Crystallographic data and details of the structure refinement for (β-AlaH)(DMGH)SO4·2H2O (I), (β-AlaH)(BetH)SO4 (II) and (β-AlaH)(l-ProH)SO4 (III) are provided in Table 1 and those of (BetH)(l-ProH)SO4 (IV), (SarH)3(l-ProH)(SO4)2 (V), (β-AlaH)(l-ProH···l-Pro)SO4 (VI) and (β-AlaH)(β-AlaH···DMG)SO4 (VII) are listed in Table 2. The structure of (II) was initially determined at 200 K. With orthorhombic symmetry (Pnma, a = 12.5967(13) Å, b = 6.5528(7) Å, c = 15.9714(16) Å, V = 1318.34 Å3, Z = 4, Z′ = 0.5) all three molecules are centered on mirror planes. Evaluation of thermal parameters indicated a possible phase transition towards lower temperatures. Thus, its structure was further determined at 100K and for comparison also at 250 K and at room temperature. At RT and 250 K the structures could be reasonably refined with the orthorhombic model obtained for the 200K measurement, while at 100K the structure turned monoclinic, but affected by twinning. Due to the symmetry reduction by phase transition all three moieties are hence in general position. In Table 1 the data for (II) are provided at 100K and at RT. The presence of optically active l-proline in the structures of (III), (IV), (V) and (VI) ensures noncentrosymmetric (in cases of (IV), (V) and (VI) with polar space groups) structures.
Crystal
|
(I)
|
(II)
|
(II, RT)
|
(III)
|
Table 1
Crystallographic data and details of the structure refinement for (β-AlaH)(DMGH)SO4·2H2O (I), (β-AlaH)(BetH)SO4 (II) and (β-AlaH)(l-ProH)SO4 (III)
Empirical Formula
|
C7H22N2O10S
|
C8H20N2O8S
|
C8H20N2O8S
|
C8H18N2O8S
|
Formula mass
|
326.32
|
304.32
|
304.32
|
302.30
|
Crystal system
|
Monoclinic
|
Monoclinic
|
Orthorhombic
|
Orthorhombic
|
Space group
|
P21/c
|
P21/n
|
Pnma
|
P212121
|
a (Å)
|
6.7532(4)
|
6.5204(5)
|
12.6126(9)
|
6.8014(6)
|
b (Å)
|
8.1264(5)
|
12.5908(9)
|
6.5984(5)
|
8.3419(7)
|
c (Å)
|
27.2491(18)
|
15.9714(13)
|
16.0080(12)
|
23.868(2)
|
β (°)
|
93.947(3)
|
91.995(3)
|
|
|
V (Å3)
|
1491.86(16)
|
1310.41(17)
|
1332.23(17)
|
1354.2(2)
|
Z
|
4
|
4
|
4
|
4
|
Crystal size (mm3)
|
0.200×0.175×0.125
|
0.200×0.200×0.030
|
0.200×0.200×0.030
|
0.400×0.225×0.075
|
ρcalc.(g cm−3)
|
1.453
|
1.543
|
1.517
|
1.483
|
Temperature (K)
|
200(2)
|
100(2)
|
296(2)
|
200(2)
|
2θmax
|
66.28
|
66.67
|
66.68
|
66.44
|
µ (mm–1)
|
0.266
|
0.286
|
0.281
|
0.276
|
F(000)
|
696
|
648
|
648
|
640
|
Absorption-correction
|
Multi-scan
|
Multi-scan
|
Multi-scan
|
Multi-scan
|
Index ranges (hkl)
|
±10, ±12 ±41
|
±10, ±19, ±24
|
±19, ±10, ±24
|
±10, ±12, ±36
|
Reflections collected
|
52981
|
54742
|
49616
|
52415
|
Independent reflections (Rint)
|
5690 (0.0358)
|
4919
|
2745(0.0452)
|
5183 (0.0306)
|
Data with Fo> 2σ (Fo)
|
4568
|
4146
|
2267
|
4834
|
Parameters refined/restrained
|
201/4
|
182/0
|
134/0
|
178/0
|
Flack parameter [27]
|
-
|
-
|
-
|
0.00(7)
|
R1a/ wR2b (I > 2σ(I))
|
0.0373/0.0933
|
0.0526/0.1580
|
0.0373/0.0929
|
0.0421/0.1089
|
R1a/ wR2b (for all Fo2)
|
0.0519/0.1012
|
0.0678/0.1730
|
0.0493/0.0998
|
0.0464/0.1125
|
Δρfin (max/min) [e Å–3]
|
0.37/-0.41
|
0.715/-0.656
|
0.479/-0.349
|
0.898/-0.718
|
Crystal
|
(IV)
|
(V)
|
(VI)
|
(VII)
|
Table 2
Crystallographic data and details of the structure refinement for (BetH)(l-ProH)SO4 (IV), (SarH)3(l-ProH)(SO4)2 (V), (β-AlaH)(l-ProH···l-Pro)SO4 (VI) and (β-AlaH)(β-AlaH···DMG)SO4 (VII)
Empirical Formula
|
C10H22N2O8S
|
C7H17N2O8S
|
C13H27N3O10S
|
C10H25N3O10S
|
Formula mass
|
330.35
|
289.28
|
417.43
|
379.39
|
Crystal system
|
Monoclinic
|
Monoclinic
|
Monoclinic
|
Monoclinic
|
Space group
|
P21
|
P21
|
P21
|
P21/c
|
a (Å)
|
10.6892(9)
|
12.2825(10)
|
10.9363(9)
|
6.6937(5)
|
b (Å)
|
6.6606(6)
|
7.9528(6)
|
6.4049(5)
|
15.5321(12)
|
c (Å)
|
11.4629(10)
|
14.2202(12)
|
13.8622(11)
|
16.0803(12)
|
β (°)
|
114.340(3)
|
114.475(3)
|
97.484(2)
|
93.036(2)
|
V (Å3)
|
743.58(11)
|
1264.22(18)
|
962.72(13)
|
1669.5(2)
|
Z
|
2
|
2
|
2
|
4
|
Crystal size (mm3)
|
0.35×0.20×0.10
|
0.30×0.15×0.10
|
0.45×0.30×0.75
|
0.30×0.25×0.20
|
ρcalc.(g cm−3)
|
1.475
|
1.520
|
1.440
|
1.509
|
Temperature (K)
|
200(2)
|
200(2)
|
200(2)
|
200(2)
|
2θmax
|
66.44
|
61.12
|
66.50
|
66.56
|
µ (mm–1)
|
0.258
|
0.292
|
0.225
|
0.251
|
F(000)
|
352
|
612
|
444
|
808
|
Absorption-correction
|
Multi-scan
|
Multi-scan
|
Multi-scan
|
Multi-scan
|
Index ranges
|
±16, ±10, ±17
|
±17, ±11, ±20
|
±16, ±9, ±21
|
±10, ±23, ±24
|
Reflections collected
|
27652
|
42197
|
38230
|
61543
|
Independent reflections
|
5703
|
7737
|
7314
|
6403
|
(Rint)
|
(0.0286)
|
(0.0478)
|
(0.0370)
|
(0.0365)
|
Data with Fo> 2σ (Fo)
|
4958
|
6510
|
6382
|
5298
|
Parameters refined/restrained
|
226/44
|
337/2
|
249/1
|
226/0
|
Flack parameter [27]
|
-0.08(7)
|
0.12(3)
|
0.01(2)
|
-
|
R1a/ wR2b (I > 2σ(I))
|
0.0450/0.1139
|
0.0640/0.1552
|
0.0406/0.0984
|
0.0382/0.1003
|
R1a/ wR2b (for all Fo2)
|
0.0553/0.1213
|
0.0797/0.1644
|
0.0503/0.1037
|
0.0497/0.1068
|
Δρfin (max/min) [e Å–3]
|
0.79/-0.54
|
1.57/-0.88
|
0.49/-0.46
|
0.69/-0.40
|
The structures of (β-AlaH)(DMGH)SO 4 ·2H 2 O ( I ) and (β-AlaH)(BetH)SO 4 (II)
The asymmetric part of the unit cell of (I) contains one formula unit (Fig. 1), i.e. one β-alaninium cation, one dimethylglycinium cation, one sulfate anion and two H2O molecules.
Bonds
|
(I)
|
(II)
|
(II, RT)
|
Table 3
Selected bond lengths (in Å) for (β-AlaH)(DMGH)SO4·2H2O (I) at 200K and (β-AlaH)(BetH)SO4 (II) at 100K and at room temperature
|
A
|
A
|
A
|
C1-O1
|
1.3186(14)
|
1.324(3)
|
1.316(2)
|
C1-O2
|
1.2046(14)
|
1.208(3)
|
1.202(2)
|
C1-C2
|
1.5074(16)
|
1.516(3)
|
1.505(2)
|
C2-C3
|
1.5152(16)
|
1.518(3)
|
1.511(2)
|
C3-N1
|
1.4888(14)
|
1.483(3)
|
1.486(2)
|
|
B
|
B
|
B
|
C1-O1
|
1.3022(15)
|
1.319(3)
|
1.3104(19)
|
C1-O2
|
1.2101(16)
|
1.212(3)
|
1.2016(19)
|
C1-C2
|
1.5085(18)
|
1.511(3)
|
1.506(2)
|
C2-N1
|
1.4823(16)
|
1.499(3)
|
1.5016(18)
|
N1-C3
|
1.4914(17)
|
1.508(3)
|
1.501(2)
|
N1-C4
|
1.4870(16)
|
1.495(3)
|
1.4924(15)
|
N1-C5 (N1-C4 i)
|
-
|
1.494(3)
|
1.4924(15)
|
S1-O1
|
1.4714(9)
|
1.5037(16)
|
1.4906(11)
|
S1-O2
|
1.4828(9)
|
1.4827(19)
|
1.4571(10)
|
S1-O3(S1-O2i)
|
1.4632(9)
|
1.4707(18)
|
1.4571(10)
|
S1-O4
|
1.4587(9)
|
1.4561(17)
|
1.4411(13)
|
(i) x, -y + 3/2, z |
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 4
Hydrogen bond parameters (in Å and °) for (β-AlaH)(DMGH)SO4·2H2O (I)
O1A-H1A···O2 i
|
0.84
|
1.77
|
2.6076(12)
|
177
|
O1B-H1B···O2W ii
|
0.90
|
1.66
|
2.5512(15)
|
169
|
N1A-H11A···O1
|
0.91
|
1.88
|
2.7863(13)
|
176
|
N1A-H12A···O2 iii
|
0.91
|
1.91
|
2.8065(13)
|
170
|
N1A-H13A···O3 iv
|
0.91
|
1.85
|
2.7558(13)
|
176
|
N1B-H11B···O1 v
|
0.93
|
1.91
|
2.7773(12)
|
154
|
O1W-H11W···O4
|
0.84(2)
|
1.98(2)
|
2.8222(15)
|
175(2)
|
O1W-H12W···O2B vi
|
0.78(2)
|
2.06(3)
|
2.8252(15)
|
169(2)
|
O2W-H21W···O4
|
0.79(2)
|
2.14(3)
|
2.8523(16)
|
149(2)
|
O2W-H22W···O1W vii
|
0.88(2)
|
1.86(2)
|
2.7344(17)
|
175(2)
|
Symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) -x + 1, y-1/2, -z + 1/2; (iii) -x + 1, -y + 2, -z + 1; |
(iv) x-1, y, z; (v) x, y-1, z; (vi) x, y + 1, z; (vii) x + 1, y, z.
Selected bond lengths for (I), provided in Table 3, are as expected for both cations, β-alaninium (A) as well as dimethylglycinium (B). Hydrogen bond parameters are shown in Table 4, the packing diagram is illustrated in Fig. 2.
The carboxyl group of the β-alaninium cation forms an O1A-H1A···O2 hydrogen bond with the sulfate anion (Table 4). Consequently, the bond length S1-O2 is longer than others (Table 3). The carboxyl group of the dimethylglycinium cation exhibits a stronger hydrogen bond O1B-H1B···O2W with one of the H2O molecules. The NH3+ group of the β-alaninium cation is part of hydrogen bonds with O1, O2 and O3 oxygen atoms of three nearest sulfate anions (Table 4). The dimethylglycinium cation additionally establishes a hydrogen bond N1B-H11B···O1 with the nearest sulfate anion. The H2O molecule W1 forms one hydrogen bond with the sulfate anion via the O4 atom and with the carbonyl oxygen atom O2B of the closest dimethylglycinium cation, the H2O molecule W2 with a second H2O molecule and with the sulfate anion via the same O4 atom. The mean value of S-O distances of the sulfate anion in (I) is 1.469 Å.
In Table 1 crystallographic data of (β-AlaH)(BetH)SO4 (II) are provided at 100K and at room temperature. At 100K the salt (II) has monoclinic symmetry in space group P21/c. In Fig. 3.1 the asymmetric unit is shown which contains one formula unit. Atoms of all three moieties are on general positions. Selected bond lengths are listed in Table 3. Hydrogen bond parameters are provided in Table 5, the packing diagram is shown in Fig. 4.1. The strongest hydrogen bonds are formed by carboxyl groups of β-alaninium and betainium cations (Table 5). The bonds S1-O1 (1.5037 Å) and S1-O2 (1.4827 Å) are lengthened compared to two other bond of sulfate anion S1-O3 (1.4707 Å), S1-O4 (1.4561 Å) (Table 3), respectively. At 100K the mean value of S-O distances of the sulfate anion in (II) is 1.478 Å. The NH3+ group of the β-alaninium cation forms three hydrogen bonds with the nearest sulfate anion and a weaker hydrogen bond with the carbonyl O2B atom. There are also C-H···O contacts. Of these, the C2B-H22B···O3 contact can be considered as hydrogen bond.
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 5.1
Hydrogen bond parameters (in Å and °) for (β-AlaH)(BetH)SO4 (II) at 100K
O1A-H1A···O2
|
0.89
|
1.81
|
2.690(2)
|
171
|
O1B-H1B···O1
|
1.03
|
1.50
|
2.530(2)
|
171
|
N1A-H11A···O3 i
|
0.91
|
1.84
|
2.744(3)
|
169
|
N1A-H12A···O2 ii
|
0.91
|
2.00
|
2.894(3)
|
165
|
N1A-H13A···O1 iii
|
0.91
|
2.06
|
2.891(3)
|
151
|
N1A-H13A···O2B iii
|
0.91
|
2.30
|
2.879(3)
|
121
|
C2B-H22B···O3 iv
|
0.99
|
2.26
|
3.180(3)
|
154
|
C3B-H31B···O4 v
|
0.98
|
2.42
|
3.314(3)
|
152
|
C4B-H41B···O2B
|
0.98
|
2.37
|
3.007(3)
|
122
|
C5B-H53B···O2B
|
0.98
|
2.37
|
2.995(3)
|
121
|
Symmetry code: (i) x + 1/2, -y + 1/2, z-1/2; (ii) x- 1/2, -y + 1/2, z-1/2; (iii) -x + 3/2, y-1/2, -z + 1/2; |
(iv) x + 1/2, -y + 1/2, z + 1/2; (v) -x + 3/2, -y-1/2, z + 1/2.
In the 200K-100K interval a phase transition takes place. At 200K up to room temperature the salt (II) has orthorhombic symmetry (space group Pnma). Crystallographic data of (II) at RT are provided in Table 1. Selected bond lengths are listed in Table 3. The numbers of formula units in the unit cells at 100K as well as at 200K, 250K and RT are the same (Z = 4), while Z′ = 1 at 100K but Z′ = 0.5 at 200K, 250K and RT. In Fig. 3.2 the asymmetric unit at RT is shown; all three moieties are centered on the plane of symmetry. At 100K the carboxyl groups of the β-alaninium and betainium cations are only approximately in the same plane (torsion angles O1AO2AO1BO2B and H1AO2AH1BO2B are 2.80° and 10.44°, respectively). Upon the phase transition LT→HT all three moieties move slightly, the torsion angles O1AO2AO1BO2B and H1AO2AH1BO2B are 0.00° and their centers are exactly in the same plane. As a result, the atoms O2 and O3 become equivalent, the H1A atom establishes a bifurcated hydrogen bond with O2 and O2i, and the carboxyl group of the betainium cation forms a hydrogen bond O1B-H1B···O1 (Table 5.2, Fig. 4.2).
The mean value of S-O distances of the sulfate anion in (II) at RT is 1.461 Å vs. 1.478 at 100K.
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 5.2
Hydrogen bond parameters (in Å and °) for (β-AlaH)(BetH)SO4 (II) at RT
O1A-H1A···O2
|
0.78(3)
|
2.30(3)
|
2.9995(18)
|
149.0(4)
|
O1A-H1A···O2 i
|
0.78(3)
|
2.30(3)
|
2.9995(18)
|
149.0(4)
|
O1B-H1B···O1
|
0.91(3)
|
1.62(3)
|
2.5328(17)
|
175(3)
|
N1A-H11A···O2 ii
|
0.878(17)
|
1.969(17)
|
2.8432(16)
|
173.2(15)
|
N1A-H12A···O1 iii
|
0.91(3)
|
2.07(3)
|
2.915(2)
|
153(2)
|
N1A-H12A···O2B iii
|
0.91(3)
|
2.31(2)
|
2.8881(18)
|
120.9(19)
|
C2B-H21B···O2 iv
|
0.941(14)
|
2.430
|
3.3303(15)
|
160.1(11)
|
C2B-H21B···O2 v
|
0.94(3)
|
2.430
|
3.334(2)
|
156(2)
|
C4B-H41B···O4
|
0.96
|
2.38
|
2.9974(18)
|
122
|
Symmetry code: (i) x, -y + 3/2, z; (ii) -x + 3/2, y + 1/2, z-1/2; (iii) x + 1/2, y, -z + 1/2; |
(iv) -x + 3/2, -y + 1, z + 1/2; (v) x-1/2, y, -z + 3/2. |
A related salt, the hexafluorosilicate monohydrate (b-AlaH)(BetH)SiF6·H2O has been described [5] in space group P21/n with Z = 12.
The structures of (b-AlaH)(l-ProH)SO4 (III) and (BetH)(l-ProH)SO4 (IV)
The salt (b-AlaH)(l-ProH)SO4 (III) crystallizes in the acentric orthorhombic space group P212121 due to the presence of l-proline (Table 1). The asymmetric part of the unit cell of (III) also contains one formula unit (Fig. 5), i.e. each one b-alaninium and l-prolinium cation and one sulfate anion. The hexafluorosilicate salt (b-AlaH)(L-ProH)SiF6 [5] - contrary to (b-AlaH)(L-ProH)SO4 (III) - is described with lower symmetry in the space group P21.
Table 6
Selected bond lengths (in Å) for (β-AlaH)(l-ProH)SO4 (III) and (BetH)(l-ProH)SO4 (IV)
|
(III)
|
(IV)
|
Bonds
|
A
|
A
|
C1-O1
|
1.323(2)
|
1.307(2)
|
C1-O2
|
1.209(2)
|
1.200(2)
|
C1-C2
|
1.505(2)
|
1.522(2)
|
C2-C3
|
1.512(2)
|
-
|
C3-N1
|
1.4908(19)
|
-
|
C2-N1
|
-
|
1.4978(18)
|
N1-C3
|
|
1.5026(19)
|
N1-C4
|
|
1.502(3)
|
N1-C5
|
|
1.496(3)
|
|
B
|
B
|
C1-O1
|
1.301(2)
|
1.310(3)
|
C1-O2
|
1.190(3)
|
1.207(2)
|
C1-C2
|
1.513(3)
|
1.510(3)
|
C2-C3
|
1.519(3)
|
1.521(3)
|
C3-C4
|
1.445(5)
|
1.510(4)
|
C4-C5
|
1.507(4)
|
1.479(4)
|
C5-N1
|
1.511(2)
|
1.451(3)
|
N1-C2
|
1.498(2)
|
1.488(3)
|
S1-O1
|
1.4568(14)
|
1.4654(15)
|
S1-O2
|
1.4751(13)
|
1.478(2) (1.432(7))
|
S1-O3
|
1.4557(14)
|
1.451(2) (1.527(6))
|
S1-O4
|
1.4884(13)
|
1.451(2) (1.436(6))
|
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 7
Hydrogen bond parameters (in Å and °) for (β-AlaH)(l-ProH)SO4 (III)
O1A-H1A···O4 i
|
0.81
|
1.79
|
2.602(2)
|
174
|
O1B-H1B···O3
|
0.90
|
1.68
|
2.570(2)
|
168
|
N1A-H11A···O4 ii
|
0.91
|
1.90
|
2.794(2)
|
169
|
N1A-H12A···O2
|
0.91
|
1.84
|
2.748(2)
|
175
|
N1A-H13A···O1 iii
|
0.91
|
1.90
|
2.800(2)
|
172
|
N1B-H11B···O2A iv
|
0.91
|
2.37
|
2.986(2)
|
125
|
N1B-H11B···O2B
|
0.91
|
2.18
|
2.671(2)
|
113
|
N1B-H12B···O2 v
|
0.91
|
1.80
|
2.701(3)
|
170
|
Symmetry code: (i) x-1/2, -y + 3/2, -z + 1; (ii) x-1/2, -y + 1/2, -z + 1; (iii) x-1, y, z; |
(iv) -x + 1, y + 1/2, -z + 1/2; (v) -x + 1, y + 1/2, -z + 1/2. |
Selected bond lengths, having expected values, are provided in Table 6. Hydrogen bond parameters are shown in Table 7 and the packing diagram in Fig. 6. The carboxyl groups of both cations form hydrogen bonds O1A-H1A···O4 and O1B-H1B···O3 with the sulfate anion. The NH3+ group of the b-alaninium cation exhibits hydrogen bonds with O1, O2 and O4 oxygen atoms of three nearest sulfate anions (Table 7). The oxygen atom O4 forms two hydrogen bonds and the respective S1-O4 bond is longer (Table 6). The NH2+ group of the l-prolinium cation establishes hydrogen bonds with the O2 oxygen atom of the nearest sulfate anion and a weak hydrogen bond with a carbonyl oxygen atom of the b-alaninium cation (Table 7). The mean value of S-O bonds in (III) is 1.469 Å.
The salt (BetaH)(l-ProH)SO4 (IV) crystallizes in the polar monoclinic space group P21 (Table 2). The asymmetric part of the unit cell of (IV) also contains one formula unit (Fig. 7), i.e. one betainium cation, one l-prolinium cation and one sulfate anion. Oxygen atoms O2, O3, O4 of the sulfate anion are disordered by rotation along the O1-S1 bond. Selected bond lengths are provided in Table 6. The mean value of S1-O(1–4) bonds is 1.461 Å.
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 8
Hydrogen bond parameters (in Å and °) for (BetH)(l-ProH)SO4 (IV)
O1A-H1A···O1
|
0.93
|
1.62
|
2.543(3)
|
170
|
O1B-H1B···O2` i
|
0.75
|
2.14
|
2.859(19)
|
160
|
O1B-H1B···O3 i
|
0.75
|
1.81
|
2.523(4)
|
158
|
O1B-H1B···O3` i
|
0.75
|
2.32
|
2.90(2)
|
133
|
N1B-H11B···O3` ii
|
0.91
|
1.76
|
2.543(10)
|
142
|
N1B-H11B···O4 ii
|
0.91
|
2.01
|
2.888(4)
|
161
|
N1B-H12B···O4
|
0.91
|
1.97
|
2.856(4)
|
163
|
N1B-H12B···O4`
|
0.91
|
1.86
|
2.769(12)
|
172
|
C2A-H21A···O3 iii
|
0.99
|
2.37
|
3.219(4)
|
143
|
C2A-H21A···O3` iii
|
0.99
|
2.44
|
3.391(11)
|
162
|
C2A-H22A···O1 iv
|
0.99
|
2.28
|
3.200(4)
|
154
|
C3A-H33A···O3 iii
|
0.98
|
2.20
|
3.069(5)
|
147
|
C4A-H41A···O2A
|
0.98
|
2.35
|
2.986(4)
|
122
|
C4A-H43A···O2` v
|
0.98
|
2.21
|
3.168(12)
|
165
|
C5A-H51A···O2 v
|
0.98
|
2.26
|
3.178(4)
|
156
|
C5A-H53A···O2A
|
0.98
|
2.39
|
3.017(4)
|
121
|
C2B-H2B···O2A ii
|
1.00
|
2.36
|
3.316(3)
|
161
|
Symmetry code: (i) x, y-1, z; (ii) -x + 1, y-1/2, -z + 1; (iii) -x + 1, y-1/2, -z; (iv) -x + 1, y + 1/2, -z; (v) x + 1, y, z. |
Hydrogen bonds parameters are listed in Table 8 and a packing diagram is shown in Fig. 8. The carboxyl group of the betainium cation forms a hydrogen bond O1A-H1A···O1 with the sulfate anion, while the carboxyl group of the l-prolinium cation is part of three contacts with O2`, O3 and O3` atoms (Table 8). The NH2+ group of the l-prolinium cation shows hydrogen bonds N1B-H11B···O3`, N1B-H11B···O4 and N1B-H12B···O4, N1B-H12B···O4`. Additionally, there are short C-H···O contacts (Table 8). Some of them: C2A-H22A···O1, C3A-H33···O3, C4A-H43A···O2` and C5B-H51B···O2 are rather short and can be considered as hydrogen bonds.
The structure of (SarH) 3 (l-ProH)(SO 4 ) 2 (V)
The compound (SarH)3(l-ProH)(SO4)2 (V) crystallizes in the polar monoclinic space group P21 (Table 2). The asymmetric unit contains one formula unit: three sarcosinium cations (A, B, C), one l-prolinium cation (marked as D-moiety) and two sulfate anions (Fig. 9). Selected bond lengths, provided in Table 9, show expected values. The mean S-O distances are 1.474 and 1.461 Å for S1 and S2, respectively.
Bonds
|
A
|
B
|
C
|
Table 9
Selected bond lengths (in Å) for (SarH)3(l-ProH)(SO4)2 (V)
C1-O1
|
1.309(6)
|
1.311(6)
|
1.309(6)
|
C1-O2
|
1.191(7)
|
1.211(6)
|
1.210(7)
|
C1-C2
|
1.523(8)
|
1.508(7)
|
1.510(7)
|
C2-N1
|
1.476(7)
|
1.468(6)
|
1.482(6)
|
N1-C3
|
1.530(3)
|
1.484(6)
|
1.488(6)
|
C1D-O1D
|
1.317(6)
|
C3D-C4D
|
1.531(8)
|
C1D-O2D
|
1.212(6)
|
C4D-C5D
|
1.538(8)
|
C1D-C2D
|
1.499(7)
|
C5D-N1D
|
1.487(7)
|
C2D-C3D
|
1.526(7)
|
N1D-C2D
|
1.485(6)
|
S1-O11
|
1.476(4)
|
S2-O21
|
1.468(4)
|
S1-O12
|
1.488(4)
|
S2-O22
|
1.446(5)
|
S1-O13
|
1.454(4)
|
S2-O23
|
1.460(6)
|
S1-O14
|
1.480(4)
|
S2-O24
|
1.469(4)
|
Hydrogen bond parameters are listed in Table 10 and the packing diagram is shown in Fig. 10.
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 10
Hydrogen bond parameters (in Å and °) for (SarH)3(l-ProH)(SO4)2 (V)
O1A-H1A···O21 i
|
0.95
|
1.67
|
2.563(6)
|
154
|
O1B-H1B···O14 ii
|
0.95
|
1.69
|
2.555(5)
|
151
|
O1C-H1C···O22
|
0.96
|
1.67
|
2.598(8)
|
163
|
O1D-H1D···O12 iii
|
0.93
|
1.67
|
2.585(5)
|
168
|
N1A-H11A···O22 iv
|
0.91
|
2.30
|
2.968(8)
|
130
|
N1A-H11A···O2C iv
|
0.91
|
2.23
|
2.872(7)
|
127
|
N1A-H12A···O12
|
0.91
|
1.95
|
2.834(6)
|
164
|
N1B-H11B···O24
|
0.91
|
1.92
|
2.814(5)
|
168
|
N1B-H12B···O24 iii
|
0.91
|
1.87
|
2.770(6)
|
170
|
N1C-H11C···O11 v
|
0.91
|
1.84
|
2.726(6)
|
164
|
N1C-H12C···O11 vi
|
0.91
|
1.94
|
2.839(5)
|
167
|
N1D-H11D···O21
|
0.91
|
1.99
|
2.804(5)
|
147
|
N1D-H12D···O13 ii
|
0.91
|
2.08
|
2.866(5)
|
144
|
N1D-H12D···O2B
|
0.91
|
2.36
|
2.824(5)
|
112
|
C3B-H33B···O1C
|
0.98
|
2.39
|
3.321(7)
|
158
|
C2C-H21C···O13 v
|
0.99
|
2.44
|
3.173(6)
|
131
|
C2C-H22C···O14 vii
|
0.99
|
2.27
|
3.212(6)
|
158
|
Symmetry code: (i) -x + 1, y + 1/2, -z + 1; (ii) x, y, z-1; (iii) -x + 1, y-1/2, -z + 1; (iv) x-1, y, z; |
(v) -x + 1, y + 1/2, -z + 2; (vi) x + 1, y, z; (vii) -x + 1, y-1/2, -z + 2. |
Carboxyl groups of all four cations form hydrogen bonds with anions exhibiting O···O distances in the interval 2.556-2.599 Å, the NH2+ groups of sarcosinium and l-prolinium cations establish mainly hydrogen bonds with sulfate anions. There are only two weak bifurcated hydrogen bonds N1A-H11A···O2C / O22 and N1D-H12D···O2B / O13 with carbonyl oxygen atoms of C- and B-sarcosinium cations (Fig. 10, Table 10). In addition, there are three relatively short C-H···O contacts (Table 10). The contact C2C-H22C···O14 (-x+1, y-1/2, -z+2) may be considered as hydrogen bond.
The structures of (β-AlaH)(l-ProH···l-Pro)SO 4 (VI) and (β-AlaH)(β-AlaH···DMG)SO4 (VII)
The salt (β-AlaH)(l-ProH···l-Pro)SO4 (VI) crystallizes in the polar monoclinic space group P21 (Table 2). The asymmetric unit of (VI) contains one formula unit: one β-alaninium cation, one (l-prolinium···l-proline) dimeric cation and a sulfate anion (Fig. 11). The hexafluorosilicate analog of (β-AlaH)(l-ProH···l-Pro)SO4 (VI) is the salt (β-AlaH)(l-ProH···l-Pro)SiF6 with the same symmetry [5]. Both compounds are isotypic, if one ignores the differences regarding the SO4 and SiF6 groups.
Selected bond lengths of (VI) are provided in Table 11, hydrogen bond parameters in Table 12 and the packing diagram is shown in Fig. 12.
Bonds
|
A
|
Bonds
|
B
|
C
|
Bonds
|
|
Table 11
Selected bond lengths (in Å) for (β-AlaH)(l-ProH···l-Pro)SO4 (VI)
C1-O1
|
1.318(2)
|
C1-O1
|
1.290(3)
|
1.240(2)
|
S1-O1
|
1.4719(14)
|
C1-O2
|
1.199(3)
|
C1-O2
|
1.227(2)
|
1.259(3)
|
S1-O2
|
1.476(2)
|
C1-C2
|
1.505(3)
|
C1-C2
|
1.506(3)
|
1.521(3)
|
S1-O3
|
1.4639(14)
|
C2-C3
|
1.510(2)
|
C2-C3
|
1.519(3)
|
1.526(3)
|
S1-O4
|
1.466(2)
|
C3-N1
|
1.491(2)
|
C3-C4
|
1.530(4)
|
1.530(3)
|
|
|
|
|
C4-C5
|
1.512(4)
|
1.516(3)
|
|
|
|
|
C5-N1
|
1.498(4)
|
1.474(3)
|
|
|
|
|
N1-C2
|
1.490(3)
|
1.488(3)
|
|
|
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
Table 12
Hydrogen bond parameters (in Å and °) for (β-AlaH)(l-ProH···l-Pro)SO4 (VI)
O1A-H1A···O3
|
0.75
|
1.85
|
2.600(2)
|
176
|
O1B-H1B···O2C i
|
1.15
|
1.32
|
2.450(3)
|
164
|
N1A-H11A···O2 ii
|
0.91
|
1.98
|
2.869(3)
|
164
|
N1A-H12A···O1 iii
|
0.91
|
1.85
|
2.754(2)
|
173
|
N1A-H13A···O4 iv
|
0.91
|
1.91
|
2.804(3)
|
166
|
N1B-H11B···O1C
|
0.91
|
1.96
|
2.854(2)
|
167
|
N1B-H12B···O2 v
|
0.91
|
2.04
|
2.925(3)
|
164
|
N1B-H12B···O3 v
|
0.91
|
2.37
|
3.036(3)
|
130
|
N1C-H11C···O4 iii
|
0.91
|
2.22
|
2.860(4)
|
127
|
N1C-H12C···O1C
|
0.91
|
2.22
|
2.712(3)
|
113
|
C2B-H2B···O3 v
|
1.00
|
2.42
|
3.051(3)
|
120
|
Symmetry code: (i) x, y + 1, z; (ii) -x + 1, y + 1/2, -z; (iii) x-1, y, z; (iv) -x + 1, y-1/2, -z; (v) -x + 1, y + 1/2, -x + 1. |
The b-alaninium cation forms a hydrogen bond O1A-H1A···O3 with the sulfate anion. The dimeric cation (l-ProH···l-Pro) is characterized by a strong O1B-H1B···O2C hydrogen bond with a short O···O distance of 2.450(3) Å which is close to 2.438(2) Å observed in the structure of (b-AlaH)(l-ProH···l-Pro)SiF6 [5]. The bond lengths C1B-O1B (1.290(3)) Å and C1C-O2C (1.259(3) Å) are expected for such hydrogen bonds and close to the respective values (1.289(2) Å and (1.265(2) Å) found in the structure of (b-AlaH)(l-ProH···l-Pro)SiF6 [5].
The NH3+ group of the β-alaninium cation takes part in hydrogen bonds with three nearest sulfate anions via O1, O2 and O4 atoms. So, the β-alaninium cation is surrounded by four sulfate anions. The NH2+ groups of l-prolinium and l-proline have hydrogen contacts with two nearest anions via O2 and O4 atoms and also with two (l-ProH···l-Pro) cations via the carbonyl oxygen atom O1C (Table 12). The bond lengths S-O are close to each other with a mean value of 1.469 Å.
The salt (β-AlaH)(β-AlaH···DMG)SO4 (VII) is monoclinic with centrosymmetric space group P21/c (Table 2), the asymmetric unit of (VII) also contains one formula unit: one β-alaninium cation, one (β-alaninium···dimethylglycine) dimeric cation and one sulfate anion (Fig. 13).
Selected bond lengths of (VII) are provided in Table 13, hydrogen bond parameters in Table 14 and the packing diagram in Fig. 14. The β-alaninium C-cation forms a hydrogen bond O1C-H1C···O2 with the sulfate anion with an O···O distance of 2.5976(13) Å, while the β-alaninium A-cation exhibits a hydrogen bond O1A-H1A···O1B with dimethylglycine and an O···O distance of 2.5295(12) Å (Table 12).
Table 13
Selected bond lengths (in Å) for (β-AlaH)(β-AlaH···DMG)SO4 (VII)
Bonds
|
A
|
C
|
C1-O1
|
1.3026(14)
|
1.3132(16)
|
C1-O2
|
1.2200(14)
|
1.2125(16)
|
C1-C2
|
1.5076(15)
|
1.5080(17)
|
C2-C3
|
1.5167(15)
|
1.5136(17)
|
C3-N1
|
1.4877(15)
|
1.4848(15)
|
|
B
|
|
C1-O1
|
1.2642(14)
|
|
C1-O2
|
1.2370(14)
|
|
C1-C2
|
1.5274(17)
|
|
C2-N1
|
1.4808(17)
|
|
N1-C3
|
1.4897(17)
|
|
N1-C4
|
1.4879(19)
|
|
S1-O1
|
1.4879(9)
|
|
S1-O2
|
1.4869(9)
|
|
S1-O3
|
1.4506(9)
|
|
S1-O4
|
1.4697(10)
|
|
Table 14
Hydrogen bond parameters (in Å and °) for (β-AlaH)(β-AlaH···DMG)SO4 (VII)
D-H···A
|
D-H
|
H···A
|
D···A
|
DHA
|
O1A-H1A···O1B
|
0.89
|
1.64
|
2.5295(12)
|
172
|
N1A-H11A···O4 i
|
0.91
|
1.86
|
2.7674(14)
|
178
|
N1A-H12A···O2 ii
|
0.91
|
2.01
|
2.8481(13)
|
151
|
N1A-H13A···O1 iii
|
0.91
|
1.95
|
2.8487(14)
|
169
|
N1B-H11B···O1
|
1.00
|
2.32
|
3.1196(14)
|
137
|
N1B-H11B···O4
|
1.00
|
2.26
|
2.9658(14)
|
126
|
O1C-H1C···O2 i
|
0.91
|
1.69
|
2.5976(13)
|
174
|
N1C-H11C···O2A iv
|
0.91
|
1.91
|
2.8150(13)
|
174
|
N1C-H12C···O2B v
|
0.91
|
1.90
|
2.8095(14)
|
177
|
N1C-H13C···O1 iv
|
0.91
|
1.90
|
2.7873(13)
|
165
|
C3B-H32B···O3
|
0.98
|
2.34
|
3.2977(18)
|
167
|
C4B-H41B···O2B
|
0.98
|
2.43
|
3.387(2)
|
166
|
Symmetry code: (i) -x + 1, y + 1/2, -z + 1/2; (ii) x, -y + 1/2, z-1/2; (iii) -x + 2, y + 1/2, -z + 1/2; |
(iv) x-1, y, z; (v) -x + 1, -y + 1, -z + 1; (vi) x, -y + 1/2, z + 1/2.
The NH3+ group of β-alaninium A-cation takes part in hydrogen bonds with O1, O2 and O4 oxygen atoms of three nearest sulfate anions (Table 14). The N1B-H11B group of dimethylglycine forms a hydrogen bond with the nearest anion via the O4 atom. The NH3+ group of β-alaninium C-cation exhibits hydrogen bonds with the O1 atom, further with the carbonyl oxygen atom O2A of the A-cation and with O2B of dimethylglycine. Thus, O1, O2 and O4 atoms of sulfate anion contribute to each two hydrogen bonds, while the atom O3 does not form any N-H···O type hydrogen bond. In the structure of (VII) there are two short C-H···O contacts (Table 14), which can be considered weak hydrogen bonds. Among S-O bonds the bond S1-O3 is the shortest (Table 13), possibly because lacking a N-H···O type hydrogen bond with the O3 atom. The mean S-O distance in (VII) is 1.474 Å.