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In the crystal structure of [Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O, the CuII atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi-coordination distance. Pairs of inversion-related N—H...N hydrogen bonds of the so-called Watson–Crick type, augmented by two C—H...N contacts, link adjacent complexes into an infinite one-dimensional chain running in the [101] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103028385/fa1041sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103028385/fa1041Isup2.hkl
Contains datablock I

CCDC reference: 233105

Comment top

In recent years, the anionic dicyanamide ligand has attracted much interest, in the form of MII(dca)2 [where M is Ni, Co or Cu, and dca N(CN)2], as a new class of molecule-based magnetic materials (Batten et al., 1998; Batten & Murray, 2001; Manson et al., 1999). In the field of crystal engineering, the number of X-ray crystal structures of compounds with the dca anion showing one-, two- and three-dimensional networks has increased enormously in the last few years (e.g. Kohout et al., 2000; Vangdal et al., 2002; Mohamadou et al., 2003; Kooijman et al., 2002; Shi et al., 2003).

Dicyanamide itself is an interesting anionic bridging ligand and can act as a monodentate, bidentate or even tridentate ligand (Mroziński et al., 1997; Escuer et al., 2000). Various coordination modes of the dicyanamide ligand and the metal can occur, such as monodentate bonding via the nitrile atom, coordination via the amide atom (Marshall et al., 2002; Mohamadou et al., 2003; Shi et al., 2003; Vangdal et al., 2002), and even µ4 and µ5 coordination, where nitrile atoms bridge two metal atoms (Chow & Britton, 1975; Shi et al., 2002). However, in most cases monodentate or bidentate coordination via the nitrile N atom is found.

In the field of supramolecular chemistry, not only are direct metal-ligand bonds of interest, but hydrogen bonding is also of great importance (Beatty, 2001; Rodríguez-Martin et al., 2002; Nedelcu et al., 2003; Kutasi et al., 2002; Riggio et al., 2001). One ligand with interesting hydrogen-bonding properties is the recently developed di-2-pyrimidylamine (abbreviated as dipm). The dipm molecule can both donate and accept hydrogen bonds, and has a more or less linear donor-acceptor array of type ADA. This type of array is capable of forming so-called Watson-Crick-type hydrogen bonds (van Albada et al., 2002), as was also shown in the literature with the first generation ligand 2-aminopyrimidine (van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).

To date, only one X-ray crystal structure determination of a dipm-containing complex has been published, [Cu(dipm)(CO3)(H2O)]·2H2O (van Albada et al., 2002). In this paper, we present the crystal structure of a new complex of copper with the dipm molecule as ligand, which has the formulation [Cu(dca)(dipm)2(tms)], (I), where tms is the trifluoromethylsulfonate anion. An atomic displacement ellipsoid plot of this complex is given in Fig. 1, together with the atomic labelling scheme. Selected geometric parameters are given in Table 1. \sch

The geometry around the CuII ion in (I) is distorted octahedral, with the basal plane formed by two pyrimidinyl N atoms of one of the coordinating dipm molecules (N111 and N121), one pyrimidinyl N atom of the second coordinating dipm molecule (N211) and a nitrile N atom (N2) of the dca ligand. The Cu—N distances are in the range 1.972 (2)–2.021 (2) Å. The trans-basal angles are 176.41 (8) (N111—Cu1—N211) and 165.33 (9)° (N2—Cu1—N121). The apical positions are occupied by a pyrimidinyl N atom (N221) of the second dipm ligand, at a distance of 2.208 (2) Å, and by an O atom (O1) of the trifluoromethylsulfonate anion, at a semi-coordination distance of 2.747 (2) Å.

The dipm molecules in (I) show a significant difference in conformation. The angle between the least-squares planes through the pyrimidine rings is 33.71 (12)° in the ligand containing atom N11 and 11.73 (13)° in the molecule containing atom N21. In the dipm-copper-carbonate complex reported previously, the dipm molecule is virtually planar, with a ring-ring angle of 1.80 (11)°.

The lattice of (I) is stabilized by two crystallographically independent hydrogen-bonding systems, both of the so-called Watson-Crick type (Fig. 2). The systems are formed by donation of a hydrogen bond by the amine N atom of a dipm molecule (either N11 or N21) to a non-coordinating pyrimidinyl N atom of an inversion-related dipm molecule (N113 or N213, respectively). Due to the crystallographic inversion symmetry, a hydrogen-bonded ring is formed with unitary graph-set R22(8) (Bernstein et al., 1995). The hydrogen-bonded system involving atom N11 is formed around the inversion centre at (1/2,1/2,1/2), while that involving atom N21 is formed around the centre at (0,1/2,0). Geometric details are given in Table 2.

The hydrogen-bonded systems link the copper complexes into an infinite one-dimensional chain running in the [101] direction. Within each chain, the copper complexes are linked alternately by hydrogen-bonded systems involving atoms N11 or N21 (Fig. 2). This arrangement of hydrogen-bonded dipm molecules may facilitate the formation of two C—H···N contacts adjacent to the N—H···N hydrogen bonds, resulting in the formation of a quadruply hydrogen-bonded array of type DADA (a review of quadruply hydrogen-bonded systems is given by Sijbesma & Meijer, 2003). Due to the deviations from planarity of the dipm molecules, the C—H···N contacts are somewhat long, especially that involving C114—H114 (Table 2). However, these contacts may still play a role in the stabilization of the hydrogen-bonded network of (I). The dipm-copper-carbonate complex reported previously displayed a similar hydrogen-bonded structure (van Albada et al., 2002).

The non-coordinating nitrile moiety of the dca anion in (I) does not accept any hydrogen bonds. There is a close contact [2.947 (4) Å, i.e. approximately 0.2 Å less than the sum of the Van der Waals radii] between atom N3 of the dca anion and atom C122(1 - x, y - 1/2, 1/2 - z) of a dipm molecule. Atom N3 also displays a short contact to atom C112 of the same dipm molecule, at 3.086 (3) Å. Contacts of the type C N···C(sp2)X3, where X = C, N, O, P, S or halogen, are not unsual. The July 2003 update of the Cambridge Structural Database (Allen, 2002) contains approximately 150 examples with N···C distances in the range 2.8–3.2 Å, 23 of which display contact distances shorter than the value observed in the crystal structure of (I).

The electron paramagnetic resonance (EPR) spectrum for (I), measured as a polycrystalline powder at room temperature and at 77 K, shows an axial S = 1/2 signal, with g = 2.06, a value typical for CuII and in agreement with a dx2-y2 ground state.

Experimental top

The dipm ligand was synthesized using the method of Yao et al. (2000). Metal salts and solvents were commercially available and used without further purification. The title compound was synthesized by mixing equimolar amounts of copper(II) trifluoromethylsulfonate, sodium dicyanamide and di-2-pyrimidylamine in an ethanol/water (Ratio?) mixture. After standing in air at room temperature for about two weeks, blue-green block-shaped crystals of (I) were formed, which were suitable for X-ray structure determination. IR analysis: the characteristic trifluoromethanesulfonate vibrations are observed at 1255, 1246, 1223, 1154 and 1026 cm-1 (van Albada et al., 1997, 1998). The characteristic IR vibrations for the dicyanamide anion are found in the 2400–2100 cm-1 region (Kohout et al., 2000). The νs + νas(C—N) is observed as two weak-to-medium bands at 2361 and 2294 cm-1, and the ν(CN) is observed as two medium-to-strong bands at 2238 and 2167 cm-1. These vibrations occur in the ranges found for other polymeric copper(II) dicyanamide compounds (Kohout et al., 2000; Riggio et al., 2001; van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).

Refinement top

An absorption correction based on multiple measurements of symmetry-related reflections had little influence on Rint, R1 and the residual density. The correction was therefore not considered necessary and was not applied to the reflection data. The amine H atoms were located in a difference Fourier map and their coordinates were refined. The other H atoms were placed in calculated positions, riding on their carrier atoms. Uiso(H) values were set to 1.5 or 1.2 times Ueq(parent atom) for amine H atoms and other H atoms, respectively. The unit cell contains two symmetry-related cavities located on the crystallographic inversion centres at (1/2,0,1/2) and (1/2,1/2,0), filled with disordered solvent, probably ethanol. The volume of each cavity is 81 Å3. Attempts to model an ethanol molecule into the solvent density did not result in an acceptable model. There are no groups lining the cavity which could accept a hydrogen bond from the solvent. The contribution of the disordered solvent to the scattering factors has been taken into account with PLATON/SQUEEZE (Spek, 2003; van der Sluis & Spek, 1990). A total of 24 e was found in each cavity, corresponding to approximately one ethanol molecule per cavity. Where relevant, the crystal data reported earlier in this paper are given without the contribution of the disordered solvent. Taking into account the presence of one ethanol molecule per cavity, the following values are obtained: C19H14CuF3N13O3S·0.5C2H6O, Mr = 648.05, µ = 1.065 mm-1, F(000) = 1312 and Dx = 1.708 Mg m-3.

Structure description top

In recent years, the anionic dicyanamide ligand has attracted much interest, in the form of MII(dca)2 [where M is Ni, Co or Cu, and dca N(CN)2], as a new class of molecule-based magnetic materials (Batten et al., 1998; Batten & Murray, 2001; Manson et al., 1999). In the field of crystal engineering, the number of X-ray crystal structures of compounds with the dca anion showing one-, two- and three-dimensional networks has increased enormously in the last few years (e.g. Kohout et al., 2000; Vangdal et al., 2002; Mohamadou et al., 2003; Kooijman et al., 2002; Shi et al., 2003).

Dicyanamide itself is an interesting anionic bridging ligand and can act as a monodentate, bidentate or even tridentate ligand (Mroziński et al., 1997; Escuer et al., 2000). Various coordination modes of the dicyanamide ligand and the metal can occur, such as monodentate bonding via the nitrile atom, coordination via the amide atom (Marshall et al., 2002; Mohamadou et al., 2003; Shi et al., 2003; Vangdal et al., 2002), and even µ4 and µ5 coordination, where nitrile atoms bridge two metal atoms (Chow & Britton, 1975; Shi et al., 2002). However, in most cases monodentate or bidentate coordination via the nitrile N atom is found.

In the field of supramolecular chemistry, not only are direct metal-ligand bonds of interest, but hydrogen bonding is also of great importance (Beatty, 2001; Rodríguez-Martin et al., 2002; Nedelcu et al., 2003; Kutasi et al., 2002; Riggio et al., 2001). One ligand with interesting hydrogen-bonding properties is the recently developed di-2-pyrimidylamine (abbreviated as dipm). The dipm molecule can both donate and accept hydrogen bonds, and has a more or less linear donor-acceptor array of type ADA. This type of array is capable of forming so-called Watson-Crick-type hydrogen bonds (van Albada et al., 2002), as was also shown in the literature with the first generation ligand 2-aminopyrimidine (van Albada, Quiroz-Castro et al., 2000; van Albada, Smeets et al., 2000).

To date, only one X-ray crystal structure determination of a dipm-containing complex has been published, [Cu(dipm)(CO3)(H2O)]·2H2O (van Albada et al., 2002). In this paper, we present the crystal structure of a new complex of copper with the dipm molecule as ligand, which has the formulation [Cu(dca)(dipm)2(tms)], (I), where tms is the trifluoromethylsulfonate anion. An atomic displacement ellipsoid plot of this complex is given in Fig. 1, together with the atomic labelling scheme. Selected geometric parameters are given in Table 1. \sch

The geometry around the CuII ion in (I) is distorted octahedral, with the basal plane formed by two pyrimidinyl N atoms of one of the coordinating dipm molecules (N111 and N121), one pyrimidinyl N atom of the second coordinating dipm molecule (N211) and a nitrile N atom (N2) of the dca ligand. The Cu—N distances are in the range 1.972 (2)–2.021 (2) Å. The trans-basal angles are 176.41 (8) (N111—Cu1—N211) and 165.33 (9)° (N2—Cu1—N121). The apical positions are occupied by a pyrimidinyl N atom (N221) of the second dipm ligand, at a distance of 2.208 (2) Å, and by an O atom (O1) of the trifluoromethylsulfonate anion, at a semi-coordination distance of 2.747 (2) Å.

The dipm molecules in (I) show a significant difference in conformation. The angle between the least-squares planes through the pyrimidine rings is 33.71 (12)° in the ligand containing atom N11 and 11.73 (13)° in the molecule containing atom N21. In the dipm-copper-carbonate complex reported previously, the dipm molecule is virtually planar, with a ring-ring angle of 1.80 (11)°.

The lattice of (I) is stabilized by two crystallographically independent hydrogen-bonding systems, both of the so-called Watson-Crick type (Fig. 2). The systems are formed by donation of a hydrogen bond by the amine N atom of a dipm molecule (either N11 or N21) to a non-coordinating pyrimidinyl N atom of an inversion-related dipm molecule (N113 or N213, respectively). Due to the crystallographic inversion symmetry, a hydrogen-bonded ring is formed with unitary graph-set R22(8) (Bernstein et al., 1995). The hydrogen-bonded system involving atom N11 is formed around the inversion centre at (1/2,1/2,1/2), while that involving atom N21 is formed around the centre at (0,1/2,0). Geometric details are given in Table 2.

The hydrogen-bonded systems link the copper complexes into an infinite one-dimensional chain running in the [101] direction. Within each chain, the copper complexes are linked alternately by hydrogen-bonded systems involving atoms N11 or N21 (Fig. 2). This arrangement of hydrogen-bonded dipm molecules may facilitate the formation of two C—H···N contacts adjacent to the N—H···N hydrogen bonds, resulting in the formation of a quadruply hydrogen-bonded array of type DADA (a review of quadruply hydrogen-bonded systems is given by Sijbesma & Meijer, 2003). Due to the deviations from planarity of the dipm molecules, the C—H···N contacts are somewhat long, especially that involving C114—H114 (Table 2). However, these contacts may still play a role in the stabilization of the hydrogen-bonded network of (I). The dipm-copper-carbonate complex reported previously displayed a similar hydrogen-bonded structure (van Albada et al., 2002).

The non-coordinating nitrile moiety of the dca anion in (I) does not accept any hydrogen bonds. There is a close contact [2.947 (4) Å, i.e. approximately 0.2 Å less than the sum of the Van der Waals radii] between atom N3 of the dca anion and atom C122(1 - x, y - 1/2, 1/2 - z) of a dipm molecule. Atom N3 also displays a short contact to atom C112 of the same dipm molecule, at 3.086 (3) Å. Contacts of the type C N···C(sp2)X3, where X = C, N, O, P, S or halogen, are not unsual. The July 2003 update of the Cambridge Structural Database (Allen, 2002) contains approximately 150 examples with N···C distances in the range 2.8–3.2 Å, 23 of which display contact distances shorter than the value observed in the crystal structure of (I).

The electron paramagnetic resonance (EPR) spectrum for (I), measured as a polycrystalline powder at room temperature and at 77 K, shows an axial S = 1/2 signal, with g = 2.06, a value typical for CuII and in agreement with a dx2-y2 ground state.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), showing the atom-numbering scheme and with displacement ellipsoids at the 50% probability level. H atoms bonded to C atoms have been omitted for clarity.
[Figure 2] Fig. 2. A plot showing a fragment of the hydrogen-bonded network in (I) in the [101] direction. The hydrogen-bonded ring involving atom N11 is accentuated in light grey and that involving atom N21 in dark grey. H atoms not involved in hydrogen bonding have been omitted for clarity.
Bis[bis(pyrimidin-2-yl-κN)amine](dicyanamido- κN1)(trifluoromethanesulfonato-κO)copper(II) ethanol hemisolvate top
Crystal data top
[Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6OF(000) = 1260
Mr = 625.05Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set.
Monoclinic, P21/cDx = 1.648 Mg m3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 9.972 (2) ÅCell parameters from 304 reflections
b = 13.751 (2) Åθ = 2.0–25.0°
c = 18.516 (4) ŵ = 1.02 mm1
β = 97.047 (8)°T = 150 K
V = 2519.8 (8) Å3Block, blue-green
Z = 40.2 × 0.1 × 0.1 mm
Data collection top
Nonius Kappa CCD area-detector
diffractometer
3766 reflections with I > 2σ(I)
Radiation source: Rotating anodeRint = 0.119
Graphite monochromatorθmax = 27.4°, θmin = 1.9°
Detector resolution: 18.4 pixels mm-1h = 1212
φ scans and ω scans with κ offsetk = 1717
56102 measured reflectionsl = 2323
5712 independent reflections
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) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0468P)2]
where P = (Fo2 + 2Fc2)/3
5712 reflections(Δ/σ)max = 0.001
367 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
[Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6OV = 2519.8 (8) Å3
Mr = 625.05Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.972 (2) ŵ = 1.02 mm1
b = 13.751 (2) ÅT = 150 K
c = 18.516 (4) Å0.2 × 0.1 × 0.1 mm
β = 97.047 (8)°
Data collection top
Nonius Kappa CCD area-detector
diffractometer
3766 reflections with I > 2σ(I)
56102 measured reflectionsRint = 0.119
5712 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.36 e Å3
5712 reflectionsΔρmin = 0.55 e Å3
367 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All s.u.s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.24153 (3)0.50090 (2)0.25102 (1)0.0184 (1)
S10.15554 (9)0.25256 (6)0.35456 (4)0.0410 (3)
F10.1753 (2)0.17557 (14)0.48504 (10)0.0562 (7)
F20.36370 (19)0.22129 (16)0.45168 (11)0.0663 (9)
F30.2260 (2)0.32628 (14)0.48366 (9)0.0538 (7)
O10.2312 (2)0.32820 (14)0.32466 (10)0.0386 (7)
O20.0182 (2)0.2769 (2)0.36276 (15)0.0836 (13)
O30.1737 (3)0.15685 (18)0.32620 (14)0.0829 (13)
N10.3835 (3)0.25713 (17)0.13134 (14)0.0363 (9)
N20.3122 (2)0.41020 (17)0.18235 (12)0.0260 (8)
N30.6131 (3)0.22466 (16)0.09952 (13)0.0330 (9)
N110.3461 (2)0.50682 (15)0.42174 (11)0.0171 (7)
N210.1101 (2)0.55680 (16)0.08638 (12)0.0218 (7)
N1110.4262 (2)0.51345 (14)0.30691 (11)0.0173 (7)
N1130.5737 (2)0.50088 (14)0.41791 (11)0.0187 (7)
N1210.1662 (2)0.56215 (14)0.33589 (11)0.0178 (7)
N1230.1623 (2)0.57220 (16)0.46456 (11)0.0231 (7)
N2110.0578 (2)0.47928 (14)0.19397 (11)0.0183 (7)
N2130.0622 (2)0.44870 (16)0.07676 (11)0.0225 (7)
N2210.2523 (2)0.63107 (15)0.18212 (11)0.0208 (7)
N2230.2380 (2)0.68547 (16)0.05900 (12)0.0252 (8)
C10.3509 (3)0.3393 (2)0.15861 (14)0.0256 (10)
C20.5080 (3)0.24374 (18)0.11442 (14)0.0239 (9)
C30.2345 (3)0.2428 (2)0.44805 (17)0.0336 (11)
C1120.4503 (3)0.50744 (17)0.37992 (13)0.0162 (8)
C1140.6788 (3)0.50861 (18)0.37973 (14)0.0228 (9)
C1150.6640 (3)0.52306 (19)0.30534 (14)0.0245 (9)
C1160.5348 (3)0.52276 (18)0.27052 (14)0.0211 (8)
C1220.2201 (3)0.54849 (17)0.40552 (14)0.0182 (8)
C1240.0482 (3)0.6226 (2)0.45290 (15)0.0287 (9)
C1250.0101 (3)0.64883 (19)0.38402 (15)0.0272 (10)
C1260.0514 (3)0.61543 (18)0.32654 (15)0.0222 (9)
C2120.0344 (3)0.49427 (18)0.12168 (14)0.0182 (8)
C2140.1451 (3)0.3900 (2)0.10746 (14)0.0268 (9)
C2150.1360 (3)0.3762 (2)0.18219 (15)0.0270 (9)
C2160.0309 (3)0.42104 (18)0.22321 (14)0.0227 (9)
C2220.2038 (3)0.62727 (18)0.11168 (14)0.0209 (8)
C2240.3304 (3)0.75317 (19)0.07920 (15)0.0279 (10)
C2250.3864 (3)0.76385 (18)0.15084 (14)0.0256 (9)
C2260.3431 (3)0.70199 (19)0.20041 (14)0.0246 (9)
H30.370 (3)0.5074 (17)0.4693 (14)0.0260*
H50.090 (3)0.555 (2)0.0395 (15)0.0330*
H1140.767600.503900.404900.0270*
H1150.739700.532700.279600.0290*
H1160.521100.529300.219100.0250*
H1240.004900.641500.493600.0340*
H1250.089100.688100.376900.0330*
H1260.012000.630200.278500.0270*
H2140.213300.356200.077000.0320*
H2150.199500.337500.203600.0320*
H2160.019500.411000.274400.0270*
H2240.358700.795300.043400.0330*
H2250.452400.812300.164800.0310*
H2260.378500.709200.250100.0290*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0180 (2)0.0234 (2)0.0129 (2)0.0009 (1)0.0021 (1)0.0014 (1)
S10.0414 (5)0.0448 (5)0.0331 (5)0.0157 (4)0.0100 (4)0.0112 (4)
F10.0609 (14)0.0579 (12)0.0464 (12)0.0185 (10)0.0071 (10)0.0251 (10)
F20.0313 (12)0.1089 (18)0.0568 (14)0.0190 (11)0.0024 (10)0.0155 (12)
F30.0728 (15)0.0511 (12)0.0391 (11)0.0087 (11)0.0136 (10)0.0051 (10)
O10.0423 (13)0.0414 (12)0.0315 (12)0.0127 (10)0.0024 (10)0.0045 (10)
O20.0257 (14)0.138 (3)0.083 (2)0.0064 (15)0.0095 (13)0.0698 (19)
O30.147 (3)0.0470 (16)0.0524 (17)0.0349 (17)0.0033 (17)0.0130 (13)
N10.0369 (16)0.0254 (14)0.0477 (17)0.0049 (12)0.0098 (13)0.0149 (12)
N20.0253 (14)0.0300 (14)0.0222 (13)0.0004 (11)0.0006 (10)0.0066 (11)
N30.0386 (17)0.0266 (14)0.0332 (15)0.0068 (12)0.0023 (13)0.0001 (11)
N110.0161 (11)0.0242 (12)0.0104 (11)0.0018 (10)0.0010 (9)0.0009 (10)
N210.0249 (13)0.0293 (13)0.0098 (11)0.0080 (10)0.0034 (10)0.0018 (10)
N1110.0181 (12)0.0205 (12)0.0130 (11)0.0007 (9)0.0007 (9)0.0007 (9)
N1130.0169 (11)0.0220 (12)0.0163 (11)0.0003 (10)0.0013 (9)0.0010 (9)
N1210.0180 (12)0.0165 (11)0.0178 (12)0.0006 (9)0.0018 (9)0.0004 (9)
N1230.0185 (13)0.0327 (13)0.0181 (12)0.0005 (10)0.0020 (10)0.0023 (10)
N2110.0196 (12)0.0234 (12)0.0114 (11)0.0002 (9)0.0003 (9)0.0004 (9)
N2130.0228 (13)0.0278 (13)0.0159 (12)0.0058 (10)0.0018 (10)0.0004 (10)
N2210.0242 (13)0.0243 (12)0.0128 (12)0.0028 (10)0.0022 (9)0.0002 (9)
N2230.0271 (14)0.0278 (13)0.0195 (12)0.0070 (11)0.0014 (10)0.0006 (10)
C10.0215 (16)0.0317 (18)0.0225 (16)0.0063 (13)0.0011 (12)0.0009 (13)
C20.0362 (19)0.0167 (15)0.0178 (15)0.0001 (13)0.0004 (13)0.0000 (11)
C30.0284 (18)0.0366 (19)0.0352 (19)0.0027 (14)0.0016 (14)0.0067 (15)
C1120.0193 (14)0.0149 (13)0.0138 (13)0.0022 (11)0.0001 (10)0.0004 (11)
C1140.0171 (14)0.0259 (16)0.0245 (15)0.0003 (12)0.0014 (11)0.0004 (12)
C1150.0169 (15)0.0321 (17)0.0247 (16)0.0007 (12)0.0031 (12)0.0011 (12)
C1160.0212 (15)0.0265 (15)0.0154 (14)0.0001 (12)0.0018 (12)0.0018 (11)
C1220.0185 (15)0.0153 (14)0.0198 (15)0.0027 (11)0.0016 (12)0.0001 (11)
C1240.0248 (16)0.0369 (17)0.0253 (16)0.0042 (14)0.0069 (13)0.0037 (13)
C1250.0211 (16)0.0307 (17)0.0290 (17)0.0049 (12)0.0003 (13)0.0010 (13)
C1260.0213 (15)0.0238 (15)0.0197 (15)0.0017 (12)0.0044 (12)0.0005 (11)
C2120.0179 (13)0.0191 (14)0.0172 (14)0.0025 (12)0.0005 (11)0.0006 (11)
C2140.0237 (16)0.0303 (16)0.0255 (17)0.0057 (13)0.0007 (13)0.0018 (13)
C2150.0247 (16)0.0331 (17)0.0238 (16)0.0080 (13)0.0056 (12)0.0013 (13)
C2160.0280 (16)0.0266 (15)0.0136 (14)0.0010 (12)0.0030 (12)0.0008 (11)
C2220.0212 (15)0.0234 (15)0.0171 (14)0.0004 (12)0.0018 (11)0.0013 (12)
C2240.0360 (18)0.0242 (16)0.0231 (16)0.0072 (13)0.0023 (13)0.0034 (12)
C2250.0325 (17)0.0196 (15)0.0231 (16)0.0045 (12)0.0032 (13)0.0016 (12)
C2260.0316 (17)0.0225 (15)0.0173 (15)0.0017 (12)0.0064 (12)0.0035 (12)
Geometric parameters (Å, º) top
Cu1—O12.747 (2)N123—C1241.327 (4)
Cu1—N21.972 (2)N211—C2121.346 (3)
Cu1—N1112.006 (2)N211—C2161.354 (3)
Cu1—N1212.008 (2)N213—C2121.348 (3)
Cu1—N2112.021 (2)N213—C2141.332 (4)
Cu1—N2212.208 (2)N221—C2261.346 (3)
S1—O11.435 (2)N221—C2221.335 (3)
S1—O21.436 (2)N223—C2221.338 (3)
S1—O31.437 (3)N223—C2241.331 (4)
S1—C31.817 (3)C114—C1151.382 (4)
F1—C31.331 (4)C115—C1161.368 (4)
F2—C31.316 (4)C124—C1251.383 (4)
F3—C31.332 (3)C125—C1261.371 (4)
N1—C11.295 (4)C214—C2151.389 (4)
N1—C21.330 (4)C114—H1140.9509
N2—C11.155 (4)C215—C2161.364 (4)
N3—C21.146 (4)C115—H1150.9502
N11—C1121.370 (3)C116—H1160.9494
N11—C1221.380 (4)C124—H1240.9496
N21—C2121.363 (3)C224—C2251.383 (4)
N21—C2221.387 (3)C225—C2261.360 (4)
N111—C1121.346 (3)C125—H1250.9508
N111—C1161.350 (4)C126—H1260.9493
N11—H30.88 (3)C214—H2140.9500
N113—C1141.338 (4)C215—H2150.9502
N113—C1121.343 (4)C216—H2160.9508
N121—C1221.348 (3)C224—H2240.9490
N121—C1261.352 (3)C225—H2250.9498
N21—H50.87 (3)C226—H2260.9493
N123—C1221.337 (3)
Cu1···N113.206 (2)N211···C1263.094 (3)
Cu1···N213.259 (2)N213···N21x3.001 (3)
S1···C2163.692 (3)N113···H3viii2.10 (3)
S1···H2163.0595N121···H2162.9203
F1···O22.941 (3)N221···C2122.986 (3)
F1···O32.950 (3)N221···C1163.421 (4)
F2···O12.946 (3)N221···N1113.159 (3)
F2···O32.948 (3)N221···N1213.216 (3)
F2···C224i3.202 (4)N221···N23.095 (3)
F2···C225i3.364 (4)N221···N2112.876 (3)
F2···C2ii3.212 (3)N123···H224xi2.9300
F3···O12.951 (3)N223···C214x3.276 (3)
F3···O22.937 (3)N123···H114viii2.6479
F3···N113.041 (3)N211···H1262.6722
F3···C124iii3.184 (4)N213···H5x2.14 (3)
F3···N1ii3.195 (3)N223···H214x2.5648
F3···H124iii2.4317C2···C112i3.276 (3)
O1···F22.946 (3)C2···F2v3.212 (3)
O1···F32.951 (3)C2···H226i2.6651
O1···N23.064 (3)C112···N3ix3.086 (3)
O1···N113.174 (3)C112···C2ix3.276 (3)
O1···N1113.246 (3)C114···C224i3.598 (4)
O1···C1123.369 (3)C114···C225i3.461 (4)
O1···C1223.387 (3)C114···N123viii3.307 (3)
O1···C2163.284 (3)C116···C2263.287 (4)
O2···C2163.246 (4)C122···N3ix2.947 (4)
O2···F12.941 (3)C124···F3iii3.184 (4)
O2···F32.937 (3)C126···C2163.331 (4)
O2···C222iv3.101 (4)C112···H225i3.0041
O3···F22.948 (3)C212···O3xii3.275 (4)
O3···F12.950 (3)C114···H225i3.0682
O3···C212iv3.275 (4)C214···N3xiii3.304 (4)
O1···H2162.8003C114···H3viii2.90 (3)
O2···H2162.4632C214···N223x3.276 (3)
O3···H115i2.8130C216···S13.692 (3)
O3···H126iv2.5379C116···H2263.0001
N1···F3v3.195 (3)C216···C1263.331 (4)
N2···O13.064 (3)C216···O23.246 (4)
N2···N213.226 (3)C222···O2xii3.101 (4)
N2···N1112.826 (3)C224···N3vii3.438 (4)
N2···N2112.742 (3)C224···F2ix3.202 (4)
N2···N2213.095 (3)C224···C114ix3.598 (4)
N2···C1163.017 (4)C225···F2ix3.364 (4)
N2···C2123.084 (4)C225···C114ix3.461 (4)
N2···C2223.383 (3)C125···H114xiii3.0407
N3···N11i3.055 (3)C126···H2163.0277
N3···C214vi3.304 (4)C226···C1163.287 (4)
N3···C112i3.086 (3)C214···H5x2.94 (3)
N3···C122i2.947 (4)C216···H115xiii3.0441
N3···N121i3.259 (3)C216···H1263.0653
N3···C224vii3.438 (4)C226···H1162.9595
N11···N113viii2.981 (3)C226···H215xii3.0506
N11···Cu13.206 (2)H3···N113viii2.10 (3)
N11···F33.041 (3)H3···C114viii2.90 (3)
N11···O13.174 (3)H5···N213x2.14 (3)
N11···N3ix3.055 (3)H5···C214x2.94 (3)
N21···N213x3.001 (3)H114···C125vi3.0407
N21···N23.226 (3)H114···N123viii2.6479
N21···Cu13.259 (2)H115···C216vi3.0441
N2···H1162.6715H115···O3ix2.8130
N3···H226i2.7835H116···N22.6715
N3···H224vii2.7092H116···C2262.9595
N3···H214vi2.5729H124···F3iii2.4317
N111···O13.246 (3)H126···N2112.6722
N111···N22.826 (3)H126···C2163.0653
N111···N1212.793 (3)H126···O3xii2.5379
N111···N2213.159 (3)H214···N3xiii2.5729
N111···C1222.951 (4)H214···N223x2.5648
N111···C2263.301 (3)H215···C226iv3.0506
N113···N11viii2.981 (3)H216···S13.0595
N121···C2163.313 (3)H216···O12.8003
N121···N3ix3.259 (3)H216···O22.4632
N121···N1112.793 (3)H216···N1212.9203
N121···N2112.945 (3)H216···C1263.0277
N121···N2213.216 (3)H224···N3vii2.7092
N121···C1122.948 (4)H224···N123xiv2.9300
N123···C114viii3.307 (3)H225···C112ix3.0041
N211···N2212.876 (3)H225···C114ix3.0682
N211···C2223.021 (3)H226···N1112.9078
N111···H2262.9078H226···C1163.0001
N211···N1212.945 (3)H226···N3ix2.7835
N211···N22.742 (3)H226···C2ix2.6651
O1—Cu1—N279.13 (8)S1—C3—F2111.9 (2)
O1—Cu1—N11184.62 (7)F2—C3—F3106.9 (2)
O1—Cu1—N12186.20 (7)S1—C3—F3111.2 (2)
O1—Cu1—N21192.61 (7)N11—C112—N111120.9 (2)
O1—Cu1—N221174.31 (7)N11—C112—N113114.4 (2)
N2—Cu1—N11190.52 (8)N111—C112—N113124.7 (2)
N2—Cu1—N121165.33 (9)N113—C114—C115122.9 (3)
N2—Cu1—N21186.72 (8)C114—C115—C116116.7 (3)
N2—Cu1—N22195.38 (9)N111—C116—C115122.1 (2)
N111—Cu1—N12188.17 (8)N11—C122—N123113.3 (2)
N111—Cu1—N211176.41 (8)N121—C122—N123125.9 (3)
N111—Cu1—N22196.99 (8)N11—C122—N121120.8 (2)
N121—Cu1—N21193.93 (8)N123—C124—C125122.8 (3)
N121—Cu1—N22199.29 (8)C124—C125—C126116.8 (3)
N211—Cu1—N22185.56 (8)N121—C126—C125122.3 (3)
O1—S1—O2115.16 (15)N21—C212—N213113.2 (2)
O1—S1—O3115.28 (15)N211—C212—N213124.5 (2)
O1—S1—C3103.54 (13)N21—C212—N211122.3 (2)
O2—S1—O3114.63 (17)N213—C214—C215122.7 (3)
O2—S1—C3102.94 (15)C115—C114—H114118.53
O3—S1—C3102.78 (14)N113—C114—H114118.57
Cu1—O1—S1150.64 (12)C214—C215—C216116.4 (3)
C1—N1—C2119.9 (3)C114—C115—H115121.73
Cu1—N2—C1160.3 (2)C116—C115—H115121.62
C112—N11—C122127.4 (2)C115—C116—H116118.92
C212—N21—C222132.0 (2)N111—C116—H116118.95
Cu1—N111—C112123.52 (18)N211—C216—C215122.7 (2)
Cu1—N111—C116119.51 (17)N221—C222—N223126.5 (2)
C112—N111—C116116.9 (2)N21—C222—N223113.2 (2)
C122—N11—H3109.9 (19)N21—C222—N221120.4 (2)
C112—N11—H3115.6 (19)N223—C224—C225121.9 (3)
C112—N113—C114116.4 (2)C125—C124—H124118.67
Cu1—N121—C126121.27 (17)N123—C124—H124118.56
C122—N121—C126115.5 (2)C126—C125—H125121.63
Cu1—N121—C122123.13 (17)C224—C225—C226117.2 (3)
C212—N21—H5112.9 (19)C124—C125—H125121.56
C222—N21—H5114.9 (19)N221—C226—C225122.9 (2)
C122—N123—C124116.2 (2)N121—C126—H126118.85
Cu1—N211—C212122.18 (18)C125—C126—H126118.85
Cu1—N211—C216118.20 (17)N213—C214—H214118.67
C212—N211—C216116.5 (2)C215—C214—H214118.64
C212—N213—C214116.9 (2)C214—C215—H215121.79
Cu1—N221—C222119.68 (16)C216—C215—H215121.79
C222—N221—C226115.2 (2)N211—C216—H216118.71
Cu1—N221—C226121.40 (17)C215—C216—H216118.64
C222—N223—C224116.3 (2)N223—C224—H224119.06
N1—C1—N2175.0 (3)C225—C224—H224119.05
N1—C2—N3174.7 (3)C224—C225—H225121.37
F1—C3—F2108.1 (2)C226—C225—H225121.46
F1—C3—F3106.5 (2)N221—C226—H226118.58
S1—C3—F1112.0 (2)C225—C226—H226118.53
N2—Cu1—O1—S1114.7 (2)C122—N11—C112—N11128.0 (4)
N111—Cu1—O1—S1153.8 (2)C122—N11—C112—N113152.5 (2)
N121—Cu1—O1—S165.2 (2)C112—N11—C122—N12126.3 (4)
N211—Cu1—O1—S128.5 (2)C112—N11—C122—N123153.6 (2)
O1—Cu1—N111—C11254.09 (18)C222—N21—C212—N21112.3 (4)
O1—Cu1—N111—C116121.85 (18)C222—N21—C212—N213169.0 (3)
N2—Cu1—N111—C112133.11 (19)C212—N21—C222—N22112.6 (4)
N2—Cu1—N111—C11642.82 (19)C212—N21—C222—N223168.5 (3)
N121—Cu1—N111—C11232.27 (19)C216—N211—C212—N2136.4 (4)
N121—Cu1—N111—C116151.80 (18)Cu1—N211—C212—N2125.3 (3)
N221—Cu1—N111—C112131.41 (19)Cu1—N211—C212—N213153.2 (2)
N221—Cu1—N111—C11652.66 (19)Cu1—N211—C216—C215158.0 (2)
O1—Cu1—N121—C12251.13 (19)C212—N211—C216—C2152.5 (4)
O1—Cu1—N121—C126124.55 (19)C112—N111—C116—H116177.98
N111—Cu1—N121—C12233.6 (2)C216—N211—C212—N21175.1 (2)
N111—Cu1—N121—C126150.72 (19)Cu1—N111—C116—H1165.81
N211—Cu1—N121—C122143.5 (2)C214—N213—C212—N2114.7 (4)
N211—Cu1—N121—C12632.2 (2)C214—N213—C212—N21176.7 (2)
N221—Cu1—N121—C122130.38 (19)C212—N213—C214—C2151.0 (4)
N221—Cu1—N121—C12653.9 (2)C112—N113—C114—H114179.63
O1—Cu1—N211—C212134.19 (19)Cu1—N221—C222—N2121.0 (3)
O1—Cu1—N211—C21625.09 (18)Cu1—N221—C222—N223157.7 (2)
N2—Cu1—N211—C21255.24 (19)Cu1—N121—C126—H1267.39
N2—Cu1—N211—C216104.04 (19)C122—N121—C126—H126176.61
N121—Cu1—N211—C212139.45 (19)C226—N221—C222—N2230.9 (4)
N121—Cu1—N211—C21661.28 (19)Cu1—N221—C226—C225156.2 (2)
N221—Cu1—N211—C21240.41 (19)C226—N221—C222—N21179.6 (2)
N221—Cu1—N211—C216160.31 (19)C222—N221—C226—C2252.0 (4)
N2—Cu1—N221—C22247.4 (2)C122—N123—C124—H124179.16
N2—Cu1—N221—C226109.9 (2)C222—N223—C224—C2251.0 (4)
N111—Cu1—N221—C222138.6 (2)C224—N223—C222—N21178.2 (2)
N111—Cu1—N221—C22618.7 (2)C224—N223—C222—N2210.6 (4)
N121—Cu1—N221—C222132.2 (2)N113—C114—C115—H115175.74
N121—Cu1—N221—C22670.6 (2)H114—C114—C115—C116175.66
N211—Cu1—N221—C22238.9 (2)N213—C214—C215—C2164.4 (4)
N211—Cu1—N221—C226163.8 (2)H114—C114—C115—H1154.31
O2—S1—O1—Cu116.6 (3)C114—C115—C116—H116176.96
O3—S1—O1—Cu1120.4 (2)H115—C115—C116—N111177.00
C3—S1—O1—Cu1128.2 (2)C214—C215—C216—N2112.5 (4)
O1—S1—C3—F1179.3 (2)H115—C115—C116—H1163.01
O1—S1—C3—F259.2 (2)N223—C224—C225—C2260.0 (4)
O1—S1—C3—F360.2 (2)H124—C124—C125—H1253.54
O2—S1—C3—F159.0 (2)N123—C124—C125—H125176.37
O2—S1—C3—F2179.4 (2)H124—C124—C125—C126176.40
O2—S1—C3—F360.0 (2)C224—C225—C226—N2211.6 (4)
O3—S1—C3—F160.4 (2)C124—C125—C126—H126177.75
O3—S1—C3—F261.2 (2)H125—C125—C126—N121177.83
O3—S1—C3—F3179.4 (2)H125—C125—C126—H1262.20
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z+1; (iv) x, y1/2, z+1/2; (v) x, y+1/2, z1/2; (vi) x+1, y, z; (vii) x+1, y+1, z; (viii) x+1, y+1, z+1; (ix) x+1, y+1/2, z+1/2; (x) x, y+1, z; (xi) x, y+3/2, z+1/2; (xii) x, y+1/2, z+1/2; (xiii) x1, y, z; (xiv) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H3···N113viii0.88 (3)2.10 (3)2.981 (3)176 (2)
N21—H5···N213x0.87 (3)2.14 (3)3.001 (3)174 (3)
C114—H114···N123viii0.952.653.307 (3)127
C214—H214···N223x0.952.563.276 (3)132
C124—H124···F3iii0.952.433.184 (4)136
C216—H216···O20.952.463.246 (4)140
Symmetry codes: (iii) x, y+1, z+1; (viii) x+1, y+1, z+1; (x) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O
Mr625.05
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)9.972 (2), 13.751 (2), 18.516 (4)
β (°) 97.047 (8)
V3)2519.8 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.02
Crystal size (mm)0.2 × 0.1 × 0.1
Data collection
DiffractometerNonius Kappa CCD area-detector
Absorption correction?
No. of measured, independent and
observed [I > 2σ(I)] reflections
56102, 5712, 3766
Rint0.119
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.104, 1.04
No. of reflections5712
No. of parameters367
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.55

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.

Selected geometric parameters (Å, º) top
Cu1—O12.747 (2)Cu1—N1212.008 (2)
Cu1—N21.972 (2)Cu1—N2112.021 (2)
Cu1—N1112.006 (2)Cu1—N2212.208 (2)
O1—Cu1—N279.13 (8)N111—Cu1—N12188.17 (8)
O1—Cu1—N11184.62 (7)N111—Cu1—N211176.41 (8)
O1—Cu1—N12186.20 (7)N111—Cu1—N22196.99 (8)
O1—Cu1—N21192.61 (7)N121—Cu1—N21193.93 (8)
O1—Cu1—N221174.31 (7)N121—Cu1—N22199.29 (8)
N2—Cu1—N11190.52 (8)N211—Cu1—N22185.56 (8)
N2—Cu1—N121165.33 (9)C1—N1—C2119.9 (3)
N2—Cu1—N21186.72 (8)C112—N11—C122127.4 (2)
N2—Cu1—N22195.38 (9)C212—N21—C222132.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H3···N113i0.88 (3)2.10 (3)2.981 (3)176 (2)
N21—H5···N213ii0.87 (3)2.14 (3)3.001 (3)174 (3)
C114—H114···N123i0.952.653.307 (3)127
C214—H214···N223ii0.952.563.276 (3)132
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z.
 

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