organic papers
o1616
Elgemeie and Jones C16H14ClN5OC2H6O DOI: 10.1107/S1600536804020689 Acta Cryst.(2004). E60, o1616±o1618 Acta Crystallographica Section EStructure Reports
Online
ISSN 1600-5368
5-Amino-3-anilino-
N
-(chlorophenyl)-1
H
-pyrazole-4-carboxamide ethanol solvate
Galal H. Elgemeieaand Peter G. Jonesb*
aChemistry Department, Faculty of Science, Helwan University, Helwan, Cairo, Egypt, and bInstitut fuÈr Anorganische und Analytische Chemie, Technische UniversitaÈt Braunschweig, Postfach 3329, 38023 Braunschweig, Germany
Correspondence e-mail: p.jones@tu-bs.de
Key indicators
Single-crystal X-ray study
T= 173 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.035
wRfactor = 0.083
Data-to-parameter ratio = 12.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
In the title compound, C16H14ClN5OC2H6O, the main residue
is approximately planar except for the aniline group. Classical intramolecular hydrogen bonds are observed from the amino N atom to the carbonyl O atom and from the carboxamide N atom to the aniline N atom. Four further hydrogen bonds connect the residues to form layers parallel to (101).
Comment
During the course of our studies directed toward exploring the synthetic potential of ketene dithioacetals for new classes of
novel antimetabolites (Elgemeie et al., 1997, 1999, 2000), we
have recently reported various successful approaches for the synthesis of mercaptopurine and thioguanine analogues by the reaction of ketene dithioacetals with diazoles containing
amino and active methylene functions (Elgemeieet al., 1998,
2001, 2002).
In an extension of this work, the present paper describes a novel synthesis of a 5-aminopyrazole by the reaction of a
ketene N,S-acetal with an amine. The cyanoacetanilide
deri-vative (1) reacted with phenyl isothiocyanate in KOH±EtOH
to give the corresponding stable potassium salt, (2). The latter, on alkylation with methyl iodide in ethanol, afforded the novel
ketene N,S-acetal (3). Reaction of compound (3) with
hydrazine in re¯uxing ethanol gave the corresponding 5-aminopyrazole derivative (4). The structure (4) was supported
by its mass (m/z = 327), which agrees with the empirical
formula. In order to establish unambiguously the structure and stereospeci®ty of the product (4), its crystal structure was determined.
The X-ray analysis (Fig. 1) con®rms the exclusive presence of the pyrazole form (4) in the solid state. The compound crystallizes with one molecule of ethanol, which is well ordered. Bond lengths and angles may be regarded as normal. Apart from the aniline group, the molecule is approximately planar (r.m.s. deviation of all other non-H atoms: 0.102 AÊ), a form supported by the intramolecular hydrogen bonds from N3 to O1 and from N5 to N4 (and perhaps also from C17 to O1). The aniline group makes an interplanar angle of
81.55 (3) to the main plane.
The ethanol molecule is hydrogen bonded to atom N2. This hydrogen bond, together with three classical intermolecular hydrogen bonds, combine to form layers of residues parallel to (101) (Table 2 and Fig. 2). The potential hydrogen-bond donor N3ÐH031 is, however, not involved in hydrogen bonding. The
layers are linked by a Cl Cl interaction: Cl Clv =
3.6286 (11) AÊ, with C15ÐCl Clv = 101.82 (7) [symmetry
code: (v)ÿx, 2ÿy, 1ÿz].
Experimental
A mixture of ketene N,S-acetal (3) (0.01 mol) and hydrazine (0.01 mol) was re¯uxed in ethanol for 30 min. The solid product was collected and recrystallized from ethanol in 78% yield (m.p. 388 K) and contained crystals suitable for X-ray analysis.
Crystal data C16H14ClN5OC2H6O
Mr= 373.84 Monoclinic,P21=n
a= 10.6757 (10) AÊ
b= 7.7798 (9) AÊ
c= 21.919 (2) AÊ
= 99.14 (1)
V= 1797.3 (3) AÊ3
Z= 4
Dx= 1.382 Mg mÿ3 MoKradiation Cell parameters from 63
re¯ections
= 4.5±12.5
= 0.24 mmÿ1
T= 173 (2) K Tablet, colourless 0.40.40.3 mm Data collection
SiemensP4 diffractometer
!scans
Absorption correction: none 4927 measured re¯ections 3167 independent re¯ections 2349 re¯ections withI> 2(I)
Rint= 0.022
max= 25.0
h=ÿ12!12
k=ÿ9!4
l= 0!25
3 standard re¯ections every 247 re¯ections intensity decay: none Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.035
wR(F2) = 0.083
S= 0.93 3167 re¯ections 260 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.0484P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.19 e AÊÿ3
min=ÿ0.27 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
N1ÐN2 1.378 (2)
C5ÐN1ÐN2 112.53 (15) C3ÐN2ÐN1 104.24 (14)
N4ÐC3ÐC4ÐC5 175.67 (16) N4ÐC3ÐC4ÐC6 ÿ1.0 (3) C5ÐC4ÐC6ÐN5 ÿ177.41 (15)
C6ÐN5ÐC12ÐC17 ÿ8.0 (3) N5ÐC12ÐC17ÐC16 179.20 (16)
organic papers
Acta Cryst.(2004). E60, o1616±o1618 Elgemeie and Jones C16H14ClN5OC2H6O
o1617
Figure 1
The formula unit of compound (4) in the crystal. Displacement ellipsoids are drawn at the 50% probability level. H-atom radii are arbitrary.
Figure 2
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N3ÐH032 O1 0.87 (2) 2.41 (2) 2.914 (2) 117.4 (18) N5ÐH05 N4 0.83 (2) 2.26 (2) 2.955 (2) 142.0 (18) N1ÐH01 O99i 0.92 (2) 1.90 (2) 2.801 (2) 165.6 (17)
N3ÐH032 O1ii 0.87 (2) 2.22 (2) 2.950 (2) 142 (2)
N4ÐH04 O99iii 0.876 (19) 2.30 (2) 3.163 (2) 170.7 (17)
O99ÐH099 N2 0.83 (2) 1.96 (2) 2.7928 (19) 176 (2) C17ÐH17 O1 0.95 2.28 2.884 (2) 121 C21ÐH21 O1iv 0.95 2.56 3.494 (2) 167
Symmetry codes: (i)3
2ÿx;yÿ12;12ÿz; (ii) 1ÿx;ÿy;1ÿz; (iii)32ÿx;12y;12ÿz; (iv) 1
2ÿx;12y;12ÿz.
H atoms attached to N or O atoms were re®ned freely. Methyl H atoms were identi®ed in a difference synthesis, idealized and re®ned as a rigid group (CÐH = 0.98 AÊ and HÐCÐH = 109.5) allowed to rotate but not tip. Other H atoms were included using a riding model with ®xed CÐH bond lengths (aromatic = 0.95 AÊ and methylene = 0.99 AÊ);Uiso(H) values were ®xed at 1.2Ueqof the parent C atom.
Data collection:XSCANS(Fait, 1991); cell re®nement:XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
We thank Mr A. Weinkauf for technical assistance.
References
Elgemeie, G. H., El-Ezbawy, S. R. & El-Aziz, H. A. (2001).Synth. Commun.
31, 2453±2458.
Elgemeie, G. H., Elghandour, A. H., Ali, H. A. & Abdel-Azzez, H. M. (1999).
J. Chem. Res.(S), pp. 6±7.
Elgemeie, G. H., Elghandour, A. H., Ali, H. A. & Hussein, A. M. (2002).Synth. Commun.32, 2245±2253.
Elgemeie, G. H., Elghandour, A. H., Elzanate, A. M. & Ahmed, S. A. (1997).J. Chem. Soc. Perkin Trans.1, pp. 3285±3289.
Elgemeie, G. H., Elghandour, A. H., Elzanate, A. M. & Ahmed, S. A. (1998).J. Chem. Res.(S), pp. 162±163.
Elgemeie, G. H., Elghandour, A. H., Elzanate, A. M. & Masoud, W. A. (2000).
Phosphorus Sulfur Silicon,163, 91±97.
Fait, J. (1991).XSCANS.Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Siemens (1994).XP.Version 5.03. Siemens Analytical X-ray Instruments Inc.,
Madison, Wisconsin, USA.
organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, o1616–o1618
supporting information
Acta Cryst. (2004). E60, o1616–o1618 [https://doi.org/10.1107/S1600536804020689]
5-Amino-3-anilino-
N
-(chlorophenyl)-1
H
-pyrazole-4-carboxamide ethanol
solvate
Galal H. Elgemeie and Peter G. Jones
5-Amino-3-anilino-N-(chlorophenyl)-1H-pyrazole-4-carboxamide ethanol solvate
Crystal data
C16H14ClN5O·C2H6O Mr = 373.84 Monoclinic, P21/n a = 10.6757 (10) Å
b = 7.7798 (9) Å
c = 21.919 (2) Å
β = 99.14 (1)°
V = 1797.3 (3) Å3 Z = 4
F(000) = 784
Dx = 1.382 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 63 reflections
θ = 4.5–12.5°
µ = 0.24 mm−1 T = 173 K Tablet, colourless 0.4 × 0.4 × 0.3 mm
Data collection
Siemens P4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω scans
4927 measured reflections 3167 independent reflections 2349 reflections with I > 2σ(I)
Rint = 0.022
θmax = 25.0°, θmin = 3.2°
h = −12→12
k = −9→4
l = 0→25
3 standard reflections every 247 reflections intensity decay: none
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.035 wR(F2) = 0.083 S = 0.93 3167 reflections 260 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0484P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.19 e Å−3
supporting information
sup-2 Acta Cryst. (2004). E60, o1616–o1618
Special details
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.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.7737 (0.0015) x + 2.0537 (0.0022) y + 13.5119 (0.0046) z = 9.4223 (0.0013)
* -0.0203 (0.0014) C3 * 0.0704 (0.0015) C4 * 0.0405 (0.0015) C5 * 0.0243 (0.0015) C12 * 0.1520 (0.0015) C13 * 0.1260 (0.0015) C14 * -0.0298 (0.0015) C15 * -0.1946 (0.0016) C16 * -0.1700 (0.0016) C17 * -0.0418 (0.0014) N1 * -0.0890 (0.0013) N2 * 0.0324 (0.0014) N3 * -0.1171 (0.0012) N4 * 0.0803 (0.0014) N5 * 0.1400 (0.0011) O1 * -0.0034 (0.0008) Cl
Rms deviation of fitted atoms = 0.1015
- 6.6383 (0.0052) x + 4.4211 (0.0049) y + 13.8267 (0.0091) z = 2.9976 (0.0042) Angle to previous plane (with approximate e.s.d.) = 81.55 (0.03)
* -0.0056 (0.0010) N4 * -0.0037 (0.0014) C18 * 0.0061 (0.0014) C19 * 0.0040 (0.0013) C20 * -0.0108 (0.0014) C21 * 0.0017 (0.0013) C22 * 0.0084 (0.0014) C23
Rms deviation of fitted atoms = 0.0064
============================================================================ Contacts:
3.6286 (0.0011) Cl - Cl_$5 101.82 (0.07) C15 - Cl - Cl_$5 $5 - x, -y + 2, -z + 1
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)
x y z Uiso*/Ueq
Cl 0.04477 (5) 0.81766 (7) 0.55036 (2) 0.04214 (16)
O1 0.43047 (11) 0.18838 (16) 0.46327 (5) 0.0275 (3)
N1 0.68056 (14) 0.0993 (2) 0.33798 (7) 0.0285 (4)
H01 0.7241 (17) 0.008 (3) 0.3254 (8) 0.033 (5)*
N2 0.67822 (13) 0.25984 (19) 0.31126 (6) 0.0265 (4)
C3 0.60229 (15) 0.3501 (2) 0.34070 (7) 0.0220 (4)
C4 0.55412 (15) 0.2524 (2) 0.38640 (7) 0.0216 (4)
N3 0.59107 (18) −0.0588 (2) 0.41236 (8) 0.0336 (4)
H031 0.638 (2) −0.137 (3) 0.4083 (10) 0.047 (7)*
H032 0.5647 (19) −0.052 (3) 0.4476 (10) 0.050 (7)*
N4 0.57055 (14) 0.5226 (2) 0.32321 (6) 0.0240 (3)
H04 0.6374 (18) 0.585 (2) 0.3201 (8) 0.030 (5)*
C5 0.60714 (16) 0.0899 (2) 0.38230 (7) 0.0240 (4)
N5 0.41956 (13) 0.4604 (2) 0.42298 (7) 0.0245 (3)
H05 0.4529 (17) 0.525 (3) 0.4001 (9) 0.035 (6)*
C6 0.46426 (15) 0.2960 (2) 0.42783 (7) 0.0219 (4)
C12 0.32742 (15) 0.5377 (2) 0.45327 (7) 0.0220 (4)
C13 0.30879 (16) 0.7143 (2) 0.44522 (8) 0.0262 (4)
H13 0.3569 0.7760 0.4196 0.031*
C14 0.22138 (16) 0.8007 (2) 0.47397 (8) 0.0280 (4)
supporting information
sup-3 Acta Cryst. (2004). E60, o1616–o1618
C15 0.15153 (16) 0.7103 (3) 0.51121 (8) 0.0281 (4)
C16 0.16619 (17) 0.5353 (3) 0.51826 (8) 0.0309 (4)
H16 0.1159 0.4740 0.5430 0.037*
C17 0.25357 (16) 0.4478 (3) 0.48956 (8) 0.0291 (4)
H17 0.2632 0.3270 0.4946 0.035*
C18 0.47317 (15) 0.5411 (2) 0.27066 (7) 0.0238 (4)
C19 0.47697 (17) 0.6765 (2) 0.22992 (8) 0.0296 (4)
H19 0.5442 0.7578 0.2368 0.036*
C20 0.38189 (18) 0.6928 (3) 0.17892 (8) 0.0341 (5)
H20 0.3846 0.7859 0.1511 0.041*
C21 0.28401 (18) 0.5762 (3) 0.16814 (9) 0.0337 (5)
H21 0.2204 0.5871 0.1328 0.040*
C22 0.27925 (18) 0.4431 (3) 0.20932 (9) 0.0361 (5)
H22 0.2113 0.3630 0.2026 0.043*
C23 0.37284 (17) 0.4255 (3) 0.26036 (8) 0.0307 (4)
H23 0.3685 0.3337 0.2886 0.037*
C98 0.52162 (19) 0.1041 (3) 0.16055 (9) 0.0384 (5)
H98A 0.5779 0.0086 0.1540 0.046*
H98B 0.4420 0.0940 0.1316 0.046*
H98C 0.5037 0.1003 0.2030 0.046*
C99 0.58476 (17) 0.2714 (2) 0.14991 (8) 0.0319 (4)
H99A 0.5936 0.2805 0.1058 0.038*
H99B 0.5305 0.3675 0.1597 0.038*
O99 0.70842 (12) 0.28640 (17) 0.18736 (6) 0.0300 (3)
H099 0.7003 (19) 0.283 (3) 0.2245 (10) 0.043 (6)*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Cl 0.0427 (3) 0.0409 (3) 0.0476 (3) 0.0088 (2) 0.0218 (2) −0.0045 (3)
O1 0.0332 (7) 0.0255 (7) 0.0255 (6) 0.0013 (6) 0.0100 (5) 0.0066 (6)
N1 0.0345 (9) 0.0246 (9) 0.0285 (8) 0.0100 (7) 0.0114 (7) 0.0031 (7)
N2 0.0312 (8) 0.0240 (9) 0.0258 (8) 0.0042 (7) 0.0093 (6) 0.0048 (7)
C3 0.0220 (8) 0.0225 (10) 0.0215 (8) −0.0003 (7) 0.0027 (7) −0.0011 (7)
C4 0.0240 (8) 0.0210 (10) 0.0198 (8) −0.0007 (7) 0.0035 (7) 0.0003 (7)
N3 0.0480 (11) 0.0241 (10) 0.0316 (9) 0.0073 (9) 0.0150 (8) 0.0060 (8)
N4 0.0255 (8) 0.0204 (9) 0.0268 (8) −0.0021 (7) 0.0066 (6) 0.0033 (7)
C5 0.0281 (9) 0.0234 (10) 0.0206 (8) 0.0031 (8) 0.0043 (7) 0.0018 (8)
N5 0.0280 (8) 0.0234 (9) 0.0242 (8) −0.0001 (7) 0.0108 (6) 0.0042 (7)
C6 0.0217 (8) 0.0246 (10) 0.0186 (8) −0.0027 (8) 0.0010 (7) 0.0007 (8)
C12 0.0213 (8) 0.0254 (10) 0.0197 (8) −0.0007 (8) 0.0041 (7) 0.0003 (8)
C13 0.0262 (9) 0.0278 (11) 0.0256 (9) −0.0042 (8) 0.0070 (7) 0.0032 (8)
C14 0.0294 (9) 0.0226 (10) 0.0316 (9) 0.0018 (8) 0.0034 (8) 0.0015 (8)
C15 0.0267 (9) 0.0307 (12) 0.0276 (9) 0.0037 (8) 0.0068 (7) −0.0044 (9)
C16 0.0304 (10) 0.0324 (12) 0.0323 (10) 0.0012 (9) 0.0127 (8) 0.0045 (9)
C17 0.0316 (10) 0.0241 (11) 0.0335 (10) 0.0026 (8) 0.0105 (8) 0.0045 (8)
C18 0.0248 (9) 0.0238 (10) 0.0249 (9) 0.0042 (8) 0.0109 (7) 0.0004 (8)
supporting information
sup-4 Acta Cryst. (2004). E60, o1616–o1618
C20 0.0448 (11) 0.0283 (11) 0.0312 (10) 0.0116 (10) 0.0118 (9) 0.0098 (9)
C21 0.0336 (11) 0.0360 (12) 0.0308 (10) 0.0112 (9) 0.0028 (8) 0.0013 (9)
C22 0.0298 (10) 0.0404 (13) 0.0375 (11) −0.0038 (9) 0.0034 (8) 0.0039 (10)
C23 0.0321 (10) 0.0320 (12) 0.0285 (10) −0.0035 (9) 0.0061 (8) 0.0090 (9)
C98 0.0408 (12) 0.0338 (12) 0.0400 (11) −0.0057 (10) 0.0045 (9) 0.0019 (10)
C99 0.0388 (11) 0.0286 (11) 0.0294 (10) 0.0023 (9) 0.0090 (8) 0.0012 (9)
O99 0.0338 (7) 0.0310 (8) 0.0281 (7) −0.0050 (6) 0.0138 (6) −0.0002 (6)
Geometric parameters (Å, º)
Cl—C15 1.7448 (17) C15—C16 1.376 (3)
O1—C6 1.234 (2) C16—C17 1.384 (3)
N1—C5 1.344 (2) C16—H16 0.9500
N1—N2 1.378 (2) C17—H17 0.9500
N1—H01 0.92 (2) C18—C19 1.385 (2)
N2—C3 1.316 (2) C18—C23 1.390 (2)
C3—C4 1.417 (2) C19—C20 1.391 (3)
C3—N4 1.422 (2) C19—H19 0.9500
C4—C5 1.394 (2) C20—C21 1.376 (3)
C4—C6 1.462 (2) C20—H20 0.9500
N3—C5 1.356 (2) C21—C22 1.380 (3)
N3—H031 0.81 (2) C21—H21 0.9500
N3—H032 0.87 (2) C22—C23 1.383 (2)
N4—C18 1.431 (2) C22—H22 0.9500
N4—H04 0.876 (19) C23—H23 0.9500
N5—C6 1.363 (2) C98—C99 1.501 (3)
N5—C12 1.406 (2) C98—H98A 0.9800
N5—H05 0.83 (2) C98—H98B 0.9800
C12—C17 1.393 (2) C98—H98C 0.9800
C12—C13 1.396 (2) C99—O99 1.444 (2)
C13—C14 1.381 (2) C99—H99A 0.9900
C13—H13 0.9500 C99—H99B 0.9900
C14—C15 1.383 (2) O99—H099 0.83 (2)
C14—H14 0.9500
C5—N1—N2 112.53 (15) C15—C16—C17 120.53 (17)
C5—N1—H01 123.9 (12) C15—C16—H16 119.7
N2—N1—H01 123.5 (12) C17—C16—H16 119.7
C3—N2—N1 104.24 (14) C16—C17—C12 119.77 (18)
N2—C3—C4 112.42 (16) C16—C17—H17 120.1
N2—C3—N4 120.68 (15) C12—C17—H17 120.1
C4—C3—N4 126.79 (15) C19—C18—C23 119.23 (16)
C5—C4—C3 104.13 (14) C19—C18—N4 120.23 (16)
C5—C4—C6 124.33 (15) C23—C18—N4 120.54 (16)
C3—C4—C6 131.45 (16) C18—C19—C20 119.65 (17)
C5—N3—H031 117.6 (16) C18—C19—H19 120.2
C5—N3—H032 117.7 (15) C20—C19—H19 120.2
supporting information
sup-5 Acta Cryst. (2004). E60, o1616–o1618
C3—N4—C18 115.06 (14) C21—C20—H20 119.5
C3—N4—H04 112.5 (12) C19—C20—H20 119.5
C18—N4—H04 112.2 (12) C20—C21—C22 119.23 (17)
N1—C5—N3 122.07 (17) C20—C21—H21 120.4
N1—C5—C4 106.67 (15) C22—C21—H21 120.4
N3—C5—C4 131.20 (16) C21—C22—C23 120.43 (18)
C6—N5—C12 128.81 (15) C21—C22—H22 119.8
C6—N5—H05 116.0 (14) C23—C22—H22 119.8
C12—N5—H05 115.1 (14) C22—C23—C18 120.41 (17)
O1—C6—N5 123.50 (15) C22—C23—H23 119.8
O1—C6—C4 121.29 (16) C18—C23—H23 119.8
N5—C6—C4 115.19 (15) C99—C98—H98A 109.5
C17—C12—C13 118.93 (16) C99—C98—H98B 109.5
C17—C12—N5 123.83 (17) H98A—C98—H98B 109.5
C13—C12—N5 117.23 (15) C99—C98—H98C 109.5
C14—C13—C12 120.98 (16) H98A—C98—H98C 109.5
C14—C13—H13 119.5 H98B—C98—H98C 109.5
C12—C13—H13 119.5 O99—C99—C98 112.00 (15)
C13—C14—C15 119.24 (17) O99—C99—H99A 109.2
C13—C14—H14 120.4 C98—C99—H99A 109.2
C15—C14—H14 120.4 O99—C99—H99B 109.2
C16—C15—C14 120.51 (16) C98—C99—H99B 109.2
C16—C15—Cl 119.34 (14) H99A—C99—H99B 107.9
C14—C15—Cl 120.15 (15) C99—O99—H099 109.0 (14)
C5—N1—N2—C3 0.60 (19) C6—N5—C12—C13 173.07 (16)
N1—N2—C3—C4 −0.05 (18) C17—C12—C13—C14 1.8 (3)
N1—N2—C3—N4 −176.45 (14) N5—C12—C13—C14 −179.13 (15)
N2—C3—C4—C5 −0.47 (19) C12—C13—C14—C15 0.0 (3)
N4—C3—C4—C5 175.67 (16) C13—C14—C15—C16 −1.8 (3)
N2—C3—C4—C6 −177.17 (16) C13—C14—C15—Cl 177.60 (13)
N4—C3—C4—C6 −1.0 (3) C14—C15—C16—C17 1.8 (3)
N2—C3—N4—C18 80.3 (2) Cl—C15—C16—C17 −177.61 (14)
C4—C3—N4—C18 −95.58 (19) C15—C16—C17—C12 0.1 (3)
N2—N1—C5—N3 176.73 (16) C13—C12—C17—C16 −1.8 (3)
N2—N1—C5—C4 −0.90 (19) N5—C12—C17—C16 179.20 (16)
C3—C4—C5—N1 0.80 (18) C3—N4—C18—C19 −145.85 (16)
C6—C4—C5—N1 177.80 (15) C3—N4—C18—C23 35.1 (2)
C3—C4—C5—N3 −176.53 (19) C23—C18—C19—C20 −1.1 (3)
C6—C4—C5—N3 0.5 (3) N4—C18—C19—C20 179.82 (16)
C12—N5—C6—O1 −2.6 (3) C18—C19—C20—C21 −0.2 (3)
C12—N5—C6—C4 175.73 (15) C19—C20—C21—C22 1.2 (3)
C5—C4—C6—O1 1.0 (3) C20—C21—C22—C23 −1.0 (3)
C3—C4—C6—O1 177.11 (16) C21—C22—C23—C18 −0.3 (3)
C5—C4—C6—N5 −177.41 (15) C19—C18—C23—C22 1.4 (3)
C3—C4—C6—N5 −1.3 (3) N4—C18—C23—C22 −179.59 (16)
supporting information
sup-6 Acta Cryst. (2004). E60, o1616–o1618
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N3—H032···O1 0.87 (2) 2.41 (2) 2.914 (2) 117.4 (18)
N5—H05···N4 0.83 (2) 2.26 (2) 2.955 (2) 142.0 (18)
N1—H01···O99i 0.92 (2) 1.90 (2) 2.801 (2) 165.6 (17)
N3—H032···O1ii 0.87 (2) 2.22 (2) 2.950 (2) 142 (2)
N4—H04···O99iii 0.876 (19) 2.30 (2) 3.163 (2) 170.7 (17)
O99—H099···N2 0.83 (2) 1.96 (2) 2.7928 (19) 176 (2)
C17—H17···O1 0.95 2.28 2.884 (2) 121
C21—H21···O1iv 0.95 2.56 3.494 (2) 167