CC BY
9DOI: 10.6060/tcct.2017601.5483
Для цитирования:
Бутина Ю.В., Данилова Е.А., Дмитриев М.В., Соломонов А.В. Кристаллическая структура бис[(диаминометил-1-ен)аминотиометиламмоний] сульфата. Изв. вузов. Химия и хим. технология. 2017. Т. 60. Вып. 1. С. 45-49. For citation:
Butina Yu.V., Danilova E.A., Dmitriev M.V., Solomonov А^. Crystal structure of bis[1-(diaminomethylene)-thiouron-1-ium] sulfate. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 1. P. 45-49.
УДК: 548-1
Ю.В. Бутина, Е.А. Данилова, М.В. Дмитриев, А.В. Соломонов
Юлия Валентиновна Бутина, Елена Адольфовна Данилова (ЕЗ)
Кафедра технологии тонкого органического синтеза, Ивановский государственный химико-технологический университет, просп. Шереметевский, 7, Иваново, Российская Федерация, 153000 E-mail: danilova@isuct.ru (М)
Максим Викторович Дмитриев
Кафедра органической химии, Пермский государственный национальный исследовательский университет, ул. Букирева, 15, Пермь, Российская Федерация, 614990 E-mail: maxperm@yandex.ru
Алексей Владимирович Соломонов
Weizmann Institute of Science, Herzl st., 234, Rehovot, 76000, Israel E-mail: deus-lex@yandex.ru
КРИСТАЛЛИЧЕСКАЯ СТРУКТУРА БИС[(ДИАМИНОМЕТИЛ-1-ЕН)АМИНОТИО-
МЕТИЛАММОНИЙ] СУЛЬФАТА
В данной работе представлены данные рентгеноструктурного анализа монокристалла бис[(диаминометил-1-ен)аминотиометиламмоний] сульфата, образующегося на промежуточной стадии синтеза 2-имино-4-тиобиурета. Полученный продукт охарактеризован методами ИК спектроскопии и элементного анализа. Кроме того, описаны потенциальные области применения синтезированного соединения. Структурные характеристики соединения находятся в соответствии с таковыми для тиомочевины и ее ранее изученных солей. Известно, что производные тиомочевины существуют в нескольких таутомерных формах, состояние которых в кристаллическом виде часто отличается от состояния в растворе. Так как промежуточный продукт на стадии синтеза 2-имино-4-тиобиурета выделяется в виде кристаллического порошка, а не остается в растворе, предложена измененная схема синтеза. Элементарная ячейка состоит из двух неплоских катионов 1-(диаминометилен)тиомочевины и сульфат-аниона. Полный набор рентгеноструктурных данных депонирован в Кембриджский банк структурных данных (депонент CCDC 1421710) и может быть свободно получен по запросу на сайте www.ccdc.cam.ac.uk/data_request/cif.
Ключевые слова: бис[(диаминометил-1-ен)аминотиометиламмоний] сульфат, тиомочевина, рентгеноструктурный анализ
UDC: 548-1
Yu.V. Butina, E.A. Danilova, M.V. Dmitriev, A.V. Solomonov
Yuliya V. Butina, Elena A. Danilova (E3)
Department of Fine Organic Synthesis, Ivanovo State University of Chemistry and Technology, Shere-
metievskiy ave., 7, Ivanovo, 153000, Russia
E-mail: danilova@isuct.ru (M)
Maxim V. Dmitriev
Department of Organic Chemistry, Perm State University, Bukireva st., 15, Perm, 614990, Russia
E-mail: maxperm@yandex.ru
Aleksey V. Solomonov
Weizmann Institute of Science, Herzl st., 234, Rehovot, 76000, Israel
E-mail: deus-lex@yandex.ru
CRYSTAL STRUCTURE OF BIS[1-(DIAMINOMETHYLENE)-THIOURON-1-IUM] SULFATE
In this work crystal data of bis[1-(diaminomethylene)-thiouron-1-ium] sulfate is shown. This compound was characterized by IR spectroscopy and elemental analysis. The monocrystal of this compound was obtained and the structure was confirmed by single X-ray analysis. Moreover, the work describes potential application of synthesized compound. Comparative characteristics of thiourea and its known salts are demonstrated. It is known, that derivatives of thiourea have several tautomeric forms, which can be different in crystalline state or in solution. Therefore, changed scheme of the synthesis of 2-imino-4-thiobiuret is proposed. Elemental cell of crystal consists of two 1-(diaminomethylene)thiouron-1-ium cations and one sulfat anion. A full set of X-ray diffraction data was deposited in the Cambridge Structural Database (deposit CCDC 1421710) and it can be gotten from the site www.ccdc.cam.ac.uk/data_request/cif.
Key words: bis[1-(diaminomethylene)-thiouron-1-ium] sulfate, thiourea, X-ray analysis
INTRODUCTION
1-(Diaminomethylene)thiourea (1) and its imino tautomer, namely 2-imino-4-thiobiuret (2) (Scheme 1), have several potential coordination modes and can form complexes with metal ions [1]. Compound 1 is organic ligand with multiple coordination sites, which can be used as building units for formation highly ordered supramolecular compounds with predetermined structure and properties [2].
H,N'
NH2 nh2
I I
N
1
NH NH2
, II I
H
2
Scheme 1. Tautomeric forms of 1 -(diaminomethylene)thiourea Схема 1. Таутомерные формы 1 -(диаминомегилен)тио-мочевины
H
I
NH, S
SOd2"
S
3
Fig. 1. Structure of bis[1-(diaminomethy-lene)thiouron-1-ium] sulfate
Рис. 1. Структура бис[(диаминометил-1-ен)аминотио-метиламмоний] сульфата
This property is a result of the presence of donor atoms (N and S) bearing lone pair electrons [3]. It is known, that N,N-coordination is characteristic for basic solution and S,N-coordination was observed in neutral and weakly acid media [4]. 1-(Diaminomethy-lene)thiourea forms salts both with inorganic and with organic acids. For example, the authors [2] published X-ray data of bis[1-(diaminomethylene)-thiouron-1-
ium] tetrachlorozincate. The crystal structures of several salts of 1 -(diaminomethylene)thiourea are known, namely chloride, bromide, iodide [5], perchlorate, hydrogen sulfate, dihydrogen phosphate, dihydrogen arsenate [6], hydrogen difluoride, hexafluorsilicate [7], formate and oxalate dehydrate [8]. In this article,
the crystal structure of bis[1-(diaminomethylene)thio-uron-1-ium] sulfate (3) is described for the first time (Fig. 1).
The authors [9] proposed new method of synthesis of 2 according to Scheme 2.
H2N—C—NH—C=N + Na2S203 + HzO + 2H2S04-— H2N—С—NH—С—nTh3 HSOi + 2NaHS04
NH NH S
4
H,N—С—NH—С—iÎH, HSO;+ NaOH-— H2N—C—NH—C—NH2+ NaHS04 + H20
II 'I N M
NH S NH S
2
Scheme 2. The synthesis of 2-immo-4-thiobiuret Схема 2. Синтез 2-имино-4-тиобиурета
It is known that substances having tautomeric transformations can have one state in crystalline form and other state in solution, so authors [9] expected that the formation of 2-imino-4-thiobiuret occurs through obtaining of 1-(diaminomethylene)thiourea hydrogen sulfate (4). However, we obtained the single crystal of compound formed on intermediate step of synthesis of compound 2.
EXPERIMENTAL PART
IR spectra were measured with an AVATAR 360 FT-IR spectrometer. X-Ray analysis were carried out with the monocrystal automatic diffractometer Xcalibur R with CCD-detector by standard method.
Crystal of 2C2H7N4S+ SO42" 3 was obtained from dicyandiamide (8.4 g, 0.1 mol) and sodium thio-sulfate pentahydrate (27.3 g, 0.11 mol). This mixture was dissolved in water (50 mL) under heating and then 25% sulfuric acid (36.6 mL, 0.11 mol) was added by dropwise. Reaction mixture was heated to 80°C and stirred at this temperature during 5 hours. Formed sulphur was removed by the method of hot filtration. After several days at room temperature, crystals of 3 were obtained. Yield: 14.14 g (86%). Tmit = 190-192 °C. IR: v (KBr)/cm-1: 3394 (NH2, vas), 3309 (NH2, vs), 3196, 2809, 1700 (C=N), 1631 (NH2, d), 1601, 1513, 1339, 1199 (C-N, aliph), 1109 (C=S), 1085 (S=O), 835, 750, 663, 636, 612, 545, 511, 445, 427. Found, %: C 14.41, H 4.28, N 31.97, S 28.61. C4H14N8O4S3. Calc., %: C 14.37, H 4.22, N 33.51, S 28.77.
H atoms were located in difference Fourier maps and refined with isotropic displacement parameters. The N-H distances were fixed at 0.86 (2) A using DFIX restraint. Crystal data was obtained using of computer programs: CrysAlis PRO [10], SHELXS97 [11], SHELXL97 [11], Mercury [12], publCIF [13]. A full set of X-ray diffraction data was
deposited in the Cambridge Structural Database (deposit CCDC 1421710).
RESULTS AND DISCUSSION
X-ray analysis of monocrystal 3 shown that the elemental cell contains two nonplanar 1 -(diamino-methylene)thiouron-1-ium cations and the sulfate anion linked together via N-H--O hydrogen bonds, which were formed by H atom of amino-group 1 and O atom of sulfate anion (Fig. 2).
S2Cf
Fig. 2. Fragment of crystal packing of 3 Рис. 2. Фрагмент кристаллической упаковки 3
Fig. 3. The molecular structure of the elemental cell of 3 Рис. 3. Молекулярная структура элементарной ячейки 3
The compound 3 constructed by two crystal-lographic independent cations and one anion is crystallized in centrosymmetric space group of triclinic crystal system (Fig. 3).
Sulfate-anion represents slightly distorted tetrahedron, which is typical for structures of this type. As in other salts of 1-(diaminomethylene)thiourea [6], cations consist of two planar parts twisted about each other. The dihedral angle between the mean least-squares planes of fragments N1C2N2N3 and N3C1N4S2 is 12.0°, the angle between fragments N5C3N6N7 and N7C4N8S3 is 10.2°. Double bonds C2=N3 and C3=N7 (Table) are elongated significantly and single bonds C2-N1, C2-N2, C3-N5, C3-N6 are shortened comparing with neutral molecule [1].
The C1=S2, C4=S3 bond lengths in 3 are comparable to those in thiourea (where the C=S distance is 1.683 Á) [14] and in other salts of 1-(diaminomethylene)thiourea, such as the perchlorate and the dihydrogen arsenate [6]. However, these double bonds are shortened significantly comparing with
neutral molecule [1]. Such redistribution bond length indicates delocalization of the positive charge of cations between the nitrogen atoms of the amino groups.
Table 1
Selected geometric parameters (A) for 3 Таблица 1. Избранные геометрические параметры (А) 3
bond length bond length
S2-C1 1.667 (2) S3-C4 1.662 (2)
C1-N3 1.375 (2) N7-C3 1.358 (3)
C1-N4 1.326 (2) N7-C4 1.383 (2)
N3-C2 1.366 (2) N6-C3 1.305 (2)
C2-N1 1.302 (2) N5-C3 1.314 (2)
C2-N2 1.305 (3) N8-C4 1.318 (2)
CONCLUSIONS
Crystal of bis[1-(diaminomethylene)-thiou-ron-1-ium] sulfate was obtained and characterized by X-ray analysis for the first time. Thus, the synthesis of 2-imino-4-thiobiuret carries out according to Scheme 3.
2H2N—C=N-C=N + 3Na2S203 + H20 + 3H2S04-
NH2
H2N—C=NH—С—NH2
I II nh2 s
3
S04 + 2NaHS04 + 2Na2S04 + S + S02
H,N—C=NH—С—NHo
I "
NH,
S04 + 2NH4OH-— 2H,N—С—NH—С—NH2 + (NH4)2S04 + 2HzO
II II
NH S
2
2
Scheme 3. The synthesis of 2-imino-4-thiobiuret Схема 3. Синтез 2-имино-4-тиобиурета
This work has been made by Financial support from Russian Scientific Foundation, grant 14-23-00204.
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12. Macrae C.F., Bruno I.J., Chisholm J.A., Edgington P.R., McCabe P., Pidcock E., Rodriguez-Monge L., Taylor R., Streek J., Wood P.A. Mercury CSD 2.0 - new features for the visualization and investigation of crystal structures. J. Appl. Cryst. 2008. V. 41. N 2. P. 466-470. DOI: 10.1107/S0021889807067908.
13. Westrip S.P. PublCIF: software for editing, validating and formatting crystallographic information files. J. Appl. Cryst. 2010. V. 43. N 4. P. 920-925. DOI: 10.1107/S0021889810022120.
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Поступила в редакцию 22.09.2016 Принята к опубликованию 17.11.2016
Received 22.09.2016 Accepted 17.11.2016
