4-[(Methoxy­glycyl)­carbonyl]­tetra­thia­fulvalene

Batsanov, A.S.; Viles, S.L.; Moore, A.J.

doi:10.1107/S160053680500396X

organic compounds

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ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o648-o650

https://doi.org/10.1107/S160053680500396X

4-[(Methoxyglycyl)carbonyl]tetrathiafulvalene

Andrei S. Batsanov,^a ^* Sarah L. Viles ^b and Adrian J. Moore ^b

^aDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England, and ^bSunderland Pharmacy School – Drug Design and Synthesis, University of Sunderland, Wharncliffe Street, Sunderland SR1 3SD, England
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk

(Received 1 February 2005; accepted 3 February 2005; online 12 February 2005)

The title compound, C₁₀H₉NO₃S₄, has a nearly planar tetrathiafulvalene–amide moiety and an ester group normal to it. Molecules in the crystal structure are linked by S⋯O interactions and N—H⋯O hydrogen bonds.

Comment

The chemistry of tetrathiafulvalene (TTF) and its derivatives has been at the forefront of research in the field of organic conductors for over 30 years (Bendikov et al., 2004 ). As the physical properties displayed by these materials depend on the intermolecular architecture, tetrathiafulvalene derivatives bearing substituents which can participate in hydrogen bonding have been actively investigated as an approach to improving the dimensionality of intermolecular interactions in their charge-transfer complexes (Fourmigué & Batail, 2004 ). Derivatives bearing functionalities such as alcohols, amides, thioamides, amines, and carboxylic and nucleic acids have all been studied. Booth et al. (1998 ) investigated the incorporation of TTF-bearing amino acids into a polypeptide backbone with the aim of controlling the spatial arrangements of the TTF units. In the present paper, we report the crystal structure of tetrathiafulvalene bearing a pendant glycine methyl ester chain to investigate potential hydrogen bonding in the neutral state which may, possibly, be manifested in charge-transfer complexes and radical ion salts.

In the title molecule, (I) (Fig. 1), the TTF-amide moiety is nearly planar, except for a small folding along the S1⋯S2 vector [6.8 (1)°] and a twist around the C2—C7 bond [8.5 (1)°]. The planar ester moiety, however, is inclined to the plane of the adjacent amido group by 86.1 (1)°. Such a conformation hinders the formation of a continuous stacking motif, although molecules do form centrosymmetric face-to-face dimers with a longitudinal offset, so that a dithiole ring of one molecule overlaps with the central C1=C4 bond of another. The mean planes of the two TTF moieties within the dimer are strictly parallel, with an interplanar separation of 3.48 (1) Å. Bond distances in (I) are similar to those in the two previously studied amide derivatives of TTF (Batsanov et al., 1994 , 1995 ). In particular, the bond distances S1—C2 [1.759 (1) Å] and S2—C3 [1.728 (1) Å] differ substantially, due to π-conjugation with the amide C7=O1 bond.

In the crystal structure, intermolecular N—H⋯O hydrogen bonds (Table 2) link the molecules into infinite chains, parallel to the b axis. The chains are further linked into a three-dimensional motif (Fig. 2) by intermolecular S⋯O contacts [S2⋯O3ⁱ = 3.055 (1) Å and S4⋯O2ⁱⁱ = 3.243 (1) Å; symmetry codes: (i) −x, y − ½, ½ − z; (ii) x + 1, ½ − y, z − ½], which are substantially shorter than the sum of van der Waals radii of S and O (3.39 Å) according to Rowland & Taylor (1996 ).

Figure 1
The molecular structure of (I

), showing atomic displacement ellipsoids drawn at the 50% probability level.

Figure 2
The crystal packing of (I

), showing hydrogen bonds (dashed) and short S⋯O contacts (dotted lines) [symmetry codes: (i) −x, y − ½, ½ − z; (ii) x + 1, ½ − y, z − ½; (iii) −x, y + ½, ½ − z].

Experimental

Dry triethylamine (0.63 ml, 4.53 mol) was added to a solution of glycine methyl ester hydrochloride, MeO₂CCH₂NH₃⁺·Cl⁻ (0.21 g, 1.66 mmol), in dry dichloromethane (20 ml) and the solution was stirred for 30 min at room temperature under dry nitrogen. A solution of 4-fluorocarbonyltetrathiafulvalene (0.38 g, 1.52 mmol) (Cooke et al., 1999 ) in dry dichloromethane (20 ml) was added and stirring continued overnight. The organics were washed with water (3 × 25 ml), dried over MgSO₄ and evaporated. Column chromatography of the residue, eluting initially with dichloromethane to remove trace impurities, and subsequently ethyl acetate afforded (I) (0.42, yield 87%) as a red crystalline solid, m/z (LC–MS) 318.9 (M⁺, 100%); ¹H NMR (CDCl₃): δ 8.96 (1H, t, J 5.8), 7.57 (1H, s), 6.75 (2H, s), 3.91 (2H, d, J 5.8), 3.65 (3H, s); IR (KBr) (cm⁻¹): 3324, 3034, 1741, 1613, 1543, 1213. A crystal of X-ray quality was grown by slow evaporation of an ethyl acetate solution (m.p. 325–327 K).

Crystal data

C₁₀H₉NO₃S₄
M_r = 319.42
Monoclinic, P2₁/c
a = 8.9306 (11) Å
b = 10.0106 (12) Å
c = 14.4694 (17) Å
β = 94.02 (1)°
V = 1290.4 (3) Å³
Z = 4
D_x = 1.644 Mg m⁻³
Mo Kα radiation
Cell parameters from 896 reflections
θ = 12.1–26.4°
μ = 0.73 mm⁻¹
T = 120 (2) K
Plate, red
0.24 × 0.23 × 0.08 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
ω scans
Absorption correction: by integration (XPREP in SHELXTL; Bruker, 2001 ) T_min = 0.825, T_max = 0.945
15591 measured reflections
3448 independent reflections
2992 reflections with I > 2σ(I)
R_int = 0.040
θ_max = 29.1°
h = −12 → 12
k = −13 → 13
l = −19 → 19

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.075
S = 1.04
3448 reflections
199 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.041P)² + 0.4425P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—C1	1.7562 (14)
S1—C2	1.7590 (14)
S2—C3	1.7281 (14)
S2—C1	1.7644 (14)
S3—C5	1.7430 (16)
S3—C4	1.7603 (14)
S4—C6	1.7302 (16)
S4—C4	1.7560 (14)
O1—C7	1.2413 (16)
O2—C9	1.2012 (18)
O3—C9	1.3359 (16)
O3—C10	1.4524 (18)
N—C7	1.3405 (18)
N—C8	1.4463 (17)
C1—C4	1.3465 (19)
C2—C3	1.3402 (19)
C2—C7	1.4818 (18)
C5—C6	1.325 (2)
C8—C9	1.521 (2)

C1—S1—C2	94.33 (6)
C3—S2—C1	94.93 (7)
C5—S3—C4	94.76 (7)
C6—S4—C4	94.91 (7)
C9—O3—C10	117.19 (12)
C7—N—C8	119.19 (12)
S1—C1—S2	114.66 (7)
C3—C2—C7	127.85 (12)
C3—C2—S1	117.44 (10)
C7—C2—S1	114.68 (9)
C2—C3—S2	118.05 (11)
S4—C4—S3	114.33 (7)
C6—C5—S3	117.56 (12)
C5—C6—S4	118.41 (12)
O1—C7—N	122.00 (12)
O1—C7—C2	119.67 (12)
N—C7—C2	118.32 (12)

C3—C2—C7—N	7.7 (2)
C2—C7—N—C8	−179.08 (12)
C7—N—C8—C9	−76.58 (16)
N—C8—C9—O3	156.57 (11)
C8—C9—O3—C10	179.65 (12)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H1N⋯O1ⁱ	0.84 (2)	2.13 (2)	2.9688 (15)	177.0 (19)
Symmetry code: (i) $[-x,y-{\script{1\over 2}},{\script{1\over 2}}-z]$ .

All H atoms were located in a difference Fourier map and refined freely in an isotropic approximation, bond distances Csp³—H = 0.91 (2)–0.97 (2) Å and Csp²—H = 0.86 (2)–0.94 (3) Å.

Data collection: SMART (Bruker, 1998 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053680500396X/cv6459sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053680500396X/cv6459Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

4-[(Methoxyglycyl)carbonyl]tetrathiafulvalene top

Crystal data top

C₁₀H₉NO₃S₄	F(000) = 656
M_r = 319.42	D_x = 1.644 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 425–427 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.9306 (11) Å	Cell parameters from 896 reflections
b = 10.0106 (12) Å	θ = 12.1–26.4°
c = 14.4694 (17) Å	µ = 0.73 mm⁻¹
β = 94.02 (1)°	T = 120 K
V = 1290.4 (3) Å³	Plate, red
Z = 4	0.24 × 0.23 × 0.08 mm

Data collection top

SMART 1K CCD area-detector diffractometer	3448 independent reflections
Radiation source: fine-focus sealed tube	2992 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 8 pixels mm^-1	θ_max = 29.1°, θ_min = 2.3°
ω scans	h = −12→12
Absorption correction: integration (XPREP in SHELXTL; Bruker, 2001)	k = −13→13
T_min = 0.825, T_max = 0.945	l = −19→19
15591 measured reflections

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)] = 0.028	Hydrogen site location: difference Fourier map
wR(F²) = 0.075	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.041P)² + 0.4425P] where P = (F_o² + 2F_c²)/3
3448 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Special details top

Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different φ and/or 2θ angles and each scan (10 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.42 cm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.31654 (4)	0.50901 (4)	0.20571 (3)	0.02545 (10)
S2	0.37980 (4)	0.24574 (3)	0.12324 (2)	0.02162 (9)
S3	0.63853 (4)	0.61947 (3)	0.12774 (2)	0.02232 (9)
S4	0.68464 (4)	0.34903 (4)	0.05305 (3)	0.02224 (9)
O1	0.02409 (11)	0.54268 (9)	0.27543 (7)	0.0204 (2)
O2	−0.06966 (12)	0.33910 (11)	0.46168 (7)	0.0278 (2)
O3	−0.27565 (11)	0.46906 (10)	0.44306 (7)	0.0229 (2)
N	−0.06180 (13)	0.33054 (12)	0.26651 (8)	0.0199 (2)
H1N	−0.049 (2)	0.250 (2)	0.2532 (13)	0.033 (5)*
C1	0.43760 (15)	0.41264 (14)	0.14217 (9)	0.0192 (3)
C2	0.17682 (15)	0.38517 (13)	0.20570 (9)	0.0167 (2)
C3	0.20686 (15)	0.26681 (14)	0.16786 (9)	0.0184 (3)
H3	0.143 (2)	0.1965 (19)	0.1643 (12)	0.023 (4)*
C4	0.56732 (15)	0.45663 (13)	0.11097 (9)	0.0180 (3)
C5	0.80147 (17)	0.58979 (17)	0.07135 (12)	0.0291 (3)
H5	0.863 (3)	0.656 (2)	0.0678 (15)	0.046 (6)*
C6	0.82101 (18)	0.46829 (17)	0.03798 (13)	0.0329 (4)
H6	0.899 (3)	0.434 (3)	0.0050 (18)	0.072 (8)*
C7	0.04009 (15)	0.42488 (13)	0.25122 (9)	0.0166 (2)
C8	−0.19709 (16)	0.36759 (14)	0.30959 (10)	0.0197 (3)
H81	−0.239 (2)	0.4480 (19)	0.2811 (12)	0.026 (4)*
H82	−0.267 (2)	0.2993 (19)	0.3017 (12)	0.027 (5)*
C9	−0.16922 (16)	0.38916 (13)	0.41340 (10)	0.0193 (3)
C10	−0.2678 (2)	0.50040 (17)	0.54129 (11)	0.0271 (3)
H101	−0.241 (3)	0.428 (3)	0.5770 (15)	0.052 (6)*
H102	−0.190 (3)	0.565 (3)	0.5534 (16)	0.059 (7)*
H103	−0.358 (3)	0.537 (2)	0.5529 (15)	0.053 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02847 (19)	0.01606 (17)	0.0340 (2)	−0.00665 (13)	0.01746 (15)	−0.00825 (13)
S2	0.02446 (18)	0.01328 (16)	0.02883 (18)	−0.00260 (12)	0.01403 (14)	−0.00290 (12)
S3	0.02395 (18)	0.01692 (17)	0.02674 (18)	−0.00515 (13)	0.00641 (14)	−0.00386 (13)
S4	0.01893 (17)	0.01847 (17)	0.03028 (19)	−0.00185 (13)	0.00848 (13)	−0.00419 (13)
O1	0.0228 (5)	0.0133 (4)	0.0257 (5)	0.0007 (4)	0.0059 (4)	−0.0016 (4)
O2	0.0263 (5)	0.0292 (6)	0.0283 (5)	0.0084 (5)	0.0058 (4)	0.0069 (4)
O3	0.0251 (5)	0.0212 (5)	0.0231 (5)	0.0066 (4)	0.0067 (4)	−0.0002 (4)
N	0.0219 (6)	0.0131 (5)	0.0257 (6)	0.0011 (4)	0.0090 (5)	−0.0015 (4)
C1	0.0220 (7)	0.0150 (6)	0.0216 (6)	−0.0021 (5)	0.0078 (5)	−0.0019 (5)
C2	0.0192 (6)	0.0137 (6)	0.0178 (6)	−0.0012 (5)	0.0048 (5)	0.0016 (5)
C3	0.0194 (6)	0.0150 (6)	0.0215 (6)	−0.0022 (5)	0.0072 (5)	0.0007 (5)
C4	0.0205 (6)	0.0151 (6)	0.0187 (6)	−0.0018 (5)	0.0044 (5)	−0.0014 (5)
C5	0.0199 (7)	0.0261 (8)	0.0423 (9)	−0.0086 (6)	0.0088 (6)	−0.0039 (7)
C6	0.0196 (7)	0.0287 (8)	0.0521 (10)	−0.0067 (6)	0.0152 (7)	−0.0069 (7)
C7	0.0188 (6)	0.0152 (6)	0.0161 (6)	0.0019 (5)	0.0032 (5)	0.0014 (5)
C8	0.0171 (6)	0.0168 (6)	0.0260 (7)	−0.0006 (5)	0.0061 (5)	−0.0010 (5)
C9	0.0199 (6)	0.0132 (6)	0.0258 (6)	−0.0004 (5)	0.0081 (5)	0.0033 (5)
C10	0.0345 (9)	0.0247 (8)	0.0228 (7)	0.0039 (7)	0.0073 (6)	−0.0012 (6)

Geometric parameters (Å, º) top

S1—C1	1.7562 (14)	N—H1N	0.84 (2)
S1—C2	1.7590 (14)	C1—C4	1.3465 (19)
S2—C3	1.7281 (14)	C2—C3	1.3402 (19)
S2—C1	1.7644 (14)	C2—C7	1.4818 (18)
S3—C5	1.7430 (16)	C3—H3	0.905 (19)
S3—C4	1.7603 (14)	C5—C6	1.325 (2)
S4—C6	1.7302 (16)	C5—H5	0.86 (2)
S4—C4	1.7560 (14)	C6—H6	0.94 (3)
O1—C7	1.2413 (16)	C8—C9	1.521 (2)
O2—C9	1.2012 (18)	C8—H81	0.966 (19)
O3—C9	1.3359 (16)	C8—H82	0.927 (19)
O3—C10	1.4524 (18)	C10—H101	0.91 (2)
N—C7	1.3405 (18)	C10—H102	0.96 (3)
N—C8	1.4463 (17)	C10—H103	0.91 (2)

C1—S1—C2	94.33 (6)	S3—C5—H5	116.9 (15)
C3—S2—C1	94.93 (7)	C5—C6—S4	118.41 (12)
C5—S3—C4	94.76 (7)	C5—C6—H6	130.0 (17)
C6—S4—C4	94.91 (7)	S4—C6—H6	111.6 (17)
C9—O3—C10	117.19 (12)	O1—C7—N	122.00 (12)
C7—N—C8	119.19 (12)	O1—C7—C2	119.67 (12)
C7—N—H1N	122.2 (14)	N—C7—C2	118.32 (12)
C8—N—H1N	118.6 (14)	N—C8—C9	112.23 (12)
C4—C1—S1	124.86 (11)	N—C8—H81	109.7 (11)
C4—C1—S2	120.46 (11)	C9—C8—H81	109.5 (11)
S1—C1—S2	114.66 (7)	N—C8—H82	109.5 (11)
C3—C2—C7	127.85 (12)	C9—C8—H82	106.7 (11)
C3—C2—S1	117.44 (10)	H81—C8—H82	109.1 (15)
C7—C2—S1	114.68 (9)	O2—C9—O3	125.26 (13)
C2—C3—S2	118.05 (11)	O2—C9—C8	125.35 (13)
C2—C3—H3	124.6 (11)	O3—C9—C8	109.36 (12)
S2—C3—H3	117.4 (11)	O3—C10—H101	112.1 (15)
C1—C4—S4	121.03 (11)	O3—C10—H102	108.1 (14)
C1—C4—S3	124.59 (11)	H101—C10—H102	106 (2)
S4—C4—S3	114.33 (7)	O3—C10—H103	106.5 (14)
C6—C5—S3	117.56 (12)	H101—C10—H103	115 (2)
C6—C5—H5	125.5 (15)	H102—C10—H103	109 (2)

C3—C2—C7—N	7.7 (2)	N—C8—C9—O3	156.57 (11)
C2—C7—N—C8	−179.08 (12)	C8—C9—O3—C10	179.65 (12)
C7—N—C8—C9	−76.58 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H1N···O1ⁱ	0.84 (2)	2.13 (2)	2.9688 (15)	177.0 (19)

Symmetry code: (i) −x, y−1/2, −z+1/2.

Acknowledgements

SLV thanks the University of Sunderland for financial support.

References

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