Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113018465/sk3501sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113018465/sk3501IIIsup4.hkl |
CCDC references: 962900; 962901; 962902
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 RRRR–SSSS chiral centre distribution, and the non-centrosymmetric L2 with an RRRS–SRSR 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.
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.
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).
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 SR–RS–SR 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.
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).
[Cu(ClO4)2(C18H40N4)] | Z = 2 |
Mr = 546.93 | F(000) = 574 |
Monoclinic, P21/n | Dx = 1.527 Mg m−3 |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71069 Å |
a = 8.460 (5) Å | µ = 1.19 mm−1 |
b = 9.162 (5) Å | T = 295 K |
c = 15.506 (5) Å | Block, dark blue |
β = 98.097 (5)° | 0.22 × 0.20 × 0.16 mm |
V = 1189.9 (10) Å3 |
Oxford Gemini S Ultra CCD area-detector diffractometer | 2878 independent reflections |
Radiation source: fine-focus sealed tube | 2167 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ω scans, thick slices | θmax = 29.0°, θmin = 3.7° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −10→10 |
Tmin = 0.72, Tmax = 0.82 | k = −12→12 |
15029 measured reflections | l = −20→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-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 parameters | Δρmax = 0.51 e Å−3 |
21 restraints | Δρmin = −0.43 e Å−3 |
[Cu(ClO4)2(C18H40N4)] | V = 1189.9 (10) Å3 |
Mr = 546.93 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.460 (5) Å | µ = 1.19 mm−1 |
b = 9.162 (5) Å | T = 295 K |
c = 15.506 (5) Å | 0.22 × 0.20 × 0.16 mm |
β = 98.097 (5)° |
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 = 0.82 | Rint = 0.043 |
15029 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 21 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.51 e Å−3 |
2878 reflections | Δρmin = −0.43 e Å−3 |
145 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.02898 (16) | |
N1 | 0.4505 (3) | 0.2941 (2) | 0.45378 (15) | 0.0317 (5) | |
H1N | 0.5419 | 0.2440 | 0.4720 | 0.038* | |
N2 | 0.6097 (3) | 0.5614 (3) | 0.39787 (15) | 0.0307 (5) | |
H2N | 0.7123 | 0.5294 | 0.4097 | 0.037* | |
C1 | 0.3340 (4) | 0.2316 (3) | 0.5067 (2) | 0.0427 (7) | |
H11 | 0.3335 | 0.1259 | 0.5025 | 0.051* | |
H12 | 0.2274 | 0.2670 | 0.4858 | 0.051* | |
C2 | 0.4173 (4) | 0.2601 (3) | 0.35834 (19) | 0.0394 (7) | |
C3 | 0.5438 (4) | 0.3370 (3) | 0.3131 (2) | 0.0425 (7) | |
H31 | 0.6477 | 0.3054 | 0.3414 | 0.051* | |
H32 | 0.5325 | 0.3020 | 0.2535 | 0.051* | |
C4 | 0.5448 (4) | 0.5016 (3) | 0.31030 (19) | 0.0380 (7) | |
H4 | 0.4345 | 0.5356 | 0.2953 | 0.046* | |
C5 | 0.6170 (4) | 0.7222 (3) | 0.4003 (2) | 0.0389 (7) | |
H51 | 0.5133 | 0.7630 | 0.3782 | 0.047* | |
H52 | 0.6939 | 0.7571 | 0.3642 | 0.047* | |
C6 | 0.4368 (6) | 0.0957 (4) | 0.3448 (3) | 0.0674 (12) | |
H61 | 0.3550 | 0.0440 | 0.3693 | 0.101* | |
H62 | 0.5397 | 0.0650 | 0.3730 | 0.101* | |
H63 | 0.4278 | 0.0751 | 0.2836 | 0.101* | |
C7 | 0.2503 (4) | 0.3076 (5) | 0.3206 (2) | 0.0593 (10) | |
H71 | 0.2318 | 0.4052 | 0.3394 | 0.089* | |
H72 | 0.1737 | 0.2428 | 0.3404 | 0.089* | |
H73 | 0.2394 | 0.3050 | 0.2582 | 0.089* | |
C8 | 0.6409 (5) | 0.5541 (5) | 0.2400 (2) | 0.0665 (11) | |
H81 | 0.6398 | 0.6588 | 0.2380 | 0.100* | |
H82 | 0.5943 | 0.5161 | 0.1845 | 0.100* | |
H83 | 0.7491 | 0.5204 | 0.2532 | 0.100* | |
Cl1 | 0.12730 (10) | 0.71769 (11) | 0.45681 (6) | 0.0578 (3) | |
O1 | 0.2075 (6) | 0.8512 (4) | 0.4664 (4) | 0.194 (3) | |
O2 | 0.2372 (3) | 0.6183 (4) | 0.4265 (2) | 0.1006 (12) | |
O3 | 0.0985 (4) | 0.6695 (5) | 0.5393 (2) | 0.1091 (13) | |
O4 | −0.0135 (3) | 0.7212 (6) | 0.4002 (2) | 0.136 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0318 (3) | 0.0265 (2) | 0.0293 (3) | −0.00251 (19) | 0.00673 (18) | −0.00051 (18) |
N1 | 0.0339 (12) | 0.0264 (11) | 0.0348 (13) | −0.0001 (9) | 0.0051 (10) | −0.0004 (9) |
N2 | 0.0289 (11) | 0.0320 (12) | 0.0315 (12) | −0.0007 (10) | 0.0054 (9) | 0.0012 (10) |
C1 | 0.0465 (17) | 0.0379 (16) | 0.0447 (18) | −0.0152 (14) | 0.0103 (14) | −0.0030 (13) |
C2 | 0.0470 (17) | 0.0364 (15) | 0.0339 (16) | −0.0046 (13) | 0.0022 (13) | −0.0065 (12) |
C3 | 0.0499 (18) | 0.0444 (17) | 0.0343 (16) | 0.0010 (14) | 0.0103 (13) | −0.0086 (13) |
C4 | 0.0420 (16) | 0.0433 (16) | 0.0292 (15) | −0.0008 (13) | 0.0073 (12) | 0.0009 (12) |
C5 | 0.0408 (16) | 0.0344 (15) | 0.0427 (17) | −0.0056 (13) | 0.0100 (13) | 0.0061 (13) |
C6 | 0.106 (3) | 0.0377 (18) | 0.061 (2) | −0.011 (2) | 0.021 (2) | −0.0166 (17) |
C7 | 0.048 (2) | 0.072 (3) | 0.053 (2) | −0.0143 (18) | −0.0087 (16) | 0.0025 (19) |
C8 | 0.089 (3) | 0.075 (3) | 0.041 (2) | −0.020 (2) | 0.026 (2) | −0.0010 (19) |
Cl1 | 0.0399 (4) | 0.0706 (6) | 0.0644 (6) | 0.0109 (4) | 0.0122 (4) | 0.0171 (5) |
O1 | 0.154 (5) | 0.062 (3) | 0.380 (10) | −0.007 (3) | 0.088 (6) | 0.025 (4) |
O2 | 0.0576 (18) | 0.139 (3) | 0.101 (3) | 0.037 (2) | −0.0036 (17) | −0.032 (2) |
O3 | 0.086 (2) | 0.178 (4) | 0.063 (2) | 0.012 (3) | 0.0095 (18) | 0.027 (2) |
O4 | 0.0468 (17) | 0.287 (6) | 0.074 (2) | 0.047 (3) | 0.0024 (16) | 0.062 (3) |
Cu1—N2 | 2.025 (2) | C3—H32 | 0.9700 |
Cu1—N2i | 2.025 (2) | C4—C8 | 1.527 (4) |
Cu1—N1 | 2.040 (2) | C4—H4 | 0.9800 |
Cu1—N1i | 2.040 (2) | C5—C1i | 1.504 (4) |
Cu1—O2i | 2.589 (3) | C5—H51 | 0.9700 |
Cu1—O2 | 2.589 (3) | C5—H52 | 0.9700 |
N1—C1 | 1.484 (4) | C6—H61 | 0.9600 |
N1—C2 | 1.500 (4) | C6—H62 | 0.9600 |
N1—H1N | 0.9100 | C6—H63 | 0.9600 |
N2—C5 | 1.475 (4) | C7—H71 | 0.9600 |
N2—C4 | 1.495 (4) | C7—H72 | 0.9600 |
N2—H2N | 0.9100 | C7—H73 | 0.9600 |
C1—C5i | 1.504 (4) | C8—H81 | 0.9600 |
C1—H11 | 0.9700 | C8—H82 | 0.9600 |
C1—H12 | 0.9700 | C8—H83 | 0.9600 |
C2—C7 | 1.516 (5) | Cl1—O4 | 1.377 (3) |
C2—C3 | 1.531 (4) | Cl1—O1 | 1.397 (4) |
C2—C6 | 1.533 (5) | Cl1—O3 | 1.407 (3) |
C3—C4 | 1.509 (4) | Cl1—O2 | 1.427 (3) |
C3—H31 | 0.9700 | ||
N2—Cu1—N2i | 180.000 (1) | C2—C3—H31 | 107.6 |
N2—Cu1—N1 | 94.38 (10) | C4—C3—H32 | 107.6 |
N2i—Cu1—N1 | 85.62 (10) | C2—C3—H32 | 107.6 |
N2—Cu1—N1i | 85.62 (10) | H31—C3—H32 | 107.1 |
N2i—Cu1—N1i | 94.38 (10) | N2—C4—C3 | 110.1 (2) |
N1—Cu1—N1i | 180.0 | N2—C4—C8 | 111.7 (3) |
N2—Cu1—O2i | 90.05 (11) | C3—C4—C8 | 110.0 (3) |
N2i—Cu1—O2i | 89.95 (11) | N2—C4—H4 | 108.4 |
N1—Cu1—O2i | 83.60 (11) | C3—C4—H4 | 108.4 |
N1i—Cu1—O2i | 96.40 (11) | C8—C4—H4 | 108.4 |
N2—Cu1—O2 | 89.95 (11) | N2—C5—C1i | 108.1 (2) |
N2i—Cu1—O2 | 90.05 (11) | N2—C5—H51 | 110.1 |
N1—Cu1—O2 | 96.40 (11) | C1i—C5—H51 | 110.1 |
N1i—Cu1—O2 | 83.60 (11) | N2—C5—H52 | 110.1 |
O2i—Cu1—O2 | 180.000 (1) | C1i—C5—H52 | 110.1 |
C1—N1—C2 | 114.8 (2) | H51—C5—H52 | 108.4 |
C1—N1—Cu1 | 106.40 (17) | C2—C6—H61 | 109.5 |
C2—N1—Cu1 | 122.66 (18) | C2—C6—H62 | 109.5 |
C1—N1—H1N | 103.6 | H61—C6—H62 | 109.5 |
C2—N1—H1N | 103.6 | C2—C6—H63 | 109.5 |
Cu1—N1—H1N | 103.6 | H61—C6—H63 | 109.5 |
C5—N2—C4 | 113.4 (2) | H62—C6—H63 | 109.5 |
C5—N2—Cu1 | 106.27 (17) | C2—C7—H71 | 109.5 |
C4—N2—Cu1 | 117.28 (18) | C2—C7—H72 | 109.5 |
C5—N2—H2N | 106.4 | H71—C7—H72 | 109.5 |
C4—N2—H2N | 106.4 | C2—C7—H73 | 109.5 |
Cu1—N2—H2N | 106.4 | H71—C7—H73 | 109.5 |
N1—C1—C5i | 107.9 (2) | H72—C7—H73 | 109.5 |
N1—C1—H11 | 110.1 | C4—C8—H81 | 109.5 |
C5i—C1—H11 | 110.1 | C4—C8—H82 | 109.5 |
N1—C1—H12 | 110.1 | H81—C8—H82 | 109.5 |
C5i—C1—H12 | 110.1 | C4—C8—H83 | 109.5 |
H11—C1—H12 | 108.4 | H81—C8—H83 | 109.5 |
N1—C2—C7 | 110.8 (3) | H82—C8—H83 | 109.5 |
N1—C2—C3 | 108.1 (2) | O4—Cl1—O1 | 114.2 (3) |
C7—C2—C3 | 111.4 (3) | O4—Cl1—O3 | 110.0 (2) |
N1—C2—C6 | 109.3 (3) | O1—Cl1—O3 | 108.8 (3) |
C7—C2—C6 | 110.0 (3) | O4—Cl1—O2 | 110.5 (2) |
C3—C2—C6 | 107.1 (3) | O1—Cl1—O2 | 105.3 (3) |
C4—C3—C2 | 118.7 (3) | O3—Cl1—O2 | 107.6 (2) |
C4—C3—H31 | 107.6 | Cl1—O2—Cu1 | 132.95 (19) |
N2—Cu1—N1—C1 | −166.96 (19) | Cu1—N1—C2—C3 | 46.1 (3) |
N2i—Cu1—N1—C1 | 13.04 (19) | C1—N1—C2—C6 | −65.9 (4) |
O2i—Cu1—N1—C1 | 103.5 (2) | Cu1—N1—C2—C6 | 162.4 (2) |
O2—Cu1—N1—C1 | −76.5 (2) | N1—C2—C3—C4 | −66.7 (4) |
N2—Cu1—N1—C2 | −31.9 (2) | C7—C2—C3—C4 | 55.3 (4) |
N2i—Cu1—N1—C2 | 148.1 (2) | C6—C2—C3—C4 | 175.6 (3) |
O2i—Cu1—N1—C2 | −121.5 (2) | C5—N2—C4—C3 | 179.1 (2) |
O2—Cu1—N1—C2 | 58.5 (2) | Cu1—N2—C4—C3 | −56.3 (3) |
N1—Cu1—N2—C5 | 163.30 (18) | C5—N2—C4—C8 | 56.7 (4) |
N1i—Cu1—N2—C5 | −16.70 (18) | Cu1—N2—C4—C8 | −178.7 (2) |
O2i—Cu1—N2—C5 | −113.11 (19) | C2—C3—C4—N2 | 74.4 (4) |
O2—Cu1—N2—C5 | 66.89 (19) | C2—C3—C4—C8 | −162.2 (3) |
N1—Cu1—N2—C4 | 35.2 (2) | C4—N2—C5—C1i | 173.7 (2) |
N1i—Cu1—N2—C4 | −144.8 (2) | Cu1—N2—C5—C1i | 43.4 (3) |
O2i—Cu1—N2—C4 | 118.8 (2) | O4—Cl1—O2—Cu1 | −165.5 (3) |
O2—Cu1—N2—C4 | −61.2 (2) | O1—Cl1—O2—Cu1 | 70.6 (4) |
C2—N1—C1—C5i | −179.1 (2) | O3—Cl1—O2—Cu1 | −45.3 (4) |
Cu1—N1—C1—C5i | −40.1 (3) | N2—Cu1—O2—Cl1 | −130.2 (3) |
C1—N1—C2—C7 | 55.5 (3) | N2i—Cu1—O2—Cl1 | 49.8 (3) |
Cu1—N1—C2—C7 | −76.2 (3) | N1—Cu1—O2—Cl1 | 135.4 (3) |
C1—N1—C2—C3 | 177.8 (2) | N1i—Cu1—O2—Cl1 | −44.6 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.91 | 2.37 | 3.266 (6) | 170 |
N2—H2N···O3i | 0.91 | 2.48 | 3.293 (5) | 149 |
C7—H71···O2 | 0.96 | 2.37 | 3.296 (6) | 162 |
C3—H32···O4ii | 0.97 | 2.48 | 3.448 (5) | 177 |
C5—H52···O4iii | 0.97 | 2.48 | 3.126 (5) | 124 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1, y, z. |
[Zn(NO3)2(C18H40N4)] | Z = 4 |
Mr = 473.88 | F(000) = 1008 |
Monoclinic, C2/c | Dx = 1.449 Mg m−3 |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.9252 (9) Å | µ = 1.17 mm−1 |
b = 11.7664 (5) Å | T = 295 K |
c = 15.5628 (10) Å | Block, white |
β = 113.352 (8)° | 0.42 × 0.18 × 0.18 mm |
V = 2173.0 (2) Å3 |
Oxford Gemini S Ultra CCD area-detector diffractometer | 2475 independent reflections |
Radiation source: fine-focus sealed tube | 1687 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans, thick slices | θmax = 29.0°, θmin = 3.8° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −17→12 |
Tmin = 0.72, Tmax = 0.82 | k = −14→15 |
4791 measured reflections | l = −21→19 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-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 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
[Zn(NO3)2(C18H40N4)] | V = 2173.0 (2) Å3 |
Mr = 473.88 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.9252 (9) Å | µ = 1.17 mm−1 |
b = 11.7664 (5) Å | T = 295 K |
c = 15.5628 (10) Å | 0.42 × 0.18 × 0.18 mm |
β = 113.352 (8)° |
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 = 0.82 | Rint = 0.032 |
4791 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.46 e Å−3 |
2475 reflections | Δρmin = −0.35 e Å−3 |
136 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.2500 | 0.2500 | 0.5000 | 0.0412 (2) | |
N1 | 0.1962 (2) | 0.4203 (2) | 0.48729 (17) | 0.0354 (6) | |
H1N | 0.1221 | 0.4158 | 0.4482 | 0.042* | |
N2 | 0.2863 (2) | 0.25408 (19) | 0.38136 (16) | 0.0326 (5) | |
H2N | 0.2201 | 0.2447 | 0.3309 | 0.039* | |
C1 | 0.1925 (3) | 0.4475 (3) | 0.5787 (2) | 0.0464 (8) | |
H11 | 0.1458 | 0.5140 | 0.5727 | 0.056* | |
H12 | 0.2679 | 0.4643 | 0.6241 | 0.056* | |
C2 | 0.2408 (2) | 0.5102 (3) | 0.4429 (2) | 0.0384 (7) | |
C3 | 0.2513 (3) | 0.4596 (3) | 0.3561 (2) | 0.0413 (7) | |
H31 | 0.2699 | 0.5211 | 0.3232 | 0.050* | |
H32 | 0.1776 | 0.4316 | 0.3153 | 0.050* | |
C4 | 0.3363 (2) | 0.3636 (3) | 0.3686 (2) | 0.0384 (7) | |
H4 | 0.4036 | 0.3788 | 0.4254 | 0.046* | |
C5 | 0.3551 (3) | 0.1524 (3) | 0.3883 (2) | 0.0445 (8) | |
H51 | 0.4320 | 0.1663 | 0.4320 | 0.053* | |
H52 | 0.3561 | 0.1355 | 0.3277 | 0.053* | |
C6 | 0.1564 (3) | 0.6092 (3) | 0.4103 (3) | 0.0649 (11) | |
H61 | 0.1439 | 0.6392 | 0.4627 | 0.097* | |
H62 | 0.0864 | 0.5824 | 0.3639 | 0.097* | |
H63 | 0.1863 | 0.6679 | 0.3838 | 0.097* | |
C7 | 0.3531 (3) | 0.5563 (3) | 0.5121 (3) | 0.0520 (9) | |
H71 | 0.4038 | 0.4942 | 0.5393 | 0.078* | |
H72 | 0.3414 | 0.5980 | 0.5605 | 0.078* | |
H73 | 0.3850 | 0.6057 | 0.4799 | 0.078* | |
C8 | 0.3707 (3) | 0.3609 (3) | 0.2856 (3) | 0.0603 (10) | |
H81 | 0.4253 | 0.3019 | 0.2948 | 0.090* | |
H82 | 0.4028 | 0.4328 | 0.2804 | 0.090* | |
H83 | 0.3056 | 0.3462 | 0.2293 | 0.090* | |
N3 | 0.5248 (2) | 0.2577 (3) | 0.64525 (19) | 0.0452 (7) | |
O1 | 0.43588 (19) | 0.3035 (2) | 0.59374 (18) | 0.0608 (7) | |
O2 | 0.5319 (3) | 0.1550 (3) | 0.6448 (3) | 0.1232 (16) | |
O3 | 0.6044 (2) | 0.3154 (3) | 0.6959 (2) | 0.0821 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0579 (4) | 0.0316 (3) | 0.0469 (3) | 0.0046 (2) | 0.0342 (3) | 0.0012 (2) |
N1 | 0.0316 (12) | 0.0328 (14) | 0.0405 (14) | −0.0015 (11) | 0.0131 (11) | −0.0020 (11) |
N2 | 0.0299 (12) | 0.0397 (15) | 0.0275 (12) | −0.0029 (10) | 0.0107 (10) | −0.0027 (11) |
C1 | 0.058 (2) | 0.0361 (18) | 0.051 (2) | 0.0042 (15) | 0.0275 (17) | −0.0102 (15) |
C2 | 0.0337 (15) | 0.0292 (16) | 0.0479 (18) | −0.0001 (12) | 0.0116 (14) | 0.0038 (14) |
C3 | 0.0375 (16) | 0.0435 (19) | 0.0368 (17) | −0.0053 (14) | 0.0083 (14) | 0.0082 (14) |
C4 | 0.0331 (15) | 0.0475 (19) | 0.0347 (15) | −0.0093 (14) | 0.0136 (13) | −0.0007 (14) |
C5 | 0.0470 (18) | 0.050 (2) | 0.0462 (18) | 0.0042 (16) | 0.0287 (16) | −0.0053 (16) |
C6 | 0.068 (2) | 0.044 (2) | 0.082 (3) | 0.0154 (18) | 0.029 (2) | 0.016 (2) |
C7 | 0.053 (2) | 0.044 (2) | 0.058 (2) | −0.0114 (16) | 0.0204 (18) | −0.0083 (17) |
C8 | 0.069 (2) | 0.068 (3) | 0.058 (2) | −0.007 (2) | 0.040 (2) | 0.004 (2) |
N3 | 0.0314 (14) | 0.057 (2) | 0.0388 (15) | −0.0074 (14) | 0.0047 (12) | 0.0091 (14) |
O1 | 0.0375 (13) | 0.0563 (16) | 0.0648 (16) | −0.0029 (12) | −0.0050 (12) | 0.0074 (13) |
O2 | 0.068 (2) | 0.070 (2) | 0.160 (4) | 0.0120 (17) | −0.031 (2) | −0.004 (2) |
O3 | 0.0571 (16) | 0.086 (2) | 0.0676 (19) | −0.0298 (16) | −0.0128 (14) | 0.0190 (16) |
Zn1—N2 | 2.078 (2) | C3—H31 | 0.9700 |
Zn1—N2i | 2.078 (2) | C3—H32 | 0.9700 |
Zn1—N1 | 2.104 (2) | C4—C8 | 1.524 (4) |
Zn1—N1i | 2.104 (2) | C4—H4 | 0.9800 |
Zn1—O1 | 2.349 (2) | C5—C1i | 1.508 (4) |
Zn1—O1i | 2.349 (2) | C5—H51 | 0.9700 |
N1—C1 | 1.477 (4) | C5—H52 | 0.9700 |
N1—C2 | 1.498 (4) | C6—H61 | 0.9600 |
N1—H1N | 0.9100 | C6—H62 | 0.9600 |
N2—C5 | 1.469 (4) | C6—H63 | 0.9600 |
N2—C4 | 1.490 (4) | C7—H71 | 0.9600 |
N2—H2N | 0.9100 | C7—H72 | 0.9600 |
C1—C5i | 1.508 (4) | C7—H73 | 0.9600 |
C1—H11 | 0.9700 | C8—H81 | 0.9600 |
C1—H12 | 0.9700 | C8—H82 | 0.9600 |
C2—C7 | 1.524 (4) | C8—H83 | 0.9600 |
C2—C3 | 1.532 (4) | N3—O2 | 1.212 (4) |
C2—C6 | 1.538 (4) | N3—O3 | 1.224 (4) |
C3—C4 | 1.533 (4) | N3—O1 | 1.235 (3) |
N2i—Zn1—N2 | 180.0 | C2—C3—H31 | 107.6 |
N2i—Zn1—N1 | 85.58 (9) | C4—C3—H31 | 107.6 |
N2—Zn1—N1 | 94.42 (9) | C2—C3—H32 | 107.6 |
N2i—Zn1—N1i | 94.42 (9) | C4—C3—H32 | 107.6 |
N2—Zn1—N1i | 85.58 (9) | H31—C3—H32 | 107.0 |
N1—Zn1—N1i | 180.0 | N2—C4—C8 | 112.5 (3) |
N2i—Zn1—O1 | 89.41 (10) | N2—C4—C3 | 109.1 (2) |
N2—Zn1—O1 | 90.59 (10) | C8—C4—C3 | 110.0 (3) |
N1—Zn1—O1 | 91.23 (9) | N2—C4—H4 | 108.4 |
N1i—Zn1—O1 | 88.77 (9) | C8—C4—H4 | 108.4 |
N2i—Zn1—O1i | 90.59 (10) | C3—C4—H4 | 108.4 |
N2—Zn1—O1i | 89.41 (10) | N2—C5—C1i | 110.1 (2) |
N1—Zn1—O1i | 88.77 (9) | N2—C5—H51 | 109.6 |
N1i—Zn1—O1i | 91.23 (9) | C1i—C5—H51 | 109.6 |
O1—Zn1—O1i | 180.00 (7) | N2—C5—H52 | 109.6 |
C1—N1—C2 | 117.1 (2) | C1i—C5—H52 | 109.6 |
C1—N1—Zn1 | 104.59 (18) | H51—C5—H52 | 108.2 |
C2—N1—Zn1 | 122.88 (18) | C2—C6—H61 | 109.5 |
C1—N1—H1N | 103.2 | C2—C6—H62 | 109.5 |
C2—N1—H1N | 103.2 | H61—C6—H62 | 109.5 |
Zn1—N1—H1N | 103.2 | C2—C6—H63 | 109.5 |
C5—N2—C4 | 115.6 (2) | H61—C6—H63 | 109.5 |
C5—N2—Zn1 | 105.00 (18) | H62—C6—H63 | 109.5 |
C4—N2—Zn1 | 113.65 (17) | C2—C7—H71 | 109.5 |
C5—N2—H2N | 107.4 | C2—C7—H72 | 109.5 |
C4—N2—H2N | 107.4 | H71—C7—H72 | 109.5 |
Zn1—N2—H2N | 107.4 | C2—C7—H73 | 109.5 |
N1—C1—C5i | 109.4 (2) | H71—C7—H73 | 109.5 |
N1—C1—H11 | 109.8 | H72—C7—H73 | 109.5 |
C5i—C1—H11 | 109.8 | C4—C8—H81 | 109.5 |
N1—C1—H12 | 109.8 | C4—C8—H82 | 109.5 |
C5i—C1—H12 | 109.8 | H81—C8—H82 | 109.5 |
H11—C1—H12 | 108.2 | C4—C8—H83 | 109.5 |
N1—C2—C7 | 111.0 (3) | H81—C8—H83 | 109.5 |
N1—C2—C3 | 108.5 (2) | H82—C8—H83 | 109.5 |
C7—C2—C3 | 111.6 (3) | O2—N3—O3 | 120.7 (3) |
N1—C2—C6 | 109.6 (3) | O2—N3—O1 | 119.0 (3) |
C7—C2—C6 | 108.4 (3) | O3—N3—O1 | 120.3 (3) |
C3—C2—C6 | 107.6 (3) | N3—O1—Zn1 | 138.2 (2) |
C2—C3—C4 | 119.0 (3) | ||
N2i—Zn1—N1—C1 | 14.07 (19) | Zn1—N1—C2—C3 | 41.0 (3) |
N2—Zn1—N1—C1 | −165.93 (19) | C1—N1—C2—C6 | −69.9 (3) |
O1—Zn1—N1—C1 | −75.25 (19) | Zn1—N1—C2—C6 | 158.2 (2) |
O1i—Zn1—N1—C1 | 104.75 (19) | N1—C2—C3—C4 | −65.4 (3) |
N2i—Zn1—N1—C2 | 150.8 (2) | C7—C2—C3—C4 | 57.2 (4) |
N2—Zn1—N1—C2 | −29.2 (2) | C6—C2—C3—C4 | 176.1 (3) |
O1—Zn1—N1—C2 | 61.5 (2) | C5—N2—C4—C8 | 53.9 (4) |
O1i—Zn1—N1—C2 | −118.5 (2) | Zn1—N2—C4—C8 | 175.4 (2) |
N1—Zn1—N2—C5 | 165.03 (19) | C5—N2—C4—C3 | 176.3 (2) |
N1i—Zn1—N2—C5 | −14.97 (19) | Zn1—N2—C4—C3 | −62.2 (3) |
O1—Zn1—N2—C5 | 73.75 (19) | C2—C3—C4—N2 | 80.6 (3) |
O1i—Zn1—N2—C5 | −106.25 (19) | C2—C3—C4—C8 | −155.5 (3) |
N1—Zn1—N2—C4 | 37.7 (2) | C4—N2—C5—C1i | 168.0 (2) |
N1i—Zn1—N2—C4 | −142.3 (2) | Zn1—N2—C5—C1i | 41.9 (3) |
O1—Zn1—N2—C4 | −53.53 (19) | O2—N3—O1—Zn1 | 11.2 (6) |
O1i—Zn1—N2—C4 | 126.47 (19) | O3—N3—O1—Zn1 | −168.8 (3) |
C2—N1—C1—C5i | 179.7 (2) | N2i—Zn1—O1—N3 | 81.4 (3) |
Zn1—N1—C1—C5i | −40.6 (3) | N2—Zn1—O1—N3 | −98.6 (3) |
C1—N1—C2—C7 | 49.9 (4) | N1—Zn1—O1—N3 | 167.0 (3) |
Zn1—N1—C2—C7 | −82.0 (3) | N1i—Zn1—O1—N3 | −13.0 (3) |
C1—N1—C2—C3 | 172.9 (2) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.91 | 2.11 | 2.983 (5) | 159 |
C7—H71···O1 | 0.96 | 2.38 | 3.245 (4) | 150 |
N2—H2N···O3ii | 0.91 | 2.16 | 3.024 (4) | 159 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
[CuCl(C18H40N4)(H2O)]Cl | Z = 4 |
Mr = 436.94 | F(000) = 932 |
Monoclinic, P21/c | Dx = 1.381 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0350 (4) Å | µ = 1.31 mm−1 |
b = 11.6288 (2) Å | T = 295 K |
c = 13.8132 (4) Å | Block, blue–violet |
β = 111.255 (3)° | 0.32 × 0.18 × 0.12 mm |
V = 2101.10 (9) Å3 |
Oxford Gemini S Ultra CCD area-detector diffractometer | 5230 independent reflections |
Radiation source: fine-focus sealed tube | 4195 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans, thick slices | θmax = 29.1°, θmin = 3.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | h = −18→18 |
Tmin = 0.72, Tmax = 0.82 | k = −15→15 |
45230 measured reflections | l = −18→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H 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 parameters | Δρmax = 0.86 e Å−3 |
3 restraints | Δρmin = −0.34 e Å−3 |
[CuCl(C18H40N4)(H2O)]Cl | V = 2101.10 (9) Å3 |
Mr = 436.94 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.0350 (4) Å | µ = 1.31 mm−1 |
b = 11.6288 (2) Å | T = 295 K |
c = 13.8132 (4) Å | 0.32 × 0.18 × 0.12 mm |
β = 111.255 (3)° |
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 = 0.82 | Rint = 0.045 |
45230 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 3 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.86 e Å−3 |
5230 reflections | Δρmin = −0.34 e Å−3 |
235 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.25910 (2) | 0.57454 (2) | 0.455119 (19) | 0.03022 (9) | |
N1 | 0.27191 (14) | 0.74432 (15) | 0.42025 (15) | 0.0326 (4) | |
H1N | 0.3171 | 0.7411 | 0.3869 | 0.064 (9)* | |
N2 | 0.37329 (13) | 0.57811 (15) | 0.59458 (13) | 0.0298 (4) | |
H2N | 0.4309 | 0.5557 | 0.5840 | 0.036 (7)* | |
C1 | 0.17558 (19) | 0.7735 (2) | 0.33555 (18) | 0.0399 (5) | |
H11 | 0.1844 | 0.8425 | 0.3002 | 0.048* | |
H12 | 0.1223 | 0.7877 | 0.3633 | 0.048* | |
C2 | 0.31681 (19) | 0.83539 (19) | 0.4997 (2) | 0.0394 (5) | |
C3 | 0.4118 (2) | 0.7847 (2) | 0.5834 (2) | 0.0501 (6) | |
H31 | 0.4562 | 0.7555 | 0.5492 | 0.060* | |
H32 | 0.4480 | 0.8472 | 0.6282 | 0.060* | |
C4 | 0.3978 (2) | 0.6907 (2) | 0.65141 (19) | 0.0444 (6) | |
H4 | 0.3401 | 0.7116 | 0.6719 | 0.053* | |
C5 | 0.35013 (17) | 0.4874 (2) | 0.65651 (17) | 0.0368 (5) | |
H51 | 0.2958 | 0.5124 | 0.6794 | 0.044* | |
H52 | 0.4102 | 0.4709 | 0.7174 | 0.044* | |
C6 | 0.3551 (3) | 0.9363 (2) | 0.4506 (3) | 0.0675 (9) | |
H61 | 0.4050 | 0.9086 | 0.4237 | 0.101* | |
H62 | 0.3855 | 0.9939 | 0.5024 | 0.101* | |
H63 | 0.2985 | 0.9691 | 0.3951 | 0.101* | |
C7 | 0.2386 (2) | 0.8806 (2) | 0.5418 (2) | 0.0506 (7) | |
H71 | 0.1907 | 0.9289 | 0.4907 | 0.076* | |
H72 | 0.2724 | 0.9244 | 0.6037 | 0.076* | |
H73 | 0.2029 | 0.8173 | 0.5578 | 0.076* | |
C8 | 0.4935 (2) | 0.6806 (3) | 0.7503 (2) | 0.0572 (8) | |
H81 | 0.5515 | 0.6630 | 0.7318 | 0.086* | |
H82 | 0.4838 | 0.6204 | 0.7934 | 0.086* | |
H83 | 0.5049 | 0.7521 | 0.7875 | 0.086* | |
Cl1 | 0.40429 (4) | 0.56190 (5) | 0.35862 (5) | 0.04264 (15) | |
Cl2 | 0.08968 (5) | 0.40873 (7) | 0.65903 (6) | 0.0604 (2) | |
N1' | 0.23177 (13) | 0.41166 (14) | 0.49404 (14) | 0.0284 (4) | |
H1N' | 0.1771 | 0.4194 | 0.5142 | 0.035 (7)* | |
N2' | 0.14008 (13) | 0.56947 (14) | 0.31823 (13) | 0.0286 (4) | |
H2N' | 0.0820 | 0.5748 | 0.3328 | 0.042 (7)* | |
C1' | 0.31760 (18) | 0.3817 (2) | 0.59060 (19) | 0.0408 (5) | |
H11' | 0.3744 | 0.3520 | 0.5739 | 0.049* | |
H12' | 0.2963 | 0.3227 | 0.6281 | 0.049* | |
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' | 0.0877 | 0.2969 | 0.2716 | 0.043* | |
H32' | 0.0574 | 0.3832 | 0.3420 | 0.043* | |
C4' | 0.13266 (17) | 0.4612 (2) | 0.25817 (17) | 0.0346 (5) | |
H4' | 0.1982 | 0.4481 | 0.2496 | 0.042* | |
C5' | 0.14629 (19) | 0.6745 (2) | 0.26105 (17) | 0.0386 (5) | |
H51' | 0.0807 | 0.6895 | 0.2066 | 0.046* | |
H52' | 0.1969 | 0.6645 | 0.2291 | 0.046* | |
C6' | 0.1624 (2) | 0.2126 (2) | 0.4567 (2) | 0.0508 (7) | |
H61' | 0.2165 | 0.1831 | 0.5165 | 0.076* | |
H62' | 0.1404 | 0.1541 | 0.4042 | 0.076* | |
H6C' | 0.1060 | 0.2352 | 0.4761 | 0.076* | |
C7' | 0.29152 (19) | 0.2815 (2) | 0.3843 (2) | 0.0465 (6) | |
H71' | 0.3252 | 0.3489 | 0.3724 | 0.070* | |
H72' | 0.2675 | 0.2359 | 0.3222 | 0.070* | |
H73' | 0.3388 | 0.2373 | 0.4397 | 0.070* | |
C8' | 0.0485 (2) | 0.4669 (3) | 0.1507 (2) | 0.0514 (7) | |
H81' | −0.0155 | 0.4843 | 0.1578 | 0.077* | |
H82' | 0.0436 | 0.3941 | 0.1164 | 0.077* | |
H83' | 0.0646 | 0.5259 | 0.1105 | 0.077* | |
O1W | 0.11027 (19) | 0.6332 (2) | 0.5439 (2) | 0.0669 (6) | |
H1WA | 0.104 (2) | 0.581 (2) | 0.5840 (18) | 0.060 (10)* | |
H1WB | 0.0525 (13) | 0.638 (3) | 0.4959 (17) | 0.066 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03170 (15) | 0.02389 (14) | 0.02826 (14) | −0.00177 (10) | 0.00272 (11) | 0.00005 (10) |
N1 | 0.0353 (10) | 0.0273 (9) | 0.0379 (10) | 0.0000 (7) | 0.0164 (8) | −0.0027 (7) |
N2 | 0.0252 (9) | 0.0325 (9) | 0.0285 (9) | −0.0021 (7) | 0.0060 (7) | −0.0032 (7) |
C1 | 0.0452 (13) | 0.0298 (11) | 0.0427 (13) | 0.0060 (10) | 0.0135 (11) | 0.0062 (10) |
C2 | 0.0443 (13) | 0.0270 (11) | 0.0492 (14) | −0.0040 (10) | 0.0196 (11) | −0.0068 (10) |
C3 | 0.0413 (14) | 0.0452 (14) | 0.0638 (17) | −0.0123 (11) | 0.0191 (13) | −0.0175 (13) |
C4 | 0.0423 (14) | 0.0424 (13) | 0.0413 (13) | −0.0035 (11) | 0.0064 (11) | −0.0135 (11) |
C5 | 0.0326 (11) | 0.0450 (13) | 0.0279 (11) | −0.0004 (10) | 0.0049 (9) | 0.0047 (9) |
C6 | 0.082 (2) | 0.0450 (16) | 0.090 (2) | −0.0228 (15) | 0.049 (2) | −0.0089 (16) |
C7 | 0.0584 (17) | 0.0447 (14) | 0.0569 (16) | −0.0008 (12) | 0.0306 (14) | −0.0136 (12) |
C8 | 0.0488 (16) | 0.0580 (17) | 0.0476 (15) | 0.0002 (13) | −0.0033 (12) | −0.0205 (13) |
Cl1 | 0.0353 (3) | 0.0472 (3) | 0.0505 (3) | 0.0073 (2) | 0.0215 (3) | 0.0000 (3) |
Cl2 | 0.0458 (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) |
O1W | 0.0698 (16) | 0.0588 (14) | 0.0749 (16) | −0.0134 (12) | 0.0296 (14) | 0.0034 (12) |
Cu1—N2 | 2.0106 (17) | C8—H81 | 0.9600 |
Cu1—N2' | 2.0197 (17) | C8—H82 | 0.9600 |
Cu1—N1' | 2.0429 (17) | C8—H83 | 0.9600 |
Cu1—N1 | 2.0555 (18) | N1'—C1' | 1.479 (3) |
Cu1—Cl1 | 2.8143 (6) | N1'—C2' | 1.506 (3) |
Cu1—O1W | 2.861 (2) | N1'—H1N' | 0.9100 |
N1—C1 | 1.471 (3) | N2'—C5' | 1.474 (3) |
N1—C2 | 1.490 (3) | N2'—C4' | 1.491 (3) |
N1—H1N | 0.9100 | N2'—H2N' | 0.9100 |
N2—C5 | 1.467 (3) | C1'—H11' | 0.9700 |
N2—C4 | 1.501 (3) | C1'—H12' | 0.9700 |
N2—H2N | 0.9100 | C2'—C7' | 1.526 (3) |
C1—C5' | 1.500 (3) | C2'—C3' | 1.531 (3) |
C1—H11 | 0.9700 | C2'—C6' | 1.534 (3) |
C1—H12 | 0.9700 | C3'—C4' | 1.524 (3) |
C2—C7 | 1.511 (3) | C3'—H31' | 0.9700 |
C2—C3 | 1.532 (4) | C3'—H32' | 0.9700 |
C2—C6 | 1.546 (4) | C4'—C8' | 1.527 (3) |
C3—C4 | 1.499 (4) | C4'—H4' | 0.9800 |
C3—H31 | 0.9700 | C5'—H51' | 0.9700 |
C3—H32 | 0.9700 | C5'—H52' | 0.9700 |
C4—C8 | 1.533 (3) | C6'—H61' | 0.9600 |
C4—H4 | 0.9800 | C6'—H62' | 0.9600 |
C5—C1' | 1.499 (3) | C6'—H6C' | 0.9600 |
C5—H51 | 0.9700 | C7'—H71' | 0.9600 |
C5—H52 | 0.9700 | C7'—H72' | 0.9600 |
C6—H61 | 0.9600 | C7'—H73' | 0.9600 |
C6—H62 | 0.9600 | C8'—H81' | 0.9600 |
C6—H63 | 0.9600 | C8'—H82' | 0.9600 |
C7—H71 | 0.9600 | C8'—H83' | 0.9600 |
C7—H72 | 0.9600 | O1W—H1WA | 0.844 (10) |
C7—H73 | 0.9600 | O1W—H1WB | 0.843 (10) |
N2—Cu1—N2' | 177.48 (7) | C4—C8—H81 | 109.5 |
N2—Cu1—N1' | 85.84 (7) | C4—C8—H82 | 109.5 |
N2'—Cu1—N1' | 92.80 (7) | H81—C8—H82 | 109.5 |
N2—Cu1—N1 | 95.60 (7) | C4—C8—H83 | 109.5 |
N2'—Cu1—N1 | 85.50 (7) | H81—C8—H83 | 109.5 |
N1'—Cu1—N1 | 173.19 (7) | H82—C8—H83 | 109.5 |
N2—Cu1—Cl1 | 89.56 (5) | C1'—N1'—C2' | 114.33 (17) |
N2'—Cu1—Cl1 | 92.88 (5) | C1'—N1'—Cu1 | 106.65 (13) |
N1'—Cu1—Cl1 | 108.27 (5) | C2'—N1'—Cu1 | 120.96 (13) |
N1—Cu1—Cl1 | 78.42 (5) | C1'—N1'—H1N' | 104.4 |
N2—Cu1—O1W | 92.11 (8) | C2'—N1'—H1N' | 104.4 |
N2'—Cu1—O1W | 85.61 (7) | Cu1—N1'—H1N' | 104.4 |
N1'—Cu1—O1W | 82.66 (7) | C5'—N2'—C4' | 114.04 (17) |
N1—Cu1—O1W | 90.63 (7) | C5'—N2'—Cu1 | 106.74 (13) |
Cl1—Cu1—O1W | 169.04 (5) | C4'—N2'—Cu1 | 114.38 (13) |
C1—N1—C2 | 116.27 (18) | C5'—N2'—H2N' | 107.1 |
C1—N1—Cu1 | 105.96 (14) | C4'—N2'—H2N' | 107.1 |
C2—N1—Cu1 | 124.03 (15) | Cu1—N2'—H2N' | 107.1 |
C1—N1—H1N | 102.4 | N1'—C1'—C5 | 108.89 (18) |
C2—N1—H1N | 102.4 | N1'—C1'—H11' | 109.9 |
Cu1—N1—H1N | 102.4 | C5—C1'—H11' | 109.9 |
C5—N2—C4 | 112.31 (18) | N1'—C1'—H12' | 109.9 |
C5—N2—Cu1 | 106.00 (13) | C5—C1'—H12' | 109.9 |
C4—N2—Cu1 | 118.10 (14) | H11'—C1'—H12' | 108.3 |
C5—N2—H2N | 106.6 | N1'—C2'—C7' | 110.59 (18) |
C4—N2—H2N | 106.6 | N1'—C2'—C3' | 108.23 (16) |
Cu1—N2—H2N | 106.6 | C7'—C2'—C3' | 110.9 (2) |
N1—C1—C5' | 108.21 (18) | N1'—C2'—C6' | 110.08 (19) |
N1—C1—H11 | 110.1 | C7'—C2'—C6' | 109.5 (2) |
C5'—C1—H11 | 110.1 | C3'—C2'—C6' | 107.50 (19) |
N1—C1—H12 | 110.1 | C4'—C3'—C2' | 118.11 (18) |
C5'—C1—H12 | 110.1 | C4'—C3'—H31' | 107.8 |
H11—C1—H12 | 108.4 | C2'—C3'—H31' | 107.8 |
N1—C2—C7 | 111.0 (2) | C4'—C3'—H32' | 107.8 |
N1—C2—C3 | 107.60 (18) | C2'—C3'—H32' | 107.8 |
C7—C2—C3 | 113.5 (2) | H31'—C3'—H32' | 107.1 |
N1—C2—C6 | 109.8 (2) | N2'—C4'—C3' | 109.18 (17) |
C7—C2—C6 | 108.7 (2) | N2'—C4'—C8' | 112.2 (2) |
C3—C2—C6 | 106.1 (2) | C3'—C4'—C8' | 109.7 (2) |
C4—C3—C2 | 118.5 (2) | N2'—C4'—H4' | 108.6 |
C4—C3—H31 | 107.7 | C3'—C4'—H4' | 108.6 |
C2—C3—H31 | 107.7 | C8'—C4'—H4' | 108.6 |
C4—C3—H32 | 107.7 | N2'—C5'—C1 | 108.87 (18) |
C2—C3—H32 | 107.7 | N2'—C5'—H51' | 109.9 |
H31—C3—H32 | 107.1 | C1—C5'—H51' | 109.9 |
C3—C4—N2 | 111.4 (2) | N2'—C5'—H52' | 109.9 |
C3—C4—C8 | 110.0 (2) | C1—C5'—H52' | 109.9 |
N2—C4—C8 | 111.1 (2) | H51'—C5'—H52' | 108.3 |
C3—C4—H4 | 108.1 | C2'—C6'—H61' | 109.5 |
N2—C4—H4 | 108.1 | C2'—C6'—H62' | 109.5 |
C8—C4—H4 | 108.1 | H61'—C6'—H62' | 109.5 |
N2—C5—C1' | 108.58 (18) | C2'—C6'—H6C' | 109.5 |
N2—C5—H51 | 110.0 | H61'—C6'—H6C' | 109.5 |
C1'—C5—H51 | 110.0 | H62'—C6'—H6C' | 109.5 |
N2—C5—H52 | 110.0 | C2'—C7'—H71' | 109.5 |
C1'—C5—H52 | 110.0 | C2'—C7'—H72' | 109.5 |
H51—C5—H52 | 108.4 | H71'—C7'—H72' | 109.5 |
C2—C6—H61 | 109.5 | C2'—C7'—H73' | 109.5 |
C2—C6—H62 | 109.5 | H71'—C7'—H73' | 109.5 |
H61—C6—H62 | 109.5 | H72'—C7'—H73' | 109.5 |
C2—C6—H63 | 109.5 | C4'—C8'—H81' | 109.5 |
H61—C6—H63 | 109.5 | C4'—C8'—H82' | 109.5 |
H62—C6—H63 | 109.5 | H81'—C8'—H82' | 109.5 |
C2—C7—H71 | 109.5 | C4'—C8'—H83' | 109.5 |
C2—C7—H72 | 109.5 | H81'—C8'—H83' | 109.5 |
H71—C7—H72 | 109.5 | H82'—C8'—H83' | 109.5 |
C2—C7—H73 | 109.5 | Cu1—O1W—H1WA | 112 (2) |
H71—C7—H73 | 109.5 | Cu1—O1W—H1WB | 109 (2) |
H72—C7—H73 | 109.5 | H1WA—O1W—H1WB | 105.7 (15) |
N2—Cu1—N1—C1 | −162.71 (14) | N2'—Cu1—N1'—C1' | 173.32 (15) |
N2'—Cu1—N1—C1 | 15.02 (14) | Cl1—Cu1—N1'—C1' | 79.36 (14) |
Cl1—Cu1—N1—C1 | 108.89 (14) | O1W—Cu1—N1'—C1' | −101.47 (15) |
O1W—Cu1—N1—C1 | −70.53 (15) | N2—Cu1—N1'—C2' | −141.72 (15) |
N2—Cu1—N1—C2 | −24.24 (18) | N2'—Cu1—N1'—C2' | 40.40 (15) |
N2'—Cu1—N1—C2 | 153.49 (18) | Cl1—Cu1—N1'—C2' | −53.56 (15) |
Cl1—Cu1—N1—C2 | −112.64 (17) | O1W—Cu1—N1'—C2' | 125.61 (15) |
O1W—Cu1—N1—C2 | 67.94 (17) | N1'—Cu1—N2'—C5' | −172.51 (14) |
N1'—Cu1—N2—C5 | −19.68 (14) | N1—Cu1—N2'—C5' | 14.10 (14) |
N1—Cu1—N2—C5 | 153.64 (14) | Cl1—Cu1—N2'—C5' | −64.04 (13) |
Cl1—Cu1—N2—C5 | −128.04 (13) | O1W—Cu1—N2'—C5' | 105.08 (14) |
O1W—Cu1—N2—C5 | 62.80 (14) | N1'—Cu1—N2'—C4' | −45.39 (15) |
N1'—Cu1—N2—C4 | −146.61 (17) | N1—Cu1—N2'—C4' | 141.22 (15) |
N1—Cu1—N2—C4 | 26.71 (17) | Cl1—Cu1—N2'—C4' | 63.08 (14) |
Cl1—Cu1—N2—C4 | 105.04 (16) | O1W—Cu1—N2'—C4' | −127.80 (15) |
O1W—Cu1—N2—C4 | −64.13 (17) | C2'—N1'—C1'—C5 | 171.92 (18) |
C2—N1—C1—C5' | 176.73 (19) | Cu1—N1'—C1'—C5 | 35.5 (2) |
Cu1—N1—C1—C5' | −41.1 (2) | N2—C5—C1'—N1' | −54.7 (2) |
C1—N1—C2—C7 | 51.7 (3) | C1'—N1'—C2'—C7' | −58.1 (2) |
Cu1—N1—C2—C7 | −83.0 (2) | Cu1—N1'—C2'—C7' | 71.6 (2) |
C1—N1—C2—C3 | 176.4 (2) | C1'—N1'—C2'—C3' | −179.74 (18) |
Cu1—N1—C2—C3 | 41.7 (2) | Cu1—N1'—C2'—C3' | −50.1 (2) |
C1—N1—C2—C6 | −68.6 (3) | C1'—N1'—C2'—C6' | 63.0 (2) |
Cu1—N1—C2—C6 | 156.75 (19) | Cu1—N1'—C2'—C6' | −167.32 (15) |
N1—C2—C3—C4 | −67.7 (3) | N1'—C2'—C3'—C4' | 64.4 (2) |
C7—C2—C3—C4 | 55.5 (3) | C7'—C2'—C3'—C4' | −57.0 (3) |
C6—C2—C3—C4 | 174.8 (2) | C6'—C2'—C3'—C4' | −176.7 (2) |
C2—C3—C4—N2 | 75.5 (3) | C5'—N2'—C4'—C3' | −172.51 (18) |
C2—C3—C4—C8 | −160.9 (2) | Cu1—N2'—C4'—C3' | 64.2 (2) |
C5—N2—C4—C3 | −174.81 (19) | C5'—N2'—C4'—C8' | −50.7 (3) |
Cu1—N2—C4—C3 | −51.0 (2) | Cu1—N2'—C4'—C8' | −173.95 (16) |
C5—N2—C4—C8 | 62.2 (3) | C2'—C3'—C4'—N2' | −74.6 (2) |
Cu1—N2—C4—C8 | −174.01 (18) | C2'—C3'—C4'—C8' | 162.1 (2) |
C4—N2—C5—C1' | 175.00 (18) | C4'—N2'—C5'—C1 | −168.11 (18) |
Cu1—N2—C5—C1' | 44.7 (2) | Cu1—N2'—C5'—C1 | −40.8 (2) |
N2—Cu1—N1'—C1' | −8.80 (15) | N1—C1—C5'—N2' | 56.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.91 | 2.52 | 3.135 (2) | 125 |
C7—H73···O1W | 0.96 | 2.48 | 3.400 (4) | 161 |
C7′—H71′···Cl1 | 0.96 | 2.75 | 3.697 (3) | 170 |
N2—H2N···Cl1i | 0.91 | 2.55 | 3.369 (2) | 149 |
N1′—H1N′···Cl2 | 0.91 | 2.70 | 3.531 (2) | 152 |
N2′—H2N′···Cl2ii | 0.91 | 2.46 | 3.361 (2) | 171 |
O1W—H1WA···Cl2 | 0.85 (2) | 2.30 (2) | 3.123 (3) | 165 (2) |
O1W—H1WB···Cl2ii | 0.84 (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 |
Mr | 546.93 | 473.88 | 436.94 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 295 | 295 | 295 |
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) |
V (Å3) | 1189.9 (10) | 2173.0 (2) | 2101.10 (9) |
Z | 2 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.19 | 1.17 | 1.31 |
Crystal size (mm) | 0.22 × 0.20 × 0.16 | 0.42 × 0.18 × 0.18 | 0.32 × 0.18 × 0.12 |
Data collection | |||
Diffractometer | Oxford Gemini S Ultra CCD area-detector diffractometer | Oxford Gemini S Ultra CCD area-detector diffractometer | Oxford Gemini S Ultra CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
Tmin, Tmax | 0.72, 0.82 | 0.72, 0.82 | 0.72, 0.82 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15029, 2878, 2167 | 4791, 2475, 1687 | 45230, 5230, 4195 |
Rint | 0.043 | 0.032 | 0.045 |
(sin θ/λ)max (Å−1) | 0.683 | 0.682 | 0.684 |
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 reflections | 2878 | 2475 | 5230 |
No. of parameters | 145 | 136 | 235 |
No. of restraints | 21 | 0 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.51, −0.43 | 0.46, −0.35 | 0.86, −0.34 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.91 | 2.37 | 3.266 (6) | 170 |
N2—H2N···O3i | 0.91 | 2.48 | 3.293 (5) | 149 |
C7—H71···O2 | 0.96 | 2.37 | 3.296 (6) | 162 |
C3—H32···O4ii | 0.97 | 2.48 | 3.448 (5) | 177 |
C5—H52···O4iii | 0.97 | 2.48 | 3.126 (5) | 124 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.91 | 2.11 | 2.983 (5) | 159 |
C7—H71···O1 | 0.96 | 2.38 | 3.245 (4) | 150 |
N2—H2N···O3ii | 0.91 | 2.16 | 3.024 (4) | 159 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, z−1/2. |
Cu1—N2 | 2.0106 (17) | Cu1—N1 | 2.0555 (18) |
Cu1—N2' | 2.0197 (17) | Cu1—Cl1 | 2.8143 (6) |
Cu1—N1' | 2.0429 (17) | Cu1—O1W | 2.861 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.91 | 2.52 | 3.135 (2) | 125 |
C7—H73···O1W | 0.96 | 2.48 | 3.400 (4) | 161 |
C7'—H71'···Cl1 | 0.96 | 2.75 | 3.697 (3) | 170 |
N2—H2N···Cl1i | 0.91 | 2.55 | 3.369 (2) | 149 |
N1'—H1N'···Cl2 | 0.91 | 2.70 | 3.531 (2) | 152 |
N2'—H2N'···Cl2ii | 0.91 | 2.46 | 3.361 (2) | 171 |
O1W—H1WA···Cl2 | 0.85 (2) | 2.30 (2) | 3.123 (3) | 165 (2) |
O1W—H1WB···Cl2ii | 0.84 (2) | 2.40 (2) | 3.204 (3) | 160 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1. |