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

Zhou, Y.; Wang, Z.; Yang, G.; Ng, S.W.

doi:10.1107/S1600536811025797

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1037

doi:10.1107/S1600536811025797

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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:N^2′]

Yuanyuan Zhou,^a Zhaoyang Wang,^a Guang Yang ^a and Seik Weng Ng ^b,^c ^*

^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 Cd^II 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 ).

Experimental

Crystal data

[CdI₂(C₂₂H₃₀N₄)]
M_r = 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 ) T_min = 0.763, T_max = 1.000
14901 measured reflections
2951 independent reflections
2589 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.134
S = 1.18
2951 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 1.12 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Data collection: CrystalClear (Rigaku, 2006); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025797/wm2507sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025797/wm2507Isup2.hkl

checkCIF report

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 Cd^II 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%.

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

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:N^2'] top

Crystal data top

[CdI₂(C₂₂H₃₀N₄)]	F(000) = 1376
M_r = 716.70	D_x = 1.848 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3092 reflections
a = 22.118 (8) Å	θ = 2.1–30.6°
b = 6.840 (2) Å	µ = 3.26 mm⁻¹
c = 17.057 (6) Å	T = 293 K
β = 93.407 (5)°	Cuboid, colorless
V = 2575.8 (16) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku Saturn 724 CCD diffractometer	2951 independent reflections
Radiation source: fine-focus sealed tube	2589 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2006)	h = −28→28
T_min = 0.763, T_max = 1.000	k = −8→8
14901 measured reflections	l = −22→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.134	w = 1/[σ²(F_o²) + (0.0555P)² + 7.4182P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.001
2951 reflections	Δρ_max = 1.12 e Å⁻³
137 parameters	Δρ_min = −0.74 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00092 (15)

Crystal data top

[CdI₂(C₂₂H₃₀N₄)]	V = 2575.8 (16) Å³
M_r = 716.70	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.118 (8) Å	µ = 3.26 mm⁻¹
b = 6.840 (2) Å	T = 293 K
c = 17.057 (6) Å	0.20 × 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)
T_min = 0.763, T_max = 1.000	R_int = 0.041
14901 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.18	Δρ_max = 1.12 e Å⁻³
2951 reflections	Δρ_min = −0.74 e Å⁻³
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

	x	y	z	U_iso*/U_eq
I1	0.53637 (2)	0.41499 (7)	0.12116 (3)	0.0692 (2)
Cd1	0.5000	0.60117 (8)	0.2500	0.0424 (2)
N1	0.43399 (19)	0.8146 (7)	0.1908 (2)	0.0438 (10)
N2	0.44190 (19)	0.8589 (6)	0.1144 (2)	0.0421 (10)
H2	0.4695	0.8045	0.0863	0.051*
C1	0.3667 (4)	0.9231 (11)	0.2924 (4)	0.071 (2)
H1A	0.3239	0.8970	0.2889	0.106*
H1B	0.3741	1.0464	0.3181	0.106*
H1C	0.3873	0.8213	0.3220	0.106*
C2	0.3894 (2)	0.9304 (8)	0.2115 (3)	0.0433 (12)
C3	0.3678 (2)	1.0496 (8)	0.1477 (3)	0.0409 (11)
C4	0.4023 (2)	0.9968 (8)	0.0868 (3)	0.0421 (11)
C5	0.4040 (3)	1.0599 (9)	0.0030 (3)	0.0554 (15)
H5A	0.3636	1.0599	−0.0210	0.083*
H5B	0.4287	0.9710	−0.0246	0.083*
H5C	0.4206	1.1892	0.0009	0.083*
C6	0.3180 (3)	1.1960 (10)	0.1503 (3)	0.0590 (16)
H6A	0.3353	1.3203	0.1674	0.071*
H6B	0.2905	1.1547	0.1893	0.071*
C7	0.2817 (2)	1.2271 (8)	0.0728 (3)	0.0438 (12)
C8	0.2379 (2)	1.0890 (7)	0.0473 (4)	0.0469 (13)
C9	0.2061 (2)	1.1132 (8)	−0.0256 (3)	0.0460 (12)
C10	0.1571 (3)	0.9684 (10)	−0.0503 (5)	0.0701 (19)
H10A	0.1639	0.9195	−0.1018	0.105*
H10B	0.1183	1.0318	−0.0512	0.105*
H10C	0.1578	0.8617	−0.0137	0.105*
C11	0.2249 (3)	0.9125 (9)	0.0990 (5)	0.0687 (19)
H11A	0.2565	0.8998	0.1397	0.103*
H11B	0.2232	0.7962	0.0675	0.103*
H11C	0.1868	0.9310	0.1223	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0695 (3)	0.0714 (4)	0.0668 (3)	0.0130 (2)	0.0040 (2)	−0.0205 (2)
Cd1	0.0394 (3)	0.0439 (3)	0.0428 (3)	0.000	−0.0077 (2)	0.000
N1	0.039 (2)	0.053 (3)	0.038 (2)	0.007 (2)	−0.0068 (18)	−0.001 (2)
N2	0.037 (2)	0.048 (2)	0.041 (2)	0.0054 (19)	−0.0001 (18)	−0.0006 (19)
C1	0.084 (5)	0.087 (5)	0.040 (3)	0.029 (4)	0.004 (3)	−0.001 (3)
C2	0.043 (3)	0.048 (3)	0.037 (3)	0.003 (2)	−0.010 (2)	−0.005 (2)
C3	0.037 (3)	0.046 (3)	0.038 (2)	0.007 (2)	−0.008 (2)	−0.005 (2)
C4	0.044 (3)	0.039 (3)	0.042 (3)	0.003 (2)	−0.006 (2)	−0.001 (2)
C5	0.067 (4)	0.058 (3)	0.042 (3)	0.018 (3)	0.010 (3)	0.001 (3)
C6	0.060 (4)	0.072 (4)	0.043 (3)	0.025 (3)	−0.008 (3)	−0.011 (3)
C7	0.039 (3)	0.045 (3)	0.047 (3)	0.017 (2)	−0.007 (2)	−0.005 (2)
C8	0.040 (3)	0.039 (3)	0.062 (3)	0.007 (2)	−0.001 (2)	0.006 (2)
C9	0.036 (3)	0.042 (3)	0.060 (3)	0.006 (2)	−0.004 (2)	−0.009 (2)
C10	0.052 (4)	0.055 (4)	0.101 (5)	−0.002 (3)	−0.011 (4)	−0.016 (4)
C11	0.050 (4)	0.063 (4)	0.093 (5)	0.004 (3)	0.009 (3)	0.024 (4)

Geometric parameters (Å, º) top

I1—Cd1	2.7034 (8)	C5—H5B	0.9600
Cd1—N1ⁱ	2.260 (4)	C5—H5C	0.9600
Cd1—N1	2.260 (4)	C6—C7	1.520 (7)
Cd1—I1ⁱ	2.7034 (8)	C6—H6A	0.9700
N1—C2	1.329 (7)	C6—H6B	0.9700
N1—N2	1.358 (6)	C7—C9ⁱⁱ	1.392 (8)
N2—C4	1.353 (6)	C7—C8	1.403 (8)
N2—H2	0.8800	C8—C9	1.403 (8)
C1—C2	1.497 (8)	C8—C11	1.532 (8)
C1—H1A	0.9600	C9—C7ⁱⁱ	1.392 (8)
C1—H1B	0.9600	C9—C10	1.509 (8)
C1—H1C	0.9600	C10—H10A	0.9600
C2—C3	1.420 (7)	C10—H10B	0.9600
C3—C4	1.375 (7)	C10—H10C	0.9600
C3—C6	1.491 (7)	C11—H11A	0.9600
C4—C5	1.494 (7)	C11—H11B	0.9600
C5—H5A	0.9600	C11—H11C	0.9600

N1ⁱ—Cd1—N1	99.6 (2)	C4—C5—H5C	109.5
N1ⁱ—Cd1—I1	116.88 (12)	H5A—C5—H5C	109.5
N1—Cd1—I1	98.99 (11)	H5B—C5—H5C	109.5
N1ⁱ—Cd1—I1ⁱ	98.99 (11)	C3—C6—C7	114.9 (4)
N1—Cd1—I1ⁱ	116.88 (12)	C3—C6—H6A	108.5
I1—Cd1—I1ⁱ	123.80 (4)	C7—C6—H6A	108.5
C2—N1—N2	105.2 (4)	C3—C6—H6B	108.5
C2—N1—Cd1	137.3 (4)	C7—C6—H6B	108.5
N2—N1—Cd1	117.2 (3)	H6A—C6—H6B	107.5
C4—N2—N1	111.9 (4)	C9ⁱⁱ—C7—C8	120.3 (5)
C4—N2—H2	124.1	C9ⁱⁱ—C7—C6	120.1 (5)
N1—N2—H2	124.1	C8—C7—C6	119.6 (5)
C2—C1—H1A	109.5	C7—C8—C9	119.7 (5)
C2—C1—H1B	109.5	C7—C8—C11	120.2 (5)
H1A—C1—H1B	109.5	C9—C8—C11	120.1 (5)
C2—C1—H1C	109.5	C7ⁱⁱ—C9—C8	120.0 (5)
H1A—C1—H1C	109.5	C7ⁱⁱ—C9—C10	121.0 (5)
H1B—C1—H1C	109.5	C8—C9—C10	119.0 (5)
N1—C2—C3	111.1 (5)	C9—C10—H10A	109.5
N1—C2—C1	121.4 (5)	C9—C10—H10B	109.5
C3—C2—C1	127.5 (5)	H10A—C10—H10B	109.5
C4—C3—C2	104.6 (4)	C9—C10—H10C	109.5
C4—C3—C6	130.0 (5)	H10A—C10—H10C	109.5
C2—C3—C6	125.4 (5)	H10B—C10—H10C	109.5
N2—C4—C3	107.2 (4)	C8—C11—H11A	109.5
N2—C4—C5	118.8 (5)	C8—C11—H11B	109.5
C3—C4—C5	133.9 (5)	H11A—C11—H11B	109.5
C4—C5—H5A	109.5	C8—C11—H11C	109.5
C4—C5—H5B	109.5	H11A—C11—H11C	109.5
H5A—C5—H5B	109.5	H11B—C11—H11C	109.5

N1ⁱ—Cd1—N1—C2	−76.4 (5)	N1—N2—C4—C5	−178.8 (5)
I1—Cd1—N1—C2	164.2 (5)	C2—C3—C4—N2	−1.1 (6)
I1ⁱ—Cd1—N1—C2	28.8 (6)	C6—C3—C4—N2	179.4 (6)
N1ⁱ—Cd1—N1—N2	96.0 (4)	C2—C3—C4—C5	179.3 (6)
I1—Cd1—N1—N2	−23.4 (4)	C6—C3—C4—C5	−0.2 (11)
I1ⁱ—Cd1—N1—N2	−158.7 (3)	C4—C3—C6—C7	29.6 (9)
C2—N1—N2—C4	−1.4 (6)	C2—C3—C6—C7	−149.9 (5)
Cd1—N1—N2—C4	−176.1 (3)	C3—C6—C7—C9ⁱⁱ	−99.5 (7)
N2—N1—C2—C3	0.7 (6)	C3—C6—C7—C8	77.4 (7)
Cd1—N1—C2—C3	173.7 (4)	C9ⁱⁱ—C7—C8—C9	−0.5 (9)
N2—N1—C2—C1	179.2 (5)	C6—C7—C8—C9	−177.5 (5)
Cd1—N1—C2—C1	−7.7 (9)	C9ⁱⁱ—C7—C8—C11	179.5 (5)
N1—C2—C3—C4	0.3 (6)	C6—C7—C8—C11	2.6 (8)
C1—C2—C3—C4	−178.2 (6)	C7—C8—C9—C7ⁱⁱ	0.5 (9)
N1—C2—C3—C6	179.9 (5)	C11—C8—C9—C7ⁱⁱ	−179.5 (5)
C1—C2—C3—C6	1.4 (9)	C7—C8—C9—C10	−177.1 (5)
N1—N2—C4—C3	1.6 (6)	C11—C8—C9—C10	2.9 (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)]
M_r	716.70
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	22.118 (8), 6.840 (2), 17.057 (6)
β (°)	93.407 (5)
V (Å³)	2575.8 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.26
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku Saturn 724 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2006)
T_min, T_max	0.763, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	14901, 2951, 2589
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.134, 1.18
No. of reflections	2951
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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

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