catena-Poly[[diiodidocadmium(II)]-μ-4,4′-di-4-pyridyl-2,2′-disulfanediyldipyrimidine]

Zhu, H.-B.

doi:10.1107/S1600536809051162

catena-Poly[[diiodidocadmium(II)]-μ-4,4′-di-4-pyridyl-2,2′-disulfanediyldipyrimidine]

In the title compound, [CdI₂(C₁₈H₁₂N₆S₂)]_n, the 4,4′-di-4-pyridyl-2,2′-disulfanediyldipyrimidine (L) ligand bridges two Cd^II centers, forming polymeric zigzag chains extending along the b axis. The Cd^II ions are coordinated by two N atoms from two L ligands and two iodide anions in a distorted tetrahedral geometry.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809051162/cv2663sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809051162/cv2663Isup2.hkl Contains datablock I

CCDC reference: 766634

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.007 Å
R factor = 0.027
wR factor = 0.057
Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  I2     --  Cd1     ..       7.44 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         66

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        100 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Over past few years, organic aromatic disulfide has received considerable attention due to both its conformational flexibility and axial chirality (Horikoshi et al., 2006). In our previous study, we have reported two one-dimensional Zn^II and Fe^II coordination polymers with the ligand L ( = 2, 2'-dithiobis(4-pyridin-4-ylpyrimidine) (Zhu et al., 2009). Herein, we report new one-dimensional Cd^II coordination chain generated by althernative linking of Cd center and ligand L.

The Cd^II ion in the title complex adopts a tetrahedral coordination geometry completed by two N atoms from two ligands L [Cd1—N1 2.287 (3) Å; Cd1—N6 2.289 (4) Å] and two I anions [I1—Cd1 2.6938 (4) Å; I2—Cd1 2.6962 (4) Å]. In L, the C—S—S—C torsion angle is 84.1 (2)°.

Related literature top

For coordination polymers with 4,4'-dipyridinedisulfide, see: Horikoshi et al. (2006). For coordination complexes with the title ligand L, see: Zhu et al. (2009).

Experimental top

Slowly added is the CH₂Cl₂ (5 ml) solution of ligand L (0.1 mmol) into the CdI₂ (0.1 mmol) solution in methanol (10 ml). The mixture was kept on standing for three days to give single crystals suitable for X-ray diffraction analysis.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The coordination environment of the Cd^II center in the title compound with 30% probability displacement ellipsoids. Unlabelled atoms are related with the labelled ones by symmetry operation (x, y + 1, z). H atoms omitted for clarity.

catena-Poly[[diiodidocadmium(II)]-µ-4,4'-di-4-pyridyl-2,2'- disulfanediyldipyrimidine] top

Crystal data top

[CdI₂(C₁₈H₁₂N₆S₂)]	Z = 2
M_r = 742.69	F(000) = 696
Triclinic, P1	D_x = 2.114 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.0145 (7) Å	Cell parameters from 4037 reflections
b = 10.7294 (8) Å	θ = 2.3–25.5°
c = 11.7217 (9) Å	µ = 3.78 mm⁻¹
α = 93.133 (1)°	T = 298 K
β = 109.886 (1)°	Block, colourless
γ = 97.726 (1)°	0.20 × 0.15 × 0.12 mm
V = 1166.81 (15) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4037 independent reflections
Radiation source: fine-focus sealed tube	3073 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→11
T_min = 1.9, T_max = 28.9	k = −12→12
5935 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.057	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0238P)²] where P = (F_o² + 2F_c²)/3
4037 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[CdI₂(C₁₈H₁₂N₆S₂)]	γ = 97.726 (1)°
M_r = 742.69	V = 1166.81 (15) Å³
Triclinic, P1	Z = 2
a = 10.0145 (7) Å	Mo Kα radiation
b = 10.7294 (8) Å	µ = 3.78 mm⁻¹
c = 11.7217 (9) Å	T = 298 K
α = 93.133 (1)°	0.20 × 0.15 × 0.12 mm
β = 109.886 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4037 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3073 reflections with I > 2σ(I)
T_min = 1.9, T_max = 28.9	R_int = 0.015
5935 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.057	H-atom parameters constrained
S = 0.99	Δρ_max = 0.35 e Å⁻³
4037 reflections	Δρ_min = −0.35 e Å⁻³
262 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.

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

	x	y	z	U_iso*/U_eq
I2	1.04050 (3)	0.30244 (3)	−0.04759 (3)	0.06234 (11)
I1	0.58853 (3)	0.01728 (3)	−0.20478 (3)	0.07768 (13)
Cd1	0.80005 (3)	0.17348 (3)	−0.02843 (3)	0.05367 (11)
S1	0.66738 (13)	0.72678 (11)	0.58132 (11)	0.0647 (3)
S2	0.83801 (13)	0.63432 (12)	0.62502 (11)	0.0666 (3)
N1	0.6891 (4)	0.3069 (3)	0.0542 (3)	0.0487 (9)
N2	0.6043 (3)	0.5841 (3)	0.3679 (3)	0.0466 (8)
N3	0.4190 (4)	0.6770 (3)	0.4080 (4)	0.0593 (10)
C6	0.5105 (4)	0.5314 (3)	0.2591 (4)	0.0426 (10)
C4	0.7136 (4)	0.4798 (4)	0.2009 (4)	0.0526 (11)
H4A	0.7736	0.5465	0.2565	0.063*
C9	0.5529 (4)	0.6526 (4)	0.4357 (4)	0.0508 (11)
C8	0.3282 (5)	0.6238 (4)	0.2986 (5)	0.0618 (13)
H8A	0.2334	0.6379	0.2739	0.074*
C3	0.7684 (4)	0.4046 (4)	0.1332 (4)	0.0523 (11)
H3B	0.8655	0.4238	0.1437	0.063*
C5	0.5695 (4)	0.4544 (3)	0.1849 (4)	0.0423 (10)
C2	0.5492 (5)	0.2843 (4)	0.0378 (4)	0.0632 (13)
H2B	0.4911	0.2178	−0.0191	0.076*
C1	0.4868 (5)	0.3542 (4)	0.1005 (4)	0.0606 (13)
H1A	0.3889	0.3343	0.0864	0.073*
C7	0.3683 (4)	0.5492 (4)	0.2207 (4)	0.0530 (11)
H7A	0.3026	0.5122	0.1454	0.064*
N5	0.9147 (3)	0.7871 (3)	0.4735 (3)	0.0474 (8)
C13	1.0157 (4)	0.8354 (4)	0.4271 (4)	0.0493 (11)
C14	0.9704 (4)	0.9207 (4)	0.3321 (4)	0.0459 (10)
C10	0.9551 (5)	0.7070 (4)	0.5546 (4)	0.0571 (12)
N4	1.0789 (5)	0.6629 (4)	0.5948 (4)	0.0815 (13)
C18	1.0671 (4)	0.9895 (4)	0.2893 (4)	0.0548 (12)
H18A	1.1651	0.9878	0.3252	0.066*
C15	0.8267 (5)	0.9313 (4)	0.2767 (5)	0.0637 (13)
H15A	0.7576	0.8889	0.3036	0.076*
C12	1.1494 (5)	0.7979 (5)	0.4649 (5)	0.0737 (14)
H12A	1.2198	0.8306	0.4345	0.088*
C11	1.1754 (6)	0.7115 (6)	0.5484 (5)	0.0934 (18)
H11A	1.2650	0.6856	0.5736	0.112*
C17	1.0191 (5)	1.0597 (4)	0.1950 (5)	0.0566 (12)
H17A	1.0864	1.1044	0.1676	0.068*
N6	0.8813 (4)	1.0678 (3)	0.1399 (3)	0.0537 (9)
C16	0.7870 (5)	1.0040 (4)	0.1829 (5)	0.0697 (14)
H16A	0.6900	1.0097	0.1470	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I2	0.04535 (17)	0.0650 (2)	0.0747 (2)	−0.00692 (14)	0.02573 (16)	−0.00033 (16)
I1	0.04633 (19)	0.0866 (2)	0.0967 (3)	−0.00948 (16)	0.03348 (19)	−0.0232 (2)
Cd1	0.04412 (19)	0.05401 (19)	0.0674 (3)	0.00516 (14)	0.02683 (18)	0.00403 (16)
S1	0.0556 (7)	0.0817 (8)	0.0595 (9)	0.0022 (6)	0.0296 (7)	−0.0090 (7)
S2	0.0583 (8)	0.0876 (9)	0.0536 (9)	0.0064 (6)	0.0201 (6)	0.0158 (7)
N1	0.043 (2)	0.051 (2)	0.053 (2)	0.0078 (17)	0.0185 (18)	0.0044 (18)
N2	0.0358 (19)	0.053 (2)	0.053 (2)	0.0038 (16)	0.0198 (18)	0.0010 (17)
N3	0.048 (2)	0.063 (2)	0.073 (3)	0.0126 (19)	0.028 (2)	0.005 (2)
C6	0.036 (2)	0.040 (2)	0.053 (3)	0.0036 (18)	0.017 (2)	0.009 (2)
C4	0.043 (2)	0.056 (3)	0.056 (3)	0.003 (2)	0.016 (2)	−0.002 (2)
C9	0.043 (3)	0.053 (2)	0.059 (3)	0.003 (2)	0.024 (2)	0.007 (2)
C8	0.042 (3)	0.066 (3)	0.085 (4)	0.019 (2)	0.028 (3)	0.014 (3)
C3	0.032 (2)	0.066 (3)	0.059 (3)	0.002 (2)	0.020 (2)	0.005 (2)
C5	0.037 (2)	0.044 (2)	0.049 (3)	0.0089 (18)	0.019 (2)	0.010 (2)
C2	0.043 (3)	0.063 (3)	0.076 (4)	−0.003 (2)	0.020 (3)	−0.019 (3)
C1	0.041 (2)	0.064 (3)	0.074 (4)	0.002 (2)	0.021 (2)	−0.008 (3)
C7	0.043 (3)	0.059 (3)	0.053 (3)	0.009 (2)	0.011 (2)	0.004 (2)
N5	0.0379 (19)	0.061 (2)	0.042 (2)	0.0099 (16)	0.0132 (17)	0.0014 (18)
C13	0.045 (2)	0.055 (2)	0.050 (3)	0.007 (2)	0.021 (2)	−0.009 (2)
C14	0.038 (2)	0.054 (2)	0.047 (3)	0.0098 (19)	0.018 (2)	−0.004 (2)
C10	0.045 (3)	0.077 (3)	0.050 (3)	0.014 (2)	0.016 (2)	0.002 (3)
N4	0.066 (3)	0.125 (4)	0.070 (3)	0.038 (3)	0.033 (3)	0.037 (3)
C18	0.036 (2)	0.061 (3)	0.068 (4)	0.004 (2)	0.022 (2)	0.000 (2)
C15	0.040 (3)	0.087 (3)	0.075 (4)	0.008 (2)	0.031 (3)	0.024 (3)
C12	0.047 (3)	0.113 (4)	0.076 (4)	0.027 (3)	0.033 (3)	0.024 (3)
C11	0.059 (3)	0.154 (6)	0.087 (5)	0.052 (4)	0.034 (3)	0.046 (4)
C17	0.043 (3)	0.054 (3)	0.077 (4)	0.001 (2)	0.029 (3)	0.003 (3)
N6	0.046 (2)	0.054 (2)	0.069 (3)	0.0120 (17)	0.028 (2)	0.0135 (18)
C16	0.038 (3)	0.091 (4)	0.092 (4)	0.017 (2)	0.033 (3)	0.034 (3)

Geometric parameters (Å, º) top

I2—Cd1	2.6962 (4)	C2—H2B	0.9300
I1—Cd1	2.6938 (5)	C1—H1A	0.9300
Cd1—N1	2.287 (3)	C7—H7A	0.9300
Cd1—N6ⁱ	2.290 (4)	N5—C10	1.314 (5)
S1—C9	1.771 (4)	N5—C13	1.360 (5)
S1—S2	2.0205 (19)	C13—C12	1.383 (6)
S2—C10	1.774 (4)	C13—C14	1.470 (6)
N1—C3	1.326 (5)	C14—C18	1.383 (5)
N1—C2	1.334 (5)	C14—C15	1.386 (6)
N2—C9	1.325 (4)	C10—N4	1.330 (6)
N2—C6	1.338 (5)	N4—C11	1.325 (6)
N3—C9	1.334 (5)	C18—C17	1.359 (6)
N3—C8	1.336 (5)	C18—H18A	0.9300
C6—C7	1.383 (5)	C15—C16	1.362 (6)
C6—C5	1.480 (5)	C15—H15A	0.9300
C4—C5	1.378 (5)	C12—C11	1.370 (7)
C4—C3	1.388 (5)	C12—H12A	0.9300
C4—H4A	0.9300	C11—H11A	0.9300
C8—C7	1.376 (5)	C17—N6	1.326 (5)
C8—H8A	0.9300	C17—H17A	0.9300
C3—H3B	0.9300	N6—C16	1.343 (5)
C5—C1	1.381 (5)	N6—Cd1ⁱⁱ	2.290 (4)
C2—C1	1.367 (5)	C16—H16A	0.9300

N1—Cd1—N6ⁱ	96.12 (11)	C5—C1—H1A	120.0
N1—Cd1—I1	106.24 (9)	C8—C7—C6	117.1 (4)
N6ⁱ—Cd1—I1	108.88 (8)	C8—C7—H7A	121.4
N1—Cd1—I2	109.95 (8)	C6—C7—H7A	121.4
N6ⁱ—Cd1—I2	104.57 (8)	C10—N5—C13	115.5 (4)
I1—Cd1—I2	126.810 (15)	N5—C13—C12	119.8 (4)
C9—S1—S2	104.45 (14)	N5—C13—C14	116.3 (4)
C10—S2—S1	106.08 (18)	C12—C13—C14	123.7 (4)
C3—N1—C2	117.0 (3)	C18—C14—C15	116.6 (4)
C3—N1—Cd1	119.2 (2)	C18—C14—C13	122.1 (4)
C2—N1—Cd1	123.3 (3)	C15—C14—C13	121.3 (4)
C9—N2—C6	116.3 (3)	N5—C10—N4	129.3 (4)
C9—N3—C8	114.5 (3)	N5—C10—S2	121.9 (3)
N2—C6—C7	121.2 (3)	N4—C10—S2	108.7 (4)
N2—C6—C5	115.6 (3)	C11—N4—C10	114.0 (5)
C7—C6—C5	123.3 (4)	C17—C18—C14	120.1 (4)
C5—C4—C3	119.2 (4)	C17—C18—H18A	120.0
C5—C4—H4A	120.4	C14—C18—H18A	120.0
C3—C4—H4A	120.4	C16—C15—C14	119.9 (4)
N2—C9—N3	127.8 (4)	C16—C15—H15A	120.1
N2—C9—S1	120.2 (3)	C14—C15—H15A	120.1
N3—C9—S1	112.0 (3)	C11—C12—C13	118.2 (4)
N3—C8—C7	123.1 (4)	C11—C12—H12A	120.9
N3—C8—H8A	118.4	C13—C12—H12A	120.9
C7—C8—H8A	118.4	N4—C11—C12	123.1 (5)
N1—C3—C4	123.3 (4)	N4—C11—H11A	118.5
N1—C3—H3B	118.4	C12—C11—H11A	118.5
C4—C3—H3B	118.4	N6—C17—C18	123.5 (4)
C4—C5—C1	117.2 (3)	N6—C17—H17A	118.2
C4—C5—C6	119.8 (4)	C18—C17—H17A	118.2
C1—C5—C6	122.9 (3)	C17—N6—C16	116.9 (4)
N1—C2—C1	123.2 (4)	C17—N6—Cd1ⁱⁱ	123.1 (3)
N1—C2—H2B	118.4	C16—N6—Cd1ⁱⁱ	119.9 (3)
C1—C2—H2B	118.4	N6—C16—C15	123.0 (4)
C2—C1—C5	120.0 (4)	N6—C16—H16A	118.5
C2—C1—H1A	120.0	C15—C16—H16A	118.5

C9—S1—S2—C10	84.1 (2)	N3—C8—C7—C6	−1.0 (6)
N6ⁱ—Cd1—N1—C3	76.8 (3)	N2—C6—C7—C8	0.5 (6)
I1—Cd1—N1—C3	−171.5 (3)	C5—C6—C7—C8	−179.6 (4)
I2—Cd1—N1—C3	−31.2 (3)	C10—N5—C13—C12	0.9 (6)
N6ⁱ—Cd1—N1—C2	−95.6 (4)	C10—N5—C13—C14	177.3 (3)
I1—Cd1—N1—C2	16.2 (4)	N5—C13—C14—C18	171.0 (3)
I2—Cd1—N1—C2	156.5 (3)	C12—C13—C14—C18	−12.8 (6)
C9—N2—C6—C7	0.4 (5)	N5—C13—C14—C15	−12.1 (5)
C9—N2—C6—C5	−179.5 (3)	C12—C13—C14—C15	164.2 (4)
C6—N2—C9—N3	−1.0 (6)	C13—N5—C10—N4	−2.6 (7)
C6—N2—C9—S1	−180.0 (3)	C13—N5—C10—S2	−180.0 (3)
C8—N3—C9—N2	0.6 (6)	S1—S2—C10—N5	−11.3 (4)
C8—N3—C9—S1	179.6 (3)	S1—S2—C10—N4	170.8 (3)
S2—S1—C9—N2	−18.5 (3)	N5—C10—N4—C11	2.6 (8)
S2—S1—C9—N3	162.4 (3)	S2—C10—N4—C11	−179.7 (4)
C9—N3—C8—C7	0.4 (6)	C15—C14—C18—C17	−2.1 (6)
C2—N1—C3—C4	2.3 (6)	C13—C14—C18—C17	175.0 (4)
Cd1—N1—C3—C4	−170.5 (3)	C18—C14—C15—C16	1.9 (6)
C5—C4—C3—N1	−1.2 (6)	C13—C14—C15—C16	−175.2 (4)
C3—C4—C5—C1	−0.3 (6)	N5—C13—C12—C11	0.5 (7)
C3—C4—C5—C6	178.2 (4)	C14—C13—C12—C11	−175.7 (4)
N2—C6—C5—C4	−26.6 (5)	C10—N4—C11—C12	−0.9 (8)
C7—C6—C5—C4	153.5 (4)	C13—C12—C11—N4	−0.4 (9)
N2—C6—C5—C1	151.8 (4)	C14—C18—C17—N6	0.6 (6)
C7—C6—C5—C1	−28.1 (6)	C18—C17—N6—C16	1.2 (6)
C3—N1—C2—C1	−2.0 (7)	C18—C17—N6—Cd1ⁱⁱ	−175.0 (3)
Cd1—N1—C2—C1	170.5 (4)	C17—N6—C16—C15	−1.4 (7)
N1—C2—C1—C5	0.6 (7)	Cd1ⁱⁱ—N6—C16—C15	174.9 (4)
C4—C5—C1—C2	0.6 (6)	C14—C15—C16—N6	−0.1 (7)
C6—C5—C1—C2	−177.9 (4)

Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[CdI₂(C₁₈H₁₂N₆S₂)]
M_r	742.69
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.0145 (7), 10.7294 (8), 11.7217 (9)
α, β, γ (°)	93.133 (1), 109.886 (1), 97.726 (1)
V (Å³)	1166.81 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.78
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	1.9, 28.9
No. of measured, independent and observed [I > 2σ(I)] reflections	5935, 4037, 3073
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.057, 0.99
No. of reflections	4037
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.35

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

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