4-Nitro-aniline-picric acid (2/1).

In the title adduct, C(6)H(3)N(3)O(7)·0.5C(6)H(6)N(2)O(2), the complete 4-nitro-aniline mol-ecule is generated by a crystallographic twofold axis with two C atoms and two N atoms lying on the axis. The mol-ecular components are linked into two dimensional corrugated layers running parallel to the (001) plane by a combination of inter-molecular N-H⋯O and C-H⋯O hydrogen bonds. The phenolic oxygen and two sets of nitro oxygen atoms in the picric acid were found to be disordered with occupancies of 0.81 (2):0.19 (2) and 0.55 (3):0.45 (3) and 0.77 (4):0.23 (4), respectively.

Related literature

For background to picrate derivatives, see: Harrison et al. (2007 ▶); Pascard et al. (1982 ▶); Pearson et al. (2007 ▶); Wang et al. (2003 ▶).

Experimental

Crystal data

C6H3N3O7·0.5C6H6N2O2

M = 298.18

Orthorhombic,

a = 23.534 (2) Å

b = 9.3318 (8) Å

c = 10.5047 (9) Å

V = 2307.0 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.16 mm−1

T = 298 K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: none

16332 measured reflections

2855 independent reflections

2154 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.136

S = 1.06

2855 reflections

241 parameters

18 restraints

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.26 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037416/bg2290sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037416/bg2290Isup2.hkl

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

C6H3N3O7·0.5C6H6N2O2	F(000) = 1216
Mr = 298.18	Dx = 1.717 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 5243 reflections
a = 23.534 (2) Å	θ = 2.4–27.1°
b = 9.3318 (8) Å	µ = 0.16 mm−1
c = 10.5047 (9) Å	T = 298 K
V = 2307.0 (3) Å3	Block, red
Z = 8	0.30 × 0.20 × 0.10 mm

Bruker SMART APEX CCD area-detector diffractometer	2154 reflections with I > 2σ(I)
Radiation source: fine focus sealed Siemens Mo tube	Rint = 0.033
graphite	θmax = 28.3°, θmin = 2.4°
0.3° wide ω exposures scans	h = −30→31
16332 measured reflections	k = −12→12
2855 independent reflections	l = −13→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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.136	w = 1/[σ2(Fo2) + (0.0712P)2 + 0.2759P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2855 reflections	Δρmax = 0.22 e Å−3
241 parameters	Δρmin = −0.26 e Å−3
18 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (9)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	Occ. (<1)
C1	0.66852 (7)	0.40572 (18)	0.75606 (17)	0.0504 (4)
H1	0.6733	0.5023	0.7753	0.061*	0.194 (3)
C2	0.69244 (6)	0.29633 (18)	0.83061 (16)	0.0496 (4)
C3	0.68653 (7)	0.15487 (18)	0.80130 (17)	0.0517 (4)
H3	0.7032	0.0852	0.8524	0.062*
C4	0.65585 (7)	0.11617 (18)	0.69592 (17)	0.0511 (4)
C5	0.63050 (7)	0.21640 (19)	0.61822 (16)	0.0508 (4)
H5	0.6098	0.1890	0.5468	0.061*	0.806 (3)
C6	0.63686 (6)	0.35912 (17)	0.65015 (16)	0.0488 (4)
C7	0.5000	0.6849 (3)	0.2500	0.0505 (5)
C8	0.52386 (7)	0.76184 (19)	0.35141 (16)	0.0533 (4)
H8	0.5397	0.7127	0.4198	0.064*
C9	0.52404 (7)	0.90824 (19)	0.35084 (15)	0.0533 (4)
H9	0.5403	0.9585	0.4181	0.064*
C10	0.5000	0.9812 (3)	0.2500	0.0515 (6)
N4	0.5000	0.5397 (3)	0.2500	0.0760 (7)
H4A	0.5148	0.4936	0.3127	0.091*
N5	0.5000	1.1374 (3)	0.2500	0.0705 (6)
N1	0.72518 (7)	0.33052 (17)	0.94650 (15)	0.0607 (4)
N2	0.64972 (8)	−0.03633 (18)	0.66686 (19)	0.0733 (5)
N3	0.60883 (7)	0.46447 (16)	0.56958 (16)	0.0598 (4)
O1	0.67753 (7)	0.54438 (16)	0.78695 (17)	0.0670 (6)	0.81 (2)
H1A	0.6603	0.5962	0.7370	0.080*	0.806 (3)
O2	0.7225 (5)	0.4511 (5)	0.9832 (7)	0.084 (2)	0.55 (3)
O3	0.7584 (9)	0.2434 (12)	0.980 (2)	0.130 (5)	0.55 (3)
O5	0.6212 (4)	−0.0676 (7)	0.5744 (6)	0.100 (2)	0.77 (4)
O4	0.6739 (6)	−0.1218 (7)	0.7350 (9)	0.108 (2)	0.77 (4)
O1'	0.6057 (3)	0.1603 (7)	0.5099 (6)	0.079 (3)	0.19 (2)
H1'	0.6101	0.0731	0.5088	0.119*	0.194 (3)
O2'	0.7386 (8)	0.4462 (8)	0.9798 (8)	0.093 (3)	0.45 (3)
O3'	0.7319 (7)	0.2298 (7)	1.0257 (8)	0.082 (3)	0.45 (3)
O4'	0.6609 (16)	−0.120 (3)	0.752 (2)	0.106 (8)	0.23 (4)
O5'	0.6331 (17)	−0.077 (3)	0.5624 (14)	0.108 (8)	0.23 (4)
O6	0.58058 (7)	0.42228 (16)	0.48088 (16)	0.0820 (5)
O7	0.61414 (7)	0.59241 (15)	0.59443 (18)	0.0839 (5)
O8	0.52462 (9)	1.20034 (17)	0.33516 (17)	0.1041 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0482 (8)	0.0479 (9)	0.0552 (10)	−0.0025 (6)	0.0033 (7)	−0.0010 (7)
C2	0.0454 (8)	0.0525 (9)	0.0508 (9)	−0.0017 (7)	−0.0013 (7)	−0.0044 (7)
C3	0.0508 (8)	0.0497 (9)	0.0545 (10)	0.0053 (7)	−0.0042 (7)	−0.0011 (7)
C4	0.0519 (9)	0.0474 (9)	0.0541 (10)	0.0002 (7)	−0.0010 (7)	−0.0065 (7)
C5	0.0465 (8)	0.0576 (10)	0.0483 (9)	−0.0035 (7)	−0.0009 (7)	−0.0014 (8)
C6	0.0445 (8)	0.0505 (9)	0.0515 (10)	−0.0010 (7)	0.0029 (7)	0.0063 (7)
C7	0.0487 (11)	0.0499 (12)	0.0531 (13)	0.000	0.0063 (10)	0.000
C8	0.0554 (9)	0.0604 (10)	0.0441 (9)	0.0068 (7)	−0.0050 (7)	0.0052 (7)
C9	0.0587 (10)	0.0594 (10)	0.0417 (9)	0.0001 (7)	−0.0079 (7)	−0.0046 (7)
C10	0.0584 (13)	0.0478 (12)	0.0482 (13)	0.000	−0.0035 (10)	0.000
N4	0.1002 (18)	0.0528 (13)	0.0750 (17)	0.000	−0.0071 (14)	0.000
N5	0.0951 (17)	0.0549 (13)	0.0614 (14)	0.000	−0.0084 (13)	0.000
N1	0.0598 (9)	0.0596 (9)	0.0626 (10)	−0.0030 (7)	−0.0093 (7)	−0.0083 (8)
N2	0.0863 (12)	0.0529 (9)	0.0805 (13)	0.0035 (9)	−0.0180 (10)	−0.0131 (9)
N3	0.0598 (9)	0.0540 (9)	0.0657 (10)	−0.0041 (7)	−0.0051 (8)	0.0115 (7)
O1	0.0826 (12)	0.0428 (8)	0.0757 (12)	−0.0040 (7)	−0.0190 (9)	−0.0021 (7)
O2	0.103 (4)	0.060 (2)	0.090 (3)	0.002 (3)	−0.024 (2)	−0.039 (3)
O3	0.137 (8)	0.103 (4)	0.149 (9)	0.046 (4)	−0.097 (7)	−0.042 (4)
O5	0.110 (3)	0.066 (2)	0.124 (5)	0.015 (2)	−0.059 (3)	−0.038 (3)
O4	0.151 (4)	0.047 (2)	0.127 (5)	0.0128 (19)	−0.064 (4)	−0.011 (3)
O1'	0.093 (5)	0.075 (5)	0.070 (5)	−0.001 (4)	−0.025 (4)	0.002 (4)
O2'	0.123 (7)	0.084 (4)	0.073 (3)	−0.062 (4)	−0.037 (3)	0.030 (4)
O3'	0.110 (6)	0.058 (3)	0.078 (4)	0.012 (3)	−0.040 (3)	−0.002 (2)
O4'	0.20 (2)	0.045 (7)	0.068 (8)	0.000 (9)	0.011 (13)	0.001 (5)
O5'	0.174 (18)	0.098 (13)	0.052 (8)	−0.035 (11)	0.004 (10)	−0.026 (7)
O6	0.1017 (11)	0.0681 (9)	0.0763 (10)	−0.0034 (8)	−0.0344 (9)	0.0128 (7)
O7	0.0925 (10)	0.0513 (8)	0.1079 (12)	−0.0020 (7)	−0.0244 (9)	0.0104 (8)
O8	0.1598 (18)	0.0609 (9)	0.0916 (12)	−0.0151 (10)	−0.0387 (11)	−0.0121 (9)

C1—O1	1.351 (2)	C9—C10	1.381 (2)
C1—C2	1.404 (2)	C9—H9	0.9300
C1—C6	1.408 (2)	C10—C9i	1.381 (2)
C1—H1	0.9300	C10—N5	1.457 (3)
C2—C3	1.363 (2)	N4—H4A	0.8600
C2—N1	1.476 (2)	N5—O8i	1.2169 (18)
C3—C4	1.370 (2)	N5—O8	1.2169 (18)
C3—H3	0.9300	N1—O2'	1.178 (6)
C4—C5	1.377 (2)	N1—O3	1.182 (5)
C4—N2	1.463 (2)	N1—O2	1.191 (5)
C5—C6	1.382 (2)	N1—O3'	1.265 (5)
C5—O1'	1.382 (6)	N2—O4	1.214 (5)
C5—H5	0.9300	N2—O5	1.216 (4)
C6—N3	1.455 (2)	N2—O4'	1.221 (10)
C7—N4	1.355 (3)	N2—O5'	1.225 (10)
C7—C8	1.402 (2)	N3—O6	1.210 (2)
C7—C8i	1.402 (2)	N3—O7	1.228 (2)
C8—C9	1.366 (2)	O1—H1A	0.8200
C8—H8	0.9300	O1'—H1'	0.8200
O1—C1—C2	119.97 (16)	C10—C9—H9	120.2
O1—C1—C6	124.67 (16)	C9—C10—C9i	120.9 (2)
C2—C1—C6	115.35 (15)	C9—C10—N5	119.56 (11)
C2—C1—H1	122.3	C9i—C10—N5	119.56 (11)
C6—C1—H1	122.3	C7—N4—H4A	120.0
C3—C2—C1	122.50 (16)	O8i—N5—O8	122.3 (3)
C3—C2—N1	116.69 (15)	O8i—N5—C10	118.85 (13)
C1—C2—N1	120.81 (15)	O8—N5—C10	118.85 (13)
C2—C3—C4	119.45 (16)	O2'—N1—O3	111.4 (6)
C2—C3—H3	120.3	O3—N1—O2	126.1 (5)
C4—C3—H3	120.3	O2'—N1—O3'	116.8 (5)
C3—C4—C5	121.88 (16)	O2—N1—O3'	119.7 (6)
C3—C4—N2	118.49 (16)	O2'—N1—C2	125.7 (5)
C5—C4—N2	119.63 (16)	O3—N1—C2	116.3 (4)
C4—C5—C6	117.63 (16)	O2—N1—C2	116.3 (4)
C4—C5—O1'	114.4 (3)	O3'—N1—C2	116.6 (4)
C6—C5—O1'	127.7 (3)	O4—N2—O5	124.9 (4)
C4—C5—H5	121.2	O5—N2—O4'	123.6 (15)
C6—C5—H5	121.2	O4—N2—O5'	118.4 (16)
C5—C6—C1	123.16 (15)	O4'—N2—O5'	122.1 (15)
C5—C6—N3	117.44 (15)	O4—N2—C4	118.0 (4)
C1—C6—N3	119.39 (15)	O5—N2—C4	117.0 (3)
N4—C7—C8	120.81 (11)	O4'—N2—C4	116.7 (13)
N4—C7—C8i	120.81 (11)	O5'—N2—C4	121.3 (13)
C8—C7—C8i	118.4 (2)	O6—N3—O7	122.38 (16)
C9—C8—C7	120.67 (16)	O6—N3—C6	118.48 (15)
C9—C8—H8	119.7	O7—N3—C6	119.13 (16)
C7—C8—H8	119.7	C1—O1—H1A	109.5
C8—C9—C10	119.70 (16)	C5—O1'—H1'	109.5
C8—C9—H9	120.2
O1—C1—C2—C3	−177.52 (17)	C9—C10—N5—O8i	−175.18 (14)
C6—C1—C2—C3	1.3 (2)	C9i—C10—N5—O8i	4.82 (14)
O1—C1—C2—N1	3.0 (2)	C9—C10—N5—O8	4.82 (14)
C6—C1—C2—N1	−178.16 (14)	C9i—C10—N5—O8	−175.18 (14)
C1—C2—C3—C4	−0.5 (3)	C3—C2—N1—O2'	173.0 (10)
N1—C2—C3—C4	179.01 (15)	C1—C2—N1—O2'	−7.5 (10)
C2—C3—C4—C5	−0.1 (3)	C3—C2—N1—O3	24.2 (17)
C2—C3—C4—N2	−179.55 (16)	C1—C2—N1—O3	−156.3 (17)
C3—C4—C5—C6	−0.1 (3)	C3—C2—N1—O2	−168.1 (6)
N2—C4—C5—C6	179.26 (16)	C1—C2—N1—O2	11.4 (6)
C3—C4—C5—O1'	174.3 (4)	C3—C2—N1—O3'	−18.2 (9)
N2—C4—C5—O1'	−6.3 (5)	C1—C2—N1—O3'	161.3 (9)
C4—C5—C6—C1	1.1 (2)	C3—C4—N2—O4	−2.7 (9)
O1'—C5—C6—C1	−172.5 (5)	C5—C4—N2—O4	177.9 (9)
C4—C5—C6—N3	−178.51 (15)	C3—C4—N2—O5	178.4 (6)
O1'—C5—C6—N3	7.9 (5)	C5—C4—N2—O5	−1.0 (6)
O1—C1—C6—C5	177.14 (16)	C3—C4—N2—O4'	16 (2)
C2—C1—C6—C5	−1.6 (2)	C5—C4—N2—O4'	−163 (2)
O1—C1—C6—N3	−3.3 (3)	C3—C4—N2—O5'	−165 (2)
C2—C1—C6—N3	177.95 (14)	C5—C4—N2—O5'	15 (2)
N4—C7—C8—C9	179.68 (12)	C5—C6—N3—O6	1.5 (2)
C8i—C7—C8—C9	−0.32 (12)	C1—C6—N3—O6	−178.11 (17)
C7—C8—C9—C10	0.6 (2)	C5—C6—N3—O7	−179.18 (17)
C8—C9—C10—C9i	−0.31 (12)	C1—C6—N3—O7	1.2 (2)
C8—C9—C10—N5	179.68 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ii	0.93	2.55	3.442 (10)	161
C9—H9···O5iii	0.93	2.53	3.286 (4)	139
N4—H4A···O6	0.86	2.44	3.2677 (16)	161
O1—H1A···O7	0.82	1.85	2.553 (2)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2i	0.93	2.55	3.442 (10)	161
C9—H9⋯O5ii	0.93	2.53	3.286 (4)	139
N4—H4A⋯O6	0.86	2.44	3.2677 (16)	161
O1—H1A⋯O7	0.82	1.85	2.553 (2)	143

Symmetry codes: (i) ; (ii) .