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The crystal structure of the title complex, [Cu(C
7H
8N
4)
2(H
2O)
2](ClO
4)
2, consists of a discrete centrosymmetric [Cu(C
7H
8N
4)
2(H
2O)
2]
2+ cation and two perchlorate anions. The Cu
II centre is six-coordinated by four N donors from the two pyrazole rings [Cu—N 1.998 (2) and 2.032 (3) Å] and two O atoms from the water molecules occupying the apical sites [Cu—O 2.459 (3) Å]. The coordination geometry of the complex can be described as octahedral. There is a unique three-dimensional network in which the perchlorate units are linked by a combination of strong O—H
O and weak C—H
O hydrogen bonds.
Supporting information
CCDC reference: 152600
The ligand bis(pyrazol-1-yl)methane was prepared according to the method described by Tang et al. (1998). An aqueous solution (5 ml) of [Cu(ClO4)2]·6H2O (180.6 mg, 0.5 mmol) was added dropwise to a stirred methanol solution (5 ml) of bis(pyrazol-1-yl)methane (241 mg, 1.0 mmol). The clear dark-blue solution was left in the refrigerator for two weeks. Dark-blue single crystals of (I) were then obtained by slow evaporation. The crystals were filtered off, washed with water and methanol and dried in vacuo (yield 74%). Analysis calculated for C 28.27, H 3.39, N 18.84%; found: C 28.63, H 3.79, N 18.42%. FT—IR data (KBr pellet, cm-1): 2968 (w), 1519 (versus), 1458 (s), 1394 (m), 1338 (s), 1282 (s), 1094 (s).
All H atoms were located geometrically and refined in calculated positions.
Data collection: SMART 1000 Operation Manual (Bruker, 1998a); cell refinement: SMART 1000 Operation Manual; data reduction: SAINT (Bruker, 1998b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.
diaquabis[bis(pyrazol-1-yl-
κN2)methane]copper(II) diperchlorate
top
Crystal data top
[Cu(C7H8N4)2(H2O)2]2ClO4 | Z = 1 |
Mr = 594.82 | F(000) = 303 |
Triclinic, P1 | Dx = 1.726 Mg m−3 |
a = 8.221 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.223 (1) Å | Cell parameters from 2357 reflections |
c = 9.483 (1) Å | θ = 2.5–25.0° |
α = 109.144 (2)° | µ = 1.26 mm−1 |
β = 101.536 (2)° | T = 298 K |
γ = 114.010 (2)° | Block, blue |
V = 572.25 (12) Å3 | 0.20 × 0.15 × 0.10 mm |
Data collection top
Bruker SMART 1000 diffractometer | 1771 reflections with I > 2σ(I) |
ω scans | Rint = 0.014 |
Absorption correction: integration (North et al., 1968) | θmax = 25.0° |
Tmin = 0.787, Tmax = 0.885 | h = −8→9 |
2407 measured reflections | k = −10→10 |
2012 independent reflections | l = −11→11 |
Refinement top
Refinement on F2 | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.042 | w = 1/[σ2(Fo2) + (0.085P)2 + 0.3155P] P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.124 | (Δ/σ)max = 0.036 |
S = 1.02 | Δρmax = 0.55 e Å−3 |
2012 reflections | Δρmin = −0.46 e Å−3 |
200 parameters | |
Crystal data top
[Cu(C7H8N4)2(H2O)2]2ClO4 | γ = 114.010 (2)° |
Mr = 594.82 | V = 572.25 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.221 (1) Å | Mo Kα radiation |
b = 9.223 (1) Å | µ = 1.26 mm−1 |
c = 9.483 (1) Å | T = 298 K |
α = 109.144 (2)° | 0.20 × 0.15 × 0.10 mm |
β = 101.536 (2)° | |
Data collection top
Bruker SMART 1000 diffractometer | 2012 independent reflections |
Absorption correction: integration (North et al., 1968) | 1771 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.885 | Rint = 0.014 |
2407 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 200 parameters |
wR(F2) = 0.124 | All H-atom parameters refined |
S = 1.02 | Δρmax = 0.55 e Å−3 |
2012 reflections | Δρmin = −0.46 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.0000 | 0.0000 | 0.0000 | 0.0374 (2) | |
Cl1 | 0.90584 (13) | 0.25931 (12) | 0.58392 (11) | 0.0547 (3) | |
N1 | 0.1752 (4) | −0.0963 (3) | 0.0310 (3) | 0.0387 (6) | |
N2 | 0.3327 (4) | −0.0137 (4) | 0.1689 (3) | 0.0391 (6) | |
O1 | −0.1090 (5) | −0.0595 (5) | 0.2089 (4) | 0.0665 (8) | |
C1 | 0.1851 (6) | −0.2284 (5) | −0.0717 (4) | 0.0463 (8) | |
C7 | 0.3656 (5) | 0.1380 (5) | 0.3076 (4) | 0.0430 (7) | |
C3 | 0.4380 (5) | −0.0934 (5) | 0.1521 (5) | 0.0492 (8) | |
C2 | 0.3471 (6) | −0.2313 (5) | 0.0012 (5) | 0.0528 (9) | |
O4 | 0.8366 (8) | 0.3719 (7) | 0.5763 (7) | 0.1356 (19) | |
O5 | 1.0153 (7) | 0.2648 (6) | 0.4832 (6) | 0.142 (2) | |
O3 | 1.0295 (7) | 0.3248 (5) | 0.7427 (5) | 0.1180 (16) | |
O2 | 0.7578 (7) | 0.0812 (5) | 0.5171 (5) | 0.1241 (19) | |
N3 | 0.2267 (4) | 0.2505 (4) | 0.1524 (3) | 0.0419 (6) | |
N4 | 0.3821 (4) | 0.2784 (3) | 0.2660 (3) | 0.0389 (6) | |
C6 | 0.5334 (5) | 0.4432 (5) | 0.3232 (4) | 0.0469 (8) | |
C5 | 0.4778 (6) | 0.5256 (5) | 0.2469 (5) | 0.0554 (9) | |
C4 | 0.2868 (6) | 0.4019 (5) | 0.1414 (5) | 0.0503 (9) | |
H2O | −0.055 (8) | 0.038 (5) | 0.303 (4) | 0.11 (2)* | |
H1O | −0.114 (10) | −0.147 (6) | 0.234 (7) | 0.11 (2)* | |
H6 | 0.646 (6) | 0.474 (5) | 0.399 (4) | 0.041 (9)* | |
H7B | 0.254 (5) | 0.102 (4) | 0.340 (4) | 0.038 (8)* | |
H1 | 0.100 (5) | −0.297 (5) | −0.169 (5) | 0.036 (9)* | |
H7A | 0.490 (5) | 0.187 (5) | 0.394 (5) | 0.044 (9)* | |
H4 | 0.218 (6) | 0.406 (5) | 0.070 (5) | 0.054 (12)* | |
H2 | 0.383 (6) | −0.306 (5) | −0.050 (5) | 0.050 (10)* | |
H3 | 0.550 (7) | −0.052 (6) | 0.239 (5) | 0.064 (12)* | |
H5 | 0.555 (8) | 0.636 (7) | 0.268 (6) | 0.094 (17)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0315 (3) | 0.0318 (3) | 0.0398 (3) | 0.0177 (2) | 0.0051 (2) | 0.0098 (2) |
Cl1 | 0.0460 (5) | 0.0466 (5) | 0.0543 (5) | 0.0169 (4) | 0.0051 (4) | 0.0215 (4) |
N1 | 0.0371 (14) | 0.0368 (14) | 0.0367 (13) | 0.0217 (12) | 0.0074 (11) | 0.0115 (11) |
N2 | 0.0357 (14) | 0.0400 (14) | 0.0386 (14) | 0.0212 (12) | 0.0081 (11) | 0.0161 (12) |
O1 | 0.074 (2) | 0.085 (2) | 0.0594 (18) | 0.0519 (19) | 0.0303 (16) | 0.0360 (17) |
C1 | 0.052 (2) | 0.0414 (19) | 0.0412 (19) | 0.0276 (17) | 0.0131 (17) | 0.0122 (16) |
C7 | 0.0431 (18) | 0.0457 (18) | 0.0350 (16) | 0.0232 (16) | 0.0085 (15) | 0.0162 (15) |
C3 | 0.0415 (18) | 0.052 (2) | 0.061 (2) | 0.0299 (17) | 0.0139 (17) | 0.0286 (18) |
C2 | 0.056 (2) | 0.051 (2) | 0.065 (2) | 0.0389 (19) | 0.0258 (19) | 0.0247 (19) |
O4 | 0.139 (4) | 0.120 (4) | 0.133 (4) | 0.091 (3) | 0.001 (3) | 0.040 (3) |
O5 | 0.098 (3) | 0.113 (4) | 0.126 (4) | 0.013 (3) | 0.053 (3) | 0.008 (3) |
O3 | 0.119 (3) | 0.082 (3) | 0.076 (2) | 0.031 (2) | −0.030 (2) | 0.020 (2) |
O2 | 0.118 (3) | 0.078 (3) | 0.077 (2) | −0.020 (2) | −0.010 (2) | 0.045 (2) |
N3 | 0.0381 (14) | 0.0376 (15) | 0.0425 (15) | 0.0194 (12) | 0.0086 (12) | 0.0144 (12) |
N4 | 0.0345 (13) | 0.0362 (14) | 0.0356 (13) | 0.0164 (12) | 0.0083 (11) | 0.0103 (11) |
C6 | 0.0347 (17) | 0.0396 (18) | 0.0445 (19) | 0.0122 (15) | 0.0104 (15) | 0.0069 (15) |
C5 | 0.051 (2) | 0.0348 (19) | 0.067 (2) | 0.0150 (17) | 0.0218 (19) | 0.0188 (18) |
C4 | 0.054 (2) | 0.0394 (19) | 0.056 (2) | 0.0247 (17) | 0.0151 (18) | 0.0215 (17) |
Geometric parameters (Å, º) top
Cu1—N1i | 1.998 (2) | N2—C3 | 1.346 (4) |
Cu1—N1 | 1.998 (2) | N2—C7 | 1.450 (4) |
Cu1—N3i | 2.032 (3) | C1—C2 | 1.387 (5) |
Cu1—N3 | 2.032 (3) | C7—N4 | 1.437 (4) |
Cl1—O4 | 1.386 (4) | C3—C2 | 1.353 (6) |
Cl1—O3 | 1.399 (4) | N3—C4 | 1.327 (4) |
Cl1—O2 | 1.401 (4) | N3—N4 | 1.363 (4) |
Cl1—O5 | 1.436 (5) | N4—C6 | 1.342 (4) |
N1—C1 | 1.331 (4) | C6—C5 | 1.349 (6) |
N1—N2 | 1.354 (4) | C5—C4 | 1.390 (6) |
| | | |
N1i—Cu1—N1 | 180.00 (10) | C3—N2—C7 | 129.6 (3) |
N1i—Cu1—N3i | 89.31 (11) | N1—N2—C7 | 119.8 (2) |
N1—Cu1—N3i | 90.69 (11) | N1—C1—C2 | 110.5 (3) |
N1i—Cu1—N3 | 90.69 (11) | N4—C7—N2 | 110.1 (3) |
N1—Cu1—N3 | 89.31 (11) | N2—C3—C2 | 107.7 (3) |
N3i—Cu1—N3 | 180.0 (3) | C3—C2—C1 | 105.7 (3) |
O4—Cl1—O3 | 110.0 (3) | C4—N3—N4 | 104.9 (3) |
O4—Cl1—O2 | 112.6 (3) | C4—N3—Cu1 | 131.5 (3) |
O3—Cl1—O2 | 113.2 (3) | N4—N3—Cu1 | 121.0 (2) |
O4—Cl1—O5 | 105.4 (4) | C6—N4—N3 | 111.0 (3) |
O3—Cl1—O5 | 108.8 (3) | C6—N4—C7 | 129.7 (3) |
O2—Cl1—O5 | 106.4 (3) | N3—N4—C7 | 119.3 (3) |
C1—N1—N2 | 105.5 (3) | N4—C6—C5 | 107.6 (3) |
C1—N1—Cu1 | 131.6 (2) | C6—C5—C4 | 105.7 (3) |
N2—N1—Cu1 | 122.3 (2) | N3—C4—C5 | 110.9 (4) |
C3—N2—N1 | 110.6 (3) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O3ii | 0.90 (6) | 2.08 (7) | 2.923 (7) | 155 (7) |
O1—H2O···O5iii | 0.89 (4) | 1.98 (4) | 2.847 (7) | 165 (6) |
C3—H3···O2 | 0.94 (5) | 2.40 (4) | 3.278 (6) | 157 (5) |
C6—H6···O5iv | 0.92 (5) | 2.52 (5) | 3.208 (7) | 132 (4) |
C7—H7A···O4 | 0.98 (4) | 2.48 (5) | 3.434 (8) | 163 (4) |
C7—H7B···O1 | 0.99 (4) | 2.52 (4) | 3.325 (6) | 138 (3) |
C7—H7B···O2ii | 0.99 (4) | 2.47 (4) | 3.015 (6) | 114 (3) |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Cu(C7H8N4)2(H2O)2]2ClO4 |
Mr | 594.82 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.221 (1), 9.223 (1), 9.483 (1) |
α, β, γ (°) | 109.144 (2), 101.536 (2), 114.010 (2) |
V (Å3) | 572.25 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.26 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Bruker SMART 1000 diffractometer |
Absorption correction | Integration (North et al., 1968) |
Tmin, Tmax | 0.787, 0.885 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2407, 2012, 1771 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.124, 1.02 |
No. of reflections | 2012 |
No. of parameters | 200 |
No. of restraints | ? |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.55, −0.46 |
Selected geometric parameters (Å, º) topCu1—N1 | 1.998 (2) | Cu1—N3 | 2.032 (3) |
| | | |
N1i—Cu1—N1 | 180.00 (10) | N1—Cu1—N3 | 89.31 (11) |
N1—Cu1—N3i | 90.69 (11) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O3ii | 0.90 (6) | 2.08 (7) | 2.923 (7) | 155 (7) |
O1—H2O···O5iii | 0.89 (4) | 1.98 (4) | 2.847 (7) | 165 (6) |
C3—H3···O2 | 0.94 (5) | 2.40 (4) | 3.278 (6) | 157 (5) |
C6—H6···O5iv | 0.92 (5) | 2.52 (5) | 3.208 (7) | 132 (4) |
C7—H7A···O4 | 0.98 (4) | 2.48 (5) | 3.434 (8) | 163 (4) |
C7—H7B···O1 | 0.99 (4) | 2.52 (4) | 3.325 (6) | 138 (3) |
C7—H7B···O2ii | 0.99 (4) | 2.47 (4) | 3.015 (6) | 114 (3) |
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1. |
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The self-assembly of metal compounds into one-, two- and three-dimensional supramolecular architectures is of considerable current interest for potential applications because the macroscopic physical properties of crystals are defined by the intermolecular electronic interactions presented in the solid state (Lehn, 1990; Burrows et al., 1995). Consequently, there is a need for the development and study of strong and highly directional intermolecular interactions, which are able to generate predetermined molecular arrangements. The high directionality of strong (O—H···O) and weak (C—H···O) hydrogen bonds makes them useful in crystal design for the preparation of molecular materials with controlled physical properties (Etter, 1991; Desiraju, 1991; Desiraju & Steiner, 1999). The interactions of strong and weak hydrogen bonds play vital roles for molecular recognition in a wide variety of biological systems (Chao & Chen, 1996; Reddy et al., 1993), as well as influencing crystal packing in crystallography, and some important results have been reviewed by Chen & Suslick (1993) and Hanck et al. (1988). The lengths, angles and directional properties of C—H···O bonds have been exploited by Pedireddi & Desiraju (1992) and Steiner & Desiraju (1998). Although it has long been known that perchlorate anions can form hydrogen bonds in crystals, the tetradendate perchlorate-bridged three-dimensional structure has not been reported. We describe herein the title compound, (I), which forms a unique three-dimensional network by means of strong and weak hydrogen bonds with tetradendate perchlorate in bridging mode. \sch
The X-ray structure analysis of (I) shows that the CuII atom is six-coordinated by four N atoms, originating from two chelated bis(pyrazol-1-yl)methane rings interacting at 60.26°, and by two O atoms from the water molecules (Fig. 1) The axial Cu—O bond distance of 2.459 (3) Å is significantly longer than the Cu—N bond lengths of 1.998 (2) and 2.032 (3) Å in the equatorial plane, due to the pronounced Jahn-Teller effect. The bis(pyrazol-1-yl)methane ligands are in a six-membered boat configuration in the complex, as observed in the analogous NiII complex (Langenberg et al., 1997).
The most striking feature of complex (I) resides in its ability to form three types of hydrogen bonds (Fig. 2). The H atoms from the ligand in the cation unit [Cu(C7H8N4)2(H2O)2]2+ have been activated by the positive charge due to the coordination of N atoms to the Cu2+ cation. Each perchlorate anion forms acceptors of hydrogen bonds with three adjacent [Cu(C7H8N4)2(H2O)2]2+ cations, giving a three-dimensional network (Fig. 3). The lengths of the hydrogen bonds are variable due to differences in C—H and/or O—H acidity. The C···O separations occur in the range 3.277–3.464 Å, well within the range of 3.0–4.0 Å reported for C···O separations (Desiraju, 1991). The smallest bond angle is 148.7°. The O···O distances of 2.847 and 2.926 Å are shorter than the C···O distances.
The C—H···O contacts primarily indicate electrostatic rather than van der Waals character and govern the crystal packing. Transmission of magnetic interactions through hydrogen bonds was first observed in transition metal complexes (Figgis et al., 1993), but hydrogen-bonded organic ferromagnets have now become the focus of interest (Zhang & Baumgarten, 1997). The work described here is a unique case of perchlorate forming a component of a supramolecular network.