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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2382.
Published online 2009 September 9. doi:  10.1107/S1600536809035545
PMCID: PMC2970409

N 1,N 4-Bis(2-thienylmethyl­ene)cyclo­hexane-1,4-diamine

Abstract

The title compound, C16H18N2S2, lies about an inversion center with only half of the mol­ecule in the asymmetric unit. The cyclo­hexane ring adopts a chair conformation, and the terminal thio­phene rings are in a transoid orientation, with an S(...)S separation between the two terminal 2-thio­phene rings of 11.6733 (9) Å.

Related literature

For a general introduction to coordination polymers, see: Batten et al. (2009 [triangle]); Perry et al. (2009 [triangle]); Robin & Fromm (2006 [triangle]). For structurally related compounds, see: Yun et al. (2009 [triangle]). For related linking ligands containing terminal thio­phene rings, see: Lee & Lee (2007 [triangle]); Huh et al. (2008 [triangle]); Kim & Lee (2008 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2382-scheme1.jpg

Experimental

Crystal data

  • C16H18N2S2
  • M r = 302.44
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2382-efi1.jpg
  • a = 6.2173 (4) Å
  • b = 7.4999 (5) Å
  • c = 17.1289 (12) Å
  • β = 97.047 (3)°
  • V = 792.67 (9) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.33 mm−1
  • T = 296 K
  • 0.46 × 0.24 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.864, T max = 0.937
  • 9045 measured reflections
  • 1889 independent reflections
  • 1590 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.032
  • wR(F 2) = 0.089
  • S = 1.02
  • 1889 reflections
  • 127 parameters
  • All H-atom parameters refined
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035545/pv2205sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035545/pv2205Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a Korea Science and Engineering Foundation (KOSEF) grant funded by the Korean government (MEST) (grant No. 2009-007996).

supplementary crystallographic information

Comment

Design and construction of coordination polymers (or metal–organic frameworks, MOFs) are currently under intensive study due to their desirable applications in catalysis, nonlinear optical activity, spin crossover, luminescence, long-range magnetism, adsorption–desorption, and gas storage (Batten et al., 2009; Perry IV et al., 2009; Robin & Fromm, 2006). In preparing such polymers, appropriate linking ligands play a fundamental role. We have continually reported long bis(pyridine)-, bis(furan)-, bis(thiophene)-, and (pyridine–amine)-type linking ligands and their coordination polymers (Yun et al. 2009). As an extension to our ongoing study of novel linking ligands and their coordination polymers, we have prepared a long, potential linking ligand containing an intervening cyclohexane ring with two terminal thiophene rings.

The molecular structure of the title compound (Fig. 1) contains an intervening cyclohexane ring between two iminethiophene (—N═CH—2-thiophene) fragments. The cyclohexane ring fragment adopts a chair conformation. The imine fragments occupy the equatorial sites of the cyclohexane ring and are trans with respect to each other. The terminal thiophene rings also adopt an overall transoid conformation. The S···S separation between the two terminal 2-thiophene rings is 11.6733 (9) Å. Several related linking ligands containing terminal thiophene rings were previously employed to obtain coordination networks: (2-thiophene)—CH═NN═CH—(2-thiophene) (Lee & Lee, 2007; Huh et al., 2008) and (3-thiophene)—CH═NN═CH—(3-thiophene) (Kim & Lee, 2008).

Experimental

At room temperature, trans-1,4-diaminocyclohexane (1.0 g, 8.76 mmol) was added to 2-thiophene carboxaldehyde (1.72 ml, 18.72 mmol) in 80 ml methanol. After adding dichloromethane (50 ml) and three drops of formic acid, the mixture was stirred for 15 h, and then the solvent was removed under vacuum. The resulting solid was extracted with dichloromethane (150 ml) and washed with water (30 ml × 3). The organic phase was dried over MgSO4 and then filtered. All the solvent was removed to give white crude solid, which was recrystallized from dichloromethane/hexane to give colorless crystals of the title compound suitable for X-ray crystallographic study (2.05 g, 6.78 mmol, 77%). mp: 511–513 K.

Refinement

All H atoms were located from difference maps and refined isotropically.

Figures

Fig. 1.
Molecular structure of the title compound showing 50% probability displacement ellipsoids. Symmetry code for the atoms with A in their labels: -x+2, -y+2, -z+2.

Crystal data

C16H18N2S2F(000) = 320
Mr = 302.44Dx = 1.267 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5365 reflections
a = 6.2173 (4) Åθ = 2.4–28.2°
b = 7.4999 (5) ŵ = 0.33 mm1
c = 17.1289 (12) ÅT = 296 K
β = 97.047 (3)°Block, colourless
V = 792.67 (9) Å30.46 × 0.24 × 0.20 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer1889 independent reflections
Radiation source: sealed tube1590 reflections with I > 2σ(I)
graphiteRint = 0.022
[var phi] and ω scansθmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −8→8
Tmin = 0.864, Tmax = 0.937k = −8→9
9045 measured reflectionsl = −22→19

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089All H-atom parameters refined
S = 1.02w = 1/[σ2(Fo2) + (0.0484P)2 + 0.1406P] where P = (Fo2 + 2Fc2)/3
1889 reflections(Δ/σ)max = 0.001
127 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = −0.18 e Å3

Special details

Experimental. IR (KBr, cm-1): 3443 (w), 3103 (w), 2923 (m), 2852 (w), 1626 (s), 1430 (m), 1306 (w), 1210 (m), 1084 (m), 944 (m), 847 (m), 730 (s), 498 (m).
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)

xyzUiso*/Ueq
S10.65706 (5)0.42717 (5)0.78995 (2)0.04947 (14)
N10.78346 (18)0.71526 (15)0.91441 (7)0.0458 (3)
C10.4495 (3)0.2897 (2)0.75469 (10)0.0554 (4)
C20.2791 (3)0.3032 (2)0.79591 (10)0.0575 (4)
C30.3138 (2)0.42688 (19)0.85814 (9)0.0488 (3)
C40.51420 (19)0.50601 (18)0.86246 (7)0.0396 (3)
C50.6024 (2)0.64140 (18)0.91770 (7)0.0412 (3)
C60.8511 (2)0.85271 (18)0.97279 (8)0.0430 (3)
C70.8308 (3)1.0366 (2)0.93470 (10)0.0527 (4)
C81.0844 (2)0.8189 (2)1.00708 (10)0.0516 (3)
H10.465 (3)0.218 (2)0.7107 (11)0.069 (5)*
H20.157 (3)0.239 (3)0.7840 (10)0.070 (5)*
H30.218 (2)0.4550 (19)0.8910 (10)0.051 (4)*
H50.518 (2)0.6691 (19)0.9570 (9)0.050 (4)*
H60.761 (2)0.847 (2)1.0152 (9)0.053 (4)*
H7A0.687 (3)1.058 (2)0.9140 (12)0.074 (6)*
H7B0.909 (3)1.037 (2)0.8896 (11)0.061 (5)*
H8B1.176 (3)0.821 (2)0.9662 (10)0.056 (4)*
H8A1.104 (3)0.705 (2)1.0311 (10)0.059 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0449 (2)0.0531 (2)0.0512 (2)−0.00126 (14)0.00905 (15)−0.00792 (15)
N10.0473 (6)0.0465 (6)0.0443 (6)−0.0070 (5)0.0087 (5)−0.0088 (5)
C10.0617 (9)0.0484 (8)0.0545 (8)−0.0023 (7)0.0005 (7)−0.0112 (7)
C20.0523 (8)0.0552 (9)0.0631 (9)−0.0150 (7)−0.0003 (7)−0.0052 (7)
C30.0445 (7)0.0532 (8)0.0491 (7)−0.0066 (6)0.0077 (6)−0.0008 (6)
C40.0400 (6)0.0389 (6)0.0393 (6)0.0006 (5)0.0035 (5)0.0025 (5)
C50.0418 (6)0.0428 (7)0.0389 (6)0.0016 (5)0.0051 (5)0.0000 (5)
C60.0450 (7)0.0441 (7)0.0407 (6)−0.0041 (5)0.0084 (5)−0.0076 (6)
C70.0531 (8)0.0492 (8)0.0518 (8)0.0023 (6)−0.0091 (7)−0.0035 (6)
C80.0544 (8)0.0397 (8)0.0584 (9)0.0050 (6)−0.0030 (7)−0.0044 (6)

Geometric parameters (Å, °)

S1—C11.7038 (16)C5—H50.928 (15)
S1—C41.7181 (13)C6—C81.518 (2)
N1—C51.2619 (16)C6—C71.524 (2)
N1—C61.4616 (16)C6—H60.971 (16)
C1—C21.347 (2)C7—C8i1.522 (2)
C1—H10.941 (18)C7—H7A0.94 (2)
C2—C31.410 (2)C7—H7B0.960 (19)
C2—H20.900 (18)C8—C7i1.522 (2)
C3—C41.3736 (18)C8—H8B0.954 (16)
C3—H30.894 (15)C8—H8A0.951 (17)
C4—C51.4492 (19)
C1—S1—C491.62 (7)N1—C6—C7110.09 (11)
C5—N1—C6117.53 (11)C8—C6—C7109.96 (12)
C2—C1—S1112.26 (12)N1—C6—H6109.6 (9)
C2—C1—H1129.0 (11)C8—C6—H6108.2 (9)
S1—C1—H1118.7 (11)C7—C6—H6109.8 (9)
C1—C2—C3112.85 (14)C8i—C7—C6111.09 (12)
C1—C2—H2122.3 (11)C8i—C7—H7A111.4 (11)
C3—C2—H2124.8 (11)C6—C7—H7A110.0 (11)
C4—C3—C2112.27 (13)C8i—C7—H7B111.0 (11)
C4—C3—H3122.4 (10)C6—C7—H7B108.7 (10)
C2—C3—H3125.3 (10)H7A—C7—H7B104.5 (15)
C3—C4—C5127.31 (12)C6—C8—C7i111.86 (12)
C3—C4—S1110.99 (11)C6—C8—H8B109.9 (10)
C5—C4—S1121.69 (9)C7i—C8—H8B106.4 (10)
N1—C5—C4123.14 (12)C6—C8—H8A112.4 (10)
N1—C5—H5121.5 (10)C7i—C8—H8A110.0 (10)
C4—C5—H5115.3 (10)H8B—C8—H8A106.0 (13)
N1—C6—C8109.16 (11)

Symmetry codes: (i) −x+2, −y+2, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2205).

References

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  • Huh, H. S., Kim, S. H., Yun, S. Y. & Lee, S. W. (2008). Polyhedron, 27, 1229–1237.
  • Kim, S. H. & Lee, S. W. (2008). Inorg. Chim. Acta, 361, 137–144.
  • Lee, H. H. & Lee, S. W. (2007). Bull. Korean Chem. Soc.28, 421–426.
  • Perry, J. J. IV, Perman, J. A. & Zaworotko, M. J. (2009). Chem. Soc. Rev.38, 1400–1417. [PubMed]
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  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography