The structures of 5-nitro-3-thiomorpholino-1
H-indazole, C
11H
12N
4O
2S, (II
a), and 3-(4-methylpiperazino)-5-nitro-1
H-indazole–methanol–water (2/1/1), 2C
12H
15N
5O
2·CH
3OH·H
2O, (III
a), are described. In the crystal lattice of (II
a), the molecules are linked into dimers by N—H
N hydrogen bonds. The asymmetric unit of (III
a) contains two independent molecules of the indazole moiety, one molecule of methanol and one of water. The three components of (III
a) are linked by hydrogen bonds to form double chains running along the
x axis. π-Stacking involving the indazole moieties occurs in both compounds.
Supporting information
CCDC references: 174833; 174834
Verbindungen (IIa) und (IIIa) wurden bei der Einwirkung von Thiomorpholin bzw.
N-Methylpiperazin auf 2,5-Dinitroindazol synthetisiert. Die
Einkristalle von (IIa) und (IIIa) wurden aus Methanol erhalten. Die Verbindung
(IIIa) kristallisiert unter Einschlu\&s von Lösungsmitteln. Query.
Alle H-Atome wurden in (IIa) und (IIIa) aus Differenz-Fourier-Synthesen
ermittelt. Die N1—H Atome in (IIa) und (IIIa) und diese von Lösungsmitteln
in (IIIa) wurden frei verfeinert. Die übrigen H-Atome wurden mit Hilfe des
Reitermodells verfeinert; C—H = 0.93–0.97 Å query und U(H) =
1,2Uäq(C). Die Rotation der Methylgruppen in (IIIa) um ihre lokale
dreizählige Achse wurde als zusätzlicher Parameter verfeinert. Please
provide C—H data in CIF format for (IIIa).
For both compounds, data collection: KM-4 Software (Kuma Diffraction, 1991); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: WinGX (Farrugia, 1999) und SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: WinGX und SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX und ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX und SHELXL97.
(IIa) 5-Nitro-3-thiomorpholino-1
H-indazole
top
Crystal data top
C11H12N4O2S | F(000) = 552 |
Mr = 264.31 | Dx = 1.488 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
a = 4.3897 (8) Å | Cell parameters from 37 reflections |
b = 10.4102 (10) Å | θ = 14.7–25.1° |
c = 25.829 (3) Å | µ = 2.46 mm−1 |
β = 91.166 (12)° | T = 293 K |
V = 1180.1 (3) Å3 | Needle, yellow |
Z = 4 | 0.43 × 0.18 × 0.08 mm |
Data collection top
Kuma KM-4 diffractometer | 1769 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 70.1°, θmin = 3.4° |
ω/2θ scans | h = 0→5 |
Absorption correction: ψ-scan (North et al., 1968) | k = 0→12 |
Tmin = 0.528, Tmax = 0.821 | l = −31→31 |
2499 measured reflections | 2 standard reflections every 100 reflections |
2192 independent reflections | intensity decay: 3.6% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0725P)2 + 0.5353P] where P = (Fo2 + 2Fc2)/3 |
2192 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C11H12N4O2S | V = 1180.1 (3) Å3 |
Mr = 264.31 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 4.3897 (8) Å | µ = 2.46 mm−1 |
b = 10.4102 (10) Å | T = 293 K |
c = 25.829 (3) Å | 0.43 × 0.18 × 0.08 mm |
β = 91.166 (12)° | |
Data collection top
Kuma KM-4 diffractometer | 1769 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.034 |
Tmin = 0.528, Tmax = 0.821 | 2 standard reflections every 100 reflections |
2499 measured reflections | intensity decay: 3.6% |
2192 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.29 e Å−3 |
2192 reflections | Δρmin = −0.23 e Å−3 |
167 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 | 0.2350 (5) | 0.39993 (19) | 0.01773 (8) | 0.0452 (5) | |
H1A | 0.144 (7) | 0.416 (3) | −0.0115 (11) | 0.060 (8)* | |
N2 | 0.1906 (4) | 0.49003 (18) | 0.05557 (7) | 0.0421 (4) | |
C3 | 0.3505 (5) | 0.4511 (2) | 0.09667 (8) | 0.0362 (5) | |
C4 | 0.6950 (5) | 0.2481 (2) | 0.11285 (8) | 0.0379 (5) | |
H4 | 0.7552 | 0.2635 | 0.1470 | 0.045* | |
C5 | 0.7940 (5) | 0.1419 (2) | 0.08615 (8) | 0.0409 (5) | |
C6 | 0.7094 (5) | 0.1156 (2) | 0.03465 (9) | 0.0452 (5) | |
H6 | 0.7835 | 0.0423 | 0.0186 | 0.054* | |
C7 | 0.5206 (6) | 0.1960 (2) | 0.00787 (8) | 0.0444 (5) | |
H7 | 0.4635 | 0.1797 | −0.0264 | 0.053* | |
C8 | 0.4159 (5) | 0.3043 (2) | 0.03411 (8) | 0.0384 (5) | |
C9 | 0.4997 (5) | 0.33121 (19) | 0.08587 (8) | 0.0348 (4) | |
N10 | 0.3739 (4) | 0.52494 (17) | 0.14136 (7) | 0.0381 (4) | |
C11 | 0.2603 (6) | 0.4597 (2) | 0.18796 (8) | 0.0438 (5) | |
H11A | 0.3349 | 0.3720 | 0.1887 | 0.053* | |
H11B | 0.0395 | 0.4567 | 0.1861 | 0.053* | |
C12 | 0.3607 (6) | 0.5271 (2) | 0.23732 (9) | 0.0508 (6) | |
H12A | 0.5815 | 0.5293 | 0.2393 | 0.061* | |
H12B | 0.2897 | 0.4788 | 0.2668 | 0.061* | |
S13 | 0.21585 (15) | 0.68925 (6) | 0.24065 (2) | 0.0528 (2) | |
C14 | 0.3614 (6) | 0.7410 (2) | 0.17972 (10) | 0.0523 (6) | |
H14A | 0.2948 | 0.8284 | 0.1730 | 0.063* | |
H14B | 0.5822 | 0.7411 | 0.1817 | 0.063* | |
C15 | 0.2576 (6) | 0.6564 (2) | 0.13526 (9) | 0.0481 (6) | |
H15A | 0.0367 | 0.6546 | 0.1336 | 0.058* | |
H15B | 0.3291 | 0.6922 | 0.1030 | 0.058* | |
N16 | 0.9967 (5) | 0.0516 (2) | 0.11267 (8) | 0.0544 (5) | |
O17 | 1.0914 (5) | 0.0766 (2) | 0.15609 (8) | 0.0709 (6) | |
O18 | 1.0684 (7) | −0.0459 (2) | 0.08947 (9) | 0.0947 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0451 (12) | 0.0511 (11) | 0.0391 (10) | 0.0083 (9) | −0.0064 (8) | −0.0038 (8) |
N2 | 0.0374 (11) | 0.0473 (10) | 0.0415 (10) | 0.0078 (8) | −0.0026 (8) | −0.0028 (8) |
C3 | 0.0280 (11) | 0.0407 (11) | 0.0399 (10) | 0.0028 (8) | 0.0017 (8) | −0.0005 (8) |
C4 | 0.0318 (12) | 0.0422 (11) | 0.0397 (10) | 0.0011 (8) | 0.0014 (8) | −0.0020 (8) |
C5 | 0.0343 (12) | 0.0400 (11) | 0.0485 (12) | 0.0048 (9) | 0.0045 (9) | 0.0008 (9) |
C6 | 0.0428 (14) | 0.0416 (12) | 0.0515 (13) | 0.0044 (9) | 0.0092 (10) | −0.0077 (9) |
C7 | 0.0452 (14) | 0.0485 (12) | 0.0395 (11) | 0.0001 (10) | 0.0018 (9) | −0.0079 (9) |
C8 | 0.0306 (12) | 0.0435 (11) | 0.0410 (11) | −0.0010 (8) | 0.0003 (8) | −0.0016 (8) |
C9 | 0.0264 (10) | 0.0388 (10) | 0.0394 (10) | 0.0007 (8) | 0.0036 (8) | −0.0032 (8) |
N10 | 0.0370 (10) | 0.0384 (9) | 0.0391 (9) | 0.0059 (7) | 0.0014 (7) | −0.0021 (7) |
C11 | 0.0454 (14) | 0.0442 (12) | 0.0419 (11) | 0.0028 (10) | 0.0060 (9) | 0.0000 (9) |
C12 | 0.0577 (17) | 0.0538 (13) | 0.0410 (12) | 0.0110 (11) | 0.0007 (10) | −0.0011 (10) |
S13 | 0.0537 (4) | 0.0569 (4) | 0.0479 (4) | 0.0097 (3) | 0.0017 (3) | −0.0127 (3) |
C14 | 0.0563 (16) | 0.0439 (12) | 0.0566 (14) | 0.0075 (10) | 0.0011 (11) | −0.0063 (10) |
C15 | 0.0574 (16) | 0.0432 (12) | 0.0437 (12) | 0.0128 (10) | −0.0005 (10) | −0.0009 (9) |
N16 | 0.0559 (14) | 0.0524 (12) | 0.0552 (12) | 0.0179 (10) | 0.0063 (10) | 0.0015 (9) |
O17 | 0.0765 (15) | 0.0763 (13) | 0.0594 (12) | 0.0331 (11) | −0.0106 (10) | −0.0007 (10) |
O18 | 0.134 (2) | 0.0702 (14) | 0.0790 (14) | 0.0584 (15) | −0.0100 (14) | −0.0143 (11) |
Geometric parameters (Å, º) top
N1—C8 | 1.337 (3) | N10—C15 | 1.469 (3) |
N1—N2 | 1.371 (3) | N10—C11 | 1.477 (3) |
N1—H1A | 0.86 (3) | C11—C12 | 1.513 (3) |
N2—C3 | 1.324 (3) | C11—H11A | 0.9700 |
C3—N10 | 1.389 (3) | C11—H11B | 0.9700 |
C3—C9 | 1.440 (3) | C12—S13 | 1.806 (3) |
C4—C5 | 1.378 (3) | C12—H12A | 0.9700 |
C4—C9 | 1.395 (3) | C12—H12B | 0.9700 |
C4—H4 | 0.9300 | S13—C14 | 1.793 (3) |
C5—C6 | 1.400 (3) | C14—C15 | 1.510 (3) |
C5—N16 | 1.456 (3) | C14—H14A | 0.9700 |
C6—C7 | 1.357 (3) | C14—H14B | 0.9700 |
C6—H6 | 0.9300 | C15—H15A | 0.9700 |
C7—C8 | 1.398 (3) | C15—H15B | 0.9700 |
C7—H7 | 0.9300 | N16—O17 | 1.216 (3) |
C8—C9 | 1.408 (3) | N16—O18 | 1.223 (3) |
| | | |
C8—N1—N2 | 112.08 (18) | N10—C11—C12 | 112.06 (19) |
C8—N1—H1A | 133 (2) | N10—C11—H11A | 109.2 |
N2—N1—H1A | 115.1 (19) | C12—C11—H11A | 109.2 |
C3—N2—N1 | 106.35 (17) | N10—C11—H11B | 109.2 |
N2—C3—N10 | 121.76 (18) | C12—C11—H11B | 109.2 |
N2—C3—C9 | 110.22 (18) | H11A—C11—H11B | 107.9 |
N10—C3—C9 | 127.91 (19) | C11—C12—S13 | 112.15 (17) |
C5—C4—C9 | 116.40 (19) | C11—C12—H12A | 109.2 |
C5—C4—H4 | 121.8 | S13—C12—H12A | 109.2 |
C9—C4—H4 | 121.8 | C11—C12—H12B | 109.2 |
C4—C5—C6 | 123.5 (2) | S13—C12—H12B | 109.2 |
C4—C5—N16 | 118.6 (2) | H12A—C12—H12B | 107.9 |
C6—C5—N16 | 117.9 (2) | C14—S13—C12 | 96.15 (11) |
C7—C6—C5 | 120.7 (2) | C15—C14—S13 | 112.63 (19) |
C7—C6—H6 | 119.6 | C15—C14—H14A | 109.1 |
C5—C6—H6 | 119.6 | S13—C14—H14A | 109.1 |
C6—C7—C8 | 117.0 (2) | C15—C14—H14B | 109.1 |
C6—C7—H7 | 121.5 | S13—C14—H14B | 109.1 |
C8—C7—H7 | 121.5 | H14A—C14—H14B | 107.8 |
N1—C8—C7 | 130.3 (2) | N10—C15—C14 | 111.29 (19) |
N1—C8—C9 | 107.12 (19) | N10—C15—H15A | 109.4 |
C7—C8—C9 | 122.6 (2) | C14—C15—H15A | 109.4 |
C4—C9—C8 | 119.81 (19) | N10—C15—H15B | 109.4 |
C4—C9—C3 | 135.95 (19) | C14—C15—H15B | 109.4 |
C8—C9—C3 | 104.21 (18) | H15A—C15—H15B | 108.0 |
C3—N10—C15 | 114.00 (17) | O17—N16—O18 | 122.9 (2) |
C3—N10—C11 | 113.72 (17) | O17—N16—C5 | 119.3 (2) |
C15—N10—C11 | 113.20 (17) | O18—N16—C5 | 117.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 (3) | 2.09 (3) | 2.871 (3) | 151 (3) |
Symmetry code: (i) −x, −y+1, −z. |
(IIIa) 3-(4-methylpiperazino)-5-nitro-1
H-indazole methanol hemisolvate water
hemisolvate
top
Crystal data top
C12H15N5O2·0.5CH4O·0.5H2O | Z = 4 |
Mr = 286.32 | F(000) = 608 |
Triclinic, P1 | Dx = 1.348 Mg m−3 |
a = 7.3742 (11) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 12.1765 (13) Å | Cell parameters from 25 reflections |
c = 16.6356 (16) Å | θ = 14.6–29.8° |
α = 78.650 (9)° | µ = 0.83 mm−1 |
β = 84.958 (10)° | T = 293 K |
γ = 74.596 (11)° | Prism, yellow |
V = 1410.9 (3) Å3 | 0.50 × 0.20 × 0.15 mm |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 75.0°, θmin = 2.7° |
Graphite monochromator | h = 0→9 |
ω/2θ scans | k = −14→15 |
5919 measured reflections | l = −19→19 |
5457 independent reflections | 2 standard reflections every 100 reflections |
4475 reflections with I > 2σ(I) | intensity decay: 2.8% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.124 | w = 1/[σ2(Fo2) + (0.0739P)2 + 0.2199P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
5457 reflections | Δρmax = 0.29 e Å−3 |
394 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0044 (5) |
Crystal data top
C12H15N5O2·0.5CH4O·0.5H2O | γ = 74.596 (11)° |
Mr = 286.32 | V = 1410.9 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.3742 (11) Å | Cu Kα radiation |
b = 12.1765 (13) Å | µ = 0.83 mm−1 |
c = 16.6356 (16) Å | T = 293 K |
α = 78.650 (9)° | 0.50 × 0.20 × 0.15 mm |
β = 84.958 (10)° | |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.019 |
5919 measured reflections | 2 standard reflections every 100 reflections |
5457 independent reflections | intensity decay: 2.8% |
4475 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.29 e Å−3 |
5457 reflections | Δρmin = −0.22 e Å−3 |
394 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 | |
N1A | 0.5873 (2) | 0.17644 (12) | 0.50232 (8) | 0.0531 (3) | |
H1A | 0.513 (3) | 0.2400 (19) | 0.5258 (13) | 0.072 (6)* | |
N2A | 0.59407 (19) | 0.18026 (11) | 0.41905 (8) | 0.0498 (3) | |
C3A | 0.6985 (2) | 0.07817 (12) | 0.40660 (8) | 0.0415 (3) | |
C4A | 0.8610 (2) | −0.11015 (12) | 0.51045 (9) | 0.0440 (3) | |
H4A | 0.9134 | −0.1592 | 0.4735 | 0.053* | |
C5A | 0.8842 (2) | −0.14677 (13) | 0.59343 (9) | 0.0488 (3) | |
C6A | 0.8116 (2) | −0.07567 (16) | 0.65169 (9) | 0.0534 (4) | |
H6A | 0.8334 | −0.1042 | 0.7070 | 0.064* | |
C7A | 0.7092 (2) | 0.03498 (15) | 0.62709 (9) | 0.0525 (4) | |
H7A | 0.6602 | 0.0835 | 0.6647 | 0.063* | |
C8A | 0.6801 (2) | 0.07336 (13) | 0.54268 (9) | 0.0453 (3) | |
C9A | 0.75645 (19) | 0.00291 (12) | 0.48361 (8) | 0.0405 (3) | |
N10A | 0.74905 (18) | 0.05867 (10) | 0.32749 (7) | 0.0443 (3) | |
C11A | 0.7865 (3) | −0.05855 (12) | 0.31170 (9) | 0.0542 (4) | |
H11A | 0.6688 | −0.0804 | 0.3133 | 0.065* | |
H11B | 0.8644 | −0.1117 | 0.3541 | 0.065* | |
C12A | 0.8854 (2) | −0.06742 (14) | 0.22882 (10) | 0.0542 (4) | |
H12A | 1.0090 | −0.0537 | 0.2292 | 0.065* | |
H12B | 0.9021 | −0.1450 | 0.2179 | 0.065* | |
N13A | 0.77749 (19) | 0.01646 (11) | 0.16416 (7) | 0.0478 (3) | |
C14A | 0.7565 (2) | 0.13285 (13) | 0.18035 (9) | 0.0519 (4) | |
H14A | 0.6873 | 0.1894 | 0.1368 | 0.062* | |
H14B | 0.8798 | 0.1469 | 0.1810 | 0.062* | |
C15A | 0.6532 (2) | 0.14686 (12) | 0.26165 (9) | 0.0496 (4) | |
H15A | 0.6466 | 0.2231 | 0.2727 | 0.060* | |
H15B | 0.5256 | 0.1404 | 0.2592 | 0.060* | |
C16A | 0.8717 (3) | 0.00421 (18) | 0.08408 (10) | 0.0694 (5) | |
H16A | 0.8009 | 0.0612 | 0.0422 | 0.083* | |
H16B | 0.8801 | −0.0718 | 0.0737 | 0.083* | |
H16C | 0.9960 | 0.0152 | 0.0838 | 0.083* | |
N17A | 0.9904 (2) | −0.26529 (13) | 0.62187 (9) | 0.0620 (4) | |
O18A | 1.0605 (3) | −0.32644 (12) | 0.57141 (9) | 0.0860 (5) | |
O19A | 1.0069 (2) | −0.29991 (14) | 0.69602 (8) | 0.0895 (5) | |
N1B | 0.37863 (19) | 0.20137 (11) | 1.01678 (8) | 0.0486 (3) | |
H1B | 0.388 (3) | 0.1300 (18) | 1.0453 (12) | 0.060 (5)* | |
N2B | 0.46019 (18) | 0.21700 (10) | 0.93936 (7) | 0.0449 (3) | |
C3B | 0.43370 (19) | 0.33004 (11) | 0.91500 (8) | 0.0390 (3) | |
C4B | 0.26769 (19) | 0.50621 (11) | 0.98791 (8) | 0.0397 (3) | |
H4B | 0.2878 | 0.5666 | 0.9472 | 0.048* | |
C5B | 0.1737 (2) | 0.52695 (12) | 1.06061 (8) | 0.0418 (3) | |
C6B | 0.1428 (2) | 0.43887 (14) | 1.12457 (9) | 0.0479 (3) | |
H6B | 0.0794 | 0.4576 | 1.1728 | 0.057* | |
C7B | 0.2062 (2) | 0.32564 (13) | 1.11570 (9) | 0.0494 (3) | |
H7B | 0.1873 | 0.2660 | 1.1573 | 0.059* | |
C8B | 0.3010 (2) | 0.30239 (12) | 1.04151 (8) | 0.0424 (3) | |
C9B | 0.33190 (19) | 0.39118 (11) | 0.97748 (8) | 0.0384 (3) | |
N10B | 0.50691 (17) | 0.37635 (9) | 0.84001 (7) | 0.0416 (3) | |
C11B | 0.3736 (2) | 0.47104 (13) | 0.78940 (9) | 0.0492 (4) | |
H11C | 0.3103 | 0.5288 | 0.8222 | 0.059* | |
H11D | 0.2790 | 0.4409 | 0.7704 | 0.059* | |
C12B | 0.4756 (2) | 0.52626 (12) | 0.71677 (9) | 0.0511 (4) | |
H12C | 0.3859 | 0.5874 | 0.6834 | 0.061* | |
H12D | 0.5647 | 0.5606 | 0.7358 | 0.061* | |
N13B | 0.57576 (18) | 0.44036 (10) | 0.66718 (7) | 0.0459 (3) | |
C14B | 0.7102 (2) | 0.34840 (13) | 0.71804 (9) | 0.0493 (3) | |
H14C | 0.8023 | 0.3808 | 0.7367 | 0.059* | |
H14D | 0.7765 | 0.2910 | 0.6855 | 0.059* | |
C15B | 0.6121 (2) | 0.29096 (12) | 0.79118 (9) | 0.0462 (3) | |
H15C | 0.5266 | 0.2536 | 0.7727 | 0.055* | |
H15D | 0.7044 | 0.2320 | 0.8248 | 0.055* | |
C16B | 0.6694 (3) | 0.49476 (17) | 0.59518 (11) | 0.0664 (5) | |
H16D | 0.5770 | 0.5520 | 0.5617 | 0.080* | |
H16E | 0.7364 | 0.4369 | 0.5641 | 0.080* | |
H16F | 0.7563 | 0.5311 | 0.6125 | 0.080* | |
N17B | 0.09981 (18) | 0.64694 (11) | 1.07158 (8) | 0.0491 (3) | |
O18B | 0.1380 (2) | 0.72332 (10) | 1.01893 (8) | 0.0708 (4) | |
O19B | 0.00189 (17) | 0.66605 (11) | 1.13346 (8) | 0.0639 (3) | |
O20 | 0.5799 (2) | 0.00435 (10) | 0.87007 (8) | 0.0599 (3) | |
H20A | 0.547 (3) | 0.069 (2) | 0.8893 (15) | 0.090 (7)* | |
H20B | 0.475 (4) | 0.006 (2) | 0.8518 (16) | 0.087 (8)* | |
O21 | 0.37362 (18) | 0.32482 (11) | 0.60064 (8) | 0.0641 (3) | |
H21A | 0.423 (3) | 0.370 (2) | 0.6273 (15) | 0.089 (7)* | |
C22 | 0.1798 (3) | 0.37059 (17) | 0.60628 (14) | 0.0696 (5) | |
H22A | 0.1332 | 0.3447 | 0.6605 | 0.083* | |
H22B | 0.1204 | 0.3450 | 0.5669 | 0.083* | |
H22C | 0.1519 | 0.4536 | 0.5954 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1A | 0.0621 (8) | 0.0497 (7) | 0.0462 (7) | −0.0061 (6) | 0.0040 (6) | −0.0194 (6) |
N2A | 0.0594 (8) | 0.0433 (6) | 0.0442 (6) | −0.0054 (5) | 0.0021 (5) | −0.0140 (5) |
C3A | 0.0458 (7) | 0.0393 (6) | 0.0399 (7) | −0.0104 (5) | 0.0020 (5) | −0.0106 (5) |
C4A | 0.0468 (8) | 0.0435 (7) | 0.0420 (7) | −0.0134 (6) | 0.0016 (6) | −0.0072 (5) |
C5A | 0.0498 (8) | 0.0513 (8) | 0.0450 (8) | −0.0176 (7) | −0.0029 (6) | −0.0012 (6) |
C6A | 0.0543 (9) | 0.0718 (10) | 0.0374 (7) | −0.0253 (8) | −0.0011 (6) | −0.0053 (7) |
C7A | 0.0552 (9) | 0.0673 (10) | 0.0407 (7) | −0.0207 (8) | 0.0047 (6) | −0.0186 (7) |
C8A | 0.0449 (8) | 0.0508 (8) | 0.0433 (7) | −0.0148 (6) | 0.0038 (6) | −0.0147 (6) |
C9A | 0.0420 (7) | 0.0437 (7) | 0.0378 (7) | −0.0142 (6) | 0.0031 (5) | −0.0099 (5) |
N10A | 0.0564 (7) | 0.0365 (6) | 0.0368 (6) | −0.0058 (5) | 0.0009 (5) | −0.0085 (4) |
C11A | 0.0802 (11) | 0.0366 (7) | 0.0396 (7) | −0.0053 (7) | 0.0035 (7) | −0.0080 (6) |
C12A | 0.0637 (10) | 0.0474 (8) | 0.0450 (8) | 0.0002 (7) | 0.0020 (7) | −0.0145 (6) |
N13A | 0.0595 (8) | 0.0458 (6) | 0.0364 (6) | −0.0101 (5) | 0.0039 (5) | −0.0103 (5) |
C14A | 0.0690 (10) | 0.0446 (8) | 0.0419 (7) | −0.0174 (7) | 0.0008 (7) | −0.0044 (6) |
C15A | 0.0645 (9) | 0.0367 (7) | 0.0424 (7) | −0.0042 (6) | −0.0017 (6) | −0.0072 (6) |
C16A | 0.0866 (13) | 0.0729 (11) | 0.0430 (9) | −0.0119 (10) | 0.0135 (8) | −0.0156 (8) |
N17A | 0.0694 (9) | 0.0578 (8) | 0.0531 (8) | −0.0164 (7) | −0.0073 (7) | 0.0058 (6) |
O18A | 0.1203 (13) | 0.0528 (7) | 0.0712 (9) | 0.0005 (7) | −0.0162 (8) | −0.0044 (6) |
O19A | 0.1045 (12) | 0.0877 (10) | 0.0535 (8) | −0.0077 (8) | −0.0066 (7) | 0.0195 (7) |
N1B | 0.0625 (8) | 0.0353 (6) | 0.0440 (6) | −0.0110 (5) | 0.0016 (5) | −0.0010 (5) |
N2B | 0.0527 (7) | 0.0366 (6) | 0.0432 (6) | −0.0089 (5) | −0.0010 (5) | −0.0057 (5) |
C3B | 0.0418 (7) | 0.0357 (6) | 0.0383 (6) | −0.0081 (5) | −0.0023 (5) | −0.0060 (5) |
C4B | 0.0419 (7) | 0.0372 (6) | 0.0401 (7) | −0.0111 (5) | −0.0019 (5) | −0.0059 (5) |
C5B | 0.0418 (7) | 0.0421 (7) | 0.0428 (7) | −0.0091 (6) | −0.0039 (5) | −0.0120 (5) |
C6B | 0.0493 (8) | 0.0553 (8) | 0.0381 (7) | −0.0118 (7) | 0.0029 (6) | −0.0098 (6) |
C7B | 0.0579 (9) | 0.0487 (8) | 0.0388 (7) | −0.0155 (7) | 0.0017 (6) | −0.0003 (6) |
C8B | 0.0463 (7) | 0.0388 (7) | 0.0405 (7) | −0.0106 (6) | −0.0032 (5) | −0.0032 (5) |
C9B | 0.0400 (7) | 0.0379 (6) | 0.0368 (6) | −0.0098 (5) | −0.0029 (5) | −0.0053 (5) |
N10B | 0.0464 (6) | 0.0349 (5) | 0.0382 (6) | −0.0034 (5) | 0.0022 (5) | −0.0053 (4) |
C11B | 0.0537 (8) | 0.0434 (7) | 0.0398 (7) | 0.0031 (6) | 0.0016 (6) | −0.0050 (6) |
C12B | 0.0635 (9) | 0.0393 (7) | 0.0442 (8) | −0.0060 (6) | 0.0005 (6) | −0.0034 (6) |
N13B | 0.0484 (7) | 0.0469 (6) | 0.0382 (6) | −0.0088 (5) | 0.0028 (5) | −0.0046 (5) |
C14B | 0.0449 (8) | 0.0494 (8) | 0.0479 (8) | −0.0044 (6) | 0.0039 (6) | −0.0080 (6) |
C15B | 0.0502 (8) | 0.0372 (6) | 0.0456 (7) | −0.0025 (6) | 0.0034 (6) | −0.0083 (5) |
C16B | 0.0685 (11) | 0.0710 (11) | 0.0510 (9) | −0.0165 (9) | 0.0109 (8) | 0.0020 (8) |
N17B | 0.0499 (7) | 0.0475 (7) | 0.0517 (7) | −0.0088 (5) | −0.0035 (5) | −0.0176 (6) |
O18B | 0.0946 (10) | 0.0427 (6) | 0.0717 (8) | −0.0142 (6) | 0.0115 (7) | −0.0136 (6) |
O19B | 0.0633 (7) | 0.0664 (7) | 0.0623 (7) | −0.0068 (6) | 0.0082 (6) | −0.0305 (6) |
O20 | 0.0729 (9) | 0.0408 (6) | 0.0640 (7) | −0.0134 (5) | −0.0050 (6) | −0.0053 (5) |
O21 | 0.0585 (7) | 0.0674 (7) | 0.0706 (8) | −0.0071 (6) | 0.0033 (6) | −0.0368 (6) |
C22 | 0.0585 (10) | 0.0598 (10) | 0.0929 (14) | −0.0137 (8) | 0.0019 (9) | −0.0238 (10) |
Geometric parameters (Å, º) top
N1A—C8A | 1.337 (2) | C3B—N10B | 1.3900 (17) |
N1A—N2A | 1.3739 (18) | C3B—C9B | 1.4382 (18) |
N1A—H1A | 0.95 (2) | C4B—C5B | 1.3736 (19) |
N2A—C3A | 1.3212 (18) | C4B—C9B | 1.3947 (18) |
C3A—N10A | 1.3845 (17) | C4B—H4B | 0.9300 |
C3A—C9A | 1.4457 (19) | C5B—C6B | 1.404 (2) |
C4A—C5A | 1.376 (2) | C5B—N17B | 1.4592 (18) |
C4A—C9A | 1.394 (2) | C6B—C7B | 1.366 (2) |
C4A—H4A | 0.9300 | C6B—H6B | 0.9300 |
C5A—C6A | 1.403 (2) | C7B—C8B | 1.404 (2) |
C5A—N17A | 1.455 (2) | C7B—H7B | 0.9300 |
C6A—C7A | 1.360 (2) | C8B—C9B | 1.4108 (19) |
C6A—H6A | 0.9300 | N10B—C15B | 1.4615 (17) |
C7A—C8A | 1.406 (2) | N10B—C11B | 1.4718 (17) |
C7A—H7A | 0.9300 | C11B—C12B | 1.506 (2) |
C8A—C9A | 1.4131 (19) | C11B—H11C | 0.9700 |
N10A—C11A | 1.4520 (18) | C11B—H11D | 0.9700 |
N10A—C15A | 1.4570 (18) | C12B—N13B | 1.4635 (19) |
C11A—C12A | 1.511 (2) | C12B—H12C | 0.9700 |
C11A—H11A | 0.9700 | C12B—H12D | 0.9700 |
C11A—H11B | 0.9700 | N13B—C16B | 1.461 (2) |
C12A—N13A | 1.456 (2) | N13B—C14B | 1.4621 (19) |
C12A—H12A | 0.9700 | C14B—C15B | 1.508 (2) |
C12A—H12B | 0.9700 | C14B—H14C | 0.9700 |
N13A—C14A | 1.4599 (19) | C14B—H14D | 0.9700 |
N13A—C16A | 1.463 (2) | C15B—H15C | 0.9700 |
C14A—C15A | 1.510 (2) | C15B—H15D | 0.9700 |
C14A—H14A | 0.9700 | C16B—H16D | 0.9600 |
C14A—H14B | 0.9700 | C16B—H16E | 0.9600 |
C15A—H15A | 0.9700 | C16B—H16F | 0.9600 |
C15A—H15B | 0.9700 | N17B—O18B | 1.2193 (18) |
C16A—H16A | 0.9600 | N17B—O19B | 1.2287 (17) |
C16A—H16B | 0.9600 | O20—H20A | 0.88 (3) |
C16A—H16C | 0.9600 | O20—H20B | 0.85 (3) |
N17A—O18A | 1.221 (2) | O21—C22 | 1.392 (2) |
N17A—O19A | 1.2282 (19) | O21—H21A | 0.93 (3) |
N1B—C8B | 1.3394 (19) | C22—H22A | 0.9600 |
N1B—N2B | 1.3729 (17) | C22—H22B | 0.9600 |
N1B—H1B | 0.89 (2) | C22—H22C | 0.9600 |
N2B—C3B | 1.3223 (17) | | |
| | | |
C8A—N1A—N2A | 112.22 (12) | N2B—C3B—N10B | 121.61 (12) |
C8A—N1A—H1A | 126.8 (13) | N2B—C3B—C9B | 110.57 (12) |
N2A—N1A—H1A | 120.7 (13) | N10B—C3B—C9B | 127.74 (12) |
C3A—N2A—N1A | 106.08 (12) | C5B—C4B—C9B | 117.45 (12) |
N2A—C3A—N10A | 120.16 (13) | C5B—C4B—H4B | 121.3 |
N2A—C3A—C9A | 110.77 (12) | C9B—C4B—H4B | 121.3 |
N10A—C3A—C9A | 128.89 (12) | C4B—C5B—C6B | 123.50 (13) |
C5A—C4A—C9A | 117.83 (13) | C4B—C5B—N17B | 118.27 (13) |
C5A—C4A—H4A | 121.1 | C6B—C5B—N17B | 118.23 (13) |
C9A—C4A—H4A | 121.1 | C7B—C6B—C5B | 119.83 (13) |
C4A—C5A—C6A | 123.41 (15) | C7B—C6B—H6B | 120.1 |
C4A—C5A—N17A | 118.05 (14) | C5B—C6B—H6B | 120.1 |
C6A—C5A—N17A | 118.54 (14) | C6B—C7B—C8B | 117.69 (13) |
C7A—C6A—C5A | 119.90 (14) | C6B—C7B—H7B | 121.2 |
C7A—C6A—H6A | 120.0 | C8B—C7B—H7B | 121.2 |
C5A—C6A—H6A | 120.0 | N1B—C8B—C7B | 130.40 (13) |
C6A—C7A—C8A | 117.62 (14) | N1B—C8B—C9B | 107.32 (12) |
C6A—C7A—H7A | 121.2 | C7B—C8B—C9B | 122.27 (13) |
C8A—C7A—H7A | 121.2 | C4B—C9B—C8B | 119.25 (12) |
N1A—C8A—C7A | 129.99 (14) | C4B—C9B—C3B | 136.82 (13) |
N1A—C8A—C9A | 107.31 (13) | C8B—C9B—C3B | 103.91 (11) |
C7A—C8A—C9A | 122.67 (14) | C3B—N10B—C15B | 114.88 (11) |
C4A—C9A—C8A | 118.54 (13) | C3B—N10B—C11B | 115.45 (11) |
C4A—C9A—C3A | 137.89 (13) | C15B—N10B—C11B | 110.91 (11) |
C8A—C9A—C3A | 103.57 (12) | N10B—C11B—C12B | 110.35 (12) |
C3A—N10A—C11A | 118.86 (12) | N10B—C11B—H11C | 109.6 |
C3A—N10A—C15A | 116.26 (11) | C12B—C11B—H11C | 109.6 |
C11A—N10A—C15A | 113.73 (11) | N10B—C11B—H11D | 109.6 |
N10A—C11A—C12A | 110.71 (13) | C12B—C11B—H11D | 109.6 |
N10A—C11A—H11A | 109.5 | H11C—C11B—H11D | 108.1 |
C12A—C11A—H11A | 109.5 | N13B—C12B—C11B | 110.68 (12) |
N10A—C11A—H11B | 109.5 | N13B—C12B—H12C | 109.5 |
C12A—C11A—H11B | 109.5 | C11B—C12B—H12C | 109.5 |
H11A—C11A—H11B | 108.1 | N13B—C12B—H12D | 109.5 |
N13A—C12A—C11A | 110.93 (12) | C11B—C12B—H12D | 109.5 |
N13A—C12A—H12A | 109.5 | H12C—C12B—H12D | 108.1 |
C11A—C12A—H12A | 109.5 | C16B—N13B—C14B | 111.41 (13) |
N13A—C12A—H12B | 109.5 | C16B—N13B—C12B | 110.65 (13) |
C11A—C12A—H12B | 109.5 | C14B—N13B—C12B | 109.12 (11) |
H12A—C12A—H12B | 108.0 | N13B—C14B—C15B | 111.10 (12) |
C12A—N13A—C14A | 108.93 (12) | N13B—C14B—H14C | 109.4 |
C12A—N13A—C16A | 110.30 (13) | C15B—C14B—H14C | 109.4 |
C14A—N13A—C16A | 110.70 (13) | N13B—C14B—H14D | 109.4 |
N13A—C14A—C15A | 110.73 (12) | C15B—C14B—H14D | 109.4 |
N13A—C14A—H14A | 109.5 | H14C—C14B—H14D | 108.0 |
C15A—C14A—H14A | 109.5 | N10B—C15B—C14B | 110.44 (12) |
N13A—C14A—H14B | 109.5 | N10B—C15B—H15C | 109.6 |
C15A—C14A—H14B | 109.5 | C14B—C15B—H15C | 109.6 |
H14A—C14A—H14B | 108.1 | N10B—C15B—H15D | 109.6 |
N10A—C15A—C14A | 110.50 (12) | C14B—C15B—H15D | 109.6 |
N10A—C15A—H15A | 109.5 | H15C—C15B—H15D | 108.1 |
C14A—C15A—H15A | 109.5 | N13B—C16B—H16D | 109.5 |
N10A—C15A—H15B | 109.5 | N13B—C16B—H16E | 109.5 |
C14A—C15A—H15B | 109.5 | H16D—C16B—H16E | 109.5 |
H15A—C15A—H15B | 108.1 | N13B—C16B—H16F | 109.5 |
N13A—C16A—H16A | 109.5 | H16D—C16B—H16F | 109.5 |
N13A—C16A—H16B | 109.5 | H16E—C16B—H16F | 109.5 |
H16A—C16A—H16B | 109.5 | O18B—N17B—O19B | 123.20 (13) |
N13A—C16A—H16C | 109.5 | O18B—N17B—C5B | 118.48 (13) |
H16A—C16A—H16C | 109.5 | O19B—N17B—C5B | 118.32 (13) |
H16B—C16A—H16C | 109.5 | H20A—O20—H20B | 99 (2) |
O18A—N17A—O19A | 122.45 (16) | C22—O21—H21A | 104.5 (15) |
O18A—N17A—C5A | 119.02 (14) | O21—C22—H22A | 109.5 |
O19A—N17A—C5A | 118.52 (16) | O21—C22—H22B | 109.5 |
C8B—N1B—N2B | 111.78 (12) | H22A—C22—H22B | 109.5 |
C8B—N1B—H1B | 128.0 (12) | O21—C22—H22C | 109.5 |
N2B—N1B—H1B | 120.0 (12) | H22A—C22—H22C | 109.5 |
C3B—N2B—N1B | 106.41 (11) | H22B—C22—H22C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O21 | 0.95 (2) | 1.84 (2) | 2.7606 (17) | 161.2 (19) |
N1B—H1B···O20i | 0.89 (2) | 1.91 (2) | 2.7838 (17) | 164.6 (17) |
O20—H20A···N2B | 0.88 (3) | 2.05 (3) | 2.9315 (18) | 177 (2) |
O20—H20B···N13Aii | 0.85 (3) | 2.00 (3) | 2.830 (2) | 166 (2) |
O21—H21A···N13B | 0.93 (3) | 1.82 (3) | 2.7282 (19) | 165 (2) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1. |
Experimental details
| (IIa) | (IIIa) |
Crystal data |
Chemical formula | C11H12N4O2S | C12H15N5O2·0.5CH4O·0.5H2O |
Mr | 264.31 | 286.32 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 4.3897 (8), 10.4102 (10), 25.829 (3) | 7.3742 (11), 12.1765 (13), 16.6356 (16) |
α, β, γ (°) | 90, 91.166 (12), 90 | 78.650 (9), 84.958 (10), 74.596 (11) |
V (Å3) | 1180.1 (3) | 1410.9 (3) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.46 | 0.83 |
Crystal size (mm) | 0.43 × 0.18 × 0.08 | 0.50 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Kuma KM-4 diffractometer | Kuma KM-4 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) | – |
Tmin, Tmax | 0.528, 0.821 | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2499, 2192, 1769 | 5919, 5457, 4475 |
Rint | 0.034 | 0.019 |
(sin θ/λ)max (Å−1) | 0.610 | 0.627 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.128, 1.04 | 0.042, 0.124, 1.04 |
No. of reflections | 2192 | 5457 |
No. of parameters | 167 | 394 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.23 | 0.29, −0.22 |
Hydrogen-bond geometry (Å, º) for (IIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 (3) | 2.09 (3) | 2.871 (3) | 151 (3) |
Symmetry code: (i) −x, −y+1, −z. |
Hydrogen-bond geometry (Å, º) for (IIIa) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O21 | 0.95 (2) | 1.84 (2) | 2.7606 (17) | 161.2 (19) |
N1B—H1B···O20i | 0.89 (2) | 1.91 (2) | 2.7838 (17) | 164.6 (17) |
O20—H20A···N2B | 0.88 (3) | 2.05 (3) | 2.9315 (18) | 177 (2) |
O20—H20B···N13Aii | 0.85 (3) | 2.00 (3) | 2.830 (2) | 166 (2) |
O21—H21A···N13B | 0.93 (3) | 1.82 (3) | 2.7282 (19) | 165 (2) |
Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1. |
Die Titelverbindungen, (IIa) und (IIIa), entstehen bei der Einwirkung von Thiomorpholin bzw. N-Methylpiperazin auf 2,5-Dinitroindazol, (I), infolge einer nucleophilen cine-Substitution der N2-Nitrogruppe. Als Nebenprodukte werden dabei die aus 3,5-Dinitroindazol [Isomerisierungsprodukt von (I)] und den erwähnten cyclischen Aminen zusammengesetzten Molekularverbindungen (IIb) und (IIIb) isoliert (Schema). Letztere wurden von uns bereits röntgenographisch untersucht (Gzella & Wrzeciono, 1991; Gzella et al., 1994). In dieser Mitteilung soll über die röntgenographische Analyse der 3-Amino-5-nitroindazole (IIa) und (IIIa) berichtet werden. \sch
In der unabhängigen Einheit der Elementarzelle von (IIa) befindet sich ein Molekül (Abb. 1), von (IIIa) zwei Moleküle A und B des 3-Amino-5-nitroindazols und je ein Molekül Methanol und Wasser (Abb. 2). Die Indazol-Moleküle A und B von (IIIa) unterscheiden sich voneinander nur geringfügig. Mit Hilfe der kleinsten Quadrate-Anpassung (Spek, 1990) wurde eine gewichtete Wurzel aus der mittleren quadratischen Abweichung von 0.193 Å gefunden. Die maximalen Abweichungen beziehen sich auf die Atome C12 und C15 der Methylpiperazingruppe und betragen 0.377 und 0.332 Å. Die Geometrie des 5-Nitroindazolfragmentes in (IIa) ist mit dem von (IIIa) vergleichbar.
Im Kristall von (IIa) sind die Moleküle über Wasserstoffbrückenbindungen N1—H1A···N2i [Symmetrieoperator: (i) -x, 1 - y, -z; Tabelle 1] zu Dimeren verbunden. Im Kristallgitter von (IIIa) sind die Methanol- und Wasser-Moleküle mit den Indazol-Molekülen A und B über Wasserstoffbrückenbindungen in zur z-Achse parallelen Doppel-Ketten gebunden, wobei sich das Methanol-Molekül an der Bildung der Wasserstoffbrücken sowohl als Protonen-Donor (O21—H21A···N13B) als auch als Akzeptor (N1A—H1A···O21) beteiligt und das O20 Atom des Wasser-Moleküls einmal als Protonen-Akzeptor [N1B—H1B···O20ii; Symmetrieoperator: (ii) 1 - x, -y, 2 - z] und zweimal als Protonen-Donor [O20—H20A···N2B und O20—H20B···N13Aiii; Symmetrieoperator: (iii) 1 - x, -y, 1 - z] auftritt (Tabelle 2). Die Wasser-Moleküle binden die einzelnen Ketten über die O20—H20A···N2B Wasserstoffbrückenbindungen in die oben erwähnten Doppel-Ketten. Die durch Wasserstoffbrücken verbundenen Atome N1B, N2B, N1Bii, N2Bii, O20 und O20ii bilden einen sechsgliedrigen gefalteten Ring (gewichtete Wurzel aus der mittleren quadratischen Abweichung: 0.1080 Å), der auf dem Symmetrie-Zentrum liegt.
Die Indazolsysteme in (IIa) und (IIIa) sind erwartungsgemä\&s annähernd flach. Die grö\&sten Abweichungen von den Indazolebenen weisen die Atome C9 in (IIa) [-0.0150 (19) Å], C3A und C9B in (IIIa) [0.0249 (11) und -0.0091 (12) Å] auf.
In (IIa) und (IIIa) weicht die Nitrogruppe aus der Ebene des Indazolsystems nur geringfügig ab. Für die Interplanarwinkel wurden Werte von 4.49 (18)° in (IIa), 2.41 (6) und 5.95 (8)° in (IIIa) (Molekül A und B) ermittelt.
Der mit dem C3-Atom verbundene Thiomorpholin- bzw. N-Methylpiperazinring liegt in (IIa) bzw. (IIIa) in der Sesselform vor. Der Interplanarwinkel zwischen der Thiomorpholin- bzw. Piperazin-Mittelebene und der Indazolebene beträgt in (IIa) 37.51 (6)°, in (IIIa) 10.51 (4) und 26.26 (5)° (Molekül A und B). Die Indazolebenen A und B in (IIIa) bilden einen Interplanarwinkel von 32.34 (3)°.
Im Kristallgitter von (IIa) und (IIIa) liegen die Indazolsysteme parallel zueinander. In (IIa) und in den Molekülen A von (IIIa) überlagern sich diese teilweize und bilden auf diese Weize Säulen, die sich in Richtung der x-Achse entwickeln. Die Abstände zwischen den Indazolebenen betragen in (IIa) 3.510 (4) Å [Ind···Indiv; Symmetrieoperator: (iv) 1 + x, y, z], in (IIIa) zwischen den Indazolebenen A abwechselnd 3.598 (5) Å [Ind···Indv; Symetrieoperator: (v) 1 - x, -y, 1 - z] und 3.387 (5) Å [Ind···Indvi; Symetrieoperator: (vi) 2 - x, -y, 1 - z]. Die Indazolsysteme in den Molekülen B von (IIIa) bilden Paare [Ind···Indvii 3.474 (8) Å; Symetrieoperator: (vii) -x, 1 - y, 2 - z]. Die gefundenen Abstände zwischen den einzelnen Indazolebenen weisen auf gegenseitige π-Elektronen-Wechselwirkungen hin.