4-Nitroaniline-2,4,6-trimethoxybenz-aldehyde (1/1).

In the title co-crystal, C(6)H(6)N(2)O(2.)C(10)H(12)O(4), the two components are held together by an N-H⋯O(aldehyde) hydrogen bond. Adjacent co-crystals are linked by weaker N-H⋯O(nitro) hydrogen bonds, forming a linear chain. The two aromatic rings of the components are aligned at 75.2 (1)°. The crystal studied was a non-merohedral twin with a 24% minor component.

Related literature

For some examples of co-crystals of 4-nitro­aniline, see: Bertolasi et al. (2001 ▶); Dederer & Gieren (1979 ▶); Huang et al. (1996 ▶); Koshima et al. (1996 ▶); Rashid & Deschamps (2006 ▶); Singh et al. (2003 ▶); Smith et al. (1997 ▶); Weber (1981 ▶); Zaitu et al. (1995 ▶). For the treatment of non-merohedral twins, see: Spek (2009 ▶).

Experimental

Crystal data

C6H6N2O2·C10H12O4

M = 334.32

Monoclinic,

a = 7.4409 (11) Å

b = 30.022 (5) Å

c = 6.9400 (11) Å

β = 93.237 (3)°

V = 1547.9 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.15 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer

8127 measured reflections

2722 independent reflections

1834 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.124

S = 1.01

2722 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.41 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810023664/si2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023664/si2271Isup2.hkl

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

C6H6N2O2·C10H12O4	F(000) = 704
Mr = 334.32	Dx = 1.435 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1019 reflections
a = 7.4409 (11) Å	θ = 2.7–24.4°
b = 30.022 (5) Å	µ = 0.11 mm−1
c = 6.9400 (11) Å	T = 100 K
β = 93.237 (3)°	Prism, yellow
V = 1547.9 (4) Å3	0.15 × 0.10 × 0.05 mm
Z = 4

Bruker SMART APEX diffractometer	1834 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
graphite	θmax = 25.0°, θmin = 1.4°
ω scans	h = −8→8
8127 measured reflections	k = −32→35
2722 independent reflections	l = −8→8

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0537P)2 + 0.141P] where P = (Fo2 + 2Fc2)/3
2722 reflections	(Δ/σ)max = 0.001
221 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

	x	y	z	Uiso*/Ueq
O1	0.7019 (2)	0.57392 (6)	0.7861 (3)	0.0238 (5)
O2	0.7670 (2)	0.61120 (6)	0.4418 (2)	0.0182 (4)
O3	1.3371 (2)	0.57367 (6)	0.1850 (2)	0.0203 (4)
O4	1.1646 (2)	0.51253 (6)	0.7725 (2)	0.0176 (4)
O5	0.0363 (2)	0.80574 (6)	0.5273 (3)	0.0266 (5)
O6	−0.0908 (2)	0.74324 (7)	0.4450 (3)	0.0291 (5)
N1	0.6593 (3)	0.67379 (7)	0.7727 (3)	0.0233 (5)
H11	0.7505	0.6884	0.8209	0.028*
H12	0.6631	0.6452	0.7670	0.028*
N2	0.0398 (3)	0.76456 (7)	0.5159 (3)	0.0193 (5)
C1	0.8433 (3)	0.55435 (8)	0.7589 (4)	0.0177 (6)
H1	0.8764	0.5314	0.8482	0.021*
C2	0.9658 (3)	0.56212 (8)	0.6066 (3)	0.0152 (6)
C3	0.9285 (3)	0.59010 (8)	0.4462 (4)	0.0154 (6)
C4	1.0482 (3)	0.59515 (8)	0.3011 (4)	0.0155 (6)
H4	1.0203	0.6140	0.1936	0.019*
C5	1.2098 (3)	0.57189 (8)	0.3175 (4)	0.0157 (6)
C6	1.2542 (3)	0.54410 (8)	0.4744 (4)	0.0170 (6)
H6	1.3662	0.5289	0.4834	0.020*
C7	1.1335 (3)	0.53914 (8)	0.6155 (3)	0.0144 (6)
C8	0.7184 (3)	0.63908 (9)	0.2781 (4)	0.0216 (6)
H8A	0.5983	0.6516	0.2923	0.032*
H8B	0.7179	0.6213	0.1597	0.032*
H8C	0.8061	0.6633	0.2709	0.032*
C9	1.3034 (3)	0.60080 (8)	0.0177 (4)	0.0198 (6)
H9A	1.4039	0.5980	−0.0669	0.030*
H9B	1.2913	0.6320	0.0570	0.030*
H9C	1.1920	0.5910	−0.0516	0.030*
C10	1.3340 (3)	0.48903 (9)	0.7879 (4)	0.0193 (6)
H10A	1.3403	0.4709	0.9054	0.029*
H10B	1.4332	0.5106	0.7934	0.029*
H10C	1.3436	0.4697	0.6751	0.029*
C11	0.5099 (3)	0.69579 (9)	0.7057 (3)	0.0168 (6)
C12	0.3577 (3)	0.67245 (9)	0.6292 (4)	0.0189 (6)
H12A	0.3622	0.6409	0.6183	0.023*
C13	0.2034 (3)	0.69466 (9)	0.5705 (4)	0.0186 (6)
H13	0.1006	0.6786	0.5216	0.022*
C14	0.1986 (3)	0.74094 (8)	0.5832 (4)	0.0165 (6)
C15	0.3483 (3)	0.76498 (8)	0.6542 (3)	0.0162 (6)
H15	0.3440	0.7966	0.6610	0.019*
C16	0.5015 (3)	0.74254 (9)	0.7139 (4)	0.0176 (6)
H16	0.6040	0.7588	0.7617	0.021*

	U11	U22	U33	U12	U13	U23
O1	0.0193 (10)	0.0228 (11)	0.0302 (11)	0.0076 (8)	0.0082 (8)	0.0052 (9)
O2	0.0152 (9)	0.0201 (10)	0.0195 (10)	0.0065 (8)	0.0028 (7)	0.0045 (8)
O3	0.0188 (10)	0.0228 (11)	0.0200 (10)	0.0060 (8)	0.0070 (8)	0.0085 (8)
O4	0.0163 (9)	0.0172 (10)	0.0195 (10)	0.0054 (7)	0.0023 (7)	0.0049 (8)
O5	0.0257 (11)	0.0204 (12)	0.0337 (12)	0.0076 (9)	0.0015 (8)	0.0010 (9)
O6	0.0173 (10)	0.0360 (13)	0.0332 (12)	−0.0005 (9)	−0.0068 (9)	−0.0050 (10)
N1	0.0213 (12)	0.0170 (13)	0.0311 (13)	0.0035 (10)	−0.0030 (10)	−0.0009 (11)
N2	0.0183 (12)	0.0219 (14)	0.0178 (12)	0.0011 (10)	0.0028 (9)	−0.0001 (10)
C1	0.0207 (14)	0.0123 (14)	0.0201 (14)	0.0010 (12)	0.0005 (11)	0.0014 (11)
C2	0.0160 (13)	0.0131 (14)	0.0165 (13)	−0.0013 (10)	0.0012 (10)	−0.0016 (11)
C3	0.0133 (13)	0.0136 (14)	0.0189 (13)	0.0016 (11)	−0.0017 (10)	−0.0027 (11)
C4	0.0157 (13)	0.0139 (14)	0.0171 (13)	−0.0008 (10)	0.0015 (10)	−0.0010 (11)
C5	0.0154 (13)	0.0147 (14)	0.0174 (13)	−0.0017 (11)	0.0039 (10)	−0.0015 (11)
C6	0.0136 (13)	0.0142 (14)	0.0230 (14)	0.0022 (11)	−0.0003 (11)	0.0002 (11)
C7	0.0190 (14)	0.0098 (14)	0.0141 (13)	−0.0002 (10)	−0.0012 (10)	−0.0018 (11)
C8	0.0207 (14)	0.0211 (16)	0.0227 (14)	0.0046 (12)	−0.0017 (11)	0.0062 (12)
C9	0.0239 (15)	0.0173 (15)	0.0185 (14)	0.0015 (11)	0.0035 (11)	0.0044 (12)
C10	0.0148 (13)	0.0199 (15)	0.0230 (14)	0.0057 (11)	0.0004 (11)	0.0045 (12)
C11	0.0205 (14)	0.0186 (15)	0.0118 (13)	0.0037 (11)	0.0052 (11)	−0.0005 (11)
C12	0.0246 (14)	0.0121 (14)	0.0200 (14)	−0.0020 (12)	0.0025 (11)	0.0003 (11)
C13	0.0175 (14)	0.0218 (16)	0.0166 (14)	−0.0044 (12)	0.0029 (11)	−0.0013 (12)
C14	0.0154 (13)	0.0175 (15)	0.0168 (13)	0.0009 (11)	0.0011 (10)	0.0009 (11)
C15	0.0212 (14)	0.0122 (14)	0.0158 (13)	−0.0003 (11)	0.0056 (11)	−0.0014 (11)
C16	0.0165 (13)	0.0210 (16)	0.0152 (13)	0.0000 (11)	0.0011 (11)	−0.0023 (11)

O1—C1	1.229 (3)	C6—C7	1.374 (3)
O2—C3	1.357 (3)	C6—H6	0.9500
O2—C8	1.441 (3)	C8—H8A	0.9800
O3—C5	1.358 (3)	C8—H8B	0.9800
O3—C9	1.428 (3)	C8—H8C	0.9800
O4—C7	1.360 (3)	C9—H9A	0.9800
O4—C10	1.444 (3)	C9—H9B	0.9800
O5—N2	1.239 (3)	C9—H9C	0.9800
O6—N2	1.242 (3)	C10—H10A	0.9800
N1—C11	1.352 (3)	C10—H10B	0.9800
N1—H11	0.8600	C10—H10C	0.9800
N1—H12	0.8600	C11—C16	1.406 (4)
N2—C14	1.434 (3)	C11—C12	1.410 (3)
C1—C2	1.454 (3)	C12—C13	1.370 (3)
C1—H1	0.9500	C12—H12A	0.9500
C2—C3	1.409 (3)	C13—C14	1.393 (3)
C2—C7	1.424 (3)	C13—H13	0.9500
C3—C4	1.390 (3)	C14—C15	1.394 (3)
C4—C5	1.389 (3)	C15—C16	1.368 (3)
C4—H4	0.9500	C15—H15	0.9500
C5—C6	1.397 (3)	C16—H16	0.9500
C3—O2—C8	118.10 (19)	O2—C8—H8C	109.5
C5—O3—C9	118.39 (19)	H8A—C8—H8C	109.5
C7—O4—C10	117.03 (19)	H8B—C8—H8C	109.5
C11—N1—H11	120.0	O3—C9—H9A	109.5
C11—N1—H12	120.0	O3—C9—H9B	109.5
H11—N1—H12	120.0	H9A—C9—H9B	109.5
O5—N2—O6	121.4 (2)	O3—C9—H9C	109.5
O5—N2—C14	119.5 (2)	H9A—C9—H9C	109.5
O6—N2—C14	119.1 (2)	H9B—C9—H9C	109.5
O1—C1—C2	127.8 (2)	O4—C10—H10A	109.5
O1—C1—H1	116.1	O4—C10—H10B	109.5
C2—C1—H1	116.1	H10A—C10—H10B	109.5
C3—C2—C7	117.2 (2)	O4—C10—H10C	109.5
C3—C2—C1	124.5 (2)	H10A—C10—H10C	109.5
C7—C2—C1	118.3 (2)	H10B—C10—H10C	109.5
O2—C3—C4	122.4 (2)	N1—C11—C16	120.7 (2)
O2—C3—C2	115.5 (2)	N1—C11—C12	120.9 (2)
C4—C3—C2	122.1 (2)	C16—C11—C12	118.3 (2)
C3—C4—C5	118.2 (2)	C13—C12—C11	120.8 (2)
C3—C4—H4	120.9	C13—C12—H12A	119.6
C5—C4—H4	120.9	C11—C12—H12A	119.6
O3—C5—C4	123.9 (2)	C12—C13—C14	119.4 (2)
O3—C5—C6	114.1 (2)	C12—C13—H13	120.3
C4—C5—C6	122.0 (2)	C14—C13—H13	120.3
C7—C6—C5	119.0 (2)	C15—C14—C13	121.1 (2)
C7—C6—H6	120.5	C15—C14—N2	119.1 (2)
C5—C6—H6	120.5	C13—C14—N2	119.7 (2)
O4—C7—C6	123.1 (2)	C16—C15—C14	119.2 (2)
O4—C7—C2	115.4 (2)	C16—C15—H15	120.4
C6—C7—C2	121.5 (2)	C14—C15—H15	120.4
O2—C8—H8A	109.5	C15—C16—C11	121.2 (2)
O2—C8—H8B	109.5	C15—C16—H16	119.4
H8A—C8—H8B	109.5	C11—C16—H16	119.4
O1—C1—C2—C3	−9.3 (4)	C5—C6—C7—C2	−0.9 (4)
O1—C1—C2—C7	172.5 (2)	C3—C2—C7—O4	179.9 (2)
C8—O2—C3—C4	1.2 (3)	C1—C2—C7—O4	−1.8 (3)
C8—O2—C3—C2	−177.9 (2)	C3—C2—C7—C6	0.2 (3)
C7—C2—C3—O2	179.5 (2)	C1—C2—C7—C6	178.6 (2)
C1—C2—C3—O2	1.3 (4)	N1—C11—C12—C13	176.7 (2)
C7—C2—C3—C4	0.5 (3)	C16—C11—C12—C13	−2.2 (4)
C1—C2—C3—C4	−177.7 (2)	C11—C12—C13—C14	1.3 (4)
O2—C3—C4—C5	−179.5 (2)	C12—C13—C14—C15	0.2 (4)
C2—C3—C4—C5	−0.5 (4)	C12—C13—C14—N2	177.8 (2)
C9—O3—C5—C4	−0.4 (3)	O5—N2—C14—C15	−2.2 (3)
C9—O3—C5—C6	179.3 (2)	O6—N2—C14—C15	176.9 (2)
C3—C4—C5—O3	179.4 (2)	O5—N2—C14—C13	−179.9 (2)
C3—C4—C5—C6	−0.2 (4)	O6—N2—C14—C13	−0.8 (3)
O3—C5—C6—C7	−178.8 (2)	C13—C14—C15—C16	−0.6 (4)
C4—C5—C6—C7	0.9 (4)	N2—C14—C15—C16	−178.3 (2)
C10—O4—C7—C6	0.3 (3)	C14—C15—C16—C11	−0.3 (4)
C10—O4—C7—C2	−179.4 (2)	N1—C11—C16—C15	−177.2 (2)
C5—C6—C7—O4	179.5 (2)	C12—C11—C16—C15	1.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H12···O1	0.86	2.16	3.016 (3)	172
N1—H11···O5i	0.86	2.50	3.288 (3)	152
N1—H11···O6i	0.86	2.50	3.293 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H12⋯O1	0.86	2.16	3.016 (3)	172
N1—H11⋯O5i	0.86	2.50	3.288 (3)	152
N1—H11⋯O6i	0.86	2.50	3.293 (3)	154

Symmetry code: (i) .