Acta Cryst.(2002). E58, o1277±o1279 DOI: 10.1107/S1600536802019050 Chan, Yang and Szeto C18H16N6S62+2ClO42ÿ
o1277
organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
cyclo
-Bis[2-methylsulfanyl-6-([1,3,4]thia-diazol-2-ylsulfanylmethyl)pyridinium]
diperchlorate
Kannie Wai Yan Chan, Chi Yang and Lap Szeto*
Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, People's Republic of China
Correspondence e-mail: lszeto@hkucc.hku.hk
Key indicators
Single-crystal X-ray study
T= 301 K
Mean(C±C) = 0.005 AÊ
Rfactor = 0.080
wRfactor = 0.051
Data-to-parameter ratio = 13.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, C18H16N6S62+2ClO4ÿ, the macrocyclic
cation shows a twisted conformation and possesses crystal-lographic twofold symmetry. This conformation is stabilized
by intramolecular NÐH N and CÐH N hydrogen bonds.
In the crystal, the cations and anions are connected through
CÐH O hydrogen bonds.
Comment
Lanthanide(III) complexes, especially those of Gd3+, Eu3+and
Tb3+, have a variety of applications as luminescent biomedical
diagnostic and therapeutic agents, such as magnetic resonance imaging contrast agents, RNA hydrolysis catalysts and ¯uor-escence imaging agents (Laiet al., 2002; Lamet al., 2001; Li &
Wong, 2002). The macrocyclic ligand cyclo
-bis(2-methyl-sulfanyl-6-([1,3,4]thiadiazol-2-ylsulfanylmethyl)pyridine) has more than one organic chromophore, which may have effec-tive energy transfer and luminescent enhancement. Moreover, its preorganized structure, with six donor N atoms, may prompt in forming thermodynamically and kinetically stable Ln complexes. These are important features for further molecular exploration and for the development of new phar-maceutical compounds. Herein we report the structure of this macrocyclic ligand in a diprotonated form, as its perchloric salt, (I).
The asymmetric unit of (I) contains one-half of the C18H16N6S62+cation, with the other half related by a
crystal-lographic twofold axis (S1 and S4 lie on the twofold axis), and
a ClO4ÿ anion (Fig. 1). The macrocyclic cation exhibits a
twisted conformation. This conformation is stabilized by
intramolecular NÐH N and CÐH N hydrogen bonds,
with N N and C N distances in the ranges 2.999 (4)±
3.097 (4) and 2.870 (4)±2.958 (4) AÊ, respectively (Table 2). The two thiadiazole rings form dihedral angles of 45.1 (2) and
66.7 (2)with each pyridine ring. The dihedral angle between
the two symmetry-related pyridine rings is 91.1 (2), while the
two thiadiazole rings have a dihedral angle of 47.6 (2). In the
crystal, the cations and anions are linked, through CÐH O
hydrogen bonds (Table 2), to form a three-dimensional
organic papers
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Chan, Yang and Szeto C18H16N6S62+2ClO42ÿ Acta Cryst.(2002). E58, o1277±o1279network structure. The structure is further stabilized by
face-to-face ±-stacking interactions of pyridine rings, with a
Cg Cgi distance of 3.822 (2) AÊ [Cg and Cgi denote the
centroids of the pyridine rings at (x, y, z) and (1
2ÿx, 12ÿy,
1ÿz), respectively].
Experimental
Compound (I) was prepared according to the procedures reported by Yang & Wong (2001). Crystals suitable for X-ray data collection were obtained by slow evaporation of a CH2Cl2/MeOH (3:1;v:v) solution
of the compound at room temperature. Crystal data
C18H16N6S62+2ClO4ÿ
Mr= 707.69 Monoclinic,C2=c a= 12.311 (3) AÊ b= 14.700 (2) AÊ c= 15.205 (3) AÊ = 98.79 (2) V= 2719.2 (9) AÊ3
Z= 4
Dx= 1.729 Mg mÿ3 MoKradiation Cell parameters from 25
re¯ections = 2.5±14
= 0.76 mmÿ1
T= 301.2 K Block, yellow 0.450.360.15 mm
Data collection
Rigaku AFC-7Rdiffractometer !/2scans
Absorption correction: scan (Northet al., 1968) Tmin= 0.916,Tmax= 0.999
2629 measured re¯ections 2399 independent re¯ections 2399 re¯ections withI> 0
Rint= 0.037
max= 25
h= 0!14 k= 0!17 l=ÿ18!17 3 standard re¯ections
every 250 re¯ections intensity decay: 0.1%
Re®nement
Re®nement onF R= 0.080 wR= 0.051 S= 1.40 2399 re¯ections 183 parameters
H-atom parameters constrained
w= 1/[2(F
o) + (0.008Fo)2] (/)max< 0.001
max= 0.51 e AÊÿ3
min=ÿ0.32 e AÊÿ3
Extinction correction: Zachariasen type 2 Gaussian isotropic Extinction coef®cient: 5.8529 (2)
Table 1
Selected geometric parameters (AÊ,).
S1ÐC1 1.719 (4)
S2ÐC1 1.743 (4)
S2ÐC2 1.816 (4)
S3ÐC8 1.806 (4)
S3ÐC9 1.742 (4)
S4ÐC9 1.706 (4)
N1ÐN1i 1.384 (6)
N1ÐC1 1.295 (4)
N2ÐC3 1.349 (4)
N2ÐC7 1.357 (4)
N3ÐN3i 1.388 (6)
N3ÐC9 1.292 (4)
C2ÐC3 1.490 (4)
C3ÐC4 1.374 (5)
C4ÐC5 1.377 (5)
C5ÐC6 1.369 (5)
C6ÐC7 1.375 (4)
C7ÐC8 1.484 (5)
C1ÐS1ÐC1i 86.3 (2)
C1ÐS2ÐC2 99.6 (2) C8ÐS3ÐC9 99.1 (2) C9iÐS4ÐC9 87.1 (2)
N1iÐN1ÐC1 111.9 (2)
C3ÐN2ÐC7 123.3 (3) N3iÐN3ÐC9 111.9 (2)
S1ÐC1ÐS2 119.5 (2) S1ÐC1ÐN1 115.0 (3) S2ÐC1ÐN1 125.5 (3) S2ÐC2ÐC3 113.6 (2) N2ÐC3ÐC2 119.2 (3)
N2ÐC3ÐC4 118.4 (3) C2ÐC3ÐC4 122.4 (3) C3ÐC4ÐC5 120.0 (3) C4ÐC5ÐC6 119.9 (3) C5ÐC6ÐC7 120.3 (3) N2ÐC7ÐC6 118.0 (3) N2ÐC7ÐC8 119.4 (3) C6ÐC7ÐC8 122.5 (3) S3ÐC8ÐC7 111.5 (2) S3ÐC9ÐS4 120.1 (2) S3ÐC9ÐN3 125.3 (3) S4ÐC9ÐN3 114.6 (3)
Symmetry code: (i)ÿx;y;1 2ÿz.
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH2N N1 0.87 2.20 2.999 (4) 153 N2ÐH2N N3 0.87 2.59 3.097 (4) 118 C2ÐH2B N1 0.95 2.57 2.958 (4) 105 C8ÐH8B N3 0.95 2.47 2.870 (4) 105 C2ÐH2B O4ii 0.95 2.42 3.275 (5) 149
C8ÐH8A O1iii 0.95 2.53 3.463 (5) 165
C8ÐH8B O1iv 0.95 2.58 3.307 (5) 133
C8ÐH8B O3iv 0.95 2.50 3.339 (4) 148
Symmetry codes: (ii)1
2ÿx;12y;12ÿz; (iii)ÿx;ÿy;1ÿz; (iv)xÿ12;12y;z.
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with NÐH and CÐH distances ®xed at 0.87 and 0.95 AÊ, respectively. All unique re¯ections were included in the re®nement onFand, as a result, theRvalue is high (0.080).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Mole-cular Structure Corporation, 1992); program(s) used to solve struc-ture: SIR92 (Altomare et al., 1994); program(s) used to re®ne structure:TEXSAN; molecular graphics:ORTEPII (Johnson, 1976); software used to prepare material for publication:TEXSAN.
The authors are grateful for ®nancial support from the Hong Kong Research Grants Council. WYC acknowledges the receipt of a postgraduate studentship administered by The University of Hong Kong.
Figure 1
References
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435.
Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Lai, P. W., Wong, W. T., Li, K. F. & Cheah, K. W. (2002).New J. Chem.26, 576± 581.
Lam, W. H., Wong, W. T., Wen, G., Zhang, X. X. & Gao, S. (2001).New J. Chem.25, 531±533.
Li, C. & Wong, W. T. (2002).Chem. Commun.pp. 2034±2035.
Molecular Structure Corporation (1992).MSC/AFC Diffractometer Control SoftwareandTEXSAN.MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.
Yang, C. & Wong, W. T. (2001).J. Mater. Chem.11, 2898±2900.
supporting information
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Acta Cryst. (2002). E58, o1277–o1279
supporting information
Acta Cryst. (2002). E58, o1277–o1279 [https://doi.org/10.1107/S1600536802019050]
cyclo
-Bis[2-methylsulfanyl-6-([1,3,4]thiadiazol-2-ylsulfanylmethyl)pyridinium]
diperchlorate
Kannie Wai Yan Chan, Chi Yang and Lap Szeto
(I)
Crystal data
C18H16N6S62+·2ClO42− Mr = 707.69
Monoclinic, C2/c Hall symbol: -C 2yc a = 12.311 (3) Å b = 14.700 (2) Å c = 15.205 (3) Å β = 98.79 (2)° V = 2719.2 (9) Å3 Z = 4
F(000) = 1440.00 Dx = 1.729 Mg m−3
Mo Kα radiation, λ = 0.7107 Å Cell parameters from 25 reflections θ = 2.5–14°
µ = 0.76 mm−1 T = 301 K Block, yellow
0.45 × 0.36 × 0.15 mm
Data collection
Rigaku AFC-7R diffractometer
Radiation source: X-ray tube Graphite monochromator ω/2θ scans
Absorption correction: ψ scan (North et al., 1968)
Tmin = 0.916, Tmax = 0.999 2629 measured reflections
2399 independent reflections 2399 reflections with I > 0 Rint = 0.037
θmax = 25°, θmin = 2° h = 0→14
k = 0→17 l = −18→17
3 standard reflections every 250 reflections intensity decay: 0.1%
Refinement
Refinement on F
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.080 wR(F2) = 0.051 S = 1.40 2399 reflections 183 parameters 0 restraints
H-atom parameters constrained w = 1/[(σ)2(Fo) + (p/2)2(Fo)2] p = 0.016 (Δ/σ)max < 0.001
Δρmax = 0.51 e Å−3 Δρmin = −0.32 e Å−3 Extinction correction:
Zachariasen_type_2_Gaussian_isotropic Extinction coefficient: 5.8529
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
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Acta Cryst. (2002). E58, o1277–o1279
S3 −0.05192 (8) 0.38241 (7) 0.42764 (6) 0.0511 (3) S4 0.0000 0.43897 (9) 0.2500 0.0643 (5) O1 0.1958 (3) −0.2868 (2) 0.3430 (2) 0.083 (1) O2 0.1213 (3) −0.4248 (2) 0.3847 (2) 0.077 (1) O3 0.3052 (3) −0.4153 (2) 0.3726 (2) 0.094 (1) O4 0.1762 (3) −0.4092 (2) 0.2446 (2) 0.097 (1) N1 0.0323 (2) 0.0578 (2) 0.2915 (2) 0.0462 (9) N2 0.0825 (2) 0.1636 (2) 0.4615 (2) 0.0353 (8) N3 −0.0119 (3) 0.2733 (2) 0.2932 (2) 0.054 (1) C1 0.0556 (3) −0.0239 (2) 0.3201 (2) 0.043 (1) C2 0.2206 (3) 0.0499 (2) 0.4376 (2) 0.045 (1) C3 0.1767 (3) 0.1200 (2) 0.4936 (2) 0.0384 (9) C4 0.2292 (3) 0.1428 (2) 0.5771 (2) 0.047 (1) C5 0.1865 (3) 0.2098 (3) 0.6251 (2) 0.052 (1) C6 0.0899 (3) 0.2515 (2) 0.5908 (2) 0.046 (1) C7 0.0360 (3) 0.2278 (2) 0.5080 (2) 0.0352 (9) C8 −0.0704 (3) 0.2691 (2) 0.4688 (2) 0.045 (1) C9 −0.0214 (3) 0.3548 (2) 0.3227 (2) 0.0387 (10) H2A 0.2920 0.0329 0.4657 0.0543 H2B 0.2253 0.0759 0.3811 0.0543 H2N 0.0511 0.1469 0.4087 0.0787 H4 0.2950 0.1124 0.6016 0.0558 H5 0.2240 0.2269 0.6819 0.0621 H6 0.0599 0.2971 0.6243 0.0552 H8A −0.1170 0.2720 0.5131 0.0536 H8B −0.1037 0.2321 0.4209 0.0536
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Acta Cryst. (2002). E58, o1277–o1279
C7 0.042 (2) 0.033 (2) 0.033 (2) −0.007 (2) 0.014 (2) −0.003 (1) C8 0.039 (2) 0.051 (2) 0.047 (2) 0.000 (2) 0.015 (2) −0.008 (2) C9 0.037 (2) 0.035 (2) 0.042 (2) 0.006 (2) 0.000 (2) −0.001 (2)
Geometric parameters (Å, º)
Cl1—O1 1.434 (3) N2—H2N 0.87 Cl1—O2 1.434 (3) N3—N3i 1.388 (6) Cl1—O3 1.428 (3) N3—C9 1.292 (4) Cl1—O4 1.408 (3) C2—C3 1.490 (4) S1—C1 1.719 (4) C2—H2A 0.95 S1—C1i 1.719 (4) C2—H2B 0.95 S2—C1 1.743 (4) C3—C4 1.374 (5) S2—C2 1.816 (4) C4—C5 1.377 (5) S3—C8 1.806 (4) C4—H4 0.95 S3—C9 1.742 (4) C5—C6 1.369 (5) S4—C9 1.706 (4) C5—H5 0.95 S4—C9i 1.706 (4) C6—C7 1.375 (4) N1—N1i 1.384 (6) C6—H6 0.95 N1—C1 1.295 (4) C7—C8 1.484 (5) N2—C3 1.349 (4) C8—H8A 0.95 N2—C7 1.357 (4) C8—H8B 0.95
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Acta Cryst. (2002). E58, o1277–o1279
C3—C2—H2B 108.4 S3—C9—N3 125.3 (3) H2A—C2—H2B 109.5 S4—C9—N3 114.6 (3)
Symmetry code: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N2—H2N···N1 0.87 2.20 2.999 (4) 153 N2—H2N···N3 0.87 2.59 3.097 (4) 118 C2—H2B···N1 0.95 2.57 2.958 (4) 105 C8—H8B···N3 0.95 2.47 2.870 (4) 105 C2—H2B···O4ii 0.95 2.42 3.275 (5) 149 C8—H8A···O1iii 0.95 2.53 3.463 (5) 165 C8—H8B···O1iv 0.95 2.58 3.307 (5) 133 C8—H8B···O3iv 0.95 2.50 3.339 (4) 148
