Bis(2-amino-5-benzyl-3-eth­oxy­carbonyl-4,5,6,7-tetra­hydro­thieno[3,2-c]pyridin-5-ium) bis­(4-meth­oxy­phen­yl)di­phos­phon­ate

Akkurt, M.; Mague, J.T.; Mohamed, S.K.; Younes, S.H.H.; Albayati, M.R.

doi:10.1107/S1600536814003766

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages o348-o349

doi:10.1107/S1600536814003766

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Bis(2-amino-5-benzyl-3-ethoxycarbonyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-5-ium) bis(4-methoxyphenyl)diphosphonate

Mehmet Akkurt,^a Joel T. Mague,^b Shaaban K. Mohamed,^c,^d Sabry H. H. Younes ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^dChemistry Department, Faculty of Science, Mini University, 61519 El-Minia, Egypt, ^eDepartment of Chemistry, Faculty of Science, Sohag University, 82524 Sohag, Egypt, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

(Received 13 February 2014; accepted 18 February 2014; online 22 February 2014)

The asymmetric unit of the title salt, 2C₁₇H₂₁N₂O₂S⁺·C₁₄H₁₄O₇P₂²⁻, contains half of a centrosymmetric bis(4-methoxyphenyl)diphosphonate anion and one 2-amino-5-benzyl-3-ethoxycarbonyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-5-ium cation. In the anion, the O atoms of the diphosphonate group are disordered over two positions with equal occupancies. In the cation, the ethyl group is disordered over two orientations with a refined occupancy ratio of 0.753 (5):0.247 (5), and the tetrahydropyridinium ring adopts a distorted half-chair conformation. In the crystal, the ions are linked by C—H⋯O, N—H⋯O and C—H⋯S hydrogen bonds into a three-dimensional network.

CCDC reference: 987723

Related literature

For medicinal applications of tetrahydrothienopyridines, see: Bernardino et al. (2006 ); Attaby et al. (1999 ); Kling et al. (2005 ); Baker & White (2009 ); Huber et al. (2009 ); Andersen et al. (2002 ); Boschellia et al. (2005 ); Tumeya et al. (2008 ). For a similar structure, see: Meng et al. (2011 ). For analysis of ring puckering, see: Cremer & Pople (1975 ).

Experimental

Crystal data

2C₁₇H₂₁N₂O₂S⁺·C₁₄H₁₄O₇P₂²⁻
M_r = 991.05
Monoclinic, P 2₁ /c
a = 14.9420 (9) Å
b = 10.8718 (7) Å
c = 16.0773 (10) Å
β = 114.3270 (8)°
V = 2379.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 150 K
0.23 × 0.19 × 0.05 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ) T_min = 0.81, T_max = 0.99
41576 measured reflections
5955 independent reflections
4481 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.132
S = 1.04
5955 reflections
317 parameters
28 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O4A	0.93 (2)	1.79 (3)	2.699 (4)	165 (2)
N1—H1N⋯O4B	0.93 (2)	1.72 (2)	2.641 (4)	171 (2)
N2—H2N⋯O5Aⁱ	0.95 (3)	1.98 (3)	2.894 (4)	160 (3)
N2—H2N⋯O5Bⁱ	0.95 (3)	1.77 (3)	2.686 (4)	162 (3)
N2—H3N⋯O1	0.84 (3)	2.11 (3)	2.761 (3)	135 (3)
C6—H6⋯O5Bⁱⁱ	0.95	2.37	3.273 (4)	159
C7—H7A⋯O4Bⁱⁱ	0.99	2.44	3.373 (4)	157
C7—H7B⋯S1ⁱⁱ	0.99	2.69	3.591 (2)	152
C8—H8A⋯O5Bⁱⁱ	0.99	2.57	3.488 (4)	154
C18—H18B⋯O1ⁱⁱⁱ	0.98	2.60	3.251 (4)	124
C20—H20⋯O1ⁱⁱⁱ	0.95	2.59	3.524 (3)	168
Symmetry codes: (i) $[x, -y+{\script{5\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 987723

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814003766/rz5105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814003766/rz5105Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814003766/rz5105Isup3.cml

checkCIF report

Comment top

Tetrahydrothieno pyridine-containing compounds are well known bioactive molecules due to their significant pharmaceutical and medicinal properties (Baker & White, 2009; Huber et al., 2009; Andersen et al., 2002; Boschellia et al., 2005). They are used in the treatment of various stages of inflammation such as in chronic inflammatory rheumatism, degenerative rheumatism, oto-rhino-laryngology, stomatology, post-operative surgery and in traumatology (Kling et al., 2005). They are also used in medicine as allosteric adenosine receptor modulators and in the treatment of adenosine-sensitive cardiac arrhythmias (Bernardino et al., 2006; Attaby et al., 1999; Tumeya et al., 2008). As part of our on-going study to synthesize bio-hetero molecules, we report the synthesis and crystal structure of the title compound (I).

As seen in Fig. 1, the asymmetric unit of (I) consist of one cation and half of an anion. In the cation, the tetrahydropyridinium ring (N1/C8–C12) adopts a distorted half-chair conformation [puckering parameters (Cremer & Pople, 1975) are Q_T = 0.525 (2) Å, θ = 52.8 (2) ° and, φ = 341.7 (3) °]. The terminal phenyl ring (C1–C6) makes a dihedral angle of 90.02 (1)° with the thiophene ring (S1/C9/C10/C13/C14). All bond lengths and bond angles in (I) are within normal ranges when compared to those found in a similar structure (Meng et al., 2011). In the crystal structure, the molecules are linked via intermolecular C—H···O, N—H···O and C—H···S hydrogen bonds (Table 1), forming three dimensional network.

Related literature top

For medicinal applications of tetrahydrothienopyridines, see: Bernardino et al. (2006); Attaby et al. (1999); Kling et al. (2005); Baker & White (2009); Huber et al. (2009); Andersen et al. (2002); Boschellia et al. (2005); Tumeya et al. (2008). For a similar structure, see: Meng et al. (2011). For analysis of ring puckering, see: Cremer & Pople (1975).

Experimental top

A mixture of 1 mmol (316 mg) ethyl 2-amino-5-benzyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridine-3-carboxylate and 1 mmol (404.5 mg) of Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide) in 30 ml acetonitrile was refluxed and monitored by TLC until completion (ca 6 h). The mixture was cooled to ambient temperature and the resulting solid product was collected by filtration, washed with diethyl ether and crystallized from ethanol in 84% yield. Plate-like yellow crystals suitable for X-ray analysis were prepared by slow evaporation of an ethanol solution of the title compound at room temperature over two days. M.p. 478 K.

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL-2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

Fig. 1. View of the title compound with displacement ellipsoids for non-H atoms drawn at the 30% probability level. Only one component of the disordered atoms (except atom O6) is shown. Symmetry codes: (a) 1-x, -y, 1-z; (b) x, -1+y, z.

Bis(2-amino-5-benzyl-3-ethoxycarbonyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-5-ium) bis(4-methoxyphenyl)diphosphonate top

Crystal data top

2C₁₇H₂₁N₂O₂S⁺·C₁₄H₁₄O₇P₂²⁻	F(000) = 1044
M_r = 991.05	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9946 reflections
a = 14.9420 (9) Å	θ = 2.3–28.3°
b = 10.8718 (7) Å	µ = 0.24 mm⁻¹
c = 16.0773 (10) Å	T = 150 K
β = 114.3270 (8)°	Plate, pale yellow
V = 2379.8 (3) Å³	0.23 × 0.19 × 0.05 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	5955 independent reflections
Radiation source: fine-focus sealed tube	4481 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 8.3660 pixels mm^-1	θ_max = 28.4°, θ_min = 2.3°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −14→14
T_min = 0.81, T_max = 0.99	l = −21→21
41576 measured reflections

Refinement top

Refinement on F²	28 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.132	w = 1/[σ²(F_o²) + (0.0554P)² + 1.6086P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
5955 reflections	Δρ_max = 0.77 e Å⁻³
317 parameters	Δρ_min = −0.62 e Å⁻³

Crystal data top

2C₁₇H₂₁N₂O₂S⁺·C₁₄H₁₄O₇P₂²⁻	V = 2379.8 (3) Å³
M_r = 991.05	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.9420 (9) Å	µ = 0.24 mm⁻¹
b = 10.8718 (7) Å	T = 150 K
c = 16.0773 (10) Å	0.23 × 0.19 × 0.05 mm
β = 114.3270 (8)°

Data collection top

Bruker SMART APEX CCD diffractometer	5955 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2013)	4481 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.99	R_int = 0.058
41576 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	28 restraints
wR(F²) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.77 e Å⁻³
5955 reflections	Δρ_min = −0.62 e Å⁻³
317 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	Occ. (<1)
P1	0.57869 (4)	1.03372 (5)	0.46675 (4)	0.0305 (2)
O3	0.86773 (11)	0.62642 (14)	0.61933 (12)	0.0427 (5)
O4A	0.5173 (2)	1.0157 (3)	0.3725 (2)	0.0309 (5)	0.500
O4B	0.5512 (2)	1.0296 (3)	0.3642 (2)	0.0309 (5)	0.500
O5A	0.5998 (2)	1.1419 (3)	0.5154 (2)	0.0309 (5)	0.500
O5B	0.6358 (2)	1.1646 (3)	0.4900 (2)	0.0309 (5)	0.500
O6	0.52418 (18)	1.0374 (2)	0.53284 (18)	0.0274 (8)	0.500
C18	0.96967 (18)	0.6470 (3)	0.6554 (2)	0.0581 (10)
C19	0.80643 (15)	0.72531 (19)	0.58665 (14)	0.0316 (6)
C20	0.83752 (15)	0.8459 (2)	0.59149 (16)	0.0361 (6)
C21	0.76781 (15)	0.93886 (19)	0.55603 (15)	0.0346 (6)
C22	0.66850 (14)	0.91441 (18)	0.51714 (13)	0.0272 (5)
C23	0.63917 (15)	0.7916 (2)	0.51452 (15)	0.0344 (6)
C24	0.70699 (16)	0.69865 (19)	0.54824 (16)	0.0370 (7)
S1	0.58537 (4)	1.08926 (4)	0.08978 (3)	0.0289 (1)
O1	0.91131 (13)	1.09586 (18)	0.27696 (13)	0.0560 (7)
O2	0.87989 (13)	0.92245 (18)	0.33537 (13)	0.0570 (6)
N1	0.49957 (14)	0.85683 (15)	0.23756 (12)	0.0331 (5)
N2	0.75816 (16)	1.19991 (18)	0.13051 (15)	0.0400 (6)
C1	0.31772 (17)	0.8669 (2)	0.18867 (15)	0.0381 (7)
C2	0.29320 (18)	0.9500 (2)	0.24134 (16)	0.0423 (7)
C3	0.2121 (2)	1.0252 (3)	0.2017 (2)	0.0544 (10)
C4	0.1555 (2)	1.0191 (3)	0.1092 (2)	0.0628 (11)
C5	0.1785 (2)	0.9363 (3)	0.0564 (2)	0.0629 (10)
C6	0.25792 (19)	0.8596 (3)	0.09563 (17)	0.0501 (8)
C7	0.40835 (18)	0.7891 (2)	0.23008 (16)	0.0412 (7)
C8	0.48723 (16)	0.91160 (19)	0.14823 (14)	0.0331 (6)
C9	0.58213 (16)	0.96802 (17)	0.15942 (14)	0.0304 (6)
C10	0.67162 (16)	0.94260 (18)	0.22578 (14)	0.0323 (6)
C11	0.68191 (17)	0.8442 (2)	0.29481 (15)	0.0386 (7)
C12	0.58719 (18)	0.77301 (19)	0.27059 (15)	0.0399 (7)
C13	0.71049 (16)	1.11013 (18)	0.15399 (14)	0.0317 (6)
C14	0.74755 (16)	1.02343 (19)	0.22349 (14)	0.0330 (6)
C15	0.85221 (18)	1.0206 (2)	0.27950 (16)	0.0423 (7)
C16A	0.9874 (3)	0.9227 (4)	0.3882 (4)	0.0673 (10)	0.753 (5)
C17A	1.0074 (3)	0.8018 (4)	0.4371 (3)	0.0673 (10)	0.753 (5)
C17B	1.0233 (8)	0.8259 (10)	0.3766 (6)	0.0673 (10)	0.247 (5)
C16B	0.9693 (9)	0.8858 (11)	0.4036 (11)	0.0673 (10)	0.247 (5)
H18A	1.00440	0.56880	0.67590	0.0870*
H18B	0.98850	0.70380	0.70710	0.0870*
H18C	0.98720	0.68280	0.60810	0.0870*
H20	0.90560	0.86510	0.61870	0.0430*
H21	0.78940	1.02150	0.55880	0.0420*
H23	0.57110	0.77220	0.48900	0.0410*
H24	0.68560	0.61580	0.54520	0.0440*
H2	0.33250	0.95530	0.30510	0.0510*
H2N	0.7183 (19)	1.261 (3)	0.0898 (18)	0.0480*
H3N	0.816 (2)	1.207 (3)	0.1698 (18)	0.0480*
H4	0.10050	1.07210	0.08190	0.0750*
H3	0.19530	1.08130	0.23830	0.0650*
H1N	0.5116 (18)	0.919 (2)	0.2803 (17)	0.0400*
H7A	0.40010	0.71460	0.19220	0.0490*
H7B	0.41660	0.76230	0.29170	0.0490*
H8A	0.46820	0.84700	0.10060	0.0400*
H8B	0.43500	0.97490	0.12920	0.0400*
H11A	0.70120	0.88250	0.35560	0.0460*
H11B	0.73470	0.78670	0.29840	0.0460*
H12A	0.58000	0.71220	0.22240	0.0480*
H12B	0.59020	0.72750	0.32500	0.0480*
H16A	1.00820	0.99200	0.43200	0.0810*	0.753 (5)
H16B	1.02190	0.92850	0.34740	0.0810*	0.753 (5)
H17A	1.07800	0.79360	0.47450	0.1010*	0.753 (5)
H17B	0.98540	0.73480	0.39240	0.1010*	0.753 (5)
H17C	0.97190	0.79790	0.47650	0.1010*	0.753 (5)
H5	0.13940	0.93220	−0.00740	0.0750*
H6	0.27220	0.80100	0.05900	0.0600*
H16C	1.00540	0.96010	0.43580	0.0810*	0.247 (5)
H16D	0.95610	0.83530	0.44850	0.0810*	0.247 (5)
H17D	1.08390	0.80320	0.42890	0.1010*	0.247 (5)
H17E	1.03950	0.87620	0.33410	0.1010*	0.247 (5)
H17F	0.98900	0.75130	0.34540	0.1010*	0.247 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0343 (3)	0.0305 (3)	0.0281 (3)	0.0102 (2)	0.0143 (2)	0.0061 (2)
O3	0.0398 (9)	0.0337 (8)	0.0528 (10)	0.0139 (7)	0.0172 (8)	0.0100 (7)
O4A	0.0354 (11)	0.0229 (7)	0.0312 (8)	0.0003 (8)	0.0104 (7)	0.0002 (6)
O4B	0.0354 (11)	0.0229 (7)	0.0312 (8)	0.0003 (8)	0.0104 (7)	0.0002 (6)
O5A	0.0354 (11)	0.0229 (7)	0.0312 (8)	0.0003 (8)	0.0104 (7)	0.0002 (6)
O5B	0.0354 (11)	0.0229 (7)	0.0312 (8)	0.0003 (8)	0.0104 (7)	0.0002 (6)
O6	0.0248 (13)	0.0284 (14)	0.0272 (13)	0.0006 (10)	0.0090 (11)	−0.0027 (11)
C18	0.0409 (14)	0.0554 (16)	0.076 (2)	0.0206 (12)	0.0220 (14)	0.0182 (14)
C19	0.0343 (10)	0.0285 (10)	0.0324 (10)	0.0085 (8)	0.0143 (9)	0.0052 (8)
C20	0.0260 (10)	0.0333 (11)	0.0446 (12)	0.0019 (8)	0.0101 (9)	−0.0016 (9)
C21	0.0338 (11)	0.0246 (9)	0.0425 (12)	−0.0002 (8)	0.0128 (9)	−0.0027 (9)
C22	0.0297 (9)	0.0261 (9)	0.0246 (9)	0.0036 (8)	0.0101 (8)	−0.0001 (7)
C23	0.0273 (10)	0.0327 (11)	0.0403 (12)	−0.0019 (8)	0.0110 (9)	0.0037 (9)
C24	0.0375 (11)	0.0256 (10)	0.0459 (13)	0.0000 (9)	0.0153 (10)	0.0073 (9)
S1	0.0363 (3)	0.0210 (2)	0.0283 (2)	0.0004 (2)	0.0121 (2)	0.0003 (2)
O1	0.0402 (10)	0.0589 (12)	0.0560 (12)	−0.0101 (9)	0.0069 (9)	−0.0114 (9)
O2	0.0447 (10)	0.0558 (11)	0.0514 (11)	0.0127 (8)	0.0006 (8)	0.0041 (9)
N1	0.0489 (11)	0.0207 (8)	0.0293 (9)	−0.0042 (7)	0.0156 (8)	0.0009 (7)
N2	0.0404 (11)	0.0345 (10)	0.0403 (11)	−0.0099 (9)	0.0117 (9)	−0.0042 (9)
C1	0.0497 (13)	0.0345 (11)	0.0335 (11)	−0.0167 (10)	0.0205 (10)	−0.0019 (9)
C2	0.0475 (13)	0.0459 (13)	0.0367 (12)	−0.0138 (11)	0.0206 (11)	−0.0036 (10)
C3	0.0537 (16)	0.0502 (15)	0.0687 (19)	−0.0110 (12)	0.0347 (15)	−0.0037 (13)
C4	0.0482 (16)	0.0642 (19)	0.074 (2)	−0.0049 (14)	0.0231 (15)	0.0188 (16)
C5	0.0553 (17)	0.082 (2)	0.0424 (15)	−0.0182 (16)	0.0111 (13)	0.0112 (15)
C6	0.0586 (16)	0.0548 (15)	0.0355 (12)	−0.0186 (13)	0.0181 (12)	−0.0054 (11)
C7	0.0596 (15)	0.0274 (10)	0.0388 (12)	−0.0115 (10)	0.0224 (11)	0.0014 (9)
C8	0.0439 (12)	0.0271 (10)	0.0276 (10)	−0.0048 (9)	0.0139 (9)	0.0024 (8)
C9	0.0416 (11)	0.0210 (9)	0.0282 (10)	0.0026 (8)	0.0139 (9)	0.0004 (8)
C10	0.0409 (11)	0.0232 (9)	0.0317 (10)	0.0060 (8)	0.0138 (9)	−0.0019 (8)
C11	0.0492 (13)	0.0290 (10)	0.0334 (11)	0.0087 (9)	0.0127 (10)	0.0053 (9)
C12	0.0596 (14)	0.0215 (9)	0.0351 (11)	0.0051 (9)	0.0161 (11)	0.0041 (9)
C13	0.0388 (11)	0.0239 (9)	0.0327 (11)	−0.0001 (8)	0.0149 (9)	−0.0076 (8)
C14	0.0378 (11)	0.0265 (10)	0.0318 (10)	0.0035 (8)	0.0115 (9)	−0.0059 (8)
C15	0.0428 (13)	0.0408 (13)	0.0361 (12)	0.0074 (10)	0.0090 (10)	−0.0073 (10)
C16A	0.0518 (16)	0.0641 (19)	0.0685 (19)	0.0069 (13)	0.0073 (13)	0.0263 (15)
C17A	0.0518 (16)	0.0641 (19)	0.0685 (19)	0.0069 (13)	0.0073 (13)	0.0263 (15)
C17B	0.0518 (16)	0.0641 (19)	0.0685 (19)	0.0069 (13)	0.0073 (13)	0.0263 (15)
C16B	0.0518 (16)	0.0641 (19)	0.0685 (19)	0.0069 (13)	0.0073 (13)	0.0263 (15)

Geometric parameters (Å, º) top

S1—C9	1.743 (2)	C1—C6	1.393 (3)
S1—C13	1.739 (2)	C2—C3	1.381 (4)
P1—O4A	1.425 (3)	C3—C4	1.377 (4)
P1—O5B	1.622 (3)	C4—C5	1.375 (4)
P1—O6	1.583 (3)	C5—C6	1.373 (4)
P1—C22	1.801 (2)	C8—C9	1.486 (3)
P1—O6ⁱ	1.723 (3)	C9—C10	1.352 (3)
P1—O4B	1.527 (3)	C10—C11	1.503 (3)
P1—O5A	1.375 (3)	C10—C14	1.448 (3)
O3—C18	1.407 (4)	C11—C12	1.517 (4)
O3—C19	1.369 (3)	C13—C14	1.391 (3)
O5A—O6	1.705 (4)	C14—C15	1.448 (4)
O1—C15	1.217 (3)	C16A—C17A	1.497 (6)
O2—C16A	1.476 (6)	C16B—C17B	1.246 (19)
O2—C15	1.346 (3)	C2—H2	0.9500
O2—C16B	1.393 (16)	C3—H3	0.9500
N1—C8	1.494 (3)	C4—H4	0.9500
N1—C7	1.510 (3)	C5—H5	0.9500
N1—C12	1.501 (3)	C6—H6	0.9500
N2—C13	1.351 (3)	C7—H7A	0.9900
N1—H1N	0.93 (2)	C7—H7B	0.9900
N2—H2N	0.95 (3)	C8—H8A	0.9900
N2—H3N	0.84 (3)	C8—H8B	0.9900
C19—C20	1.382 (3)	C11—H11A	0.9900
C19—C24	1.385 (3)	C11—H11B	0.9900
C20—C21	1.394 (3)	C12—H12A	0.9900
C21—C22	1.378 (3)	C12—H12B	0.9900
C22—C23	1.401 (3)	C16A—H16A	0.9900
C23—C24	1.375 (3)	C16A—H16B	0.9900
C18—H18A	0.9800	C16B—H16C	0.9900
C18—H18B	0.9800	C16B—H16D	0.9900
C18—H18C	0.9800	C17A—H17C	0.9800
C20—H20	0.9500	C17A—H17A	0.9800
C21—H21	0.9500	C17A—H17B	0.9800
C23—H23	0.9500	C17B—H17D	0.9800
C24—H24	0.9500	C17B—H17E	0.9800
C1—C2	1.387 (3)	C17B—H17F	0.9800
C1—C7	1.500 (4)

C9—S1—C13	91.43 (11)	S1—C9—C8	120.79 (16)
O4A—P1—O5B	114.38 (17)	S1—C9—C10	112.42 (18)
O4A—P1—O6	115.68 (17)	C9—C10—C11	119.7 (2)
O4A—P1—O5A	128.22 (19)	C11—C10—C14	127.5 (2)
O4A—P1—O6ⁱ	75.99 (16)	C9—C10—C14	112.75 (19)
O4B—P1—O5A	122.41 (18)	C10—C11—C12	111.89 (19)
O4B—P1—O5B	99.01 (16)	N1—C12—C11	111.51 (17)
O4B—P1—O6	137.86 (16)	N2—C13—C14	129.3 (2)
O4B—P1—C22	106.48 (14)	S1—C13—C14	111.32 (17)
O4B—P1—O6ⁱ	98.48 (15)	S1—C13—N2	119.36 (17)
O5A—P1—O6	69.98 (16)	C10—C14—C13	112.0 (2)
O5A—P1—C22	113.97 (15)	C10—C14—C15	128.92 (19)
O5A—P1—O6ⁱ	112.18 (16)	C13—C14—C15	119.0 (2)
O5B—P1—O6	100.98 (14)	O1—C15—O2	121.9 (2)
O5B—P1—C22	107.72 (13)	O1—C15—C14	125.3 (2)
O5B—P1—O6ⁱ	141.12 (14)	O2—C15—C14	112.8 (2)
O6—P1—C22	102.14 (11)	O2—C16A—C17A	103.6 (4)
O4A—P1—C22	114.41 (15)	O2—C16B—C17B	115.1 (12)
O6ⁱ—P1—C22	100.12 (11)	C1—C2—H2	120.00
O6—P1—O6ⁱ	45.77 (13)	C3—C2—H2	120.00
C18—O3—C19	118.2 (2)	C2—C3—H3	120.00
P1—O5A—O6	60.75 (15)	C4—C3—H3	120.00
P1—O6—O5A	49.27 (13)	C3—C4—H4	120.00
P1—O6—P1ⁱ	134.23 (16)	C5—C4—H4	120.00
P1ⁱ—O6—O5A	162.2 (2)	C4—C5—H5	120.00
C15—O2—C16A	110.2 (3)	C6—C5—H5	120.00
C15—O2—C16B	133.2 (6)	C1—C6—H6	120.00
C8—N1—C12	109.04 (19)	C5—C6—H6	120.00
C7—N1—C8	111.58 (18)	N1—C7—H7A	109.00
C7—N1—C12	111.06 (17)	N1—C7—H7B	109.00
C8—N1—H1N	109.4 (15)	C1—C7—H7A	109.00
C12—N1—H1N	107.8 (17)	C1—C7—H7B	109.00
C7—N1—H1N	107.9 (18)	H7A—C7—H7B	108.00
C13—N2—H2N	116.4 (19)	N1—C8—H8A	110.00
C13—N2—H3N	111 (2)	N1—C8—H8B	110.00
H2N—N2—H3N	128 (3)	C9—C8—H8A	110.00
O3—C19—C20	124.5 (2)	C9—C8—H8B	110.00
O3—C19—C24	115.60 (19)	H8A—C8—H8B	108.00
C20—C19—C24	119.8 (2)	C10—C11—H11A	109.00
C19—C20—C21	119.2 (2)	C10—C11—H11B	109.00
C20—C21—C22	122.0 (2)	C12—C11—H11A	109.00
P1—C22—C23	120.47 (17)	C12—C11—H11B	109.00
P1—C22—C21	121.92 (16)	H11A—C11—H11B	108.00
C21—C22—C23	117.56 (19)	N1—C12—H12A	109.00
C22—C23—C24	121.2 (2)	N1—C12—H12B	109.00
C19—C24—C23	120.2 (2)	C11—C12—H12A	109.00
O3—C18—H18B	110.00	C11—C12—H12B	109.00
O3—C18—H18C	109.00	H12A—C12—H12B	108.00
H18A—C18—H18B	110.00	O2—C16A—H16A	111.00
O3—C18—H18A	110.00	O2—C16A—H16B	111.00
H18A—C18—H18C	109.00	C17A—C16A—H16A	111.00
H18B—C18—H18C	109.00	C17A—C16A—H16B	111.00
C21—C20—H20	120.00	H16A—C16A—H16B	109.00
C19—C20—H20	120.00	O2—C16B—H16D	109.00
C20—C21—H21	119.00	C17B—C16B—H16C	108.00
C22—C21—H21	119.00	C17B—C16B—H16D	108.00
C24—C23—H23	119.00	H16C—C16B—H16D	107.00
C22—C23—H23	119.00	O2—C16B—H16C	109.00
C23—C24—H24	120.00	H17A—C17A—H17C	109.00
C19—C24—H24	120.00	H17B—C17A—H17C	110.00
C2—C1—C6	118.6 (2)	C16A—C17A—H17A	109.00
C6—C1—C7	120.5 (2)	C16A—C17A—H17B	109.00
C2—C1—C7	120.9 (2)	C16A—C17A—H17C	109.00
C1—C2—C3	120.4 (2)	H17A—C17A—H17B	109.00
C2—C3—C4	120.1 (3)	C16B—C17B—H17D	110.00
C3—C4—C5	120.0 (3)	C16B—C17B—H17E	109.00
C4—C5—C6	120.2 (3)	C16B—C17B—H17F	109.00
C1—C6—C5	120.6 (3)	H17D—C17B—H17E	109.00
N1—C7—C1	112.38 (18)	H17D—C17B—H17F	110.00
N1—C8—C9	108.32 (18)	H17E—C17B—H17F	109.00
C8—C9—C10	126.54 (19)

C13—S1—C9—C10	−1.85 (18)	C7—N1—C8—C9	−175.70 (17)
C13—S1—C9—C8	172.78 (18)	C8—N1—C12—C11	67.0 (2)
C9—S1—C13—C14	2.30 (17)	C12—N1—C7—C1	−174.44 (18)
C9—S1—C13—N2	−179.77 (19)	C8—N1—C7—C1	−52.6 (2)
C22—P1—O5A—O6	−94.76 (15)	O3—C19—C24—C23	179.1 (2)
O5B—P1—O5A—O6	−179.4 (4)	C24—C19—C20—C21	−1.1 (3)
O4B—P1—O6—O5A	−116.6 (2)	C20—C19—C24—C23	0.3 (3)
O6ⁱ—P1—O5A—O6	18.13 (17)	O3—C19—C20—C21	−179.7 (2)
O4A—P1—O6—O5A	−123.7 (2)	C19—C20—C21—C22	0.8 (3)
O6ⁱ—P1—O6—O5A	−156.3 (2)	C20—C21—C22—P1	−177.16 (18)
O4A—P1—O6—P1ⁱ	32.6 (3)	C20—C21—C22—C23	0.2 (3)
O4B—P1—O6—P1ⁱ	39.7 (3)	C21—C22—C23—C24	−1.0 (3)
O5A—P1—O6—P1ⁱ	156.3 (3)	P1—C22—C23—C24	176.45 (18)
O5B—P1—O6—P1ⁱ	156.6 (2)	C22—C23—C24—C19	0.7 (3)
O5B—P1—O6—O5A	0.31 (19)	C7—C1—C6—C5	−175.7 (3)
C22—P1—O6—O5A	111.34 (16)	C2—C1—C7—N1	−82.4 (3)
O4B—P1—O5A—O6	134.7 (2)	C7—C1—C2—C3	177.0 (3)
O4Bⁱ—P1ⁱ—O6—P1	154.3 (2)	C6—C1—C7—N1	95.7 (3)
O5Aⁱ—P1ⁱ—O6—P1	24.1 (3)	C2—C1—C6—C5	2.4 (4)
O5Bⁱ—P1ⁱ—O6—P1	38.4 (3)	C6—C1—C2—C3	−1.1 (4)
O6ⁱ—P1ⁱ—O6—P1	0.02 (18)	C1—C2—C3—C4	−0.7 (4)
C22ⁱ—P1ⁱ—O6—P1	−97.2 (2)	C2—C3—C4—C5	1.3 (5)
O4A—P1—C22—C23	−56.9 (2)	C3—C4—C5—C6	−0.1 (5)
O4B—P1—C22—C23	−79.8 (2)	C4—C5—C6—C1	−1.8 (5)
O5A—P1—C22—C23	142.2 (2)	N1—C8—C9—S1	−153.96 (15)
O5B—P1—C22—C23	174.75 (19)	N1—C8—C9—C10	19.9 (3)
O6—P1—C22—C23	68.9 (2)	S1—C9—C10—C11	177.33 (16)
O6ⁱ—P1—C22—C23	22.2 (2)	S1—C9—C10—C14	0.9 (2)
O6—P1—C22—C21	−113.8 (2)	C8—C9—C10—C11	3.1 (3)
O6ⁱ—P1—C22—C21	−160.46 (19)	C8—C9—C10—C14	−173.3 (2)
O5A—P1—C22—C21	−40.5 (2)	C9—C10—C11—C12	8.0 (3)
O4Aⁱ—P1ⁱ—O6—P1	150.0 (3)	C14—C10—C11—C12	−176.1 (2)
O4B—P1—C22—C21	97.5 (2)	C9—C10—C14—C13	0.8 (3)
C22—P1—O6—P1ⁱ	−92.4 (2)	C9—C10—C14—C15	−176.2 (2)
O5B—P1—C22—C21	−7.9 (2)	C11—C10—C14—C13	−175.2 (2)
O4A—P1—O5A—O6	107.5 (2)	C11—C10—C14—C15	7.8 (4)
O4A—P1—C22—C21	120.4 (2)	C10—C11—C12—N1	−42.3 (3)
O6ⁱ—P1—O6—P1ⁱ	0.00 (16)	S1—C13—C14—C10	−2.2 (2)
C18—O3—C19—C24	177.2 (2)	N2—C13—C14—C15	−2.5 (4)
C18—O3—C19—C20	−4.1 (3)	S1—C13—C14—C15	175.15 (17)
C16A—O2—C15—O1	−0.6 (4)	N2—C13—C14—C10	−179.9 (2)
C16A—O2—C15—C14	178.1 (3)	C10—C14—C15—O1	−175.9 (2)
C15—O2—C16A—C17A	−173.1 (3)	C10—C14—C15—O2	5.5 (3)
C7—N1—C12—C11	−169.64 (18)	C13—C14—C15—O1	7.3 (4)
C12—N1—C8—C9	−52.7 (2)	C13—C14—C15—O2	−171.4 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4A	0.93 (2)	1.79 (3)	2.699 (4)	165 (2)
N1—H1N···O4B	0.93 (2)	1.72 (2)	2.641 (4)	171 (2)
N2—H2N···O5Aⁱⁱ	0.95 (3)	1.98 (3)	2.894 (4)	160 (3)
N2—H2N···O5Bⁱⁱ	0.95 (3)	1.77 (3)	2.686 (4)	162 (3)
N2—H3N···O1	0.84 (3)	2.11 (3)	2.761 (3)	135 (3)
C6—H6···O5Bⁱⁱⁱ	0.95	2.37	3.273 (4)	159
C7—H7A···O4Bⁱⁱⁱ	0.99	2.44	3.373 (4)	157
C7—H7B···S1ⁱⁱⁱ	0.99	2.69	3.591 (2)	152
C8—H8A···O5Bⁱⁱⁱ	0.99	2.57	3.488 (4)	154
C18—H18B···O1^iv	0.98	2.60	3.251 (4)	124
C20—H20···O1^iv	0.95	2.59	3.524 (3)	168

Symmetry codes: (ii) x, −y+5/2, z−1/2; (iii) −x+1, y−1/2, −z+1/2; (iv) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O4A	0.93 (2)	1.79 (3)	2.699 (4)	165 (2)
N1—H1N···O4B	0.93 (2)	1.72 (2)	2.641 (4)	171 (2)
N2—H2N···O5Aⁱ	0.95 (3)	1.98 (3)	2.894 (4)	160 (3)
N2—H2N···O5Bⁱ	0.95 (3)	1.77 (3)	2.686 (4)	162 (3)
N2—H3N···O1	0.84 (3)	2.11 (3)	2.761 (3)	135 (3)
C6—H6···O5Bⁱⁱ	0.95	2.37	3.273 (4)	159
C7—H7A···O4Bⁱⁱ	0.99	2.44	3.373 (4)	157
C7—H7B···S1ⁱⁱ	0.99	2.69	3.591 (2)	152
C8—H8A···O5Bⁱⁱ	0.99	2.57	3.488 (4)	154
C18—H18B···O1ⁱⁱⁱ	0.98	2.60	3.251 (4)	124
C20—H20···O1ⁱⁱⁱ	0.95	2.59	3.524 (3)	168

Symmetry codes: (i) x, −y+5/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, −y+2, −z+1.

Acknowledgements

Manchester Metropolitan University, Tulane University and Erciyes University are gratefully acknowledged for supporting this study. The support of Tulane University for the Tulane Crystallography Laboratory is gratefully acknowledged.

References

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Volume 70| Part 3| March 2014| Pages o348-o349

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2-amino-5-benzyl-3-eth­­oxy­carbonyl-4,5,6,7-tetra­hydro­thieno[3,2-c]pyridin-5-ium) bis­­(4-meth­­oxy­phen­yl)di­phos­phon­ate

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Experimental

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Data collection

Refinement

Supporting information

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organic compounds

Bis(2-amino-5-benzyl-3-ethoxycarbonyl-4,5,6,7-tetrahydrothieno[3,2-c]pyridin-5-ium) bis(4-methoxyphenyl)diphosphonate