organic compounds
Dimethylammonium 2-amino-5-nitroterephthalate hemihydrate
aMax-Eyth-Strasse 2, 24118 Kiel, Germany
*Correspondence e-mail: stock@ac.uni-kiel.de
The 2H8N+·C8H5N2O6−·0.5H2O, comprises a monodeprotonated 2-amino-5-nitroterephthalate anion and a dimethylammonium counter-ion on general positions and a water molecule that lies on a twofold rotation axis. Extensive hydrogen bonding is observed between the carboxylate group and the dimethylammonium ion, the water molecule and the carboxylic acid group, as well as between the amino group, the water molecule and the carboxylic acid group (N—H⋯O and O—H⋯O hydrogen bonds are involved).
of the title compound, CKeywords: crystal structure; dimethylammonium 2-amino-5-nitroterephtalate; functionalized terephthalic acid; H-bonding.
CCDC reference: 1446285
Structure description
The title compound comprises a mono-deprotonated benzene 1,4-dicarboxylic acid with an NH2 and an NO2 group at the 2- and 5-positions, respectively (Fig. 1). Charge balance is accomplished with a dimethylammonium counter-cation. Extensive N—H⋯O and O—H⋯O hydrogen bonding between the cation, the anion and the water molecule leads to a three-dimensional structure (Table 1, Fig. 2).
Functionalized terephthalate ions are of special interest for the synthesis of porous coordination polymers in order to tune host–guest interactions within functionalized pore surfaces (Biswas et al., 2011). A compound with the same cation but the non-functionalized terephthalate ion, which does not contain an additional water molecule, has been reported (Zhao et al., 2007). Extensive hydrogen bonding is also observed in this structure. Thus, the terephthalate ions are linked to each other by O—H⋯O hydrogen bonds, forming a one-dimensional polymeric chain. In addition, the terephthalate anions and dimethylammonium cations are connected into a three-dimensional structure by N—H⋯O hydrogen-bonds (Zhao et al., 2007).
Synthesis and crystallization
Dimethylammonium 2-amino-5-nitroterephtalate hemi hydrate was obtained from 10 mg 2-amino-5-nitro-terephthalic acid (0.18 mmol), 0.256 ml DMF and 0.244 ml H2O. A 2 ml teflon-lined steel autoclave was used for the synthesis. The reactor was heated to 150°C for 24 h then cooled down to room temperature over 12 h, to give crystals suitable for X-ray data collection.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
|
Structural data
CCDC reference: 1446285
10.1107/S2414314616000481/sj4003sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616000481/sj4003Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616000481/sj4003Isup3.cml
Dimethylammonium 2-amino-5-nitroterephtalate hemi hydrate was obtained from 10 mg 2-amino-5-nitro-terephthalic acid (0.18 mmol), 0.256 ml DMF and 244 ml H2O. A 2 ml teflon lined steel autoclave was used for the synthesis. The reactor was heated to 150 °C for 24 h then cooled down to room temperature over 12 h, to give crystals suitable for X-ray data collection.
Dimethylammonium 2-amino-5-nitroterephtalate hemi hydrate was obtained from 10 mg 2-amino-5-nitro-terephthalic acid (0.18 mmol), 0.256 ml DMF and 244 ml H2O. A 2 ml teflon-lined steel autoclave was used for the synthesis. The reactor was heated to 150°C for 24 h then cooled down to room temperature over 12 h, to give crystals suitable for X-ray data collection.
The title compound consists of a mono-deprotonated benzene 1,4-dicarboxylic acid with an NH2 and an NO2 group at the 2- and 5-positions, respectively, Fig. 1. Charge balance is accomplished with a dimethylammonium counter-cation. Extensive N—H···O and O—H···O hydrogen bonding, Table 1, between the cation, the anion and the water molecule leads to a three-dimensional structure, Fig. 2.
Functionalized terephthalate ions are of special interest for the synthesis of porous coordination polymers in order to tune host–guest interactions within functionalized pore surfaces (Biswas et al., 2011). A compound with the same cation but the non-functionalized terephthalate ion, which does not contain an additional water molecule, has been reported (Zhao et al., 2007). Extensive hydrogen bonding is also observed in this structure. Thus, the terephthalate ions are linked to each other by O—H···O hydrogen bonds, forming a one-dimensional polymeric chain. In addition, the terephthalate anions and dimethylammonium cations are connected into a three-dimensional structure by N—H···O hydrogen-bonds (Zhao et al., 2007).
Data collection: X-AREA (Stoe, 2008); cell
X-AREA (Stoe, 2008); data reduction: X-AREA (Stoe, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. : The asymmetric unit of the title compound showing the atom labelling with displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. | |
Fig. 2. : Crystal packing of the title compound viewed along the crystallographic b axis. Hydrogen bonds are shown as dashed lines. |
2C2H8N+·2C8H5N2O6−·H2O | F(000) = 1176 |
Mr = 560.48 | Dx = 1.425 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 21.494 (4) Å | Cell parameters from 9323 reflections |
b = 6.4300 (13) Å | θ = 2.1–25° |
c = 19.193 (4) Å | µ = 0.12 mm−1 |
β = 99.98 (3)° | T = 293 K |
V = 2612.5 (9) Å3 | Needle, brown |
Z = 4 | 0.21 × 0.12 × 0.05 mm |
Stoe IPDS-1 diffractometer | 1218 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.087 |
Phi scan | θmax = 25.0°, θmin = 2.2° |
Absorption correction: numerical (X-SHAPE and X-RED; Stoe, 2008) | h = −25→25 |
Tmin = 0.96, Tmax = 0.98 | k = −7→7 |
8870 measured reflections | l = −22→22 |
2305 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.060P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2305 reflections | Δρmax = 0.17 e Å−3 |
191 parameters | Δρmin = −0.23 e Å−3 |
2C2H8N+·2C8H5N2O6−·H2O | V = 2612.5 (9) Å3 |
Mr = 560.48 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 21.494 (4) Å | µ = 0.12 mm−1 |
b = 6.4300 (13) Å | T = 293 K |
c = 19.193 (4) Å | 0.21 × 0.12 × 0.05 mm |
β = 99.98 (3)° |
Stoe IPDS-1 diffractometer | 2305 independent reflections |
Absorption correction: numerical (X-SHAPE and X-RED; Stoe, 2008) | 1218 reflections with I > 2σ(I) |
Tmin = 0.96, Tmax = 0.98 | Rint = 0.087 |
8870 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.17 e Å−3 |
2305 reflections | Δρmin = −0.23 e Å−3 |
191 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1647 (2) | 0.5874 (7) | 0.6545 (3) | 0.0857 (13) | |
H1A | 0.1554 | 0.6218 | 0.7003 | 0.103* | |
H1B | 0.1810 | 0.7079 | 0.6343 | 0.103* | |
H1C | 0.1268 | 0.5418 | 0.6243 | 0.103* | |
C2 | 0.2293 (2) | 0.3567 (7) | 0.5941 (2) | 0.0754 (12) | |
H2A | 0.2602 | 0.2476 | 0.6026 | 0.091* | |
H2B | 0.1926 | 0.3071 | 0.5628 | 0.091* | |
H2C | 0.2468 | 0.4732 | 0.5728 | 0.091* | |
N1 | 0.21164 (14) | 0.4215 (5) | 0.66167 (15) | 0.0564 (7) | |
H3A | 0.1965 | 0.3117 | 0.6815 | 0.091 (14)* | |
H3B | 0.2462 | 0.4640 | 0.6906 | 0.085 (14)* | |
C3 | 0.38888 (14) | 0.5454 (5) | 0.67852 (15) | 0.0394 (7) | |
C4 | 0.37102 (14) | 0.6636 (5) | 0.61645 (15) | 0.0432 (7) | |
C5 | 0.38628 (15) | 0.5967 (5) | 0.55256 (15) | 0.0482 (8) | |
H5 | 0.3741 | 0.6770 | 0.5122 | 0.064 (10)* | |
C6 | 0.41882 (14) | 0.4154 (5) | 0.54760 (15) | 0.0432 (7) | |
C7 | 0.43852 (14) | 0.2946 (5) | 0.61005 (15) | 0.0438 (8) | |
C8 | 0.42165 (15) | 0.3674 (5) | 0.67438 (15) | 0.0452 (8) | |
H8 | 0.4337 | 0.2893 | 0.7153 | 0.057 (10)* | |
C9 | 0.36954 (16) | 0.5969 (5) | 0.74900 (15) | 0.0439 (7) | |
C10 | 0.43132 (15) | 0.3464 (6) | 0.47806 (16) | 0.0498 (8) | |
N2 | 0.33726 (14) | 0.8558 (5) | 0.61761 (15) | 0.0572 (8) | |
N3 | 0.47084 (14) | 0.1170 (5) | 0.61051 (16) | 0.0613 (8) | |
H6A | 0.4812 | 0.0484 | 0.6493 | 0.077 (13)* | |
H6B | 0.4813 | 0.0712 | 0.5721 | 0.076 (13)* | |
O1 | 0.31397 (11) | 0.5663 (4) | 0.75635 (12) | 0.0555 (6) | |
O2 | 0.41281 (11) | 0.6591 (4) | 0.79741 (11) | 0.0609 (7) | |
O3 | 0.40789 (14) | 0.4728 (4) | 0.42515 (13) | 0.0717 (8) | |
H9 | 0.4136 | 0.4220 | 0.3876 | 0.17 (3)* | |
O4 | 0.45861 (13) | 0.1878 (5) | 0.46819 (12) | 0.0748 (8) | |
O5 | 0.33347 (14) | 0.9371 (4) | 0.67470 (13) | 0.0740 (8) | |
O6 | 0.31376 (18) | 0.9364 (5) | 0.56135 (15) | 0.1048 (13) | |
O7 | 0.5000 | 0.9096 (6) | 0.7500 | 0.0556 (9) | |
H7 | 0.529 (2) | 0.826 (7) | 0.737 (2) | 0.100 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.089 (3) | 0.071 (3) | 0.095 (3) | 0.013 (2) | 0.009 (2) | −0.005 (2) |
C2 | 0.076 (3) | 0.085 (3) | 0.066 (3) | −0.001 (2) | 0.014 (2) | −0.010 (2) |
N1 | 0.0667 (19) | 0.0524 (19) | 0.0493 (16) | −0.0100 (15) | 0.0074 (15) | 0.0073 (14) |
C3 | 0.0457 (17) | 0.0415 (18) | 0.0313 (15) | −0.0016 (15) | 0.0076 (13) | −0.0029 (12) |
C4 | 0.0538 (18) | 0.0402 (19) | 0.0362 (16) | 0.0059 (15) | 0.0092 (13) | 0.0002 (13) |
C5 | 0.063 (2) | 0.048 (2) | 0.0341 (17) | 0.0029 (16) | 0.0104 (14) | 0.0042 (14) |
C6 | 0.0530 (18) | 0.044 (2) | 0.0338 (16) | 0.0026 (15) | 0.0096 (13) | −0.0021 (13) |
C7 | 0.0474 (18) | 0.044 (2) | 0.0402 (18) | 0.0049 (15) | 0.0076 (14) | −0.0007 (13) |
C8 | 0.0552 (19) | 0.048 (2) | 0.0331 (16) | 0.0017 (16) | 0.0096 (13) | 0.0048 (14) |
C9 | 0.057 (2) | 0.043 (2) | 0.0333 (16) | −0.0007 (15) | 0.0129 (14) | 0.0009 (13) |
C10 | 0.058 (2) | 0.054 (2) | 0.0387 (17) | 0.0031 (17) | 0.0117 (15) | −0.0022 (16) |
N2 | 0.075 (2) | 0.0490 (19) | 0.0479 (17) | 0.0158 (15) | 0.0123 (14) | 0.0025 (14) |
N3 | 0.082 (2) | 0.058 (2) | 0.0458 (17) | 0.0266 (16) | 0.0178 (14) | 0.0051 (14) |
O1 | 0.0532 (14) | 0.0672 (17) | 0.0488 (13) | −0.0041 (11) | 0.0169 (10) | −0.0068 (11) |
O2 | 0.0691 (16) | 0.0805 (19) | 0.0338 (11) | −0.0170 (13) | 0.0105 (11) | −0.0075 (11) |
O3 | 0.106 (2) | 0.0723 (19) | 0.0376 (13) | 0.0244 (15) | 0.0160 (14) | 0.0045 (12) |
O4 | 0.101 (2) | 0.075 (2) | 0.0511 (15) | 0.0311 (17) | 0.0185 (13) | −0.0058 (13) |
O5 | 0.118 (2) | 0.0561 (17) | 0.0507 (16) | 0.0237 (15) | 0.0234 (14) | −0.0048 (12) |
O6 | 0.165 (3) | 0.096 (2) | 0.0505 (16) | 0.075 (2) | 0.0096 (18) | 0.0136 (16) |
O7 | 0.059 (2) | 0.056 (2) | 0.052 (2) | 0.000 | 0.0088 (16) | 0.000 |
C1—N1 | 1.458 (5) | C5—H5 | 0.9300 |
C1—H1A | 0.9600 | C6—C7 | 1.430 (4) |
C1—H1B | 0.9600 | C6—C10 | 1.475 (4) |
C1—H1C | 0.9600 | C7—N3 | 1.336 (4) |
C2—N1 | 1.474 (4) | C7—C8 | 1.425 (4) |
C2—H2A | 0.9600 | C8—H8 | 0.9300 |
C2—H2B | 0.9600 | C9—O1 | 1.243 (4) |
C2—H2C | 0.9600 | C9—O2 | 1.261 (4) |
N1—H3A | 0.8900 | C10—O4 | 1.208 (4) |
N1—H3B | 0.8900 | C10—O3 | 1.330 (4) |
C3—C8 | 1.354 (4) | N2—O6 | 1.225 (4) |
C3—C4 | 1.409 (4) | N2—O5 | 1.229 (3) |
C3—C9 | 1.519 (4) | N3—H6A | 0.8600 |
C4—C5 | 1.391 (4) | N3—H6B | 0.8600 |
C4—N2 | 1.435 (4) | O3—H9 | 0.8200 |
C5—C6 | 1.371 (4) | O7—H7 | 0.89 (4) |
N1—C1—H1A | 109.5 | C6—C5—H5 | 119.2 |
N1—C1—H1B | 109.5 | C4—C5—H5 | 119.2 |
H1A—C1—H1B | 109.5 | C5—C6—C7 | 119.0 (3) |
N1—C1—H1C | 109.5 | C5—C6—C10 | 119.6 (3) |
H1A—C1—H1C | 109.5 | C7—C6—C10 | 121.4 (3) |
H1B—C1—H1C | 109.5 | N3—C7—C8 | 119.0 (3) |
N1—C2—H2A | 109.5 | N3—C7—C6 | 123.3 (3) |
N1—C2—H2B | 109.5 | C8—C7—C6 | 117.7 (3) |
H2A—C2—H2B | 109.5 | C3—C8—C7 | 122.8 (3) |
N1—C2—H2C | 109.5 | C3—C8—H8 | 118.6 |
H2A—C2—H2C | 109.5 | C7—C8—H8 | 118.6 |
H2B—C2—H2C | 109.5 | O1—C9—O2 | 124.6 (3) |
C1—N1—C2 | 113.8 (3) | O1—C9—C3 | 118.9 (3) |
C1—N1—H3A | 108.8 | O2—C9—C3 | 116.4 (3) |
C2—N1—H3A | 108.8 | O4—C10—O3 | 121.8 (3) |
C1—N1—H3B | 108.8 | O4—C10—C6 | 124.5 (3) |
C2—N1—H3B | 108.8 | O3—C10—C6 | 113.7 (3) |
H3A—N1—H3B | 107.7 | O6—N2—O5 | 121.7 (3) |
C8—C3—C4 | 118.3 (3) | O6—N2—C4 | 118.9 (3) |
C8—C3—C9 | 117.5 (3) | O5—N2—C4 | 119.5 (3) |
C4—C3—C9 | 124.0 (3) | C7—N3—H6A | 120.0 |
C5—C4—C3 | 120.5 (3) | C7—N3—H6B | 120.0 |
C5—C4—N2 | 118.5 (3) | H6A—N3—H6B | 120.0 |
C3—C4—N2 | 121.0 (3) | C10—O3—H9 | 109.5 |
C6—C5—C4 | 121.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3B···O1 | 0.89 | 1.87 | 2.761 (4) | 175 |
N1—H3A···O1i | 0.89 | 2.01 | 2.880 (4) | 164 |
N3—H6B···O4 | 0.86 | 2.11 | 2.736 (4) | 130 |
N3—H6B···O4ii | 0.86 | 2.32 | 3.035 (4) | 141 |
N3—H6A···O7iii | 0.86 | 2.10 | 2.959 (3) | 173 |
O3—H9···O2iv | 0.82 | 1.80 | 2.614 (3) | 169 |
O7—H7···O2v | 0.89 (4) | 1.85 (4) | 2.743 (3) | 176 (4) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) x, −y+1, z−1/2; (v) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H3B···O1 | 0.89 | 1.87 | 2.761 (4) | 174.8 |
N1—H3A···O1i | 0.89 | 2.01 | 2.880 (4) | 164.1 |
N3—H6B···O4 | 0.86 | 2.11 | 2.736 (4) | 129.7 |
N3—H6B···O4ii | 0.86 | 2.32 | 3.035 (4) | 140.8 |
N3—H6A···O7iii | 0.86 | 2.10 | 2.959 (3) | 172.7 |
O3—H9···O2iv | 0.82 | 1.80 | 2.614 (3) | 168.7 |
O7—H7···O2v | 0.89 (4) | 1.85 (4) | 2.743 (3) | 176 (4) |
Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) x, −y+1, z−1/2; (v) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | 2C2H8N+·2C8H5N2O6−·H2O |
Mr | 560.48 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 21.494 (4), 6.4300 (13), 19.193 (4) |
β (°) | 99.98 (3) |
V (Å3) | 2612.5 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.21 × 0.12 × 0.05 |
Data collection | |
Diffractometer | Stoe IPDS1 |
Absorption correction | Numerical (X-SHAPE and X-RED; Stoe, 2008) |
Tmin, Tmax | 0.96, 0.98 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8870, 2305, 1218 |
Rint | 0.087 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.139, 1.00 |
No. of reflections | 2305 |
No. of parameters | 191 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.23 |
Computer programs: X-AREA (Stoe, 2008), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).
Acknowledgements
The authors would like to thank Inke Jess for collecting the single-crystal data.
References
Biswas, S., Ahnfeldt, T. & Stock, N. (2011). Inorg. Chem. 50, 9518–9526. CrossRef PubMed Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stoe (2008). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, W.-X., Gao, Y.-X., Dong, S.-F., Li, Y. & Zhang, W.-P. (2007). Acta Cryst. E63, o2728. Web of Science CSD CrossRef IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.