metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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catena-Poly[[di­iodidocadmium]-μ-[4,4′-(2,3,5,6-tetra­methyl-1,4-phenyl­ene)bis­­(methyl­ene)]bis­­(3,5-di­methyl-1H-pyrazole)-κ2N2:N2′]

aDepartment of Chemistry, Zhengzhou University, Zhengzhou 450001, People's Republic of China, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and c Chemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my

(Received 28 June 2011; accepted 29 June 2011; online 6 July 2011)

The heterocylic ligand of the polymeric title compound, [CdI2(C22H30N4)], links two adjacent CdI2 units, forming a chain running parallel to [[\overline{1}]01]. The CdII atom is located on a twofold rotation axis and shows a distorted tetra­hedral CdI2N2 coordination. The mid-point of the benzene ring of the ligand lies on a center of inversion. There are no classical hydrogen-bonding inter­actions present.

Related literature

For the synthesis of the ligand, see: Trofimenko (1970[Trofimenko, S. (1970). J. Am. Chem. Soc. 92, 5118-5126.]).

[Scheme 1]

Experimental

Crystal data
  • [CdI2(C22H30N4)]

  • Mr = 716.70

  • Monoclinic, C 2/c

  • a = 22.118 (8) Å

  • b = 6.840 (2) Å

  • c = 17.057 (6) Å

  • β = 93.407 (5)°

  • V = 2575.8 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.26 mm−1

  • T = 293 K

  • 0.20 × 0.20 × 0.20 mm

Data collection
  • Rigaku Saturn 724 CCD diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2006[Rigaku (2006). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]) Tmin = 0.763, Tmax = 1.000

  • 14901 measured reflections

  • 2951 independent reflections

  • 2589 reflections with I > 2σ(I)

  • Rint = 0.041

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.134

  • S = 1.18

  • 2951 reflections

  • 137 parameters

  • H-atom parameters constrained

  • Δρmax = 1.12 e Å−3

  • Δρmin = −0.74 e Å−3

Data collection: CrystalClear (Rigaku, 2006[Rigaku (2006). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

The heterocyclic ligand is a new member of the class of geminal bis-(1-pyrazol-1-yl)alkanes developed fourty years ago by Trofimenko, who also investigated its coordination abilities (Trofimenko, 1970). However, no crystal structures of adducts of the parent 4,4'-(1,4-phenylene)bis(methylene)bis(3,5-dimethyl-1H-pyrazole) ligand have been reported to date.

The heterocylic ligand of the polymeric title compound CdI2(C22H30N4) (Fig. 1) links two adjacent CdI2 units to form a chain running parallel to [101]. The CdII atom shows a distorted tetrahedral CdI2N2 coordination. The 1H-pyrazole H atom is not involved in hydrogen bonding interactions, presumably due to the presence of the bulky methyl group and the CdI2 unit in its vicinity.

Related literature top

For the synthesis of the ligand, see: Trofimenko (1970).

Experimental top

A solution of cadmium diiodide (7.3 mg, 0.02 mmol) in methanol (2 ml) was added to a solution of 4,4'-(2,3,5,6-tetramethyl-1,4-phenylene)bis(methylene)bis(3,5-dimethyl-1H-pyrazole) (3.5 mg, 0.01 mmol) in ethanol (2 ml). The solution was allowed to evaporate for several days to afford colorless crystals in 80% yield. Calc. for C22H30N4CdI2: C 36.87, H 4.22, N 7.82%. Found: C 36.71, H 4.25, N 7.69%.

Refinement top

H atoms were placed in calculated positions [C—H 0.93–0.98 Å, N–H 0.88 Å; U(H) = 1.2–1.5Ueq(C,N)]. The highest peak in the final difference Fourier map is in the vicinity (1.35 Å) of H10B.

Computing details top

Data collection: CrystalClear (Rigaku, 2006); cell refinement: CrystalClear (Rigaku, 2006); data reduction: CrystalClear (Rigaku, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Figure 1. Thermal ellipsoid plot of a portion of the polymeric chain structure of CdI2(C22H30N4). Ellipsoids are drawn at the 50% probability level. [Symmetry code: i) -x+1/2, -y+5/2, -z.]
catena-Poly[[diiodidocadmium]-µ-[4,4'-(2,3,5,6-tetramethyl- 1,4-phenylene)bis(methylene)]bis(3,5-dimethyl-1H-pyrazole)- κ2N2:N2'] top
Crystal data top
[CdI2(C22H30N4)]F(000) = 1376
Mr = 716.70Dx = 1.848 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3092 reflections
a = 22.118 (8) Åθ = 2.1–30.6°
b = 6.840 (2) ŵ = 3.26 mm1
c = 17.057 (6) ÅT = 293 K
β = 93.407 (5)°Cuboid, colorless
V = 2575.8 (16) Å30.20 × 0.20 × 0.20 mm
Z = 4
Data collection top
Rigaku Saturn 724 CCD
diffractometer
2951 independent reflections
Radiation source: fine-focus sealed tube2589 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2006)
h = 2828
Tmin = 0.763, Tmax = 1.000k = 88
14901 measured reflectionsl = 2221
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)] = 0.054H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0555P)2 + 7.4182P]
where P = (Fo2 + 2Fc2)/3
S = 1.18(Δ/σ)max = 0.001
2951 reflectionsΔρmax = 1.12 e Å3
137 parametersΔρmin = 0.74 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00092 (15)
Crystal data top
[CdI2(C22H30N4)]V = 2575.8 (16) Å3
Mr = 716.70Z = 4
Monoclinic, C2/cMo Kα radiation
a = 22.118 (8) ŵ = 3.26 mm1
b = 6.840 (2) ÅT = 293 K
c = 17.057 (6) Å0.20 × 0.20 × 0.20 mm
β = 93.407 (5)°
Data collection top
Rigaku Saturn 724 CCD
diffractometer
2951 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2006)
2589 reflections with I > 2σ(I)
Tmin = 0.763, Tmax = 1.000Rint = 0.041
14901 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.18Δρmax = 1.12 e Å3
2951 reflectionsΔρmin = 0.74 e Å3
137 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.53637 (2)0.41499 (7)0.12116 (3)0.0692 (2)
Cd10.50000.60117 (8)0.25000.0424 (2)
N10.43399 (19)0.8146 (7)0.1908 (2)0.0438 (10)
N20.44190 (19)0.8589 (6)0.1144 (2)0.0421 (10)
H20.46950.80450.08630.051*
C10.3667 (4)0.9231 (11)0.2924 (4)0.071 (2)
H1A0.32390.89700.28890.106*
H1B0.37411.04640.31810.106*
H1C0.38730.82130.32200.106*
C20.3894 (2)0.9304 (8)0.2115 (3)0.0433 (12)
C30.3678 (2)1.0496 (8)0.1477 (3)0.0409 (11)
C40.4023 (2)0.9968 (8)0.0868 (3)0.0421 (11)
C50.4040 (3)1.0599 (9)0.0030 (3)0.0554 (15)
H5A0.36361.05990.02100.083*
H5B0.42870.97100.02460.083*
H5C0.42061.18920.00090.083*
C60.3180 (3)1.1960 (10)0.1503 (3)0.0590 (16)
H6A0.33531.32030.16740.071*
H6B0.29051.15470.18930.071*
C70.2817 (2)1.2271 (8)0.0728 (3)0.0438 (12)
C80.2379 (2)1.0890 (7)0.0473 (4)0.0469 (13)
C90.2061 (2)1.1132 (8)0.0256 (3)0.0460 (12)
C100.1571 (3)0.9684 (10)0.0503 (5)0.0701 (19)
H10A0.16390.91950.10180.105*
H10B0.11831.03180.05120.105*
H10C0.15780.86170.01370.105*
C110.2249 (3)0.9125 (9)0.0990 (5)0.0687 (19)
H11A0.25650.89980.13970.103*
H11B0.22320.79620.06750.103*
H11C0.18680.93100.12230.103*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0695 (3)0.0714 (4)0.0668 (3)0.0130 (2)0.0040 (2)0.0205 (2)
Cd10.0394 (3)0.0439 (3)0.0428 (3)0.0000.0077 (2)0.000
N10.039 (2)0.053 (3)0.038 (2)0.007 (2)0.0068 (18)0.001 (2)
N20.037 (2)0.048 (2)0.041 (2)0.0054 (19)0.0001 (18)0.0006 (19)
C10.084 (5)0.087 (5)0.040 (3)0.029 (4)0.004 (3)0.001 (3)
C20.043 (3)0.048 (3)0.037 (3)0.003 (2)0.010 (2)0.005 (2)
C30.037 (3)0.046 (3)0.038 (2)0.007 (2)0.008 (2)0.005 (2)
C40.044 (3)0.039 (3)0.042 (3)0.003 (2)0.006 (2)0.001 (2)
C50.067 (4)0.058 (3)0.042 (3)0.018 (3)0.010 (3)0.001 (3)
C60.060 (4)0.072 (4)0.043 (3)0.025 (3)0.008 (3)0.011 (3)
C70.039 (3)0.045 (3)0.047 (3)0.017 (2)0.007 (2)0.005 (2)
C80.040 (3)0.039 (3)0.062 (3)0.007 (2)0.001 (2)0.006 (2)
C90.036 (3)0.042 (3)0.060 (3)0.006 (2)0.004 (2)0.009 (2)
C100.052 (4)0.055 (4)0.101 (5)0.002 (3)0.011 (4)0.016 (4)
C110.050 (4)0.063 (4)0.093 (5)0.004 (3)0.009 (3)0.024 (4)
Geometric parameters (Å, º) top
I1—Cd12.7034 (8)C5—H5B0.9600
Cd1—N1i2.260 (4)C5—H5C0.9600
Cd1—N12.260 (4)C6—C71.520 (7)
Cd1—I1i2.7034 (8)C6—H6A0.9700
N1—C21.329 (7)C6—H6B0.9700
N1—N21.358 (6)C7—C9ii1.392 (8)
N2—C41.353 (6)C7—C81.403 (8)
N2—H20.8800C8—C91.403 (8)
C1—C21.497 (8)C8—C111.532 (8)
C1—H1A0.9600C9—C7ii1.392 (8)
C1—H1B0.9600C9—C101.509 (8)
C1—H1C0.9600C10—H10A0.9600
C2—C31.420 (7)C10—H10B0.9600
C3—C41.375 (7)C10—H10C0.9600
C3—C61.491 (7)C11—H11A0.9600
C4—C51.494 (7)C11—H11B0.9600
C5—H5A0.9600C11—H11C0.9600
N1i—Cd1—N199.6 (2)C4—C5—H5C109.5
N1i—Cd1—I1116.88 (12)H5A—C5—H5C109.5
N1—Cd1—I198.99 (11)H5B—C5—H5C109.5
N1i—Cd1—I1i98.99 (11)C3—C6—C7114.9 (4)
N1—Cd1—I1i116.88 (12)C3—C6—H6A108.5
I1—Cd1—I1i123.80 (4)C7—C6—H6A108.5
C2—N1—N2105.2 (4)C3—C6—H6B108.5
C2—N1—Cd1137.3 (4)C7—C6—H6B108.5
N2—N1—Cd1117.2 (3)H6A—C6—H6B107.5
C4—N2—N1111.9 (4)C9ii—C7—C8120.3 (5)
C4—N2—H2124.1C9ii—C7—C6120.1 (5)
N1—N2—H2124.1C8—C7—C6119.6 (5)
C2—C1—H1A109.5C7—C8—C9119.7 (5)
C2—C1—H1B109.5C7—C8—C11120.2 (5)
H1A—C1—H1B109.5C9—C8—C11120.1 (5)
C2—C1—H1C109.5C7ii—C9—C8120.0 (5)
H1A—C1—H1C109.5C7ii—C9—C10121.0 (5)
H1B—C1—H1C109.5C8—C9—C10119.0 (5)
N1—C2—C3111.1 (5)C9—C10—H10A109.5
N1—C2—C1121.4 (5)C9—C10—H10B109.5
C3—C2—C1127.5 (5)H10A—C10—H10B109.5
C4—C3—C2104.6 (4)C9—C10—H10C109.5
C4—C3—C6130.0 (5)H10A—C10—H10C109.5
C2—C3—C6125.4 (5)H10B—C10—H10C109.5
N2—C4—C3107.2 (4)C8—C11—H11A109.5
N2—C4—C5118.8 (5)C8—C11—H11B109.5
C3—C4—C5133.9 (5)H11A—C11—H11B109.5
C4—C5—H5A109.5C8—C11—H11C109.5
C4—C5—H5B109.5H11A—C11—H11C109.5
H5A—C5—H5B109.5H11B—C11—H11C109.5
N1i—Cd1—N1—C276.4 (5)N1—N2—C4—C5178.8 (5)
I1—Cd1—N1—C2164.2 (5)C2—C3—C4—N21.1 (6)
I1i—Cd1—N1—C228.8 (6)C6—C3—C4—N2179.4 (6)
N1i—Cd1—N1—N296.0 (4)C2—C3—C4—C5179.3 (6)
I1—Cd1—N1—N223.4 (4)C6—C3—C4—C50.2 (11)
I1i—Cd1—N1—N2158.7 (3)C4—C3—C6—C729.6 (9)
C2—N1—N2—C41.4 (6)C2—C3—C6—C7149.9 (5)
Cd1—N1—N2—C4176.1 (3)C3—C6—C7—C9ii99.5 (7)
N2—N1—C2—C30.7 (6)C3—C6—C7—C877.4 (7)
Cd1—N1—C2—C3173.7 (4)C9ii—C7—C8—C90.5 (9)
N2—N1—C2—C1179.2 (5)C6—C7—C8—C9177.5 (5)
Cd1—N1—C2—C17.7 (9)C9ii—C7—C8—C11179.5 (5)
N1—C2—C3—C40.3 (6)C6—C7—C8—C112.6 (8)
C1—C2—C3—C4178.2 (6)C7—C8—C9—C7ii0.5 (9)
N1—C2—C3—C6179.9 (5)C11—C8—C9—C7ii179.5 (5)
C1—C2—C3—C61.4 (9)C7—C8—C9—C10177.1 (5)
N1—N2—C4—C31.6 (6)C11—C8—C9—C102.9 (8)
Symmetry codes: (i) x+1, y, z+1/2; (ii) x+1/2, y+5/2, z.

Experimental details

Crystal data
Chemical formula[CdI2(C22H30N4)]
Mr716.70
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)22.118 (8), 6.840 (2), 17.057 (6)
β (°) 93.407 (5)
V3)2575.8 (16)
Z4
Radiation typeMo Kα
µ (mm1)3.26
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku Saturn 724 CCD
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2006)
Tmin, Tmax0.763, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
14901, 2951, 2589
Rint0.041
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.134, 1.18
No. of reflections2951
No. of parameters137
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.12, 0.74

Computer programs: CrystalClear (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

 

Acknowledgements

We thank Zhengzhou University and the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationRigaku (2006). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTrofimenko, S. (1970). J. Am. Chem. Soc. 92, 5118–5126.  CrossRef CAS Web of Science Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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