4-Nitro­phenol–piperazine (2/1)

Nagapandiselvi, P.; Muralidharan, S.; Srinivasan, T.; Goplalakrishnan, R.; Velmurugan, D.

doi:10.1107/S1600536813015328

organic compounds

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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Page o1044

https://doi.org/10.1107/S1600536813015328

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4-Nitrophenol–piperazine (2/1)

Perumal Nagapandiselvi,^a Srinivasan Muralidharan,^a Thothadri Srinivasan,^b Rengaswamy Goplalakrishnan ^a and Devadasan Velmurugan ^b ^*

^aDepartment of Physics, Anna University, Chennai 600 025, India, and ^bCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 20 May 2013; accepted 3 June 2013; online 8 June 2013)

In the title adduct, C₆H₅NO₃·0.5C₄H₁₀N₂, the piperazine ring possesses inversion symmetry and has a chair conformation. Its mean plane makes a dihedral angle of 65.45 (7)° with the 4-nitrophenol ring. In the crystal, the piperazine ring is linked to two 4-nitrophenol molecules via O—H⋯N hydrogen bonds. The molecules are also linked via bifurcated N—H⋯(O,O) hydrogen bonds involving the NO₂ O atoms, forming a two-dimensional network lying parallel to (102). The networks are linked via C—H⋯O hydrogen bonds, forming a three-dimensional structure.

Related literature

For the biological properties of piperazine compounds, see: Foroumadi et al. (2007 ); Upadhayaya et al. (2004 ); Chen et al. (2006 ); Cunico et al. (2009 ); Smits et al. (2008 ); Becker et al. (2006 ).

Experimental

Crystal data

C₆H₅NO₃·0.5C₄H₁₀N₂
M_r = 182.18
Monoclinic, P 2₁ /c
a = 6.1879 (2) Å
b = 19.9274 (7) Å
c = 6.9846 (2) Å
β = 91.199 (1)°
V = 861.07 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.968, T_max = 0.979
12570 measured reflections
1763 independent reflections
1437 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.111
S = 1.04
1763 reflections
126 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N2ⁱ	0.82	1.82	2.6210 (16)	167
N2—H2A⋯O1	0.796 (19)	2.58 (2)	3.2437 (17)	141.4 (17)
N2—H2A⋯O2	0.796 (19)	2.557 (19)	3.2273 (17)	142.8 (19)
C2—H2⋯O1ⁱ	0.93	2.51	3.3428 (17)	149
C6—H6⋯O3ⁱⁱ	0.93	2.57	3.5035 (17)	179
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813015328/su2605sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015328/su2605Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813015328/su2605Isup3.cml

checkCIF report

Comment top

Piperazine-based research has attracted considerable attention in recent years. A broad range of compounds displaying antibacterial (Foroumadi et al., 2007), antifungal (Upadhayaya et al., 2004), anticancer (Chen et al., 2006), antiparasitic (Cunico et al., 2009), antihistamin (Smits et al., 2008), and antidepressive activities (Becker et al., 2006) have been found to contain this versatile core. In view of these important properties, we have undertaken the X-ray diffraction study of the title compound.

In the title adduct, C₆H₅N₁O₃, 0.5(C₄H₁₀N₂), the piperazine ring (N2/C7/C8/N2a/C7a/C8a) possesses inversion symmetry. It adopts a chair conformation and its mean plane makes a dihedral angle of 65.45 (7)° with the 4-nitrophenol ring (C1-C6).

In the crystal, the piperazine ring is linked to two 4-nitrophenol molecules via O-H···N hydrogen bonds (Table 1 and Fig 2). The molecules are also linked via bifurcated N-H···O/O hydrogen bonds, involving the NO₂ O atoms, forming a two-dimensional network lying parallel to (102). These networks are linked via C-H···O hydrogen bonds forming a three-dimensional structure (Table 1).

Related literature top

For the biological properties of piperazine compounds, see: Foroumadi et al. (2007); Upadhayaya et al. (2004); Chen et al. (2006); Cunico et al. (2009); Smits et al. (2008); Becker et al. (2006).

Experimental top

Piperazine 4-nitrophenol was synthesized by mixing an equimolar mixture (1:1) of anhydrous piperazine and 4-nitrophenol in methanol. The resultant solution was stirred magnetically at room temperature and filtered into a clean beaker. The filtrate was kept in a constant temperature bath at 308 K. Yellow block-like crystals suitable for x-ray diffraction were harvested from the solution within a day.

Structure description top

For the biological properties of piperazine compounds, see: Foroumadi et al. (2007); Upadhayaya et al. (2004); Chen et al. (2006); Cunico et al. (2009); Smits et al. (2008); Becker et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2012) and PLATON (Spek, 2009); 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 atom labelling. Displacement ellipsoids are drawn at the 30% probability level (symmetry code: (a) = -x+2, -y, -z+1).
	Fig. 2. The crystal packing of the title compound viewed along the a axis. The N-H···O, O-H···N and C-H···O hydrogen bonds are shown as dashed lines; see Table 1 for details. The H atoms not involved in hydrogen bonding have been omitted for clarity.

4-Nitrophenol–piperazine (2/1) top

Crystal data top

C₆H₅NO₃·0.5C₄H₁₀N₂	F(000) = 384
M_r = 182.18	D_x = 1.405 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1763 reflections
a = 6.1879 (2) Å	θ = 2.0–26.4°
b = 19.9274 (7) Å	µ = 0.11 mm⁻¹
c = 6.9846 (2) Å	T = 293 K
β = 91.199 (1)°	Block, yellow
V = 861.07 (5) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEXII area-detector diffractometer	1763 independent reflections
Radiation source: fine-focus sealed tube	1437 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and φ scans	θ_max = 26.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −7→7
T_min = 0.968, T_max = 0.979	k = −24→24
12570 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0534P)² + 0.1751P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1763 reflections	Δρ_max = 0.19 e Å⁻³
126 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (4)

Crystal data top

C₆H₅NO₃·0.5C₄H₁₀N₂	V = 861.07 (5) Å³
M_r = 182.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1879 (2) Å	µ = 0.11 mm⁻¹
b = 19.9274 (7) Å	T = 293 K
c = 6.9846 (2) Å	0.30 × 0.25 × 0.20 mm
β = 91.199 (1)°

Data collection top

Bruker SMART APEXII area-detector diffractometer	1763 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1437 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.979	R_int = 0.024
12570 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.19 e Å⁻³
1763 reflections	Δρ_min = −0.17 e Å⁻³
126 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.

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 > 2sigma(F²) is used only for calculating R-factors(gt) 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
C1	0.3284 (2)	0.39314 (6)	0.57841 (18)	0.0431 (3)
C2	0.2308 (2)	0.33121 (6)	0.61501 (19)	0.0446 (3)
H2	0.0929	0.3300	0.6654	0.053*
C3	0.3365 (2)	0.27233 (6)	0.57715 (19)	0.0436 (3)
H3	0.2711	0.2313	0.6019	0.052*
C4	0.5409 (2)	0.27456 (6)	0.50202 (18)	0.0412 (3)
C5	0.6389 (2)	0.33516 (7)	0.45997 (18)	0.0460 (3)
H5	0.7756	0.3359	0.4072	0.055*
C6	0.5330 (2)	0.39403 (7)	0.4966 (2)	0.0474 (3)
H6	0.5974	0.4348	0.4670	0.057*
C7	0.8041 (2)	−0.00321 (8)	0.3919 (2)	0.0604 (4)
H7A	0.7274	−0.0085	0.2703	0.073*
H7B	0.6982	0.0024	0.4911	0.073*
C8	1.0620 (3)	0.06407 (7)	0.5674 (2)	0.0615 (4)
H8A	0.9605	0.0707	0.6697	0.074*
H8B	1.1545	0.1033	0.5618	0.074*
N1	0.65536 (19)	0.21262 (6)	0.46944 (16)	0.0506 (3)
N2	0.9439 (2)	0.05619 (6)	0.38520 (18)	0.0515 (3)
O1	0.84102 (19)	0.21550 (6)	0.4113 (2)	0.0764 (4)
O2	0.56486 (19)	0.15891 (5)	0.50020 (17)	0.0672 (3)
O3	0.23383 (18)	0.45125 (5)	0.61778 (16)	0.0628 (3)
H3A	0.1330	0.4447	0.6898	0.094*
H2A	0.867 (3)	0.0873 (10)	0.362 (3)	0.071 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0508 (7)	0.0362 (6)	0.0425 (7)	0.0028 (5)	0.0080 (5)	−0.0010 (5)
C2	0.0394 (6)	0.0439 (7)	0.0507 (7)	0.0000 (5)	0.0092 (5)	−0.0019 (5)
C3	0.0464 (7)	0.0370 (6)	0.0473 (7)	−0.0033 (5)	0.0015 (6)	−0.0022 (5)
C4	0.0439 (7)	0.0420 (7)	0.0376 (6)	0.0076 (5)	−0.0014 (5)	−0.0052 (5)
C5	0.0397 (7)	0.0547 (8)	0.0438 (7)	0.0013 (5)	0.0079 (5)	−0.0017 (6)
C6	0.0521 (8)	0.0420 (7)	0.0486 (7)	−0.0058 (6)	0.0106 (6)	0.0011 (5)
C7	0.0445 (7)	0.0688 (10)	0.0680 (9)	−0.0099 (7)	0.0014 (6)	0.0101 (8)
C8	0.0785 (10)	0.0362 (7)	0.0703 (10)	−0.0139 (7)	0.0146 (8)	−0.0050 (6)
N1	0.0530 (7)	0.0529 (7)	0.0458 (6)	0.0152 (5)	−0.0031 (5)	−0.0079 (5)
N2	0.0537 (7)	0.0356 (6)	0.0658 (8)	0.0096 (5)	0.0141 (6)	0.0094 (5)
O1	0.0564 (7)	0.0762 (8)	0.0972 (10)	0.0210 (6)	0.0138 (6)	−0.0163 (6)
O2	0.0812 (8)	0.0428 (6)	0.0776 (8)	0.0125 (5)	0.0034 (6)	−0.0018 (5)
O3	0.0740 (7)	0.0385 (5)	0.0772 (8)	0.0080 (5)	0.0329 (6)	0.0014 (5)

Geometric parameters (Å, º) top

C1—O3	1.3290 (15)	C7—N2	1.4673 (18)
C1—C6	1.3995 (19)	C7—C8ⁱ	1.493 (2)
C1—C2	1.4000 (17)	C7—H7A	0.9700
C2—C3	1.3720 (18)	C7—H7B	0.9700
C2—H2	0.9300	C8—N2	1.463 (2)
C3—C4	1.3799 (19)	C8—C7ⁱ	1.493 (2)
C3—H3	0.9300	C8—H8A	0.9700
C4—C5	1.3855 (18)	C8—H8B	0.9700
C4—N1	1.4434 (16)	N1—O1	1.2279 (16)
C5—C6	1.3706 (18)	N1—O2	1.2290 (16)
C5—H5	0.9300	N2—H2A	0.80 (2)
C6—H6	0.9300	O3—H3A	0.8200

O3—C1—C6	118.65 (11)	N2—C7—H7A	109.7
O3—C1—C2	122.45 (12)	C8ⁱ—C7—H7A	109.7
C6—C1—C2	118.90 (11)	N2—C7—H7B	109.7
C3—C2—C1	120.60 (12)	C8ⁱ—C7—H7B	109.7
C3—C2—H2	119.7	H7A—C7—H7B	108.2
C1—C2—H2	119.7	N2—C8—C7ⁱ	110.09 (12)
C2—C3—C4	119.37 (12)	N2—C8—H8A	109.6
C2—C3—H3	120.3	C7ⁱ—C8—H8A	109.6
C4—C3—H3	120.3	N2—C8—H8B	109.6
C3—C4—C5	121.15 (11)	C7ⁱ—C8—H8B	109.6
C3—C4—N1	119.28 (12)	H8A—C8—H8B	108.2
C5—C4—N1	119.57 (12)	O1—N1—O2	122.10 (12)
C6—C5—C4	119.55 (12)	O1—N1—C4	118.54 (12)
C6—C5—H5	120.2	O2—N1—C4	119.36 (12)
C4—C5—H5	120.2	C8—N2—C7	110.05 (11)
C5—C6—C1	120.37 (12)	C8—N2—H2A	112.3 (14)
C5—C6—H6	119.8	C7—N2—H2A	106.6 (14)
C1—C6—H6	119.8	C1—O3—H3A	109.5
N2—C7—C8ⁱ	109.63 (11)

O3—C1—C2—C3	−178.17 (12)	O3—C1—C6—C5	177.78 (12)
C6—C1—C2—C3	2.1 (2)	C2—C1—C6—C5	−2.5 (2)
C1—C2—C3—C4	−0.1 (2)	C3—C4—N1—O1	−176.52 (12)
C2—C3—C4—C5	−1.5 (2)	C5—C4—N1—O1	2.59 (19)
C2—C3—C4—N1	177.55 (11)	C3—C4—N1—O2	3.58 (19)
C3—C4—C5—C6	1.2 (2)	C5—C4—N1—O2	−177.31 (11)
N1—C4—C5—C6	−177.93 (11)	C7ⁱ—C8—N2—C7	59.04 (16)
C4—C5—C6—C1	0.9 (2)	C8ⁱ—C7—N2—C8	−58.77 (17)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2ⁱⁱ	0.82	1.82	2.6210 (16)	167
N2—H2A···O1	0.796 (19)	2.58 (2)	3.2437 (17)	141.4 (17)
N2—H2A···O2	0.796 (19)	2.557 (19)	3.2273 (17)	142.8 (19)
C2—H2···O1ⁱⁱ	0.93	2.51	3.3428 (17)	149
C6—H6···O3ⁱⁱⁱ	0.93	2.57	3.5035 (17)	179

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

Experimental details

Crystal data
Chemical formula	C₆H₅NO₃·0.5C₄H₁₀N₂
M_r	182.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.1879 (2), 19.9274 (7), 6.9846 (2)
β (°)	91.199 (1)
V (Å³)	861.07 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.968, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	12570, 1763, 1437
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.111, 1.04
No. of reflections	1763
No. of parameters	126
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), 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
O3—H3A···N2ⁱ	0.82	1.82	2.6210 (16)	167
N2—H2A···O1	0.796 (19)	2.58 (2)	3.2437 (17)	141.4 (17)
N2—H2A···O2	0.796 (19)	2.557 (19)	3.2273 (17)	142.8 (19)
C2—H2···O1ⁱ	0.93	2.51	3.3428 (17)	149
C6—H6···O3ⁱⁱ	0.93	2.57	3.5035 (17)	179

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

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. TS and DV thank the UGC (SAP–CAS) for the departmental facilities. TS also thanks DST Inspire for a fellowship.

References

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