Preparation and structure of aminium thiosulfates
Preparation and X-ray structures of selected aminium thiosulfates
Agnieszka Dąbrowska, Jarosław Chojnacki*
Gdansk University of Technology, Department of Inorganic Chemistry, G. Narutowicza St. 11 / 12, 80-233 Gdańsk, Poland, Tel: +48 58
3472776, Fax: +48 58 3472694
Received; accepted
Supplementary information
Table 1S.Selected geometric parameters (Å, °) for (1), (3), (6).
(1)
S1—O1
S1—O2
S1—O3
S1—S2
S3—O4
S3—O6
S3—O5
S3—S4
N1—C1
C1—C4
C1—C3
C1—C2
1.459 (3)
1.471 (2)
1.476 (3)
2.0162 (13)
1.460 (3)
1.469 (3)
1.471 (3)
2.0176 (13)
1.523 (4)
1.515 (5)
1.516 (5)
1.520 (5)
N2—C5
C5—C7
C5—C6
C5—C8
N3—C9
C9—C11
C9—C12
C9—C10
N4—C13
C13—C16
C13—C14
C13—C15
1.509 (4)
1.517 (6)
1.523 (5)
1.527 (5)
1.505 (4)
1.523 (5)
1.529 (5)
1.530 (5)
1.511 (4)
1.510 (5)
1.524 (5)
1.532 (5)
O1—S1—O2
O1—S1—O3
O2—S1—O3
O1—S1—S2
O2—S1—S2
O3—S1—S2
O4—S3—O6
O4—S3—O5
O6—S3—O5
O4—S3—S4
O6—S3—S4
O5—S3—S4
C4—C1—C3
N3—C9—C11
109.14 (15)
111.06 (17)
110.81 (18)
108.51 (12)
109.73 (12)
107.54 (12)
111.18 (18)
108.87 (15)
111.33 (18)
107.97 (12)
108.25 (13)
109.16 (13)
113.3 (4)
107.4 (3)
111.5 (3)
110.8 (3)
111.3 (3)
107.1 (3)
106.7 (3)
107.3 (3)
106.5 (3)
107.5 (3)
110.9 (4)
108.6 (3)
110.9 (4)
112.2 (4)
107.9 (3)
111.6 (3)
N3—C9—C12
C11—C9—
C12
N3—C9—C10
C11—C9—
C10
107.7 (3)
112.2 (3)
C12—C9—C10
C4—C1—C2
C3—C1—C2
C4—C1—N1
C3—C1—N1
C2—C1—N1
N2—C5—C7
N2—C5—C6
C7—C5—C6
N2—C5—C8
C7—C5—C8
C6—C5—C8
C16—C13—N4
C16—C13—
C14
N4—C13—C14
C16—C13—
C15
N4—C13—C15
C14—C13—
C15
*Correspondence
106.7 (3)
111.0 (3)
108.0 (3)
111.6 (4)
105.5 (3)
112.0 (4)
author (e-mail:[email protected])
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
Title
Preparation and X-ray structures of selected aminium thiosulfates
File Name
Document1
Date
29.07.2017
Page
1 (7)
(3)
N1—C1
N1—C1A
C1—C2
C1—C6
C2—C3
C3—C4
C4—C5
C5—C6
C1A—C2A
C1A—C6
C2A—C3A
C3A—C4A
C4A—C5A
C5A—C6
N2—C7
C7—C12
C7—C8
C8—C9
C9—C10
C10—C11
C11—C12
N3—C13
C13—C14
C13—C18
C14—C15
C15—C16
C16—C17
C17—C18
N4—C19
C19—C24
C19—C20
C1—N1—C1A
N1—C1—C2
N1—C1—C6
C2—C1—C6
C1—C2—C3
C4—C3—C2
C3—C4—C5
C6—C5—C4
C2A—C1A—N1
C2A—C1A—C6
N1—C1A—C6
C3A—C2A—
C1A
C4A—C3A—
C2A
C3A—C4A—
C5A
C4A—C5A—C6
C5—C6—C1
C5—C6—C1A
C1—C6—C1A
C5—C6—C5A
C1—C6—C5A
1.432 (9)
1.623 (12)
1.496 (16)
1.546 (10)
1.513 (12)
1.506 (12)
1.510 (14)
1.507 (13)
1.513 (18)
1.662 (12)
1.500 (14)
1.494 (14)
1.495 (15)
1.728 (17)
1.476 (6)
1.358 (9)
1.502 (8)
1.540 (9)
1.394 (11)
1.502 (12)
1.583 (10)
1.481 (6)
1.397 (10)
1.474 (9)
1.652 (13)
1.439 (15)
1.370 (14)
1.588 (11)
1.483 (5)
1.504 (6)
1.512 (6)
32.5 (4)
108.5 (9)
112.7 (7)
104.9 (9)
116.2 (12)
110.1 (14)
115.8 (15)
105.9 (11)
108.2 (10)
104.1 (9)
98.0 (7)
109.6 (17)
1.509 (7)
1.501 (9)
1.541 (9)
1.521 (7)
1.465 (6)
1.428 (8)
1.515 (7)
1.555 (9)
1.532 (13)
1.383 (10)
1.504 (8)
1.465 (3)
1.467 (3)
1.467 (3)
1.9830 (17)
1.394 (6)
1.432 (6)
1.510 (8)
1.975 (4)
1.438 (13)
1.441 (15)
1.515 (13)
1.952 (11)
1.407 (9)
1.407 (9)
1.435 (5)
1.466 (7)
1.466 (7)
2.015 (3)
2.015 (3)
C26—C25—C30
N5—C25—C30
C25—C26—C27
C28—C27—C26
C29—C28—C27
C28—C29—C30
C29—C30—C25
O3—S1—O1
O3—S1—O2
O1—S1—O2
O3—S1—S2
O1—S1—S2
112.5 (5)
111.2 (4)
111.6 (6)
108.7 (7)
114.9 (8)
115.1 (7)
111.9 (5)
109.5 (2)
110.5 (2)
108.3 (2)
108.43 (15)
111.25 (16)
116 (2)
O2—S1—S2
108.97 (17)
109 (2)
O4—S3—O6
115.0 (4)
105.0 (17)
110.4 (8)
113.2 (7)
31.4 (4)
42.4 (7)
114.7 (8)
O4—S3—O5
O6—S3—O5
O4—S3—S4
O6—S3—S4
O5—S3—S4
O4A—S3A—
O5A
O4A—S3A—
O6A
O5A—S3A—
O6A
O4A—S3A—
104.8 (7)
106.0 (5)
116.6 (5)
112.7 (3)
99.4 (4)
104.4 (14)
C1A—C6—C5A
95.1 (8)
C12—C7—N2
114.5 (5)
C12—C7—C8
115.1 (6)
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
C20—C21
C21—C22
C22—C23
C23—C24
N5—C25
C25—C26
C25—C30
C26—C27
C27—C28
C28—C29
C29—C30
S1—O3
S1—O1
S1—O2
S1—S2
S3—O4
S3—O6
S3—O5
S3—S4
S3A—O4A
S3A—O5A
S3A—O6A
S3A—S4A
S5—O10
S5—O10i
S5—O8
S5—O9i
S5—O9
S5—S6i
S5—S6
104.2 (10)
118.3 (15)
114.3 (8)
Title
Preparation and X-ray structures of selected aminium thiosulfates
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Date
29.07.2017
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N2—C7—C8
111.1 (4)
C7—C8—C9
109.1 (6)
C10—C9—C8
C9—C10—C11
C10—C11—C12
C7—C12—C11
C14—C13—C18
C14—C13—N3
C18—C13—N3
C13—C14—C15
C16—C15—C14
C17—C16—C15
C16—C17—C18
C13—C18—C17
N4—C19—C24
N4—C19—C20
C24—C19—C20
C21—C20—C19
C22—C21—C20
C21—C22—C23
C24—C23—C22
C19—C24—C23
113.9 (8)
112.3 (8)
108.7 (7)
111.6 (7)
111.6 (6)
113.5 (6)
110.7 (5)
106.4 (8)
106.3 (10)
111.3 (11)
110.6 (9)
109.0 (7)
110.8 (3)
110.5 (3)
111.3 (4)
111.5 (4)
111.4 (5)
111.3 (6)
110.6 (5)
110.6 (4)
S4A
O5A—S3A—
S4A
O6A—S3A—
S4A
O10—S5—O10i
O10—S5—O8
O10i—S5—O8
O10—S5—O9i
O10i—S5—O9i
O8—S5—O9i
O10—S5—O9
O10i—S5—O9
O8—S5—O9
O9i—S5—O9
O10—S5—S6i
O10i—S5—S6i
O8—S5—S6i
O9i—S5—S6i
O9—S5—S6i
O10—S5—S6
O10i—S5—S6
O8—S5—S6
O9i—S5—S6
O9—S5—S6
115.7 (13)
99.8 (7)
145.0 (8)
107.5 (4)
107.5 (4)
61.1 (6)
111.1 (6)
101.9 (4)
111.1 (6)
61.1 (6)
101.9 (3)
156.2 (7)
47.3 (6)
111.8 (5)
120.71 (10)
103.1 (3)
64.0 (4)
111.8 (5)
47.3 (6)
120.71 (10)
64.0 (4)
103.1 (3)
Symmetry code: (i) −x, y, −z+1/2.
(6)
S1—O2
S1—O3
S1—O1
S1—S2
O2—S1—O3
O2—S1—O1
O3—S1—O1
O2—S1—S2
O3—S1—S2
N1—C3—
C2—C1
1.4550 (19)
1.4578 (19)
1.4596 (18)
1.9967 (8)
109.75 (13)
110.08 (14)
110.60 (13)
110.11 (9)
108.59 (9)
N1—C3
C1—C1i
C1—C2
C3—C2
O1—S1—S2
C1i—C1—C2
N1—C3—C2
C3—C2—C1
1.487 (3)
1.513 (5)
1.516 (3)
1.500 (3)
107.67 (8)
113.7 (3)
112.05 (19)
111.9 (2)
−171.7 (2)
C1i—C1—
C2—C3
−175.5 (3)
Symmetry code: (i) −x+1, −y+1, −z+1.
Table 2S.Hydrogen-bond geometry (Å, °) for (1).
D—H···A
N1—H1A···O3i
N1—H1B···O5ii
N1—H1C···O6
N1—H1C···S4
N2—H2D···S4
N2—H2E···O1
N2—H2F···O7iii
N3—H3E···O4
N3—H3F···S2
N3—H3F···S1
N4—H4D···O2iii
N4—H4E···O6iv
N4—H4F···S2
O7—H7W···O5ii
O7—H7W···S3ii
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
D—H
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.81 (2)
0.81 (2)
H···A
1.95
1.92
2.41
2.63
2.53
1.96
2.14
1.94
2.53
3.01
1.92
1.99
2.67
2.13 (2)
2.92 (3)
D···A
2.834 (4)
2.789 (4)
3.010 (4)
3.502 (3)
3.422 (3)
2.847 (4)
2.908 (4)
2.824 (4)
3.417 (3)
3.730 (3)
2.807 (4)
2.863 (4)
3.522 (3)
2.915 (4)
3.633 (3)
D—H···A
173
167
125
167
178
174
144
170
177
140
175
167
162
163 (5)
150 (5)
Title
Preparation and X-ray structures of selected aminium thiosulfates
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O7—H7V···S4
O8—H8W···O2iii
O8—H8W···S1iii
O8—H8V···S2
O8—H8V···S1
0.81 (2)
0.84 (2)
0.84 (2)
0.83 (2)
0.83 (2)
2.53 (2)
2.12 (2)
2.94 (3)
2.54 (2)
3.03 (3)
3.334 (3)
2.928 (4)
3.631 (3)
3.363 (3)
3.714 (3)
177 (5)
162 (4)
140 (4)
177 (4)
142 (4)
Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x,
y−1, z.
Table 3S.Hydrogen-bond geometry (Å, °) for (3).
D—H···A
D—H
H···A
D···A
N1—H1A···O9ii
N1—H1B···O1
N1—H1C···S2ii
N2—H2E···O6A
N2—H2E···O4
N2—H2F···O3iii
N2—H2F···S1iii
N2—H2G···O2
N3—H3E···O9
N3—H3E···S5
N3—H3F···O8ii
N3—H3G···O1
N3—H3G···S1
N4—H4E···O3iii
N4—
H4F···O6Aiii
N4—
H4F···S4Aiii
N4—H4G···O4A
N4—H4G···O4
N4—H4G···S3A
N5—H5E···O5iv
N5—H5F···O5A
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
0.89
2.04
2.02
2.44
1.87
1.99
1.97
2.93
1.92
2.03
2.89
1.99
2.04
2.88
2.09
2.925 (8)
2.775 (5)
3.309 (4)
2.748 (12)
2.801 (8)
2.847 (5)
3.796 (4)
2.806 (5)
2.904 (8)
3.746 (4)
2.863 (5)
2.908 (5)
3.749 (4)
2.942 (5)
D—
H···A
170
142
167
169
152
169
164
177
165
163
169
166
166
161
0.89
2.44
3.046 (12)
126
0.89
2.42
3.296 (7)
166
0.89
0.89
0.89
0.89
0.89
1.97
2.02
2.95
2.30
1.82
2.831 (11)
2.847 (10)
3.820 (14)
3.084 (12)
2.66 (3)
163
154
168
147
157
Symmetry codes: (ii) x, y+1, z; (iii) x, y−1, z; (iv) −x+1/2, −y+1/2,
−z.
Table 4S. Hydrogen-bond geometry (Å, °) for (6).
D—H···A
D—H
H···A
D···A
N1—H1A···S2ii
N1—H1B···O2
N1—H1C···S2iii
N2—H4A···O1iv
N2—H4A···O3v
N2—H4B···O3vi
N2—H4B···O1vi
N2—H4D···O2
0.89
0.89
0.89
0.87 (2)
0.87 (2)
0.87 (2)
0.87 (2)
0.87 (2)
2.39
1.92
2.48
2.18 (3)
2.47 (3)
2.02 (2)
2.86 (3)
2.08 (2)
3.243 (2)
2.801 (3)
3.334 (2)
2.921 (3)
2.910 (3)
2.883 (3)
3.485 (4)
2.902 (3)
D—
H···A
161
171
162
143 (3)
112 (3)
174 (3)
130 (3)
159 (3)
Symmetry codes: (ii) x, y−1, z; (iii) x, −y+1/2, z+1/2; (iv) −x,
−y+1, −z; (v) −x, y−1/2, −z+1/2; (vi) x, −y+3/2, z+1/2.
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
Title
Preparation and X-ray structures of selected aminium thiosulfates
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Date
29.07.2017
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Fig. 1S.Crystal packing in (tBuNH3)2S2O3 × H2O (1). Layer structures are parallel to (001).
Fig. 2S. Layers parallel to (101) in crystals of (cC6H11NH3)2S2O3
(3). For clarity hydrogen atoms are not shown.
Fig. 3S. Hydrogen bond reinforced infinite rods in crystals of
(cC6H11NH3)2S2O3 (3). Note a twofold rotation axes at [0, y, ¼]
andan inversion center at [ ¼, ¼, 0]. Plane (101) at z = ¼ , {i.e.
plane (404)} intersects the rod (and the layer).
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
Title
Preparation and X-ray structures of selected aminium thiosulfates
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29.07.2017
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Fig. 4S. Packing of ions in crystals of (6).
Fig. 5S. Bis(tert-butylammonium) (1) thiosulfate TG/DTG curves.
Fig. 6S. TG/DTG curves for 1,3-propylenediammonium thiosulfate (4).
Details of structure determinations
Two wrong reflections (0 -8 3) and (0 -8 5) were omitted in
refinement of (1). The high residual electron density in (1)
is difficult to explain, but it may come from minor contribution of “defects” being Me2CH-CH2-NH2 or sec-BuNH2
amine substituted in the position of tBuNH2. The 1H NMR
spectrum of the amine (see Figure 7S) indeed shows some
impurities, however their exact composition is uncertain.
Structure of (3) contains one cyclohexyl group (C1-C6)
disordered over two positions with sof’s of
0.559/0.441(11). The group was restrained by fixing the
same distances between related C-atoms in both parts. Additionally one thiosulfate anion (S3-S4) was refined as
disordered over two positions with probabilities
0.743/0.257(8). Thiosulfate S5-S6 was found on two-fold
rotation axis and as such was refined with occupation factor
equal to half, using PART -1 instruction. Alert B related to
short H6B...H1D contact is caused by lack of splitting of
C6 atom in the disordered residue.
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
Title
Preparation and X-ray structures of selected aminium thiosulfates
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Structure of (6) is fully ordered. Hydrogen atoms attached
to N2 atom were refined constrained to the same N-H bond
length. Hydrogen atoms at N1 atom were refined in the
standard way with torsions defined by electron density
maximum (AFIX 137).
Fig. 7S. 1H NMR spectrum taken for starting tert-butylamine (in
CDCl3, 500MHz, reference TMS).
Author
Agnieszka Dąbrowska,
Jarosław Chojnacki
Title
Preparation and X-ray structures of selected aminium thiosulfates
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29.07.2017
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