Retracted: 2-Amino-3,5-dinitro­benzoic acid–ammonia (1/1)

The title complex, C₇H₅N₃O₆·NH₃, contains one 2-amino-3,5-dinitro­benzoic acid mol­ecule and one ammonia mol­ecule. In the crystal structure, inter­molecular N—H...N and N—H...O hydrogen bonds result in the formation of a supra­molecular network structure; intramolecular N—H...O hydrogen bonds are also present.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.052
• wR factor = 0.182
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N3     -   C2      ..       9.11 su
PLAT417_ALERT_2_B Short Inter D-H..H-D       H3A    ..  H4C     ..       1.44 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O2     ..  O2      ..       2.55 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.29
PLAT334_ALERT_2_C Small Average Benzene C-C Dist.  C1     -C6            1.35 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4C    ..  O3      ..       2.62 Ang.

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          6

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to carboxyl groups are one of the most important classes of biological ligands, the coordination of metal-carboxyl groups complexes are of critical importance in biological systems, organic materials and coordination chemistry. Recently, carboxyl groups with variable coordination modes have been used to construct metal-organic supramolecular structures (McCann et al., 1996; McCann et al., 1995; Wai et al., 1990; Yaghi et al., 1996; Min & Lee 2002; Maira et al., 2001). We originally attempted to synthesize complexes featuring Nd metal chains by reaction of the neodymium(III) ion with 2-amino-3,5-dinitrobenzoic acid ligand. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one (C₇H₅N₃O₆) molecule and one ammonia molecule.

In the crystal structure, intramolecular N—H···O and intermolecular N—H···N and N—H···O hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.

Related literature

For general backgroud, see: Desiraju (1995, 1997); Braga et al. (1998); McCann et al. (1996, 1995); Wai et al. (1990); Yaghi et al. (1996); Min & Lee (2002); Maira et al. (2001). For bond-length data, see: Allen et al. (1987).

S2. Experimental

Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Neodymium (III) nitrate hexahydrate (219.1 mg, 0.5 mmol), 2-amino-3,5-dinitrobenzoic acid (227.2 mg, 1 mmol), ammonia (0.5 mol/l, 2 ml) and distilled water (6 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 443 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.

S3. Refinement

H4A, H4B and H4C (for NH₃) were located in difference syntheses and refined isotropically [N—H = 0.778 (16)–0.82 (4) Å and U_iso(H) = 0.069 (4)–0.083 (12) Ų]. The remaining H atoms were positioned geometrically, with O—H = 0.82 Å (for OH), N—H = 0.86 Å (for NH₂) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,N,O), where x = 1.5 for OH H, and x = 1.2 for all other H atoms.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

2-Amino-3,5-dinitrobenzoic acid–ammonia (1/1)

Crystal data

C7H5N3O6·NH3	F(000) = 1008
Mr = 244.17	Dx = 1.759 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1487 reflections
a = 24.825 (14) Å	θ = 3.0–26.8°
b = 6.594 (3) Å	µ = 0.16 mm^−1
c = 12.0862 (16) Å	T = 273 K
β = 111.262 (5)°	Prism, colorless
V = 1843.8 (14) Å^3	0.24 × 0.15 × 0.14 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	1907 independent reflections
Radiation source: fine-focus sealed tube	979 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 26.7°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −31→31
Tmin = 0.964, Tmax = 0.978	k = −8→8
6167 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.182	w = 1/[σ^2(Fo^2) + (0.1152P)^2 + 0.02P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1907 reflections	Δρmax = 0.44 e Å^−3
168 parameters	Δρmin = −0.25 e Å^−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0065 (17)

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	0.53274 (9)	0.2533 (4)	1.04676 (19)	0.0731 (7)
H1	0.5650	0.2393	1.0435	0.110*
O2	0.50729 (11)	0.2169 (5)	0.8598 (2)	0.1064 (11)
O3	0.29271 (9)	0.1316 (4)	0.63188 (18)	0.0808 (8)
O4	0.24242 (9)	0.3056 (4)	0.7047 (2)	0.0792 (8)
O5	0.30605 (10)	0.3709 (4)	1.1124 (2)	0.0863 (8)
O6	0.39263 (12)	0.2999 (5)	1.2184 (2)	0.0986 (10)
N1	0.28701 (11)	0.2278 (4)	0.7102 (2)	0.0606 (7)
N2	0.35427 (12)	0.3209 (4)	1.1251 (2)	0.0662 (8)
N3	0.40261 (9)	0.2101 (4)	0.73014 (18)	0.0557 (7)
H3A	0.3750	0.2048	0.6620	0.067*
H3B	0.4379	0.2017	0.7348	0.067*
N4	0.63149 (11)	0.2285 (4)	1.0268 (2)	0.0568 (7)
C1	0.43521 (12)	0.2456 (4)	0.9345 (2)	0.0546 (8)
C2	0.39110 (13)	0.2306 (5)	0.8246 (3)	0.0571 (8)
C3	0.33508 (12)	0.2443 (4)	0.8191 (3)	0.0536 (7)
C4	0.32277 (12)	0.2740 (4)	0.9167 (2)	0.0557 (8)
H4	0.2847	0.2875	0.9122	0.067*
C5	0.36697 (13)	0.2838 (4)	1.0218 (2)	0.0544 (7)
C6	0.42248 (13)	0.2684 (5)	1.0317 (3)	0.0561 (8)
H6	0.4519	0.2737	1.1060	0.067*
C7	0.49499 (13)	0.2388 (5)	0.9438 (3)	0.0631 (8)
H4A	0.6614 (9)	0.228 (5)	1.078 (2)	0.074 (11)*
H4C	0.6283 (13)	0.205 (5)	0.9598 (16)	0.083 (12)*
H4B	0.6006 (11)	0.242 (12)	1.036 (4)	0.069 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0398 (13)	0.1105 (19)	0.0614 (14)	−0.0010 (12)	0.0094 (11)	−0.0005 (11)
O2	0.0449 (14)	0.216 (3)	0.0616 (15)	0.0038 (15)	0.0227 (12)	0.0008 (15)
O3	0.0561 (14)	0.122 (2)	0.0605 (13)	−0.0053 (13)	0.0163 (11)	−0.0104 (13)
O4	0.0376 (13)	0.126 (2)	0.0702 (15)	0.0098 (12)	0.0144 (11)	0.0057 (13)
O5	0.0611 (16)	0.128 (2)	0.0805 (15)	0.0064 (13)	0.0389 (13)	−0.0095 (14)
O6	0.078 (2)	0.164 (3)	0.0521 (14)	0.0105 (16)	0.0222 (14)	−0.0059 (14)
N1	0.0416 (15)	0.0910 (19)	0.0474 (14)	−0.0014 (12)	0.0141 (11)	0.0051 (12)
N2	0.0572 (18)	0.085 (2)	0.0593 (16)	0.0009 (14)	0.0248 (15)	−0.0027 (13)
N3	0.0239 (11)	0.111 (2)	0.0325 (11)	0.0005 (10)	0.0105 (9)	−0.0036 (11)
N4	0.0288 (13)	0.0847 (19)	0.0506 (16)	0.0018 (12)	0.0068 (12)	0.0018 (13)
C1	0.0385 (16)	0.073 (2)	0.0517 (17)	−0.0004 (13)	0.0160 (14)	0.0004 (13)
C2	0.0434 (16)	0.075 (2)	0.0527 (17)	0.0018 (13)	0.0172 (14)	0.0010 (13)
C3	0.0401 (16)	0.0689 (19)	0.0501 (16)	−0.0014 (12)	0.0145 (13)	0.0037 (13)
C4	0.0444 (17)	0.0661 (19)	0.0570 (18)	0.0023 (12)	0.0189 (15)	0.0048 (13)
C5	0.0502 (17)	0.0672 (19)	0.0493 (16)	0.0027 (13)	0.0223 (14)	0.0016 (12)
C6	0.0426 (16)	0.072 (2)	0.0509 (16)	−0.0012 (13)	0.0137 (13)	−0.0012 (13)
C7	0.0405 (17)	0.093 (2)	0.0538 (18)	−0.0022 (14)	0.0150 (15)	0.0039 (14)

Geometric parameters (Å, º)

O1—C7	1.261 (3)	N4—H4C	0.799 (16)
O1—H1	0.8200	N4—H4B	0.82 (4)
O2—C7	1.171 (4)	N4—H4A	0.778 (16)
O3—N1	1.190 (3)	C1—C6	1.331 (4)
O4—N1	1.200 (3)	C1—C2	1.385 (4)
O5—N2	1.197 (3)	C1—C7	1.447 (4)
O6—N2	1.191 (3)	C2—C3	1.371 (4)
N1—C3	1.424 (4)	C3—C4	1.336 (4)
N2—C5	1.415 (4)	C4—C5	1.346 (4)
N3—C2	1.281 (4)	C4—H4	0.9300
N3—H3A	0.8600	C5—C6	1.343 (4)
N3—H3B	0.8600	C6—H6	0.9300
C7—O1—H1	109.5	C2—C1—C7	120.3 (3)
O3—N1—O4	123.9 (3)	N3—C2—C3	120.9 (3)
O3—N1—C3	118.3 (3)	N3—C2—C1	120.5 (3)
O4—N1—C3	117.8 (3)	C3—C2—C1	118.5 (3)
O6—N2—O5	124.9 (3)	C4—C3—C2	121.3 (3)
O6—N2—C5	117.3 (3)	C4—C3—N1	116.3 (3)
O5—N2—C5	117.8 (3)	C2—C3—N1	122.4 (3)
C2—N3—H3A	120.0	C3—C4—C5	118.1 (3)
C2—N3—H3B	120.0	C3—C4—H4	120.9
H3A—N3—H3B	120.0	C5—C4—H4	120.9
H4C—N4—H4B	114 (3)	C6—C5—C4	122.6 (3)
H4C—N4—H4A	122 (3)	C6—C5—N2	119.0 (3)
H4B—N4—H4A	124 (3)	C4—C5—N2	118.3 (3)
H4B—N4—H4C	114 (3)	C1—C6—C5	119.6 (3)
H4A—N4—H4C	122 (3)	C1—C6—H6	120.2
H4C—N4—H4B	114 (3)	C5—C6—H6	120.2
H4A—N4—H4B	124 (3)	O2—C7—O1	122.1 (3)
H4C—N4—H4B	114 (3)	O2—C7—C1	121.2 (3)
C6—C1—C2	119.7 (3)	O1—C7—C1	116.7 (3)
C6—C1—C7	120.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4C···O3^i	0.80 (2)	2.62 (3)	3.201 (4)	130 (3)
N4—H4C···N3^i	0.80 (2)	2.14 (2)	2.910 (4)	161 (3)
N4—H4A···O4^ii	0.78 (2)	2.05 (2)	2.822 (4)	173 (3)
N3—H3B···O2^i	0.86	2.07	2.820 (4)	145
N3—H3A···N4^i	0.86	2.23	2.910 (4)	135
N4—H4B···O2	0.82 (4)	2.52 (4)	3.012 (4)	120 (3)
N4—H4B···O1	0.82 (4)	1.74 (2)	2.554 (3)	175 (6)
N3—H3A···O3	0.86	2.00	2.602 (3)	126
N3—H3B···O2	0.86	1.84	2.501 (3)	133

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