6H-Dipyrido[1,2-a:2′,1′-d][1,3,5]triazin-5-ium bromide monohydrate

Jiang, X.-W.; Zhang, H.-Q.; Sun, Z.-D.; Shan, Y.-K.

doi:10.1107/S2414314616001802

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160180

https://doi.org/10.1107/S2414314616001802

Open

access

6H-Dipyrido[1,2-a:2′,1′-d][1,3,5]triazin-5-ium bromide monohydrate

Xian-Wu Jiang,^a Heng-Qiang Zhang,^b Zhuo-Dong Sun ^a and Yong-Kui Shan ^a ^*

^aSchool of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, People's Republic of China, and ^bDepartment of Chemistry, Hebei Normal University for Nationalities, Chengde 067000, People's Republic of China
^*Correspondence e-mail: ykshan@chem.ecnu.edu.cn

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 25 January 2016; accepted 29 January 2016; online 10 February 2016)

In the cation of the title compound, C₁₁H₁₀N₃⁺·Br⁻·H₂O, the central 1,3,5-triazinium ring has a flattened boat conformation and the outer heterocyclic rings are nearly planar [maximum deviations = 0.010 (4) and 0.009 (4) Å] and twisted with respect to each other with a dihedral angle of 22.87 (19)°. In the crystal, classical O—H⋯Br hydrogen bonds and weak C—H⋯Br and C—H⋯O hydrogen bonds link the cations, bromide anions and water molecules of crystallization into a three-dimensional supramolecular network.

Keywords: crystal structure; salt; dipyridotriazinium; bromide; hydrogen bonding.

CCDC reference: 1450784

Structure description

N-Heterocyclic carbene ligands (NHC) have been shown to have wide applicability in co ordination chemistry and catalysis (Lee et al., 2004 ). The preparation of chelating bis(NHC) ligands is also receiving much attention, since they can provide additional air and moisture stability for the metal centers (Lee & Cheng, 2010 ). Knowledge of the crystal structure of such benzoicacid derivatives gives us not only information about nuclearity of the complex molecule, but is important in understanding the behaviour of these compounds with respect to the mechanisms of pharmacological activities and physiological activities (Niu et al., 2008 ). Therefore, we have synthesized the title compound, (I), and report its crystal structure here.

The molecular structure of (I) is shown in Fig. 1, the compound crystallized with a structural configuration in which the pyridine ring (C1–C5/N3) is twisted by a dihedral angle of 10.92 (4)° with respect to a plane defined by the azacyanine ring (N1–C5–N3–C6–N2–C7). In the crystal, classical O—H⋯Br hydrogen bonds and weak C—H⋯Br and C—H⋯O hydrogen bonds (Table 1 link the cations, bromide anions and water molecules of crystallization into a three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯Br1	0.85 (5)	2.67 (4)	3.423 (4)	147 (4)
O1—H2W⋯Br1ⁱ	0.84 (3)	2.52 (3)	3.346 (4)	169 (3)
C1—H1⋯Br1ⁱ	0.93	2.81	3.704 (4)	161
C3—H3⋯Br1ⁱⁱ	0.93	2.89	3.714 (4)	149
C10—H10⋯O1ⁱⁱⁱ	0.93	2.57	3.353 (6)	143
C11—H11⋯O1	0.93	2.46	3.326 (7)	155
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x-1, y-1, z; (iii) -x+2, -y+1, -z+1.

Figure 1
The molecular structure of (I), with displacement ellipsoids shown at the 30% probability level.

Synthesis and crystallization

A mixture of 2-aminopyridine (1.0 g, 0.01 mol) and dibromomethane (15 ml, 0.2 mol) was added to a flask (100 ml) and was stirred at 366 K in an oil bath for 3 h. The progress of the reaction was monitored by detecting NH₃ released from the reaction system using wet pH paper. The reaction mixture was treated by reduced pressure distillation to remove the unreacted dibromomethane. The resulting pale-yellow powder was washed with 30 ml of propanone.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₃⁺·Br⁻·H₂O
M_r	282.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.4965 (5), 11.9528 (10), 17.7702 (18)
β (°)	95.354 (3)
V (Å³)	1162.38 (19)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.52
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.465, 0.532
No. of measured, independent and observed [I > 2σ(I)] reflections	12145, 1995, 1446
R_int	0.131
(sin θ/λ)_max (Å⁻¹)	0.589

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.088, 1.02
No. of reflections	1990
No. of parameters	153
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.35
Computer programs: APEX2 (Bruker, 2014), SAINT (Bruker, 2014), XPREP (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012 ), XCIF (Sheldrick, 2008).

Structural data

CCDC reference: 1450784

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314616001802/xu4001sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001802/xu4001Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616001802/xu4001Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT and XPREP (Bruker, 2014); 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: XCIF (Sheldrick, 2008).

6H-Dipyrido[1,2-a:2',1'-d][1,3,5]triazin-5-ium bromide monohydrate top

Crystal data top

C₁₁H₁₀N₃⁺·Br⁻·H₂O	F(000) = 568
M_r = 282.14	D_x = 1.612 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 5.4965 (5) Å	Cell parameters from 2457 reflections
b = 11.9528 (10) Å	θ = 2.3–23.1°
c = 17.7702 (18) Å	µ = 3.52 mm⁻¹
β = 95.354 (3)°	T = 296 K
V = 1162.38 (19) Å³	Block, yellow
Z = 4	0.22 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD diffractometer	1995 independent reflections
Radiation source: fine-focus sealed tube	1446 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.131
phi and ω scans	θ_max = 24.7°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −6→6
T_min = 0.465, T_max = 0.532	k = −14→13
12145 measured reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.035P)² + 0.0521P] where P = (F_o² + 2F_c²)/3
1990 reflections	(Δ/σ)_max = 0.001
153 parameters	Δρ_max = 0.36 e Å⁻³
3 restraints	Δρ_min = −0.35 e Å⁻³

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 > 2sigma(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	U_iso*/U_eq
Br1	0.93554 (8)	0.66573 (3)	0.26282 (2)	0.04207 (17)
C1	0.5912 (8)	0.0190 (3)	0.3352 (2)	0.0397 (11)
H1	0.7233	0.0375	0.3085	0.048*
C2	0.4882 (8)	−0.0834 (3)	0.3270 (3)	0.0473 (12)
H2	0.5507	−0.1368	0.2960	0.057*
C3	0.2855 (8)	−0.1071 (3)	0.3663 (3)	0.0444 (11)
H3	0.2094	−0.1764	0.3600	0.053*
C4	0.1982 (7)	−0.0316 (3)	0.4131 (2)	0.0369 (10)
H4	0.0655	−0.0500	0.4395	0.044*
C5	0.3060 (7)	0.0751 (3)	0.4225 (2)	0.0303 (9)
C6	0.5855 (8)	0.2109 (3)	0.3795 (2)	0.0353 (10)
H6A	0.7528	0.2125	0.3663	0.042*
H6B	0.4843	0.2518	0.3412	0.042*
C7	0.3739 (7)	0.2364 (3)	0.4914 (2)	0.0302 (9)
C8	0.3438 (8)	0.3013 (3)	0.5566 (2)	0.0370 (10)
H8	0.2089	0.2889	0.5834	0.044*
C9	0.5064 (8)	0.3803 (3)	0.5803 (3)	0.0427 (11)
H9	0.4842	0.4212	0.6236	0.051*
C10	0.7098 (8)	0.4018 (3)	0.5402 (3)	0.0456 (11)
H10	0.8238	0.4559	0.5571	0.055*
C11	0.7370 (8)	0.3432 (3)	0.4771 (3)	0.0391 (10)
H11	0.8696	0.3576	0.4496	0.047*
H1W	0.978 (11)	0.454 (3)	0.311 (3)	0.14 (3)*
H2W	1.068 (9)	0.351 (2)	0.305 (2)	0.067 (17)*
N1	0.2284 (6)	0.1499 (3)	0.47091 (19)	0.0346 (8)
N2	0.5713 (5)	0.2625 (2)	0.45281 (19)	0.0288 (8)
N3	0.5015 (5)	0.0957 (2)	0.38257 (18)	0.0291 (8)
O1	1.0672 (10)	0.4049 (3)	0.3351 (2)	0.0842 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0455 (3)	0.0433 (3)	0.0378 (3)	−0.0017 (2)	0.00566 (19)	−0.0088 (2)
C1	0.037 (2)	0.046 (3)	0.038 (3)	0.003 (2)	0.010 (2)	−0.002 (2)
C2	0.050 (3)	0.043 (3)	0.050 (3)	0.009 (2)	0.006 (2)	−0.010 (2)
C3	0.046 (3)	0.031 (2)	0.054 (3)	−0.004 (2)	−0.006 (2)	0.003 (2)
C4	0.031 (2)	0.038 (2)	0.042 (3)	−0.0063 (19)	0.004 (2)	0.0038 (19)
C5	0.025 (2)	0.038 (2)	0.028 (2)	−0.0028 (17)	0.0021 (18)	0.0053 (18)
C6	0.038 (2)	0.038 (2)	0.031 (2)	−0.0105 (19)	0.010 (2)	0.0017 (18)
C7	0.028 (2)	0.033 (2)	0.030 (2)	0.0051 (18)	0.0036 (18)	0.0027 (17)
C8	0.035 (2)	0.038 (2)	0.037 (3)	0.0067 (19)	0.004 (2)	−0.0009 (18)
C9	0.053 (3)	0.037 (2)	0.037 (3)	0.010 (2)	−0.001 (2)	−0.012 (2)
C10	0.047 (3)	0.036 (2)	0.051 (3)	−0.005 (2)	−0.012 (2)	−0.004 (2)
C11	0.037 (2)	0.032 (2)	0.048 (3)	−0.005 (2)	0.002 (2)	0.003 (2)
N1	0.0292 (18)	0.0397 (19)	0.036 (2)	−0.0064 (15)	0.0086 (16)	−0.0057 (16)
N2	0.0267 (18)	0.0277 (16)	0.033 (2)	−0.0011 (14)	0.0062 (15)	0.0006 (14)
N3	0.0251 (17)	0.0322 (18)	0.0305 (19)	−0.0007 (14)	0.0043 (15)	−0.0003 (14)
O1	0.146 (4)	0.051 (2)	0.055 (3)	−0.005 (3)	0.008 (3)	−0.005 (2)

Geometric parameters (Å, º) top

C1—C2	1.351 (6)	C6—H6B	0.9700
C1—N3	1.367 (4)	C7—N1	1.337 (5)
C1—H1	0.9300	C7—N2	1.373 (4)
C2—C3	1.398 (5)	C7—C8	1.416 (5)
C2—H2	0.9300	C8—C9	1.340 (6)
C3—C4	1.345 (5)	C8—H8	0.9300
C3—H3	0.9300	C9—C10	1.404 (6)
C4—C5	1.410 (5)	C9—H9	0.9300
C4—H4	0.9300	C10—C11	1.343 (6)
C5—N1	1.338 (5)	C10—H10	0.9300
C5—N3	1.364 (4)	C11—N2	1.368 (5)
C6—N2	1.450 (5)	C11—H11	0.9300
C6—N3	1.455 (5)	O1—H1W	0.851 (10)
C6—H6A	0.9700	O1—H2W	0.844 (10)

C2—C1—N3	120.1 (4)	N1—C7—C8	122.3 (3)
C2—C1—H1	119.9	N2—C7—C8	116.3 (4)
N3—C1—H1	119.9	C9—C8—C7	121.1 (4)
C1—C2—C3	118.4 (4)	C9—C8—H8	119.4
C1—C2—H2	120.8	C7—C8—H8	119.4
C3—C2—H2	120.8	C8—C9—C10	120.6 (4)
C4—C3—C2	121.3 (4)	C8—C9—H9	119.7
C4—C3—H3	119.4	C10—C9—H9	119.7
C2—C3—H3	119.4	C11—C10—C9	118.9 (4)
C3—C4—C5	120.7 (4)	C11—C10—H10	120.5
C3—C4—H4	119.7	C9—C10—H10	120.5
C5—C4—H4	119.7	C10—C11—N2	120.6 (4)
N1—C5—N3	121.9 (3)	C10—C11—H11	119.7
N1—C5—C4	121.7 (3)	N2—C11—H11	119.7
N3—C5—C4	116.4 (3)	C7—N1—C5	118.3 (3)
N2—C6—N3	109.0 (3)	C11—N2—C7	122.4 (3)
N2—C6—H6A	109.9	C11—N2—C6	119.6 (3)
N3—C6—H6A	109.9	C7—N2—C6	117.6 (3)
N2—C6—H6B	109.9	C5—N3—C1	123.1 (3)
N3—C6—H6B	109.9	C5—N3—C6	117.3 (3)
H6A—C6—H6B	108.3	C1—N3—C6	118.5 (3)
N1—C7—N2	121.3 (3)	H1W—O1—H2W	103.9 (17)

N3—C1—C2—C3	1.8 (7)	C10—C11—N2—C6	171.8 (4)
C1—C2—C3—C4	−2.1 (7)	N1—C7—N2—C11	−173.2 (4)
C2—C3—C4—C5	1.5 (7)	C8—C7—N2—C11	2.8 (5)
C3—C4—C5—N1	−177.3 (4)	N1—C7—N2—C6	14.0 (5)
C3—C4—C5—N3	−0.7 (6)	C8—C7—N2—C6	−170.1 (4)
N1—C7—C8—C9	173.2 (4)	N3—C6—N2—C11	148.2 (3)
N2—C7—C8—C9	−2.7 (6)	N3—C6—N2—C7	−38.8 (5)
C7—C8—C9—C10	0.9 (7)	N1—C5—N3—C1	177.1 (4)
C8—C9—C10—C11	1.0 (7)	C4—C5—N3—C1	0.5 (6)
C9—C10—C11—N2	−1.0 (6)	N1—C5—N3—C6	−15.1 (6)
N2—C7—N1—C5	13.9 (6)	C4—C5—N3—C6	168.3 (4)
C8—C7—N1—C5	−161.9 (4)	C2—C1—N3—C5	−1.1 (7)
N3—C5—N1—C7	−13.3 (6)	C2—C1—N3—C6	−168.7 (4)
C4—C5—N1—C7	163.2 (4)	N2—C6—N3—C5	39.3 (5)
C10—C11—N2—C7	−1.0 (6)	N2—C6—N3—C1	−152.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Br1	0.85 (5)	2.67 (4)	3.423 (4)	147 (4)
O1—H2W···Br1ⁱ	0.84 (3)	2.52 (3)	3.346 (4)	169 (3)
C1—H1···Br1ⁱ	0.93	2.81	3.704 (4)	161
C3—H3···Br1ⁱⁱ	0.93	2.89	3.714 (4)	149
C10—H10···O1ⁱⁱⁱ	0.93	2.57	3.353 (6)	143
C11—H11···O1	0.93	2.46	3.326 (7)	155

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x−1, y−1, z; (iii) −x+2, −y+1, −z+1.

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (No. 21303058), the Shanghai Municipal Natural Science Foundation (No. 13ZR1412400), the key project of the Shanghai Science and Technology Committee (No. 11JC1403400; 14231200300) and the program for the Outstanding Young-aged Innovative Talents of Higher Learning Institutions of Hebei Province (No. BJ201404).

References

Bruker (2014). APEX2, SADABS, SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Lee, H. M. & Cheng, P.-Y. (2010). Acta Cryst. E66, o2308. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, H.-M., Lu, C.-Y., Chen, C.-Y., Chen, W.-L., Lin, H.-C., Chiu, P.-L. & Cheng, P.-Y. (2004). Tetrahedron, 60, 5807–5825. Web of Science CSD CrossRef CAS Google Scholar
Niu, Y.-Y., Wu, B.-L., Guo, X.-L., Song, Y.-L., Liu, X.-C., Zhang, H.-Y., Hou, H.-W., Niu, C.-Y. & Ng, S.-W. (2008). Cryst. Growth Des. 8, 2393–2401. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160180

https://doi.org/10.1107/S2414314616001802

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6H-Dipyrido[1,2-a:2′,1′-d][1,3,5]triazin-5-ium bromide monohydrate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds