4-Nitro-phenol-piperazine (2/1).

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-nitro-phenol ring. In the crystal, the piperazine ring is linked to two 4-nitro-phenol mol-ecules via O-H⋯N hydrogen bonds. The mol-ecules 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 = 182.18

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.111

S = 1.04

1763 reflections

126 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.17 e Å−3

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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813015328/su2605sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015328/su2605Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813015328/su2605Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H5NO3·0.5C4H10N2	F(000) = 384
Mr = 182.18	Dx = 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

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

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(Fo2) + (0.0534P)2 + 0.1751P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1763 reflections	Δρmax = 0.19 e Å−3
126 parameters	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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

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) ; (ii) .