4-Nitro­phthalamide

Abstract

In the title compound, C₈H₇N₃O₄ (systematic name: 4-nitro­benzene-1,2-dicarboxamide), each of the substituents is twisted out of the plane of the benzene ring to which it is attached [dihedral angles of 11.36 (2)° for the nitro group, and 60.89 (6) and 34.39 (6)° for the amide groups]. The amide groups are orientated to either side of the least-squares plane through the benzene ring with the amine groups being directed furthest apart. In the crystal, a three-dimensional architecture is established by a network of N—H⋯O hydrogen bonds.

Related literature  

For background to the synthesis of functional phthalocyanines, see: Chin et al. (2012 ▶). For the structure of the 1,2-dicarboxamide derivative, see: Hamada et al. (2012 ▶). For the synthesis, see: Rasmussen et al. (1978 ▶).

Experimental  

Crystal data  

• C₈H₇N₃O₄

• M _r = 209.17

• Monoclinic,

• a = 7.7425 (2) Å

• b = 9.6634 (2) Å

• c = 12.1276 (3) Å

• β = 106.008 (3)°

• V = 872.19 (4) ų

• Z = 4

• Cu Kα radiation

• μ = 1.13 mm⁻¹

• T = 100 K

• 0.40 × 0.30 × 0.20 mm

Data collection  

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▶) T _min = 0.668, T _max = 1.000

• 7908 measured reflections

• 1821 independent reflections

• 1748 reflections with I > 2σ(I)

• R _int = 0.029

Refinement  

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.090

• S = 1.03

• 1821 reflections

• 164 parameters

• 4 restraints

• All H-atom parameters refined

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

CCDC reference: 985960

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1i	0.87 (1)	2.22 (1)	3.0718 (13)	164 (2)
N2—H22⋯O3ii	0.88 (1)	2.10 (1)	2.9628 (12)	168 (2)
N3—H31⋯O1iii	0.88 (1)	2.42 (1)	3.1288 (13)	138 (1)
N3—H31⋯O3iv	0.88 (1)	2.35 (1)	3.0979 (12)	143 (1)
N3—H32⋯O4v	0.87 (1)	2.00 (1)	2.8498 (13)	167 (2)

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

supplementary crystallographic information

2. Structural commentary

As part of our on-going study of functional phthalocyanines, we have previously reported the synthesis and structure of 4-(prop-2-ylnyl­oxy)phthalo­nitrile, prepared from 4-nitro­phthalo­nitrile (Chin et al. (2012). The latter, in turn, is prepared by dehydration of the title compound. As the structure of the title compound is not reported, herein its crystal structure determination is described.

In the title compound, Fig. 1, each of the nitro [the O1—N1—C1—C2 torsion angle is 168.48 (10)°], N2-amide [C3—C4—C7—O3 114.92 (12)°] and N3-amide [C6—C5—C8—O4 142.80 (11)°] groups are twisted out of the plane of the benzene ring to which they are attached. The relative orientation of the amide-O atoms places them in positions on either side of the benzene ring, with the amine groups similarly orientated but directed away from each other. As such, there are no intra­molecular hydrogen bonding contacts. Very similar conformations were found for the two independent molecules comprising the asymmetric unit of the 1,2–dicarboxamide parent compound (Hamada et al., 2012).

In the crystal packing, each N—H H atoms forms a N—H···O hydrogen bond with H31 being bifurcated (Table 1); both O1 and O3 accept two hydrogen bonds. The result is a three-dimensional architecture that can be described globally as comprising columns of molecules aligned along the a axis (Fig. 2).

5. Synthesis and crystallization

The title compound was prepared by modification of a literature procedure (Rasmussen et al., 1978). 4-Nitro­phthalimide and concentrated NH₄OH were stirred at room temperature for 24 h. The precipitate (an off-white powder) was filtered under vacuum and washed with cold water to provide the title compound in 0.68 g yield (63.8 %). M.pt: 465–469 K (literature: 462–464 K). Crystals for the X-ray study were grown from slow evaporation of its aqueous solution.

6. Refinement

All C-bound H atoms were refined freely. The N—H atoms were located from difference map and refined with N—H = 0.88±0.01 Å, and with unrestrained U_iso(H).

Figures

Fig. 1.

The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

Fig. 2.

A view of the unit-cell contents of (I) in projection down the a axis. The N—H···O hydrogen bonds are shown as orange dashed lines.

Crystal data

C8H7N3O4	F(000) = 432
Mr = 209.17	Dx = 1.593 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4480 reflections
a = 7.7425 (2) Å	θ = 3.8–76.2°
b = 9.6634 (2) Å	µ = 1.13 mm−1
c = 12.1276 (3) Å	T = 100 K
β = 106.008 (3)°	Prism, colourless
V = 872.19 (4) Å3	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	1821 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1748 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.029
Detector resolution: 10.4041 pixels mm-1	θmax = 76.4°, θmin = 6.0°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→12
Tmin = 0.668, Tmax = 1.000	l = −14→15
7908 measured reflections

Refinement

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	All H-atom parameters refined
S = 1.03	w = 1/[σ2(Fo2) + (0.0552P)2 + 0.2944P] where P = (Fo2 + 2Fc2)/3
1821 reflections	(Δ/σ)max < 0.001
164 parameters	Δρmax = 0.33 e Å−3
4 restraints	Δρmin = −0.25 e Å−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	0.61481 (11)	0.80745 (8)	0.55898 (7)	0.0202 (2)
O2	0.54207 (13)	0.79742 (9)	0.37347 (8)	0.0266 (2)
O3	1.04596 (10)	0.17952 (8)	0.51619 (7)	0.0160 (2)
O4	0.91323 (12)	0.23508 (8)	0.72189 (7)	0.0192 (2)
N1	0.60572 (12)	0.74606 (10)	0.46837 (8)	0.0177 (2)
N2	0.76591 (13)	0.09066 (10)	0.45344 (8)	0.0171 (2)
H21	0.6511 (13)	0.1037 (17)	0.4443 (14)	0.025 (4)*
H22	0.809 (2)	0.0070 (11)	0.4535 (14)	0.025 (4)*
N3	1.04060 (14)	0.44255 (10)	0.77908 (8)	0.0182 (2)
H31	1.096 (2)	0.4063 (17)	0.8462 (10)	0.027 (4)*
H32	1.050 (2)	0.5306 (10)	0.7667 (13)	0.025 (4)*
C1	0.67444 (14)	0.60364 (11)	0.47498 (10)	0.0154 (2)
C2	0.63660 (14)	0.52513 (12)	0.37619 (10)	0.0171 (2)
H2	0.566 (2)	0.5640 (18)	0.3011 (14)	0.030 (4)*
C3	0.70007 (15)	0.38986 (12)	0.38425 (10)	0.0164 (2)
H3	0.677 (2)	0.3367 (15)	0.3164 (13)	0.018 (3)*
C4	0.80132 (14)	0.33683 (11)	0.48911 (9)	0.0141 (2)
C5	0.83839 (14)	0.41940 (11)	0.58825 (9)	0.0137 (2)
C6	0.77318 (15)	0.55445 (11)	0.58101 (10)	0.0150 (2)
H6	0.795 (2)	0.6102 (16)	0.6473 (13)	0.019 (3)*
C7	0.88135 (15)	0.19421 (11)	0.49017 (9)	0.0137 (2)
C8	0.93594 (14)	0.35831 (11)	0.70270 (9)	0.0146 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0180 (4)	0.0139 (4)	0.0287 (5)	0.0015 (3)	0.0063 (3)	−0.0027 (3)
O2	0.0284 (5)	0.0171 (4)	0.0269 (5)	0.0051 (3)	−0.0047 (4)	0.0061 (3)
O3	0.0152 (4)	0.0130 (4)	0.0202 (4)	0.0004 (3)	0.0053 (3)	−0.0006 (3)
O4	0.0283 (4)	0.0105 (4)	0.0193 (4)	0.0000 (3)	0.0076 (3)	0.0020 (3)
N1	0.0128 (4)	0.0128 (5)	0.0258 (5)	−0.0002 (3)	0.0024 (4)	0.0013 (4)
N2	0.0153 (5)	0.0111 (5)	0.0246 (5)	0.0009 (4)	0.0049 (4)	−0.0017 (4)
N3	0.0265 (5)	0.0115 (5)	0.0147 (5)	−0.0005 (4)	0.0021 (4)	0.0017 (3)
C1	0.0135 (5)	0.0105 (5)	0.0221 (6)	0.0003 (4)	0.0050 (4)	0.0024 (4)
C2	0.0148 (5)	0.0169 (5)	0.0187 (5)	0.0003 (4)	0.0032 (4)	0.0029 (4)
C3	0.0170 (5)	0.0149 (5)	0.0170 (5)	−0.0009 (4)	0.0045 (4)	−0.0012 (4)
C4	0.0136 (5)	0.0109 (5)	0.0185 (5)	−0.0012 (4)	0.0057 (4)	0.0003 (4)
C5	0.0138 (5)	0.0113 (5)	0.0167 (5)	−0.0008 (4)	0.0053 (4)	0.0012 (4)
C6	0.0157 (5)	0.0118 (5)	0.0180 (5)	−0.0017 (4)	0.0058 (4)	−0.0011 (4)
C7	0.0177 (5)	0.0118 (5)	0.0124 (5)	0.0002 (4)	0.0055 (4)	−0.0002 (4)
C8	0.0177 (5)	0.0112 (5)	0.0161 (5)	0.0018 (4)	0.0069 (4)	−0.0002 (4)

Geometric parameters (Å, º)

O1—N1	1.2336 (13)	C1—C2	1.3796 (16)
O2—N1	1.2252 (13)	C1—C6	1.3862 (15)
O3—C7	1.2338 (14)	C2—C3	1.3904 (16)
O4—C8	1.2351 (14)	C2—H2	0.997 (16)
N1—C1	1.4698 (14)	C3—C4	1.3945 (15)
N2—C7	1.3338 (14)	C3—H3	0.945 (15)
N2—H21	0.874 (9)	C4—C5	1.4050 (15)
N2—H22	0.875 (9)	C4—C7	1.5097 (14)
N3—C8	1.3280 (15)	C5—C6	1.3934 (15)
N3—H31	0.881 (9)	C5—C8	1.5058 (14)
N3—H32	0.870 (9)	C6—H6	0.943 (16)
O2—N1—O1	123.47 (10)	C4—C3—H3	121.1 (9)
O2—N1—C1	118.45 (10)	C3—C4—C5	120.16 (10)
O1—N1—C1	118.09 (9)	C3—C4—C7	118.00 (9)
C7—N2—H21	119.9 (11)	C5—C4—C7	121.64 (9)
C7—N2—H22	118.1 (11)	C6—C5—C4	119.54 (10)
H21—N2—H22	120.6 (15)	C6—C5—C8	120.41 (10)
C8—N3—H31	116.6 (11)	C4—C5—C8	119.89 (9)
C8—N3—H32	122.9 (10)	C1—C6—C5	118.50 (10)
H31—N3—H32	120.4 (15)	C1—C6—H6	121.1 (9)
C2—C1—C6	123.21 (10)	C5—C6—H6	120.4 (9)
C2—C1—N1	118.72 (10)	O3—C7—N2	123.29 (10)
C6—C1—N1	118.06 (10)	O3—C7—C4	119.99 (9)
C1—C2—C3	118.01 (10)	N2—C7—C4	116.51 (9)
C1—C2—H2	121.2 (10)	O4—C8—N3	123.42 (10)
C3—C2—H2	120.8 (10)	O4—C8—C5	119.37 (10)
C2—C3—C4	120.57 (10)	N3—C8—C5	117.20 (9)
C2—C3—H3	118.2 (9)
O2—N1—C1—C2	−11.31 (15)	C2—C1—C6—C5	0.37 (17)
O1—N1—C1—C2	168.48 (10)	N1—C1—C6—C5	179.78 (9)
O2—N1—C1—C6	169.25 (10)	C4—C5—C6—C1	−0.61 (16)
O1—N1—C1—C6	−10.96 (15)	C8—C5—C6—C1	−176.01 (10)
C6—C1—C2—C3	0.44 (17)	C3—C4—C7—O3	114.92 (12)
N1—C1—C2—C3	−178.96 (10)	C5—C4—C7—O3	−60.00 (14)
C1—C2—C3—C4	−1.02 (16)	C3—C4—C7—N2	−60.02 (13)
C2—C3—C4—C5	0.79 (16)	C5—C4—C7—N2	125.05 (11)
C2—C3—C4—C7	−174.21 (10)	C6—C5—C8—O4	142.80 (11)
C3—C4—C5—C6	0.05 (16)	C4—C5—C8—O4	−32.58 (15)
C7—C4—C5—C6	174.86 (9)	C6—C5—C8—N3	−35.96 (14)
C3—C4—C5—C8	175.47 (10)	C4—C5—C8—N3	148.66 (11)
C7—C4—C5—C8	−9.71 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1i	0.87 (1)	2.22 (1)	3.0718 (13)	164 (2)
N2—H22···O3ii	0.88 (1)	2.10 (1)	2.9628 (12)	168 (2)
N3—H31···O1iii	0.88 (1)	2.42 (1)	3.1288 (13)	138 (1)
N3—H31···O3iv	0.88 (1)	2.35 (1)	3.0979 (12)	143 (1)
N3—H32···O4v	0.87 (1)	2.00 (1)	2.8498 (13)	167 (2)

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