4-(Furan-2-carbon­yl)piperazin-1-ium 3,5-di­nitro­benzoate

Channappa N Kavitha; Manpreet Kaur; Jerry P Jasinski; Ray J Butcher; HS Yathirajan

doi:10.1107/S160053681401126X

. 2014 May 24;70(Pt 6):o700–o701. doi: 10.1107/S160053681401126X

4-(Furan-2-carbonyl)piperazin-1-ium 3,5-dinitrobenzoate

Channappa N Kavitha ^a, Manpreet Kaur ^a, Jerry P Jasinski ^b,^*, Ray J Butcher ^c, HS Yathirajan ^a

PMCID: PMC4051063 PMID: 24940274

Abstract

In the cation of the title salt, C₉H₁₃N₂O₂ ⁺·C₇H₃N₂O₆ ⁻, the piperazine ring adopts a slightly distorted chair conformation. Twofold rotational disorder is exhibited by the furan ring in a 0.430 (4):0.570 (4) ratio. In the crystal, N—H⋯O hydrogen bonds link the ions into chains along [010]. Additional weak C—H⋯O interactions are observed, leading to a supramolecular layer parallel to (011).

Related literature

For the synthesis of the drug Prazosin {systematic name: 2-[4-(2-furoyl)piperazin-1-yl]-6,7-dimethoxyquinazolin-4-amine}, see: Honkanen et al. (1980 ▶). For the drug 1(2-furoyl)piperazine, used in the treatment of high blood pressure and anxiety, see: Brogden et al. (1977 ▶). For therapeutic uses of piperazines, see: Brockunier et al. (2004 ▶); Bogatcheva et al. (2006 ▶). For the use of the piperazine moiety in the construction of bioactive molecules, see: Choudhary et al. (2006 ▶). For a related structure, see: Dayananda et al. (2012 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). graphic file with name e-70-0o700-scheme1.jpg

Experimental

Crystal data

C₉H₁₃N₂O₂ ⁺·C₇H₃N₂O₆ ⁻
M _r = 392.33
Orthorhombic,
a = 9.6060 (2) Å
b = 10.4572 (2) Å
c = 33.8766 (7) Å
V = 3402.97 (13) Å³
Z = 8
Cu Kα radiation
μ = 1.08 mm⁻¹
T = 173 K
0.28 × 0.22 × 0.18 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.863, T _max = 1.000
21195 measured reflections
3352 independent reflections
2915 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.02
3352 reflections
270 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401126X/tk5314sup1.cif

e-70-0o700-sup1.cif^{(31.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401126X/tk5314Isup2.hkl

e-70-0o700-Isup2.hkl^{(184.1KB, hkl)}

Click here for additional data file.^{(7KB, cml)}

Supporting information file. DOI: 10.1107/S160053681401126X/tk5314Isup3.cml

CCDC reference: 1003444

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2B—H2BA⋯O1A ⁱ	0.99	2.51	3.1607 (16)	123
N2B—H2BA⋯O2A ⁱ	0.99	1.72	2.7093 (16)	176
N2B—H2BB⋯O1A ⁱⁱ	0.99	1.77	2.7424 (16)	166
C5A—H5A⋯O2A ⁱⁱⁱ	0.95	2.47	3.3170 (18)	148
C9B—H9B⋯O6A ^iv	0.95	2.44	3.183 (6)	134
C8BB—H8BB⋯O3A ^v	0.95	2.50	3.395 (5)	158
C2B—H2BC⋯O1B ⁱ	0.99	2.59	3.2300 (19)	122

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

CNK thanks the University of Mysore for research facilities and is also grateful to the Principal, Maharani’s Science College for Women, Mysore, for giving permission to undertake research. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

1. Chemical context

2. Structural commentary

1(2-Furoyl)piperazine, used to synthesise the drug Prazosin (Honkanen et al., 1980), is the first of a new class of anti-hypertensives. It is a sympatholytic drug used to treat high blood pressure and anxiety (Brogden et al.,1977). Piperazines are found in biologically active compounds across a number of different therapeutic areas (Brockunier et al., 2004; Bogatcheva et al., 2006). The piperazine moiety is extensively employed to construct various bioactive molecules with anti-bacterial and anti-malarial activity, and as anti-psychotic agents (Choudhary et al., 2006). The crystal structures of a similar salt viz., cinnarizinium 3,5-dinitrosalicylate (Dayananda et al., 2012) has been reported. In view of the above importance of piperazines, this paper reports the crystal structure of the title salt, (I) C₉H₁₃N₂O₂⁺. C₇H₃N₂O₆^-.

The title compound, (I), crystallizes with one independent piperazinium cation and a 3,5-dinitrobenzoate anion in the asymmetric unit (Fig. 1). In the cation, the piperazine ring adopts a slightly distorted chair conformation with puckering parameters Q, θ, and φ = 0.5552 (15)Å, 173.13 (14)° and 4.2 (14)°, respectively (Cremer & Pople, 1975). Two-fold rotational disorder is exhibited by the furan ring in a 0.430 (4):0.570 (4) ratio represents two different conformations of the molecule that exist in the same crystal form. N—H···O intermolecular hydrogen bonds link the cations and anions into infinite 1-D chains along [0 1 0] (Fig. 2). Additional weak C—H···O intermolecular interactions are observed (Table 1) forming chains along [0 0 1] resulting in a 2-D supramolecular network structure.

3. Supramolecular features

4. Database survey

5. Synthesis and crystallization

1(2-Furoyl)piperazine (0.9 g, 0.005 mol) and 3,5-dinitrobenzoic acid (1.0 g, 0.005 mol) were dissolved in N,N-dimethylformamide and stirred for 10 minutes at 333 K. The resulting solution was allowed to cool slowly at room temperature. The crystals of salt (I) (M.pt: 453–459 K) appeared after a few days.

6. Refinement

All of the H atoms were placed in their calculated positions and then refined using the riding model with atom—H lengths of 0.95 Å (CH); 0.99 Å (CH₂) and 0.92 Å (NH₂), and with U_iso = 1.2 x U_eq(parent atom). Owing to poor agreement, the following reflections were omitted from the final cycles of refinement: (2 2 2), (1 2 3), (1 0 6), (0 2 2), (0 4 1), (2 3 0), (1 2 4), (2 1 2), (1 2 1), (2 3 2) and (1 1 13).