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Acta Cryst. (2009). E65, m1396    [ doi:10.1107/S1600536809042056 ]

catena-Poly[[copper(II)-bis[[mu]-bis(3,5-dimethyl-1H-pyrazol-4-yl) selenide]] bis(perchlorate)]

M. Seredyuk, M. Haukka, V. A. Pavlenko and I. O. Fritsky

Abstract top

In the title compound, {[Cu(C10H14N4Se)2](ClO4)2}n, the CuII ion is located on a twofold rotation axis and has a tetragonally distorted square-planar geometry constituted by four N atoms. A pair of bis(3,5-dimethyl-1H-pyrazol-4-yl) selenide (L) ligands bridges the copper centers into a polymeric chain extending along [001]. The perchlorate anions are involved in intermolecular N-H...O hydrogen bonding, which links the chains into layers parallel to the bc plane.

Comment top

Molecular self-assembly through donor-acceptor interactions becomes one of the most elaborated research areas in coordination chemistry. The primary interest here is the development of functional materials with useful properties. Particularly, infinite molecular polymeric arrays are potentially applicable as specifically ordered crystalline substances with reversible selective sorption (Farha et al., 2009), electrical conductivity (Shibahara et al., 2007) and molecular magnetism functionality (Ohba et al., 2009).

The title compound, [Cu(cis-µ-L)2](ClO4)2, was readily prepared by mixing aquoeous solution of Cu(ClO4)2.6H2O and methanolic solution of the ligand bis(3,5-dimethyl-1H-pyrazolyl)selenide (L) prepared according to Seredyuk et al. (2007). A tetragonally distorted square-planar environment of the CuII ion is formed by four non-coplanar nitrogen atoms of propeller-like arranged pyrazolyl cycles (distances Cu–N are 1.982 (5) and 1.967 (5) Å, two diagonal angles N–Cu–N are 163.6 (3) and 168.8 (3)°, respectively). Symmetrically equivalent ligand molecules in cis-bonding configuration are linked to CuII ion in a double-stranded bridge fashion (Fig. 1.). By repeats, they form linear chain running along the c axis within which each copper atom deviates from the average position by a value of ±0.068 (5) Å (Fig. 2). The NH group of each pyrazole cycle is involved in hydrogen bonding with perchlorate group resulting in the formation of a three-dimensional hybrid network.

Related literature top

For the potential applications of coordination polymers, see: Farha et al. (2009); Ohba et al. (2009); Shibahara et al. (2007). For our studies of similar complexes with different dimensionality, see Seredyuk et al. (2007).

Experimental top

A solution of Cu(ClO4)2.6H2O (0.065 g) in water (10 ml) was mixed with a solution of L.H2O (0.1 g) in methanol (10 ml) and was set aside for one week after which brown crystals of the title compound were isolated. Found C, 29.83, H, 3.65, N, 13.81. C20H28Cl2CuN8O8Se2 requires C, 29.99, H, 3.52, N, 13.99.

Refinement top

All H atoms were geometrically positioned (C—H 0.98 Å; N—H 0.88 Å), and refined as riding, with Uiso(H) = 1.2-1.5 Ueq(C, N). The crystal studied was a twin, so matrix (100) was used in the refinement of the crystal structure.

Computing details top

Data collection: COLLECT (Bruker-Nonius, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: DIAMOND (Brandenburg, 2006).

Figures top
[Figure 1] Fig. 1. A portion of the crystal structure of the title compound showing the labeling scheme and 50% probabilty displacement ellipsoids [symmetry codes: (i) –x, 1–y, –z, (ii) –x, y, -0.5–z, (iii) x, 1–y, -1/2 + z]. H atoms are omitted for clarity.
[Figure 2] Fig. 2. A packing diagram of the title compound viewed along the b-axis. H atoms are omitted for clarity.
catena-Poly[[copper(II)-bis[µ-bis(3,5-dimethyl-1H- pyrazol-4-yl) selenide]] bis(perchlorate)] top
Crystal data top
[Cu(C10H14N4Se)2](ClO4)2F(000) = 1596
Mr = 800.86Dx = 1.758 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3400 reflections
a = 28.398 (6) Åθ = 2.9–27.5°
b = 7.5865 (15) ŵ = 3.36 mm−1
c = 18.517 (4) ÅT = 120 K
β = 130.69 (3)°Plates, brown
V = 3025.1 (17) Å30.2 × 0.15 × 0.05 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		3415 independent reflections
Radiation source: fine-focus sealed tube2799 reflections with I > 2σ(I)
graphiteRint = 0.074
ω–scansθmax = 27.5°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −36→34
Tmin = 0.552, Tmax = 0.845k = −9→9
13077 measured reflectionsl = −24→22
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0574P)2 + 8.3063P]
where P = (Fo2 + 2Fc2)/3
3415 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 2.18 e Å−3
0 restraintsΔρmin = −1.00 e Å−3
Crystal data top
[Cu(C10H14N4Se)2](ClO4)2V = 3025.1 (17) Å3
Mr = 800.86Z = 4
Monoclinic, C2/cMo Kα radiation
a = 28.398 (6) ŵ = 3.36 mm−1
b = 7.5865 (15) ÅT = 120 K
c = 18.517 (4) Å0.2 × 0.15 × 0.05 mm
β = 130.69 (3)°
Data collection top
Nonius KappaCCD
diffractometer		3415 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2799 reflections with I > 2σ(I)
Tmin = 0.552, Tmax = 0.845Rint = 0.074
13077 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.115Δρmax = 2.18 e Å−3
S = 1.04Δρmin = −1.00 e Å−3
3415 reflectionsAbsolute structure: ?
191 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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
Cu10.00000.48037 (13)−0.25000.0124 (2)
Se10.15222 (2)0.73993 (6)0.14892 (4)0.01476 (14)
Cl10.13436 (8)0.99852 (19)0.36166 (12)0.0307 (4)
O10.1340 (3)1.0280 (6)0.2844 (4)0.0369 (12)
O20.1537 (3)1.1562 (6)0.4173 (3)0.0430 (13)
O30.1753 (2)0.8577 (5)0.4177 (4)0.0410 (14)
O40.0732 (2)0.9468 (7)0.3248 (4)0.0510 (14)
N10.0655 (2)0.5177 (6)−0.1109 (3)0.0144 (10)
N20.1167 (2)0.4166 (6)−0.0546 (3)0.0146 (10)
H40.12570.3301−0.07550.017*
N30.0637 (2)0.5450 (6)0.2384 (3)0.0125 (10)
N40.1183 (2)0.4511 (6)0.2931 (3)0.0131 (10)
H30.12840.37390.33670.016*
C10.0190 (3)0.7707 (8)−0.0923 (4)0.0237 (14)
H11A0.00360.8098−0.15480.036*
H11B0.03670.8713−0.04860.036*
H11C−0.01550.7211−0.09870.036*
C20.0679 (3)0.6330 (7)−0.0538 (4)0.0141 (12)
C30.1216 (3)0.6022 (7)0.0402 (4)0.0128 (12)
C40.1526 (3)0.4643 (7)0.0377 (4)0.0146 (11)
C50.2128 (3)0.3741 (9)0.1141 (5)0.0268 (15)
H19A0.20570.27920.14200.040*
H19B0.24220.45950.16370.040*
H19C0.23000.32450.08670.040*
C60.0155 (3)0.7705 (8)0.1110 (5)0.0217 (14)
H8A−0.01600.70910.05080.033*
H8B0.03280.86800.10000.033*
H8C−0.00350.81680.13620.033*
C70.0657 (3)0.6460 (7)0.1804 (4)0.0140 (12)
C80.1218 (3)0.6135 (7)0.1993 (4)0.0128 (11)
C90.1539 (3)0.4907 (7)0.2723 (4)0.0148 (12)
C100.2162 (3)0.4049 (8)0.3247 (5)0.0250 (14)
H17A0.21050.27920.30880.037*
H17B0.24070.41880.39350.037*
H17C0.23800.46080.30610.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0104 (4)0.0185 (5)0.0111 (5)0.0000.0082 (4)0.000
Se10.0156 (2)0.0179 (3)0.0128 (3)−0.0062 (2)0.0101 (3)−0.0039 (2)
Cl10.0342 (8)0.0231 (7)0.0390 (9)0.0019 (7)0.0258 (8)0.0063 (7)
O10.052 (3)0.032 (3)0.038 (3)−0.003 (2)0.034 (3)−0.001 (2)
O20.068 (4)0.030 (2)0.027 (3)0.000 (3)0.029 (3)0.003 (2)
O30.055 (4)0.022 (2)0.064 (4)0.013 (2)0.048 (3)0.016 (2)
O40.037 (3)0.070 (4)0.048 (3)−0.017 (3)0.029 (3)−0.011 (3)
N10.015 (3)0.016 (2)0.012 (2)0.002 (2)0.008 (2)−0.0016 (18)
N20.013 (3)0.016 (2)0.012 (2)0.0048 (19)0.007 (2)−0.0009 (18)
N30.012 (2)0.018 (2)0.010 (2)0.004 (2)0.008 (2)0.0002 (18)
N40.011 (2)0.015 (2)0.010 (2)0.0013 (19)0.005 (2)0.0022 (17)
C10.024 (4)0.021 (3)0.017 (3)0.009 (3)0.010 (3)0.001 (2)
C20.012 (3)0.017 (3)0.016 (3)0.001 (2)0.011 (3)0.001 (2)
C30.015 (3)0.014 (3)0.011 (3)−0.003 (2)0.009 (2)0.001 (2)
C40.015 (3)0.017 (2)0.014 (3)0.001 (2)0.011 (3)0.001 (2)
C50.021 (4)0.033 (4)0.024 (3)0.007 (3)0.013 (3)0.003 (3)
C60.015 (3)0.026 (3)0.022 (3)0.004 (3)0.010 (3)0.011 (2)
C70.017 (3)0.014 (3)0.011 (3)−0.001 (2)0.009 (3)−0.001 (2)
C80.014 (3)0.015 (3)0.010 (3)−0.001 (2)0.009 (2)−0.003 (2)
C90.012 (3)0.017 (3)0.016 (3)−0.001 (2)0.009 (2)−0.001 (2)
C100.020 (3)0.031 (3)0.029 (3)0.006 (3)0.018 (3)0.008 (3)
Geometric parameters (Å, °) top
Cu1—N3i1.967 (5)C1—H11A0.9800
Cu1—N3ii1.967 (5)C1—H11B0.9800
Cu1—N11.982 (5)C1—H11C0.9800
Cu1—N1iii1.982 (5)C2—C31.396 (8)
Se1—C81.893 (5)C3—C41.387 (8)
Se1—C31.902 (5)C4—C51.497 (8)
Cl1—O31.413 (5)C5—H19A0.9800
Cl1—O21.434 (5)C5—H19B0.9800
Cl1—O11.442 (5)C5—H19C0.9800
Cl1—O41.447 (5)C6—C71.478 (8)
N1—C21.339 (7)C6—H8A0.9800
N1—N21.347 (6)C6—H8B0.9800
N2—C41.349 (7)C6—H8C0.9800
N2—H40.8800C7—C81.413 (8)
N3—C71.349 (7)C8—C91.386 (8)
N3—N41.373 (6)C9—C101.502 (8)
N3—Cu1i1.967 (5)C10—H17A0.9800
N4—C91.330 (7)C10—H17B0.9800
N4—H30.8800C10—H17C0.9800
C1—C21.497 (8)
N3i—Cu1—N3ii168.8 (3)C4—C3—C2106.5 (5)
N3i—Cu1—N191.28 (16)C4—C3—Se1126.0 (4)
N3ii—Cu1—N190.32 (16)C2—C3—Se1127.0 (4)
N3i—Cu1—N1iii90.32 (16)N2—C4—C3105.9 (5)
N3ii—Cu1—N1iii91.28 (16)N2—C4—C5121.9 (5)
N1—Cu1—N1iii163.6 (3)C3—C4—C5132.2 (5)
C8—Se1—C3101.66 (19)C4—C5—H19A109.5
O3—Cl1—O2110.9 (3)C4—C5—H19B109.5
O3—Cl1—O1108.4 (3)H19A—C5—H19B109.5
O2—Cl1—O1109.5 (3)C4—C5—H19C109.5
O3—Cl1—O4107.6 (3)H19A—C5—H19C109.5
O2—Cl1—O4110.2 (4)H19B—C5—H19C109.5
O1—Cl1—O4110.2 (4)C7—C6—H8A109.5
C2—N1—N2106.7 (5)C7—C6—H8B109.5
C2—N1—Cu1129.9 (4)H8A—C6—H8B109.5
N2—N1—Cu1123.3 (3)C7—C6—H8C109.5
N1—N2—C4111.7 (4)H8A—C6—H8C109.5
N1—N2—H4124.1H8B—C6—H8C109.5
C4—N2—H4124.1N3—C7—C8109.2 (5)
C7—N3—N4105.7 (4)N3—C7—C6122.5 (5)
C7—N3—Cu1i131.4 (4)C8—C7—C6128.3 (5)
N4—N3—Cu1i122.9 (3)C9—C8—C7106.1 (5)
C9—N4—N3112.0 (4)C9—C8—Se1126.9 (4)
C9—N4—H3124.0C7—C8—Se1126.3 (4)
N3—N4—H3124.0N4—C9—C8107.1 (5)
C2—C1—H11A109.5N4—C9—C10120.8 (5)
C2—C1—H11B109.5C8—C9—C10132.0 (5)
H11A—C1—H11B109.5C9—C10—H17A109.5
C2—C1—H11C109.5C9—C10—H17B109.5
H11A—C1—H11C109.5H17A—C10—H17B109.5
H11B—C1—H11C109.5C9—C10—H17C109.5
N1—C2—C3109.1 (5)H17A—C10—H17C109.5
N1—C2—C1121.8 (5)H17B—C10—H17C109.5
C3—C2—C1129.1 (5)
N3i—Cu1—N1—C2−53.2 (5)N1—N2—C4—C5−178.8 (5)
N3ii—Cu1—N1—C2138.0 (5)C2—C3—C4—N2−1.3 (6)
N1iii—Cu1—N1—C242.3 (5)Se1—C3—C4—N2−174.1 (4)
N3i—Cu1—N1—N2122.9 (4)C2—C3—C4—C5178.5 (6)
N3ii—Cu1—N1—N2−45.9 (4)Se1—C3—C4—C55.7 (9)
N1iii—Cu1—N1—N2−141.6 (4)N4—N3—C7—C80.3 (6)
C2—N1—N2—C4−0.4 (6)Cu1i—N3—C7—C8−179.0 (4)
Cu1—N1—N2—C4−177.3 (4)N4—N3—C7—C6−178.8 (5)
C7—N3—N4—C90.7 (6)Cu1i—N3—C7—C62.0 (9)
Cu1i—N3—N4—C9180.0 (4)N3—C7—C8—C9−1.0 (6)
N2—N1—C2—C3−0.4 (6)C6—C7—C8—C9177.9 (6)
Cu1—N1—C2—C3176.2 (4)N3—C7—C8—Se1−172.0 (4)
N2—N1—C2—C1178.4 (5)C6—C7—C8—Se17.0 (9)
Cu1—N1—C2—C1−5.0 (8)C3—Se1—C8—C997.2 (5)
N1—C2—C3—C41.1 (6)C3—Se1—C8—C7−93.7 (5)
C1—C2—C3—C4−177.6 (6)N3—N4—C9—C8−1.3 (6)
N1—C2—C3—Se1173.8 (4)N3—N4—C9—C10179.1 (5)
C1—C2—C3—Se1−4.9 (9)C7—C8—C9—N41.4 (6)
C8—Se1—C3—C4−91.4 (5)Se1—C8—C9—N4172.3 (4)
C8—Se1—C3—C297.3 (5)C7—C8—C9—C10−179.1 (6)
N1—N2—C4—C31.1 (6)Se1—C8—C9—C10−8.3 (9)
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1, z−1/2; (iii) −x, y, −z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O3ii0.882.062.912 (6)161
N4—H3···O2iv0.882.022.879 (6)166
Symmetry codes: (ii) x, −y+1, z−1/2; (iv) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H4···O3i0.882.062.912 (6)161
N4—H3···O2ii0.882.022.879 (6)166
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, y−1, z.
references
References top

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