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The title compound, [Cu(C9H7N2O)2]·2CH3OH, contains a crystallographically centrosymmetric near-regular square planar CuII centre with trans-disposed chelating ligands. The complex mol­ecules associate into a one-dimensional polymeric chain via hydrogen bonding to the solvent mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101017656/bm1476sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101017656/bm1476Isup2.hkl
Contains datablock I

CCDC reference: 180127

Comment top

We have recently described that complexation of CuCl2 or CuBr2 by 3{5}-tertbutylpyrazole in basic MeOH leads to a novel heptacopper aggregate structure, which is templated by N—H···X (X- = Cl-, Br-) hydrogen bonding between the pyrazole ligands and non-coordinated halide anions (Liu et al., 2001). As an extension of this work, we were keen to examine the Cu(II) chemistry of pyrazole ligands containing additional hydrogen-bonding functionality, in addition to the N—H group of the pyrazole ring. 2-(Pyrazol-3-yl)phenol(HL) is one such ligand that is readily available (Catalan et al., 1992), and we now report the structure of the mononuclear complex [CuL2]·2CH3OH (I). No other complexes of L- have been previously crystallographically characterized, although the crystal structure of one complex of the closely related ligand 2-(5-methylpyrazol-3-yl)phenol (HL'), [FeL'2(CH3OH)2]NO3·CH3OH, has been reported (Ainscough et al., 1980).

The asymmetric unit of the crystals contains half a complex molecule, with Cu1 lying on the crystallographic inversion centre at 1/2, 1/2, 1/2, together with one molecule of methanol. As in [FeL'2(CH3OH)2]NO3·CH3OH (Ainscough et al., 1980), the L- ligands in I chelate to the Cu ion through their pyrazole N and phenoxide O donors, giving a four-coordinate Cu(II) centre with a trans-N2O2 donor set. The coordination geometry at Cu1 is strictly planar by symmetry, and is almost perfectly square. The Cu(II) ion stands proud of the least squares plane of the chelating ligand, by 0.5784 (13) Å. This is also manifested in the dihedral angle between the square plane of donors at Cu1 [Cu1, N2, O13, N2i, O13i] and the least squares plane of the L- ligand [N2–O13], which is 24.73 (7)°. The pyrazole and phenoxide moieties of the ligand are twisted with respect to each other, with the dihedral angle between the least squares planes [N2–C7] and [C8–O13] being 16.37 (11)°.

The methanol molecule accepts a hydrogen bond from the L- pyrrolic N—H group, and donates a hydrogen bond to the phenoxide O-donor of a neighbouring molecule related by x, y, 1 - z. This affords a one-dimensional polymeric chain of hydrogen-bonded molecules, running parallel to the z-axis of the unit cell. Adjacent chains are linked by a ππ interaction between the phenyl rings C7–C12 and C7iii–C12iii (related by -x, 1 - y, 1 - z). The interacting rings are strictly coplanar by symmetry and are separated by 3.410 (5) Å, with their centroids being offset by 1.24 Å. These parameters imply a ππ interaction that is only weakly electrostatically attractive (Hunter & Sanders, 1990).

Experimental top

A mixture of 2-(pyrazol-3-yl)phenol (0.32 g, 2.0 mmol; Catalan et al., 1992), CuBr2 (0.22 g, 1.0 mmol) and NaOH (0.040 g, 1 mmol) in MeOH (50 cm3) was stirred at room temperature for 16 hrs, yielding a brown solution. Concentration of this solution to about half its original volume afforded a dark precipitate, which was removed by filtration. Storage of the filtrate at 263 K afforded dark brown plates, which slowly degraded in vacuo. The dried material reproducibly analyses for [CuL2].xCH3OH.(2 - x)H2O (x = ca 1/2). Found C, 53.4; H, 4.5; N, 12.9%. Calcd for C18H14CuN4O2·1.5CH3OH·0.5H2O C, 53.4; H, 4.8; N, 12.8%.

Refinement top

All H atoms were located in the Fourier difference map and allowed to refine freely. Refined C—H distances ranged from 0.88 (3)–1.02 (4) Å, while N3—H3 = 0.88 (3) and O15—H15 = 0.75 (3) Å.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1996); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.

Figures top
[Figure 1] Fig. 1. A view of the title compound with 50% probability displacement ellipsoids, showing the atom numbering scheme employed. H atoms have arbitrary radii. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, y, 1 - z].
Bis[2-(pyrazol-3-yl)phenolato]copper(II) methanol disolvate top
Crystal data top
C18H14CuN4O2·2(CH4O)F(000) = 462
Mr = 445.96Dx = 1.559 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.5210 (2) ÅCell parameters from 10193 reflections
b = 15.6270 (4) Åθ = 2.8–27.5°
c = 8.3657 (3) ŵ = 1.19 mm1
β = 105.000 (1)°T = 150 K
V = 949.72 (5) Å3Plate, brown
Z = 20.19 × 0.15 × 0.03 mm
Data collection top
Nonius KappaCCD
diffractometer
2172 independent reflections
Radiation source: fine-focus sealed tube1952 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.8°
Area detector scansh = 99
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 2020
Tmin = 0.806, Tmax = 0.965l = 1010
10193 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034All H-atom parameters refined
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.053P)2 + 0.359P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2172 reflectionsΔρmax = 0.37 e Å3
178 parametersΔρmin = 0.51 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.032 (5)
Crystal data top
C18H14CuN4O2·2(CH4O)V = 949.72 (5) Å3
Mr = 445.96Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.5210 (2) ŵ = 1.19 mm1
b = 15.6270 (4) ÅT = 150 K
c = 8.3657 (3) Å0.19 × 0.15 × 0.03 mm
β = 105.000 (1)°
Data collection top
Nonius KappaCCD
diffractometer
2172 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1952 reflections with I > 2σ(I)
Tmin = 0.806, Tmax = 0.965Rint = 0.038
10193 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.093All H-atom parameters refined
S = 1.06Δρmax = 0.37 e Å3
2172 reflectionsΔρmin = 0.51 e Å3
178 parameters
Special details top

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi=0 degree settings 1 degree omega exposures for chi=90 degree settings

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

Refinement. Structure solution was achieved by direct methods using SHELXS97 (Sheldrick, 1990), while least squares refinement used SHELXL97 (Sheldrick, 1997). No disorder was detected during refinement. All non-H atoms were refined anisotropically, and no restraints were applied.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.02096 (15)
N20.3506 (2)0.41544 (9)0.35599 (18)0.0236 (3)
N30.3799 (2)0.38621 (10)0.21270 (18)0.0264 (3)
H30.462 (4)0.4056 (16)0.163 (3)0.037 (6)*
C40.2536 (3)0.32732 (13)0.1430 (2)0.0311 (4)
H40.267 (3)0.2998 (16)0.044 (3)0.038 (6)*
C50.1370 (3)0.31699 (13)0.2437 (2)0.0304 (4)
H50.034 (3)0.2756 (16)0.229 (3)0.035 (6)*
C60.2005 (2)0.37442 (11)0.3765 (2)0.0234 (4)
C70.1216 (2)0.39339 (11)0.5144 (2)0.0230 (4)
C80.2203 (2)0.43845 (11)0.6562 (2)0.0230 (4)
C90.1342 (2)0.45397 (12)0.7839 (2)0.0266 (4)
H90.193 (3)0.4867 (14)0.877 (3)0.026 (6)*
C100.0437 (3)0.42674 (12)0.7724 (2)0.0284 (4)
H100.093 (3)0.4383 (15)0.862 (3)0.033 (6)*
C110.1427 (3)0.38374 (12)0.6313 (2)0.0282 (4)
H110.274 (3)0.3651 (17)0.621 (3)0.041 (7)*
C120.0601 (3)0.36810 (12)0.5050 (2)0.0273 (4)
H120.129 (3)0.3408 (15)0.411 (3)0.034 (6)*
O130.39371 (16)0.46636 (9)0.67637 (15)0.0251 (3)
C140.6207 (4)0.31413 (15)0.0520 (3)0.0429 (5)
H14A0.638 (5)0.282 (2)0.057 (5)0.080 (10)*
H14B0.526 (5)0.289 (2)0.121 (4)0.064 (9)*
H14C0.723 (5)0.307 (2)0.087 (4)0.068 (10)*
O150.5817 (2)0.40058 (9)0.02642 (17)0.0306 (3)
H150.533 (4)0.4182 (18)0.110 (4)0.040 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0228 (2)0.0222 (2)0.0183 (2)0.00240 (10)0.00616 (13)0.00010 (10)
N20.0268 (7)0.0240 (7)0.0211 (7)0.0006 (6)0.0085 (5)0.0005 (6)
N30.0319 (8)0.0286 (8)0.0208 (7)0.0018 (6)0.0104 (6)0.0030 (6)
C40.0383 (10)0.0311 (9)0.0238 (9)0.0046 (8)0.0077 (8)0.0047 (7)
C50.0344 (10)0.0304 (9)0.0258 (9)0.0073 (8)0.0070 (7)0.0033 (7)
C60.0258 (8)0.0219 (8)0.0217 (8)0.0005 (6)0.0044 (6)0.0016 (6)
C70.0240 (8)0.0226 (8)0.0231 (8)0.0003 (6)0.0070 (6)0.0038 (6)
C80.0237 (8)0.0227 (8)0.0225 (8)0.0005 (6)0.0059 (6)0.0042 (6)
C90.0295 (9)0.0279 (9)0.0231 (8)0.0004 (7)0.0079 (7)0.0005 (7)
C100.0298 (9)0.0294 (9)0.0301 (9)0.0025 (7)0.0149 (7)0.0041 (7)
C110.0235 (8)0.0269 (9)0.0348 (10)0.0002 (7)0.0088 (7)0.0068 (7)
C120.0262 (9)0.0257 (9)0.0291 (9)0.0028 (7)0.0056 (7)0.0028 (7)
O130.0237 (6)0.0329 (7)0.0192 (6)0.0041 (5)0.0062 (5)0.0009 (5)
C140.0498 (14)0.0331 (11)0.0526 (14)0.0054 (10)0.0254 (12)0.0043 (10)
O150.0360 (7)0.0325 (7)0.0224 (7)0.0030 (6)0.0061 (6)0.0015 (5)
Geometric parameters (Å, º) top
Cu1—N21.9390 (15)C8—C91.406 (3)
Cu1—O131.9243 (12)C9—C101.384 (3)
N2—C61.347 (2)C9—H90.94 (3)
N2—N31.353 (2)C10—C111.395 (3)
N3—C41.343 (2)C10—H100.94 (2)
N3—H30.88 (3)C11—C121.379 (3)
C4—C51.374 (3)C11—H111.01 (3)
C4—H40.96 (3)C12—H120.93 (2)
C5—C61.412 (2)C14—O151.411 (3)
C5—H50.99 (3)C14—H14A1.02 (4)
C6—C71.458 (3)C14—H14B0.88 (3)
C7—C121.405 (3)C14—H14C0.90 (4)
C7—C81.414 (2)O15—H150.75 (3)
C8—O131.344 (2)
O13i—Cu1—O13180O13—C8—C7123.29 (16)
O13—Cu1—N290.07 (6)C9—C8—C7118.58 (16)
O13—Cu1—N2i89.93 (6)C10—C9—C8121.44 (17)
N2—Cu1—N2i180C10—C9—H9117.5 (15)
C6—N2—N3106.65 (14)C8—C9—H9120.9 (16)
C6—N2—Cu1127.96 (12)C9—C10—C11120.11 (17)
N3—N2—Cu1125.39 (12)C9—C10—H10117.5 (14)
C4—N3—N2110.90 (16)C11—C10—H10122.4 (14)
C4—N3—H3122.3 (17)C12—C11—C10119.09 (17)
N2—N3—H3126.5 (17)C12—C11—H11120.6 (14)
N3—C4—C5107.82 (17)C10—C11—H11120.3 (14)
N3—C4—H4117.5 (14)C11—C12—C7122.11 (18)
C5—C4—H4134.5 (15)C11—C12—H12118.0 (14)
C4—C5—C6105.59 (17)C7—C12—H12119.9 (14)
C4—C5—H5127.1 (14)C8—O13—Cu1125.08 (11)
C6—C5—H5127.2 (14)O15—C14—H14A109 (2)
N2—C6—C5109.03 (16)O15—C14—H14B111 (2)
N2—C6—C7122.02 (16)H14A—C14—H14B105 (3)
C5—C6—C7128.90 (17)O15—C14—H14C114 (2)
C12—C7—C8118.64 (17)H14A—C14—H14C108 (3)
C12—C7—C6119.17 (16)H14B—C14—H14C110 (3)
C8—C7—C6122.17 (16)C14—O15—H15106 (2)
O13—C8—C9118.13 (15)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O150.88 (3)2.02 (3)2.815 (2)150 (2)
O15—H15···O13ii0.75 (3)1.97 (3)2.724 (2)177 (3)
Symmetry code: (ii) x, y, z1.

Experimental details

Crystal data
Chemical formulaC18H14CuN4O2·2(CH4O)
Mr445.96
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)7.5210 (2), 15.6270 (4), 8.3657 (3)
β (°) 105.000 (1)
V3)949.72 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.19
Crystal size (mm)0.19 × 0.15 × 0.03
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.806, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
10193, 2172, 1952
Rint0.038
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.093, 1.06
No. of reflections2172
No. of parameters178
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.37, 0.51

Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1996), DENZO-SMN, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), local program.

Selected geometric parameters (Å, º) top
Cu1—N21.9390 (15)Cu1—O131.9243 (12)
O13—Cu1—N290.07 (6)O13—Cu1—N2i89.93 (6)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O150.88 (3)2.02 (3)2.815 (2)150 (2)
O15—H15···O13ii0.75 (3)1.97 (3)2.724 (2)177 (3)
Symmetry code: (ii) x, y, z1.
 

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