organic compounds
Bis(6-nitro-1,10-phenanthrolin-1-ium) 2,5-dicarboxyterephthalate
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
*Correspondence e-mail: zklong76@163.com
In the structure of the title 2:1 proton-transfer compound, 2C12H8N3O2+·C10H4O82−, the 6-nitro-1,10-phenanthroline molecules act as proton sponges, accepting protons from pyromellitic acid. The –NO2 group of one of the 6-nitro-1,10-phenanthrolin-1-ium cations is disordered and was refined with a site-occupancy ratio of 0.624 (15):0.376 (15). Two –COOH(–COO−) groups of the 2,5-dicarboxyterephthalate dianion are disordered and were refined with site-occupancy ratios of 0.769 (4):0.231 (4) and 0.766 (5):0.234 (5). The –NO2 group of the second cation is also disordered about a pseudo-twofold rotation axis and was refined with a site-occupancy ratio of 0.903 (3):0.097 (3). There is an intramolecular O—H⋯O hydrogen bond in the anion. The phenanthroline rings of the two cations are inclined to one another by 31.3 (1)°. In the anions, considering the major components only, the carboxylic acid groups (–COOH) are inclined to the benzene ring by 17.3 (2) and 22.3 (3)°. The carboxylate groups (–COO−) are twisted by 9.3 (2) and 13.6 (6)° with respect to the benzene ring. In the crystal, adjacent 2,5-dicarboxyterephthalate anions are linked via O—H⋯O hydrogen bonds, forming chains propagating along [010]. The cations are attached to the chain of anions by N—H⋯O hydrogen bonds.
CCDC reference: 984707
Related literature
For related structures involving pyromellitic acid, see: Li et al. (2003); Guo et al. (2007); Fabelo et al. (2008); Zhong (2013).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 984707
10.1107/S1600536814002414/su2687sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002414/su2687Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002414/su2687Isup3.cml
0.1 mmol 5-nitro-1,10-phenanthroline, 0.1 mmol 1,2,4,5-benzenetetracarboxylic acid, and 2.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 383 K for 72 h, whereupon pink block-shaped crystals of the title compound were obtained.
The NH H atoms and the carboxyl H atoms were located from difference electron-density maps. In the final cycles of
they were included in calculated positions and treated as riding atoms: N—H = 0.87 Å and O—H = 0.83 Å withUiso(H) = 1.2Ueq(N) and = 1.5Ueq(O). The C bound H atoms were positioned geometrically and allowed to ride on their parent atoms: C—H = 0.94 Å with Uiso(H) = 1.2Ueq(C). The –NO2 group (atoms O3/O4) of the one of the 5-nitro-1,10-phenanthrolin-1-ium cations was refined with a site-occupancy ratio of 0.624 (15):0.376 (15). Two –COOH(–COO-) groups (atoms O7/O8 and O9) of the 2,5-dicarboxyterephthalate dianion are disordered and were refined with site-occupancy ratios of 0.769 (4):0.231 (4) and 0.766 (5):0.234 (5), respectively. The –NO2 group (atoms N1/O1/O2) of the second cation is also disordered about a pseudo twofold rotation axis and was refined with a site-occupancy ratio of 0.903 (3):0.097 (3).Data collection: CrystalClear (Rigaku, 2007); cell
CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Only the major components of the disordered atoms are shown. There is an intramolecular O—H···O hydrogen bond in the anion shown as a thin dashed line (See Table 1 for details). | |
Fig. 2. A view along the a axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details; symmetry codes: (i) x, y + 1, z; (ii) x + 1, y - 1, z; (iii) -x + 1, -y + 2, -z; (iv) x, - y + 1, z; (v) x, y + 1, z]. |
2C12H8N3O2+·C10H4O82− | Z = 2 |
Mr = 704.56 | F(000) = 724 |
Triclinic, P1 | Dx = 1.620 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.5937 (6) Å | Cell parameters from 9974 reflections |
b = 9.8302 (7) Å | θ = 2.3–27.2° |
c = 18.8700 (14) Å | µ = 0.13 mm−1 |
α = 77.810 (2)° | T = 223 K |
β = 83.622 (2)° | Block, pink |
γ = 68.025 (2)° | 0.25 × 0.20 × 0.15 mm |
V = 1444.05 (18) Å3 |
Rigaku Mercury CCD diffractometer | 5237 independent reflections |
Radiation source: fine-focus sealed tube | 3942 reflections with I > 2σ(I) |
Graphite Monochromator monochromator | Rint = 0.036 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.3°, θmin = 2.3° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | k = −11→11 |
Tmin = 0.969, Tmax = 0.981 | l = −22→22 |
30563 measured reflections |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.191 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0939P)2 + 1.9537P] where P = (Fo2 + 2Fc2)/3 |
5237 reflections | (Δ/σ)max = 0.001 |
518 parameters | Δρmax = 0.72 e Å−3 |
24 restraints | Δρmin = −0.73 e Å−3 |
2C12H8N3O2+·C10H4O82− | γ = 68.025 (2)° |
Mr = 704.56 | V = 1444.05 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.5937 (6) Å | Mo Kα radiation |
b = 9.8302 (7) Å | µ = 0.13 mm−1 |
c = 18.8700 (14) Å | T = 223 K |
α = 77.810 (2)° | 0.25 × 0.20 × 0.15 mm |
β = 83.622 (2)° |
Rigaku Mercury CCD diffractometer | 5237 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 3942 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.981 | Rint = 0.036 |
30563 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 24 restraints |
wR(F2) = 0.191 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.72 e Å−3 |
5237 reflections | Δρmin = −0.73 e Å−3 |
518 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. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.3137 (4) | 0.3400 (3) | 0.5554 (2) | 0.0744 (12) | 0.903 (3) |
O1' | 0.491 (4) | −0.164 (2) | 0.6658 (19) | 0.0744 (12) | 0.097 (3) |
O2 | 0.3275 (5) | 0.1593 (4) | 0.64151 (19) | 0.0756 (12) | 0.903 (3) |
O2' | 0.381 (4) | 0.069 (3) | 0.6705 (19) | 0.0756 (12) | 0.097 (3) |
O3 | −0.1801 (12) | 0.5821 (17) | 0.2706 (6) | 0.068 (3) | 0.624 (15) |
O3' | −0.123 (3) | 0.582 (3) | 0.2876 (10) | 0.094 (7) | 0.376 (15) |
O4 | 0.0292 (11) | 0.4192 (7) | 0.2234 (3) | 0.065 (3) | 0.624 (15) |
O4' | −0.0960 (19) | 0.4854 (14) | 0.1923 (7) | 0.082 (5) | 0.376 (15) |
O5 | 0.5115 (3) | 0.4118 (3) | 0.20188 (16) | 0.0523 (7) | |
O6 | 0.2903 (4) | 0.4939 (3) | 0.27486 (15) | 0.0641 (9) | |
H6O | 0.2334 | 0.5721 | 0.2898 | 0.096* | |
O7' | 0.1076 (4) | 0.8482 (3) | 0.33626 (16) | 0.0324 (8) | 0.769 (4) |
O7 | 0.1737 (14) | 0.8568 (10) | 0.3577 (6) | 0.0324 (8) | 0.231 (4) |
O8' | 0.3302 (4) | 0.6580 (3) | 0.38628 (16) | 0.0420 (8) | 0.769 (4) |
O8 | 0.2274 (13) | 0.6234 (9) | 0.3520 (5) | 0.0420 (8) | 0.231 (4) |
O9 | 0.5320 (5) | 1.1519 (3) | 0.11200 (17) | 0.0479 (11) | 0.766 (5) |
O9' | 0.3760 (13) | 1.1813 (10) | 0.1143 (5) | 0.045 (3) | 0.234 (5) |
O10 | 0.4440 (6) | 1.1561 (4) | 0.22447 (18) | 0.0537 (11) | 0.766 (5) |
H10O | 0.4491 | 1.2406 | 0.2125 | 0.081* | 0.766 (5) |
O10' | 0.5481 (17) | 1.1344 (13) | 0.2056 (6) | 0.0537 (11) | 0.234 (5) |
H10' | 0.5945 | 1.0636 | 0.2383 | 0.081* | 0.234 (5) |
O11 | 0.6743 (3) | 0.9654 (3) | 0.04547 (15) | 0.0536 (7) | |
O12 | 0.7415 (5) | 0.7292 (3) | 0.04701 (17) | 0.0751 (11) | |
N1 | 0.3874 (4) | 0.2155 (4) | 0.58681 (16) | 0.0355 (8) | 0.903 (3) |
N1' | 0.475 (2) | −0.0347 (19) | 0.6420 (9) | 0.0355 (8) | 0.097 (3) |
H12A | 0.5463 | −0.0502 | 0.6377 | 0.043* | 0.903 (3) |
N2 | 0.8495 (3) | 0.1032 (3) | 0.39818 (13) | 0.0283 (6) | |
H2N' | 0.9372 | 0.0357 | 0.3824 | 0.034* | 0.097 (3) |
N3 | 0.9666 (3) | −0.1817 (3) | 0.47071 (13) | 0.0245 (6) | |
H3N | 1.0141 | −0.1538 | 0.4300 | 0.029* | 0.903 (3) |
N4 | −0.0665 (5) | 0.5579 (4) | 0.2275 (2) | 0.0570 (9) | |
N5 | 0.2343 (4) | 0.7762 (3) | 0.02188 (14) | 0.0364 (7) | |
N6 | 0.1136 (3) | 1.0338 (3) | 0.07212 (14) | 0.0336 (6) | |
H6N | 0.1811 | 1.0217 | 0.0341 | 0.040* | |
C1 | 0.5424 (4) | 0.1202 (4) | 0.55391 (17) | 0.0293 (7) | |
H1A | 0.4448 | 0.1871 | 0.5728 | 0.035* | 0.097 (3) |
C2 | 0.6201 (4) | 0.1748 (3) | 0.48754 (16) | 0.0258 (7) | |
C3 | 0.7642 (4) | 0.0698 (3) | 0.45973 (15) | 0.0231 (6) | |
C4 | 0.7944 (4) | 0.2422 (3) | 0.36302 (17) | 0.0334 (7) | |
H4 | 0.8522 | 0.2669 | 0.3199 | 0.040* | |
C5 | 0.6551 (4) | 0.3547 (3) | 0.38622 (18) | 0.0355 (8) | |
H5 | 0.6222 | 0.4526 | 0.3596 | 0.043* | |
C6 | 0.5674 (4) | 0.3217 (3) | 0.44759 (18) | 0.0330 (7) | |
H6 | 0.4723 | 0.3964 | 0.4633 | 0.040* | |
C7 | 0.8291 (3) | −0.0827 (3) | 0.49830 (15) | 0.0222 (6) | |
C8 | 1.0286 (4) | −0.3212 (3) | 0.50596 (17) | 0.0299 (7) | |
H8 | 1.1248 | −0.3884 | 0.4863 | 0.036* | |
C9 | 0.9570 (4) | −0.3723 (4) | 0.57085 (18) | 0.0346 (8) | |
H9 | 1.0041 | −0.4721 | 0.5944 | 0.042* | |
C10 | 0.8179 (4) | −0.2759 (4) | 0.59978 (17) | 0.0327 (7) | |
H10 | 0.7677 | −0.3083 | 0.6436 | 0.039* | |
C11 | 0.7504 (4) | −0.1275 (3) | 0.56345 (16) | 0.0261 (7) | |
C12 | 0.6032 (4) | −0.0210 (4) | 0.58953 (17) | 0.0307 (7) | |
C13 | −0.0143 (5) | 0.6806 (4) | 0.18440 (19) | 0.0414 (9) | |
C14 | 0.0943 (4) | 0.6569 (4) | 0.12056 (18) | 0.0389 (8) | |
C15 | 0.1353 (4) | 0.7798 (4) | 0.08272 (17) | 0.0315 (7) | |
C16 | 0.2957 (5) | 0.6494 (4) | −0.0025 (2) | 0.0450 (9) | |
H16 | 0.3643 | 0.6450 | −0.0451 | 0.054* | |
C17 | 0.2641 (6) | 0.5225 (4) | 0.0315 (2) | 0.0543 (10) | |
H17 | 0.3117 | 0.4345 | 0.0122 | 0.065* | |
C18 | 0.1644 (5) | 0.5253 (4) | 0.0926 (2) | 0.0512 (10) | |
H18 | 0.1428 | 0.4393 | 0.1160 | 0.061* | |
C19 | 0.0706 (4) | 0.9189 (4) | 0.10846 (16) | 0.0308 (7) | |
C20 | 0.0556 (5) | 1.1644 (4) | 0.0928 (2) | 0.0434 (9) | |
H20 | 0.0873 | 1.2428 | 0.0661 | 0.052* | |
C21 | −0.0522 (5) | 1.1882 (5) | 0.1538 (2) | 0.0524 (10) | |
H21 | −0.0954 | 1.2823 | 0.1675 | 0.063* | |
C22 | −0.0935 (5) | 1.0725 (5) | 0.1930 (2) | 0.0469 (9) | |
H22 | −0.1623 | 1.0857 | 0.2352 | 0.056* | |
C23 | −0.0344 (4) | 0.9347 (4) | 0.17093 (17) | 0.0360 (8) | |
C24 | −0.0752 (4) | 0.8099 (4) | 0.20862 (18) | 0.0411 (9) | |
H24 | −0.1452 | 0.8184 | 0.2507 | 0.049* | |
C25 | 0.4054 (5) | 0.5133 (4) | 0.23522 (19) | 0.0401 (9) | |
C26 | 0.4305 (4) | 0.6590 (3) | 0.21941 (16) | 0.0254 (6) | |
C27 | 0.3503 (4) | 0.7690 (3) | 0.26201 (16) | 0.0251 (6) | |
C28 | 0.2554 (4) | 0.7475 (3) | 0.33295 (16) | 0.0299 (7) | |
C29 | 0.3697 (4) | 0.9063 (3) | 0.24121 (16) | 0.0283 (7) | |
H29 | 0.3145 | 0.9802 | 0.2693 | 0.034* | |
C30 | 0.4667 (4) | 0.9397 (3) | 0.18090 (16) | 0.0274 (7) | |
C31 | 0.4709 (5) | 1.0956 (4) | 0.16873 (18) | 0.0449 (10) | |
C32 | 0.5472 (4) | 0.8295 (3) | 0.13834 (16) | 0.0273 (7) | |
C33 | 0.6613 (4) | 0.8400 (4) | 0.07175 (17) | 0.0340 (8) | |
C34 | 0.5260 (4) | 0.6923 (3) | 0.15919 (16) | 0.0268 (7) | |
H34 | 0.5796 | 0.6187 | 0.1307 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.064 (2) | 0.0355 (18) | 0.093 (3) | 0.0035 (16) | 0.0379 (19) | −0.0064 (17) |
O1' | 0.064 (2) | 0.0355 (18) | 0.093 (3) | 0.0035 (16) | 0.0379 (19) | −0.0064 (17) |
O2 | 0.065 (2) | 0.070 (3) | 0.057 (2) | 0.0023 (19) | 0.0344 (18) | −0.0056 (18) |
O2' | 0.065 (2) | 0.070 (3) | 0.057 (2) | 0.0023 (19) | 0.0344 (18) | −0.0056 (18) |
O3 | 0.059 (5) | 0.075 (4) | 0.063 (5) | −0.036 (5) | 0.018 (4) | 0.015 (4) |
O3' | 0.090 (14) | 0.104 (10) | 0.071 (11) | −0.043 (12) | 0.026 (9) | 0.020 (9) |
O4 | 0.102 (6) | 0.051 (4) | 0.058 (3) | −0.048 (4) | 0.003 (3) | −0.006 (3) |
O4' | 0.096 (11) | 0.066 (7) | 0.106 (9) | −0.056 (8) | 0.017 (8) | −0.020 (7) |
O5 | 0.0588 (17) | 0.0277 (13) | 0.0744 (19) | −0.0193 (12) | 0.0006 (14) | −0.0126 (13) |
O6 | 0.093 (2) | 0.070 (2) | 0.0496 (17) | −0.0616 (19) | 0.0145 (16) | −0.0015 (14) |
O7' | 0.0319 (19) | 0.0326 (14) | 0.0226 (17) | −0.0022 (14) | 0.0039 (13) | −0.0037 (12) |
O7 | 0.0319 (19) | 0.0326 (14) | 0.0226 (17) | −0.0022 (14) | 0.0039 (13) | −0.0037 (12) |
O8' | 0.0454 (19) | 0.0321 (16) | 0.0299 (16) | 0.0002 (13) | 0.0076 (13) | 0.0028 (13) |
O8 | 0.0454 (19) | 0.0321 (16) | 0.0299 (16) | 0.0002 (13) | 0.0076 (13) | 0.0028 (13) |
O9 | 0.075 (3) | 0.0351 (18) | 0.0397 (19) | −0.0317 (18) | 0.0217 (17) | −0.0100 (14) |
O9' | 0.053 (8) | 0.029 (5) | 0.057 (7) | −0.024 (5) | −0.009 (5) | 0.005 (5) |
O10 | 0.094 (4) | 0.0337 (17) | 0.045 (2) | −0.040 (2) | 0.0231 (19) | −0.0130 (15) |
O10' | 0.094 (4) | 0.0337 (17) | 0.045 (2) | −0.040 (2) | 0.0231 (19) | −0.0130 (15) |
O11 | 0.0618 (18) | 0.0396 (15) | 0.0605 (17) | −0.0292 (13) | 0.0254 (14) | −0.0053 (13) |
O12 | 0.109 (3) | 0.064 (2) | 0.073 (2) | −0.0548 (19) | 0.0611 (19) | −0.0440 (17) |
N1 | 0.0292 (17) | 0.0409 (19) | 0.0323 (17) | −0.0057 (14) | 0.0047 (13) | −0.0140 (14) |
N1' | 0.0292 (17) | 0.0409 (19) | 0.0323 (17) | −0.0057 (14) | 0.0047 (13) | −0.0140 (14) |
N2 | 0.0332 (15) | 0.0240 (13) | 0.0267 (13) | −0.0109 (11) | 0.0042 (11) | −0.0044 (11) |
N3 | 0.0264 (13) | 0.0217 (13) | 0.0247 (13) | −0.0092 (10) | 0.0057 (10) | −0.0049 (10) |
N4 | 0.066 (3) | 0.071 (3) | 0.046 (2) | −0.044 (2) | 0.0018 (18) | 0.0004 (18) |
N5 | 0.0405 (17) | 0.0386 (16) | 0.0285 (14) | −0.0132 (13) | 0.0065 (12) | −0.0088 (12) |
N6 | 0.0363 (15) | 0.0400 (16) | 0.0277 (14) | −0.0168 (13) | 0.0070 (11) | −0.0116 (12) |
C1 | 0.0217 (16) | 0.0374 (18) | 0.0308 (17) | −0.0081 (14) | 0.0014 (13) | −0.0164 (14) |
C2 | 0.0225 (15) | 0.0272 (16) | 0.0289 (16) | −0.0068 (12) | −0.0027 (12) | −0.0110 (13) |
C3 | 0.0227 (15) | 0.0238 (15) | 0.0241 (15) | −0.0098 (12) | −0.0003 (12) | −0.0052 (12) |
C4 | 0.044 (2) | 0.0289 (17) | 0.0267 (16) | −0.0151 (15) | 0.0006 (14) | −0.0007 (13) |
C5 | 0.043 (2) | 0.0213 (16) | 0.0372 (18) | −0.0068 (14) | −0.0065 (15) | −0.0010 (13) |
C6 | 0.0302 (17) | 0.0253 (16) | 0.0383 (18) | −0.0014 (13) | −0.0043 (14) | −0.0097 (14) |
C7 | 0.0208 (15) | 0.0248 (15) | 0.0225 (14) | −0.0093 (12) | −0.0005 (11) | −0.0060 (12) |
C8 | 0.0297 (17) | 0.0232 (15) | 0.0335 (17) | −0.0054 (13) | −0.0009 (13) | −0.0061 (13) |
C9 | 0.0413 (19) | 0.0237 (16) | 0.0364 (18) | −0.0120 (14) | −0.0037 (15) | 0.0016 (13) |
C10 | 0.0381 (19) | 0.0339 (18) | 0.0265 (16) | −0.0182 (15) | 0.0023 (13) | 0.0018 (14) |
C11 | 0.0259 (16) | 0.0313 (16) | 0.0246 (15) | −0.0145 (13) | 0.0013 (12) | −0.0062 (12) |
C12 | 0.0281 (17) | 0.0405 (19) | 0.0277 (16) | −0.0164 (14) | 0.0066 (13) | −0.0113 (14) |
C13 | 0.043 (2) | 0.055 (2) | 0.0313 (18) | −0.0286 (18) | −0.0008 (15) | 0.0009 (16) |
C14 | 0.041 (2) | 0.045 (2) | 0.0332 (18) | −0.0209 (17) | −0.0028 (15) | −0.0015 (15) |
C15 | 0.0331 (18) | 0.0369 (18) | 0.0263 (16) | −0.0156 (14) | 0.0014 (13) | −0.0055 (13) |
C16 | 0.052 (2) | 0.039 (2) | 0.043 (2) | −0.0147 (17) | 0.0113 (17) | −0.0165 (17) |
C17 | 0.066 (3) | 0.038 (2) | 0.061 (3) | −0.0191 (19) | 0.011 (2) | −0.0184 (19) |
C18 | 0.064 (3) | 0.038 (2) | 0.056 (2) | −0.0261 (19) | 0.007 (2) | −0.0073 (18) |
C19 | 0.0302 (17) | 0.0432 (19) | 0.0221 (15) | −0.0161 (15) | −0.0002 (13) | −0.0075 (14) |
C20 | 0.047 (2) | 0.044 (2) | 0.045 (2) | −0.0211 (17) | 0.0122 (17) | −0.0201 (17) |
C21 | 0.057 (3) | 0.055 (2) | 0.054 (2) | −0.023 (2) | 0.0160 (19) | −0.031 (2) |
C22 | 0.044 (2) | 0.066 (3) | 0.038 (2) | −0.0224 (19) | 0.0148 (16) | −0.0285 (19) |
C23 | 0.0324 (18) | 0.055 (2) | 0.0256 (16) | −0.0192 (16) | 0.0024 (13) | −0.0133 (15) |
C24 | 0.0369 (19) | 0.066 (3) | 0.0248 (17) | −0.0262 (18) | 0.0030 (14) | −0.0050 (16) |
C25 | 0.055 (2) | 0.0309 (18) | 0.0377 (19) | −0.0223 (17) | −0.0136 (17) | 0.0062 (15) |
C26 | 0.0263 (16) | 0.0225 (15) | 0.0263 (15) | −0.0094 (12) | −0.0037 (12) | 0.0004 (12) |
C27 | 0.0249 (15) | 0.0244 (15) | 0.0251 (15) | −0.0087 (12) | −0.0012 (12) | −0.0026 (12) |
C28 | 0.0340 (18) | 0.0208 (15) | 0.0310 (17) | −0.0074 (14) | 0.0059 (14) | −0.0047 (13) |
C29 | 0.0324 (17) | 0.0255 (16) | 0.0253 (16) | −0.0086 (13) | 0.0032 (13) | −0.0066 (12) |
C30 | 0.0292 (16) | 0.0250 (16) | 0.0271 (16) | −0.0101 (13) | 0.0007 (12) | −0.0030 (12) |
C31 | 0.054 (2) | 0.0260 (17) | 0.049 (2) | −0.0144 (17) | 0.0295 (19) | −0.0101 (16) |
C32 | 0.0310 (17) | 0.0283 (16) | 0.0240 (15) | −0.0129 (13) | 0.0012 (12) | −0.0050 (12) |
C33 | 0.042 (2) | 0.0395 (19) | 0.0274 (17) | −0.0221 (16) | 0.0069 (14) | −0.0117 (15) |
C34 | 0.0313 (17) | 0.0247 (15) | 0.0253 (15) | −0.0101 (13) | 0.0004 (13) | −0.0069 (12) |
O1—N1 | 1.203 (4) | C4—C5 | 1.395 (5) |
O1'—N1' | 1.219 (18) | C4—H4 | 0.9400 |
O1'—H12A | 1.3632 | C5—C6 | 1.358 (5) |
O2—N1 | 1.220 (4) | C5—H5 | 0.9400 |
O2'—N1' | 1.223 (19) | C6—H6 | 0.9400 |
O3—N4 | 1.184 (10) | C7—C11 | 1.405 (4) |
O3'—N4 | 1.218 (17) | C8—C9 | 1.391 (5) |
O4—N4 | 1.316 (7) | C8—H8 | 0.9400 |
O4'—N4 | 1.177 (10) | C9—C10 | 1.360 (5) |
O5—C25 | 1.296 (4) | C9—H9 | 0.9400 |
O6—C25 | 1.221 (5) | C10—C11 | 1.402 (4) |
O6—H6O | 0.8300 | C10—H10 | 0.9400 |
O7'—C28 | 1.290 (4) | C11—C12 | 1.424 (4) |
O7—C28 | 1.200 (8) | C12—H12A | 1.0218 |
O8'—C28 | 1.243 (4) | C13—C24 | 1.339 (5) |
O8—C28 | 1.300 (8) | C13—C14 | 1.443 (5) |
O9—C31 | 1.253 (4) | C14—C18 | 1.396 (5) |
O9'—C31 | 1.317 (7) | C14—C15 | 1.412 (5) |
O10—C31 | 1.273 (4) | C15—C19 | 1.437 (5) |
O10—H10O | 0.8300 | C16—C17 | 1.385 (5) |
O10'—C31 | 1.214 (7) | C16—H16 | 0.9400 |
O10'—H10' | 0.8300 | C17—C18 | 1.358 (6) |
O11—C33 | 1.269 (4) | C17—H17 | 0.9400 |
O12—C33 | 1.209 (4) | C18—H18 | 0.9400 |
N1—C1 | 1.472 (4) | C19—C23 | 1.402 (4) |
N1'—C12 | 1.423 (16) | C20—C21 | 1.397 (5) |
N1'—H12A | 0.5737 | C20—H20 | 0.9400 |
N2—C4 | 1.316 (4) | C21—C22 | 1.362 (6) |
N2—C3 | 1.350 (4) | C21—H21 | 0.9400 |
N2—H2N' | 0.8700 | C22—C23 | 1.394 (5) |
N3—C8 | 1.324 (4) | C22—H22 | 0.9400 |
N3—C7 | 1.353 (4) | C23—C24 | 1.425 (5) |
N3—H3N | 0.8700 | C24—H24 | 0.9400 |
N4—C13 | 1.492 (5) | C25—C26 | 1.491 (4) |
N5—C16 | 1.319 (4) | C26—C34 | 1.382 (4) |
N5—C15 | 1.349 (4) | C26—C27 | 1.406 (4) |
N6—C20 | 1.319 (4) | C27—C29 | 1.390 (4) |
N6—C19 | 1.346 (4) | C27—C28 | 1.506 (4) |
N6—H6N | 0.8700 | C29—C30 | 1.391 (4) |
C1—C12 | 1.339 (5) | C29—H29 | 0.9400 |
C1—C2 | 1.449 (4) | C30—C32 | 1.407 (4) |
C1—H1A | 0.9400 | C30—C31 | 1.514 (4) |
C2—C6 | 1.409 (4) | C32—C34 | 1.397 (4) |
C2—C3 | 1.415 (4) | C32—C33 | 1.516 (4) |
C3—C7 | 1.446 (4) | C34—H34 | 0.9400 |
C25—O6—H6O | 109.5 | C18—C14—C13 | 127.1 (3) |
C31—O10—H10O | 109.5 | C15—C14—C13 | 116.4 (3) |
C31—O10'—H10' | 109.5 | N5—C15—C14 | 123.7 (3) |
O1—N1—O2 | 121.6 (3) | N5—C15—C19 | 116.1 (3) |
O1—N1—C1 | 119.7 (3) | C14—C15—C19 | 120.2 (3) |
O2—N1—C1 | 118.1 (3) | N5—C16—C17 | 123.2 (3) |
O2'—N1'—O1' | 123 (3) | N5—C16—H16 | 118.4 |
O2'—N1'—C12 | 123 (2) | C17—C16—H16 | 118.4 |
O1'—N1'—C12 | 112.6 (19) | C18—C17—C16 | 120.0 (4) |
O2'—N1'—H12A | 125.2 | C18—C17—H17 | 120.0 |
O1'—N1'—H12A | 91.8 | C16—C17—H17 | 120.0 |
C4—N2—C3 | 117.3 (3) | C17—C18—C14 | 119.4 (4) |
C4—N2—H2N' | 121.3 | C17—C18—H18 | 120.3 |
C3—N2—H2N' | 121.3 | C14—C18—H18 | 120.3 |
C8—N3—C7 | 119.7 (3) | N6—C19—C23 | 120.2 (3) |
C8—N3—H3N | 120.2 | N6—C19—C15 | 119.1 (3) |
C7—N3—H3N | 120.2 | C23—C19—C15 | 120.7 (3) |
O4'—N4—O3 | 103.7 (8) | N6—C20—C21 | 121.0 (4) |
O4'—N4—O3' | 128.7 (14) | N6—C20—H20 | 119.5 |
O4'—N4—O4 | 55.9 (7) | C21—C20—H20 | 119.5 |
O3—N4—O4 | 119.8 (8) | C22—C21—C20 | 118.8 (4) |
O3'—N4—O4 | 116.5 (14) | C22—C21—H21 | 120.6 |
O4'—N4—C13 | 114.4 (6) | C20—C21—H21 | 120.6 |
O3—N4—C13 | 121.3 (8) | C21—C22—C23 | 120.5 (3) |
O3'—N4—C13 | 112.0 (14) | C21—C22—H22 | 119.8 |
O4—N4—C13 | 118.4 (4) | C23—C22—H22 | 119.8 |
C16—N5—C15 | 117.2 (3) | C22—C23—C19 | 117.9 (3) |
C20—N6—C19 | 121.5 (3) | C22—C23—C24 | 123.4 (3) |
C20—N6—H6N | 119.3 | C19—C23—C24 | 118.7 (3) |
C19—N6—H6N | 119.3 | C13—C24—C23 | 120.3 (3) |
C12—C1—C2 | 123.1 (3) | C13—C24—H24 | 119.8 |
C12—C1—N1 | 114.5 (3) | C23—C24—H24 | 119.8 |
C2—C1—N1 | 122.4 (3) | O6—C25—O5 | 123.2 (3) |
C12—C1—H1A | 118.5 | O6—C25—C26 | 122.0 (3) |
C2—C1—H1A | 118.5 | O5—C25—C26 | 114.7 (3) |
C6—C2—C3 | 116.3 (3) | C34—C26—C27 | 118.3 (3) |
C6—C2—C1 | 126.9 (3) | C34—C26—C25 | 120.1 (3) |
C3—C2—C1 | 116.8 (3) | C27—C26—C25 | 121.5 (3) |
N2—C3—C2 | 123.7 (3) | C29—C27—C26 | 118.5 (3) |
N2—C3—C7 | 116.3 (2) | C29—C27—C28 | 115.8 (3) |
C2—C3—C7 | 119.9 (3) | C26—C27—C28 | 125.4 (3) |
N2—C4—C5 | 123.6 (3) | O7—C28—O8' | 103.2 (6) |
N2—C4—H4 | 118.2 | O8'—C28—O7' | 124.4 (3) |
C5—C4—H4 | 118.2 | O7—C28—O8 | 122.1 (7) |
C6—C5—C4 | 119.6 (3) | O8'—C28—O8 | 62.8 (5) |
C6—C5—H5 | 120.2 | O7'—C28—O8 | 103.2 (5) |
C4—C5—H5 | 120.2 | O7—C28—C27 | 117.5 (6) |
C5—C6—C2 | 119.5 (3) | O8'—C28—C27 | 120.0 (3) |
C5—C6—H6 | 120.3 | O7'—C28—C27 | 114.0 (3) |
C2—C6—H6 | 120.3 | O8—C28—C27 | 117.3 (5) |
N3—C7—C11 | 120.4 (3) | C27—C29—C30 | 123.3 (3) |
N3—C7—C3 | 119.1 (3) | C27—C29—H29 | 118.3 |
C11—C7—C3 | 120.5 (3) | C30—C29—H29 | 118.3 |
N3—C8—C9 | 122.6 (3) | C29—C30—C32 | 118.2 (3) |
N3—C8—H8 | 118.7 | C29—C30—C31 | 114.3 (3) |
C9—C8—H8 | 118.7 | C32—C30—C31 | 127.5 (3) |
C10—C9—C8 | 119.2 (3) | O10'—C31—O9 | 90.6 (7) |
C10—C9—H9 | 120.4 | O9—C31—O10 | 118.9 (3) |
C8—C9—H9 | 120.4 | O10'—C31—O9' | 126.0 (8) |
C9—C10—C11 | 119.2 (3) | O9—C31—O9' | 58.6 (5) |
C9—C10—H10 | 120.4 | O10—C31—O9' | 113.0 (6) |
C11—C10—H10 | 120.4 | O10'—C31—C30 | 123.9 (6) |
C10—C11—C7 | 118.9 (3) | O9—C31—C30 | 122.9 (3) |
C10—C11—C12 | 122.4 (3) | O10—C31—C30 | 116.5 (3) |
C7—C11—C12 | 118.7 (3) | O9'—C31—C30 | 110.1 (5) |
C1—C12—C11 | 121.1 (3) | C34—C32—C30 | 118.2 (3) |
C1—C12—N1' | 104.9 (8) | C34—C32—C33 | 114.5 (3) |
C11—C12—N1' | 132.8 (8) | C30—C32—C33 | 127.2 (3) |
C1—C12—H12A | 118.9 | O12—C33—O11 | 122.0 (3) |
C11—C12—H12A | 119.9 | O12—C33—C32 | 119.7 (3) |
C24—C13—C14 | 123.8 (3) | O11—C33—C32 | 118.2 (3) |
C24—C13—N4 | 115.9 (3) | C26—C34—C32 | 123.5 (3) |
C14—C13—N4 | 120.4 (3) | C26—C34—H34 | 118.3 |
C18—C14—C15 | 116.6 (3) | C32—C34—H34 | 118.3 |
O1—N1—C1—C12 | −172.9 (4) | C15—N5—C16—C17 | −0.5 (6) |
O2—N1—C1—C12 | −1.0 (5) | N5—C16—C17—C18 | 0.6 (7) |
O1—N1—C1—C2 | 5.9 (5) | C16—C17—C18—C14 | 0.2 (7) |
O2—N1—C1—C2 | 177.7 (3) | C15—C14—C18—C17 | −0.9 (6) |
C12—C1—C2—C6 | −178.3 (3) | C13—C14—C18—C17 | 179.8 (4) |
N1—C1—C2—C6 | 3.1 (5) | C20—N6—C19—C23 | −1.7 (5) |
C12—C1—C2—C3 | 1.6 (4) | C20—N6—C19—C15 | 178.9 (3) |
N1—C1—C2—C3 | −177.0 (3) | N5—C15—C19—N6 | −1.1 (4) |
C4—N2—C3—C2 | 0.5 (4) | C14—C15—C19—N6 | 179.0 (3) |
C4—N2—C3—C7 | −178.7 (3) | N5—C15—C19—C23 | 179.5 (3) |
C6—C2—C3—N2 | −0.6 (4) | C14—C15—C19—C23 | −0.4 (5) |
C1—C2—C3—N2 | 179.4 (3) | C19—N6—C20—C21 | 0.5 (5) |
C6—C2—C3—C7 | 178.5 (3) | N6—C20—C21—C22 | 1.7 (6) |
C1—C2—C3—C7 | −1.4 (4) | C20—C21—C22—C23 | −2.5 (6) |
C3—N2—C4—C5 | 0.4 (5) | C21—C22—C23—C19 | 1.3 (6) |
N2—C4—C5—C6 | −1.2 (5) | C21—C22—C23—C24 | −178.8 (4) |
C4—C5—C6—C2 | 1.0 (5) | N6—C19—C23—C22 | 0.8 (5) |
C3—C2—C6—C5 | −0.2 (4) | C15—C19—C23—C22 | −179.8 (3) |
C1—C2—C6—C5 | 179.8 (3) | N6—C19—C23—C24 | −179.1 (3) |
C8—N3—C7—C11 | −1.0 (4) | C15—C19—C23—C24 | 0.3 (5) |
C8—N3—C7—C3 | 179.2 (3) | C14—C13—C24—C23 | 0.2 (6) |
N2—C3—C7—N3 | −1.1 (4) | N4—C13—C24—C23 | −179.3 (3) |
C2—C3—C7—N3 | 179.7 (3) | C22—C23—C24—C13 | 179.9 (3) |
N2—C3—C7—C11 | 179.0 (3) | C19—C23—C24—C13 | −0.2 (5) |
C2—C3—C7—C11 | −0.2 (4) | O6—C25—C26—C34 | −160.3 (3) |
C7—N3—C8—C9 | 0.6 (5) | O5—C25—C26—C34 | 17.6 (4) |
N3—C8—C9—C10 | −0.1 (5) | O6—C25—C26—C27 | 15.7 (5) |
C8—C9—C10—C11 | 0.0 (5) | O5—C25—C26—C27 | −166.5 (3) |
C9—C10—C11—C7 | −0.3 (5) | C34—C26—C27—C29 | 0.5 (4) |
C9—C10—C11—C12 | 178.7 (3) | C25—C26—C27—C29 | −175.5 (3) |
N3—C7—C11—C10 | 0.8 (4) | C34—C26—C27—C28 | −173.9 (3) |
C3—C7—C11—C10 | −179.3 (3) | C25—C26—C27—C28 | 10.1 (5) |
N3—C7—C11—C12 | −178.2 (3) | C29—C27—C28—O7 | 15.9 (8) |
C3—C7—C11—C12 | 1.7 (4) | C26—C27—C28—O7 | −169.5 (7) |
C2—C1—C12—C11 | −0.2 (5) | C29—C27—C28—O8' | −110.8 (4) |
N1—C1—C12—C11 | 178.6 (3) | C26—C27—C28—O8' | 63.8 (4) |
C2—C1—C12—N1' | −169.0 (9) | C29—C27—C28—O7' | 55.7 (4) |
N1—C1—C12—N1' | 9.8 (9) | C26—C27—C28—O7' | −129.7 (3) |
C10—C11—C12—C1 | 179.5 (3) | C29—C27—C28—O8 | 176.4 (6) |
C7—C11—C12—C1 | −1.5 (5) | C26—C27—C28—O8 | −9.0 (7) |
C10—C11—C12—N1' | −15.3 (13) | C26—C27—C29—C30 | −1.0 (5) |
C7—C11—C12—N1' | 163.6 (12) | C28—C27—C29—C30 | 173.9 (3) |
O2'—N1'—C12—C1 | −32 (3) | C27—C29—C30—C32 | 0.9 (5) |
O1'—N1'—C12—C1 | 162 (3) | C27—C29—C30—C31 | −179.7 (3) |
O2'—N1'—C12—C11 | 161 (3) | C29—C30—C31—O10' | 73.5 (9) |
O1'—N1'—C12—C11 | −5 (3) | C32—C30—C31—O10' | −107.2 (9) |
O4'—N4—C13—C24 | 140.4 (9) | C29—C30—C31—O9 | −169.8 (4) |
O3—N4—C13—C24 | 15.0 (9) | C32—C30—C31—O9 | 9.6 (6) |
O3'—N4—C13—C24 | −16.8 (13) | C29—C30—C31—O10 | 25.4 (5) |
O4—N4—C13—C24 | −156.7 (5) | C32—C30—C31—O10 | −155.2 (4) |
O4'—N4—C13—C14 | −39.1 (10) | C29—C30—C31—O9' | −104.9 (6) |
O3—N4—C13—C14 | −164.6 (7) | C32—C30—C31—O9' | 74.4 (7) |
O3'—N4—C13—C14 | 163.6 (13) | C29—C30—C32—C34 | −0.4 (4) |
O4—N4—C13—C14 | 23.7 (6) | C31—C30—C32—C34 | −179.7 (3) |
C24—C13—C14—C18 | 179.0 (4) | C29—C30—C32—C33 | −178.5 (3) |
N4—C13—C14—C18 | −1.5 (6) | C31—C30—C32—C33 | 2.2 (5) |
C24—C13—C14—C15 | −0.3 (5) | C34—C32—C33—O12 | −9.3 (5) |
N4—C13—C14—C15 | 179.2 (3) | C30—C32—C33—O12 | 168.9 (4) |
C16—N5—C15—C14 | −0.4 (5) | C34—C32—C33—O11 | 173.5 (3) |
C16—N5—C15—C19 | 179.7 (3) | C30—C32—C33—O11 | −8.3 (5) |
C18—C14—C15—N5 | 1.1 (5) | C27—C26—C34—C32 | 0.0 (4) |
C13—C14—C15—N5 | −179.5 (3) | C25—C26—C34—C32 | 176.1 (3) |
C18—C14—C15—C19 | −179.0 (3) | C30—C32—C34—C26 | −0.1 (5) |
C13—C14—C15—C19 | 0.4 (5) | C33—C32—C34—C26 | 178.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6O···O8 | 0.83 | 1.36 | 2.031 (10) | 135 |
O6—H6O···O8′ | 0.83 | 2.50 | 3.024 (4) | 123 |
O10—H10O···O5i | 0.83 | 1.92 | 2.724 (4) | 164 |
N2—H2N′···O7′ii | 0.87 | 2.16 | 3.012 (4) | 165 |
N3—H3N···O7′ii | 0.87 | 1.86 | 2.695 (4) | 160 |
N2—H2N′···O7ii | 0.87 | 2.21 | 3.078 (9) | 172 |
N3—H3N···O7ii | 0.87 | 1.84 | 2.678 (11) | 162 |
N6—H6N···O11iii | 0.87 | 1.85 | 2.712 (4) | 168 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y−1, z; (iii) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6O···O8 | 0.83 | 1.36 | 2.031 (10) | 135 |
O6—H6O···O8' | 0.83 | 2.50 | 3.024 (4) | 123 |
O10—H10O···O5i | 0.83 | 1.92 | 2.724 (4) | 164 |
N2—H2N'···O7'ii | 0.87 | 2.16 | 3.012 (4) | 165 |
N3—H3N···O7'ii | 0.87 | 1.86 | 2.695 (4) | 160 |
N2—H2N'···O7ii | 0.87 | 2.21 | 3.078 (9) | 172 |
N3—H3N···O7ii | 0.87 | 1.84 | 2.678 (11) | 162 |
N6—H6N···O11iii | 0.87 | 1.85 | 2.712 (4) | 168 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y−1, z; (iii) −x+1, −y+2, −z. |
Acknowledgements
This work was supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2013–10).
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Pyromellitic (PMA) acid (Li et al., 2003; Fabelo et al., 2008) has been widely use in constructing interesting supramolecular networks because it can act not only as an hydrogen bond acceptor but also as an hydrogen bond donor, depending upon the number of deprotonated carboxylate groups present. Proton-transfer compounds of PMA with 1,10-phenanthroline for example 1,10-Phenanthrolinium trihydrogen-1,2,4,5-benzenetetracarboxylate monohydrate [Guo et al., 2007] and a substituted phenanthroline 2,9-Dimethyl-1,10-phenanthrolin-1-ium 2,4,5-tricarboxybenzoate monohydrate [Zhong, 2013] have been synthesized and reported. The title compound was obtained using PMA and 6-nitro-1,10-phenanthroline, via a thermal reaction and we report herein on its crystal structure.
The asymmetric unit of the title compound consists of two 6-nitro-1,10-phenanthrolin-1-ium cations, one 2,5-dicarboxyterephthalate anion, Fig. 1. The proton transfer is from two carboxyl groups to the ring N atoms (N3 and N6) of the 5-nitro-1,10-phenanthroline cations. In the anion, the dihedral angles between the benzene ring of PMA2- and the mean-planes of the COOH (COO-) groups are 17.3 (2) ° for (O5/C25/O6), 22.3 (3) ° for (O9/C31/O10), 13.6 (6) ° for (O7/C28/O8) and 9.3 (2)° for (O11/C33/O12). An intramolecular O—H···O hydrogen bond is observed in the anion (Fig. 1 and Table 1).
In the crystal, adjacent PMA2- anions interact via O—H···O hydrogen bonds, forming one-dimensional chains along the b axis, and the 6-nitro-1,10-phenanthrolin-1-ium cations are attached to the PMA2- anions by N—H···O hydrogen bonds (Fig. 2 and Table 1).