In the crystal structure of the proton-transfer complex of (8-quinolinyl)urea (QUR) with 3,5-dinitrosalicylic acid (DNSA), 8-ureidoquinolinium 3,5-dinitrosalicylate, [(QUR)
+ (DNSA)
−] or C
10H
10N
3O
+·C
7H
3N
2O
7−, the hetero–N atom of QUR is protonated and, together with all urea protons, is involved in extensive hydrogen-bonding associations which result in a three-dimensional network polymer [N
O 2.711–3.251 (2) Å]. In addition, the quinolinium proton is involved in an intramolecular hydrogen bond with a urea–N atom [N—N 2.841 (2) Å] and within the DNSA anions a short intramolecular O(carboxyl)
O(hydroxy) hydrogen bond is also present [O
O 2.492 (2) Å].
Supporting information
CCDC reference: 172226
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.002 Å
- R factor = 0.045
- wR factor = 0.125
- Data-to-parameter ratio = 13.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Synthesis was carried out by initially mixing together equimolar quantities (1 mmol) of 3,5-dinitrosalicylic acid and (8-quinolinyl)urea at which stage
reaction was observed as a colour change to orange-yellow. 50 ml of 80%
ethanol/water were added to the product and the mixture was heated with
stirring until the volume was reduced to ca 40 ml. Crystals were
obtained after partial room temperature evaporation of the filtered solution.
The positional parameters only for those atoms which are involved in hydrogen
bonding (H1, H11, H21, H22 and H72; located by difference methods) were
refined. All other H atoms were placed in calculated positions and included in
the refinement in the riding-model approximation.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure
Corporation, 1999a).; cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: TEXSAN for Windows.
Crystal data top
C10H10N3O+·C7H3N2O7− | Z = 2 |
Mr = 415.32 | F(000) = 428 |
Triclinic, P1 | Dx = 1.594 Mg m−3 |
Hall symbol: -P 1 | Melting point = 512–517 K |
a = 13.061 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 13.898 (2) Å | Cell parameters from 25 reflections |
c = 4.8910 (17) Å | θ = 12.6–17.7° |
α = 93.33 (2)° | µ = 0.13 mm−1 |
β = 93.21 (2)° | T = 295 K |
γ = 101.764 (14)° | Blocky prism, yellow |
V = 865.6 (4) Å3 | 0.45 × 0.42 × 0.20 mm |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.058 |
Radiation source: Rigaku rotating anode | θmax = 27.5°, θmin = 3.0° |
Graphite monochromator | h = −16→16 |
ω–2θ scans | k = −18→18 |
4728 measured reflections | l = −6→2 |
3980 independent reflections | 3 standard reflections every 150 reflections |
3117 reflections with I > 2σ(I) | intensity decay: 1.4% |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0527P)2 + 0.3656P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.125 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.30 e Å−3 |
3980 reflections | Δρmin = −0.20 e Å−3 |
287 parameters | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
0 restraints | Extinction coefficient: 0.024 (4) |
Crystal data top
C10H10N3O+·C7H3N2O7− | γ = 101.764 (14)° |
Mr = 415.32 | V = 865.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 13.061 (2) Å | Mo Kα radiation |
b = 13.898 (2) Å | µ = 0.13 mm−1 |
c = 4.8910 (17) Å | T = 295 K |
α = 93.33 (2)° | 0.45 × 0.42 × 0.20 mm |
β = 93.21 (2)° | |
Data collection top
Rigaku AFC-7R diffractometer | Rint = 0.058 |
4728 measured reflections | 3 standard reflections every 150 reflections |
3980 independent reflections | intensity decay: 1.4% |
3117 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.30 e Å−3 |
3980 reflections | Δρmin = −0.20 e Å−3 |
287 parameters | |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O2 | 0.78301 (10) | 0.20887 (8) | 0.3893 (3) | 0.0393 (4) | |
O31 | 0.91186 (12) | 0.30995 (9) | 0.0466 (3) | 0.0524 (4) | |
O32 | 1.02715 (15) | 0.23432 (13) | −0.0948 (5) | 0.0863 (7) | |
O51 | 0.91153 (15) | −0.10639 (12) | −0.4119 (4) | 0.0655 (5) | |
O52 | 0.77274 (14) | −0.19269 (10) | −0.2574 (4) | 0.0641 (5) | |
O71 | 0.60217 (11) | −0.06037 (10) | 0.4942 (3) | 0.0468 (4) | |
O72 | 0.64625 (10) | 0.09837 (10) | 0.6262 (3) | 0.0414 (4) | |
N3 | 0.94176 (12) | 0.23420 (11) | −0.0062 (3) | 0.0395 (4) | |
N5 | 0.83816 (14) | −0.11582 (11) | −0.2629 (3) | 0.0433 (5) | |
C1 | 0.73654 (12) | 0.03735 (11) | 0.2635 (3) | 0.0282 (4) | |
C2 | 0.79740 (12) | 0.13500 (11) | 0.2375 (3) | 0.0284 (4) | |
C3 | 0.87482 (12) | 0.14005 (11) | 0.0394 (3) | 0.0309 (4) | |
C4 | 0.89063 (13) | 0.05914 (12) | −0.1164 (3) | 0.0332 (5) | |
C5 | 0.82707 (13) | −0.03127 (12) | −0.0861 (3) | 0.0324 (5) | |
C6 | 0.75062 (13) | −0.04258 (11) | 0.1025 (3) | 0.0306 (4) | |
C7 | 0.65524 (13) | 0.02073 (12) | 0.4699 (3) | 0.0314 (4) | |
O182 | 0.43791 (10) | −0.29935 (9) | 0.6084 (2) | 0.0382 (3) | |
N1 | 0.38575 (12) | −0.31732 (10) | 1.0419 (3) | 0.0334 (4) | |
N2 | 0.48421 (14) | −0.17027 (12) | 0.9232 (3) | 0.0441 (5) | |
N11 | 0.22207 (11) | −0.40209 (9) | 0.6391 (3) | 0.0314 (4) | |
C12 | 0.14806 (14) | −0.43657 (13) | 0.4414 (4) | 0.0388 (5) | |
C13 | 0.11796 (15) | −0.53707 (14) | 0.3695 (4) | 0.0441 (6) | |
C14 | 0.16347 (15) | −0.60047 (13) | 0.5134 (4) | 0.0419 (5) | |
C15 | 0.28873 (17) | −0.62749 (13) | 0.8874 (4) | 0.0451 (6) | |
C16 | 0.36099 (16) | −0.58817 (15) | 1.0964 (4) | 0.0466 (6) | |
C17 | 0.39303 (14) | −0.48532 (14) | 1.1474 (4) | 0.0390 (5) | |
C18 | 0.35236 (13) | −0.42061 (12) | 0.9929 (3) | 0.0314 (4) | |
C19 | 0.27294 (12) | −0.46119 (11) | 0.7850 (3) | 0.0294 (4) | |
C110 | 0.24178 (14) | −0.56459 (12) | 0.7264 (4) | 0.0348 (5) | |
C182 | 0.43746 (12) | −0.26271 (12) | 0.8434 (3) | 0.0298 (4) | |
H4 | 0.9465 | 0.0648 | −0.2457 | 0.0340* | |
H6 | 0.7098 | −0.1034 | 0.1195 | 0.0340* | |
H72 | 0.697 (2) | 0.149 (2) | 0.570 (6) | 0.069* | |
H1 | 0.4043 (17) | −0.2990 (16) | 1.205 (5) | 0.049* | |
H11 | 0.2348 (18) | −0.3373 (16) | 0.677 (5) | 0.051* | |
H12 | 0.1211 | −0.3892 | 0.3562 | 0.0340* | |
H13 | 0.0602 | −0.5568 | 0.2208 | 0.0340* | |
H14 | 0.1409 | −0.6775 | 0.4651 | 0.0340* | |
H15 | 0.2744 | −0.7017 | 0.8441 | 0.0340* | |
H16 | 0.3921 | −0.6323 | 1.2265 | 0.0340* | |
H17 | 0.4390 | −0.4578 | 1.2720 | 0.0340* | |
H21 | 0.5174 (18) | −0.1329 (17) | 0.802 (5) | 0.050* | |
H22 | 0.4795 (19) | −0.1461 (18) | 1.080 (6) | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0519 (7) | 0.0261 (6) | 0.0395 (7) | 0.0053 (5) | 0.0147 (5) | −0.0020 (5) |
O31 | 0.0616 (9) | 0.0281 (6) | 0.0656 (9) | 0.0007 (6) | 0.0193 (7) | 0.0037 (6) |
O32 | 0.0673 (11) | 0.0536 (10) | 0.1358 (19) | −0.0062 (8) | 0.0629 (12) | 0.0030 (10) |
O51 | 0.0839 (12) | 0.0546 (9) | 0.0649 (10) | 0.0233 (8) | 0.0402 (9) | −0.0041 (7) |
O52 | 0.0858 (12) | 0.0294 (7) | 0.0744 (11) | 0.0052 (7) | 0.0227 (9) | −0.0100 (7) |
O71 | 0.0488 (8) | 0.0400 (7) | 0.0477 (8) | −0.0046 (6) | 0.0176 (6) | 0.0059 (6) |
O72 | 0.0455 (7) | 0.0408 (7) | 0.0383 (7) | 0.0067 (6) | 0.0175 (6) | −0.0004 (5) |
N3 | 0.0411 (8) | 0.0329 (7) | 0.0415 (8) | −0.0021 (6) | 0.0123 (6) | 0.0023 (6) |
N5 | 0.0593 (10) | 0.0318 (7) | 0.0426 (8) | 0.0170 (7) | 0.0124 (7) | −0.0004 (6) |
C1 | 0.0297 (7) | 0.0278 (7) | 0.0271 (7) | 0.0048 (6) | 0.0047 (6) | 0.0035 (6) |
C2 | 0.0311 (8) | 0.0248 (7) | 0.0288 (7) | 0.0049 (6) | 0.0027 (6) | 0.0016 (6) |
C3 | 0.0318 (8) | 0.0266 (7) | 0.0330 (8) | 0.0015 (6) | 0.0058 (6) | 0.0030 (6) |
C4 | 0.0340 (8) | 0.0342 (8) | 0.0327 (8) | 0.0087 (6) | 0.0081 (6) | 0.0030 (6) |
C5 | 0.0404 (9) | 0.0273 (7) | 0.0310 (8) | 0.0105 (6) | 0.0049 (6) | −0.0005 (6) |
C6 | 0.0345 (8) | 0.0240 (7) | 0.0326 (8) | 0.0038 (6) | 0.0040 (6) | 0.0039 (6) |
C7 | 0.0319 (8) | 0.0337 (8) | 0.0284 (7) | 0.0047 (6) | 0.0050 (6) | 0.0046 (6) |
O182 | 0.0518 (7) | 0.0381 (6) | 0.0210 (5) | 0.0011 (5) | 0.0059 (5) | −0.0022 (5) |
N1 | 0.0437 (8) | 0.0327 (7) | 0.0194 (6) | −0.0016 (6) | 0.0051 (5) | −0.0025 (5) |
N2 | 0.0557 (10) | 0.0385 (8) | 0.0290 (7) | −0.0118 (7) | 0.0144 (7) | −0.0069 (6) |
N11 | 0.0371 (7) | 0.0239 (6) | 0.0318 (7) | 0.0034 (5) | 0.0045 (5) | −0.0012 (5) |
C12 | 0.0387 (9) | 0.0373 (9) | 0.0384 (9) | 0.0046 (7) | 0.0000 (7) | 0.0011 (7) |
C13 | 0.0390 (9) | 0.0428 (10) | 0.0441 (10) | −0.0022 (8) | 0.0015 (8) | −0.0103 (8) |
C14 | 0.0444 (10) | 0.0286 (8) | 0.0490 (10) | −0.0014 (7) | 0.0152 (8) | −0.0085 (7) |
C15 | 0.0555 (11) | 0.0291 (8) | 0.0546 (11) | 0.0126 (8) | 0.0210 (9) | 0.0062 (8) |
C16 | 0.0539 (11) | 0.0451 (10) | 0.0493 (11) | 0.0218 (9) | 0.0181 (9) | 0.0187 (9) |
C17 | 0.0406 (9) | 0.0459 (10) | 0.0322 (8) | 0.0103 (8) | 0.0076 (7) | 0.0070 (7) |
C18 | 0.0367 (8) | 0.0328 (8) | 0.0251 (7) | 0.0057 (6) | 0.0108 (6) | 0.0028 (6) |
C19 | 0.0341 (8) | 0.0259 (7) | 0.0285 (7) | 0.0051 (6) | 0.0113 (6) | 0.0004 (6) |
C110 | 0.0403 (9) | 0.0256 (7) | 0.0386 (9) | 0.0047 (6) | 0.0155 (7) | −0.0005 (6) |
C182 | 0.0322 (8) | 0.0329 (8) | 0.0224 (7) | 0.0026 (6) | 0.0035 (6) | −0.0011 (6) |
Geometric parameters (Å, º) top
O2—C2 | 1.283 (2) | C1—C2 | 1.443 (2) |
O31—N3 | 1.214 (2) | C2—C3 | 1.433 (2) |
O32—N3 | 1.219 (3) | C3—C4 | 1.379 (2) |
O51—N5 | 1.227 (3) | C4—C5 | 1.378 (2) |
O52—N5 | 1.227 (2) | C5—C6 | 1.389 (2) |
O71—C7 | 1.213 (2) | C4—H4 | 0.99 |
O72—C7 | 1.315 (2) | C6—H6 | 0.91 |
O72—H72 | 0.93 (3) | C12—C13 | 1.390 (3) |
O182—C182 | 1.2306 (18) | C13—C14 | 1.365 (3) |
N3—C3 | 1.454 (2) | C14—C110 | 1.412 (3) |
N5—C5 | 1.454 (2) | C15—C110 | 1.416 (3) |
N1—C18 | 1.415 (2) | C15—C16 | 1.361 (3) |
N1—C182 | 1.387 (2) | C16—C17 | 1.408 (3) |
N2—C182 | 1.331 (2) | C17—C18 | 1.375 (3) |
N11—C19 | 1.365 (2) | C18—C19 | 1.416 (2) |
N11—C12 | 1.323 (2) | C19—C110 | 1.419 (2) |
N1—H1 | 0.83 (2) | C12—H12 | 0.92 |
N2—H22 | 0.83 (3) | C13—H13 | 1.00 |
N2—H21 | 0.88 (2) | C14—H14 | 1.06 |
N11—H11 | 0.89 (2) | C15—H15 | 1.02 |
C1—C6 | 1.373 (2) | C16—H16 | 1.03 |
C1—C7 | 1.499 (2) | C17—H17 | 0.85 |
| | | |
C7—O72—H72 | 104.1 (17) | C3—C4—H4 | 121 |
O31—N3—O32 | 121.99 (17) | C5—C6—H6 | 120 |
O32—N3—C3 | 118.44 (15) | C1—C6—H6 | 120 |
O31—N3—C3 | 119.56 (15) | N11—C12—C13 | 120.98 (17) |
O51—N5—O52 | 123.40 (17) | C12—C13—C14 | 118.80 (18) |
O51—N5—C5 | 118.45 (16) | C13—C14—C110 | 120.67 (17) |
O52—N5—C5 | 118.14 (17) | C16—C15—C110 | 119.76 (17) |
C18—N1—C182 | 119.66 (14) | C15—C16—C17 | 120.74 (18) |
C12—N11—C19 | 123.13 (14) | C16—C17—C18 | 122.05 (18) |
C18—N1—H1 | 113.9 (15) | C17—C18—C19 | 117.39 (15) |
C182—N1—H1 | 117.3 (16) | N1—C18—C17 | 121.96 (15) |
C182—N2—H21 | 118.7 (15) | N1—C18—C19 | 120.63 (14) |
H21—N2—H22 | 120 (2) | N11—C19—C110 | 117.85 (14) |
C182—N2—H22 | 121.6 (17) | N11—C19—C18 | 120.98 (14) |
C19—N11—H11 | 121 (2) | C18—C19—C110 | 121.15 (15) |
C12—N11—H11 | 115 (2) | C14—C110—C15 | 122.74 (16) |
C2—C1—C7 | 120.22 (13) | C14—C110—C19 | 118.48 (16) |
C6—C1—C7 | 118.05 (14) | C15—C110—C19 | 118.77 (17) |
C2—C1—C6 | 121.73 (14) | N11—C12—H12 | 114 |
O2—C2—C3 | 124.58 (14) | C13—C12—H12 | 124 |
C1—C2—C3 | 114.52 (13) | C12—C13—H13 | 116 |
O2—C2—C1 | 120.87 (14) | C14—C13—H13 | 125 |
N3—C3—C2 | 120.06 (13) | C13—C14—H14 | 120 |
C2—C3—C4 | 123.52 (14) | C110—C14—H14 | 119 |
N3—C3—C4 | 116.42 (14) | C110—C15—H15 | 122 |
C3—C4—C5 | 118.55 (15) | C16—C15—H15 | 118 |
N5—C5—C4 | 119.00 (15) | C15—C16—H16 | 121 |
C4—C5—C6 | 121.51 (15) | C17—C16—H16 | 118 |
N5—C5—C6 | 119.45 (15) | C16—C17—H17 | 124 |
C1—C6—C5 | 120.11 (15) | C18—C17—H17 | 114 |
O72—C7—C1 | 116.34 (14) | O182—C182—N2 | 123.37 (15) |
O71—C7—C1 | 121.63 (15) | N1—C182—N2 | 116.05 (14) |
O71—C7—O72 | 122.02 (16) | O182—C182—N1 | 120.57 (15) |
C5—C4—H4 | 120 | | |
| | | |
O31—N3—C3—C4 | 155.18 (16) | C1—C2—C3—N3 | −179.79 (14) |
O32—N3—C3—C2 | 154.66 (19) | C1—C2—C3—C4 | 0.3 (2) |
O31—N3—C3—C2 | −24.7 (2) | C2—C3—C4—C5 | 1.7 (2) |
O32—N3—C3—C4 | −25.4 (2) | N3—C3—C4—C5 | −178.18 (14) |
O51—N5—C5—C6 | −174.05 (17) | C3—C4—C5—N5 | 175.75 (15) |
O51—N5—C5—C4 | 8.1 (2) | C3—C4—C5—C6 | −2.1 (2) |
O52—N5—C5—C6 | 6.8 (2) | N5—C5—C6—C1 | −177.51 (15) |
O52—N5—C5—C4 | −171.07 (17) | C4—C5—C6—C1 | 0.3 (2) |
C18—N1—C182—O182 | 13.3 (2) | N11—C12—C13—C14 | 2.4 (3) |
C182—N1—C18—C19 | −66.4 (2) | C12—C13—C14—C110 | −1.7 (3) |
C18—N1—C182—N2 | −167.31 (16) | C13—C14—C110—C15 | 177.82 (19) |
C182—N1—C18—C17 | 115.24 (19) | C13—C14—C110—C19 | −0.8 (3) |
C12—N11—C19—C18 | 179.37 (17) | C16—C15—C110—C14 | −177.5 (2) |
C19—N11—C12—C13 | −0.3 (3) | C110—C15—C16—C17 | −2.7 (3) |
C12—N11—C19—C110 | −2.2 (2) | C16—C15—C110—C19 | 1.1 (3) |
C6—C1—C7—O71 | −0.7 (2) | C15—C16—C17—C18 | 0.9 (3) |
C7—C1—C2—C3 | 177.93 (14) | C16—C17—C18—N1 | −179.06 (17) |
C2—C1—C7—O72 | −2.1 (2) | C16—C17—C18—C19 | 2.6 (3) |
C2—C1—C6—C5 | 1.9 (2) | C17—C18—C19—N11 | 174.15 (16) |
C6—C1—C2—O2 | 179.85 (15) | C17—C18—C19—C110 | −4.2 (2) |
C6—C1—C2—C3 | −2.1 (2) | N1—C18—C19—C110 | 177.40 (16) |
C2—C1—C7—O71 | 179.20 (16) | N1—C18—C19—N11 | −4.2 (2) |
C7—C1—C6—C5 | −178.16 (15) | N11—C19—C110—C15 | −175.94 (17) |
C7—C1—C2—O2 | −0.1 (2) | C18—C19—C110—C15 | 2.5 (3) |
C6—C1—C7—O72 | 177.93 (15) | N11—C19—C110—C14 | 2.7 (2) |
O2—C2—C3—N3 | −1.9 (2) | C18—C19—C110—C14 | −178.88 (17) |
O2—C2—C3—C4 | 178.25 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O182i | 0.83 (2) | 2.00 (2) | 2.800 (2) | 162 (2) |
N11—H11···N1 | 0.89 (2) | 2.54 (2) | 2.841 (2) | 100.3 (17) |
N11—H11···O2ii | 0.89 (2) | 1.89 (2) | 2.7111 (19) | 152.7 (17) |
N11—H11···O31ii | 0.89 (2) | 2.48 (2) | 2.837 (2) | 104.4 (17) |
N2—H21···O71 | 0.88 (2) | 2.10 (2) | 2.981 (2) | 173 (2) |
N2—H22···O71i | 0.83 (3) | 2.58 (3) | 3.251 (2) | 139 (2) |
N2—H22···O72iii | 0.83 (3) | 2.41 (3) | 3.101 (2) | 142 (2) |
O72—H72···O2 | 0.93 (3) | 1.60 (3) | 2.492 (2) | 161 (3) |
C4—H4···O51iv | 0.989 | 2.57 | 3.547 (3) | 171 |
C12—H12···O31v | 0.92 | 2.37 | 3.201 (3) | 150 |
C13—H13···O31vi | 1.00 | 2.47 | 3.326 (3) | 144 |
C14—H14···O52vii | 1.06 | 2.52 | 3.347 (3) | 135 |
C15—H15···O52viii | 1.02 | 2.60 | 3.168 (3) | 115 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z+2; (iv) −x+2, −y, −z−1; (v) −x+1, −y, −z; (vi) x−1, y−1, z; (vii) −x+1, −y−1, −z; (viii) −x+1, −y−1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C10H10N3O+·C7H3N2O7− |
Mr | 415.32 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 13.061 (2), 13.898 (2), 4.8910 (17) |
α, β, γ (°) | 93.33 (2), 93.21 (2), 101.764 (14) |
V (Å3) | 865.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.45 × 0.42 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4728, 3980, 3117 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.125, 1.04 |
No. of reflections | 3980 |
No. of parameters | 287 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.20 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O182i | 0.83 (2) | 2.00 (2) | 2.800 (2) | 162 (2) |
N11—H11···N1 | 0.89 (2) | 2.54 (2) | 2.841 (2) | 100.3 (17) |
N11—H11···O2ii | 0.89 (2) | 1.89 (2) | 2.7111 (19) | 152.7 (17) |
N11—H11···O31ii | 0.89 (2) | 2.48 (2) | 2.837 (2) | 104.4 (17) |
N2—H21···O71 | 0.88 (2) | 2.10 (2) | 2.981 (2) | 173 (2) |
N2—H22···O71i | 0.83 (3) | 2.58 (3) | 3.251 (2) | 139 (2) |
N2—H22···O72iii | 0.83 (3) | 2.41 (3) | 3.101 (2) | 142 (2) |
O72—H72···O2 | 0.93 (3) | 1.60 (3) | 2.492 (2) | 161 (3) |
C4—H4···O51iv | 0.989 | 2.57 | 3.547 (3) | 171 |
C12—H12···O31v | 0.92 | 2.37 | 3.201 (3) | 150 |
C13—H13···O31vi | 1.00 | 2.47 | 3.326 (3) | 144 |
C14—H14···O52vii | 1.06 | 2.52 | 3.347 (3) | 135 |
C15—H15···O52viii | 1.02 | 2.60 | 3.168 (3) | 115 |
Symmetry codes: (i) x, y, z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y, −z+2; (iv) −x+2, −y, −z−1; (v) −x+1, −y, −z; (vi) x−1, y−1, z; (vii) −x+1, −y−1, −z; (viii) −x+1, −y−1, −z+1. |
The nitro-substituted aromatic acid 3,5-dinitrosalicylic acid (DNSA) has proved a very useful compound for structure formation, giving a number of complexes which acquire stable crystalline lattices through hydrogen-bonding associations. These compounds may be either neutral or ionic, the latter involving proton transfer to a Lewis base acceptor. In addition, association may involve π–π interactions through the aromatic ring and its interactive nitro substituents, although the majority of reported examples primarily interact via the carboxylate group, the ortho-related hydroxy group, and to a lesser extent, the nitro groups. Issa and co-workers have categorized a large number of examples using IR spectroscopy (Hindawey et al., 1980; Issa et al., 1980, 1981), while those characterized to date by our group using X-ray diffraction are the compounds with 3-amino-1H-1,2,4-triazole (Smith et al., 1995), 8-aminoquinoline (Smith, Wermuth, Bott et al., 2001), 8-hydroxyquinoline (Smith, Wermuth & White, 2001), guanidine (Smith, Bott & Wermuth, 2001) and the isomeric aminobenzoic acids (Smith et al., 1995). In the case of the compound with 4-aminobenzoic acid, the only example is a 1:2 adduct. Neutral compounds are less common but the 1:1 adducts with urea (Smith, Baldry et al., 1997), 1,1-diethylurea (Smith et al., 2000), and a series of polymorphic solvates with dioxane (1:1) (two) and (2:1) (two) (Kumar et al., 1999) have been characterized. A series of four polymorphs is also known for the hydrates [all (1:1)] (Smith et al., 1995; Kumar et al., 1999)].
Taking into account the potential for proton transfer and the associative nature of the urea molecule, we expected the structure of the product of the interaction of the unsymmetrically substituted urea, 8-quinolinylurea (QUR) with DNSA, the (1:1) proton-transfer complex [(QUR)+(DNSA)-], to be of considerable interest. QUR is also known for its biological effects, such as cytotoxicity or mutagenic properties (Pagani et al., 1983: Smith, Hansch & Morton, 1997).
The structure (Fig. 1) shows that the hetero-N atom of QUR is protonated and gives strong intermolecular hydrogen-bonding associations with a hydroxyl O atom [N11···O2i 2.711 (2) Å; symmetry code: (i) 1 - x, -y, 1 - z] and a nitro-O atom of the same DNSA anion [N11···O31i 2.837 (2) Å]. Completing a four-centre association about the quinolinium proton is an intramolecular hydrogen bond to the first urea-N atom [N11–H11···N1 2.841 (2) Å]. The urea residue is twisted out of the plane of the quinolinyl ring [torsion angles: C17–C18–N1–C182 115.2 (2)°; C18–N1–C182–N2 - 167.3 (2)°]. All available hydrogen-bonding sites on the urea residue are utilized [N1···O182 2.800 (2) Å; N2···O71 2.981 (2) Å; N2···O71 3.251 (2) Å; N2···O72 3.101 (2) Å], giving a three-dimensional network polymer (Fig. 2). A number of C–H···O associations (Table 1) add to the stability of the structure.
The intramolecular hydrogen bond between the carboxylate group and the ortho-related hydroxyl group is dimensionally similar to those found in all of the complexes and adducts of DNSA [O72—O2 2.492 (2) Å; range 2.409–2.464 Å]. The type of intramolecular bond found here places this compound in a minor category within the series of those compounds in which the hydroxyl proton is anti-located adjacent to the carboxyl oxygen within the hydrogen bond, rather than being on the hydroxyl oxygen (this type of hydrogen bonds was also reported in the proton-transfer compounds with 3-amino-1H-1,2,4-triazole, 3-aminobenzoic acid and 4-aminobenzoic acid).