Compound (I) was synthesized according to the method of Metz & Plüg
(2005)
(see scheme). The obtained powder was stirred in dimethylformamide for 30–60 min, filtered, and dried at 353–373 K, giving 10 g of (I).
For crystals of (Ia), a suspension of compound (I) (10 mg) in
N-methylpyrrolidone (2 ml) was heated in a beaker to 477 K, then cooled
down to room temperature. The beaker was placed into a larger beaker and next
to the smaller beaker propan-2-ol (4 ml) was added. The larger beaker was
sealed and kept for 3 d. Yellow fluorescent crystals of (Ia) were
obtained, with sizes up to 0.8 × 0.4 × 0.4 mm.
For crystals of (Ib), the crystallization was carried out as for
(Ia), but butan-1-ol (2 ml) was used instead of propan-2-ol. After 2 d,
yellow fluorescent crystals of (Ib) were obtained, with sizes up to 1.2
× 1.2 × 0.4 mm.
For crystals of (Ic), the crystallization was carried out as for
(Ia), but using butan-1-ol (4 ml) instead of propan-2-ol. Yellow
fluorescent crystals of (Ic) were obtained, with sizes up to 1.8
× 0.9 × 0.9 mm.
For the phase analysis the powder samples were measured on a Stoe STADI-P
powder diffractometer [curved Ge(111) primary monochromator, Cu Kα1
radiation, λ = 1.5406 Å] in transmission geometry from 2 to 74° in 2θ.
All samples were prepared between two polyacetate films. An image-plate
position-sensitive detector (IPPSD) was used. For data acquisition the Stoe
software WinXPOW (Reference?) was used.
In (Ia) the propan-2-ol molecule is disordered across a centre of
inversion over two equally occupied sites. The C—C bonds and C—C—O
angles in this molecule were restrained to be equal with effective s.u.s of
0.02 and 0.04, respectively. The highest peak in the final difference density
map (0.72 e Å-3) is located 0.93 Å from atom H41B.
Both N-methylpyrrolidone molecules of (Ib) are disordered over
two equally occupied sites. One is located on a centre of inversion, the other
on a general position. In both of them, the atoms sharing the same site were
refined with coordinates and displacement parameters constrained to the same
values. The bonds between the methylene C atoms were restrained to 1.500 (1) Å. The highest peak in the final difference density map (0.90 e Å-3) is
located 0.43 Å from atom C54.
From the enlarged atomic displacement parameters for some atoms of the solvent
molecules in (Ia) and (Ib), it is evident that the solvent
molecules are highly disordered and that the best refined models only
approximate the true average arrangement. The geometric parameters of the
solvent molecules should therefore be considered to be only approximate.
The H atoms for (Ia), (Ib) and (Ic) were located in
difference maps, but were geometrically positioned and refined using a riding
model with fixed individual displacement parameters [Uiso(H) =
1.2Ueq(C,O) or 1.5 Ueq(Cmethyl)] and with O—H = 0.84 Å, Caromatic—H = 0.95 Å, Cmethylene—H = 0.99 Å or Cmethyl—H
= 0.98 Å. The methyl groups were allowed to rotate but not to tip. The
torsion angle about the C—O bond of each hydroxyl group was refined.
The solvent molecules in (Ic) are severely disordered and could not be
modelled. The contribution of the disordered solvent to the calculated
structure factors was taken into account following the BYPASS algorithm (van
der Sluis & Spek, 1990), implemented as the SQUEEZE option in
PLATON
(Spek, 2009). The final Fo2/Fc2 data were calculated with the
FCF
routine of PLATON and include the disordered solvent contribution.
PLATON found one void (volume 386 Å3) in the unit cell (located at
x = -0.053, y = 0.000, z = 1/2) and estimated that there
are approximately 48 electrons in this void. For calculating Mr, µ,
ρ etc. we assumed a composition of
C34H22N4O4.0.5C5H9NO.C4H10O. Although we had suppressed the
contribution of the solvent to the scattering power for (Ic), the
figures of merit remain rather high. This is most probably due to the low
quality of the crystal [expressed in R(int) = 0.0875 and R(σ) =
0.1178]. However, this crystal was the best we could obtain.
For all compounds, data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Version 2.0; Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2009).
(Ia)
p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2-
a]pyrimidin-5-ium-4-olate)–
N-methylpyrrolidone–propan-2-ol
(1/2/1)
top
Crystal data top
C34H22N4O4·2C5H9NO·C3H8O | Z = 1 |
Mr = 808.91 | F(000) = 428 |
Triclinic, P1 | Dx = 1.334 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7737 (10) Å | Cell parameters from 21638 reflections |
b = 10.4982 (11) Å | θ = 3.7–26.4° |
c = 11.7877 (12) Å | µ = 0.09 mm−1 |
α = 98.463 (8)° | T = 173 K |
β = 101.314 (8)° | Block, yellow |
γ = 104.750 (8)° | 0.53 × 0.32 × 0.26 mm |
V = 1007.07 (19) Å3 | |
Data collection top
Stoe IPDS II two-circle diffractometer | 3305 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.053 |
Graphite monochromator | θmax = 26.5°, θmin = 3.7° |
ω scans | h = −10→10 |
19547 measured reflections | k = −13→13 |
4103 independent reflections | l = −14→13 |
Refinement top
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)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.111P)2 + 0.3234P] where P = (Fo2 + 2Fc2)/3 |
4103 reflections | (Δ/σ)max < 0.001 |
290 parameters | Δρmax = 0.72 e Å−3 |
2 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
C34H22N4O4·2C5H9NO·C3H8O | γ = 104.750 (8)° |
Mr = 808.91 | V = 1007.07 (19) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.7737 (10) Å | Mo Kα radiation |
b = 10.4982 (11) Å | µ = 0.09 mm−1 |
c = 11.7877 (12) Å | T = 173 K |
α = 98.463 (8)° | 0.53 × 0.32 × 0.26 mm |
β = 101.314 (8)° | |
Data collection top
Stoe IPDS II two-circle diffractometer | 3305 reflections with I > 2σ(I) |
19547 measured reflections | Rint = 0.053 |
4103 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.057 | 2 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.72 e Å−3 |
4103 reflections | Δρmin = −0.33 e Å−3 |
290 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.55844 (17) | 0.74906 (13) | 0.44080 (13) | 0.0262 (3) | |
C2 | 0.4219 (2) | 0.64036 (16) | 0.37141 (16) | 0.0274 (4) | |
O2 | 0.29201 (16) | 0.66674 (13) | 0.34789 (14) | 0.0408 (4) | |
C3 | 0.4507 (2) | 0.51325 (16) | 0.33708 (15) | 0.0256 (4) | |
C4 | 0.6071 (2) | 0.49768 (16) | 0.36619 (15) | 0.0272 (4) | |
O4 | 0.65244 (16) | 0.39656 (12) | 0.34775 (14) | 0.0392 (4) | |
N5 | 0.74065 (17) | 0.62329 (13) | 0.42715 (13) | 0.0253 (3) | |
C6 | 0.7133 (2) | 0.74179 (16) | 0.46615 (15) | 0.0252 (4) | |
C7 | 0.8456 (2) | 0.85140 (17) | 0.53172 (17) | 0.0312 (4) | |
H7 | 0.8275 | 0.9332 | 0.5637 | 0.037* | |
C8 | 1.0004 (2) | 0.84065 (19) | 0.54965 (18) | 0.0350 (4) | |
H8 | 1.0895 | 0.9143 | 0.5952 | 0.042* | |
C9 | 1.0273 (2) | 0.71982 (19) | 0.50034 (19) | 0.0356 (4) | |
H9 | 1.1345 | 0.7128 | 0.5079 | 0.043* | |
C10 | 0.8970 (2) | 0.61409 (18) | 0.44203 (17) | 0.0315 (4) | |
H10 | 0.9138 | 0.5315 | 0.4106 | 0.038* | |
C11 | 0.52830 (19) | 0.87812 (16) | 0.47173 (16) | 0.0257 (4) | |
C12 | 0.4773 (2) | 0.90745 (16) | 0.57391 (16) | 0.0285 (4) | |
H12 | 0.4622 | 0.8442 | 0.6236 | 0.034* | |
C13 | 0.4485 (2) | 1.03164 (17) | 0.60257 (16) | 0.0285 (4) | |
H13 | 0.4135 | 1.0540 | 0.6722 | 0.034* | |
C31 | 0.3120 (2) | 0.39662 (16) | 0.26643 (15) | 0.0276 (4) | |
C32 | 0.1515 (2) | 0.38518 (18) | 0.27442 (17) | 0.0328 (4) | |
H32 | 0.1305 | 0.4533 | 0.3263 | 0.039* | |
C33 | 0.0231 (2) | 0.2760 (2) | 0.20777 (19) | 0.0397 (5) | |
H33 | −0.0844 | 0.2702 | 0.2148 | 0.048* | |
C34 | 0.0504 (3) | 0.17544 (19) | 0.13120 (19) | 0.0436 (5) | |
H34 | −0.0375 | 0.1006 | 0.0861 | 0.052* | |
C35 | 0.2072 (3) | 0.1853 (2) | 0.1212 (2) | 0.0454 (5) | |
H35 | 0.2265 | 0.1173 | 0.0681 | 0.055* | |
C36 | 0.3371 (3) | 0.29388 (18) | 0.18798 (18) | 0.0364 (4) | |
H36 | 0.4441 | 0.2985 | 0.1804 | 0.044* | |
N41 | 0.9436 (3) | 0.7366 (2) | 0.1713 (2) | 0.0613 (6) | |
C41 | 1.0889 (4) | 0.8517 (3) | 0.2230 (3) | 0.0619 (7) | |
H41A | 1.0565 | 0.9338 | 0.2398 | 0.093* | |
H41B | 1.1584 | 0.8615 | 0.1671 | 0.093* | |
H41C | 1.1491 | 0.8365 | 0.2966 | 0.093* | |
C42 | 0.8000 (5) | 0.7416 (4) | 0.1798 (3) | 0.0768 (10) | |
O42 | 0.7721 (4) | 0.8386 (3) | 0.2386 (2) | 0.0939 (9) | |
C43 | 0.6787 (4) | 0.6104 (4) | 0.1064 (3) | 0.0710 (8) | |
H43A | 0.6001 | 0.5714 | 0.1509 | 0.085* | |
H43B | 0.6182 | 0.6252 | 0.0317 | 0.085* | |
C44 | 0.7815 (5) | 0.5195 (4) | 0.0821 (4) | 0.0870 (10) | |
H44A | 0.7411 | 0.4657 | 0.0002 | 0.104* | |
H44B | 0.7817 | 0.4576 | 0.1378 | 0.104* | |
C45 | 0.9556 (4) | 0.6180 (3) | 0.1003 (2) | 0.0575 (6) | |
H45A | 1.0404 | 0.5833 | 0.1425 | 0.069* | |
H45B | 0.9786 | 0.6349 | 0.0241 | 0.069* | |
C51 | 0.4168 (8) | 0.8510 (8) | 0.0339 (8) | 0.080 (2) | 0.50 |
H51A | 0.4204 | 0.8097 | 0.1033 | 0.120* | 0.50 |
H51B | 0.4618 | 0.8039 | −0.0233 | 0.120* | 0.50 |
H51C | 0.3040 | 0.8445 | −0.0027 | 0.120* | 0.50 |
C52 | 0.5135 (14) | 0.9936 (11) | 0.0704 (10) | 0.077 (2) | 0.50 |
H52A | 0.4716 | 1.0404 | 0.1323 | 0.092* | 0.50 |
O52 | 0.6812 (5) | 1.0130 (5) | 0.1134 (5) | 0.0825 (13) | 0.50 |
H52 | 0.6984 | 0.9380 | 0.1142 | 0.099* | 0.50 |
C53 | 0.498 (3) | 1.055 (3) | −0.0312 (16) | 0.209 (15) | 0.50 |
H53A | 0.5623 | 1.1501 | −0.0080 | 0.313* | 0.50 |
H53B | 0.3835 | 1.0484 | −0.0623 | 0.313* | 0.50 |
H53C | 0.5377 | 1.0085 | −0.0923 | 0.313* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0244 (7) | 0.0194 (7) | 0.0354 (8) | 0.0099 (5) | 0.0066 (6) | 0.0023 (5) |
C2 | 0.0260 (8) | 0.0224 (8) | 0.0334 (9) | 0.0090 (6) | 0.0063 (7) | 0.0028 (6) |
O2 | 0.0267 (7) | 0.0288 (7) | 0.0619 (9) | 0.0136 (5) | 0.0010 (6) | −0.0024 (6) |
C3 | 0.0294 (8) | 0.0206 (7) | 0.0283 (8) | 0.0093 (6) | 0.0082 (7) | 0.0044 (6) |
C4 | 0.0327 (9) | 0.0202 (7) | 0.0312 (9) | 0.0109 (6) | 0.0096 (7) | 0.0051 (6) |
O4 | 0.0380 (7) | 0.0236 (6) | 0.0575 (9) | 0.0170 (5) | 0.0089 (6) | 0.0026 (6) |
N5 | 0.0262 (7) | 0.0223 (7) | 0.0314 (7) | 0.0122 (5) | 0.0085 (6) | 0.0063 (5) |
C6 | 0.0262 (8) | 0.0229 (8) | 0.0300 (8) | 0.0113 (6) | 0.0084 (6) | 0.0069 (6) |
C7 | 0.0294 (9) | 0.0238 (8) | 0.0398 (10) | 0.0097 (7) | 0.0057 (7) | 0.0052 (7) |
C8 | 0.0264 (9) | 0.0295 (9) | 0.0471 (11) | 0.0071 (7) | 0.0048 (8) | 0.0089 (8) |
C9 | 0.0245 (8) | 0.0375 (10) | 0.0494 (11) | 0.0142 (7) | 0.0101 (8) | 0.0129 (8) |
C10 | 0.0302 (9) | 0.0313 (9) | 0.0396 (10) | 0.0176 (7) | 0.0112 (7) | 0.0090 (7) |
C11 | 0.0215 (7) | 0.0192 (7) | 0.0357 (9) | 0.0091 (6) | 0.0047 (6) | 0.0012 (6) |
C12 | 0.0294 (8) | 0.0231 (8) | 0.0353 (9) | 0.0105 (6) | 0.0086 (7) | 0.0070 (6) |
C13 | 0.0291 (8) | 0.0249 (8) | 0.0338 (9) | 0.0117 (6) | 0.0102 (7) | 0.0028 (6) |
C31 | 0.0330 (9) | 0.0221 (8) | 0.0280 (8) | 0.0088 (7) | 0.0067 (7) | 0.0064 (6) |
C32 | 0.0339 (9) | 0.0278 (8) | 0.0354 (9) | 0.0077 (7) | 0.0073 (7) | 0.0060 (7) |
C33 | 0.0336 (10) | 0.0350 (10) | 0.0461 (11) | 0.0044 (8) | 0.0046 (8) | 0.0117 (8) |
C34 | 0.0448 (11) | 0.0279 (9) | 0.0441 (11) | 0.0015 (8) | −0.0054 (9) | 0.0024 (8) |
C35 | 0.0553 (13) | 0.0288 (9) | 0.0431 (11) | 0.0103 (9) | 0.0035 (9) | −0.0054 (8) |
C36 | 0.0414 (10) | 0.0275 (9) | 0.0383 (10) | 0.0108 (8) | 0.0088 (8) | 0.0009 (7) |
N41 | 0.0817 (16) | 0.0693 (14) | 0.0526 (12) | 0.0466 (12) | 0.0241 (11) | 0.0199 (10) |
C41 | 0.0725 (17) | 0.0473 (13) | 0.0646 (16) | 0.0244 (12) | 0.0064 (13) | 0.0094 (12) |
C42 | 0.103 (2) | 0.119 (3) | 0.0499 (15) | 0.076 (2) | 0.0379 (16) | 0.0416 (17) |
O42 | 0.135 (2) | 0.129 (2) | 0.0654 (13) | 0.0988 (19) | 0.0513 (14) | 0.0255 (13) |
C43 | 0.0662 (17) | 0.099 (2) | 0.0485 (15) | 0.0157 (16) | 0.0180 (13) | 0.0271 (15) |
C44 | 0.086 (2) | 0.075 (2) | 0.088 (2) | 0.0153 (18) | 0.0072 (19) | 0.0162 (18) |
C45 | 0.0821 (18) | 0.0527 (14) | 0.0486 (13) | 0.0366 (13) | 0.0191 (12) | 0.0099 (11) |
C51 | 0.052 (3) | 0.103 (6) | 0.091 (5) | 0.031 (4) | 0.029 (3) | 0.005 (4) |
C52 | 0.075 (5) | 0.124 (6) | 0.077 (5) | 0.072 (5) | 0.046 (4) | 0.048 (5) |
O52 | 0.053 (2) | 0.074 (3) | 0.120 (4) | 0.020 (2) | 0.013 (2) | 0.026 (3) |
C53 | 0.171 (18) | 0.46 (5) | 0.153 (17) | 0.23 (3) | 0.141 (16) | 0.18 (2) |
Geometric parameters (Å, º) top
N1—C6 | 1.357 (2) | C34—H34 | 0.9500 |
N1—C2 | 1.432 (2) | C35—C36 | 1.393 (3) |
N1—C11 | 1.454 (2) | C35—H35 | 0.9500 |
C2—O2 | 1.230 (2) | C36—H36 | 0.9500 |
C2—C3 | 1.436 (2) | N41—C42 | 1.297 (4) |
C3—C4 | 1.404 (2) | N41—C45 | 1.433 (3) |
C3—C31 | 1.489 (2) | N41—C41 | 1.467 (4) |
C4—O4 | 1.230 (2) | C41—H41A | 0.9800 |
C4—N5 | 1.494 (2) | C41—H41B | 0.9800 |
N5—C6 | 1.358 (2) | C41—H41C | 0.9800 |
N5—C10 | 1.379 (2) | C42—O42 | 1.250 (4) |
C6—C7 | 1.405 (2) | C42—C43 | 1.524 (5) |
C7—C8 | 1.370 (3) | C43—C44 | 1.505 (5) |
C7—H7 | 0.9500 | C43—H43A | 0.9900 |
C8—C9 | 1.411 (3) | C43—H43B | 0.9900 |
C8—H8 | 0.9500 | C44—C45 | 1.565 (5) |
C9—C10 | 1.354 (3) | C44—H44A | 0.9900 |
C9—H9 | 0.9500 | C44—H44B | 0.9900 |
C10—H10 | 0.9500 | C45—H45A | 0.9900 |
C11—C12 | 1.385 (3) | C45—H45B | 0.9900 |
C11—C13i | 1.386 (3) | C51—C52 | 1.472 (15) |
C12—C13 | 1.396 (2) | C51—H51A | 0.9800 |
C12—H12 | 0.9500 | C51—H51B | 0.9800 |
C13—C11i | 1.386 (3) | C51—H51C | 0.9800 |
C13—H13 | 0.9500 | C52—O52 | 1.410 (12) |
C31—C32 | 1.405 (3) | C52—C53 | 1.440 (12) |
C31—C36 | 1.405 (3) | C52—H52A | 1.0000 |
C32—C33 | 1.390 (3) | O52—H52 | 0.8400 |
C32—H32 | 0.9500 | C53—H53A | 0.9800 |
C33—C34 | 1.385 (3) | C53—H53B | 0.9800 |
C33—H33 | 0.9500 | C53—H53C | 0.9800 |
C34—C35 | 1.383 (3) | | |
| | | |
C6—N1—C2 | 123.90 (14) | C36—C35—H35 | 119.6 |
C6—N1—C11 | 119.28 (13) | C35—C36—C31 | 120.84 (19) |
C2—N1—C11 | 116.34 (13) | C35—C36—H36 | 119.6 |
O2—C2—N1 | 115.85 (15) | C31—C36—H36 | 119.6 |
O2—C2—C3 | 127.11 (16) | C42—N41—C45 | 117.8 (3) |
N1—C2—C3 | 117.04 (15) | C42—N41—C41 | 122.0 (3) |
C4—C3—C2 | 121.45 (15) | C45—N41—C41 | 120.0 (2) |
C4—C3—C31 | 119.53 (14) | N41—C41—H41A | 109.5 |
C2—C3—C31 | 119.00 (15) | N41—C41—H41B | 109.5 |
O4—C4—C3 | 130.07 (16) | H41A—C41—H41B | 109.5 |
O4—C4—N5 | 114.36 (15) | N41—C41—H41C | 109.5 |
C3—C4—N5 | 115.56 (14) | H41A—C41—H41C | 109.5 |
C6—N5—C10 | 120.50 (15) | H41B—C41—H41C | 109.5 |
C6—N5—C4 | 123.06 (14) | O42—C42—N41 | 124.5 (4) |
C10—N5—C4 | 116.44 (14) | O42—C42—C43 | 128.2 (3) |
N1—C6—N5 | 118.40 (15) | N41—C42—C43 | 107.3 (3) |
N1—C6—C7 | 122.63 (15) | C44—C43—C42 | 104.5 (3) |
N5—C6—C7 | 118.97 (15) | C44—C43—H43A | 110.9 |
C8—C7—C6 | 120.20 (17) | C42—C43—H43A | 110.9 |
C8—C7—H7 | 119.9 | C44—C43—H43B | 110.9 |
C6—C7—H7 | 119.9 | C42—C43—H43B | 110.9 |
C7—C8—C9 | 119.82 (17) | H43A—C43—H43B | 108.9 |
C7—C8—H8 | 120.1 | C43—C44—C45 | 104.4 (3) |
C9—C8—H8 | 120.1 | C43—C44—H44A | 110.9 |
C10—C9—C8 | 118.58 (17) | C45—C44—H44A | 110.9 |
C10—C9—H9 | 120.7 | C43—C44—H44B | 110.9 |
C8—C9—H9 | 120.7 | C45—C44—H44B | 110.9 |
C9—C10—N5 | 121.63 (16) | H44A—C44—H44B | 108.9 |
C9—C10—H10 | 119.2 | N41—C45—C44 | 101.2 (2) |
N5—C10—H10 | 119.2 | N41—C45—H45A | 111.5 |
C12—C11—C13i | 121.92 (15) | C44—C45—H45A | 111.5 |
C12—C11—N1 | 119.37 (15) | N41—C45—H45B | 111.5 |
C13i—C11—N1 | 118.71 (15) | C44—C45—H45B | 111.5 |
C11—C12—C13 | 118.83 (16) | H45A—C45—H45B | 109.3 |
C11—C12—H12 | 120.6 | C52—C51—H51A | 109.5 |
C13—C12—H12 | 120.6 | C52—C51—H51B | 109.5 |
C11i—C13—C12 | 119.25 (16) | H51A—C51—H51B | 109.5 |
C11i—C13—H13 | 120.4 | C52—C51—H51C | 109.5 |
C12—C13—H13 | 120.4 | H51A—C51—H51C | 109.5 |
C32—C31—C36 | 117.41 (16) | H51B—C51—H51C | 109.5 |
C32—C31—C3 | 121.75 (16) | O52—C52—C53 | 106.1 (7) |
C36—C31—C3 | 120.84 (16) | O52—C52—C51 | 113.6 (7) |
C33—C32—C31 | 121.17 (18) | C53—C52—C51 | 108.7 (14) |
C33—C32—H32 | 119.4 | O52—C52—H52A | 109.4 |
C31—C32—H32 | 119.4 | C53—C52—H52A | 109.4 |
C34—C33—C32 | 120.57 (19) | C51—C52—H52A | 109.4 |
C34—C33—H33 | 119.7 | C52—O52—H52 | 109.5 |
C32—C33—H33 | 119.7 | C52—C53—H53A | 109.5 |
C35—C34—C33 | 119.21 (17) | C52—C53—H53B | 109.5 |
C35—C34—H34 | 120.4 | H53A—C53—H53B | 109.5 |
C33—C34—H34 | 120.4 | C52—C53—H53C | 109.5 |
C34—C35—C36 | 120.80 (19) | H53A—C53—H53C | 109.5 |
C34—C35—H35 | 119.6 | H53B—C53—H53C | 109.5 |
| | | |
C6—N1—C2—O2 | −173.91 (17) | C4—N5—C10—C9 | −177.21 (16) |
C11—N1—C2—O2 | −1.9 (2) | C6—N1—C11—C12 | −99.30 (19) |
C6—N1—C2—C3 | 6.2 (2) | C2—N1—C11—C12 | 88.33 (19) |
C11—N1—C2—C3 | 178.17 (15) | C6—N1—C11—C13i | 80.8 (2) |
O2—C2—C3—C4 | 177.59 (18) | C2—N1—C11—C13i | −91.59 (19) |
N1—C2—C3—C4 | −2.5 (2) | C13i—C11—C12—C13 | 0.0 (3) |
O2—C2—C3—C31 | −0.8 (3) | N1—C11—C12—C13 | −179.90 (15) |
N1—C2—C3—C31 | 179.06 (14) | C11—C12—C13—C11i | 0.0 (3) |
C2—C3—C4—O4 | 177.25 (18) | C4—C3—C31—C32 | 153.47 (17) |
C31—C3—C4—O4 | −4.3 (3) | C2—C3—C31—C32 | −28.1 (2) |
C2—C3—C4—N5 | −4.0 (2) | C4—C3—C31—C36 | −27.1 (2) |
C31—C3—C4—N5 | 174.41 (14) | C2—C3—C31—C36 | 151.36 (17) |
O4—C4—N5—C6 | −172.88 (16) | C36—C31—C32—C33 | 0.4 (3) |
C3—C4—N5—C6 | 8.2 (2) | C3—C31—C32—C33 | 179.84 (16) |
O4—C4—N5—C10 | 7.5 (2) | C31—C32—C33—C34 | −0.2 (3) |
C3—C4—N5—C10 | −171.44 (15) | C32—C33—C34—C35 | −0.4 (3) |
C2—N1—C6—N5 | −2.4 (3) | C33—C34—C35—C36 | 0.8 (3) |
C11—N1—C6—N5 | −174.14 (15) | C34—C35—C36—C31 | −0.6 (3) |
C2—N1—C6—C7 | 178.16 (16) | C32—C31—C36—C35 | 0.0 (3) |
C11—N1—C6—C7 | 6.4 (3) | C3—C31—C36—C35 | −179.48 (18) |
C10—N5—C6—N1 | 174.54 (16) | C45—N41—C42—O42 | 180.0 (3) |
C4—N5—C6—N1 | −5.1 (2) | C41—N41—C42—O42 | −5.3 (4) |
C10—N5—C6—C7 | −6.0 (2) | C45—N41—C42—C43 | −0.1 (3) |
C4—N5—C6—C7 | 174.42 (15) | C41—N41—C42—C43 | 174.7 (2) |
N1—C6—C7—C8 | −176.68 (17) | O42—C42—C43—C44 | −166.1 (3) |
N5—C6—C7—C8 | 3.9 (3) | N41—C42—C43—C44 | 14.0 (3) |
C6—C7—C8—C9 | 1.1 (3) | C42—C43—C44—C45 | −20.9 (3) |
C7—C8—C9—C10 | −3.9 (3) | C42—N41—C45—C44 | −13.1 (3) |
C8—C9—C10—N5 | 1.9 (3) | C41—N41—C45—C44 | 172.0 (2) |
C6—N5—C10—C9 | 3.2 (3) | C43—C44—C45—N41 | 20.3 (3) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O52—H52···O42 | 0.84 | 2.02 | 2.691 (5) | 137 |
(Ib)
p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2-
a]pyrimidin-5-ium-4-olate)–
N-methylpyrrolidone (1/3)
top
Crystal data top
C34H22N4O4·3C5H9NO | Z = 1 |
Mr = 847.95 | F(000) = 448 |
Triclinic, P1 | Dx = 1.329 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8137 (8) Å | Cell parameters from 14799 reflections |
b = 10.1565 (9) Å | θ = 3.7–26.4° |
c = 12.7300 (11) Å | µ = 0.09 mm−1 |
α = 99.212 (7)° | T = 173 K |
β = 99.567 (7)° | Plate, yellow |
γ = 105.102 (7)° | 0.24 × 0.23 × 0.13 mm |
V = 1059.84 (16) Å3 | |
Data collection top
Stoe IPDS II two-circle diffractometer | 3513 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 26.4°, θmin = 3.6° |
ω scans | h = −10→10 |
15396 measured reflections | k = −12→12 |
4290 independent reflections | l = −15→15 |
Refinement top
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)] = 0.080 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.223 | H-atom parameters constrained |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0957P)2 + 0.9685P] where P = (Fo2 + 2Fc2)/3 |
4290 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.90 e Å−3 |
2 restraints | Δρmin = −1.05 e Å−3 |
Crystal data top
C34H22N4O4·3C5H9NO | γ = 105.102 (7)° |
Mr = 847.95 | V = 1059.84 (16) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.8137 (8) Å | Mo Kα radiation |
b = 10.1565 (9) Å | µ = 0.09 mm−1 |
c = 12.7300 (11) Å | T = 173 K |
α = 99.212 (7)° | 0.24 × 0.23 × 0.13 mm |
β = 99.567 (7)° | |
Data collection top
Stoe IPDS II two-circle diffractometer | 3513 reflections with I > 2σ(I) |
15396 measured reflections | Rint = 0.035 |
4290 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.080 | 2 restraints |
wR(F2) = 0.223 | H-atom parameters constrained |
S = 1.20 | Δρmax = 0.90 e Å−3 |
4290 reflections | Δρmin = −1.05 e Å−3 |
298 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.4405 (2) | 0.26030 (19) | 0.55528 (17) | 0.0242 (4) | |
C2 | 0.5747 (3) | 0.3720 (2) | 0.6210 (2) | 0.0265 (5) | |
O2 | 0.7048 (2) | 0.3471 (2) | 0.63636 (19) | 0.0446 (6) | |
C3 | 0.5429 (3) | 0.5000 (2) | 0.66306 (19) | 0.0237 (5) | |
C4 | 0.3872 (3) | 0.5144 (2) | 0.6418 (2) | 0.0249 (5) | |
O4 | 0.3401 (2) | 0.61624 (17) | 0.66966 (17) | 0.0354 (5) | |
N5 | 0.2570 (2) | 0.38703 (19) | 0.57638 (17) | 0.0234 (4) | |
C6 | 0.2858 (3) | 0.2665 (2) | 0.5333 (2) | 0.0232 (5) | |
C7 | 0.1571 (3) | 0.1546 (2) | 0.4680 (2) | 0.0295 (5) | |
H7 | 0.1771 | 0.0720 | 0.4346 | 0.035* | |
C8 | 0.0032 (3) | 0.1644 (3) | 0.4526 (2) | 0.0339 (6) | |
H8 | −0.0834 | 0.0894 | 0.4076 | 0.041* | |
C9 | −0.0260 (3) | 0.2863 (3) | 0.5039 (3) | 0.0366 (6) | |
H9 | −0.1327 | 0.2926 | 0.4971 | 0.044* | |
C10 | 0.1013 (3) | 0.3949 (3) | 0.5634 (2) | 0.0303 (6) | |
H10 | 0.0825 | 0.4781 | 0.5967 | 0.036* | |
C11 | 0.4702 (3) | 0.1259 (2) | 0.5251 (2) | 0.0235 (5) | |
C12 | 0.5351 (3) | 0.0990 (2) | 0.4350 (2) | 0.0260 (5) | |
H12 | 0.5584 | 0.1661 | 0.3913 | 0.031* | |
C13 | 0.5654 (3) | −0.0295 (2) | 0.4099 (2) | 0.0263 (5) | |
H13 | 0.6102 | −0.0507 | 0.3487 | 0.032* | |
C31 | 0.6781 (3) | 0.6165 (2) | 0.7364 (2) | 0.0271 (5) | |
C32 | 0.8374 (3) | 0.6368 (3) | 0.7251 (2) | 0.0369 (6) | |
H32 | 0.8596 | 0.5779 | 0.6675 | 0.044* | |
C33 | 0.9645 (3) | 0.7421 (3) | 0.7970 (3) | 0.0475 (8) | |
H33 | 1.0717 | 0.7535 | 0.7881 | 0.057* | |
C34 | 0.9348 (4) | 0.8297 (3) | 0.8811 (3) | 0.0501 (8) | |
H34 | 1.0211 | 0.9010 | 0.9301 | 0.060* | |
C35 | 0.7779 (4) | 0.8121 (3) | 0.8931 (3) | 0.0492 (8) | |
H35 | 0.7566 | 0.8722 | 0.9505 | 0.059* | |
C36 | 0.6508 (3) | 0.7070 (3) | 0.8219 (2) | 0.0380 (6) | |
H36 | 0.5440 | 0.6966 | 0.8313 | 0.046* | |
N41 | −0.0022 (13) | 0.2372 (9) | 0.8047 (6) | 0.167 (4) | 0.50 |
C41" | −0.0022 (13) | 0.2372 (9) | 0.8047 (6) | 0.167 (4) | 0.50 |
H41G | −0.0502 | 0.1586 | 0.8344 | 0.200* | 0.50 |
H41H | −0.0680 | 0.2354 | 0.7365 | 0.200* | 0.50 |
C41 | −0.1115 (13) | 0.1371 (9) | 0.7618 (9) | 0.085 (4) | 0.50 |
H41A | −0.0719 | 0.0735 | 0.7148 | 0.127* | 0.50 |
H41B | −0.1519 | 0.0915 | 0.8181 | 0.127* | 0.50 |
H41C | −0.1986 | 0.1610 | 0.7179 | 0.127* | 0.50 |
C42 | 0.1350 (6) | 0.2248 (5) | 0.7862 (4) | 0.0705 (12) | |
O42 | 0.1821 (3) | 0.1443 (3) | 0.7287 (2) | 0.0644 (7) | |
C43 | 0.2518 (9) | 0.3502 (8) | 0.8621 (4) | 0.118 (2) | 0.50 |
H43A | 0.3205 | 0.4042 | 0.8203 | 0.142* | 0.50 |
H43B | 0.3223 | 0.3196 | 0.9161 | 0.142* | 0.50 |
N43 | 0.2518 (9) | 0.3502 (8) | 0.8621 (4) | 0.118 (2) | 0.50 |
C41' | 0.4066 (11) | 0.3595 (9) | 0.8789 (7) | 0.075 (3) | 0.50 |
H41D | 0.4684 | 0.4471 | 0.9304 | 0.112* | 0.50 |
H41E | 0.4243 | 0.2805 | 0.9092 | 0.112* | 0.50 |
H41F | 0.4417 | 0.3577 | 0.8097 | 0.112* | 0.50 |
C44 | 0.1726 (11) | 0.4372 (10) | 0.9177 (6) | 0.141 (3) | |
H44A | 0.1995 | 0.5305 | 0.8986 | 0.170* | |
H44B | 0.2084 | 0.4498 | 0.9976 | 0.170* | |
C45 | −0.0004 (8) | 0.3647 (6) | 0.8815 (4) | 0.0900 (16) | |
H45A | −0.0491 | 0.3407 | 0.9433 | 0.108* | |
H45B | −0.0582 | 0.4218 | 0.8445 | 0.108* | |
N51 | 0.4449 (4) | 0.9521 (5) | 0.9636 (3) | 0.0671 (10) | 0.50 |
C52 | 0.4449 (4) | 0.9521 (5) | 0.9636 (3) | 0.0671 (10) | 0.50 |
C51 | 0.3660 (6) | 0.8360 (5) | 0.9988 (4) | 0.0997 (14) | 0.50 |
H51A | 0.2868 | 0.7734 | 0.9354 | 0.149* | 0.50 |
H51B | 0.4422 | 0.7882 | 1.0269 | 0.149* | 0.50 |
H51C | 0.3105 | 0.8625 | 1.0557 | 0.149* | 0.50 |
O52 | 0.3660 (6) | 0.8360 (5) | 0.9988 (4) | 0.0997 (14) | 0.50 |
C55 | 0.4162 (4) | 0.9703 (4) | 0.8517 (3) | 0.0587 (9) | |
H55A | 0.3115 | 0.9881 | 0.8298 | 0.070* | |
H55B | 0.4222 | 0.8888 | 0.8000 | 0.070* | |
C54 | 0.5553 (9) | 1.1015 (7) | 0.8832 (5) | 0.092 (3) | 0.50 |
H54A | 0.5189 | 1.1711 | 0.8477 | 0.110* | 0.50 |
H54B | 0.6376 | 1.0754 | 0.8472 | 0.110* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0184 (9) | 0.0166 (9) | 0.0358 (11) | 0.0063 (7) | 0.0041 (8) | 0.0004 (8) |
C2 | 0.0200 (11) | 0.0211 (11) | 0.0346 (13) | 0.0053 (9) | 0.0029 (9) | −0.0005 (9) |
O2 | 0.0212 (9) | 0.0352 (10) | 0.0668 (14) | 0.0123 (8) | −0.0029 (8) | −0.0127 (9) |
C3 | 0.0231 (11) | 0.0174 (10) | 0.0280 (12) | 0.0034 (8) | 0.0048 (9) | 0.0023 (9) |
C4 | 0.0255 (11) | 0.0158 (10) | 0.0322 (12) | 0.0051 (8) | 0.0061 (9) | 0.0041 (9) |
O4 | 0.0317 (9) | 0.0196 (8) | 0.0531 (12) | 0.0117 (7) | 0.0058 (8) | −0.0003 (8) |
N5 | 0.0189 (9) | 0.0172 (9) | 0.0339 (11) | 0.0062 (7) | 0.0045 (8) | 0.0043 (8) |
C6 | 0.0187 (10) | 0.0183 (10) | 0.0323 (12) | 0.0060 (8) | 0.0043 (9) | 0.0049 (9) |
C7 | 0.0241 (12) | 0.0193 (11) | 0.0408 (14) | 0.0053 (9) | 0.0016 (10) | 0.0022 (10) |
C8 | 0.0213 (11) | 0.0248 (12) | 0.0496 (16) | 0.0025 (9) | −0.0008 (10) | 0.0073 (11) |
C9 | 0.0193 (11) | 0.0325 (13) | 0.0583 (18) | 0.0102 (10) | 0.0044 (11) | 0.0106 (12) |
C10 | 0.0236 (12) | 0.0251 (12) | 0.0453 (15) | 0.0126 (9) | 0.0075 (10) | 0.0081 (10) |
C11 | 0.0167 (10) | 0.0171 (10) | 0.0340 (12) | 0.0062 (8) | 0.0021 (9) | −0.0003 (9) |
C12 | 0.0243 (11) | 0.0201 (11) | 0.0336 (13) | 0.0069 (9) | 0.0070 (9) | 0.0046 (9) |
C13 | 0.0239 (11) | 0.0233 (11) | 0.0318 (12) | 0.0084 (9) | 0.0082 (9) | 0.0016 (9) |
C31 | 0.0281 (12) | 0.0191 (10) | 0.0303 (13) | 0.0033 (9) | 0.0023 (9) | 0.0042 (9) |
C32 | 0.0288 (13) | 0.0332 (13) | 0.0388 (15) | −0.0018 (10) | 0.0070 (11) | −0.0021 (11) |
C33 | 0.0284 (14) | 0.0453 (17) | 0.0532 (19) | −0.0052 (12) | 0.0042 (12) | −0.0019 (14) |
C34 | 0.0401 (16) | 0.0365 (15) | 0.0507 (19) | −0.0056 (12) | −0.0079 (13) | −0.0086 (13) |
C35 | 0.0484 (17) | 0.0360 (15) | 0.0478 (18) | 0.0052 (13) | 0.0011 (14) | −0.0131 (13) |
C36 | 0.0340 (14) | 0.0294 (13) | 0.0424 (16) | 0.0059 (11) | 0.0042 (11) | −0.0058 (11) |
N41 | 0.311 (11) | 0.200 (8) | 0.156 (6) | 0.224 (8) | 0.176 (7) | 0.133 (6) |
C41" | 0.311 (11) | 0.200 (8) | 0.156 (6) | 0.224 (8) | 0.176 (7) | 0.133 (6) |
C41 | 0.090 (7) | 0.047 (5) | 0.092 (7) | 0.019 (4) | −0.028 (6) | −0.002 (5) |
C42 | 0.115 (4) | 0.068 (3) | 0.063 (2) | 0.055 (3) | 0.048 (3) | 0.036 (2) |
O42 | 0.0692 (17) | 0.0665 (16) | 0.0702 (17) | 0.0340 (14) | 0.0281 (14) | 0.0141 (13) |
C43 | 0.190 (7) | 0.171 (6) | 0.076 (3) | 0.132 (6) | 0.081 (4) | 0.076 (4) |
N43 | 0.190 (7) | 0.171 (6) | 0.076 (3) | 0.132 (6) | 0.081 (4) | 0.076 (4) |
C41' | 0.068 (5) | 0.067 (5) | 0.058 (5) | −0.026 (4) | −0.003 (4) | 0.016 (4) |
C44 | 0.166 (8) | 0.180 (8) | 0.105 (5) | 0.107 (7) | 0.026 (5) | 0.018 (5) |
C45 | 0.132 (5) | 0.095 (4) | 0.083 (3) | 0.077 (4) | 0.055 (3) | 0.029 (3) |
N51 | 0.069 (2) | 0.108 (3) | 0.0426 (18) | 0.055 (2) | 0.0138 (14) | 0.0187 (18) |
C52 | 0.069 (2) | 0.108 (3) | 0.0426 (18) | 0.055 (2) | 0.0138 (14) | 0.0187 (18) |
C51 | 0.119 (4) | 0.098 (3) | 0.109 (3) | 0.036 (3) | 0.055 (3) | 0.059 (3) |
O52 | 0.119 (4) | 0.098 (3) | 0.109 (3) | 0.036 (3) | 0.055 (3) | 0.059 (3) |
C55 | 0.063 (2) | 0.069 (2) | 0.0403 (18) | 0.0228 (18) | 0.0023 (15) | 0.0072 (16) |
C54 | 0.053 (5) | 0.115 (8) | 0.098 (8) | 0.004 (5) | 0.002 (5) | 0.047 (6) |
Geometric parameters (Å, º) top
N1—C6 | 1.366 (3) | N41—C45 | 1.487 (9) |
N1—C2 | 1.433 (3) | N41—H41G | 0.9649 |
N1—C11 | 1.460 (3) | N41—H41H | 0.9554 |
C2—O2 | 1.229 (3) | C41—H41G | 0.9486 |
C2—C3 | 1.440 (3) | C41—H41H | 1.0920 |
C3—C4 | 1.405 (3) | C41—H41A | 0.9800 |
C3—C31 | 1.494 (3) | C41—H41B | 0.9800 |
C4—O4 | 1.234 (3) | C41—H41C | 0.9800 |
C4—N5 | 1.500 (3) | C42—O42 | 1.209 (5) |
N5—C6 | 1.363 (3) | C42—C43 | 1.486 (9) |
N5—C10 | 1.379 (3) | C43—C44 | 1.433 (8) |
C6—C7 | 1.407 (3) | C43—H43A | 0.9900 |
C7—C8 | 1.370 (3) | C43—H43B | 0.9900 |
C7—H7 | 0.9500 | C41'—H43A | 1.1992 |
C8—C9 | 1.411 (4) | C41'—H43B | 0.9804 |
C8—H8 | 0.9500 | C41'—H41D | 0.9800 |
C9—C10 | 1.362 (4) | C41'—H41E | 0.9799 |
C9—H9 | 0.9500 | C41'—H41F | 0.9800 |
C10—H10 | 0.9500 | C44—C45 | 1.467 (10) |
C11—C12 | 1.384 (3) | C44—H44A | 0.9941 |
C11—C13i | 1.388 (3) | C44—H44B | 0.9905 |
C12—C13 | 1.397 (3) | C45—H45A | 0.9909 |
C12—H12 | 0.9500 | C45—H45B | 0.9895 |
C13—C11i | 1.388 (3) | N51—C52ii | 1.292 (8) |
C13—H13 | 0.9500 | N51—N51ii | 1.292 (8) |
C31—C32 | 1.400 (4) | N51—C51 | 1.386 (6) |
C31—C36 | 1.403 (4) | N51—C55 | 1.454 (5) |
C32—C33 | 1.399 (4) | C51—C54ii | 1.5028 (11) |
C32—H32 | 0.9500 | C51—H51A | 0.9800 |
C33—C34 | 1.384 (5) | C51—H51B | 0.9800 |
C33—H33 | 0.9500 | C51—H51C | 0.9800 |
C34—C35 | 1.385 (5) | C55—C54 | 1.5009 (11) |
C34—H34 | 0.9500 | C55—H55A | 0.9900 |
C35—C36 | 1.395 (4) | C55—H55B | 0.9900 |
C35—H35 | 0.9500 | C54—O52ii | 1.5028 (10) |
C36—H36 | 0.9500 | C54—C51ii | 1.5028 (10) |
N41—C41 | 1.181 (13) | C54—H54A | 0.9900 |
N41—C42 | 1.303 (8) | C54—H54B | 0.9900 |
| | | |
C6—N1—C2 | 124.38 (19) | H41H—C41—H41A | 102.1 |
C6—N1—C11 | 118.70 (18) | N41—C41—H41B | 108.7 |
C2—N1—C11 | 116.23 (17) | H41G—C41—H41B | 58.4 |
O2—C2—N1 | 116.1 (2) | H41H—C41—H41B | 146.7 |
O2—C2—C3 | 126.9 (2) | H41A—C41—H41B | 109.5 |
N1—C2—C3 | 116.99 (19) | N41—C41—H41C | 111.6 |
C4—C3—C2 | 121.6 (2) | H41G—C41—H41C | 140.5 |
C4—C3—C31 | 119.7 (2) | H41H—C41—H41C | 68.0 |
C2—C3—C31 | 118.6 (2) | H41A—C41—H41C | 109.5 |
O4—C4—C3 | 129.8 (2) | H41B—C41—H41C | 109.5 |
O4—C4—N5 | 114.5 (2) | O42—C42—N41 | 137.8 (7) |
C3—C4—N5 | 115.73 (19) | O42—C42—C43 | 120.2 (5) |
C6—N5—C10 | 120.07 (19) | N41—C42—C43 | 102.0 (6) |
C6—N5—C4 | 123.32 (18) | C44—C43—C42 | 111.9 (6) |
C10—N5—C4 | 116.58 (19) | C44—C43—H43A | 109.5 |
N5—C6—N1 | 117.89 (19) | C42—C43—H43A | 108.9 |
N5—C6—C7 | 119.4 (2) | C44—C43—H43B | 109.7 |
N1—C6—C7 | 122.7 (2) | C42—C43—H43B | 108.9 |
C8—C7—C6 | 120.1 (2) | H43A—C43—H43B | 107.9 |
C8—C7—H7 | 119.9 | H43A—C41'—H43B | 93.9 |
C6—C7—H7 | 119.9 | H43A—C41'—H41D | 98.7 |
C7—C8—C9 | 119.7 (2) | H43B—C41'—H41D | 102.8 |
C7—C8—H8 | 120.2 | H43A—C41'—H41E | 148.7 |
C9—C8—H8 | 120.2 | H43B—C41'—H41E | 67.2 |
C10—C9—C8 | 118.9 (2) | H41D—C41'—H41E | 109.5 |
C10—C9—H9 | 120.6 | H43A—C41'—H41F | 72.0 |
C8—C9—H9 | 120.6 | H43B—C41'—H41F | 146.3 |
C9—C10—N5 | 121.6 (2) | H41D—C41'—H41F | 109.5 |
C9—C10—H10 | 119.2 | H41E—C41'—H41F | 109.5 |
N5—C10—H10 | 119.2 | C43—C44—C45 | 106.0 (7) |
C12—C11—C13i | 122.0 (2) | C43—C44—H44A | 110.1 |
C12—C11—N1 | 119.8 (2) | C45—C44—H44A | 111.2 |
C13i—C11—N1 | 118.2 (2) | C43—C44—H44B | 110.0 |
C11—C12—C13 | 118.3 (2) | C45—C44—H44B | 111.0 |
C11—C12—H12 | 120.8 | H44A—C44—H44B | 108.6 |
C13—C12—H12 | 120.8 | C44—C45—N41 | 101.9 (6) |
C11i—C13—C12 | 119.7 (2) | C44—C45—H45A | 111.6 |
C11i—C13—H13 | 120.2 | N41—C45—H45A | 111.3 |
C12—C13—H13 | 120.2 | C44—C45—H45B | 111.3 |
C32—C31—C36 | 117.3 (2) | N41—C45—H45B | 111.6 |
C32—C31—C3 | 121.5 (2) | H45A—C45—H45B | 109.0 |
C36—C31—C3 | 121.1 (2) | C52ii—N51—C51 | 116.2 (5) |
C33—C32—C31 | 121.3 (3) | N51ii—N51—C51 | 116.2 (5) |
C33—C32—H32 | 119.3 | C52ii—N51—C55 | 118.8 (5) |
C31—C32—H32 | 119.3 | N51ii—N51—C55 | 118.8 (5) |
C34—C33—C32 | 120.3 (3) | C51—N51—C55 | 124.9 (4) |
C34—C33—H33 | 119.8 | N51—C51—C54ii | 93.6 (4) |
C32—C33—H33 | 119.8 | N51—C51—H51A | 106.9 |
C33—C34—C35 | 119.3 (3) | C54ii—C51—H51A | 158.3 |
C33—C34—H34 | 120.4 | N51—C51—H51B | 110.6 |
C35—C34—H34 | 120.4 | C54ii—C51—H51B | 68.4 |
C34—C35—C36 | 120.6 (3) | H51A—C51—H51B | 109.5 |
C34—C35—H35 | 119.7 | N51—C51—H51C | 110.9 |
C36—C35—H35 | 119.7 | C54ii—C51—H51C | 54.7 |
C35—C36—C31 | 121.1 (3) | H51A—C51—H51C | 109.5 |
C35—C36—H36 | 119.4 | H51B—C51—H51C | 109.5 |
C31—C36—H36 | 119.4 | N51—C55—C54 | 89.8 (4) |
C41—N41—C42 | 112.8 (8) | N51—C55—H55A | 112.0 |
C41—N41—C45 | 129.0 (9) | C54—C55—H55A | 112.7 |
C42—N41—C45 | 118.0 (9) | N51—C55—H55B | 111.6 |
C41—N41—H41G | 51.3 | C54—C55—H55B | 119.5 |
C42—N41—H41G | 107.4 | H55A—C55—H55B | 109.9 |
C45—N41—H41G | 106.7 | C55—C54—O52ii | 120.4 (5) |
C41—N41—H41H | 60.4 | C55—C54—C51ii | 120.4 (5) |
C42—N41—H41H | 107.4 | C55—C54—H54A | 106.3 |
C45—N41—H41H | 106.6 | O52ii—C54—H54A | 110.4 |
H41G—N41—H41H | 110.7 | C51ii—C54—H54A | 110.4 |
N41—C41—H41G | 52.5 | C55—C54—H54B | 103.4 |
N41—C41—H41H | 49.5 | O52ii—C54—H54B | 107.3 |
H41G—C41—H41H | 101.2 | C51ii—C54—H54B | 107.3 |
N41—C41—H41A | 108.1 | H54A—C54—H54B | 108.2 |
H41G—C41—H41A | 110.0 | | |
| | | |
C6—N1—C2—O2 | 177.1 (2) | C2—N1—C11—C13i | 94.4 (3) |
C11—N1—C2—O2 | 6.8 (3) | C13i—C11—C12—C13 | −0.2 (4) |
C6—N1—C2—C3 | −2.0 (4) | N1—C11—C12—C13 | 178.6 (2) |
C11—N1—C2—C3 | −172.3 (2) | C11—C12—C13—C11i | 0.2 (4) |
O2—C2—C3—C4 | −178.4 (3) | C4—C3—C31—C32 | −152.0 (2) |
N1—C2—C3—C4 | 0.7 (4) | C2—C3—C31—C32 | 31.6 (4) |
O2—C2—C3—C31 | −2.0 (4) | C4—C3—C31—C36 | 30.2 (4) |
N1—C2—C3—C31 | 177.0 (2) | C2—C3—C31—C36 | −146.2 (3) |
C2—C3—C4—O4 | −178.7 (3) | C36—C31—C32—C33 | 0.8 (4) |
C31—C3—C4—O4 | 5.0 (4) | C3—C31—C32—C33 | −177.1 (3) |
C2—C3—C4—N5 | 2.1 (3) | C31—C32—C33—C34 | −0.4 (5) |
C31—C3—C4—N5 | −174.2 (2) | C32—C33—C34—C35 | −0.1 (5) |
O4—C4—N5—C6 | 176.5 (2) | C33—C34—C35—C36 | 0.3 (5) |
C3—C4—N5—C6 | −4.2 (3) | C34—C35—C36—C31 | 0.0 (5) |
O4—C4—N5—C10 | −5.3 (3) | C32—C31—C36—C35 | −0.6 (4) |
C3—C4—N5—C10 | 174.1 (2) | C3—C31—C36—C35 | 177.3 (3) |
C10—N5—C6—N1 | −175.1 (2) | C41—N41—C42—O42 | 8.8 (11) |
C4—N5—C6—N1 | 3.1 (3) | C45—N41—C42—O42 | −176.1 (5) |
C10—N5—C6—C7 | 5.2 (4) | C41—N41—C42—C43 | −170.9 (8) |
C4—N5—C6—C7 | −176.6 (2) | C45—N41—C42—C43 | 4.2 (6) |
C2—N1—C6—N5 | 0.1 (4) | O42—C42—C43—C44 | 176.1 (5) |
C11—N1—C6—N5 | 170.2 (2) | N41—C42—C43—C44 | −4.1 (6) |
C2—N1—C6—C7 | 179.8 (2) | C42—C43—C44—C45 | 2.6 (7) |
C11—N1—C6—C7 | −10.1 (4) | C43—C44—C45—N41 | −0.2 (7) |
N5—C6—C7—C8 | −3.3 (4) | C41—N41—C45—C44 | 171.4 (10) |
N1—C6—C7—C8 | 177.1 (2) | C42—N41—C45—C44 | −2.8 (7) |
C6—C7—C8—C9 | −1.0 (4) | C52ii—N51—C51—C54ii | 7.2 (7) |
C7—C8—C9—C10 | 3.3 (4) | N51ii—N51—C51—C54ii | 7.2 (7) |
C8—C9—C10—N5 | −1.4 (4) | C55—N51—C51—C54ii | −175.0 (5) |
C6—N5—C10—C9 | −2.9 (4) | C52ii—N51—C55—C54 | 4.5 (6) |
C4—N5—C10—C9 | 178.8 (2) | N51ii—N51—C55—C54 | 4.5 (6) |
C6—N1—C11—C12 | 104.7 (3) | C51—N51—C55—C54 | −173.3 (6) |
C2—N1—C11—C12 | −84.5 (3) | N51—C55—C54—O52ii | −9.8 (8) |
C6—N1—C11—C13i | −76.5 (3) | N51—C55—C54—C51ii | −9.8 (8) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+2, −z+2. |
(Ic)
p-phenylenebis(2-oxo-3-phenyl-1,2-dihydropyrido[1,2-
a]pyrimidin-5-ium-4-olate)-
N-methylpyrrolidone–butan-1-ol
(2/1/2)
top
Crystal data top
C34H22N4O4·0.5C5H9NO·C4H10O | Z = 2 |
Mr = 674.24 | F(000) = 710 |
Triclinic, P1 | Dx = 1.375 Mg m−3 |
a = 5.7853 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.2219 (17) Å | Cell parameters from 8048 reflections |
c = 19.198 (2) Å | θ = 3.6–52.5° |
α = 75.321 (9)° | µ = 0.09 mm−1 |
β = 87.393 (8)° | T = 173 K |
γ = 84.740 (9)° | Needle, yellow |
V = 1628.1 (3) Å3 | 0.21 × 0.09 × 0.09 mm |
Data collection top
Stoe IPDS II two-circle diffractometer | 3364 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.088 |
Graphite monochromator | θmax = 26.4°, θmin = 3.5° |
ω scans | h = −7→7 |
23578 measured reflections | k = −18→19 |
6641 independent reflections | l = −23→23 |
Refinement top
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)] = 0.081 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.1056P)2] where P = (Fo2 + 2Fc2)/3 |
6641 reflections | (Δ/σ)max < 0.001 |
379 parameters | Δρmax = 0.64 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C34H22N4O4·0.5C5H9NO·C4H10O | γ = 84.740 (9)° |
Mr = 674.24 | V = 1628.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7853 (6) Å | Mo Kα radiation |
b = 15.2219 (17) Å | µ = 0.09 mm−1 |
c = 19.198 (2) Å | T = 173 K |
α = 75.321 (9)° | 0.21 × 0.09 × 0.09 mm |
β = 87.393 (8)° | |
Data collection top
Stoe IPDS II two-circle diffractometer | 3364 reflections with I > 2σ(I) |
23578 measured reflections | Rint = 0.088 |
6641 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.081 | 0 restraints |
wR(F2) = 0.218 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.64 e Å−3 |
6641 reflections | Δρmin = −0.28 e Å−3 |
379 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 | x | y | z | Uiso*/Ueq | |
N1 | 0.2982 (5) | 0.5182 (2) | 0.36513 (15) | 0.0295 (7) | |
C2 | 0.1188 (6) | 0.5895 (3) | 0.34382 (19) | 0.0300 (8) | |
O2 | 0.0731 (5) | 0.64010 (19) | 0.38436 (14) | 0.0375 (6) | |
C3 | 0.0042 (7) | 0.5936 (2) | 0.27836 (18) | 0.0302 (8) | |
C4 | 0.0678 (7) | 0.5334 (2) | 0.23518 (19) | 0.0323 (8) | |
O4 | −0.0094 (6) | 0.5303 (2) | 0.17716 (15) | 0.0468 (8) | |
N5 | 0.2659 (6) | 0.4651 (2) | 0.26185 (16) | 0.0346 (8) | |
C6 | 0.3801 (7) | 0.4605 (3) | 0.32395 (19) | 0.0337 (9) | |
C7 | 0.5792 (8) | 0.3992 (3) | 0.3412 (2) | 0.0451 (10) | |
H7 | 0.6619 | 0.3962 | 0.3835 | 0.054* | |
C8 | 0.6532 (10) | 0.3441 (4) | 0.2969 (3) | 0.0575 (13) | |
H8 | 0.7878 | 0.3030 | 0.3084 | 0.069* | |
C9 | 0.5313 (11) | 0.3481 (3) | 0.2351 (3) | 0.0612 (15) | |
H9 | 0.5811 | 0.3091 | 0.2048 | 0.073* | |
C10 | 0.3421 (9) | 0.4077 (3) | 0.2183 (2) | 0.0488 (12) | |
H10 | 0.2600 | 0.4103 | 0.1760 | 0.059* | |
C11 | 0.4026 (6) | 0.5091 (3) | 0.43449 (18) | 0.0282 (8) | |
C12 | 0.6821 (7) | 0.5520 (3) | 0.5055 (2) | 0.0346 (9) | |
H12 | 0.8061 | 0.5870 | 0.5097 | 0.042* | |
C13 | 0.5822 (7) | 0.5613 (3) | 0.43847 (19) | 0.0345 (9) | |
H13 | 0.6371 | 0.6028 | 0.3966 | 0.041* | |
C31 | −0.1790 (7) | 0.6692 (3) | 0.25192 (18) | 0.0319 (8) | |
C32 | −0.3799 (7) | 0.6528 (3) | 0.2207 (2) | 0.0400 (10) | |
H32 | −0.4018 | 0.5927 | 0.2181 | 0.048* | |
C33 | −0.5487 (7) | 0.7237 (3) | 0.1935 (2) | 0.0456 (11) | |
H33 | −0.6858 | 0.7107 | 0.1739 | 0.055* | |
C34 | −0.5181 (8) | 0.8129 (4) | 0.1946 (3) | 0.0545 (13) | |
H34 | −0.6301 | 0.8613 | 0.1744 | 0.065* | |
C35 | −0.3194 (9) | 0.8296 (4) | 0.2260 (3) | 0.0597 (14) | |
H35 | −0.2959 | 0.8901 | 0.2276 | 0.072* | |
C36 | −0.1545 (7) | 0.7584 (3) | 0.2550 (2) | 0.0431 (10) | |
H36 | −0.0226 | 0.7710 | 0.2775 | 0.052* | |
N1A | 0.5020 (5) | 0.30686 (18) | 0.03210 (16) | 0.0269 (6) | |
C2A | 0.3202 (6) | 0.2677 (2) | 0.08122 (19) | 0.0271 (8) | |
O2A | 0.1792 (5) | 0.32191 (17) | 0.10197 (15) | 0.0341 (6) | |
C3A | 0.3255 (6) | 0.1707 (2) | 0.10185 (19) | 0.0274 (8) | |
C4A | 0.4819 (7) | 0.1153 (2) | 0.06960 (19) | 0.0316 (8) | |
O4A | 0.4962 (6) | 0.03164 (17) | 0.07797 (17) | 0.0490 (8) | |
N5A | 0.6570 (6) | 0.16488 (19) | 0.01797 (16) | 0.0288 (7) | |
C6A | 0.6726 (6) | 0.2570 (2) | 0.00309 (18) | 0.0250 (7) | |
C7A | 0.8570 (7) | 0.2956 (2) | −0.04070 (19) | 0.0288 (8) | |
H7A | 0.8687 | 0.3595 | −0.0514 | 0.035* | |
C8A | 1.0205 (7) | 0.2414 (2) | −0.06809 (19) | 0.0305 (8) | |
H8A | 1.1477 | 0.2673 | −0.0965 | 0.037* | |
C9A | 0.9987 (8) | 0.1469 (3) | −0.0539 (2) | 0.0371 (9) | |
H9A | 1.1098 | 0.1089 | −0.0731 | 0.045* | |
C10A | 0.8185 (8) | 0.1114 (2) | −0.0128 (2) | 0.0372 (10) | |
H10A | 0.8011 | 0.0481 | −0.0047 | 0.045* | |
C11A | 0.5049 (6) | 0.4063 (2) | 0.01474 (19) | 0.0265 (7) | |
C12A | 0.3504 (7) | 0.4594 (2) | −0.0352 (2) | 0.0304 (8) | |
H12A | 0.2492 | 0.4314 | −0.0590 | 0.037* | |
C13A | 0.3447 (6) | 0.5547 (2) | −0.05015 (19) | 0.0276 (8) | |
H13A | 0.2393 | 0.5920 | −0.0840 | 0.033* | |
C31A | 0.1641 (6) | 0.1251 (2) | 0.1598 (2) | 0.0299 (8) | |
C32A | 0.2385 (9) | 0.0396 (3) | 0.2084 (2) | 0.0465 (11) | |
H32A | 0.3889 | 0.0120 | 0.2015 | 0.056* | |
C33A | 0.0982 (10) | −0.0044 (3) | 0.2656 (3) | 0.0560 (13) | |
H33A | 0.1529 | −0.0606 | 0.2972 | 0.067* | |
C34A | −0.1261 (9) | 0.0363 (3) | 0.2754 (3) | 0.0553 (13) | |
H34A | −0.2261 | 0.0068 | 0.3130 | 0.066* | |
C35A | −0.1974 (9) | 0.1166 (4) | 0.2316 (3) | 0.0552 (13) | |
H35A | −0.3476 | 0.1438 | 0.2394 | 0.066* | |
C36A | −0.0585 (8) | 0.1619 (3) | 0.1747 (2) | 0.0443 (10) | |
H36A | −0.1162 | 0.2192 | 0.1454 | 0.053* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0302 (17) | 0.0412 (17) | 0.0189 (14) | −0.0020 (14) | −0.0076 (12) | −0.0098 (12) |
C2 | 0.0254 (19) | 0.043 (2) | 0.0242 (17) | −0.0073 (16) | −0.0014 (15) | −0.0117 (15) |
O2 | 0.0324 (15) | 0.0540 (17) | 0.0302 (14) | 0.0019 (13) | −0.0071 (11) | −0.0191 (12) |
C3 | 0.031 (2) | 0.0366 (19) | 0.0230 (17) | −0.0071 (16) | −0.0037 (15) | −0.0062 (15) |
C4 | 0.041 (2) | 0.0333 (19) | 0.0223 (17) | −0.0058 (16) | −0.0132 (16) | −0.0032 (14) |
O4 | 0.069 (2) | 0.0453 (16) | 0.0286 (14) | 0.0019 (15) | −0.0264 (14) | −0.0124 (12) |
N5 | 0.048 (2) | 0.0326 (16) | 0.0242 (15) | −0.0043 (15) | −0.0082 (14) | −0.0073 (13) |
C6 | 0.039 (2) | 0.042 (2) | 0.0214 (17) | −0.0069 (18) | −0.0066 (16) | −0.0083 (15) |
C7 | 0.046 (3) | 0.059 (3) | 0.030 (2) | 0.008 (2) | −0.0095 (19) | −0.0156 (19) |
C8 | 0.066 (3) | 0.060 (3) | 0.046 (3) | 0.018 (3) | −0.013 (2) | −0.020 (2) |
C9 | 0.094 (4) | 0.052 (3) | 0.042 (3) | 0.021 (3) | −0.023 (3) | −0.026 (2) |
C10 | 0.082 (4) | 0.037 (2) | 0.031 (2) | 0.002 (2) | −0.016 (2) | −0.0148 (17) |
C11 | 0.0239 (19) | 0.045 (2) | 0.0161 (15) | −0.0013 (16) | −0.0045 (13) | −0.0088 (14) |
C12 | 0.029 (2) | 0.050 (2) | 0.0261 (18) | −0.0127 (17) | −0.0063 (15) | −0.0075 (16) |
C13 | 0.031 (2) | 0.051 (2) | 0.0209 (17) | −0.0090 (18) | −0.0060 (15) | −0.0046 (16) |
C31 | 0.028 (2) | 0.048 (2) | 0.0193 (17) | 0.0002 (17) | −0.0025 (15) | −0.0080 (15) |
C32 | 0.035 (2) | 0.052 (2) | 0.031 (2) | −0.0102 (19) | −0.0118 (17) | −0.0014 (17) |
C33 | 0.027 (2) | 0.072 (3) | 0.031 (2) | −0.007 (2) | −0.0092 (17) | 0.001 (2) |
C34 | 0.036 (3) | 0.079 (3) | 0.049 (3) | 0.023 (2) | −0.012 (2) | −0.025 (2) |
C35 | 0.052 (3) | 0.064 (3) | 0.072 (3) | 0.028 (2) | −0.024 (3) | −0.042 (3) |
C36 | 0.032 (2) | 0.055 (3) | 0.051 (3) | 0.0081 (19) | −0.0149 (19) | −0.032 (2) |
N1A | 0.0280 (16) | 0.0193 (13) | 0.0341 (16) | 0.0039 (12) | −0.0085 (13) | −0.0089 (12) |
C2A | 0.029 (2) | 0.0259 (17) | 0.0286 (18) | 0.0045 (15) | −0.0099 (15) | −0.0127 (14) |
O2A | 0.0354 (15) | 0.0278 (13) | 0.0423 (15) | 0.0057 (11) | −0.0027 (12) | −0.0170 (11) |
C3A | 0.027 (2) | 0.0256 (17) | 0.0303 (18) | 0.0017 (14) | −0.0058 (15) | −0.0093 (14) |
C4A | 0.038 (2) | 0.0281 (18) | 0.0265 (18) | −0.0028 (16) | 0.0036 (16) | −0.0040 (14) |
O4A | 0.068 (2) | 0.0189 (13) | 0.0566 (18) | −0.0024 (13) | 0.0242 (16) | −0.0075 (12) |
N5A | 0.0347 (18) | 0.0218 (14) | 0.0280 (15) | 0.0049 (12) | −0.0012 (13) | −0.0055 (12) |
C6A | 0.034 (2) | 0.0171 (15) | 0.0237 (16) | 0.0018 (14) | −0.0069 (15) | −0.0053 (13) |
C7A | 0.033 (2) | 0.0271 (17) | 0.0258 (17) | 0.0033 (15) | −0.0078 (15) | −0.0064 (14) |
C8A | 0.035 (2) | 0.0309 (18) | 0.0242 (17) | 0.0000 (16) | −0.0036 (15) | −0.0040 (14) |
C9A | 0.047 (3) | 0.0289 (18) | 0.0307 (19) | 0.0064 (17) | 0.0101 (18) | −0.0037 (15) |
C10A | 0.053 (3) | 0.0214 (17) | 0.034 (2) | 0.0095 (17) | 0.0083 (19) | −0.0064 (15) |
C11A | 0.0281 (19) | 0.0219 (16) | 0.0295 (18) | 0.0003 (14) | −0.0052 (15) | −0.0068 (13) |
C12A | 0.035 (2) | 0.0248 (17) | 0.0337 (19) | 0.0032 (15) | −0.0146 (16) | −0.0114 (15) |
C13A | 0.030 (2) | 0.0237 (17) | 0.0305 (18) | 0.0007 (14) | −0.0109 (15) | −0.0087 (14) |
C31A | 0.027 (2) | 0.0273 (18) | 0.038 (2) | −0.0042 (15) | 0.0008 (16) | −0.0126 (15) |
C32A | 0.050 (3) | 0.037 (2) | 0.047 (2) | −0.004 (2) | 0.004 (2) | −0.0004 (18) |
C33A | 0.068 (4) | 0.040 (2) | 0.054 (3) | −0.008 (2) | 0.011 (3) | −0.001 (2) |
C34A | 0.056 (3) | 0.049 (3) | 0.061 (3) | −0.015 (2) | 0.027 (3) | −0.014 (2) |
C35A | 0.044 (3) | 0.067 (3) | 0.055 (3) | 0.004 (2) | 0.015 (2) | −0.020 (2) |
C36A | 0.043 (3) | 0.040 (2) | 0.049 (2) | 0.0006 (19) | 0.001 (2) | −0.0119 (19) |
Geometric parameters (Å, º) top
N1—C6 | 1.365 (5) | N1A—C6A | 1.373 (5) |
N1—C2 | 1.424 (5) | N1A—C2A | 1.446 (5) |
N1—C11 | 1.457 (4) | N1A—C11A | 1.467 (4) |
C2—O2 | 1.232 (4) | C2A—O2A | 1.232 (4) |
C2—C3 | 1.432 (5) | C2A—C3A | 1.426 (5) |
C3—C4 | 1.399 (5) | C3A—C4A | 1.409 (5) |
C3—C31 | 1.495 (5) | C3A—C31A | 1.491 (5) |
C4—O4 | 1.232 (4) | C4A—O4A | 1.238 (4) |
C4—N5 | 1.491 (5) | C4A—N5A | 1.499 (5) |
N5—C6 | 1.372 (5) | N5A—C6A | 1.370 (4) |
N5—C10 | 1.387 (5) | N5A—C10A | 1.393 (5) |
C6—C7 | 1.410 (6) | C6A—C7A | 1.405 (5) |
C7—C8 | 1.368 (6) | C7A—C8A | 1.373 (5) |
C7—H7 | 0.9500 | C7A—H7A | 0.9500 |
C8—C9 | 1.393 (7) | C8A—C9A | 1.410 (5) |
C8—H8 | 0.9500 | C8A—H8A | 0.9500 |
C9—C10 | 1.351 (7) | C9A—C10A | 1.347 (6) |
C9—H9 | 0.9500 | C9A—H9A | 0.9500 |
C10—H10 | 0.9500 | C10A—H10A | 0.9500 |
C11—C13 | 1.380 (5) | C11A—C12A | 1.386 (5) |
C11—C12i | 1.386 (5) | C11A—C13Aii | 1.387 (5) |
C12—C11i | 1.386 (5) | C12A—C13A | 1.403 (5) |
C12—C13 | 1.403 (5) | C12A—H12A | 0.9500 |
C12—H12 | 0.9500 | C13A—C11Aii | 1.387 (5) |
C13—H13 | 0.9500 | C13A—H13A | 0.9500 |
C31—C36 | 1.395 (6) | C31A—C36A | 1.404 (6) |
C31—C32 | 1.401 (5) | C31A—C32A | 1.438 (6) |
C32—C33 | 1.400 (6) | C32A—C33A | 1.400 (6) |
C32—H32 | 0.9500 | C32A—H32A | 0.9500 |
C33—C34 | 1.391 (7) | C33A—C34A | 1.412 (7) |
C33—H33 | 0.9500 | C33A—H33A | 0.9500 |
C34—C35 | 1.395 (7) | C34A—C35A | 1.339 (7) |
C34—H34 | 0.9500 | C34A—H34A | 0.9500 |
C35—C36 | 1.396 (6) | C35A—C36A | 1.398 (7) |
C35—H35 | 0.9500 | C35A—H35A | 0.9500 |
C36—H36 | 0.9500 | C36A—H36A | 0.9500 |
| | | |
C6—N1—C2 | 124.1 (3) | C6A—N1A—C2A | 124.3 (3) |
C6—N1—C11 | 118.9 (3) | C6A—N1A—C11A | 119.0 (3) |
C2—N1—C11 | 117.0 (3) | C2A—N1A—C11A | 116.7 (3) |
O2—C2—N1 | 116.9 (3) | O2A—C2A—C3A | 126.8 (3) |
O2—C2—C3 | 126.3 (4) | O2A—C2A—N1A | 116.3 (3) |
N1—C2—C3 | 116.7 (3) | C3A—C2A—N1A | 116.9 (3) |
C4—C3—C2 | 122.6 (4) | C4A—C3A—C2A | 122.0 (3) |
C4—C3—C31 | 118.2 (3) | C4A—C3A—C31A | 118.1 (3) |
C2—C3—C31 | 119.0 (3) | C2A—C3A—C31A | 119.9 (3) |
O4—C4—C3 | 129.8 (4) | O4A—C4A—C3A | 129.4 (3) |
O4—C4—N5 | 115.0 (3) | O4A—C4A—N5A | 115.3 (3) |
C3—C4—N5 | 115.1 (3) | C3A—C4A—N5A | 115.3 (3) |
C6—N5—C10 | 120.0 (4) | C6A—N5A—C10A | 119.6 (3) |
C6—N5—C4 | 123.4 (3) | C6A—N5A—C4A | 123.9 (3) |
C10—N5—C4 | 116.6 (3) | C10A—N5A—C4A | 116.4 (3) |
N1—C6—N5 | 117.8 (4) | N5A—C6A—N1A | 117.0 (3) |
N1—C6—C7 | 123.1 (3) | N5A—C6A—C7A | 119.4 (3) |
N5—C6—C7 | 119.1 (4) | N1A—C6A—C7A | 123.6 (3) |
C8—C7—C6 | 119.9 (4) | C8A—C7A—C6A | 120.3 (3) |
C8—C7—H7 | 120.0 | C8A—C7A—H7A | 119.9 |
C6—C7—H7 | 120.0 | C6A—C7A—H7A | 119.9 |
C7—C8—C9 | 120.1 (5) | C7A—C8A—C9A | 119.7 (4) |
C7—C8—H8 | 120.0 | C7A—C8A—H8A | 120.1 |
C9—C8—H8 | 120.0 | C9A—C8A—H8A | 120.1 |
C10—C9—C8 | 119.9 (4) | C10A—C9A—C8A | 119.1 (4) |
C10—C9—H9 | 120.1 | C10A—C9A—H9A | 120.4 |
C8—C9—H9 | 120.1 | C8A—C9A—H9A | 120.4 |
C9—C10—N5 | 121.0 (4) | C9A—C10A—N5A | 121.8 (3) |
C9—C10—H10 | 119.5 | C9A—C10A—H10A | 119.1 |
N5—C10—H10 | 119.5 | N5A—C10A—H10A | 119.1 |
C13—C11—C12i | 122.1 (3) | C12A—C11A—C13Aii | 121.5 (3) |
C13—C11—N1 | 119.2 (3) | C12A—C11A—N1A | 118.9 (3) |
C12i—C11—N1 | 118.7 (3) | C13Aii—C11A—N1A | 119.6 (3) |
C11i—C12—C13 | 119.1 (4) | C11A—C12A—C13A | 119.5 (3) |
C11i—C12—H12 | 120.5 | C11A—C12A—H12A | 120.3 |
C13—C12—H12 | 120.5 | C13A—C12A—H12A | 120.3 |
C11—C13—C12 | 118.8 (3) | C11Aii—C13A—C12A | 119.0 (3) |
C11—C13—H13 | 120.6 | C11Aii—C13A—H13A | 120.5 |
C12—C13—H13 | 120.6 | C12A—C13A—H13A | 120.5 |
C36—C31—C32 | 117.6 (4) | C36A—C31A—C32A | 114.9 (4) |
C36—C31—C3 | 121.9 (3) | C36A—C31A—C3A | 124.9 (4) |
C32—C31—C3 | 120.5 (4) | C32A—C31A—C3A | 120.1 (3) |
C33—C32—C31 | 121.0 (4) | C33A—C32A—C31A | 122.6 (4) |
C33—C32—H32 | 119.5 | C33A—C32A—H32A | 118.7 |
C31—C32—H32 | 119.5 | C31A—C32A—H32A | 118.7 |
C34—C33—C32 | 120.8 (4) | C32A—C33A—C34A | 118.6 (4) |
C34—C33—H33 | 119.6 | C32A—C33A—H33A | 120.7 |
C32—C33—H33 | 119.6 | C34A—C33A—H33A | 120.7 |
C33—C34—C35 | 118.4 (4) | C35A—C34A—C33A | 119.7 (4) |
C33—C34—H34 | 120.8 | C35A—C34A—H34A | 120.1 |
C35—C34—H34 | 120.8 | C33A—C34A—H34A | 120.1 |
C34—C35—C36 | 120.6 (5) | C34A—C35A—C36A | 122.3 (5) |
C34—C35—H35 | 119.7 | C34A—C35A—H35A | 118.9 |
C36—C35—H35 | 119.7 | C36A—C35A—H35A | 118.9 |
C31—C36—C35 | 121.5 (4) | C35A—C36A—C31A | 121.7 (4) |
C31—C36—H36 | 119.2 | C35A—C36A—H36A | 119.1 |
C35—C36—H36 | 119.2 | C31A—C36A—H36A | 119.1 |
| | | |
C6—N1—C2—O2 | −175.3 (3) | C6A—N1A—C2A—O2A | −179.5 (3) |
C11—N1—C2—O2 | 3.0 (5) | C11A—N1A—C2A—O2A | 2.5 (4) |
C6—N1—C2—C3 | 6.5 (5) | C6A—N1A—C2A—C3A | 1.9 (5) |
C11—N1—C2—C3 | −175.2 (3) | C11A—N1A—C2A—C3A | −176.1 (3) |
O2—C2—C3—C4 | 179.8 (4) | O2A—C2A—C3A—C4A | 173.9 (4) |
N1—C2—C3—C4 | −2.3 (5) | N1A—C2A—C3A—C4A | −7.6 (5) |
O2—C2—C3—C31 | 4.4 (6) | O2A—C2A—C3A—C31A | −6.8 (6) |
N1—C2—C3—C31 | −177.6 (3) | N1A—C2A—C3A—C31A | 171.6 (3) |
C2—C3—C4—O4 | −177.7 (4) | C2A—C3A—C4A—O4A | −174.4 (4) |
C31—C3—C4—O4 | −2.3 (6) | C31A—C3A—C4A—O4A | 6.4 (6) |
C2—C3—C4—N5 | −0.7 (5) | C2A—C3A—C4A—N5A | 6.0 (5) |
C31—C3—C4—N5 | 174.7 (3) | C31A—C3A—C4A—N5A | −173.3 (3) |
O4—C4—N5—C6 | 177.4 (4) | O4A—C4A—N5A—C6A | −178.3 (4) |
C3—C4—N5—C6 | −0.1 (5) | C3A—C4A—N5A—C6A | 1.4 (5) |
O4—C4—N5—C10 | 1.0 (5) | O4A—C4A—N5A—C10A | −1.7 (5) |
C3—C4—N5—C10 | −176.5 (4) | C3A—C4A—N5A—C10A | 177.9 (3) |
C2—N1—C6—N5 | −7.3 (5) | C10A—N5A—C6A—N1A | 176.9 (3) |
C11—N1—C6—N5 | 174.4 (3) | C4A—N5A—C6A—N1A | −6.7 (5) |
C2—N1—C6—C7 | 170.6 (4) | C10A—N5A—C6A—C7A | −2.6 (5) |
C11—N1—C6—C7 | −7.7 (6) | C4A—N5A—C6A—C7A | 173.8 (3) |
C10—N5—C6—N1 | −179.8 (4) | C2A—N1A—C6A—N5A | 5.0 (5) |
C4—N5—C6—N1 | 3.9 (5) | C11A—N1A—C6A—N5A | −177.0 (3) |
C10—N5—C6—C7 | 2.2 (6) | C2A—N1A—C6A—C7A | −175.5 (3) |
C4—N5—C6—C7 | −174.1 (4) | C11A—N1A—C6A—C7A | 2.4 (5) |
N1—C6—C7—C8 | −179.2 (4) | N5A—C6A—C7A—C8A | −0.2 (5) |
N5—C6—C7—C8 | −1.3 (7) | N1A—C6A—C7A—C8A | −179.7 (3) |
C6—C7—C8—C9 | −0.4 (8) | C6A—C7A—C8A—C9A | 1.9 (5) |
C7—C8—C9—C10 | 1.1 (9) | C7A—C8A—C9A—C10A | −0.8 (6) |
C8—C9—C10—N5 | −0.2 (8) | C8A—C9A—C10A—N5A | −2.1 (6) |
C6—N5—C10—C9 | −1.5 (7) | C6A—N5A—C10A—C9A | 3.8 (6) |
C4—N5—C10—C9 | 175.0 (4) | C4A—N5A—C10A—C9A | −172.8 (4) |
C6—N1—C11—C13 | 93.3 (4) | C6A—N1A—C11A—C12A | 103.1 (4) |
C2—N1—C11—C13 | −85.1 (4) | C2A—N1A—C11A—C12A | −78.8 (4) |
C6—N1—C11—C12i | −86.7 (4) | C6A—N1A—C11A—C13Aii | −79.1 (4) |
C2—N1—C11—C12i | 94.9 (4) | C2A—N1A—C11A—C13Aii | 99.0 (4) |
C12i—C11—C13—C12 | 0.1 (7) | C13Aii—C11A—C12A—C13A | −0.3 (6) |
N1—C11—C13—C12 | −179.9 (4) | N1A—C11A—C12A—C13A | 177.5 (3) |
C11i—C12—C13—C11 | −0.1 (7) | C11A—C12A—C13A—C11Aii | 0.3 (6) |
C4—C3—C31—C36 | −134.5 (4) | C4A—C3A—C31A—C36A | −149.8 (4) |
C2—C3—C31—C36 | 41.0 (5) | C2A—C3A—C31A—C36A | 30.9 (6) |
C4—C3—C31—C32 | 43.4 (5) | C4A—C3A—C31A—C32A | 34.4 (5) |
C2—C3—C31—C32 | −141.1 (4) | C2A—C3A—C31A—C32A | −144.9 (4) |
C36—C31—C32—C33 | 0.3 (6) | C36A—C31A—C32A—C33A | 1.1 (6) |
C3—C31—C32—C33 | −177.7 (4) | C3A—C31A—C32A—C33A | 177.3 (4) |
C31—C32—C33—C34 | 2.0 (6) | C31A—C32A—C33A—C34A | 0.7 (7) |
C32—C33—C34—C35 | −2.4 (7) | C32A—C33A—C34A—C35A | −1.8 (8) |
C33—C34—C35—C36 | 0.5 (8) | C33A—C34A—C35A—C36A | 1.2 (8) |
C32—C31—C36—C35 | −2.2 (6) | C34A—C35A—C36A—C31A | 0.7 (8) |
C3—C31—C36—C35 | 175.8 (4) | C32A—C31A—C36A—C35A | −1.8 (6) |
C34—C35—C36—C31 | 1.9 (8) | C3A—C31A—C36A—C35A | −177.7 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Experimental details
| (Ia) | (Ib) | (Ic) |
Crystal data |
Chemical formula | C34H22N4O4·2C5H9NO·C3H8O | C34H22N4O4·3C5H9NO | C34H22N4O4·0.5C5H9NO·C4H10O |
Mr | 808.91 | 847.95 | 674.24 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 8.7737 (10), 10.4982 (11), 11.7877 (12) | 8.8137 (8), 10.1565 (9), 12.7300 (11) | 5.7853 (6), 15.2219 (17), 19.198 (2) |
α, β, γ (°) | 98.463 (8), 101.314 (8), 104.750 (8) | 99.212 (7), 99.567 (7), 105.102 (7) | 75.321 (9), 87.393 (8), 84.740 (9) |
V (Å3) | 1007.07 (19) | 1059.84 (16) | 1628.1 (3) |
Z | 1 | 1 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.53 × 0.32 × 0.26 | 0.24 × 0.23 × 0.13 | 0.21 × 0.09 × 0.09 |
|
Data collection |
Diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer | Stoe IPDS II two-circle diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19547, 4103, 3305 | 15396, 4290, 3513 | 23578, 6641, 3364 |
Rint | 0.053 | 0.035 | 0.088 |
(sin θ/λ)max (Å−1) | 0.627 | 0.625 | 0.626 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.181, 1.06 | 0.080, 0.223, 1.20 | 0.081, 0.218, 0.95 |
No. of reflections | 4103 | 4290 | 6641 |
No. of parameters | 290 | 298 | 379 |
No. of restraints | 2 | 2 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.33 | 0.90, −1.05 | 0.64, −0.28 |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
O52—H52···O42 | 0.84 | 2.02 | 2.691 (5) | 136.5 |
Selected bond lengths in solvates (Ia)–(Ic) and CSD refcode XAKZEO, (II).
For atom numbering see Fig. 8. topBond | (Ia) | (Ib) | (Ic)* | (Ic)* | XAKZEO, (II) |
N1—C2 | 1.432 (2) | 1.433 (2) | 1.424 (5) | 1.446 (5) | 1.3961 (13) |
C2—O2 | 1.230 (2) | 1.229 (3) | 1.232 (4) | 1.232 (4) | 1.2464 (12) |
C2—C3 | 1.436 (2) | 1.440 (3) | 1.432 (5) | 1.426 (5) | 1.4273 (14) |
C3—C4 | 1.403 (2) | 1.405 (3) | 1.399 (5) | 1.409 (5) | 1.4115 (14) |
C4—O4 | 1.230 (2) | 1.234 (2) | 1.232 (4) | 1.238 (4) | 1.2225 (13) |
C4—N5 | 1.494 (2) | 1.500 (2) | 1.491 (5) | 1.499 (5) | 1.4903 (13) |
N5—C6 | 1.358 (2) | 1.363 (2) | 1.372 (5) | 1.370 (4) | 1.3575 (13) |
C6—N1 | 1.357 (2) | 1.366 (2) | 1.365 (5) | 1.373 (5) | 1.3376 (13) |
Note: (*) two independent molecules. |
Mesoionic compounds are `dipolar five- (possibly six-) membered heterocyclic compounds in which both the negative and the positive charge are delocalized, for which a totally covalent structure cannot be written, and which cannot be represented satisfactorily by any one polar structure' (IUPAC, 1995). These substances represent a small class of compounds. Pyridopyrimidinium olates based on 2,4-dioxopyrimidine are mesoionic (Friedrichsen et al., 1982; Schober & Kappe, 1988; Kappe, 1998; Fiksdahl et al., 2000). Moreover, some of them exhibit yellow solid-state fluorescence. Fluorescence in the solid state is a rather unusual property since most compounds that fluoresce in solution lose this property when they are crystallized. Recently, the phenomenon of solid-state fluorescence in an organic pigment was explained by time-dependent density functional theory (TD-DFT) calculations (Dreuw et al., 2005).
2-Oxo-3-phenyl-1,2-dihydro-pyrido[1,2-a]pyrimidin-5-ium-4-olate, (II), being a derivative of Chichibabin's malonyl α-aminopyridine (Reference?), is a mesoionic yellow compound [Plüg et al., 2000; Cambridge Structural Database (CSD; Allen, 2002) refcode XAKZEO]. It shows a high solubility in most organic solvents and it is therefore not feasible to use it as an industrially produced pigment. To enhance the insolubility, the title compound, (I), was synthesized. This compound actually shows a lower solubility and a strong yellow fluorescence (Metz & Plüg, 2005). Compound (I) is not industrially produced, either.
In order to search for different crystallographic phases, hydrates or solvates of (I), a polymorph screening was launched. Different crystallization methods used included recrystallization from various solvents and solvent mixtures by heating and subsequent slow cooling, overlaying a solution of the compound with an anti-solvent (Fock, 1888), and diffusion of an anti-solvent into a solution of the compound via the gas phase. The solvents used included the most common organic solvents, e.g. dimethylsulfoxide, N-methylpyrrolidone (NMP), N,N'-dimethylformamide, different ethers and esters, propan-2-ol (iPrOH), butan-1-ol (1-BuOH) and other alcohols, and water.
In several experiments, single crystals could be grown, and the crystal structures could be determined for three solvates, namely (I).2NMP.iPrOH, (Ia), (I).3NMP, (Ib), and a solvate with 1-BuOH and NMP, (Ic).
Compounds (Ia) and (Ib) crystallize in space group P1 with Z = 1 (Figs. 1 and 2), whereas (Ic) crystallizes in space group P1 with Z = 2. In (Ia) and (Ib) the pigment molecules (I) are situated on crystallographic inversion centres. In (Ic), there are two symmetry-independent pigment molecules, both on inversion centres (Fig. 3). The refinement of the pigment molecules of (Ic) could be performed without any difficulties, but the solvent molecules are heavily disordered. In the difference Fourier synthesis there are six peaks with electron densities of 1.0 to 2.3 e Å-3. No reasonable model could be found for a successful refinement with either NMP or butan-1-ol as solvent. A comparison with the crystal structures of (Ia) and (Ib) showed that the solvent molecules should occupy a volume of 374 Å3 per unit cell. According to Hofmann's volume increments (Hofmann, 2002), an NMP molecule has a volume of 147 Å3 and butan-1-ol one of 117 Å3. Hence, the unit cell may contain e.g. two molecules of butan-1-ol and one molecule of NMP (sum 381 Å3), or two molecules of NMP and a partial molecule of butan-1-ol. In the former case, the crystal would have a composition of 2C34H22N4O4.C5H9NO.2C4H10O. Lattice energy minimizations were performed with the aim of obtaining possible positions for the solvent molecules but the results were inconclusive. Thus, in (Ic) the contribution of the solvent molecules to the scattering was suppressed using the SQUEEZE procedure in PLATON (van der Sluis & Spek, 1990; Spek, 2009; see Experimental). By this means the void is calculated to contain about 48 electrons, which is much less than assumed by the formula 2C34H22N4O4.C5H9NO.2C4H10O (138 electrons). This indicates that the solvent positions might be only partially occupied.
The structures of (Ia) and (Ib) are pseudo-isomorphic. The lattice parameters are similar and the pigment molecules and two NMP molecules have similar arrangements in both structures, but the disordered propan-2-ol molecule in (Ia) is replaced by a disordered NMP molecule in (Ib). Correspondingly, the unit-cell volume of (Ia) is 52 Å3 smaller than that of (Ib). In all three structures, the pigment molecules are essentially planar except for the linking phenylene moieties, which are rotated out of the pyrido[1,2-a]pyrimidin-1-ium plane by 82.17 (6)° in (Ia), 79.51 (8)° in (Ib), and 88.16 (12) and 79.07 (10)° for the two independent molecules in (Ic). Thus, the phenylene moieties are oriented nearly orthogonal to the rest of the molecule, to avoid steric hindrance between the phenylene H atom and the atoms of the heterocyclic system. The terminal phenyl ring is also rotated out of the pyrido[1,2-a]pyrimidin-1-ium plane. The dihedral angles are 23.24 (7)° in (Ia), 28.76 (10)° in (Ib), and 44.79 (15) and 35.68 (15)° in (Ic). Apparently this dihedral angle can be easily influenced by the molecular packing. In (Ia) only the propan-2-ol is disordered (see Fig. 4), whereas in (Ib) all NMP molecules are disordered (Fig. 2). In one NMP molecule, the N—CH3 group (atoms N41 and C41) is disordered with a CH2 group (atom C43), whereas the C═O group maintains its position. The other NMP molecule is located on a crystallographic inversion centre between the N atom and the carbonyl C atom, which leads to a disorder of all atoms. In (Ia), the propan-2-ol molecule forms a hydrogen bond to an NMP molecule (Fig. 4, Table 1). Compounds (Ia) and (Ib) display layer structures in which the pigment and solvent molecules are arranged in alternating layers (Figs. 5 and 6). In compound (Ic), the molecules form columns in the [100] direction; the solvent molecules are embedded in channels situated between the columns (Fig. 7).
In all structures, the out-of-plane rotation of the central phenylene ring results in a cross-shaped molecular conformation which hinders efficient molecular packing (as for several spiro compounds). This may be the reason that the solvent molecules are incorporated into the crystals.
The bond lengths in the mesoionic ring system (see Table 2 and Fig. 8) are in agreement with the values found for (II). The bond lengths show that the positive charge is delocalized over the N1/C6/N5 fragment and the adjacent pyridine ring, whereas the negative charge is distributed over the O2/C2–C4/O4 fragment. Between these two fragments the conjugation is weak, as can be seen from the long N1—C2 and C4—N5 bond lengths.
Solvent-free single crystals of (I) could not be obtained. All crystals of (I) collapse when they are dried at room temperature, resulting in powders of such low crystallinity that crystal structure solution from the powder data, which nowadays can be done routinely (David et al., 1998; Nowell et al., 2002; van de Streek et al., 2009), failed. None of the powder patterns could be indexed in a reasonable way [DIVCOL06 (Boultif & Louër, 2004); MCMAILLE (Version 4.0; Bergmann et al., 2004)]. The powder patterns of (I) were unrelated to the simulated powder patterns of (Ia), (Ib) or (Ic). Therefore, the crystal structure of solvent-free compound (I) could not be determined.