Morpholine-4-nitro-phenol (1/2).

In the title adduct, 2C6H5NO3·C4H9NO, the morpholine ring adopts a chair conformation. The dihedral angle between the two nitro-phenol rings is 69.47 (9)°. The nitro groups attached to the benzene rings make dihedral angles of 3.37 (16) and 3.14 (13)° in the two mol-ecules of nitro-phenol. The crystal structure is stabilized by N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds and further consolidated by C-H⋯O inter-actions, resulting in a three-dimensional network.

Related literature

For the biological activity and synthesis of 4-(4-nitro­phen­yl)–morpholine derivatives, see: Wang et al. (2010 ▶). For a related structure, see: Wang et al. (2012 ▶).

Experimental

Crystal data

2C6H5NO3·C4H9NO

M = 365.34

Monoclinic,

a = 18.0381 (7) Å

b = 5.5673 (2) Å

c = 17.4910 (7) Å

β = 91.606 (3)°

V = 1755.82 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.963, T max = 0.973

16662 measured reflections

4354 independent reflections

2987 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.151

S = 1.05

4354 reflections

239 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.30 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 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047174/pv2605sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047174/pv2605Isup2.hkl

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

2C6H5NO3·C4H9NO	F(000) = 768
Mr = 365.34	Dx = 1.382 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4354 reflections
a = 18.0381 (7) Å	θ = 1.1–28.4°
b = 5.5673 (2) Å	µ = 0.11 mm−1
c = 17.4910 (7) Å	T = 293 K
β = 91.606 (3)°	Block, colourless
V = 1755.82 (12) Å3	0.35 × 0.30 × 0.25 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	4354 independent reflections
Radiation source: fine-focus sealed tube	2987 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω and φ scans	θmax = 28.4°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −24→24
Tmin = 0.963, Tmax = 0.973	k = −7→7
16662 measured reflections	l = −23→22

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0638P)2 + 0.4643P] where P = (Fo2 + 2Fc2)/3
4354 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.45 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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	0.53902 (9)	0.5777 (3)	0.10103 (10)	0.0565 (4)
C2	0.55081 (10)	0.3693 (4)	0.14223 (11)	0.0648 (5)
H2	0.5982	0.3048	0.1474	0.078*
C3	0.49232 (10)	0.2585 (4)	0.17542 (12)	0.0659 (5)
H3	0.5001	0.1191	0.2038	0.079*
C4	0.42092 (10)	0.3533 (3)	0.16694 (10)	0.0560 (4)
C5	0.41037 (10)	0.5620 (3)	0.12451 (11)	0.0616 (5)
H5	0.3630	0.6260	0.1183	0.074*
C6	0.46899 (10)	0.6747 (4)	0.09170 (11)	0.0628 (5)
H6	0.4617	0.8148	0.0635	0.075*
C7	0.13017 (10)	0.8918 (3)	0.31527 (9)	0.0553 (4)
C8	0.09076 (10)	0.7063 (4)	0.28005 (10)	0.0588 (4)
H8	0.0404	0.6875	0.2884	0.071*
C9	0.12639 (9)	0.5524 (3)	0.23317 (10)	0.0539 (4)
H9	0.0996	0.4294	0.2093	0.065*
C10	0.20240 (9)	0.5739 (3)	0.21978 (9)	0.0469 (4)
C11	0.24071 (10)	0.7647 (4)	0.25620 (10)	0.0585 (4)
H11	0.2911	0.7845	0.2483	0.070*
C12	0.20488 (11)	0.9213 (3)	0.30297 (10)	0.0624 (5)
H12	0.2308	1.0470	0.3264	0.075*
C13	0.11073 (9)	0.0465 (3)	0.07932 (11)	0.0572 (4)
H13A	0.0692	0.1572	0.0801	0.069*
H13B	0.1164	−0.0247	0.1298	0.069*
C14	0.09471 (11)	−0.1474 (3)	0.02155 (12)	0.0629 (5)
H14A	0.0513	−0.2372	0.0364	0.076*
H14B	0.0839	−0.0750	−0.0280	0.076*
C15	0.21931 (12)	−0.1788 (4)	−0.00757 (13)	0.0739 (6)
H15A	0.2090	−0.1040	−0.0568	0.089*
H15B	0.2600	−0.2907	−0.0134	0.089*
C16	0.24145 (10)	0.0101 (3)	0.04962 (11)	0.0594 (5)
H16A	0.2553	−0.0654	0.0979	0.071*
H16B	0.2841	0.0973	0.0317	0.071*
N1	0.60131 (9)	0.6983 (4)	0.06695 (11)	0.0732 (5)
N2	0.09282 (13)	1.0491 (3)	0.36639 (9)	0.0775 (5)
O7	0.15556 (8)	−0.3055 (2)	0.01578 (9)	0.0733 (4)
O1	0.66276 (8)	0.6053 (4)	0.07188 (11)	0.1022 (6)
O2	0.59056 (10)	0.8873 (4)	0.03293 (13)	0.1106 (7)
O3	0.36561 (7)	0.2375 (3)	0.20120 (9)	0.0792 (4)
H3A	0.3265	0.3093	0.1929	0.119*
O4	0.12927 (12)	1.2119 (3)	0.39774 (9)	0.1007 (6)
O5	0.02664 (12)	1.0156 (4)	0.37853 (11)	0.1164 (7)
O6	0.23640 (6)	0.4276 (2)	0.17466 (7)	0.0620 (3)
H6A	0.2068	0.3287	0.1572	0.093*
N3	0.17917 (8)	0.1798 (2)	0.06111 (9)	0.0483 (3)
H3B	0.1748 (10)	0.258 (3)	0.0250 (11)	0.055 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0503 (9)	0.0618 (10)	0.0574 (10)	0.0096 (8)	0.0024 (7)	−0.0051 (9)
C2	0.0521 (9)	0.0705 (12)	0.0714 (12)	0.0183 (9)	−0.0053 (8)	−0.0017 (10)
C3	0.0634 (11)	0.0604 (11)	0.0731 (13)	0.0134 (9)	−0.0087 (9)	0.0083 (10)
C4	0.0527 (9)	0.0558 (10)	0.0592 (10)	0.0030 (8)	−0.0059 (8)	−0.0037 (8)
C5	0.0475 (9)	0.0645 (11)	0.0726 (12)	0.0143 (8)	−0.0027 (8)	0.0050 (10)
C6	0.0583 (10)	0.0596 (11)	0.0708 (12)	0.0160 (8)	0.0045 (9)	0.0081 (9)
C7	0.0746 (11)	0.0519 (9)	0.0389 (8)	0.0103 (8)	−0.0055 (7)	−0.0029 (7)
C8	0.0534 (9)	0.0688 (11)	0.0541 (10)	0.0030 (8)	0.0013 (7)	−0.0060 (9)
C9	0.0514 (9)	0.0542 (9)	0.0560 (10)	−0.0084 (7)	−0.0001 (7)	−0.0106 (8)
C10	0.0504 (8)	0.0497 (8)	0.0404 (8)	−0.0022 (7)	−0.0026 (6)	0.0002 (7)
C11	0.0559 (9)	0.0685 (11)	0.0510 (10)	−0.0146 (8)	−0.0030 (7)	−0.0055 (9)
C12	0.0846 (13)	0.0552 (10)	0.0467 (9)	−0.0163 (9)	−0.0113 (9)	−0.0067 (8)
C13	0.0520 (9)	0.0584 (10)	0.0615 (10)	0.0025 (8)	0.0093 (8)	0.0002 (8)
C14	0.0641 (11)	0.0514 (10)	0.0733 (12)	−0.0119 (8)	0.0015 (9)	0.0043 (9)
C15	0.0754 (13)	0.0680 (12)	0.0786 (14)	0.0166 (10)	0.0104 (10)	−0.0227 (11)
C16	0.0511 (9)	0.0648 (11)	0.0628 (11)	0.0035 (8)	0.0099 (8)	−0.0092 (9)
N1	0.0579 (9)	0.0808 (12)	0.0816 (12)	0.0131 (8)	0.0145 (8)	0.0011 (10)
N2	0.1161 (16)	0.0702 (11)	0.0454 (9)	0.0301 (11)	−0.0100 (9)	−0.0105 (8)
O7	0.0931 (10)	0.0374 (6)	0.0891 (10)	−0.0001 (6)	−0.0031 (8)	−0.0037 (6)
O1	0.0543 (8)	0.1261 (15)	0.1269 (14)	0.0210 (9)	0.0169 (8)	0.0207 (12)
O2	0.0830 (11)	0.0936 (12)	0.1573 (18)	0.0169 (10)	0.0437 (11)	0.0417 (13)
O3	0.0595 (8)	0.0772 (9)	0.1010 (11)	−0.0002 (7)	0.0000 (7)	0.0206 (9)
O4	0.1836 (19)	0.0604 (9)	0.0576 (9)	0.0131 (11)	−0.0061 (10)	−0.0163 (7)
O5	0.1010 (14)	0.1490 (18)	0.0994 (13)	0.0500 (13)	0.0057 (11)	−0.0458 (13)
O6	0.0515 (6)	0.0723 (8)	0.0619 (7)	0.0003 (6)	−0.0010 (5)	−0.0193 (7)
N3	0.0595 (8)	0.0377 (7)	0.0476 (8)	0.0013 (6)	0.0029 (6)	0.0053 (6)

C1—C2	1.379 (3)	C12—H12	0.9300
C1—C6	1.379 (2)	C13—N3	1.483 (2)
C1—N1	1.451 (2)	C13—C14	1.501 (3)
C2—C3	1.366 (3)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.396 (2)	C14—O7	1.413 (2)
C3—H3	0.9300	C14—H14A	0.9700
C4—O3	1.343 (2)	C14—H14B	0.9700
C4—C5	1.389 (3)	C15—O7	1.419 (3)
C5—C6	1.369 (3)	C15—C16	1.498 (3)
C5—H5	0.9300	C15—H15A	0.9700
C6—H6	0.9300	C15—H15B	0.9700
C7—C12	1.380 (3)	C16—N3	1.486 (2)
C7—C8	1.388 (3)	C16—H16A	0.9700
C7—N2	1.433 (2)	C16—H16B	0.9700
C8—C9	1.360 (2)	N1—O2	1.222 (2)
C8—H8	0.9300	N1—O1	1.224 (2)
C9—C10	1.403 (2)	N2—O5	1.233 (3)
C9—H9	0.9300	N2—O4	1.238 (2)
C10—O6	1.2998 (19)	O3—H3A	0.8200
C10—C11	1.409 (2)	O6—H6A	0.8200
C11—C12	1.370 (3)	N3—H3B	0.77 (2)
C11—H11	0.9300
C2—C1—C6	121.24 (17)	N3—C13—C14	111.17 (14)
C2—C1—N1	119.60 (16)	N3—C13—H13A	109.4
C6—C1—N1	119.16 (17)	C14—C13—H13A	109.4
C3—C2—C1	119.50 (16)	N3—C13—H13B	109.4
C3—C2—H2	120.2	C14—C13—H13B	109.4
C1—C2—H2	120.2	H13A—C13—H13B	108.0
C2—C3—C4	120.37 (18)	O7—C14—C13	111.16 (15)
C2—C3—H3	119.8	O7—C14—H14A	109.4
C4—C3—H3	119.8	C13—C14—H14A	109.4
O3—C4—C5	123.20 (16)	O7—C14—H14B	109.4
O3—C4—C3	117.78 (17)	C13—C14—H14B	109.4
C5—C4—C3	119.02 (17)	H14A—C14—H14B	108.0
C6—C5—C4	120.76 (16)	O7—C15—C16	111.09 (16)
C6—C5—H5	119.6	O7—C15—H15A	109.4
C4—C5—H5	119.6	C16—C15—H15A	109.4
C5—C6—C1	119.10 (18)	O7—C15—H15B	109.4
C5—C6—H6	120.4	C16—C15—H15B	109.4
C1—C6—H6	120.4	H15A—C15—H15B	108.0
C12—C7—C8	120.62 (16)	N3—C16—C15	110.39 (15)
C12—C7—N2	120.17 (18)	N3—C16—H16A	109.6
C8—C7—N2	119.19 (18)	C15—C16—H16A	109.6
C9—C8—C7	119.44 (17)	N3—C16—H16B	109.6
C9—C8—H8	120.3	C15—C16—H16B	109.6
C7—C8—H8	120.3	H16A—C16—H16B	108.1
C8—C9—C10	121.85 (16)	O2—N1—O1	121.97 (19)
C8—C9—H9	119.1	O2—N1—C1	118.97 (16)
C10—C9—H9	119.1	O1—N1—C1	119.05 (19)
O6—C10—C9	121.87 (15)	O5—N2—O4	122.6 (2)
O6—C10—C11	120.85 (15)	O5—N2—C7	119.3 (2)
C9—C10—C11	117.26 (15)	O4—N2—C7	118.1 (2)
C12—C11—C10	121.06 (17)	C14—O7—C15	110.39 (14)
C12—C11—H11	119.5	C4—O3—H3A	109.5
C10—C11—H11	119.5	C10—O6—H6A	109.5
C11—C12—C7	119.76 (16)	C13—N3—C16	110.35 (13)
C11—C12—H12	120.1	C13—N3—H3B	113.2 (14)
C7—C12—H12	120.1	C16—N3—H3B	108.0 (14)
C6—C1—C2—C3	−1.0 (3)	C10—C11—C12—C7	0.4 (3)
N1—C1—C2—C3	178.82 (18)	C8—C7—C12—C11	−0.7 (3)
C1—C2—C3—C4	0.8 (3)	N2—C7—C12—C11	177.62 (17)
C2—C3—C4—O3	−179.62 (18)	N3—C13—C14—O7	56.0 (2)
C2—C3—C4—C5	−0.2 (3)	O7—C15—C16—N3	−57.5 (2)
O3—C4—C5—C6	179.03 (19)	C2—C1—N1—O2	−177.4 (2)
C3—C4—C5—C6	−0.4 (3)	C6—C1—N1—O2	2.4 (3)
C4—C5—C6—C1	0.3 (3)	C2—C1—N1—O1	4.0 (3)
C2—C1—C6—C5	0.4 (3)	C6—C1—N1—O1	−176.2 (2)
N1—C1—C6—C5	−179.37 (18)	C12—C7—N2—O5	−177.76 (19)
C12—C7—C8—C9	0.1 (3)	C8—C7—N2—O5	0.6 (3)
N2—C7—C8—C9	−178.17 (17)	C12—C7—N2—O4	1.0 (3)
C7—C8—C9—C10	0.6 (3)	C8—C7—N2—O4	179.30 (17)
C8—C9—C10—O6	−179.63 (17)	C13—C14—O7—C15	−60.4 (2)
C8—C9—C10—C11	−0.8 (3)	C16—C15—O7—C14	61.5 (2)
O6—C10—C11—C12	179.10 (16)	C14—C13—N3—C16	−51.7 (2)
C9—C10—C11—C12	0.3 (3)	C15—C16—N3—C13	52.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···O7i	0.77 (2)	2.46 (2)	3.000 (2)	129 (2)
N3—H3B···O4ii	0.77 (2)	2.36 (2)	3.032 (2)	147 (2)
C14—H14B···O4ii	0.97	2.55	3.322 (3)	136
O3—H3A···O6	0.82	1.77	2.590 (2)	173
O6—H6A···N3	0.82	1.93	2.607 (2)	140
C6—H6···O2iii	0.93	2.53	3.424 (3)	161
C14—H14A···O5iv	0.97	2.49	3.403 (3)	157
C15—H15B···O1v	0.97	2.48	3.400 (3)	159
C16—H16B···O2vi	0.97	2.56	3.441 (3)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯O7i	0.77 (2)	2.46 (2)	3.000 (2)	129 (2)
N3—H3B⋯O4ii	0.77 (2)	2.36 (2)	3.032 (2)	147 (2)
C14—H14B⋯O4ii	0.97	2.55	3.322 (3)	136
O3—H3A⋯O6	0.82	1.77	2.590 (2)	173
O6—H6A⋯N3	0.82	1.93	2.607 (2)	140
C6—H6⋯O2iii	0.93	2.53	3.424 (3)	161
C14—H14A⋯O5iv	0.97	2.49	3.403 (3)	157
C15—H15B⋯O1v	0.97	2.48	3.400 (3)	159
C16—H16B⋯O2vi	0.97	2.56	3.441 (3)	152

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