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Preparation and single-crystal X-ray structure determination of three co-crystals of hydrogen squarate, HSQ, with 2-aminopyrimidine, 3-aminopyridine and 4-aminopyridine, and one of squarate, SQ2-, with 8-aminoquinoline are reported. Their crystal packings are analyzed and discussed in terms of the intermolecular O—H...O, N—H...O/N and C—H...O hydrogen bonds formed. Although the fine details of the supramolecular architecture are barely rationalizable, the comparative analysis of the data makes it possible to suggest some simple rules that may be of general application for the packing of hydrogen-bonded crystals, i.e. Rule 1: `All hydrogen-bond acceptors available in a molecule will be engaged in hydrogen bonding as far as there are available donors'; Rule 2: `The hydrogen-bond acceptors will be saturated in order of decreasing strength of the hydrogen bonds formed'.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010876810100814X/na0121sup1.cif
Contains datablocks 1, 2, 3, 4

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810100814X/na01211sup2.hkl
Contains datablock 1

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810100814X/na01212sup3.hkl
Contains datablock 2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810100814X/na01213sup4.hkl
Contains datablock 3

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010876810100814X/na01214sup5.hkl
Contains datablock 4

CCDC references: 170354; 170355; 170356; 170357

Computing details top

For all compounds, data collection: CAD4 (Enraf-Nonius, 1984). Cell refinement: CAD4 Enraf-Nonius, 1984 for (1); CAD4 (Enraf-Nonius, 1984 for (2); CAD4 (Enraf-Nonius, 1984) for (3), (4). For all compounds, data reduction: MolEN (Fair, 1990; Enraf-Nonius, 1990); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPII (Johnson, 1976) for (1), (3), (4); ORTEP II (Johnson, 1976) for (2). Software used to prepare material for publication: PARST (Nardelli, 1983, 1995), SHELXL97 (Sheldrick, 1997) for (1), (2); PARST (Nardelli, 1983, 1995); SHELXL97 (Sheldrick, 1997) for (3), (4).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
(1) 2-aminopyridinium hydrogen squarate, 1:1 top
Crystal data top
C4H6N3·C4HO4Z = 2
Mr = 209.17F(000) = 216
Triclinic, P1Dx = 1.610 Mg m3
a = 8.279 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.184 (1) ÅCell parameters from 25 reflections
c = 5.353 (2) Åθ = 8–14°
α = 99.72 (2)°µ = 0.13 mm1
β = 104.05 (2)°T = 296 K
γ = 87.73 (1)°Plate, colourless
V = 431.5 (2) Å30.52 × 0.36 × 0.10 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.013
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.0°
Graphite monochromatorh = 010
ω/2θ scansk = 1313
2769 measured reflectionsl = 76
2078 independent reflections3 standard reflections every 120 min
1596 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: difference Fourier map
wR(F2) = 0.150All H-atom parameters refined
S = 1.02 w = 1/[σ2(Fo2) + (0.1114P)2]
where P = (Fo2 + 2Fc2)/3
2078 reflections(Δ/σ)max = 0.003
164 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C4H6N3·C4HO4γ = 87.73 (1)°
Mr = 209.17V = 431.5 (2) Å3
Triclinic, P1Z = 2
a = 8.279 (1) ÅMo Kα radiation
b = 10.184 (1) ŵ = 0.13 mm1
c = 5.353 (2) ÅT = 296 K
α = 99.72 (2)°0.52 × 0.36 × 0.10 mm
β = 104.05 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.013
2769 measured reflections3 standard reflections every 120 min
2078 independent reflections intensity decay: none
1596 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.150All H-atom parameters refined
S = 1.02Δρmax = 0.34 e Å3
2078 reflectionsΔρmin = 0.33 e Å3
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
xyzUiso*/Ueq
O10.29393 (18)0.12644 (14)0.1800 (3)0.0487 (4)
O20.58959 (16)0.09413 (12)0.3332 (2)0.0415 (4)
O30.47929 (16)0.36437 (12)0.6376 (2)0.0409 (3)
O40.18791 (17)0.40146 (13)0.1066 (3)0.0469 (4)
C10.3493 (2)0.19378 (16)0.0535 (3)0.0315 (4)
C20.4760 (2)0.17740 (15)0.2742 (3)0.0301 (4)
C30.4280 (2)0.30333 (15)0.4165 (3)0.0299 (4)
C40.2944 (2)0.31983 (16)0.1741 (3)0.0314 (4)
N10.74921 (18)0.29039 (13)1.0142 (3)0.0325 (3)
N20.96332 (17)0.15882 (14)1.2202 (3)0.0313 (3)
N30.8191 (2)0.08904 (16)0.7977 (3)0.0407 (4)
C50.8434 (2)0.17901 (16)1.0099 (3)0.0294 (4)
C60.7655 (2)0.38114 (16)1.2329 (4)0.0359 (4)
C70.8801 (2)0.36211 (17)1.4511 (3)0.0377 (4)
C80.9793 (2)0.24902 (18)1.4319 (3)0.0360 (4)
H10.354 (3)0.047 (2)0.209 (5)0.060 (7)*
H60.688 (3)0.459 (2)1.212 (4)0.042 (5)*
H70.888 (3)0.425 (3)1.600 (5)0.057 (7)*
H81.073 (3)0.234 (2)1.592 (5)0.058 (7)*
H100.664 (3)0.302 (3)0.868 (5)0.057 (7)*
H310.889 (3)0.017 (2)0.798 (4)0.040 (5)*
H320.740 (3)0.092 (2)0.645 (5)0.053 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0570 (8)0.0386 (7)0.0306 (7)0.0181 (6)0.0149 (6)0.0085 (5)
O20.0431 (7)0.0366 (6)0.0306 (6)0.0166 (5)0.0086 (5)0.0051 (5)
O30.0471 (7)0.0386 (7)0.0269 (6)0.0113 (5)0.0008 (5)0.0060 (5)
O40.0486 (8)0.0409 (7)0.0422 (7)0.0217 (6)0.0010 (6)0.0014 (6)
C10.0322 (8)0.0294 (7)0.0264 (8)0.0049 (6)0.0013 (6)0.0001 (6)
C20.0311 (8)0.0277 (7)0.0259 (7)0.0043 (6)0.0004 (6)0.0010 (6)
C30.0305 (8)0.0290 (7)0.0270 (8)0.0051 (6)0.0035 (6)0.0021 (6)
C40.0317 (8)0.0305 (8)0.0283 (8)0.0054 (6)0.0037 (6)0.0007 (6)
N10.0345 (7)0.0309 (7)0.0287 (7)0.0086 (5)0.0028 (6)0.0049 (5)
N20.0310 (7)0.0318 (7)0.0254 (7)0.0074 (5)0.0006 (5)0.0009 (5)
N30.0478 (9)0.0374 (8)0.0255 (8)0.0143 (7)0.0050 (6)0.0030 (6)
C50.0307 (8)0.0305 (8)0.0247 (8)0.0051 (6)0.0034 (6)0.0037 (6)
C60.0421 (9)0.0241 (7)0.0426 (10)0.0071 (6)0.0155 (7)0.0022 (7)
C70.0456 (10)0.0319 (8)0.0321 (9)0.0019 (7)0.0096 (7)0.0056 (7)
C80.0367 (9)0.0379 (9)0.0278 (8)0.0006 (7)0.0015 (7)0.0008 (7)
Geometric parameters (Å, º) top
O1—C11.304 (2)N1—H100.94 (3)
O1—H10.94 (3)N2—C81.316 (2)
O2—C21.2593 (19)N2—C51.347 (2)
O3—C31.223 (2)N3—C51.312 (2)
O4—C41.220 (2)N3—H310.92 (2)
C1—C21.405 (2)N3—H320.92 (3)
C1—C41.445 (2)C6—C71.351 (3)
C1—C32.038 (2)C6—H61.00 (2)
C2—C31.470 (2)C7—C81.392 (2)
C3—C41.516 (2)C7—H70.93 (3)
N1—C61.346 (2)C8—H81.03 (3)
N1—C51.351 (2)
C1—O1—H1112.3 (16)C6—N1—C5121.16 (15)
O1—C1—C2135.96 (15)C6—N1—H10118.5 (16)
O1—C1—C4129.96 (15)C5—N1—H10120.1 (16)
C2—C1—C494.08 (13)C8—N2—C5117.16 (15)
O1—C1—C3177.85 (14)C5—N3—H31117.7 (14)
C2—C1—C346.14 (9)C5—N3—H32126.5 (15)
C4—C1—C347.96 (9)H31—N3—H32116 (2)
O2—C2—C1136.68 (15)N3—C5—N2119.15 (15)
O2—C2—C3133.00 (15)N3—C5—N1119.85 (15)
C1—C2—C390.29 (13)N2—C5—N1121.00 (15)
O3—C3—C2133.68 (15)N1—C6—C7119.61 (15)
O3—C3—C4137.69 (15)N1—C6—H6113.5 (13)
C2—C3—C488.62 (13)C7—C6—H6126.9 (13)
O3—C3—C1177.19 (14)C6—C7—C8116.78 (16)
C2—C3—C143.57 (9)C6—C7—H7118.1 (17)
C4—C3—C145.06 (9)C8—C7—H7125.1 (17)
O4—C4—C1135.69 (16)N2—C8—C7124.15 (16)
O4—C4—C3137.32 (16)N2—C8—H8117.1 (14)
C1—C4—C386.98 (13)C7—C8—H8118.7 (14)
(2) 3-aminopyridinium. hydrogen squarate, 1:1 top
Crystal data top
C5H7N2·C4HO4Z = 4
Mr = 208.18F(000) = 432
Triclinic, P1Dx = 1.529 Mg m3
a = 3.812 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.012 (2) ÅCell parameters from 25 reflections
c = 21.942 (5) Åθ = 8–13°
α = 100.78 (2)°µ = 0.12 mm1
β = 91.66 (2)°T = 296 K
γ = 88.26 (2)°Prism, pale yellow
V = 904.1 (4) Å30.52 × 0.30 × 0.14 mm
Data collection top
Enraf Nonius CAD-4
diffractometer
Rint = 0.022
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.3°
Graphite monochromatorh = 04
ω/2θ scansk = 1314
4454 measured reflectionsl = 2827
3913 independent reflections3 standard reflections every 120 min
2471 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064All H-atom parameters refined
wR(F2) = 0.203 w = 1/[σ2(Fo2) + (0.1236P)2 + 0.1121P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.018
3913 reflectionsΔρmax = 0.35 e Å3
336 parametersΔρmin = 0.39 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (4)
Crystal data top
C5H7N2·C4HO4γ = 88.26 (2)°
Mr = 208.18V = 904.1 (4) Å3
Triclinic, P1Z = 4
a = 3.812 (1) ÅMo Kα radiation
b = 11.012 (2) ŵ = 0.12 mm1
c = 21.942 (5) ÅT = 296 K
α = 100.78 (2)°0.52 × 0.30 × 0.14 mm
β = 91.66 (2)°
Data collection top
Enraf Nonius CAD-4
diffractometer
2471 reflections with I > 2σ(I)
4454 measured reflectionsRint = 0.022
3913 independent reflections3 standard reflections every 120 min
Refinement top
R[F2 > 2σ(F2)] = 0.0640 restraints
wR(F2) = 0.203All H-atom parameters refined
S = 1.06Δρmax = 0.35 e Å3
3913 reflectionsΔρmin = 0.39 e Å3
336 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
xyzUiso*/Ueq
O110.9641 (6)0.32081 (18)0.46529 (10)0.0476 (6)
O210.7422 (6)0.61227 (18)0.44193 (11)0.0575 (7)
O310.3881 (6)0.57808 (18)0.31024 (11)0.0543 (6)
O410.6177 (6)0.29679 (18)0.33463 (11)0.0553 (6)
C110.8038 (7)0.3990 (2)0.42201 (13)0.0351 (6)
C210.7076 (7)0.5262 (2)0.41286 (13)0.0367 (6)
C310.5457 (7)0.5127 (2)0.35227 (14)0.0382 (6)
C410.6529 (7)0.3817 (2)0.36462 (13)0.0368 (6)
O120.2360 (6)0.17469 (19)0.04801 (11)0.0541 (6)
O220.1041 (6)0.11805 (19)0.05232 (10)0.0534 (6)
O320.5210 (7)0.0820 (2)0.18315 (12)0.0611 (7)
O420.6696 (6)0.19999 (18)0.17526 (10)0.0507 (6)
C120.3190 (7)0.0966 (2)0.08453 (14)0.0384 (6)
C220.2544 (7)0.0304 (2)0.08548 (13)0.0382 (6)
C320.4479 (8)0.0163 (3)0.14662 (14)0.0413 (7)
C420.5112 (7)0.1145 (2)0.14204 (13)0.0375 (6)
N110.9736 (6)0.0861 (2)0.35766 (12)0.0419 (6)
N211.0772 (9)0.1804 (3)0.28838 (15)0.0601 (8)
C511.0937 (7)0.1051 (2)0.33010 (13)0.0371 (6)
C611.2555 (7)0.1391 (2)0.38888 (14)0.0393 (7)
C711.2679 (8)0.0612 (3)0.42942 (16)0.0438 (7)
C811.1236 (8)0.0549 (3)0.41363 (15)0.0441 (7)
C910.9527 (7)0.0128 (2)0.31628 (15)0.0398 (7)
N120.8139 (6)0.4170 (2)0.14554 (13)0.0458 (6)
N221.1995 (8)0.7046 (3)0.21959 (15)0.0514 (7)
C521.0446 (7)0.6174 (2)0.17682 (15)0.0391 (6)
C620.9430 (8)0.6396 (3)0.11834 (14)0.0419 (7)
C720.7863 (9)0.5495 (3)0.07486 (17)0.0497 (8)
C820.7226 (8)0.4366 (3)0.09026 (17)0.0499 (8)
C920.9681 (8)0.5017 (3)0.19009 (15)0.0406 (7)
H111.057 (8)0.357 (3)0.4961 (16)0.048 (9)*
H120.101 (11)0.140 (4)0.003 (2)0.093 (15)*
H1100.852 (11)0.177 (4)0.342 (2)0.099 (15)*
H2110.945 (8)0.163 (3)0.2515 (17)0.045 (9)*
H2121.165 (12)0.258 (4)0.299 (2)0.090 (14)*
H611.354 (9)0.220 (3)0.4030 (17)0.061 (10)*
H711.371 (7)0.075 (3)0.4623 (14)0.028 (7)*
H811.125 (8)0.113 (3)0.4450 (16)0.052 (9)*
H910.840 (8)0.044 (3)0.2774 (16)0.045 (8)*
H1200.756 (14)0.329 (6)0.163 (3)0.14 (2)*
H2211.310 (9)0.680 (3)0.2451 (17)0.043 (10)*
H2221.283 (12)0.771 (5)0.209 (2)0.088 (14)*
H620.974 (8)0.720 (3)0.1107 (16)0.049 (9)*
H720.713 (9)0.567 (3)0.0386 (19)0.060 (11)*
H820.613 (11)0.375 (4)0.054 (2)0.084 (13)*
H921.043 (8)0.473 (3)0.2236 (15)0.038 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0696 (14)0.0269 (10)0.0463 (12)0.0210 (9)0.0208 (10)0.0072 (9)
O210.0867 (16)0.0302 (10)0.0587 (14)0.0255 (10)0.0312 (12)0.0173 (10)
O310.0739 (15)0.0323 (11)0.0564 (14)0.0238 (10)0.0241 (11)0.0073 (10)
O410.0782 (15)0.0304 (10)0.0617 (14)0.0285 (10)0.0276 (11)0.0200 (10)
C110.0410 (14)0.0219 (12)0.0422 (15)0.0123 (10)0.0024 (11)0.0035 (10)
C210.0448 (15)0.0229 (12)0.0429 (15)0.0135 (10)0.0098 (12)0.0073 (11)
C310.0442 (15)0.0213 (12)0.0490 (16)0.0128 (11)0.0049 (12)0.0052 (11)
C410.0397 (14)0.0248 (12)0.0459 (16)0.0134 (10)0.0046 (12)0.0054 (11)
O120.0777 (16)0.0357 (11)0.0514 (13)0.0196 (10)0.0222 (11)0.0154 (10)
O220.0734 (15)0.0362 (11)0.0511 (13)0.0234 (10)0.0218 (11)0.0093 (10)
O320.0820 (16)0.0399 (12)0.0663 (15)0.0250 (11)0.0279 (13)0.0230 (11)
O420.0688 (14)0.0337 (11)0.0514 (13)0.0236 (10)0.0152 (10)0.0113 (9)
C120.0438 (15)0.0283 (13)0.0441 (16)0.0099 (11)0.0025 (12)0.0083 (11)
C220.0465 (15)0.0300 (13)0.0394 (15)0.0129 (11)0.0065 (12)0.0088 (11)
C320.0490 (16)0.0298 (13)0.0467 (17)0.0141 (11)0.0076 (13)0.0107 (12)
C420.0455 (15)0.0309 (13)0.0367 (14)0.0122 (11)0.0035 (12)0.0069 (11)
N110.0463 (13)0.0250 (11)0.0538 (15)0.0143 (9)0.0033 (11)0.0042 (10)
N210.084 (2)0.0406 (15)0.0599 (19)0.0315 (14)0.0205 (16)0.0182 (14)
C510.0380 (14)0.0283 (13)0.0448 (15)0.0135 (10)0.0039 (11)0.0045 (11)
C610.0381 (14)0.0251 (13)0.0517 (17)0.0117 (10)0.0063 (12)0.0010 (12)
C710.0467 (16)0.0350 (15)0.0470 (18)0.0117 (12)0.0129 (14)0.0013 (13)
C810.0501 (17)0.0342 (14)0.0503 (17)0.0124 (12)0.0029 (13)0.0123 (13)
C910.0405 (15)0.0270 (13)0.0497 (17)0.0140 (11)0.0076 (12)0.0006 (12)
N120.0472 (14)0.0297 (12)0.0616 (17)0.0119 (10)0.0048 (12)0.0103 (11)
N220.0660 (18)0.0349 (14)0.0546 (17)0.0170 (12)0.0104 (15)0.0114 (13)
C520.0357 (14)0.0280 (13)0.0550 (17)0.0075 (10)0.0010 (12)0.0102 (12)
C620.0498 (16)0.0329 (14)0.0465 (17)0.0089 (12)0.0022 (13)0.0154 (13)
C720.0555 (19)0.0435 (17)0.053 (2)0.0103 (13)0.0119 (15)0.0160 (15)
C820.0514 (18)0.0372 (15)0.061 (2)0.0140 (13)0.0116 (15)0.0084 (14)
C920.0458 (16)0.0342 (14)0.0450 (17)0.0082 (11)0.0038 (13)0.0155 (13)
Geometric parameters (Å, º) top
O11—C111.307 (3)N21—H2120.92 (5)
O11—H110.91 (4)C51—C911.398 (3)
O21—C211.240 (3)C51—C611.404 (4)
O31—C311.215 (3)C61—C711.345 (4)
O41—C411.242 (3)C61—H610.97 (4)
C11—C411.412 (4)C71—C811.386 (4)
C11—C211.434 (3)C71—H710.80 (3)
C11—C312.037 (4)C81—H811.02 (4)
C21—C311.480 (4)C91—H910.95 (4)
C31—C411.485 (3)N12—C821.307 (4)
O12—C121.307 (3)N12—C921.353 (4)
O12—H121.11 (5)N12—H1201.13 (6)
O22—C221.239 (3)N22—C521.348 (4)
O32—C321.198 (4)N22—H2210.77 (4)
O42—C421.239 (3)N22—H2220.88 (5)
C12—C421.425 (4)C52—C621.392 (4)
C12—C221.431 (4)C52—C921.400 (4)
C22—C321.497 (4)C62—C721.378 (4)
C32—C421.490 (4)C62—H620.95 (3)
N11—C911.322 (4)C72—C821.379 (4)
N11—C811.329 (4)C72—H720.89 (4)
N11—H1101.10 (5)C82—H821.03 (5)
N21—C511.344 (4)C92—H920.89 (3)
N21—H2110.93 (4)
C11—O11—H11113 (2)H211—N21—H212116 (4)
O11—C11—C41130.0 (2)N21—C51—C91121.0 (3)
O11—C11—C21136.6 (3)N21—C51—C61122.4 (3)
C41—C11—C2193.4 (2)C91—C51—C61116.6 (3)
O11—C11—C31176.8 (2)C71—C61—C51120.8 (2)
C41—C11—C3146.81 (15)C71—C61—H61117 (2)
C21—C11—C3146.59 (16)C51—C61—H61122 (2)
O21—C21—C11136.7 (3)C61—C71—C81120.5 (3)
O21—C21—C31134.6 (2)C61—C71—H71124 (2)
C11—C21—C3188.7 (2)C81—C71—H71115 (2)
O31—C31—C21136.7 (2)N11—C81—C71118.0 (3)
O31—C31—C41134.7 (3)N11—C81—H81121.5 (19)
C21—C31—C4188.6 (2)C71—C81—H81120.5 (19)
O31—C31—C11178.4 (2)N11—C91—C51120.2 (3)
C21—C31—C1144.75 (14)N11—C91—H91117 (2)
C41—C31—C1143.89 (15)C51—C91—H91122 (2)
O41—C41—C11137.6 (2)C82—N12—C92124.1 (3)
O41—C41—C31133.1 (3)C82—N12—H120123 (3)
C11—C41—C3189.3 (2)C92—N12—H120112 (3)
C12—O12—H12119 (2)C52—N22—H221116 (3)
O12—C12—C42130.1 (2)C52—N22—H222121 (3)
O12—C12—C22136.3 (3)H221—N22—H222114 (4)
C42—C12—C2293.5 (2)N22—C52—C62121.7 (3)
O22—C22—C12137.9 (3)N22—C52—C92121.3 (3)
O22—C22—C32133.3 (3)C62—C52—C92117.0 (3)
C12—C22—C3288.8 (2)C72—C62—C52121.2 (3)
O32—C32—C42135.9 (3)C72—C62—H62122 (2)
O32—C32—C22135.7 (3)C52—C62—H62117 (2)
C42—C32—C2288.3 (2)C62—C72—C82119.2 (3)
O42—C42—C12136.8 (3)C62—C72—H72120 (3)
O42—C42—C32133.9 (3)C82—C72—H72121 (3)
C12—C42—C3289.3 (2)N12—C82—C72119.4 (3)
C91—N11—C81123.9 (2)N12—C82—H82128 (2)
C91—N11—H110114 (3)C72—C82—H82113 (2)
C81—N11—H110122 (3)N12—C92—C52119.1 (3)
C51—N21—H211123 (2)N12—C92—H92115 (2)
C51—N21—H212120 (3)C52—C92—H92125 (2)
(3) 4-aminopyridinium. hydrogen squarate, 1:1 top
Crystal data top
C5H7N2·C4HO4F(000) = 432
Mr = 208.17Dx = 1.519 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.283 (3) ÅCell parameters from 25 reflections
b = 7.068 (1) Åθ = 9–13°
c = 12.642 (2) ŵ = 0.12 mm1
β = 97.95 (2)°T = 296 K
V = 910.0 (3) Å3Irregular, colourless
Z = 40.60 × 0.36 × 0.28 mm
Data collection top
Enraf Nonius CAD-4
diffractometer
Rint = 0.030
Radiation source: fine-focus sealed tubeθmax = 30°, θmin = 2.0°
Graphite monochromatorh = 014
ω/2θ scansk = 09
2995 measured reflectionsl = 1717
2647 independent reflections3 standard reflections every 120 min
2216 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038All H-atom parameters refined
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.0708P)2 + 0.1027P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.006
2647 reflectionsΔρmax = 0.37 e Å3
169 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.036 (5)
Crystal data top
C5H7N2·C4HO4V = 910.0 (3) Å3
Mr = 208.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.283 (3) ŵ = 0.12 mm1
b = 7.068 (1) ÅT = 296 K
c = 12.642 (2) Å0.60 × 0.36 × 0.28 mm
β = 97.95 (2)°
Data collection top
Enraf Nonius CAD-4
diffractometer
Rint = 0.030
2995 measured reflections3 standard reflections every 120 min
2647 independent reflections intensity decay: none
2216 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.119All H-atom parameters refined
S = 1.07Δρmax = 0.37 e Å3
2647 reflectionsΔρmin = 0.18 e Å3
169 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
xyzUiso*/Ueq
O10.59845 (7)0.05577 (15)0.66338 (6)0.0457 (2)
O20.32737 (7)0.08695 (14)0.51635 (6)0.0411 (2)
O30.17947 (8)0.08436 (15)0.72209 (7)0.0487 (2)
O40.45477 (7)0.04539 (15)0.86903 (6)0.0470 (2)
C10.47841 (9)0.01276 (15)0.67796 (7)0.0317 (2)
C20.36216 (9)0.04806 (14)0.61246 (7)0.0305 (2)
C30.29231 (9)0.04972 (15)0.70747 (8)0.0331 (2)
C40.41782 (9)0.01104 (16)0.77413 (8)0.0330 (2)
N10.26876 (9)0.10913 (16)1.00550 (9)0.0448 (2)
N20.08527 (9)0.25390 (15)1.09656 (9)0.0414 (2)
C50.03098 (9)0.20861 (14)1.06762 (8)0.0309 (2)
C60.12367 (10)0.09898 (16)1.13391 (9)0.0377 (2)
C70.23972 (11)0.05149 (18)1.10030 (11)0.0434 (3)
C80.18319 (12)0.21439 (18)0.94043 (10)0.0436 (3)
C90.06520 (10)0.26650 (16)0.96836 (9)0.0369 (2)
H10.6106 (17)0.065 (3)0.5917 (16)0.069 (5)*
H60.1019 (15)0.057 (2)1.1991 (14)0.054 (4)*
H70.3085 (16)0.020 (3)1.1445 (14)0.062 (5)*
H80.2160 (16)0.250 (2)0.8718 (13)0.059 (4)*
H90.0049 (14)0.338 (2)0.9199 (13)0.051 (4)*
H100.3468 (19)0.067 (3)0.9859 (17)0.078 (6)*
H210.1436 (16)0.310 (3)1.0539 (14)0.057 (4)*
H220.1125 (16)0.204 (3)1.1571 (15)0.062 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0282 (4)0.0817 (7)0.0279 (4)0.0133 (4)0.0059 (3)0.0032 (4)
O20.0313 (4)0.0661 (5)0.0259 (3)0.0103 (3)0.0046 (3)0.0008 (3)
O30.0286 (4)0.0805 (7)0.0386 (4)0.0083 (4)0.0099 (3)0.0029 (4)
O40.0349 (4)0.0798 (7)0.0270 (4)0.0030 (4)0.0068 (3)0.0080 (4)
C10.0269 (4)0.0428 (5)0.0260 (4)0.0016 (4)0.0053 (3)0.0003 (4)
C20.0261 (4)0.0390 (5)0.0267 (4)0.0014 (3)0.0049 (3)0.0033 (3)
C30.0279 (4)0.0437 (5)0.0283 (4)0.0007 (3)0.0059 (3)0.0027 (4)
C40.0273 (4)0.0452 (5)0.0274 (4)0.0004 (4)0.0071 (3)0.0001 (4)
N10.0301 (4)0.0497 (6)0.0563 (6)0.0016 (4)0.0122 (4)0.0107 (5)
N20.0312 (4)0.0495 (5)0.0450 (5)0.0045 (4)0.0110 (4)0.0064 (4)
C50.0273 (4)0.0328 (5)0.0327 (4)0.0024 (3)0.0044 (3)0.0014 (3)
C60.0362 (5)0.0435 (5)0.0322 (5)0.0013 (4)0.0007 (4)0.0015 (4)
C70.0315 (5)0.0454 (6)0.0501 (6)0.0036 (4)0.0055 (4)0.0050 (5)
C80.0436 (6)0.0476 (6)0.0423 (6)0.0066 (5)0.0160 (4)0.0026 (5)
C90.0363 (5)0.0399 (5)0.0349 (5)0.0018 (4)0.0062 (4)0.0043 (4)
Geometric parameters (Å, º) top
O1—C11.3088 (12)N2—C51.3365 (13)
O1—H10.934 (19)N2—H210.847 (18)
O2—C21.2489 (12)N2—H220.922 (18)
O3—C31.2246 (12)C5—C91.4100 (14)
O4—C41.2315 (13)C5—C61.4107 (15)
C1—C21.4232 (13)C6—C71.3629 (16)
C1—C41.4407 (13)C6—H60.932 (16)
C2—C31.4823 (13)C7—H70.980 (18)
C3—C41.5032 (14)C8—C91.3605 (15)
N1—C71.3380 (18)C8—H81.006 (15)
N1—C81.3433 (18)C9—H90.955 (16)
N1—H100.92 (2)
C1—O1—H1114.2 (11)C5—N2—H22121.4 (11)
O1—C1—C2136.12 (9)H21—N2—H22116.1 (15)
O1—C1—C4130.33 (9)N2—C5—C9121.12 (10)
C2—C1—C493.55 (8)N2—C5—C6121.70 (10)
O2—C2—C1137.48 (9)C9—C5—C6117.18 (9)
O2—C2—C3132.91 (9)C7—C6—C5119.93 (10)
C1—C2—C389.60 (8)C7—C6—H6121.7 (10)
O3—C3—C2134.37 (9)C5—C6—H6118.3 (10)
O3—C3—C4136.93 (9)N1—C7—C6121.18 (11)
C2—C3—C488.70 (7)N1—C7—H7115.8 (10)
O4—C4—C1135.17 (9)C6—C7—H7122.9 (10)
O4—C4—C3136.70 (9)N1—C8—C9121.54 (11)
C1—C4—C388.13 (8)N1—C8—H8113.4 (10)
C7—N1—C8120.58 (10)C9—C8—H8125.0 (10)
C7—N1—H10116.9 (13)C8—C9—C5119.59 (11)
C8—N1—H10122.4 (13)C8—C9—H9120.0 (9)
C5—N2—H21121.3 (11)C5—C9—H9120.3 (9)
(4) 8-aminoquinolinium. squarate, 1:2 top
Crystal data top
C9H9N2·1/2(C4O4)Z = 2
Mr = 201.20F(000) = 210
Triclinic, P1Dx = 1.470 Mg m3
a = 7.209 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.861 (1) ÅCell parameters from 25 reflections
c = 8.443 (1) Åθ = 7–13°
α = 108.07 (1)°µ = 0.10 mm1
β = 91.62 (1)°T = 296 K
γ = 89.83 (1)°Irregular, brown
V = 454.7 (1) Å30.50 × 0.40 × 0.38 mm
Data collection top
Enraf Nonius CAD-4
diffractometer
Rint = 0.010
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 2.5°
Graphite monochromatorh = 010
ω/2θ scansk = 1011
2828 measured reflectionsl = 1111
2628 independent reflections3 standard reflections every 120 min
2310 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: difference Fourier map
wR(F2) = 0.130All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.0847P)2 + 0.0419P]
where P = (Fo2 + 2Fc2)/3
2628 reflections(Δ/σ)max = 0.012
172 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
C9H9N2·1/2(C4O4)γ = 89.83 (1)°
Mr = 201.20V = 454.7 (1) Å3
Triclinic, P1Z = 2
a = 7.209 (1) ÅMo Kα radiation
b = 7.861 (1) ŵ = 0.10 mm1
c = 8.443 (1) ÅT = 296 K
α = 108.07 (1)°0.50 × 0.40 × 0.38 mm
β = 91.62 (1)°
Data collection top
Enraf Nonius CAD-4
diffractometer
Rint = 0.010
2828 measured reflections3 standard reflections every 120 min
2628 independent reflections intensity decay: none
2310 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.130All H-atom parameters refined
S = 1.06Δρmax = 0.27 e Å3
2628 reflectionsΔρmin = 0.27 e Å3
172 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
xyzUiso*/Ueq
O10.08530 (12)0.13517 (10)0.27261 (9)0.0459 (2)
O20.14521 (14)0.22187 (11)0.07223 (9)0.0543 (3)
C10.03815 (13)0.06131 (12)0.12260 (11)0.0330 (2)
C20.06570 (14)0.10087 (12)0.03361 (11)0.0351 (2)
N10.20734 (11)0.46712 (10)0.37370 (10)0.03399 (19)
N20.22334 (14)0.28202 (12)0.61632 (11)0.0416 (2)
C30.19405 (16)0.54981 (15)0.25855 (14)0.0430 (2)
C40.24484 (17)0.72885 (15)0.29561 (17)0.0490 (3)
C50.31132 (16)0.81790 (14)0.45129 (17)0.0465 (3)
C60.32990 (13)0.73177 (12)0.57548 (14)0.0385 (2)
C70.27198 (11)0.55021 (11)0.53302 (11)0.03162 (19)
C80.40100 (17)0.81913 (15)0.73718 (16)0.0503 (3)
C90.40883 (18)0.72878 (18)0.85146 (15)0.0544 (3)
C100.34735 (17)0.55103 (17)0.81138 (13)0.0465 (3)
C110.27786 (13)0.45678 (13)0.65370 (11)0.0345 (2)
H10.169 (2)0.343 (3)0.341 (2)0.064 (5)*
H210.1996 (19)0.252 (2)0.7069 (19)0.048 (4)*
H220.156 (2)0.233 (2)0.520 (2)0.062 (4)*
H30.148 (2)0.467 (2)0.146 (2)0.059 (4)*
H40.228 (3)0.787 (3)0.208 (2)0.073 (5)*
H50.336 (3)0.941 (3)0.481 (2)0.079 (5)*
H80.440 (3)0.953 (3)0.758 (3)0.088 (6)*
H90.463 (3)0.789 (3)0.969 (3)0.080 (6)*
H100.350 (3)0.488 (3)0.896 (2)0.070 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0716 (5)0.0379 (4)0.0281 (3)0.0196 (3)0.0111 (3)0.0108 (3)
O20.0850 (6)0.0457 (4)0.0355 (4)0.0318 (4)0.0066 (4)0.0177 (3)
C10.0425 (4)0.0297 (4)0.0277 (4)0.0070 (3)0.0040 (3)0.0107 (3)
C20.0465 (5)0.0319 (4)0.0275 (4)0.0093 (3)0.0036 (3)0.0105 (3)
N10.0383 (4)0.0297 (4)0.0340 (4)0.0046 (3)0.0005 (3)0.0100 (3)
N20.0562 (5)0.0377 (4)0.0321 (4)0.0122 (3)0.0021 (3)0.0126 (3)
C30.0502 (5)0.0397 (5)0.0424 (5)0.0053 (4)0.0046 (4)0.0180 (4)
C40.0533 (6)0.0406 (5)0.0611 (7)0.0026 (4)0.0025 (5)0.0276 (5)
C50.0456 (5)0.0292 (4)0.0661 (7)0.0028 (4)0.0028 (5)0.0164 (4)
C60.0349 (4)0.0281 (4)0.0485 (5)0.0033 (3)0.0043 (4)0.0057 (4)
C70.0300 (4)0.0282 (4)0.0341 (4)0.0025 (3)0.0022 (3)0.0059 (3)
C80.0506 (6)0.0363 (5)0.0531 (6)0.0113 (4)0.0008 (5)0.0022 (4)
C90.0572 (6)0.0533 (6)0.0405 (5)0.0141 (5)0.0040 (5)0.0030 (5)
C100.0512 (6)0.0510 (6)0.0328 (5)0.0101 (4)0.0027 (4)0.0066 (4)
C110.0352 (4)0.0348 (4)0.0319 (4)0.0038 (3)0.0023 (3)0.0078 (3)
Geometric parameters (Å, º) top
O1—C11.2560 (11)C4—C51.3576 (18)
O2—C21.2433 (11)C4—H40.986 (19)
C1—C2i1.4595 (12)C5—C61.4169 (16)
C1—C21.4647 (12)C5—H50.94 (2)
C2—C1i1.4595 (12)C6—C81.4068 (16)
N1—C31.3280 (13)C6—C71.4204 (12)
N1—C71.3691 (12)C7—C111.4286 (13)
N1—H10.970 (19)C8—C91.364 (2)
N2—C111.3670 (12)C8—H81.05 (2)
N2—H210.888 (15)C9—C101.4019 (17)
N2—H220.913 (18)C9—H91.02 (2)
C3—C41.3914 (15)C10—C111.3874 (14)
C3—H31.016 (17)C10—H100.990 (19)
O1—C1—C2i134.23 (8)C6—C5—H5118.5 (11)
O1—C1—C2135.00 (8)C8—C6—C5122.72 (10)
C2i—C1—C290.77 (7)C8—C6—C7119.52 (10)
O2—C2—C1i135.90 (9)C5—C6—C7117.76 (10)
O2—C2—C1134.86 (9)N1—C7—C6118.34 (9)
C1i—C2—C189.23 (7)N1—C7—C11120.57 (8)
C3—N1—C7122.80 (9)C6—C7—C11121.09 (9)
C3—N1—H1117.3 (10)C9—C8—C6119.22 (10)
C7—N1—H1119.9 (10)C9—C8—H8126.3 (12)
C11—N2—H21112.3 (10)C6—C8—H8114.5 (12)
C11—N2—H22117.7 (11)C8—C9—C10121.46 (11)
H21—N2—H22120.6 (15)C8—C9—H9120.4 (11)
N1—C3—C4120.87 (10)C10—C9—H9118.1 (11)
N1—C3—H3112.4 (9)C11—C10—C9122.14 (11)
C4—C3—H3126.7 (9)C11—C10—H10117.0 (11)
C5—C4—C3118.98 (10)C9—C10—H10120.8 (11)
C5—C4—H4122.5 (11)N2—C11—C10121.07 (9)
C3—C4—H4118.5 (11)N2—C11—C7122.36 (8)
C4—C5—C6121.21 (9)C10—C11—C7116.54 (9)
C4—C5—H5120.0 (11)
Symmetry code: (i) x, y, z.

Experimental details

(1)(2)(3)(4)
Crystal data
Chemical formulaC4H6N3·C4HO4C5H7N2·C4HO4C5H7N2·C4HO4C9H9N2·1/2(C4O4)
Mr209.17208.18208.17201.20
Crystal system, space groupTriclinic, P1Triclinic, P1Monoclinic, P21/cTriclinic, P1
Temperature (K)296296296296
a, b, c (Å)8.279 (1), 10.184 (1), 5.353 (2)3.812 (1), 11.012 (2), 21.942 (5)10.283 (3), 7.068 (1), 12.642 (2)7.209 (1), 7.861 (1), 8.443 (1)
α, β, γ (°)99.72 (2), 104.05 (2), 87.73 (1)100.78 (2), 91.66 (2), 88.26 (2)90, 97.95 (2), 90108.07 (1), 91.62 (1), 89.83 (1)
V3)431.5 (2)904.1 (4)910.0 (3)454.7 (1)
Z2442
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.130.120.120.10
Crystal size (mm)0.52 × 0.36 × 0.100.52 × 0.30 × 0.140.60 × 0.36 × 0.280.50 × 0.40 × 0.38
Data collection
DiffractometerEnraf-Nonius CAD-4Enraf Nonius CAD-4Enraf Nonius CAD-4Enraf Nonius CAD-4
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2769, 2078, 1596 4454, 3913, 2471 2995, 2647, 2216 2828, 2628, 2310
Rint0.0130.0220.0300.010
(sin θ/λ)max1)0.6610.6390.7030.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.150, 1.02 0.064, 0.203, 1.06 0.038, 0.119, 1.07 0.043, 0.130, 1.06
No. of reflections2078391326472628
No. of parameters164336169172
H-atom treatmentAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refinedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.34, 0.330.35, 0.390.37, 0.180.27, 0.27

Computer programs: CAD4 (Enraf-Nonius, 1984), CAD4 Enraf-Nonius, 1984, CAD4 (Enraf-Nonius, 1984, MolEN (Fair, 1990; Enraf-Nonius, 1990), SIR92 (Altomare et al., 1994), ORTEPII (Johnson, 1976), ORTEP II (Johnson, 1976), PARST (Nardelli, 1983, 1995), SHELXL97 (Sheldrick, 1997), PARST (Nardelli, 1983, 1995); SHELXL97 (Sheldrick, 1997).

 

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