.9600O1W—H1WA0.844 (10)
C7—H730.9600O1W—H1WB0.843 (10)
N2—Cu1—N2'177.48 (7)C4—C8—H81109.5
N2—Cu1—N1'85.84 (7)C4—C8—H82109.5
N2'—Cu1—N1'92.80 (7)H81—C8—H82109.5
N2—Cu1—N195.60 (7)C4—C8—H83109.5
N2'—Cu1—N185.50 (7)H81—C8—H83109.5
N1'—Cu1—N1173.19 (7)H82—C8—H83109.5
N2—Cu1—Cl189.56 (5)C1'—N1'—C2'114.33 (17)
N2'—Cu1—Cl192.88 (5)C1'—N1'—Cu1106.65 (13)
N1'—Cu1—Cl1108.27 (5)C2'—N1'—Cu1120.96 (13)
N1—Cu1—Cl178.42 (5)C1'—N1'—H1N'104.4
N2—Cu1—O1W92.11 (8)C2'—N1'—H1N'104.4
N2'—Cu1—O1W85.61 (7)Cu1—N1'—H1N'104.4
N1'—Cu1—O1W82.66 (7)C5'—N2'—C4'114.04 (17)
N1—Cu1—O1W90.63 (7)C5'—N2'—Cu1106.74 (13)
Cl1—Cu1—O1W169.04 (5)C4'—N2'—Cu1114.38 (13)
C1—N1—C2116.27 (18)C5'—N2'—H2N'107.1
C1—N1—Cu1105.96 (14)C4'—N2'—H2N'107.1
C2—N1—Cu1124.03 (15)Cu1—N2'—H2N'107.1
C1—N1—H1N102.4N1'—C1'—C5108.89 (18)
C2—N1—H1N102.4N1'—C1'—H11'109.9
Cu1—N1—H1N102.4C5—C1'—H11'109.9
C5—N2—C4112.31 (18)N1'—C1'—H12'109.9
C5—N2—Cu1106.00 (13)C5—C1'—H12'109.9
C4—N2—Cu1118.10 (14)H11'—C1'—H12'108.3
C5—N2—H2N106.6N1'—C2'—C7'110.59 (18)
C4—N2—H2N106.6N1'—C2'—C3'108.23 (16)
Cu1—N2—H2N106.6C7'—C2'—C3'110.9 (2)
N1—C1—C5'108.21 (18)N1'—C2'—C6'110.08 (19)
N1—C1—H11110.1C7'—C2'—C6'109.5 (2)
C5'—C1—H11110.1C3'—C2'—C6'107.50 (19)
N1—C1—H12110.1C4'—C3'—C2'118.11 (18)
C5'—C1—H12110.1C4'—C3'—H31'107.8
H11—C1—H12108.4C2'—C3'—H31'107.8
N1—C2—C7111.0 (2)C4'—C3'—H32'107.8
N1—C2—C3107.60 (18)C2'—C3'—H32'107.8
C7—C2—C3113.5 (2)H31'—C3'—H32'107.1
N1—C2—C6109.8 (2)N2'—C4'—C3'109.18 (17)
C7—C2—C6108.7 (2)N2'—C4'—C8'112.2 (2)
C3—C2—C6106.1 (2)C3'—C4'—C8'109.7 (2)
C4—C3—C2118.5 (2)N2'—C4'—H4'108.6
C4—C3—H31107.7C3'—C4'—H4'108.6
C2—C3—H31107.7C8'—C4'—H4'108.6
C4—C3—H32107.7N2'—C5'—C1108.87 (18)
C2—C3—H32107.7N2'—C5'—H51'109.9
H31—C3—H32107.1C1—C5'—H51'109.9
C3—C4—N2111.4 (2)N2'—C5'—H52'109.9
C3—C4—C8110.0 (2)C1—C5'—H52'109.9
N2—C4—C8111.1 (2)H51'—C5'—H52'108.3
C3—C4—H4108.1C2'—C6'—H61'109.5
N2—C4—H4108.1C2'—C6'—H62'109.5
C8—C4—H4108.1H61'—C6'—H62'109.5
N2—C5—C1'108.58 (18)C2'—C6'—H6C'109.5
N2—C5—H51110.0H61'—C6'—H6C'109.5
C1'—C5—H51110.0H62'—C6'—H6C'109.5
N2—C5—H52110.0C2'—C7'—H71'109.5
C1'—C5—H52110.0C2'—C7'—H72'109.5
H51—C5—H52108.4H71'—C7'—H72'109.5
C2—C6—H61109.5C2'—C7'—H73'109.5
C2—C6—H62109.5H71'—C7'—H73'109.5
H61—C6—H62109.5H72'—C7'—H73'109.5
C2—C6—H63109.5C4'—C8'—H81'109.5
H61—C6—H63109.5C4'—C8'—H82'109.5
H62—C6—H63109.5H81'—C8'—H82'109.5
C2—C7—H71109.5C4'—C8'—H83'109.5
C2—C7—H72109.5H81'—C8'—H83'109.5
H71—C7—H72109.5H82'—C8'—H83'109.5
C2—C7—H73109.5Cu1—O1W—H1WA112 (2)
H71—C7—H73109.5Cu1—O1W—H1WB109 (2)
H72—C7—H73109.5H1WA—O1W—H1WB105.7 (15)
N2—Cu1—N1—C1162.71 (14)N2'—Cu1—N1'—C1'173.32 (15)
N2'—Cu1—N1—C115.02 (14)Cl1—Cu1—N1'—C1'79.36 (14)
Cl1—Cu1—N1—C1108.89 (14)O1W—Cu1—N1'—C1'101.47 (15)
O1W—Cu1—N1—C170.53 (15)N2—Cu1—N1'—C2'141.72 (15)
N2—Cu1—N1—C224.24 (18)N2'—Cu1—N1'—C2'40.40 (15)
N2'—Cu1—N1—C2153.49 (18)Cl1—Cu1—N1'—C2'53.56 (15)
Cl1—Cu1—N1—C2112.64 (17)O1W—Cu1—N1'—C2'125.61 (15)
O1W—Cu1—N1—C267.94 (17)N1'—Cu1—N2'—C5'172.51 (14)
N1'—Cu1—N2—C519.68 (14)N1—Cu1—N2'—C5'14.10 (14)
N1—Cu1—N2—C5153.64 (14)Cl1—Cu1—N2'—C5'64.04 (13)
Cl1—Cu1—N2—C5128.04 (13)O1W—Cu1—N2'—C5'105.08 (14)
O1W—Cu1—N2—C562.80 (14)N1'—Cu1—N2'—C4'45.39 (15)
N1'—Cu1—N2—C4146.61 (17)N1—Cu1—N2'—C4'141.22 (15)
N1—Cu1—N2—C426.71 (17)Cl1—Cu1—N2'—C4'63.08 (14)
Cl1—Cu1—N2—C4105.04 (16)O1W—Cu1—N2'—C4'127.80 (15)
O1W—Cu1—N2—C464.13 (17)C2'—N1'—C1'—C5171.92 (18)
C2—N1—C1—C5'176.73 (19)Cu1—N1'—C1'—C535.5 (2)
Cu1—N1—C1—C5'41.1 (2)N2—C5—C1'—N1'54.7 (2)
C1—N1—C2—C751.7 (3)C1'—N1'—C2'—C7'58.1 (2)
Cu1—N1—C2—C783.0 (2)Cu1—N1'—C2'—C7'71.6 (2)
C1—N1—C2—C3176.4 (2)C1'—N1'—C2'—C3'179.74 (18)
Cu1—N1—C2—C341.7 (2)Cu1—N1'—C2'—C3'50.1 (2)
C1—N1—C2—C668.6 (3)C1'—N1'—C2'—C6'63.0 (2)
Cu1—N1—C2—C6156.75 (19)Cu1—N1'—C2'—C6'167.32 (15)
N1—C2—C3—C467.7 (3)N1'—C2'—C3'—C4'64.4 (2)
C7—C2—C3—C455.5 (3)C7'—C2'—C3'—C4'57.0 (3)
C6—C2—C3—C4174.8 (2)C6'—C2'—C3'—C4'176.7 (2)
C2—C3—C4—N275.5 (3)C5'—N2'—C4'—C3'172.51 (18)
C2—C3—C4—C8160.9 (2)Cu1—N2'—C4'—C3'64.2 (2)
C5—N2—C4—C3174.81 (19)C5'—N2'—C4'—C8'50.7 (3)
Cu1—N2—C4—C351.0 (2)Cu1—N2'—C4'—C8'173.95 (16)
C5—N2—C4—C862.2 (3)C2'—C3'—C4'—N2'74.6 (2)
Cu1—N2—C4—C8174.01 (18)C2'—C3'—C4'—C8'162.1 (2)
C4—N2—C5—C1'175.00 (18)C4'—N2'—C5'—C1168.11 (18)
Cu1—N2—C5—C1'44.7 (2)Cu1—N2'—C5'—C140.8 (2)
N2—Cu1—N1'—C1'8.80 (15)N1—C1—C5'—N2'56.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.912.523.135 (2)125
C7—H73···O1W0.962.483.400 (4)161
C7—H71···Cl10.962.753.697 (3)170
N2—H2N···Cl1i0.912.553.369 (2)149
N1—H1N···Cl20.912.703.531 (2)152
N2—H2N···Cl2ii0.912.463.361 (2)171
O1W—H1WA···Cl20.85 (2)2.30 (2)3.123 (3)165 (2)
O1W—H1WB···Cl2ii0.84 (2)2.40 (2)3.204 (3)160 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1.

Experimental details

(I)(II)(III)
Crystal data
Chemical formula[Cu(ClO4)2(C18H40N4)][Zn(NO3)2(C18H40N4)][CuCl(C18H40N4)(H2O)]Cl
Mr546.93473.88436.94
Crystal system, space groupMonoclinic, P21/nMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)295295295
a, b, c (Å)8.460 (5), 9.162 (5), 15.506 (5)12.9252 (9), 11.7664 (5), 15.5628 (10)14.0350 (4), 11.6288 (2), 13.8132 (4)
β (°) 98.097 (5) 113.352 (8) 111.255 (3)
V3)1189.9 (10)2173.0 (2)2101.10 (9)
Z244
Radiation typeMo KαMo KαMo Kα
µ (mm1)1.191.171.31
Crystal size (mm)0.22 × 0.20 × 0.160.42 × 0.18 × 0.180.32 × 0.18 × 0.12
Data collection
DiffractometerOxford Gemini S Ultra CCD area-detector
diffractometer
Oxford 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)
Multi-scan
(CrysAlis PRO; Oxford Diffraction, 2009)
Tmin, Tmax0.72, 0.820.72, 0.820.72, 0.82
No. of measured, independent and
observed [I > 2σ(I)] reflections
15029, 2878, 2167 4791, 2475, 1687 45230, 5230, 4195
Rint0.0430.0320.045
(sin θ/λ)max1)0.6830.6820.684
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.121, 1.08 0.048, 0.127, 1.04 0.039, 0.098, 1.06
No. of reflections287824755230
No. of parameters145136235
No. of restraints2103
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.51, 0.430.46, 0.350.86, 0.34

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—N22.025 (2)Cu1—O22.589 (3)
Cu1—N12.040 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.912.373.266 (6)170
N2—H2N···O3i0.912.483.293 (5)149
C7—H71···O20.962.373.296 (6)162
C3—H32···O4ii0.972.483.448 (5)177
C5—H52···O4iii0.972.483.126 (5)124
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x+1, y, z.
Selected bond lengths (Å) for (II) top
Zn1—N22.078 (2)Zn1—O12.349 (2)
Zn1—N12.104 (2)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O2i0.912.112.983 (5)159
C7—H71···O10.962.383.245 (4)150
N2—H2N···O3ii0.912.163.024 (4)159
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x1/2, y+1/2, z1/2.
Selected bond lengths (Å) for (III) top
Cu1—N22.0106 (17)Cu1—N12.0555 (18)
Cu1—N2'2.0197 (17)Cu1—Cl12.8143 (6)
Cu1—N1'2.0429 (17)Cu1—O1W2.861 (2)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.912.523.135 (2)125
C7—H73···O1W0.962.483.400 (4)161
C7'—H71'···Cl10.962.753.697 (3)170
N2—H2N···Cl1i0.912.553.369 (2)149
N1'—H1N'···Cl20.912.703.531 (2)152
N2'—H2N'···Cl2ii0.912.463.361 (2)171
O1W—H1WA···Cl20.85 (2)2.30 (2)3.123 (3)165 (2)
O1W—H1WB···Cl2ii0.84 (2)2.40 (2)3.204 (3)160 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1.
 

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