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Acta Cryst. (2007). E63, m1864    [ doi:10.1107/S1600536807027626 ]

catena-Poly[[[diididocadmium(II)]-[mu]-3,3',5,5'-tetramethyl-4,4'-bipyrazolyl-[kappa]2N:N'] methanol solvate]

D.-Q. Li, L. Hou and S. W. Ng

Abstract top

The substituted bipyrazole heterocycle in the title compound, {[CdI2(C10H12N4)]·CH4O}n, links CdI2 units into a helical chain which runs parallel to the b axis of the monoclinic unit cell. One of the two -NH sites forms a hydrogen bond with a solvent methanol molecule. The CdII atom is in a slightly distorted tetrahedral coordination environment.

Comment top

3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl in its doubly-deprotonated form is capable of connecting to four metal sites (Boldog et al., 2001; Boldog, Rusanov et al., 2003; Boldog, Sieler et al., 2003; He et al., 2006; Ponomarova et al., 2002). The disilver(I) derivative exemplifies such a feature; the framework is porous (Zhang et al., 2007). The attempted synthesis of the cadmium derivative yielded an adduct, the neutral heterocycle binding to cadmium diiodide in a 1:1 molar stoichoimetry. The compound crystallizes with a molecule of methanol. The title compound exists as helical chain that runs along the b-axis of the unit cell; the methanol molecules are linked to the chain by hydrogen bonds, with the –NH group serving as donor.

Related literature top

For the synthesis of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Mosby (1957). For literature on other metal derivatives of 3,3',5,5'-tetramethyl-4,4'-bipyrazole, see: Boldog et al. (2001); Boldog, Rusanov et al. (2003); Boldog, Sieler et al. (2003); He et al. (2006); Ponomarova et al. (2002); Zhang et al. (2007).

Experimental top

3,3',5,5'-Tetramethyl-4,4'-bipyrazolyl was synthesized by using a reported procedure (Mosby, 1957). The ligand (0.02 g, 0.1 mmol), cadmium iodide (0.07 g, 0.2 mmol), potassium iodide (0.03 g, 0.2 mmol), methanol (5 ml) and water (5 ml) were mixed in a 15-ml Telfon-lined, stainless-steel Parr bomb. The bomb was heated at 423 K for 72 h and then cooled to room temperature at a rate of 5 K h-1. The resulting solution was left for two days to give colorless block-shaped crystals in about 70% yield.

Refinement top

All H atoms were generated geometrically (O—H 0.82, N—H 0.86 Å and C—H 0.96 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2 or 1.5Ueq(C,N,O).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of a portion of the chain structure of [(C10H12N4)I2Cd·CH4O]n; displacement ellipsoids are drawn at the 70% probability level, and H atoms as spheres of arbitrary radius. The lattice methanol is not shown. [Symmetry code (i): 1/2 − x, y − 1/2, 1/2 − z].
catena-Poly[[[diididocadmium(II)]-µ-3,3',5,5'-tetramethyl-4,4'- bipyrazolyl-κ2N:N'] methanol solvate] top
Crystal data top
[CdI2(C10H12N4)]·CH4OF000 = 1096
Mr = 588.49Dx = 2.204 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4773 reflections
a = 11.1294 (6) Åθ = 2.2–27.2º
b = 12.2109 (7) ŵ = 4.71 mm−1
c = 13.2924 (7) ÅT = 293 (2) K
β = 101.008 (1)ºBlock, colourless
V = 1773.2 (2) Å30.35 × 0.30 × 0.11 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer		3077 independent reflections
Radiation source: fine-focus sealed tube2813 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 293(2) Kθmax = 25.0º
φ and ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.255, Tmax = 0.625k = −13→14
8299 measured reflectionsl = −14→15
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)] = 0.031H-atom parameters constrained
wR(F2) = 0.090  w = 1/[σ2(Fo2) + (0.048P)2 + 2.2498P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
3077 reflectionsΔρmax = 0.93 e Å−3
178 parametersΔρmin = −0.90 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[CdI2(C10H12N4)]·CH4OV = 1773.2 (2) Å3
Mr = 588.49Z = 4
Monoclinic, P21/nMo Kα
a = 11.1294 (6) ŵ = 4.71 mm−1
b = 12.2109 (7) ÅT = 293 (2) K
c = 13.2924 (7) Å0.35 × 0.30 × 0.11 mm
β = 101.008 (1)º
Data collection top
Bruker APEX area-detector
diffractometer		3077 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2813 reflections with I > 2σ(I)
Tmin = 0.255, Tmax = 0.625Rint = 0.023
8299 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031178 parameters
wR(F2) = 0.090H-atom parameters constrained
S = 1.11Δρmax = 0.93 e Å−3
3077 reflectionsΔρmin = −0.90 e Å−3
Special details top

Experimental. High-angle reflections were omitted as their inclusion led to somewhat large peaks and deep holes near the iodine atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.70846 (4)0.50859 (4)0.42967 (3)0.06227 (15)
I20.72925 (4)0.63673 (4)0.10377 (3)0.06328 (16)
Cd10.59541 (3)0.59870 (3)0.24959 (3)0.03701 (13)
O10.1126 (6)1.2458 (4)0.5060 (4)0.0839 (15)
H10.17231.28650.51490.126*
N10.5170 (3)0.7677 (3)0.2704 (3)0.0374 (9)
N20.5426 (4)0.8568 (3)0.2178 (3)0.0406 (10)
H20.60020.85940.18300.049*
N30.0920 (3)1.0264 (3)0.3095 (3)0.0373 (9)
N40.1727 (4)1.0898 (3)0.3735 (3)0.0384 (9)
H40.15191.14470.40690.046*
C10.3664 (5)0.7180 (4)0.3772 (4)0.0488 (13)
H1A0.30660.67370.33380.073*
H1B0.32770.75790.42450.073*
H1C0.42930.67180.41450.073*
C20.4215 (4)0.7964 (4)0.3133 (4)0.0354 (10)
C30.3872 (4)0.9052 (4)0.2869 (4)0.0352 (10)
C40.4669 (4)0.9408 (4)0.2266 (4)0.0368 (10)
C50.4749 (5)1.0490 (4)0.1743 (5)0.0514 (14)
H5A0.51121.10240.22400.077*
H5B0.39431.07260.14270.077*
H5C0.52441.04120.12300.077*
C60.1046 (5)0.8661 (4)0.1984 (5)0.0523 (14)
H6A0.02990.84050.21640.078*
H6B0.16060.80600.20030.078*
H6C0.08730.89650.13060.078*
C70.1599 (4)0.9514 (4)0.2722 (4)0.0353 (10)
C80.2850 (4)0.9679 (4)0.3138 (4)0.0334 (10)
C90.2887 (4)1.0570 (4)0.3788 (4)0.0362 (10)
C100.3915 (5)1.1113 (4)0.4491 (5)0.0499 (13)
H10A0.37491.18820.45260.075*
H10B0.46601.10090.42400.075*
H10C0.39991.07980.51630.075*
C110.1035 (11)1.1962 (7)0.5970 (7)0.110 (3)
H11A0.17891.15930.62430.165*
H11B0.03781.14400.58550.165*
H11C0.08761.25060.64500.165*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0510 (2)0.0729 (3)0.0595 (3)−0.00489 (18)0.00184 (19)0.0232 (2)
I20.0582 (3)0.0767 (3)0.0645 (3)−0.00017 (19)0.0359 (2)0.0071 (2)
Cd10.02859 (19)0.0373 (2)0.0473 (2)0.00236 (13)0.01280 (16)0.00152 (15)
O10.108 (4)0.060 (3)0.090 (4)−0.007 (3)0.036 (3)−0.023 (3)
N10.034 (2)0.033 (2)0.047 (2)0.0043 (16)0.0137 (18)−0.0008 (17)
N20.034 (2)0.041 (2)0.051 (3)−0.0006 (17)0.0182 (19)0.0022 (19)
N30.0305 (19)0.040 (2)0.043 (2)0.0010 (17)0.0102 (18)−0.0054 (18)
N40.036 (2)0.038 (2)0.041 (2)0.0054 (17)0.0073 (18)−0.0076 (17)
C10.053 (3)0.041 (3)0.058 (3)0.004 (2)0.025 (3)0.006 (2)
C20.036 (2)0.035 (2)0.037 (3)0.0016 (19)0.011 (2)−0.0009 (19)
C30.029 (2)0.036 (2)0.041 (3)−0.0002 (19)0.006 (2)−0.001 (2)
C40.030 (2)0.035 (2)0.045 (3)0.0005 (19)0.008 (2)−0.001 (2)
C50.044 (3)0.048 (3)0.065 (4)0.004 (2)0.017 (3)0.013 (3)
C60.042 (3)0.050 (3)0.065 (4)0.004 (2)0.010 (3)−0.020 (3)
C70.035 (2)0.033 (2)0.040 (3)0.0041 (19)0.013 (2)−0.001 (2)
C80.033 (2)0.032 (2)0.036 (3)0.0047 (19)0.0096 (19)0.0036 (19)
C90.034 (2)0.033 (2)0.041 (3)0.0053 (19)0.006 (2)0.004 (2)
C100.047 (3)0.042 (3)0.056 (4)0.005 (2)−0.003 (3)−0.005 (2)
C110.190 (11)0.061 (4)0.091 (6)0.000 (5)0.058 (7)−0.010 (4)
Geometric parameters (Å, °) top
I1—Cd12.7154 (5)C3—C41.375 (7)
I2—Cd12.7008 (5)C3—C81.470 (6)
Cd1—N12.277 (4)C4—C51.503 (7)
Cd1—N3i2.263 (4)C5—H5A0.9600
O1—C111.374 (10)C5—H5B0.9600
O1—H10.8200C5—H5C0.9600
N1—C21.345 (6)C6—C71.482 (7)
N1—N21.353 (5)C6—H6A0.9600
N2—C41.347 (6)C6—H6B0.9600
N2—H20.8600C6—H6C0.9600
N3—C71.341 (6)C7—C81.411 (6)
N3—N41.356 (6)C8—C91.386 (7)
N3—Cd1ii2.263 (4)C9—C101.488 (7)
N4—C91.341 (6)C10—H10A0.9600
N4—H40.8600C10—H10B0.9600
C1—C21.488 (7)C10—H10C0.9600
C1—H1A0.9600C11—H11A0.9600
C1—H1B0.9600C11—H11B0.9600
C1—H1C0.9600C11—H11C0.9600
C2—C31.409 (6)
I1—Cd1—I2118.43 (2)C4—C5—H5A109.5
I1—Cd1—N1112.6 (1)C4—C5—H5B109.5
I1—Cd1—N3i112.9 (1)H5A—C5—H5B109.5
I2—Cd1—N1102.0 (1)C4—C5—H5C109.5
I2—Cd1—N3i114.6 (1)H5A—C5—H5C109.5
N1—Cd1—N3i92.7 (1)H5B—C5—H5C109.5
C11—O1—H1109.5C7—C6—H6A109.5
C2—N1—N2105.7 (4)C7—C6—H6B109.5
C2—N1—Cd1129.7 (3)H6A—C6—H6B109.5
N2—N1—Cd1122.9 (3)C7—C6—H6C109.5
C4—N2—N1111.8 (4)H6A—C6—H6C109.5
C4—N2—H2124.1H6B—C6—H6C109.5
N1—N2—H2124.1N3—C7—C8110.0 (4)
C7—N3—N4105.6 (4)N3—C7—C6122.2 (4)
C7—N3—Cd1ii133.2 (3)C8—C7—C6127.9 (4)
N4—N3—Cd1ii116.8 (3)C9—C8—C7105.4 (4)
C9—N4—N3112.2 (4)C9—C8—C3128.9 (4)
C9—N4—H4123.9C7—C8—C3125.6 (4)
N3—N4—H4123.9N4—C9—C8106.7 (4)
C2—C1—H1A109.5N4—C9—C10121.1 (4)
C2—C1—H1B109.5C8—C9—C10132.1 (4)
H1A—C1—H1B109.5C9—C10—H10A109.5
C2—C1—H1C109.5C9—C10—H10B109.5
H1A—C1—H1C109.5H10A—C10—H10B109.5
H1B—C1—H1C109.5C9—C10—H10C109.5
N1—C2—C3109.8 (4)H10A—C10—H10C109.5
N1—C2—C1121.3 (4)H10B—C10—H10C109.5
C3—C2—C1128.9 (4)O1—C11—H11A109.5
C4—C3—C2105.6 (4)O1—C11—H11B109.5
C4—C3—C8126.3 (4)H11A—C11—H11B109.5
C2—C3—C8128.0 (4)O1—C11—H11C109.5
N2—C4—C3107.1 (4)H11A—C11—H11C109.5
N2—C4—C5122.4 (4)H11B—C11—H11C109.5
C3—C4—C5130.5 (4)
N3i—Cd1—N1—C246.2 (4)C8—C3—C4—N2−177.3 (5)
I2—Cd1—N1—C2162.0 (4)C2—C3—C4—C5179.1 (5)
I1—Cd1—N1—C2−70.0 (4)C8—C3—C4—C51.2 (9)
N3i—Cd1—N1—N2−116.9 (4)N4—N3—C7—C80.2 (5)
I2—Cd1—N1—N2−1.1 (4)Cd1ii—N3—C7—C8155.2 (3)
I1—Cd1—N1—N2126.9 (3)N4—N3—C7—C6−179.9 (5)
C2—N1—N2—C40.3 (5)Cd1ii—N3—C7—C6−24.8 (7)
Cd1—N1—N2—C4166.9 (3)N3—C7—C8—C90.2 (5)
C7—N3—N4—C9−0.6 (5)C6—C7—C8—C9−179.7 (5)
Cd1ii—N3—N4—C9−160.4 (3)N3—C7—C8—C3−176.7 (4)
N2—N1—C2—C30.0 (5)C6—C7—C8—C33.4 (8)
Cd1—N1—C2—C3−165.3 (3)C4—C3—C8—C9−71.1 (7)
N2—N1—C2—C1179.5 (5)C2—C3—C8—C9111.5 (6)
Cd1—N1—C2—C114.1 (7)C4—C3—C8—C7105.1 (6)
N1—C2—C3—C4−0.3 (6)C2—C3—C8—C7−72.3 (7)
C1—C2—C3—C4−179.7 (5)N3—N4—C9—C80.8 (5)
N1—C2—C3—C8177.5 (5)N3—N4—C9—C10−176.5 (4)
C1—C2—C3—C8−1.9 (8)C7—C8—C9—N4−0.6 (5)
N1—N2—C4—C3−0.6 (6)C3—C8—C9—N4176.2 (5)
N1—N2—C4—C5−179.3 (5)C7—C8—C9—C10176.2 (5)
C2—C3—C4—N20.5 (5)C3—C8—C9—C10−7.0 (9)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O10.861.922.762 (6)168
Table 1
Selected geometric parameters (Å, °) top
I1—Cd12.7154 (5)Cd1—N12.277 (4)
I2—Cd12.7008 (5)Cd1—N3i2.263 (4)
I1—Cd1—I2118.43 (2)I2—Cd1—N1102.0 (1)
I1—Cd1—N1112.6 (1)I2—Cd1—N3i114.6 (1)
I1—Cd1—N3i112.9 (1)N1—Cd1—N3i92.7 (1)
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O10.861.922.762 (6)168
Acknowledgements top

The authors thank Yunlin [Yulin in addresses] Normal University, Sun Yat-Sen University and the University of Malaya for supporting this study.

references
References top

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