4-Nitro­phthalamide

Jan, C.Y.; Shamsudin, N.B.H.; Tan, A.L.; Young, D.J.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S1600536814002955

organic compounds

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Volume 70| Part 3| March 2014| Page o293

doi:10.1107/S1600536814002955

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4-Nitrophthalamide

Chin Yee Jan,^a Norzianah Binti Haji Shamsudin,^a Ai Ling Tan,^a David J. Young,^a ‡ Seik Weng Ng ^b,^c and Edward R. T. Tiekink ^b ^*

^aFaculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link BE 1410, Negara Brunei Darussalam, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 9 February 2014; accepted 10 February 2014; online 15 February 2014)

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.

CCDC reference: 985960

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, P 2₁ /c
a = 7.7425 (2) Å
b = 9.6634 (2) Å
c = 12.1276 (3) Å
β = 106.008 (3)°
V = 872.19 (4) Å³
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[F² > 2σ(F²)] = 0.032
wR(F²) = 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

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⋯O3^iv	0.88 (1)	2.35 (1)	3.0979 (12)	143 (1)
N3—H32⋯O4^v	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) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 985960

Crystal structure: contains datablocks general, I. DOI: 10.1107/S1600536814002955/hg5382sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814002955/hg5382Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814002955/hg5382Isup3.cml

checkCIF report

Structural commentary top

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).

Synthesis and crystallization top

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.

Refinement top

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).

Related literature top

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).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); 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).

Figures top

	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.

4-Nitrobenzene-1,2-dicarboxamide top

Crystal data top

C₈H₇N₃O₄	F(000) = 432
M_r = 209.17	D_x = 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 top

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	R_int = 0.029
Detector resolution: 10.4041 pixels mm^-1	θ_max = 76.4°, θ_min = 6.0°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −11→12
T_min = 0.668, T_max = 1.000	l = −14→15
7908 measured reflections

Refinement top

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(F_o²) + (0.0552P)² + 0.2944P] where P = (F_o² + 2F_c²)/3
1821 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.33 e Å⁻³
4 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₈H₇N₃O₄	V = 872.19 (4) Å³
M_r = 209.17	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 7.7425 (2) Å	µ = 1.13 mm⁻¹
b = 9.6634 (2) Å	T = 100 K
c = 12.1276 (3) Å	0.40 × 0.30 × 0.20 mm
β = 106.008 (3)°

Data collection top

Agilent SuperNova Dual diffractometer with an Atlas detector	1821 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1748 reflections with I > 2σ(I)
T_min = 0.668, T_max = 1.000	R_int = 0.029
7908 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	4 restraints
wR(F²) = 0.090	All H-atom parameters refined
S = 1.03	Δρ_max = 0.33 e Å⁻³
1821 reflections	Δρ_min = −0.25 e Å⁻³
164 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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···O3^iv	0.88 (1)	2.35 (1)	3.0979 (12)	143 (1)
N3—H32···O4^v	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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1ⁱ	0.874 (9)	2.221 (10)	3.0718 (13)	164.4 (15)
N2—H22···O3ⁱⁱ	0.875 (9)	2.101 (10)	2.9628 (12)	168.1 (15)
N3—H31···O1ⁱⁱⁱ	0.881 (9)	2.415 (13)	3.1288 (13)	138.4 (14)
N3—H31···O3^iv	0.881 (9)	2.351 (13)	3.0979 (12)	142.6 (14)
N3—H32···O4^v	0.870 (9)	1.996 (10)	2.8498 (13)	166.6 (15)

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.

Footnotes

‡Additional correspondence author, e-mail: david.young@ubd.edu.bn.

Acknowledgements

We gratefully acknowledge funding from the Brunei Research Council, and thank the Ministry of Higher Education (Malaysia) and the University of Malaya for funding structural studies through the High-Impact Research scheme (UM.C/HIR-MOHE/SC/03).

References

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