Literature DB >> 25705477

Crystal structure of 6,9-dimethyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one 0.40-hydrate.

Abdellah Harmaoui¹, Rachid Bouhfid², El Mokhtar Essassi³, Mohamed Saadi⁴, Lahcen El Ammari⁴.

Abstract

In the mol-ecule of the title compound, C7H9N5O·0.40H2O, the seven-membered heterocyclic ring exhibits a boat conformation, whereas the five-membered triazole ring is almost planar (r.m.s. deviation = 0.005 Å). In the crystal, centrosymmetric dimers are linked by pairs of C-H⋯O hydrogen bonds into dimers, which are further connected via O-H⋯N and C-H⋯N hydrogen bonds, forming a three-dimensional network. The structure contains a partially occupied water mol-ecule lying on a twofold axis with an occupancy factor of 0.4.

Entities: Chemical Disease Species

Keywords: 1,2,4-triazepin-8(9H)-one; crystal structure; hydrogen bonding; pharmacological and biological activities

Year: 2015 PMID： 25705477 PMCID： PMC4331897 DOI： 10.1107/S2056989014025687

Source DB: PubMed Journal: Acta Crystallogr E Crystallogr Commun

Related literature

For pharmacological and biological activities of 1,2,4-triazole and 1,2,4-triazepine derivatives, see: Gupta et al. (2011 ▸); Mathew et al. (2006 ▸); Reed et al. (2010 ▸). For related structures, see: Essassi et al. (1977 ▸); Doubia et al. (2007 ▸); Zemama et al. (2009 ▸).

Experimental

Crystal data

C7H9N5O·0.4H2O M = 186.44 Monoclinic, a = 11.4970 (18) Å b = 11.4527 (18) Å c = 14.867 (2) Å β = 109.615 (4)° V = 1843.9 (5) Å3 Z = 8 Mo Kα radiation μ = 0.10 mm−1 T = 296 K 0.40 × 0.34 × 0.30 mm

Data collection

Bruker X8 APEX diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.637, T max = 0.746 14175 measured reflections 2039 independent reflections 1600 reflections with I > 2σ(I) R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.042 wR(F 2) = 0.125 S = 1.04 2039 reflections 123 parameters H-atom parameters constrained Δρmax = 0.28 e Å−3 Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip,2010 ▸). Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014025687/rz5141sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025687/rz5141Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S2056989014025687/rz5141Isup3.cml Click here for additional data file. . DOI: 10.1107/S2056989014025687/rz5141fig1.tif The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level, showing the intermolecular O—H⋯N hydrogen bond (dashed line). Click here for additional data file. . DOI: 10.1107/S2056989014025687/rz5141fig2.tif Partiel crystal packing of the title compound, showing molecules linked through C—H⋯O and O—H⋯N hydrogen bonds (dashed lines). CCDC reference: 1035668 Additional supporting information: crystallographic information; 3D view; checkCIF report

C₇H₉N₅O·0.4H₂O	F(000) = 784
M_r = 186.44	D_x = 1.343 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2039 reflections
a = 11.4970 (18) Å	θ = 2.6–27.1°
b = 11.4527 (18) Å	µ = 0.10 mm⁻¹
c = 14.867 (2) Å	T = 296 K
β = 109.615 (4)°	Block, colourless
V = 1843.9 (5) Å³	0.40 × 0.34 × 0.30 mm
Z = 8

Bruker X8 APEX diffractometer	2039 independent reflections
Radiation source: fine-focus sealed tube	1600 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 27.1°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.637, T_max = 0.746	k = −14→14
14175 measured reflections	l = −19→19

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) = 0.125	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0565P)² + 1.2827P] where P = (F_o² + 2F_c²)/3
2039 reflections	(Δ/σ)_max < 0.001
123 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

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.

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.33958 (13)	0.65257 (14)	0.16698 (10)	0.0369 (3)
C2	0.34033 (16)	0.52181 (14)	0.16066 (11)	0.0433 (4)
H2A	0.4176	0.4962	0.1544	0.052*
H2B	0.3344	0.4885	0.2190	0.052*
C3	0.23480 (17)	0.47878 (14)	0.07690 (12)	0.0476 (4)
C4	0.33342 (14)	0.57338 (13)	−0.02393 (10)	0.0362 (3)
C5	0.46928 (15)	0.70820 (15)	−0.00967 (12)	0.0453 (4)
H5	0.5204	0.7725	0.0124	0.054*
C6	0.30729 (19)	0.70739 (19)	0.24624 (12)	0.0571 (5)
H6A	0.3102	0.7908	0.2412	0.086*
H6B	0.3652	0.6828	0.3063	0.086*
H6C	0.2256	0.6839	0.2424	0.086*
C7	0.1424 (2)	0.4639 (2)	−0.09733 (15)	0.0758 (7)
H7A	0.1563	0.4934	−0.1533	0.114*
H7B	0.0623	0.4881	−0.0976	0.114*
H7C	0.1464	0.3802	−0.0970	0.114*
N1	0.23754 (13)	0.50997 (12)	−0.01151 (9)	0.0445 (4)
N2	0.37481 (14)	0.56109 (13)	−0.09512 (10)	0.0478 (4)
N3	0.46286 (14)	0.64862 (14)	−0.08511 (10)	0.0508 (4)
N4	0.39103 (11)	0.66406 (11)	0.03305 (8)	0.0346 (3)
N5	0.36603 (12)	0.72045 (11)	0.10833 (9)	0.0388 (3)
O1	0.15060 (15)	0.42096 (14)	0.08579 (11)	0.0790 (5)
O2	0.5000	0.7639 (2)	−0.2500	0.0618 (6)	0.80
H1	0.5068	0.7196	−0.2959	0.093*	0.80

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0326 (7)	0.0460 (8)	0.0320 (7)	0.0009 (6)	0.0109 (6)	−0.0009 (6)
C2	0.0514 (9)	0.0455 (9)	0.0367 (8)	0.0024 (7)	0.0195 (7)	0.0089 (7)
C3	0.0595 (10)	0.0394 (9)	0.0497 (9)	−0.0114 (7)	0.0260 (8)	0.0005 (7)
C4	0.0434 (8)	0.0345 (7)	0.0327 (7)	−0.0018 (6)	0.0153 (6)	0.0007 (6)
C5	0.0470 (9)	0.0483 (9)	0.0455 (9)	−0.0091 (7)	0.0221 (7)	0.0049 (7)
C6	0.0644 (11)	0.0709 (12)	0.0426 (9)	0.0104 (10)	0.0265 (9)	−0.0051 (9)
C7	0.0784 (15)	0.0916 (16)	0.0559 (12)	−0.0408 (13)	0.0204 (11)	−0.0244 (11)
N1	0.0507 (8)	0.0441 (7)	0.0390 (7)	−0.0160 (6)	0.0157 (6)	−0.0057 (6)
N2	0.0624 (9)	0.0490 (8)	0.0380 (7)	−0.0019 (7)	0.0247 (7)	−0.0020 (6)
N3	0.0572 (9)	0.0588 (9)	0.0451 (8)	−0.0025 (7)	0.0287 (7)	0.0055 (7)
N4	0.0393 (7)	0.0348 (6)	0.0332 (6)	−0.0042 (5)	0.0166 (5)	−0.0007 (5)
N5	0.0427 (7)	0.0383 (7)	0.0369 (6)	−0.0023 (5)	0.0154 (5)	−0.0066 (5)
O1	0.0913 (11)	0.0827 (11)	0.0718 (10)	−0.0466 (9)	0.0389 (9)	−0.0012 (8)
O2	0.0912 (18)	0.0554 (13)	0.0507 (13)	0.000	0.0395 (13)	0.000

C1—N5	1.2788 (19)	C5—N4	1.3610 (19)
C1—C6	1.488 (2)	C5—H5	0.9300
C1—C2	1.501 (2)	C6—H6A	0.9600
C2—C3	1.500 (2)	C6—H6B	0.9600
C2—H2A	0.9700	C6—H6C	0.9600
C2—H2B	0.9700	C7—N1	1.472 (2)
C3—O1	1.216 (2)	C7—H7A	0.9600
C3—N1	1.373 (2)	C7—H7B	0.9600
C4—N2	1.306 (2)	C7—H7C	0.9600
C4—N4	1.3632 (19)	N2—N3	1.397 (2)
C4—N1	1.383 (2)	N4—N5	1.4029 (17)
C5—N3	1.294 (2)	O2—H1	0.8745

N5—C1—C6	117.59 (15)	H6A—C6—H6B	109.5
N5—C1—C2	123.80 (14)	C1—C6—H6C	109.5
C6—C1—C2	118.61 (14)	H6A—C6—H6C	109.5
C3—C2—C1	111.08 (13)	H6B—C6—H6C	109.5
C3—C2—H2A	109.4	N1—C7—H7A	109.5
C1—C2—H2A	109.4	N1—C7—H7B	109.5
C3—C2—H2B	109.4	H7A—C7—H7B	109.5
C1—C2—H2B	109.4	N1—C7—H7C	109.5
H2A—C2—H2B	108.0	H7A—C7—H7C	109.5
O1—C3—N1	121.38 (17)	H7B—C7—H7C	109.5
O1—C3—C2	122.69 (16)	C3—N1—C4	122.68 (14)
N1—C3—C2	115.92 (14)	C3—N1—C7	119.17 (15)
N2—C4—N4	110.65 (13)	C4—N1—C7	117.80 (14)
N2—C4—N1	125.12 (14)	C4—N2—N3	106.54 (13)
N4—C4—N1	124.04 (13)	C5—N3—N2	107.42 (13)
N3—C5—N4	110.76 (15)	C5—N4—C4	104.61 (13)
N3—C5—H5	124.6	C5—N4—N5	123.08 (13)
N4—C5—H5	124.6	C4—N4—N5	131.27 (12)
C1—C6—H6A	109.5	C1—N5—N4	115.05 (13)
C1—C6—H6B	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···N3ⁱ	0.97	2.58	3.449 (3)	149
C5—H5···O1ⁱⁱ	0.93	2.29	3.211 (2)	173
O2—H1···N3ⁱⁱⁱ	0.87	2.08	2.939 (2)	167

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C2H2AN3ⁱ	0.97	2.58	3.449(3)	149
C5H5O1ⁱⁱ	0.93	2.29	3.211(2)	173
O2H1N3ⁱⁱⁱ	0.87	2.08	2.939(2)	167

Symmetry codes: (i) ; (ii) ; (iii) .

6 in total

1. Efficient and novel one-pot synthesis of antifungal active 1-substituted-8-aryl-3-alkyl/aryl-4H-pyrazolo[4,5-f][1,2,4]triazolo[4,3-b][1,2,4]triazepines using solid support.

Authors: Monika Gupta; Satya Paul; Rajive Gupta
Journal: Eur J Med Chem Date: 2010-12-08 Impact factor: 6.514

2. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

3. Heterocyclic system containing bridgehead nitrogen atom: synthesis and pharmacological activities of some substituted 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles.

Authors: V Mathew; J Keshavayya; V P Vaidya
Journal: Eur J Med Chem Date: 2006-07-05 Impact factor: 6.514