organic papers
Acta Cryst.(2005). E61, o2033–o2034 doi:10.1107/S1600536805017137 Wanget al. C
15H14N4O2H2O
o2033
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
4-(4-Methoxyphenyl)-3-methyl-5-(2-pyridyl)-4
H
-1,2,4-triazole dihydrate
Zuo-Xiang Wang,* Yan Lan, Lu-Tong Yuan and Chun-Yi Liu
Department of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People’s Republic of China
Correspondence e-mail: wangzx0908@yahoo.com.cn
Key indicators
Single-crystal X-ray study
T= 295 K
Mean(C–C) = 0.002 A˚
Rfactor = 0.048
wRfactor = 0.115
Data-to-parameter ratio = 15.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
In the title compound, C15H14N4O2H2O, the 1,2,4-triazole, pyridine and benzene rings do not share a common plane. The crystal structure is stabilized by O—H N and O—H O intermolecular hydrogen-bond interactions.
Comment
Substituted 1,2,4-triazoles have attracted considerable atten-tion in recent years (Benciniet al., 1987; Koningsbruggenet al., 1997; Molineret al., 1998; Klingele & Brooker, 2003). This is mainly because of the fact that their ligand strength is in the appropriate region to give spin-crossover complexes with iron(II) salts, which could be used as molecular-based memory devices, displays and optical switches (Garciaet al., 1997; Kahn & Martinez, 1998). We have synthesized a new compound, 4-(p-methoxyphenyl)-3-methyl-5-(2-pyridyl)-1,2,4-triazole, and we report here the crystal structure of its dihydrate, (I).
The three rings of (I) do not share a common plane. The dihedral angle between the 1,2,4-triazole and pyridine rings is 38.22 (9), and that between the 1,2,4-triazole and substituted benzene rings is 82.25 (6).
Two N atoms of the 1,2,4-triazole ring form intermolecular hydrogen bonds with the water molecules (Table 2). An additional strong hydrogen-bond interaction involving the water molecules is observed.
Experimental
The title compound was synthesized by the reaction of 4,40
-dimethoxyphenylphosphazoanilide with N-acetyl-N0
-(2-pyrido-yl)hydrazine in o-dichlorobenzene at 463–473 K (Grimmel et al., 1946; Klingsberg, 1958). Single crystals suitable for X-ray diffraction were obtained by recrystallization from water.
Crystal data
C15H14N4O2H2O
Mr= 302.33 Monoclinic,P21=c
a= 11.629 (3) A˚
b= 9.927 (2) A˚
c= 14.019 (3) A˚
= 106.897 (4)
V= 1548.5 (6) A˚3
Z= 4
Dx= 1.297 Mg m
3 MoKradiation Cell parameters from 793
reflections
= 3.1–25.1
= 0.09 mm1
T= 295 (2) K Block, yellow 0.310.220.20 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Bruker, 2000)
Tmin= 0.97,Tmax= 0.98 7967 measured reflections
3038 independent reflections 2217 reflections withI> 2(I)
Rint= 0.027
max= 26.0
h=14!14
k=6!12
l=17!16
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.048
wR(F2) = 0.115
S= 0.97 3038 reflections 201 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0683P)2 + 0.0126P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.16 e A˚
3 min=0.13 e A˚
3
Table 1
Selected geometric parameters (A˚ ,).
C6—N2 1.295 (2) C6—N1 1.379 (2) C7—N3 1.278 (2) C7—N1 1.374 (2)
C11—O1 1.361 (2) C15—O1 1.414 (2) N2—N3 1.396 (2)
N2—C6—N1 110.48 (14) N2—C6—C1 122.70 (15) N1—C6—C1 126.79 (15) N3—C7—N1 111.19 (15) N3—C7—C14 126.65 (15) N1—C7—C14 122.04 (15)
C7—N1—C6 103.61 (14) C7—N1—C8 126.22 (14) C6—N1—C8 130.10 (14) C6—N2—N3 107.09 (14) C7—N3—N2 107.60 (14)
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O2—H2D N3i
0.85 2.43 2.906 (2) 116 O3—H3B N2i
0.85 2.29 2.848 (2) 124 O2—H2C O3ii
0.85 2.06 2.783 (2) 143
Symmetry codes: (i)x;y1;z; (ii)x;yþ1 2;zþ
1 2.
All H atoms were located in a difference Fourier map and allowed to ride on their parent atoms at distances of 0.85 (O—H), 0.93 (C—H aromatic) and 0.96 A˚ (C—H methyl), withUiso(H) values of 1.2–1.5
timesUeqof the parent atoms.
Data collection:SMART(Bruker, 2000); cell refinement:SAINT (Bruker, 2000); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication:SHELXTL.
References
Bencini, A., Gatteschi, D., Zanchini, C., Haasnoot, J. G., Prins, R. & Reedijk, J. (1987).J. Am. Chem. Soc.109, 2926–2931.
Bruker (2000).SMART(Version 5.625),SAINT(Version 6.01),SHELXTL
(Version 6.10) andSADABS(Version 2.03). Bruker AXS Inc., Madison, Wisconsin, USA.
Garcia, Y., Koningsbruggen, P. J., Codjovi, E., Lapouyade, R., Kahn, O. & Rabardel, L. (1997).J. Mater. Chem.7, 857–858.
Grimmel, H. W., Guenther, A. & Morgan, J. F. (1946).J. Am. Chem. Soc.68, 539–542.
Kahn, O. & Martinez, C. J. (1998).Science,279, 44–48.
Klingele, M. H. & Brooker, S. (2003).Coord. Chem. Rew.241, 119–132. Klingsberg, E. (1958).J. Org. Chem.23, 1086–1087.
Koningsbruggen, P. J., Hassnoot, J. G., Kooijman, H., Reedijk, J. & Spek, A. L. (1997).Inorg. Chem.36, 2487–2489.
Moliner, N., Munoz, M. C., Koningsbruggen, P. J. & Real, J. A. (1998).Inorg. Chim. Acta,274, 1–6.
[image:2.610.314.567.72.235.2]Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
Figure 1
supporting information
sup-1
Acta Cryst. (2005). E61, o2033–o2034
supporting information
Acta Cryst. (2005). E61, o2033–o2034 [https://doi.org/10.1107/S1600536805017137]
4-(4-Methoxyphenyl)-3-methyl-5-(2-pyridyl)-4
H
-1,2,4-triazole dihydrate
Zuo-Xiang Wang, Yan Lan, Lu-Tong Yuan and Chun-Yi Liu
4-(4-Methoxyphenyl)-3-methyl-5-(2-pyridyl)-4H-1,2,4-triazole dihydrate
Crystal data
C15H14N4O·2H2O Mr = 302.33
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.629 (3) Å
b = 9.927 (2) Å
c = 14.019 (3) Å
β = 106.897 (4)°
V = 1548.5 (6) Å3
Z = 4
F(000) = 640
Dx = 1.297 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 793 reflections
θ = 3.1–25.1°
µ = 0.09 mm−1
T = 295 K
Block, yellow
0.31 × 0.22 × 0.20 mm
Data collection
Bruker SMART APEX CCD area-detector diffractometer
Radiation source: sealed tube Graphite monochromator φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2000) Tmin = 0.97, Tmax = 0.98
7967 measured reflections 3038 independent reflections 2217 reflections with I > 2σ(I) Rint = 0.027
θmax = 26.0°, θmin = 2.6°
h = −14→14
k = −6→12
l = −17→16
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.048 wR(F2) = 0.115
S = 0.97
3038 reflections 201 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-atom parameters constrained w = 1/[σ2(F
o2) + (0.0683P)2 + 0.0126P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.16 e Å−3 Δρmin = −0.13 e Å−3
Special details
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
C1 0.22833 (15) 1.02561 (18) 0.00021 (12) 0.0352 (4)
C2 0.14031 (17) 1.08828 (18) −0.07416 (12) 0.0393 (4)
H2 0.0675 1.1121 −0.0638 0.047*
C3 0.16146 (16) 1.11542 (18) −0.16445 (13) 0.0397 (4)
H3 0.1031 1.1579 −0.2152 0.048*
C4 0.26977 (17) 1.07894 (18) −0.17843 (13) 0.0404 (4)
H4 0.2858 1.0968 −0.2384 0.048*
C5 0.35391 (17) 1.01550 (19) −0.10162 (13) 0.0397 (4)
H5 0.4266 0.9906 −0.1117 0.048*
C6 0.21045 (15) 0.99934 (17) 0.09708 (12) 0.0340 (4)
C7 0.20174 (15) 0.90787 (17) 0.23488 (12) 0.0349 (4)
C8 0.30703 (15) 0.76918 (17) 0.13809 (12) 0.0344 (4)
C9 0.24634 (16) 0.66852 (17) 0.07924 (12) 0.0363 (4)
H9 0.1647 0.6788 0.0473 0.044*
C10 0.30350 (15) 0.55065 (17) 0.06571 (13) 0.0364 (4)
H10 0.2606 0.4819 0.0258 0.044*
C11 0.42424 (16) 0.53663 (18) 0.11190 (13) 0.0389 (4)
C12 0.48557 (16) 0.63860 (17) 0.17119 (13) 0.0365 (4)
H12 0.5673 0.6287 0.2029 0.044*
C13 0.42917 (15) 0.75344 (17) 0.18435 (13) 0.0354 (4)
H13 0.4723 0.8218 0.2244 0.043*
C14 0.21062 (16) 0.80429 (18) 0.31344 (12) 0.0360 (4)
H14A 0.1651 0.8329 0.3570 0.054*
H14B 0.2933 0.7928 0.3512 0.054*
H14C 0.1792 0.7203 0.2828 0.054*
C15 0.42748 (17) 0.31490 (18) 0.04835 (14) 0.0409 (4)
H15A 0.3825 0.2709 0.0869 0.061*
H15B 0.4842 0.2527 0.0352 0.061*
H15C 0.3736 0.3453 −0.0136 0.061*
N1 0.24568 (13) 0.88606 (15) 0.15523 (10) 0.0346 (3)
N2 0.15425 (14) 1.08210 (15) 0.13926 (11) 0.0390 (4)
N3 0.14852 (13) 1.02171 (15) 0.22771 (10) 0.0384 (3)
N4 0.33564 (12) 0.98628 (14) −0.01134 (10) 0.0352 (3)
O1 0.48953 (11) 0.42649 (12) 0.10208 (9) 0.0416 (3)
O2 0.02270 (14) 0.08536 (13) 0.37332 (11) 0.0545 (4)
H2D 0.0293 0.1283 0.3227 0.065*
H2C 0.0233 0.1406 0.4198 0.082*
O3 0.06182 (14) 0.34200 (13) 0.07192 (11) 0.0527 (4)
H3B 0.1137 0.3079 0.1218 0.063*
supporting information
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Acta Cryst. (2005). E61, o2033–o2034
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0384 (9) 0.0360 (9) 0.0325 (9) −0.0038 (7) 0.0124 (7) 0.0003 (7)
C2 0.0446 (10) 0.0421 (10) 0.0316 (9) −0.0011 (8) 0.0119 (8) −0.0021 (7)
C3 0.0438 (10) 0.0408 (9) 0.0320 (9) 0.0025 (8) 0.0073 (7) 0.0016 (7)
C4 0.0560 (11) 0.0377 (9) 0.0293 (9) 0.0001 (8) 0.0153 (8) 0.0004 (7)
C5 0.0465 (9) 0.0436 (10) 0.0313 (9) −0.0029 (8) 0.0147 (7) 0.0021 (8)
C6 0.0408 (9) 0.0341 (9) 0.0305 (8) 0.0021 (7) 0.0156 (7) 0.0029 (7)
C7 0.0422 (9) 0.0354 (9) 0.0313 (8) 0.0020 (7) 0.0174 (7) −0.0001 (7)
C8 0.0430 (9) 0.0352 (9) 0.0287 (8) −0.0011 (7) 0.0161 (7) 0.0001 (7)
C9 0.0417 (9) 0.0367 (9) 0.0318 (9) −0.0041 (7) 0.0125 (7) −0.0001 (7)
C10 0.0408 (9) 0.0320 (9) 0.0365 (9) −0.0061 (7) 0.0114 (7) −0.0049 (7)
C11 0.0473 (10) 0.0336 (9) 0.0363 (10) 0.0009 (8) 0.0127 (8) 0.0010 (7)
C12 0.0431 (10) 0.0321 (8) 0.0352 (9) 0.0007 (7) 0.0130 (7) −0.0011 (7)
C13 0.0391 (9) 0.0314 (8) 0.0358 (9) −0.0038 (7) 0.0110 (7) −0.0012 (7)
C14 0.0429 (9) 0.0398 (9) 0.0301 (9) 0.0012 (7) 0.0180 (7) 0.0006 (7)
C15 0.0491 (10) 0.0309 (9) 0.0445 (10) 0.0011 (8) 0.0164 (8) −0.0052 (7)
N1 0.0417 (8) 0.0354 (7) 0.0301 (7) 0.0000 (6) 0.0155 (6) 0.0005 (6)
N2 0.0508 (8) 0.0343 (8) 0.0352 (8) 0.0035 (7) 0.0176 (7) −0.0004 (6)
N3 0.0504 (8) 0.0369 (8) 0.0322 (8) 0.0008 (7) 0.0186 (6) −0.0031 (6)
N4 0.0426 (8) 0.0342 (8) 0.0328 (8) −0.0021 (6) 0.0171 (6) −0.0005 (6)
O1 0.0503 (7) 0.0324 (7) 0.0403 (7) −0.0003 (5) 0.0102 (6) 0.0004 (5)
O2 0.0815 (10) 0.0385 (7) 0.0486 (8) 0.0095 (7) 0.0269 (7) −0.0004 (6)
O3 0.0656 (9) 0.0363 (7) 0.0560 (9) 0.0154 (6) 0.0173 (7) −0.0002 (6)
Geometric parameters (Å, º)
C1—N4 1.361 (2) C9—H9 0.9300
C1—C2 1.379 (2) C10—C11 1.372 (3)
C1—C6 1.456 (2) C10—H10 0.9300
C2—C3 1.384 (2) C11—O1 1.361 (2)
C2—H2 0.9300 C11—C12 1.371 (2)
C3—C4 1.378 (3) C12—C13 1.354 (2)
C3—H3 0.9300 C12—H12 0.9300
C4—C5 1.379 (3) C13—H13 0.9300
C4—H4 0.9300 C14—H14A 0.9600
C5—N4 1.374 (2) C14—H14B 0.9600
C5—H5 0.9300 C14—H14C 0.9600
C6—N2 1.295 (2) C15—O1 1.414 (2)
C6—N1 1.379 (2) C15—H15A 0.9600
C7—N3 1.278 (2) C15—H15B 0.9600
C7—N1 1.374 (2) C15—H15C 0.9600
C7—C14 1.488 (2) N2—N3 1.396 (2)
C8—C9 1.356 (2) O2—H2D 0.8500
C8—C13 1.388 (2) O2—H2C 0.8500
C8—N1 1.419 (2) O3—H3B 0.8500
N4—C1—C2 122.96 (16) O1—C11—C12 116.57 (15)
N4—C1—C6 116.36 (15) O1—C11—C10 123.95 (16)
C2—C1—C6 120.68 (16) C12—C11—C10 119.47 (17)
C1—C2—C3 119.28 (17) C13—C12—C11 121.12 (17)
C1—C2—H2 120.4 C13—C12—H12 119.4
C3—C2—H2 120.4 C11—C12—H12 119.4
C4—C3—C2 119.44 (17) C12—C13—C8 120.09 (16)
C4—C3—H3 120.3 C12—C13—H13 120.0
C2—C3—H3 120.3 C8—C13—H13 120.0
C3—C4—C5 118.65 (17) C7—C14—H14A 109.5
C3—C4—H4 120.7 C7—C14—H14B 109.5
C5—C4—H4 120.7 H14A—C14—H14B 109.5
N4—C5—C4 123.45 (17) C7—C14—H14C 109.5
N4—C5—H5 118.3 H14A—C14—H14C 109.5
C4—C5—H5 118.2 H14B—C14—H14C 109.5
N2—C6—N1 110.48 (14) O1—C15—H15A 109.5
N2—C6—C1 122.70 (15) O1—C15—H15B 109.5
N1—C6—C1 126.79 (15) H15A—C15—H15B 109.5
N3—C7—N1 111.19 (15) O1—C15—H15C 109.5
N3—C7—C14 126.65 (15) H15A—C15—H15C 109.5
N1—C7—C14 122.04 (15) H15B—C15—H15C 109.5
C9—C8—C13 118.83 (16) C7—N1—C6 103.61 (14)
C9—C8—N1 120.48 (15) C7—N1—C8 126.22 (14)
C13—C8—N1 120.63 (15) C6—N1—C8 130.10 (14)
C8—C9—C10 121.33 (16) C6—N2—N3 107.09 (14)
C8—C9—H9 119.3 C7—N3—N2 107.60 (14)
C10—C9—H9 119.3 C1—N4—C5 116.21 (15)
C11—C10—C9 119.14 (16) C11—O1—C15 118.03 (14)
C11—C10—H10 120.4 H2D—O2—H2C 109.5
C9—C10—H10 120.4 H3B—O3—H3C 109.5
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O2—H2D···N3i 0.85 2.43 2.906 (2) 116
O3—H3B···N2i 0.85 2.29 2.848 (2) 124
O2—H2C···O3ii 0.85 2.06 2.783 (2) 143