(E)-5-(2-Chloro­phen­yl)-7-ethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-4-ium 2,4,6-trinitro­phenolate

Betz, R.; Gerber, T.; Hosten, E.; Dayananda, A.S.; Yathirajan, H.S.; Ramesha, A.R.

doi:10.1107/S1600536812002607

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o516-o517

doi:10.1107/S1600536812002607

Open

access

(E)-5-(2-Chlorophenyl)-7-ethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-4-ium 2,4,6-trinitrophenolate

Richard Betz,^a ^* Thomas Gerber,^a Eric Hosten,^a Alaloor S. Dayananda,^b Hemmige S. Yathirajan ^b and A. R. Ramesha ^c

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa, ^bUniversity of Mysore, Department of Studies in Chemistry, Manasagangotri, Mysore 570 006, India, and ^cR. L. Fine Chem., Bangalore 560 064, India
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 10 January 2012; accepted 20 January 2012; online 25 January 2012)

In the title molecular salt, C₁₅H₁₄ClN₂OS⁺·C₆H₂N₃O₇⁻, protonation occurred on the double-bonded N atom. One of the nitro groups shows slight disorder over two orientations, with an occupancy ratio of 0.91:0.09. In the crystal, classical N—H⋯O hydrogen bonds, as well as C—H⋯O contacts connect the components into a three-dimensional network. The seven-membered ring adopts a boat-like conformation. The least-squares plane defined by its non-H atoms encloses an angle of 38.99 (6)° with the benzene ring bonded to it.

Related literature

For pharmaceutical background to benzodiazepines, see: Robol et al. (1996 ); Evans et al. (2001 ). For related structures, see: Scammells et al. (2001 ); Jasinski et al. (2010 ). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ). For puckering analysis, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₅H₁₄ClN₂OS⁺·C₆H₂N₃O₇⁻
M_r = 533.90
Monoclinic, P 2₁ /c
a = 10.5704 (2) Å
b = 20.0667 (5) Å
c = 11.3741 (2) Å
β = 110.666 (1)°
V = 2257.35 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 200 K
0.59 × 0.49 × 0.36 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ). T_min = 0.807, T_max = 0.892
21254 measured reflections
5607 independent reflections
5073 reflections with I > 2σ(I)
R_int = 0.013

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.081
S = 1.05
5607 reflections
343 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H71⋯O31	0.870 (19)	1.865 (19)	2.6847 (13)	156.3 (17)
N2—H72⋯O31ⁱ	0.836 (18)	2.047 (18)	2.8331 (13)	156.4 (16)
N2—H72⋯O362ⁱ	0.836 (18)	2.400 (17)	2.9495 (16)	123.9 (14)
C2—H2A⋯O321	0.99	2.49	3.2465 (16)	133
C2—H2B⋯O342ⁱⁱ	0.99	2.48	3.2505 (17)	134
C23—H23⋯O321ⁱⁱⁱ	0.95	2.51	3.4193 (18)	161
Symmetry codes: (i) -x+1, -y, -z; (ii) x-1, y, z-1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002607/pk2384sup1.cif

Supporting information file. DOI: 10.1107/S1600536812002607/pk2384Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002607/pk2384Isup3.hkl

Supporting information file. DOI: 10.1107/S1600536812002607/pk2384Isup4.cml

checkCIF report

Comment top

Five-atom heterocyclic fused benzodiazepine ring systems occupy a prominent place among drugs for treatment of central nervous system (CNS) disorders (Robol et al., 1996; Evans et al., 2001). The crystal structures of 6,7-dimethyl-5-phenyl-1H-thieno[2,3-e][1,4]diazepin-2(3H) -one (Scammells et al., 2001) and 5,7-dimethyl-2,3-dihydro-1H-1,4- diazepin-4-ium picrate (Jasinski et al., 2010) have been reported. In view of the importance of heterocyclic fused diazepine ring systems, the paper reports the crystal structure of the title compound.

The title compound is the picrate salt of (E)-5-(2-chlorophenyl)-7- ethyl-1H-thieno[2,3-e][1,4]diazepin-2(3H)-one. Due to involvement of the free electron pair on the – formally – sp³ hybridized nitrogen atom in amide-type resonance, protonation occurred on the double-bonded nitrogen atom. According to a puckering analysis (Cremer & Pople, 1975), the seven-membered heterocycle adopts a boat-like conformation (Q₂: 0.7754 (12) Å, Q₃: 0.2281 (12) Å, ϕ₂: 262.69 (9)°, ϕ₃: 207.4 (3)°) (Fig. 1).

In the crystal structure, classical hydrogen bonds of the N–H···O type as well as C–H···O contacts whose range falls by more than 0.2 Å below the sum of van-der-Waals radii of the corresponding atoms are apparent. While the classical hydrogen bonds are supported by both nitrogen-bound H atoms and have the phenolic as well as nitrogen-bound oxygen atoms as acceptor, the C–H···O contacts exclusively apply the latter type of oxygen atoms as acceptors. The C–H···O contacts stem from both hydrogen atoms of the intracyclic methylene group as well as the hydrogen atom in ortho position to the chlorine atom. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for the classical hydrogen bonds is DDD on the unitary level (due to bifurcation of one of the classical hydrogen bonds). The same descriptor is necessary to describe the C–H···O contacts on the identical level. Metrical information about the contacts is summarized in Table 1. In total, the entities of the title compound are connected to a three-dimensional network. The shortest intercentroid distance between two aromatic systems was measured at 4.8063 (7) Å and is apparent between the thiophene moieties of two neighbouring molecules. (Fig. 2).

Related literature top

For pharmaceutical background to benzodiazepines, see: Robol et al. (1996); Evans et al. (2001). For related structures, see: Scammells et al. (2001); Jasinski et al. (2010). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995). For puckering analysis, see: Cremer & Pople (1975).

Experimental top

(E)-5-(2-Chlorophenyl)-7-ethyl-1H-thieno[2,3-e] [1,4]diazepin-2(3H)-one was obtained as a gift sample from R. L. Fine Chem., Bengaluru, India. (E)-5-(2-Chlorophenyl)-7-ethyl-1H-thieno [2,3-e][1,4]diazepin-2(3H)-one (3.04 g, 0.01 mol) was dissolved in 10 ml of methanol and picric acid (2.29 g, 0.01 mol) was also dissolved in 10 ml of methanol. Both solutions were mixed and stirred in a beaker at 333 K for 30 minutes. The mixture was kept aside for a day at room temperature. The salt formed was filtered and dried in a vaccum desiccator over phosphorous pentoxide. The compound was recrystallized from a mixture (v:v = 1:1) of DMSO and ethanol by slow evaporation (m.p: 518 K).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with anisotropic displacement ellipsoids (drawn at 50% probability level). For clarity, only the major component of the disordered nitro group is depicted.
	Fig. 2. Intermolecular contacts, viewed approximately along [-1 -1 -1]. For clarity, only selected intermolecular contacts are depicted. Blue dashed lines show classical hydrogen bonds of the N–H···O type, green dashed lines C–H···O contacts. Symmetry operator: ⁱ -x + 1, -y, -z. Only the major component of the disordered nitro group is depicted.

(E)-5-(2-Chlorophenyl)-7-ethyl-2-oxo-2,3-dihydro-1H- thieno[2,3-e][1,4]diazepin-4-ium 2,4,6-trinitrophenolate top

Crystal data top

C₁₅H₁₄ClN₂OS⁺·C₆H₂N₃O₇⁻	F(000) = 1096
M_r = 533.90	D_x = 1.571 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 518 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.5704 (2) Å	Cell parameters from 9909 reflections
b = 20.0667 (5) Å	θ = 2.9–28.3°
c = 11.3741 (2) Å	µ = 0.32 mm⁻¹
β = 110.666 (1)°	T = 200 K
V = 2257.35 (8) Å³	Block, brown
Z = 4	0.59 × 0.49 × 0.36 mm

Data collection top

Bruker APEXII CCD diffractometer	5607 independent reflections
Radiation source: fine-focus sealed tube	5073 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.013
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008).	h = −13→14
T_min = 0.807, T_max = 0.892	k = −26→26
21254 measured reflections	l = −15→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0349P)² + 1.1718P] where P = (F_o² + 2F_c²)/3
5607 reflections	(Δ/σ)_max < 0.001
343 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₅H₁₄ClN₂OS⁺·C₆H₂N₃O₇⁻	V = 2257.35 (8) Å³
M_r = 533.90	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5704 (2) Å	µ = 0.32 mm⁻¹
b = 20.0667 (5) Å	T = 200 K
c = 11.3741 (2) Å	0.59 × 0.49 × 0.36 mm
β = 110.666 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5607 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008).	5073 reflections with I > 2σ(I)
T_min = 0.807, T_max = 0.892	R_int = 0.013
21254 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.38 e Å⁻³
5607 reflections	Δρ_min = −0.24 e Å⁻³
343 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.57956 (3)	0.230591 (16)	0.27567 (3)	0.03062 (8)
S1	0.08122 (3)	0.038903 (15)	−0.15866 (3)	0.02327 (8)
O1	0.53537 (10)	0.04170 (5)	−0.16774 (10)	0.0361 (2)
O31	0.75141 (9)	0.09665 (4)	0.21426 (8)	0.02763 (19)
O321	0.75835 (10)	0.21026 (6)	0.09075 (9)	0.0377 (2)
O322	0.96274 (13)	0.23796 (7)	0.11380 (11)	0.0495 (3)
O341	1.27262 (12)	0.24856 (6)	0.54001 (12)	0.0505 (3)
O342	1.25204 (13)	0.17919 (7)	0.67751 (12)	0.0607 (4)
N36	0.84539 (12)	0.04459 (6)	0.46335 (11)	0.0328 (3)
O361	0.8483 (2)	0.04566 (12)	0.57264 (12)	0.0591 (7)	0.913 (5)
O362	0.79227 (19)	−0.00036 (7)	0.39045 (12)	0.0432 (5)	0.913 (5)
O363	0.8925 (12)	0.0218 (6)	0.5586 (12)	0.023 (3)*	0.087 (5)
O364	0.7289 (16)	0.0258 (8)	0.3784 (12)	0.037 (4)*	0.087 (5)
N1	0.49406 (10)	0.12534 (5)	0.07439 (9)	0.01965 (19)
H71	0.5767 (19)	0.1274 (9)	0.1273 (17)	0.040 (5)*
N2	0.34466 (10)	0.03182 (5)	−0.12197 (9)	0.0216 (2)
H72	0.3224 (17)	−0.0023 (9)	−0.1669 (16)	0.033 (4)*
N32	0.87981 (11)	0.21070 (6)	0.15093 (10)	0.0277 (2)
N34	1.21470 (12)	0.20290 (6)	0.57125 (12)	0.0375 (3)
C1	0.45809 (12)	0.06515 (6)	−0.12171 (11)	0.0229 (2)
C2	0.47774 (12)	0.13264 (6)	−0.05765 (11)	0.0228 (2)
H2A	0.5588	0.1545	−0.0645	0.027*
H2B	0.3985	0.1613	−0.1002	0.027*
C3	0.39456 (11)	0.11469 (5)	0.11481 (10)	0.0186 (2)
C4	−0.11953 (12)	0.08838 (7)	−0.07592 (13)	0.0272 (3)
H4A	−0.1330	0.1015	0.0028	0.033*
H4B	−0.1627	0.0444	−0.1017	0.033*
C5	−0.18803 (14)	0.13922 (8)	−0.17752 (15)	0.0399 (3)
H5A	−0.1502	0.1835	−0.1498	0.060*
H5B	−0.2854	0.1397	−0.1933	0.060*
H5C	−0.1727	0.1273	−0.2549	0.060*
C11	0.24806 (11)	0.05778 (6)	−0.07911 (10)	0.0194 (2)
C12	0.26416 (11)	0.09611 (6)	0.02726 (10)	0.0198 (2)
C13	0.13619 (12)	0.10916 (6)	0.04104 (11)	0.0230 (2)
H13	0.1277	0.1342	0.1088	0.028*
C14	0.02920 (12)	0.08249 (6)	−0.05130 (11)	0.0232 (2)
C21	0.42065 (11)	0.11893 (6)	0.25106 (11)	0.0210 (2)
C22	0.50465 (12)	0.16687 (6)	0.33080 (11)	0.0243 (2)
C23	0.52897 (15)	0.16634 (8)	0.45900 (13)	0.0368 (3)
H23	0.5859	0.1992	0.5119	0.044*
C24	0.47029 (17)	0.11802 (9)	0.50923 (13)	0.0428 (4)
H24	0.4878	0.1174	0.5971	0.051*
C25	0.38611 (16)	0.07037 (8)	0.43273 (14)	0.0377 (3)
H25	0.3456	0.0373	0.4678	0.045*
C26	0.36134 (13)	0.07120 (7)	0.30489 (12)	0.0283 (3)
H26	0.3028	0.0387	0.2526	0.034*
C31	0.85448 (11)	0.12197 (6)	0.29523 (11)	0.0208 (2)
C32	0.92952 (12)	0.17741 (6)	0.27217 (11)	0.0225 (2)
C33	1.04736 (12)	0.20209 (6)	0.35838 (12)	0.0256 (2)
H33	1.0953	0.2371	0.3363	0.031*
C34	1.09452 (12)	0.17498 (6)	0.47757 (12)	0.0267 (3)
C35	1.02603 (13)	0.12448 (6)	0.51186 (12)	0.0280 (3)
H35	1.0569	0.1080	0.5955	0.034*
C36	0.91220 (12)	0.09847 (6)	0.42255 (11)	0.0244 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03397 (16)	0.02676 (15)	0.03248 (16)	−0.01114 (12)	0.01341 (13)	−0.00916 (11)
S1	0.01661 (13)	0.02786 (15)	0.02118 (14)	−0.00278 (10)	0.00153 (10)	−0.00509 (10)
O1	0.0307 (5)	0.0438 (6)	0.0402 (5)	−0.0040 (4)	0.0204 (4)	−0.0127 (4)
O31	0.0212 (4)	0.0225 (4)	0.0289 (4)	−0.0008 (3)	−0.0038 (3)	−0.0028 (3)
O321	0.0293 (5)	0.0464 (6)	0.0305 (5)	0.0064 (4)	0.0020 (4)	0.0102 (4)
O322	0.0465 (6)	0.0593 (7)	0.0426 (6)	−0.0143 (6)	0.0155 (5)	0.0147 (5)
O341	0.0336 (6)	0.0361 (6)	0.0629 (8)	−0.0136 (5)	−0.0065 (5)	−0.0026 (5)
O342	0.0493 (7)	0.0693 (9)	0.0367 (6)	−0.0165 (6)	−0.0183 (5)	0.0039 (6)
N36	0.0317 (6)	0.0376 (6)	0.0242 (5)	−0.0089 (5)	0.0037 (4)	0.0028 (5)
O361	0.0699 (12)	0.0805 (14)	0.0235 (6)	−0.0390 (11)	0.0124 (6)	−0.0028 (7)
O362	0.0621 (11)	0.0307 (7)	0.0354 (6)	−0.0185 (7)	0.0154 (6)	−0.0032 (5)
N1	0.0162 (4)	0.0225 (5)	0.0180 (4)	−0.0010 (4)	0.0032 (4)	−0.0027 (3)
N2	0.0201 (5)	0.0224 (5)	0.0212 (5)	−0.0016 (4)	0.0061 (4)	−0.0056 (4)
N32	0.0303 (5)	0.0265 (5)	0.0250 (5)	0.0003 (4)	0.0082 (4)	0.0009 (4)
N34	0.0264 (6)	0.0322 (6)	0.0397 (7)	−0.0035 (5)	−0.0060 (5)	−0.0066 (5)
C1	0.0205 (5)	0.0290 (6)	0.0179 (5)	−0.0004 (4)	0.0052 (4)	−0.0012 (4)
C2	0.0228 (5)	0.0253 (5)	0.0201 (5)	−0.0040 (4)	0.0074 (4)	−0.0002 (4)
C3	0.0166 (5)	0.0174 (5)	0.0194 (5)	0.0000 (4)	0.0035 (4)	−0.0028 (4)
C4	0.0158 (5)	0.0295 (6)	0.0344 (6)	−0.0011 (4)	0.0065 (5)	−0.0028 (5)
C5	0.0244 (6)	0.0466 (8)	0.0456 (8)	0.0098 (6)	0.0083 (6)	0.0099 (7)
C11	0.0168 (5)	0.0203 (5)	0.0185 (5)	−0.0011 (4)	0.0030 (4)	−0.0006 (4)
C12	0.0163 (5)	0.0213 (5)	0.0199 (5)	−0.0009 (4)	0.0041 (4)	−0.0025 (4)
C13	0.0186 (5)	0.0248 (5)	0.0247 (5)	0.0001 (4)	0.0066 (4)	−0.0043 (4)
C14	0.0177 (5)	0.0242 (5)	0.0263 (6)	0.0001 (4)	0.0059 (4)	−0.0011 (4)
C21	0.0184 (5)	0.0240 (5)	0.0195 (5)	−0.0013 (4)	0.0052 (4)	−0.0040 (4)
C22	0.0218 (5)	0.0271 (6)	0.0237 (6)	−0.0050 (4)	0.0077 (4)	−0.0051 (4)
C23	0.0376 (7)	0.0466 (8)	0.0237 (6)	−0.0133 (6)	0.0077 (5)	−0.0128 (6)
C24	0.0486 (9)	0.0593 (10)	0.0206 (6)	−0.0123 (8)	0.0125 (6)	−0.0044 (6)
C25	0.0406 (8)	0.0459 (8)	0.0302 (7)	−0.0110 (6)	0.0168 (6)	0.0014 (6)
C26	0.0278 (6)	0.0305 (6)	0.0267 (6)	−0.0073 (5)	0.0099 (5)	−0.0036 (5)
C31	0.0171 (5)	0.0210 (5)	0.0218 (5)	0.0022 (4)	0.0037 (4)	−0.0029 (4)
C32	0.0212 (5)	0.0226 (5)	0.0215 (5)	0.0022 (4)	0.0049 (4)	−0.0002 (4)
C33	0.0204 (5)	0.0226 (5)	0.0317 (6)	−0.0009 (4)	0.0065 (5)	−0.0029 (5)
C34	0.0185 (5)	0.0257 (6)	0.0283 (6)	−0.0011 (4)	−0.0014 (5)	−0.0056 (5)
C35	0.0260 (6)	0.0291 (6)	0.0223 (5)	−0.0002 (5)	0.0005 (5)	−0.0009 (5)
C36	0.0227 (5)	0.0246 (6)	0.0231 (5)	−0.0023 (4)	0.0044 (5)	−0.0004 (4)

Geometric parameters (Å, º) top

Cl1—C22	1.7337 (13)	C4—C5	1.5199 (19)
S1—C11	1.7164 (11)	C4—H4A	0.9900
S1—C14	1.7415 (12)	C4—H4B	0.9900
O1—C1	1.2102 (15)	C5—H5A	0.9800
O31—C31	1.2590 (14)	C5—H5B	0.9800
O321—N32	1.2234 (15)	C5—H5C	0.9800
O322—N32	1.2277 (15)	C11—C12	1.3925 (15)
O341—N34	1.2222 (18)	C12—C13	1.4396 (15)
O342—N34	1.2273 (18)	C13—C14	1.3528 (16)
N36—O363	1.118 (12)	C13—H13	0.9500
N36—O362	1.2196 (16)	C21—C26	1.3985 (17)
N36—O361	1.2330 (19)	C21—C22	1.4029 (16)
N36—O364	1.323 (14)	C22—C23	1.3885 (18)
N36—C36	1.4542 (16)	C23—C24	1.379 (2)
N1—C3	1.3056 (15)	C23—H23	0.9500
N1—C2	1.4574 (15)	C24—C25	1.384 (2)
N1—H71	0.870 (19)	C24—H24	0.9500
N2—C1	1.3720 (15)	C25—C26	1.3836 (18)
N2—C11	1.3795 (15)	C25—H25	0.9500
N2—H72	0.836 (18)	C26—H26	0.9500
N32—C32	1.4534 (15)	C31—C36	1.4380 (16)
N34—C34	1.4519 (15)	C31—C32	1.4431 (16)
C1—C2	1.5170 (17)	C32—C33	1.3771 (16)
C2—H2A	0.9900	C33—C34	1.3803 (18)
C2—H2B	0.9900	C33—H33	0.9500
C3—C12	1.4358 (15)	C34—C35	1.3793 (18)
C3—C21	1.4776 (15)	C35—C36	1.3745 (17)
C4—C14	1.5011 (16)	C35—H35	0.9500

C11—S1—C14	92.26 (5)	C12—C11—S1	111.57 (8)
O363—N36—O362	107.3 (6)	C11—C12—C3	122.62 (10)
O362—N36—O361	122.68 (13)	C11—C12—C13	111.32 (10)
O363—N36—O364	124.9 (9)	C3—C12—C13	125.89 (10)
O361—N36—O364	115.2 (6)	C14—C13—C12	113.81 (10)
O363—N36—C36	120.9 (6)	C14—C13—H13	123.1
O362—N36—C36	119.46 (11)	C12—C13—H13	123.1
O361—N36—C36	117.83 (12)	C13—C14—C4	130.33 (11)
O364—N36—C36	114.2 (6)	C13—C14—S1	111.02 (9)
C3—N1—C2	124.21 (10)	C4—C14—S1	118.55 (9)
C3—N1—H71	120.1 (12)	C26—C21—C22	117.76 (11)
C2—N1—H71	115.7 (12)	C26—C21—C3	118.24 (10)
C1—N2—C11	124.78 (10)	C22—C21—C3	123.97 (11)
C1—N2—H72	117.2 (11)	C23—C22—C21	120.93 (12)
C11—N2—H72	116.2 (11)	C23—C22—Cl1	116.52 (10)
O321—N32—O322	123.13 (12)	C21—C22—Cl1	122.52 (9)
O321—N32—C32	118.95 (11)	C24—C23—C22	119.79 (13)
O322—N32—C32	117.92 (11)	C24—C23—H23	120.1
O341—N34—O342	123.85 (12)	C22—C23—H23	120.1
O341—N34—C34	118.31 (12)	C23—C24—C25	120.57 (13)
O342—N34—C34	117.84 (13)	C23—C24—H24	119.7
O1—C1—N2	122.16 (12)	C25—C24—H24	119.7
O1—C1—C2	123.78 (11)	C26—C25—C24	119.56 (13)
N2—C1—C2	114.05 (10)	C26—C25—H25	120.2
N1—C2—C1	110.59 (10)	C24—C25—H25	120.2
N1—C2—H2A	109.5	C25—C26—C21	121.37 (12)
C1—C2—H2A	109.5	C25—C26—H26	119.3
N1—C2—H2B	109.5	C21—C26—H26	119.3
C1—C2—H2B	109.5	O31—C31—C36	123.67 (11)
H2A—C2—H2B	108.1	O31—C31—C32	124.57 (11)
N1—C3—C12	119.59 (10)	C36—C31—C32	111.76 (10)
N1—C3—C21	118.98 (10)	C33—C32—C31	124.39 (11)
C12—C3—C21	121.36 (10)	C33—C32—N32	116.33 (11)
C14—C4—C5	112.41 (11)	C31—C32—N32	119.27 (10)
C14—C4—H4A	109.1	C32—C33—C34	118.69 (12)
C5—C4—H4A	109.1	C32—C33—H33	120.7
C14—C4—H4B	109.1	C34—C33—H33	120.7
C5—C4—H4B	109.1	C35—C34—C33	121.57 (11)
H4A—C4—H4B	107.9	C35—C34—N34	119.12 (12)
C4—C5—H5A	109.5	C33—C34—N34	119.21 (12)
C4—C5—H5B	109.5	C36—C35—C34	118.68 (12)
H5A—C5—H5B	109.5	C36—C35—H35	120.7
C4—C5—H5C	109.5	C34—C35—H35	120.7
H5A—C5—H5C	109.5	C35—C36—C31	124.71 (11)
H5B—C5—H5C	109.5	C35—C36—N36	116.33 (11)
N2—C11—C12	129.56 (10)	C31—C36—N36	118.94 (10)
N2—C11—S1	118.77 (8)

C11—N2—C1—O1	−175.18 (12)	C22—C23—C24—C25	−0.7 (3)
C11—N2—C1—C2	5.61 (16)	C23—C24—C25—C26	0.3 (3)
C3—N1—C2—C1	−77.66 (14)	C24—C25—C26—C21	0.6 (2)
O1—C1—C2—N1	−117.45 (13)	C22—C21—C26—C25	−1.1 (2)
N2—C1—C2—N1	61.75 (13)	C3—C21—C26—C25	177.14 (13)
C2—N1—C3—C12	12.62 (17)	O31—C31—C32—C33	−175.40 (12)
C2—N1—C3—C21	−170.29 (10)	C36—C31—C32—C33	4.22 (17)
C1—N2—C11—C12	−41.65 (19)	O31—C31—C32—N32	4.86 (18)
C1—N2—C11—S1	142.17 (10)	C36—C31—C32—N32	−175.52 (10)
C14—S1—C11—N2	177.15 (10)	O321—N32—C32—C33	−152.12 (12)
C14—S1—C11—C12	0.32 (9)	O322—N32—C32—C33	28.00 (17)
N2—C11—C12—C3	−0.8 (2)	O321—N32—C32—C31	27.64 (17)
S1—C11—C12—C3	175.59 (9)	O322—N32—C32—C31	−152.24 (12)
N2—C11—C12—C13	−176.29 (12)	C31—C32—C33—C34	−3.70 (19)
S1—C11—C12—C13	0.10 (13)	N32—C32—C33—C34	176.05 (11)
N1—C3—C12—C11	32.88 (17)	C32—C33—C34—C35	−0.45 (19)
C21—C3—C12—C11	−144.13 (12)	C32—C33—C34—N34	−176.78 (12)
N1—C3—C12—C13	−152.30 (12)	O341—N34—C34—C35	−178.51 (13)
C21—C3—C12—C13	30.68 (18)	O342—N34—C34—C35	1.4 (2)
C11—C12—C13—C14	−0.65 (15)	O341—N34—C34—C33	−2.1 (2)
C3—C12—C13—C14	−175.96 (11)	O342—N34—C34—C33	177.82 (14)
C12—C13—C14—C4	−175.42 (12)	C33—C34—C35—C36	3.5 (2)
C12—C13—C14—S1	0.88 (14)	N34—C34—C35—C36	179.86 (12)
C5—C4—C14—C13	99.93 (17)	C34—C35—C36—C31	−2.8 (2)
C5—C4—C14—S1	−76.14 (14)	C34—C35—C36—N36	178.98 (12)
C11—S1—C14—C13	−0.69 (10)	O31—C31—C36—C35	178.71 (12)
C11—S1—C14—C4	176.10 (10)	C32—C31—C36—C35	−0.92 (17)
N1—C3—C21—C26	−138.62 (12)	O31—C31—C36—N36	−3.08 (18)
C12—C3—C21—C26	38.41 (16)	C32—C31—C36—N36	177.29 (11)
N1—C3—C21—C22	39.47 (17)	O363—N36—C36—C35	−7.5 (9)
C12—C3—C21—C22	−143.50 (12)	O362—N36—C36—C35	−144.83 (16)
C26—C21—C22—C23	0.68 (19)	O361—N36—C36—C35	33.3 (2)
C3—C21—C22—C23	−177.42 (12)	O364—N36—C36—C35	173.3 (8)
C26—C21—C22—Cl1	−177.61 (10)	O363—N36—C36—C31	174.1 (8)
C3—C21—C22—Cl1	4.29 (17)	O362—N36—C36—C31	36.8 (2)
C21—C22—C23—C24	0.2 (2)	O361—N36—C36—C31	−145.06 (19)
Cl1—C22—C23—C24	178.56 (13)	O364—N36—C36—C31	−5.1 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···O31	0.870 (19)	1.865 (19)	2.6847 (13)	156.3 (17)
N2—H72···O31ⁱ	0.836 (18)	2.047 (18)	2.8331 (13)	156.4 (16)
N2—H72···O362ⁱ	0.836 (18)	2.400 (17)	2.9495 (16)	123.9 (14)
C2—H2A···O321	0.99	2.49	3.2465 (16)	133
C2—H2B···O342ⁱⁱ	0.99	2.48	3.2505 (17)	134
C23—H23···O321ⁱⁱⁱ	0.95	2.51	3.4193 (18)	161

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄ClN₂OS⁺·C₆H₂N₃O₇⁻
M_r	533.90
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	10.5704 (2), 20.0667 (5), 11.3741 (2)
β (°)	110.666 (1)
V (Å³)	2257.35 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.59 × 0.49 × 0.36

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008).
T_min, T_max	0.807, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	21254, 5607, 5073
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.081, 1.05
No. of reflections	5607
No. of parameters	343
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.24

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H71···O31	0.870 (19)	1.865 (19)	2.6847 (13)	156.3 (17)
N2—H72···O31ⁱ	0.836 (18)	2.047 (18)	2.8331 (13)	156.4 (16)
N2—H72···O362ⁱ	0.836 (18)	2.400 (17)	2.9495 (16)	123.9 (14)
C2—H2A···O321	0.99	2.49	3.2465 (16)	133.2
C2—H2B···O342ⁱⁱ	0.99	2.48	3.2505 (17)	134.3
C23—H23···O321ⁱⁱⁱ	0.95	2.51	3.4193 (18)	161.4

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

Acknowledgements

ASD thanks the University of Mysore for research facilities. HSY thanks R. L. Fine Chem., Bengaluru, for the gift sample.

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2008). SADABS. Bruker Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Evans, B., Pipe, A., Clarke, L. & Banks, M. (2001). Bioorg. Med. Chem. Lett. 11, 1297–1300. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Jasinski, J. P., Butcher, R. J., Yathirajan, H. S., Narayana, B. & Prakash Kamath, K. (2010). Acta Cryst. E66, o1187–o1188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Robol, J. A., Cimarusti, M. P., Simpkins, L. M., Brown, B., Ryono, D. E., Bird, M. M., Asad, T. R., Schaeffer, N. C. & Trippodo, N. C. (1996). J. Med. Chem. 39, 494–502. CrossRef PubMed Web of Science Google Scholar
Scammells, P. J., Tranberg, C. E. & Tiekink, E. R. T. (2001). Acta Cryst. E57, o344–o345. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages o516-o517

doi:10.1107/S1600536812002607

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

(E)-5-(2-Chloro­phen­yl)-7-ethyl-2-oxo-2,3-di­hydro-1H-thieno[2,3-e][1,4]diazepin-4-ium 2,4,6-tri­nitro­phenolate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(E)-5-(2-Chlorophenyl)-7-ethyl-2-oxo-2,3-dihydro-1H-thieno[2,3-e][1,4]diazepin-4-ium 2,4,6-trinitrophenolate