1,2,4,5-Tetra­fluoro-3,6-diiodo­benzene–4-(pyridin-4-ylsulfan­yl)pyridine (1/1)

Arman, H.D.; Kaulgud, T.; Tiekink, E.R.T.

doi:10.1107/S1600536810038316

organic compounds

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Volume 66| Part 10| October 2010| Page o2683

doi:10.1107/S1600536810038316

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1,2,4,5-Tetrafluoro-3,6-diiodobenzene–4-(pyridin-4-ylsulfanyl)pyridine (1/1)

Hadi D. Arman,^a Trupta Kaulgud ^a and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 23 September 2010; accepted 25 September 2010; online 30 September 2010)

The asymmetric unit of the title 1:1 adduct, C₁₀H₈N₂S·C₆F₄I₂, comprises a half-molecule of 1,2,4,5-tetrafluoro-3,6-diiodobenzene, and half a 4-(pyridin-4-ylsulfanyl)pyridine molecule. The former is completed by crystallographic inversion symmetry, the latter by twofold symmetry, with the S atom lying on the rotation axis. The almost planar 1,2,4,5-tetrafluoro-3,6-diiodobenzene molecule (r.m.s. deviation of all 12 atoms = 0.016 Å) and twisted 4-(pyridin-4-ylsulfanyl)pyridine molecule [dihedral angle between pyridyl rings = 54.88 (13)°] are connected by N⋯I interactions [2.838 (4) Å], generating a supramolecular chain with a step-ladder topology. These chains are connected in the crystal by C—H⋯F and C—H⋯π(pyridyl) interactions.

Related literature

For related studies on co-crystal formation, see: Broker et al. (2008 ); Arman et al. (2010 ). For background to halogen bonding, see: Metrangolo et al. (2008 ); Pennington et al. (2008 ). For the desulfurization of 4-(pyridin-4-yldisulfanyl)pyridine, see: Aragoni et al. (2007 ).

Experimental

Crystal data

C₁₀H₈N₂S·C₆F₄I₂
M_r = 590.10
Monoclinic, C 2/c
a = 13.804 (5) Å
b = 5.829 (2) Å
c = 22.164 (8) Å
β = 97.989 (7)°
V = 1766.1 (11) Å³
Z = 4
Mo Kα radiation
μ = 3.72 mm⁻¹
T = 98 K
0.30 × 0.20 × 0.05 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.757, T_max = 1.000
5209 measured reflections
1823 independent reflections
1733 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.073
S = 1.07
1823 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1,C4–C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯F1ⁱ	0.95	2.52	3.213 (5)	130
C8—H8⋯Cg1ⁱⁱ	0.95	2.82	3.557 (5)	135
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ); 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: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810038316/hb5647sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038316/hb5647Isup2.hkl

checkCIF report

Comment top

As a continuation of studies into the phenomenon of co-crystallization (Broker et al., 2008; Arman et al., 2010), including investigations of halogen bonding (Pennington et al., 2008), the co-crystallization of 1,2,4,5-tetrafluoro-3,6-diiodobenzene and 4-(pyridin-4-yldisulfanyl)pyridine was investigated. This lead to the isolation of the title 1/1 co-crystal, (I), in which desulfurization of 4-(pyridin-4-yldisulfanyl)pyridine has occurred, a process that has literature precedents (Aragoni et al., 2007).

The asymmetric unit in (I) comprises half a molecule of 1,2,4,5-tetrafluoro-3,6-diiodobenzene as this is situated about a centre of inversion, Fig. 1, and half a molecule of 4-(pyridin-4-ylsulfanyl)pyridine, Fig. 2, with the S atom lying on a 2-fold axis. The C₆F₄I₂ molecule is planar with the r.m.s. deviation of all 12 atoms being 0.016 Å. The pyridyl rings in 4-(pyridin-4-ylsulfanyl)pyridine are twisted and form a dihedral angle of 54.88 (13) °.

The components of the co-crystal are connected via N···I interactions [2.838 (4) Å] to form a supramolecular chain with a step-ladder topology and with a base vector 2 0 1, Fig. 3. The chains are consolidated in the crystal packing by C—H···F and C—H···π(pyridyl) interactions, Table 1 and Fig. 4. The N···I interactions observed in (I) represents a further example of N···I—C halogen bonding (Metrangolo et al., 2008).

Related literature top

For related studies on co-crystal formation, see: Broker et al. (2008); Arman et al. (2010). For background to halogen bonding, see: Metrangolo et al. (2008); Pennington et al. (2008). For the desulfurization of 4-(pyridin-4-yldisulfanyl)pyridine, see: Aragoni et al. (2007).

Experimental top

Initially 1,2,4,5-tetrafluoro-3,6-diiodobenzene (Aldrich, 0.04 mmol) and 4-(pyridin-4-yldisulfanyl)pyridine (Aldrich, 0.04 mmol) were dissolved in a THF/acetone (1/1) mixture and after evaporation of the solvent, the powder was then dissolved in ethanol. Again, crystals did not form so the powder was dissolved in a CHCl₃/acetone (1/1) mixture. Slow evaporation of this solution deposited yellow blocks of (I) which, after crystallographic characterization, was proven to contain 4-(pyridin-4-ylsulfanyl)pyridine, indicating that desulfurization of 4-(pyridin-4-yldisulfanyl)pyridine had occurred (Aragoni et al., 2007). M. pt:. 423–427 K. IR assignment (cm^-1): 757 (m, sh); 807 (s, sh); 939 (s, sh); 1065 (s, sh); 1208 (m, sh) (C—F); 1408 (m, sh), 1456 (s, sh) C—C (aromatic); 1570 (s, sh) C═N; 2924 (s) C—H.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of 1,2,4,5-tetrafluoro-3,6-diiodobenzene found in the structure of (I) showing displacement ellipsoids at the 50% probability level. Unlabelled atoms are related across a centre of inversion.
	Fig. 2. Molecular structure of 4-(pyridin-4-yldisulfanyl)pyridine found in the structure of (I) showing displacement ellipsoids at the 50% probability level. Unlabelled atoms are related across a 2-fold axis.
	Fig. 3. The supramolecular chain in (I) sustained by N···I halogen bonds, shown as orange dashed lines.
	Fig. 4. A view in projection down the b axis showing the stacking of alternating layers of 1,2,4,5-tetrafluoro-3,6-diiodobenzene and 4-(pyridin-4-yldisulfanyl)pyridine molecules along the c axis. The N···I, C—H···F and C—H···π interactions are shown as orange, blue and purple dashed lines, respectively.

1,2,4,5-Tetrafluoro-3,6-diiodobenzene–4-(pyridin-4-ylsulfanyl)pyridine (1/1) top

Crystal data top

C₁₀H₈N₂S·C₆F₄I₂	F(000) = 1104
M_r = 590.10	D_x = 2.219 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3043 reflections
a = 13.804 (5) Å	θ = 3.0–40.2°
b = 5.829 (2) Å	µ = 3.72 mm⁻¹
c = 22.164 (8) Å	T = 98 K
β = 97.989 (7)°	Block, yellow
V = 1766.1 (11) Å³	0.30 × 0.20 × 0.05 mm
Z = 4

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	1823 independent reflections
Radiation source: fine-focus sealed tube	1733 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 26.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −17→14
T_min = 0.757, T_max = 1.000	k = −5→7
5209 measured reflections	l = −27→26

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0202P)² + 21.2619P] where P = (F_o² + 2F_c²)/3
1823 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 1.34 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₁₀H₈N₂S·C₆F₄I₂	V = 1766.1 (11) Å³
M_r = 590.10	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 13.804 (5) Å	µ = 3.72 mm⁻¹
b = 5.829 (2) Å	T = 98 K
c = 22.164 (8) Å	0.30 × 0.20 × 0.05 mm
β = 97.989 (7)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	1823 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1733 reflections with I > 2σ(I)
T_min = 0.757, T_max = 1.000	R_int = 0.027
5209 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0202P)² + 21.2619P] where P = (F_o² + 2F_c²)/3
1823 reflections	Δρ_max = 1.34 e Å⁻³
114 parameters	Δρ_min = −0.63 e Å⁻³

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
I1	0.33988 (2)	0.75767 (5)	0.089898 (12)	0.02060 (11)
F1	0.4107 (2)	0.9003 (5)	−0.03751 (12)	0.0253 (6)
F2	0.5292 (2)	0.6993 (5)	−0.10663 (12)	0.0257 (6)
C1	0.4356 (3)	0.6036 (8)	0.0360 (2)	0.0186 (9)
C2	0.4540 (3)	0.6999 (7)	−0.0181 (2)	0.0180 (9)
C3	0.5168 (3)	0.5980 (8)	−0.0534 (2)	0.0205 (9)
S1	0.0000	0.4266 (3)	0.2500	0.0201 (3)
N1	0.2103 (3)	−0.0202 (7)	0.15987 (18)	0.0248 (9)
C4	0.1787 (3)	0.1842 (9)	0.1379 (2)	0.0239 (10)
H4	0.2032	0.2404	0.1028	0.029*
C5	0.1121 (3)	0.3192 (8)	0.1635 (2)	0.0215 (9)
H5	0.0905	0.4616	0.1455	0.026*
C6	0.0779 (3)	0.2417 (8)	0.2158 (2)	0.0191 (9)
C7	0.1112 (3)	0.0326 (8)	0.2401 (2)	0.0193 (9)
H7	0.0900	−0.0242	0.2763	0.023*
C8	0.1762 (3)	−0.0926 (8)	0.2104 (2)	0.0203 (9)
H8	0.1977	−0.2373	0.2268	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01922 (17)	0.02358 (17)	0.01968 (17)	0.00034 (12)	0.00505 (11)	−0.00148 (11)
F1	0.0271 (15)	0.0212 (14)	0.0285 (15)	0.0061 (12)	0.0072 (12)	0.0045 (11)
F2	0.0288 (16)	0.0283 (14)	0.0218 (14)	0.0026 (12)	0.0099 (11)	0.0084 (11)
C1	0.013 (2)	0.023 (2)	0.020 (2)	−0.0024 (17)	0.0021 (16)	−0.0062 (17)
C2	0.015 (2)	0.017 (2)	0.021 (2)	−0.0005 (17)	−0.0009 (16)	0.0016 (16)
C3	0.021 (2)	0.023 (2)	0.018 (2)	−0.0036 (19)	0.0029 (17)	0.0006 (17)
S1	0.0203 (8)	0.0166 (7)	0.0245 (8)	0.000	0.0068 (6)	0.000
N1	0.020 (2)	0.026 (2)	0.028 (2)	0.0012 (17)	0.0057 (16)	−0.0018 (17)
C4	0.017 (2)	0.031 (3)	0.023 (2)	−0.0047 (19)	0.0040 (18)	0.0002 (19)
C5	0.022 (2)	0.020 (2)	0.022 (2)	−0.0007 (18)	0.0005 (18)	0.0007 (17)
C6	0.015 (2)	0.020 (2)	0.023 (2)	−0.0012 (17)	0.0041 (17)	−0.0043 (17)
C7	0.014 (2)	0.019 (2)	0.024 (2)	−0.0025 (17)	0.0003 (17)	−0.0017 (17)
C8	0.016 (2)	0.018 (2)	0.026 (2)	−0.0010 (17)	−0.0013 (17)	−0.0009 (17)

Geometric parameters (Å, º) top

I1—C1	2.101 (4)	N1—C4	1.337 (6)
F1—C2	1.355 (5)	C4—C5	1.389 (7)
F2—C3	1.352 (5)	C4—H4	0.9500
C1—C2	1.379 (6)	C5—C6	1.387 (6)
C1—C3ⁱ	1.375 (6)	C5—H5	0.9500
C2—C3	1.381 (6)	C6—C7	1.385 (6)
C3—C1ⁱ	1.375 (6)	C7—C8	1.392 (6)
S1—C6ⁱⁱ	1.766 (4)	C7—H7	0.9500
S1—C6	1.766 (4)	C8—H8	0.9500
N1—C8	1.342 (6)

C2—C1—C3ⁱ	116.9 (4)	C5—C4—H4	118.0
C2—C1—I1	121.8 (3)	C6—C5—C4	118.5 (4)
C3ⁱ—C1—I1	121.3 (3)	C6—C5—H5	120.7
C1—C2—F1	120.0 (4)	C4—C5—H5	120.7
C1—C2—C3	121.6 (4)	C7—C6—C5	118.6 (4)
F1—C2—C3	118.4 (4)	C7—C6—S1	124.0 (4)
F2—C3—C1ⁱ	120.3 (4)	C5—C6—S1	117.3 (3)
F2—C3—C2	118.2 (4)	C6—C7—C8	118.6 (4)
C1ⁱ—C3—C2	121.5 (4)	C6—C7—H7	120.7
C6ⁱⁱ—S1—C6	104.8 (3)	C8—C7—H7	120.7
C8—N1—C4	116.7 (4)	N1—C8—C7	123.7 (4)
N1—C4—C5	123.9 (4)	N1—C8—H8	118.2
N1—C4—H4	118.0	C7—C8—H8	118.2

C3ⁱ—C1—C2—F1	−179.1 (4)	N1—C4—C5—C6	1.7 (7)
I1—C1—C2—F1	0.6 (6)	C4—C5—C6—C7	−0.3 (7)
C3ⁱ—C1—C2—C3	0.4 (7)	C4—C5—C6—S1	175.7 (4)
I1—C1—C2—C3	−179.9 (3)	C6ⁱⁱ—S1—C6—C7	−34.9 (3)
C1—C2—C3—F2	178.2 (4)	C6ⁱⁱ—S1—C6—C5	149.3 (4)
F1—C2—C3—F2	−2.3 (6)	C5—C6—C7—C8	−1.1 (6)
C1—C2—C3—C1ⁱ	−0.4 (8)	S1—C6—C7—C8	−176.8 (3)
F1—C2—C3—C1ⁱ	179.0 (4)	C4—N1—C8—C7	0.0 (7)
C8—N1—C4—C5	−1.5 (7)	C6—C7—C8—N1	1.3 (7)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1,C4–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1ⁱⁱⁱ	0.95	2.52	3.213 (5)	130
C8—H8···Cg1^iv	0.95	2.82	3.557 (5)	135

Symmetry codes: (iii) −x+1/2, −y+3/2, −z; (iv) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂S·C₆F₄I₂
M_r	590.10
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	98
a, b, c (Å)	13.804 (5), 5.829 (2), 22.164 (8)
β (°)	97.989 (7)
V (Å³)	1766.1 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.72
Crystal size (mm)	0.30 × 0.20 × 0.05

Data collection
Diffractometer	Rigaku AFC12K/SATURN724 diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.757, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5209, 1823, 1733
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.073, 1.07
No. of reflections	1823
No. of parameters	114
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0202P)² + 21.2619P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.34, −0.63

Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1,C4–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1ⁱ	0.95	2.52	3.213 (5)	130
C8—H8···Cg1ⁱⁱ	0.95	2.82	3.557 (5)	135

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) −x+1/2, y−1/2, −z+1/2.

References

Aragoni, M. C., Arca, M., Crespo, M., Devillanova, F. A., Hursthouse, M. B., Huth, S. L., Isaia, F., Lippolis, V. & Verani, G. (2007). CrystEngComm, 9, 873–878. Web of Science CSD CrossRef CAS Google Scholar
Arman, H. D., Kaulgud, T. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2356. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Metrangolo, P., Resnati, G., Pilati, T. & Biella, S. (2008). Struct. Bond. 126, 105–136. Web of Science CrossRef CAS Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,2,4,5-Tetra­fluoro-3,6-di­iodo­benzene–4-(pyridin-4-ylsulfan­yl)pyridine (1/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

1,2,4,5-Tetrafluoro-3,6-diiodobenzene–4-(pyridin-4-ylsulfanyl)pyridine (1/1)