1-Piperonylpiperazinium 4-nitro­benzoate monohydrate

Kavitha, C.N.; Kaur, M.; Anderson, B.J.; Jasinski, J.P.; Yathirajan, H.S.

doi:10.1107/S160053681400261X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 3| March 2014| Pages o270-o271

doi:10.1107/S160053681400261X

Open

access

1-Piperonylpiperazinium 4-nitrobenzoate monohydrate

Channappa N. Kavitha,^a Manpreet Kaur,^a Brian J. Anderson,^b Jerry P. Jasinski ^b ^* and H. S. Yathirajan ^a

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 22 January 2014; accepted 5 February 2014; online 12 February 2014)

In the title hydrated salt [systematic name: 1-(1,3-benzodioxol-5-ylmethyl)piperazin-1-ium 4-nitrobenzoate monohydrate], C₁₂H₁₇N₂O₂⁺·C₇H₄NO₄⁻·H₂O, the piperazinium ring of the cation adopts a slightly distorted chair conformation. The piperonyl and piperazine rings are rotated with respect to each other with an N—C—C—C torsion angle of 45.6 (2)°. In the anion, the nitro group is almost coplanar with the adjacent benzene ring, forming a dihedral angle of only 3.9 (4)°. In the crystal, the cations, anions and water molecules are linked through N—H⋯O and O—H⋯O hydrogen bonds into chains along the a axis. In addition, weaker intermolecular C—H⋯O interactions are also observed within the chains. The anions form centrosymmetric couples through π-stacking interactions, with an intercentroid distance of 3.681 (4) Å between the benzene rings.

CCDC reference: 985155

Related literature

For the drug, piribedil {systematic name: 2-[4-(benzo[1,3]dioxol-5-ylmethyl)piperazin-1-yl]pyrimidine}, an antiparkinsonian agent, see: Millan et al. (2001 ). For piperonylpiperazine derivatives with α-adrenergic antagonist and vasodilator properties, see: Gobert et al. (2003 ); Gilbert et al. (1968 ). For the use of piperazine in the construction of various bioactive molecules, see: Choudhary et al. (2006 ). For the antimicrobial activity of piperazine derivatives, see: Kharb et al. (2012 ). For related biologically active compounds, see: Brockunier et al. (2004 ); Bogatcheva et al. (2006 ). For a review on the current pharmacological and toxicological information for piperazine derivatives, see: Elliott (2011 ). For a related structure, see: Capuano et al. (2000 ). For puckering parameters, see Cremer & Pople (1975 ). For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₇N₂O₂⁺·C₇H₄NO₄⁻·H₂O
M_r = 405.40
Triclinic, $[P \overline 1]$
a = 6.0745 (5) Å
b = 12.0617 (11) Å
c = 13.4817 (10) Å
α = 92.561 (7)°
β = 98.753 (7)°
γ = 93.326 (7)°
V = 973.20 (14) Å³
Z = 2
Cu Kα radiation
μ = 0.90 mm⁻¹
T = 173 K
0.42 × 0.36 × 0.24 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.882, T_max = 1.000
6403 measured reflections
3761 independent reflections
3196 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.120
S = 1.03
3761 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AA⋯O1Wⁱ	0.94	1.84	2.7800 (16)	172
N2A—H2AB⋯O1Bⁱⁱ	0.93	1.80	2.7262 (16)	175
C9A—H9AA⋯O2Aⁱⁱⁱ	0.99	2.58	3.3260 (19)	132
C10A—H10A⋯O1W^iv	0.99	2.51	3.2833 (19)	135
O1W—H1WA⋯O2B^v	0.90	1.76	2.6526 (16)	170
O1W—H1WB⋯O1Bⁱⁱ	0.92	1.90	2.7867 (16)	163
Symmetry codes: (i) -x, -y+1, -z; (ii) -x+1, -y+1, -z; (iii) -x, -y+1, -z+1; (iv) x-1, y, z; (v) -x+2, -y+1, -z.

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 ; Palatinus & van der Lee, 2008 ; Palatinus et al., 2012 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 985155

Crystal structure: contains datablock I. DOI: 10.1107/S160053681400261X/ld2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681400261X/ld2118Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681400261X/ld2118Isup3.cml

checkCIF report

Comment top

1-(3,4-Methylenedioxybenzyl)piperazine or 1-piperonylpiperazine is a psychoactive drug of the piperazine class and is used to synthesise the drug, piribedil, an antiparkinsonian agent (Millan et al., 2001). Piperonylpiperazine derivatives also has α-adrenergic antagonist properties (Gobert et al., 2003) and peripheral vasodilator properties (Gilbert et al., 1968). The piperazine moiety is extensively employed to construct various bioactive molecules with anti-bacterial, antimalarial activity and as antipsychotic agents (Choudhary et al., 2006). A valuable insight into recent advances on antimicrobial activity of piperazine derivatives is reported (Kharb et al., 2012). Piperazines are among the most important building blocks in today's drug discovery and are found in biologically active compounds across a number of different therapeutic areas (Brockunier et al., 2004; Bogatcheva et al., 2006). A review on the current pharmacological and toxicological information for piperazine derivatives is available (Elliott, 2011). The crystal structure of an N-piperonyl analogue of the atypical antipsychotic clozapine (Capuano et al., 2000) is reported. In continuation of our work on salts of piperonylpiperazines, this paper reports the crystal structure of the title compound, (I), C₁₂H₁₇N₂O₂⁺ . C₇H₄NO₄^- . H₂O.

The asymmetric unit of the title compound, (I), contains one independent 1-piperonylpiperazinium monocation, one 4-nitrobenzoate monoanion and one water molecule (Fig. 1). The piperazine ring in the cation adopts a slightly disordered chair conformation (puckering parameters Q, θ, and φ = 0.590 (2)Å, 3.8 (6)° and 1.68 (4)°; (Cremer & Pople, 1975). The piperonyl and piperazine rings are twisted with respect to each other with an N1A/C1A/C2A/C8A torsion angle of 45.6 (2)°. In the anion, the nitro substituent is slightly twisted from the mean plane of the phenyl ring with a dihedral angle of 3.9 (4)°. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, the cations and anions interact through N—H···O intermolecular hydrogen bonds while weak C—H···O intermolecular interactions are observed between the cations (Fig. 2). The crystal packing is stabilized by these N—H···O and O—H···O intermolecular hydrogen bonds and weak C—H···O intermolecular interactions (Table 1) involving the water molecules which form 1D chains along [1 0 0]. In addition, weak Cg5–Cg5 π–π stacking interactions with an intercentroid distance of 3.681 (4)Å (Symmetry operation 2-x, -y, -z; Cg5 is the centroid between the phenyl rings, C1B–C6B, of the anions) contribute to the crystal packing.

Related literature top

For the drug, piribedil {systematic name: 2-[4-(benzo[1,3]dioxol-5-ylmethyl)piperazin-1-yl]pyrimidine}, an antiparkinsonian agent, see: Millan et al. (2001). For piperonylpiperazine derivatives with α-adrenergic antagonist and vasodilator properties, see: Gobert et al. (2003); Gilbert et al. (1968). For the use of piperazine in the construction of various bioactive molecules, see: Choudhary et al. (2006). For the antimicrobial activity of piperazine derivatives, see: Kharb et al. (2012); For related biologically active compounds, see: Brockunier et al. (2004); Bogatcheva et al. (2006). For a review on the current pharmacological and toxicological information for piperazine derivatives, see: Elliott (2011). For a related structure, see: Capuano et al. (2000). For puckering parameters, see Cremer & Pople (1975). For standard bond lengths, see: Allen et al. (1987).

Experimental top

1-piperonylpiperazine ( 2.2g, 0.01 mol) and p-nitrobenzoic acid (1.67 g, 0.01 mol) were dissolved in hot N,N-dimethylformamide and stirred for 10 mins at 323 K. The resulting solution was allowed to cool slowly at room temperature. The crystals of the title salt appeared after a few days was used as such for x-ray studies (m. p:448-451 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007; Palatinus & van der Lee, 2008; Palatinus et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. ORTEP drawing of one independent monocation-monoanion-water molecule unit in the asymmetric unit of (I) (C₁₂H₁₇N₂O₂⁺ . C₇H₄NO₄^- . H₂O) showing the labeling scheme with 30% probability displacement ellipsoids.
	Fig. 2. Molecular packing for (I) viewed along the b axis. Dashed lines indicate N—H···O, O—H···O intermolecular hydrogen bonds and weak C—H···O intermolecular interactions. H atoms not involved in hydrogen bonding have been removed for clarity.

1-(1,3-Benzodioxol-5-ylmethyl)piperazin-1-ium 4-nitrobenzoate monohydrate top

Crystal data top

C₁₂H₁₇N₂O₂⁺·C₇H₄NO₄⁻·H₂O	Z = 2
M_r = 405.40	F(000) = 428
Triclinic, P1	D_x = 1.383 Mg m⁻³
a = 6.0745 (5) Å	Cu Kα radiation, λ = 1.54184 Å
b = 12.0617 (11) Å	Cell parameters from 2866 reflections
c = 13.4817 (10) Å	θ = 3.3–72.4°
α = 92.561 (7)°	µ = 0.90 mm⁻¹
β = 98.753 (7)°	T = 173 K
γ = 93.326 (7)°	Irregular, colourless
V = 973.20 (14) Å³	0.42 × 0.36 × 0.24 mm

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3761 independent reflections
Radiation source: Enhance (Cu) X-ray Source	3196 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	R_int = 0.021
ω scans	θ_max = 72.4°, θ_min = 3.3°
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	h = −7→7
T_min = 0.882, T_max = 1.000	k = −14→13
6403 measured reflections	l = −16→15

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0563P)² + 0.0984P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.120	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.27 e Å⁻³
3761 reflections	Δρ_min = −0.20 e Å⁻³
263 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0049 (6)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₂H₁₇N₂O₂⁺·C₇H₄NO₄⁻·H₂O	γ = 93.326 (7)°
M_r = 405.40	V = 973.20 (14) Å³
Triclinic, P1	Z = 2
a = 6.0745 (5) Å	Cu Kα radiation
b = 12.0617 (11) Å	µ = 0.90 mm⁻¹
c = 13.4817 (10) Å	T = 173 K
α = 92.561 (7)°	0.42 × 0.36 × 0.24 mm
β = 98.753 (7)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	3761 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	3196 reflections with I > 2σ(I)
T_min = 0.882, T_max = 1.000	R_int = 0.021
6403 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
3761 reflections	Δρ_min = −0.20 e Å⁻³
263 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
O1A	0.5807 (2)	0.15502 (11)	0.58196 (11)	0.0590 (4)
O2A	0.5429 (2)	0.34467 (10)	0.59022 (10)	0.0501 (3)
N1A	−0.1474 (2)	0.41016 (10)	0.31368 (9)	0.0318 (3)
N2A	−0.1698 (2)	0.54167 (10)	0.14110 (9)	0.0332 (3)
H2AA	−0.2433	0.4918	0.0891	0.040*
H2AB	−0.1248	0.6053	0.1115	0.040*
C1A	−0.1964 (3)	0.31162 (14)	0.36785 (13)	0.0403 (4)
H1AA	−0.2762	0.2532	0.3195	0.048*
H1AB	−0.2965	0.3308	0.4166	0.048*
C2A	0.0109 (3)	0.26602 (13)	0.42328 (11)	0.0369 (3)
C3A	0.0366 (3)	0.15269 (14)	0.41979 (13)	0.0446 (4)
H3A	−0.0772	0.1047	0.3811	0.054*
C4A	0.2234 (3)	0.10638 (14)	0.47100 (14)	0.0500 (4)
H4A	0.2393	0.0285	0.4678	0.060*
C5A	0.3822 (3)	0.17849 (14)	0.52603 (12)	0.0426 (4)
C6A	0.6796 (3)	0.25825 (15)	0.62731 (13)	0.0466 (4)
H6AA	0.8318	0.2712	0.6106	0.056*
H6AB	0.6907	0.2575	0.7013	0.056*
C7A	0.3587 (3)	0.29153 (13)	0.53067 (11)	0.0375 (3)
C8A	0.1769 (3)	0.33840 (13)	0.48093 (12)	0.0378 (3)
H8A	0.1632	0.4165	0.4851	0.045*
C9A	−0.3555 (2)	0.45704 (13)	0.27135 (11)	0.0337 (3)
H9AA	−0.4451	0.4722	0.3254	0.040*
H9AB	−0.4436	0.4028	0.2212	0.040*
C10A	−0.3064 (3)	0.56353 (13)	0.22182 (12)	0.0353 (3)
H10A	−0.4481	0.5943	0.1927	0.042*
H10B	−0.2245	0.6190	0.2726	0.042*
C11A	0.0375 (2)	0.48756 (13)	0.18124 (12)	0.0349 (3)
H11A	0.1350	0.5397	0.2300	0.042*
H11B	0.1200	0.4685	0.1256	0.042*
C12A	−0.0217 (3)	0.38327 (12)	0.23225 (11)	0.0336 (3)
H12A	−0.1124	0.3295	0.1826	0.040*
H12B	0.1165	0.3483	0.2598	0.040*
O1B	1.02663 (19)	0.27812 (9)	−0.04752 (9)	0.0437 (3)
O2B	1.3475 (2)	0.26959 (12)	0.05605 (11)	0.0591 (4)
O3B	0.8956 (2)	−0.16582 (12)	0.28622 (10)	0.0616 (4)
O4B	0.5845 (2)	−0.15818 (12)	0.18715 (11)	0.0595 (4)
N1B	0.7773 (2)	−0.12428 (11)	0.21838 (10)	0.0409 (3)
C1B	1.0487 (2)	0.14427 (11)	0.07692 (11)	0.0301 (3)
C2B	1.1819 (2)	0.09318 (13)	0.15270 (12)	0.0357 (3)
H2B	1.3335	0.1195	0.1723	0.043*
C3B	1.0959 (3)	0.00431 (13)	0.19982 (12)	0.0369 (3)
H3B	1.1868	−0.0319	0.2505	0.044*
C4B	0.8739 (2)	−0.02983 (12)	0.17066 (11)	0.0319 (3)
C5B	0.7362 (2)	0.02062 (12)	0.09760 (11)	0.0329 (3)
H5B	0.5832	−0.0040	0.0803	0.039*
C6B	0.8256 (2)	0.10799 (12)	0.04996 (11)	0.0329 (3)
H6B	0.7341	0.1431	−0.0013	0.039*
C7B	1.1503 (3)	0.23837 (12)	0.02427 (12)	0.0355 (3)
O1W	0.34602 (17)	0.60766 (9)	0.01811 (8)	0.0378 (3)
H1WA	0.4609	0.6478	−0.0004	0.057*
H1WB	0.2443	0.6571	0.0317	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.0637 (8)	0.0486 (8)	0.0625 (8)	0.0261 (6)	−0.0051 (7)	−0.0006 (6)
O2A	0.0471 (7)	0.0435 (7)	0.0574 (8)	0.0115 (5)	−0.0010 (6)	−0.0032 (6)
N1A	0.0333 (6)	0.0342 (6)	0.0301 (6)	0.0046 (5)	0.0096 (5)	0.0081 (5)
N2A	0.0372 (7)	0.0298 (6)	0.0332 (6)	−0.0004 (5)	0.0060 (5)	0.0086 (5)
C1A	0.0417 (8)	0.0422 (9)	0.0399 (8)	0.0020 (7)	0.0123 (7)	0.0149 (7)
C2A	0.0452 (9)	0.0383 (8)	0.0305 (7)	0.0060 (7)	0.0124 (6)	0.0105 (6)
C3A	0.0591 (10)	0.0377 (9)	0.0374 (8)	0.0035 (7)	0.0081 (7)	0.0026 (7)
C4A	0.0716 (12)	0.0331 (8)	0.0468 (10)	0.0140 (8)	0.0095 (9)	0.0039 (7)
C5A	0.0532 (10)	0.0405 (9)	0.0366 (8)	0.0172 (7)	0.0085 (7)	0.0059 (7)
C6A	0.0491 (10)	0.0522 (10)	0.0404 (9)	0.0139 (8)	0.0073 (7)	0.0065 (8)
C7A	0.0456 (9)	0.0368 (8)	0.0326 (8)	0.0072 (7)	0.0123 (6)	0.0029 (6)
C8A	0.0468 (9)	0.0317 (8)	0.0384 (8)	0.0078 (6)	0.0138 (7)	0.0081 (6)
C9A	0.0312 (7)	0.0382 (8)	0.0332 (7)	0.0041 (6)	0.0081 (6)	0.0055 (6)
C10A	0.0354 (7)	0.0349 (8)	0.0368 (8)	0.0078 (6)	0.0065 (6)	0.0053 (6)
C11A	0.0315 (7)	0.0378 (8)	0.0375 (8)	0.0017 (6)	0.0105 (6)	0.0094 (6)
C12A	0.0374 (8)	0.0328 (7)	0.0335 (7)	0.0074 (6)	0.0114 (6)	0.0067 (6)
O1B	0.0434 (6)	0.0370 (6)	0.0553 (7)	0.0035 (5)	0.0167 (5)	0.0182 (5)
O2B	0.0420 (7)	0.0654 (9)	0.0692 (9)	−0.0174 (6)	0.0100 (6)	0.0172 (7)
O3B	0.0658 (9)	0.0635 (9)	0.0555 (8)	0.0021 (7)	0.0009 (7)	0.0353 (7)
O4B	0.0504 (7)	0.0568 (8)	0.0712 (9)	−0.0115 (6)	0.0075 (7)	0.0281 (7)
N1B	0.0471 (8)	0.0380 (7)	0.0393 (7)	0.0017 (6)	0.0096 (6)	0.0128 (6)
C1B	0.0330 (7)	0.0255 (7)	0.0334 (7)	0.0031 (5)	0.0107 (6)	−0.0002 (6)
C2B	0.0300 (7)	0.0373 (8)	0.0395 (8)	0.0008 (6)	0.0050 (6)	0.0015 (6)
C3B	0.0381 (8)	0.0400 (8)	0.0327 (8)	0.0077 (6)	0.0022 (6)	0.0080 (6)
C4B	0.0390 (8)	0.0286 (7)	0.0299 (7)	0.0032 (6)	0.0092 (6)	0.0056 (6)
C5B	0.0302 (7)	0.0327 (7)	0.0350 (8)	−0.0017 (6)	0.0032 (6)	0.0062 (6)
C6B	0.0338 (7)	0.0309 (7)	0.0338 (7)	0.0033 (6)	0.0027 (6)	0.0068 (6)
C7B	0.0367 (8)	0.0295 (7)	0.0436 (9)	0.0019 (6)	0.0170 (7)	0.0028 (6)
O1W	0.0347 (5)	0.0365 (6)	0.0422 (6)	−0.0020 (4)	0.0061 (5)	0.0073 (5)

Geometric parameters (Å, º) top

O1A—C5A	1.373 (2)	C9A—C10A	1.509 (2)
O1A—C6A	1.421 (2)	C10A—H10A	0.9900
O2A—C6A	1.431 (2)	C10A—H10B	0.9900
O2A—C7A	1.3802 (19)	C11A—H11A	0.9900
N1A—C1A	1.4619 (19)	C11A—H11B	0.9900
N1A—C9A	1.4617 (18)	C11A—C12A	1.511 (2)
N1A—C12A	1.4648 (18)	C12A—H12A	0.9900
N2A—H2AA	0.9422	C12A—H12B	0.9900
N2A—H2AB	0.9268	O1B—C7B	1.2622 (19)
N2A—C10A	1.4888 (19)	O2B—C7B	1.2400 (19)
N2A—C11A	1.4913 (18)	O3B—N1B	1.2192 (18)
C1A—H1AA	0.9900	O4B—N1B	1.2231 (18)
C1A—H1AB	0.9900	N1B—C4B	1.4693 (19)
C1A—C2A	1.509 (2)	C1B—C2B	1.393 (2)
C2A—C3A	1.384 (2)	C1B—C6B	1.388 (2)
C2A—C8A	1.408 (2)	C1B—C7B	1.516 (2)
C3A—H3A	0.9500	C2B—H2B	0.9500
C3A—C4A	1.395 (2)	C2B—C3B	1.387 (2)
C4A—H4A	0.9500	C3B—H3B	0.9500
C4A—C5A	1.366 (3)	C3B—C4B	1.379 (2)
C5A—C7A	1.379 (2)	C4B—C5B	1.379 (2)
C6A—H6AA	0.9900	C5B—H5B	0.9500
C6A—H6AB	0.9900	C5B—C6B	1.385 (2)
C7A—C8A	1.367 (2)	C6B—H6B	0.9500
C8A—H8A	0.9500	O1W—H1WA	0.8987
C9A—H9AA	0.9900	O1W—H1WB	0.9158
C9A—H9AB	0.9900

C5A—O1A—C6A	106.07 (13)	C10A—C9A—H9AA	109.6
C7A—O2A—C6A	105.74 (13)	C10A—C9A—H9AB	109.6
C1A—N1A—C12A	111.33 (12)	N2A—C10A—C9A	109.95 (12)
C9A—N1A—C1A	109.81 (12)	N2A—C10A—H10A	109.7
C9A—N1A—C12A	108.99 (11)	N2A—C10A—H10B	109.7
H2AA—N2A—H2AB	107.3	C9A—C10A—H10A	109.7
C10A—N2A—H2AA	113.1	C9A—C10A—H10B	109.7
C10A—N2A—H2AB	113.7	H10A—C10A—H10B	108.2
C10A—N2A—C11A	110.93 (11)	N2A—C11A—H11A	109.7
C11A—N2A—H2AA	104.7	N2A—C11A—H11B	109.7
C11A—N2A—H2AB	106.6	N2A—C11A—C12A	109.91 (12)
N1A—C1A—H1AA	109.0	H11A—C11A—H11B	108.2
N1A—C1A—H1AB	109.0	C12A—C11A—H11A	109.7
N1A—C1A—C2A	112.76 (13)	C12A—C11A—H11B	109.7
H1AA—C1A—H1AB	107.8	N1A—C12A—C11A	110.19 (12)
C2A—C1A—H1AA	109.0	N1A—C12A—H12A	109.6
C2A—C1A—H1AB	109.0	N1A—C12A—H12B	109.6
C3A—C2A—C1A	120.29 (15)	C11A—C12A—H12A	109.6
C3A—C2A—C8A	119.60 (15)	C11A—C12A—H12B	109.6
C8A—C2A—C1A	120.09 (14)	H12A—C12A—H12B	108.1
C2A—C3A—H3A	118.8	O3B—N1B—O4B	123.48 (14)
C2A—C3A—C4A	122.45 (17)	O3B—N1B—C4B	117.98 (14)
C4A—C3A—H3A	118.8	O4B—N1B—C4B	118.52 (13)
C3A—C4A—H4A	121.6	C2B—C1B—C7B	119.39 (13)
C5A—C4A—C3A	116.74 (16)	C6B—C1B—C2B	119.79 (14)
C5A—C4A—H4A	121.6	C6B—C1B—C7B	120.82 (13)
O1A—C5A—C7A	110.07 (15)	C1B—C2B—H2B	119.6
C4A—C5A—O1A	128.41 (16)	C3B—C2B—C1B	120.75 (14)
C4A—C5A—C7A	121.52 (16)	C3B—C2B—H2B	119.6
O1A—C6A—O2A	108.35 (14)	C2B—C3B—H3B	121.1
O1A—C6A—H6AA	110.0	C4B—C3B—C2B	117.81 (14)
O1A—C6A—H6AB	110.0	C4B—C3B—H3B	121.1
O2A—C6A—H6AA	110.0	C3B—C4B—N1B	119.33 (13)
O2A—C6A—H6AB	110.0	C3B—C4B—C5B	122.89 (14)
H6AA—C6A—H6AB	108.4	C5B—C4B—N1B	117.78 (13)
C5A—C7A—O2A	109.55 (14)	C4B—C5B—H5B	120.7
C8A—C7A—O2A	127.90 (14)	C4B—C5B—C6B	118.61 (13)
C8A—C7A—C5A	122.54 (15)	C6B—C5B—H5B	120.7
C2A—C8A—H8A	121.4	C1B—C6B—H6B	119.9
C7A—C8A—C2A	117.14 (14)	C5B—C6B—C1B	120.13 (13)
C7A—C8A—H8A	121.4	C5B—C6B—H6B	119.9
N1A—C9A—H9AA	109.6	O1B—C7B—C1B	117.18 (13)
N1A—C9A—H9AB	109.6	O2B—C7B—O1B	125.94 (15)
N1A—C9A—C10A	110.19 (12)	O2B—C7B—C1B	116.88 (14)
H9AA—C9A—H9AB	108.1	H1WA—O1W—H1WB	106.6

O1A—C5A—C7A—O2A	0.01 (19)	C9A—N1A—C1A—C2A	−173.67 (12)
O1A—C5A—C7A—C8A	179.33 (15)	C9A—N1A—C12A—C11A	61.80 (15)
O2A—C7A—C8A—C2A	179.03 (14)	C10A—N2A—C11A—C12A	55.02 (16)
N1A—C1A—C2A—C3A	−135.98 (16)	C11A—N2A—C10A—C9A	−55.19 (16)
N1A—C1A—C2A—C8A	45.6 (2)	C12A—N1A—C1A—C2A	65.54 (16)
N1A—C9A—C10A—N2A	58.74 (16)	C12A—N1A—C9A—C10A	−61.96 (15)
N2A—C11A—C12A—N1A	−58.34 (16)	O3B—N1B—C4B—C3B	3.6 (2)
C1A—N1A—C9A—C10A	175.85 (12)	O3B—N1B—C4B—C5B	−176.66 (15)
C1A—N1A—C12A—C11A	−176.93 (12)	O4B—N1B—C4B—C3B	−175.27 (15)
C1A—C2A—C3A—C4A	−178.95 (15)	O4B—N1B—C4B—C5B	4.5 (2)
C1A—C2A—C8A—C7A	178.88 (13)	N1B—C4B—C5B—C6B	−178.38 (13)
C2A—C3A—C4A—C5A	0.3 (3)	C1B—C2B—C3B—C4B	−1.4 (2)
C3A—C2A—C8A—C7A	0.5 (2)	C2B—C1B—C6B—C5B	−0.6 (2)
C3A—C4A—C5A—O1A	−179.27 (16)	C2B—C1B—C7B—O1B	176.26 (13)
C3A—C4A—C5A—C7A	0.0 (3)	C2B—C1B—C7B—O2B	−4.0 (2)
C4A—C5A—C7A—O2A	−179.42 (16)	C2B—C3B—C4B—N1B	179.53 (13)
C4A—C5A—C7A—C8A	−0.1 (3)	C2B—C3B—C4B—C5B	−0.2 (2)
C5A—O1A—C6A—O2A	−4.64 (19)	C3B—C4B—C5B—C6B	1.3 (2)
C5A—C7A—C8A—C2A	−0.2 (2)	C4B—C5B—C6B—C1B	−0.9 (2)
C6A—O1A—C5A—C4A	−177.74 (18)	C6B—C1B—C2B—C3B	1.8 (2)
C6A—O1A—C5A—C7A	2.89 (19)	C6B—C1B—C7B—O1B	−3.2 (2)
C6A—O2A—C7A—C5A	−2.88 (18)	C6B—C1B—C7B—O2B	176.51 (14)
C6A—O2A—C7A—C8A	177.85 (16)	C7B—C1B—C2B—C3B	−177.71 (13)
C7A—O2A—C6A—O1A	4.63 (19)	C7B—C1B—C6B—C5B	178.89 (13)
C8A—C2A—C3A—C4A	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O1Wⁱ	0.94	1.84	2.7800 (16)	172
N2A—H2AB···O1Bⁱⁱ	0.93	1.80	2.7262 (16)	175
C9A—H9AA···O2Aⁱⁱⁱ	0.99	2.58	3.3260 (19)	132
C10A—H10A···O1W^iv	0.99	2.51	3.2833 (19)	135
O1W—H1WA···O2B^v	0.90	1.76	2.6526 (16)	170
O1W—H1WB···O1Bⁱⁱ	0.92	1.90	2.7867 (16)	163

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2A—H2AA···O1Wⁱ	0.94	1.84	2.7800 (16)	171.5
N2A—H2AB···O1Bⁱⁱ	0.93	1.80	2.7262 (16)	175.4
C9A—H9AA···O2Aⁱⁱⁱ	0.99	2.58	3.3260 (19)	132.0
C10A—H10A···O1W^iv	0.99	2.51	3.2833 (19)	134.9
O1W—H1WA···O2B^v	0.90	1.76	2.6526 (16)	169.8
O1W—H1WB···O1Bⁱⁱ	0.92	1.90	2.7867 (16)	162.8

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

Acknowledgements

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.

References

Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, England. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bogatcheva, E., Hanrahan, C., Nikonenko, B., Samala, R., Chen, P., Gearhart, J., Barbosa, F., Einck, L., Nacy, C. A. & Protopopova, M. (2006). J. Med. Chem. 49, 3045–3048. Web of Science CrossRef PubMed CAS Google Scholar
Brockunier, L. L., He, J., Colwell, L. F. Jr, Habulihaz, B., He, H., Leiting, B., Lyons, K. A., Marsilio, F., Patel, R. A., Teffera, Y., Wu, J. K., Thornberry, N. A., Weber, A. E. & Parmee, E. R. (2004). Bioorg. Med. Chem. Lett. 14, 4763–4766. Web of Science CrossRef PubMed CAS Google Scholar
Capuano, B., Crosby, I. T., Gable, R. W. & Lloyd, E. J. (2000). Acta Cryst. C56, 339–340. CSD CrossRef CAS IUCr Journals Google Scholar
Choudhary, P., Kumar, R. & Verma, K. (2006). Bioorg. Med. Chem. 14, 1819–1826. Web of Science CrossRef PubMed Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Elliott, S. (2011). Drug Test Anal. 3, 430–438. Web of Science CrossRef CAS PubMed Google Scholar
Gilbert, R., Canevari, R. J. M. J., Laubie, M. J. & Le Douarec, J. C. (1968). J. Med. Chem. 11, 1151–1155. PubMed Web of Science Google Scholar
Gobert, A., Di Cara, B., Cistarelli, L. & Millan, M. J. (2003). J. Pharmacol. Exp. Ther. 305, 338–46. Web of Science CrossRef PubMed CAS Google Scholar
Kharb, R., Bansal, K. & Sharma, A. K. (2012). Pharma Chem. 4, 2470–2488. CAS Google Scholar
Millan, M. J., Cussac, D. & Milligan, G. (2001). J. Pharmacol. Exp. Ther. 297, 876–887. Web of Science PubMed CAS Google Scholar
Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786–790. Web of Science CrossRef CAS IUCr Journals Google Scholar
Palatinus, L., Prathapa, S. J. & van Smaalen, S. (2012). J. Appl. Cryst. 45, 575–580. Web of Science CrossRef CAS IUCr Journals Google Scholar
Palatinus, L. & van der Lee, A. (2008). J. Appl. Cryst. 41, 975–984. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar