Hydro­gen bonding in substituted nitro­anilines: isolated nets in 1,3-­diamino-4-nitrobenzene and continuously interwoven nets in 3,5-­dinitro­aniline

Molecules of 1,3-diamino-4-nitrobenzene, C₆H₇N₃O₂, are linked by N-H...O hydrogen bonds [N...O 2.964 (2) and 3.021 (2) Å; N-H...O 155 and 149°] into (4,4) nets. In 3,5-di­nitro­aniline, C₆H₅N₃O₄, where Z' = 2, the mol­ecules are linked by three N-H...O hydrogen bonds [N...O 3.344 (2)-3.433 (2) Å and N-H...O 150-167°] into deeply puckered nets, each of which is interwoven with its two immediate neighbours.

Computing details

For both compounds, data collection: XPREP (Bruker, 1997); cell refinement: XPREP; data reduction: XPREP; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

(I) 1,3-diamino-4 -nitrobenzene

Crystal data

C6H7N3O2	F(000) = 320
Mr = 153.15	Dx = 1.552 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.4772 (3) Å	Cell parameters from 2145 reflections
b = 11.1379 (7) Å	θ = 2.4–33.5°
c = 13.1891 (9) Å	µ = 0.12 mm^−1
β = 94.748 (1)°	T = 293 K
V = 655.44 (8) Å^3	Block, brown
Z = 4	0.50 × 0.40 × 0.20 mm

Data collection

Bruker SMART 1000 CCD diffractometer	2480 independent reflections
Radiation source: fine-focus sealed tube	1530 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
φ scans and ω scans with κ offsets	θmax = 33.5°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→6
Tmin = 0.940, Tmax = 0.976	k = −8→16
6928 measured reflections	l = −20→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.193	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.1104P)^2] where P = (Fo^2 + 2Fc^2)/3
2480 reflections	(Δ/σ)max = 0.005
100 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	−0.2039 (3)	0.93040 (11)	0.26603 (10)	0.0354 (3)
C2	0.0065 (3)	0.83905 (12)	0.27917 (9)	0.0340 (3)
C3	0.1184 (3)	0.77840 (11)	0.20173 (9)	0.0319 (3)
C4	0.0054 (3)	0.81338 (11)	0.10629 (9)	0.0357 (3)
C5	−0.2021 (3)	0.90755 (13)	0.09345 (10)	0.0426 (4)
C6	−0.3065 (4)	0.96587 (13)	0.17012 (11)	0.0426 (3)
N1	−0.3070 (3)	0.98801 (11)	0.34336 (10)	0.0469 (3)
N3	0.3192 (3)	0.68807 (10)	0.22111 (9)	0.0399 (3)
N4	0.0990 (3)	0.75681 (13)	0.02295 (9)	0.0463 (3)
O1	0.2722 (3)	0.66839 (12)	0.03080 (9)	0.0649 (4)
O2	0.0053 (4)	0.79532 (12)	−0.05838 (8)	0.0719 (5)
H2	0.0750	0.8181	0.3453	0.041*
H5	−0.2696	0.9300	0.0276	0.051*
H6	−0.4435	1.0283	0.1594	0.051*
H11	−0.4339	1.0455	0.3324	0.056*
H12	−0.2474	0.9681	0.4047	0.056*
H31	0.3761	0.6690	0.2829	0.048*
H32	0.3893	0.6500	0.1716	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0375 (7)	0.0351 (6)	0.0335 (6)	−0.0060 (5)	0.0022 (5)	0.0004 (4)
C2	0.0366 (7)	0.0399 (7)	0.0251 (5)	−0.0035 (5)	−0.0003 (5)	0.0019 (4)
C3	0.0319 (6)	0.0360 (6)	0.0274 (5)	−0.0077 (5)	−0.0006 (4)	0.0017 (4)
C4	0.0397 (7)	0.0416 (7)	0.0254 (5)	−0.0087 (5)	−0.0001 (5)	0.0002 (4)
C5	0.0470 (8)	0.0483 (8)	0.0310 (6)	−0.0048 (6)	−0.0070 (6)	0.0090 (5)
C6	0.0453 (8)	0.0409 (7)	0.0406 (7)	0.0016 (6)	−0.0025 (6)	0.0081 (5)
N1	0.0543 (8)	0.0456 (7)	0.0416 (6)	0.0075 (6)	0.0083 (6)	−0.0018 (5)
N3	0.0434 (7)	0.0448 (7)	0.0314 (5)	0.0057 (5)	0.0014 (5)	−0.0007 (4)
N4	0.0567 (8)	0.0561 (8)	0.0257 (5)	−0.0138 (6)	0.0010 (5)	−0.0022 (5)
O1	0.0798 (10)	0.0775 (9)	0.0373 (6)	0.0166 (7)	0.0052 (6)	−0.0129 (5)
O2	0.1073 (12)	0.0841 (10)	0.0231 (5)	−0.0049 (8)	−0.0027 (6)	0.0036 (5)

Geometric parameters (Å, º)

C1—C2	1.3875 (19)	N4—O1	1.2524 (19)
C2—C3	1.3548 (18)	N4—O2	1.1983 (16)
C3—C4	1.3738 (17)	N1—H11	0.860
C4—C5	1.402 (2)	N1—H12	0.860
C5—C6	1.320 (2)	N3—H31	0.860
C6—C1	1.3679 (19)	N3—H32	0.860
C1—N1	1.3204 (17)	C2—H2	0.930
C3—N3	1.3592 (17)	C5—H5	0.930
C4—N4	1.3628 (18)	C6—H6	0.930
N1—C1—C6	117.50 (14)	O1—N4—C4	121.77 (12)
N1—C1—C2	122.49 (13)	C1—N1—H11	120.01
C6—C1—C2	119.99 (13)	C1—N1—H12	120.03
C3—C2—C1	124.13 (12)	H11—N1—H12	119.95
C2—C3—N3	120.50 (11)	C3—N3—H31	120.02
C2—C3—C4	114.72 (12)	C3—N3—H32	119.98
N3—C3—C4	124.75 (12)	H31—N3—H32	119.99
N4—C4—C3	119.56 (13)	C1—C2—H2	117.96
N4—C4—C5	119.56 (12)	C3—C2—H2	117.91
C3—C4—C5	120.87 (12)	C4—C5—H5	118.35
C6—C5—C4	123.28 (12)	C6—C5—H5	118.36
C5—C6—C1	116.96 (14)	C1—C6—H6	121.55
O2—N4—O1	121.59 (14)	C5—C6—H6	121.49
O2—N4—C4	116.63 (15)
C3—C4—N4—O1	4.5 (2)	C5—C4—N4—O1	−176.32 (14)
C3—C4—N4—O2	−176.09 (14)	C5—C4—N4—O2	3.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H12···O1^i	0.86	2.25	3.021 (2)	149
N3—H31···O2^ii	0.86	2.16	2.964 (2)	155
C2—H2···O2^ii	0.93	2.55	3.321 (2)	140

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) x+1/2, −y+3/2, z+1/2.

(II) 3,5-dinitroaniline

Crystal data

C6H5N3O4	F(000) = 752
Mr = 183.13	Dx = 1.601 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.5377 (6) Å	Cell parameters from 2507 reflections
b = 14.0119 (9) Å	θ = 2.9–26.2°
c = 12.7071 (8) Å	µ = 0.14 mm^−1
β = 90.899 (2)°	T = 293 K
V = 1519.96 (17) Å^3	Prism, yellow
Z = 8	0.60 × 0.30 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer	5510 independent reflections
Radiation source: fine-focus sealed tube	2160 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
φ scans and ω scans with κ offsets	θmax = 32.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→9
Tmin = 0.921, Tmax = 0.986	k = −21→20
15462 measured reflections	l = −18→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0622P)^2] where P = (Fo^2 + 2Fc^2)/3
5510 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	−0.09505 (19)	0.13604 (11)	0.47681 (11)	0.0452 (4)
C12	−0.1625 (2)	0.04790 (10)	0.45248 (11)	0.0465 (4)
C13	−0.26199 (19)	0.00621 (10)	0.52300 (10)	0.0432 (4)
C14	−0.30029 (19)	0.04585 (10)	0.61777 (11)	0.0447 (4)
C15	−0.23384 (18)	0.13373 (10)	0.63817 (10)	0.0416 (4)
C16	−0.1337 (2)	0.17880 (10)	0.57155 (11)	0.0453 (4)
N11	0.00886 (19)	0.17716 (11)	0.41055 (11)	0.0673 (4)
N13	−0.3320 (2)	−0.08635 (10)	0.49576 (11)	0.0574 (4)
O11	−0.2935 (2)	−0.12460 (9)	0.41392 (10)	0.0873 (5)
O12	−0.42577 (18)	−0.12016 (9)	0.55607 (11)	0.0783 (4)
N15	−0.27376 (19)	0.18180 (10)	0.73685 (11)	0.0582 (4)
O14	−0.35455 (19)	0.13944 (9)	0.79966 (10)	0.0837 (5)
O13	−0.2283 (2)	0.26350 (10)	0.74954 (12)	0.0910 (5)
C21	0.3283 (2)	0.66764 (11)	0.63478 (12)	0.0496 (4)
C22	0.4020 (2)	0.66837 (11)	0.53746 (12)	0.0502 (4)
C23	0.37386 (19)	0.59562 (11)	0.46827 (10)	0.0454 (4)
C24	0.27794 (19)	0.51921 (10)	0.48800 (11)	0.0455 (4)
C25	0.20854 (19)	0.52036 (10)	0.58532 (11)	0.0434 (4)
C26	0.2305 (2)	0.59156 (11)	0.65818 (12)	0.0495 (4)
N21	0.3533 (2)	0.73912 (11)	0.70591 (12)	0.0781 (5)
N23	0.45294 (18)	0.59746 (12)	0.36608 (11)	0.0590 (4)
O21	0.42878 (18)	0.53376 (10)	0.30377 (9)	0.0792 (4)
O22	0.5414 (2)	0.66359 (11)	0.34857 (11)	0.0919 (5)
N25	0.10897 (18)	0.43916 (10)	0.61347 (12)	0.0583 (4)
O23	0.0862 (2)	0.37794 (10)	0.54882 (12)	0.0972 (6)
O24	0.05576 (19)	0.43639 (9)	0.70161 (11)	0.0878 (5)
H12	−0.1405	0.0177	0.3893	0.056*
H14	−0.3663	0.0157	0.6649	0.054*
H16	−0.0915	0.2379	0.5896	0.054*
H1A	0.0521	0.2307	0.4270	0.081*
H1B	0.0313	0.1496	0.3522	0.081*
H22	0.4694	0.7178	0.5200	0.060*
H24	0.2611	0.4704	0.4395	0.055*
H26	0.1804	0.5889	0.7226	0.059*
H2A	0.3084	0.7374	0.7660	0.094*
H2B	0.4141	0.7859	0.6907	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0496 (10)	0.0465 (8)	0.0399 (7)	−0.0014 (7)	0.0091 (7)	0.0066 (6)
C12	0.0567 (11)	0.0502 (8)	0.0329 (7)	−0.0018 (8)	0.0075 (7)	−0.0016 (6)
C13	0.0484 (10)	0.0423 (8)	0.0388 (7)	−0.0031 (7)	0.0005 (7)	0.0036 (6)
C14	0.0435 (10)	0.0510 (8)	0.0398 (7)	0.0013 (7)	0.0081 (6)	0.0085 (6)
C15	0.0437 (10)	0.0463 (8)	0.0350 (7)	0.0068 (7)	0.0070 (6)	0.0004 (6)
C16	0.0497 (10)	0.0404 (7)	0.0458 (8)	−0.0003 (7)	0.0068 (7)	0.0005 (6)
N11	0.0814 (12)	0.0688 (9)	0.0524 (8)	−0.0248 (8)	0.0278 (8)	0.0007 (7)
N13	0.0694 (11)	0.0509 (8)	0.0518 (8)	−0.0096 (7)	−0.0050 (7)	0.0033 (7)
O11	0.1328 (15)	0.0689 (8)	0.0602 (8)	−0.0251 (9)	0.0061 (8)	−0.0195 (7)
O12	0.0860 (11)	0.0681 (8)	0.0809 (9)	−0.0324 (7)	0.0093 (8)	0.0081 (6)
N15	0.0617 (11)	0.0626 (9)	0.0509 (8)	0.0092 (8)	0.0176 (7)	−0.0074 (7)
O14	0.1172 (13)	0.0802 (9)	0.0549 (7)	0.0112 (8)	0.0425 (8)	0.0017 (6)
O13	0.0964 (13)	0.0851 (10)	0.0926 (10)	−0.0213 (9)	0.0366 (9)	−0.0450 (8)
C21	0.0536 (12)	0.0470 (8)	0.0482 (8)	−0.0015 (8)	−0.0009 (7)	0.0002 (7)
C22	0.0532 (11)	0.0445 (8)	0.0528 (9)	−0.0076 (7)	0.0046 (8)	0.0062 (7)
C23	0.0455 (10)	0.0524 (9)	0.0383 (7)	0.0023 (7)	0.0056 (7)	0.0088 (6)
C24	0.0487 (11)	0.0453 (8)	0.0424 (8)	−0.0006 (7)	0.0034 (7)	0.0000 (6)
C25	0.0428 (10)	0.0421 (8)	0.0454 (8)	−0.0029 (7)	0.0038 (7)	0.0064 (6)
C26	0.0527 (11)	0.0543 (9)	0.0417 (8)	0.0010 (8)	0.0077 (7)	0.0039 (7)
N21	0.0980 (15)	0.0693 (10)	0.0673 (10)	−0.0254 (9)	0.0136 (9)	−0.0211 (8)
N23	0.0575 (11)	0.0718 (9)	0.0480 (8)	0.0008 (8)	0.0103 (7)	0.0116 (7)
O21	0.0920 (12)	0.0963 (10)	0.0498 (7)	−0.0053 (8)	0.0191 (7)	−0.0115 (7)
O22	0.1038 (13)	0.0999 (11)	0.0730 (9)	−0.0322 (10)	0.0329 (8)	0.0166 (8)
N25	0.0569 (11)	0.0526 (8)	0.0658 (9)	−0.0051 (7)	0.0115 (8)	0.0081 (7)
O23	0.1236 (15)	0.0801 (9)	0.0886 (10)	−0.0532 (9)	0.0239 (9)	−0.0203 (8)
O24	0.1111 (14)	0.0680 (8)	0.0858 (9)	−0.0119 (8)	0.0483 (9)	0.0139 (7)

Geometric parameters (Å, º)

C11—C12	1.395 (2)	C21—C22	1.396 (2)
C12—C13	1.374 (2)	C22—C23	1.365 (2)
C13—C14	1.3704 (19)	C23—C24	1.373 (2)
C14—C15	1.379 (2)	C24—C25	1.380 (2)
C15—C16	1.367 (2)	C25—C26	1.372 (2)
C16—C11	1.389 (2)	C26—C21	1.389 (2)
C11—N11	1.3607 (19)	C21—N21	1.364 (2)
C13—N13	1.467 (2)	C23—N23	1.4732 (19)
N13—O11	1.2196 (18)	N23—O21	1.2088 (18)
N13—O12	1.2132 (18)	N23—O22	1.2181 (19)
C15—N15	1.4683 (19)	C25—N25	1.468 (2)
N15—O13	1.2188 (19)	N25—O23	1.2013 (18)
N15—O14	1.2174 (18)	N25—O24	1.2159 (18)
N11—H1A	0.86	N21—H2A	0.86
N11—H1B	0.86	N21—H2B	0.86
C12—H12	0.93	C22—H22	0.93
C14—H14	0.93	C24—H24	0.93
C16—H16	0.93	C26—H26	0.93
N11—C11—C16	121.30 (14)	N21—C21—C26	120.68 (15)
N11—C11—C12	120.57 (13)	N21—C21—C22	120.89 (15)
C16—C11—C12	118.10 (13)	C26—C21—C22	118.42 (14)
C13—C12—C11	119.27 (13)	C23—C22—C21	119.19 (14)
C14—C13—C12	123.99 (14)	C22—C23—C24	124.34 (13)
C14—C13—N13	117.62 (13)	C22—C23—N23	118.43 (14)
C12—C13—N13	118.39 (13)	C24—C23—N23	117.22 (14)
C13—C14—C15	115.09 (13)	C23—C24—C25	114.85 (13)
C16—C15—C14	123.76 (13)	C26—C25—C24	123.87 (14)
C16—C15—N15	118.21 (13)	C26—C25—N25	118.21 (13)
C14—C15—N15	118.03 (13)	C24—C25—N25	117.90 (13)
C15—C16—C11	119.78 (13)	C25—C26—C21	119.32 (14)
O12—N13—O11	123.82 (15)	O21—N23—O22	122.82 (15)
O12—N13—C13	117.81 (14)	O21—N23—C23	119.24 (15)
O11—N13—C13	118.37 (14)	O22—N23—C23	117.93 (15)
O14—N15—O13	123.63 (14)	O23—N25—O24	123.26 (15)
O14—N15—C15	118.54 (14)	O23—N25—C25	118.35 (14)
O13—N15—C15	117.78 (13)	O24—N25—C25	118.38 (15)
C11—N11—H1A	120.02	C21—N21—H2A	120.04
C11—N11—H1B	119.96	C21—N21—H2B	119.97
H1A—N11—H1B	120.02	H2A—N21—H2B	119.99
C11—C12—H12	120.41	C21—C22—H22	120.40
C13—C12—H12	120.33	C23—C22—H22	120.40
C13—C14—H14	122.48	C23—C24—H24	122.59
C15—C14—H14	122.43	C25—C24—H24	122.57
C11—C16—H16	120.08	C21—C26—H26	120.35
C15—C16—H16	120.13	C25—C26—H26	120.32
C12—C13—N13—O11	3.3 (2)	C22—C23—N23—O21	−179.71 (16)
C12—C13—N13—O12	−176.31 (15)	C22—C23—N23—O22	0.8 (2)
C14—C13—N13—O11	−176.69 (16)	C24—C23—N23—O21	1.3 (2)
C14—C13—N13—O12	3.7 (2)	C24—C23—N23—O22	−178.21 (16)
C14—C15—N15—O13	−172.40 (16)	C24—C25—N25—O23	−3.6 (2)
C14—C15—N15—O14	5.1 (2)	C24—C25—N25—O24	175.17 (15)
C16—C15—N15—O13	7.3 (2)	C26—C25—N25—O23	178.08 (16)
C16—C15—N15—O14	−175.24 (16)	C26—C25—N25—O24	−3.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H1A···O23	0.86	2.59	3.377 (2)	152
N11—H1B···O21^i	0.86	2.59	3.433 (2)	167
N21—H2B···O12^ii	0.86	2.57	3.344 (2)	150
C22—H22···O12^ii	0.93	2.48	3.315 (2)	149
C26—H26···O11^iii	0.93	2.49	3.292 (2)	145

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