D-Mannosamine hydro­chloride (2-amino-2-de­oxy-D-mannose hydro­chloride): ionic hydrogen bonding in saccharides involving chloride and aminium ions

D-Mannosamine hydro­chloride (2-amino-2-de­oxy-D-mannose hydro­chloride), C₆H₁₄NO₅⁺·Cl⁻, (I), crystallized from a methanol/ethyl acetate/n-hexane solvent mixture at room tem­per­ature in a ⁴C₁ chair conformation that is slightly distorted towards the ^C3,O5B form. A com­parison of the structural parameters of (I) with the corresponding parameters in α-D-glucosa­mine hydro­chloride, (II), and β-D-galactosamine hydro­chloride, (III)/(III′), was undertaken to evaluate the effects of ionic hydrogen bonding on structural properties. Three types of ionic hydrogen bonds are present in the crystals of (I)–(III)/(III′), i.e. N⁺—H...O, N⁺—H...Cl⁻, and O—H...Cl⁻. The exocyclic structural parameters in (I), (II), and (III)/(III′) appear to be most influenced by this bonding, especially the exocyclic hy­droxy groups, which adopt eclipsed conformations enabled by ionic hydrogen bonding to the chloride anion. Anomeric disorder was observed in crystals of (I), with an α:β ratio of 37:63. However, anomeric configuration appears to exert minimal structural effects; that is, bond lengths, bond angles, and torsion angles are essentially identical in both anomers. The observed disorder at the anomeric C atom of (I) appears to be caused by the presence of the chloride anion and atom O3 or O4 in proximal voids, which provide opportunities for hydrogen bonding to atom O1 in both axial and equatorial orientations.

Computing details

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2018); data reduction: SAINT (Bruker, 2018); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

2-Amino-2-deoxy-D-mannose hydrochloride

Crystal data

C6H14NO5^+·Cl^−	Dx = 1.540 Mg m^−3
Mr = 215.63	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 9972 reflections
a = 8.3512 (4) Å	θ = 5.9–70.4°
b = 10.0750 (5) Å	µ = 3.65 mm^−1
c = 11.0555 (6) Å	T = 120 K
V = 930.19 (8) Å^3	Block, colorless
Z = 4	0.28 × 0.20 × 0.18 mm
F(000) = 456

Data collection

Bruker PHOTON II diffractometer	1773 independent reflections
Radiation source: Ius micro-focus	1770 reflections with I > 2σ(I)
Detector resolution: 7.41 pixels mm^-1	Rint = 0.068
ω and φ–scans	θmax = 70.5°, θmin = 5.9°
Absorption correction: numerical (SADABS; Krause et al., 2015)	h = −10→10
Tmin = 0.462, Tmax = 0.589	k = −12→12
19393 measured reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + 1.3591P] where P = (Fo^2 + 2Fc^2)/3
S = 1.22	(Δ/σ)max < 0.001
1773 reflections	Δρmax = 0.22 e Å^−3
160 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Absolute structure: Flack x determined using 708 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.060 (10)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.62782 (14)	0.46942 (10)	0.83365 (9)	0.0272 (3)
O1	0.4210 (7)	0.4273 (5)	0.1434 (4)	0.0275 (16)	0.628 (11)
H1O	0.418 (19)	0.515 (17)	0.114 (14)	0.12 (6)*	0.628 (11)
O1A	0.2130 (11)	0.3879 (10)	0.2779 (9)	0.036 (3)	0.372 (11)
H1OA	0.16 (2)	0.452 (16)	0.241 (14)	0.05 (4)*	0.372 (11)
O3	0.5395 (4)	0.1644 (3)	0.4828 (3)	0.0235 (7)
H3O	0.494 (9)	0.122 (7)	0.531 (7)	0.06 (2)*
O4	0.3977 (4)	0.3747 (3)	0.6342 (3)	0.0227 (7)
H4O	0.460 (7)	0.391 (6)	0.686 (5)	0.034 (16)*
O5	0.4320 (3)	0.5213 (3)	0.3310 (2)	0.0192 (6)
O6	0.3460 (4)	0.7488 (3)	0.4689 (3)	0.0272 (7)
H6O	0.360 (8)	0.810 (6)	0.514 (5)	0.034 (14)*
N2	0.6321 (5)	0.2938 (3)	0.2770 (3)	0.0162 (7)
H2NC	0.690 (6)	0.232 (5)	0.316 (5)	0.032 (14)*
H2NB	0.631 (5)	0.285 (4)	0.201 (4)	0.006 (9)*
H2NA	0.673 (6)	0.383 (6)	0.295 (4)	0.030 (14)*
C1	0.3767 (6)	0.4101 (4)	0.2640 (4)	0.0224 (8)
H1	0.257820	0.401209	0.271205	0.027*	0.628 (11)
H1A	0.401375	0.423626	0.176312	0.027*	0.372 (11)
C2	0.4593 (5)	0.2851 (4)	0.3081 (3)	0.0172 (8)
H2	0.411714	0.206877	0.265613	0.021*
C3	0.4359 (5)	0.2680 (4)	0.4440 (3)	0.0167 (8)
H3	0.323017	0.238937	0.458421	0.020*
C4	0.4651 (5)	0.3944 (4)	0.5169 (3)	0.0157 (8)
H4	0.582936	0.409874	0.524592	0.019*
C5	0.3873 (5)	0.5150 (4)	0.4575 (3)	0.0167 (8)
H5	0.268152	0.508716	0.464874	0.020*
C6	0.4445 (6)	0.6424 (4)	0.5127 (4)	0.0217 (9)
H6A	0.437407	0.637221	0.601987	0.026*
H6B	0.557658	0.658379	0.490346	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0383 (5)	0.0222 (5)	0.0212 (4)	−0.0120 (5)	0.0001 (5)	0.0021 (4)
O1	0.046 (3)	0.021 (3)	0.016 (3)	0.007 (2)	−0.004 (2)	0.0019 (18)
O1A	0.033 (5)	0.030 (5)	0.044 (6)	0.015 (4)	−0.026 (4)	−0.010 (4)
O3	0.0240 (15)	0.0191 (14)	0.0273 (16)	0.0069 (13)	0.0075 (13)	0.0079 (13)
O4	0.0245 (16)	0.0300 (16)	0.0135 (13)	−0.0005 (13)	0.0023 (12)	0.0053 (12)
O5	0.0286 (14)	0.0154 (13)	0.0135 (12)	0.0019 (11)	0.0022 (11)	0.0002 (12)
O6	0.045 (2)	0.0156 (14)	0.0209 (14)	0.0106 (15)	−0.0004 (14)	−0.0013 (12)
N2	0.0181 (17)	0.0140 (16)	0.0165 (16)	0.0013 (14)	−0.0003 (15)	0.0025 (12)
C1	0.029 (2)	0.0185 (19)	0.0197 (18)	0.0055 (18)	−0.0071 (19)	−0.0032 (15)
C2	0.0171 (19)	0.0154 (18)	0.0192 (19)	0.0011 (15)	−0.0020 (15)	−0.0023 (15)
C3	0.0150 (18)	0.0124 (18)	0.023 (2)	0.0033 (15)	0.0035 (15)	0.0030 (16)
C4	0.0150 (18)	0.0172 (18)	0.0150 (18)	−0.0012 (15)	0.0019 (15)	0.0015 (15)
C5	0.0210 (19)	0.0152 (17)	0.0140 (16)	0.0021 (16)	0.0025 (15)	0.0011 (14)
C6	0.029 (2)	0.017 (2)	0.020 (2)	0.0000 (17)	0.0002 (17)	0.0011 (16)

Geometric parameters (Å, º)

O1—C1	1.394 (6)	N2—H2NA	0.98 (6)
O1—H1O	0.94 (17)	C1—C2	1.516 (5)
O1A—C1	1.394 (11)	C1—H1	1.0000
O1A—H1OA	0.90 (18)	C1—H1A	1.0000
O3—C3	1.422 (5)	C2—C3	1.525 (5)
O3—H3O	0.78 (8)	C2—H2	1.0000
O4—C4	1.428 (5)	C3—C4	1.527 (5)
O4—H4O	0.79 (6)	C3—H3	1.0000
O5—C1	1.420 (5)	C4—C5	1.526 (5)
O5—C5	1.448 (4)	C4—H4	1.0000
O6—C6	1.435 (5)	C5—C6	1.500 (5)
O6—H6O	0.81 (6)	C5—H5	1.0000
N2—C2	1.487 (5)	C6—H6A	0.9900
N2—H2NC	0.90 (6)	C6—H6B	0.9900
N2—H2NB	0.84 (4)
C1—O1—H1O	116 (9)	C1—C2—H2	108.8
C1—O1A—H1OA	111 (10)	C3—C2—H2	108.8
C3—O3—H3O	108 (5)	O3—C3—C2	107.6 (3)
C4—O4—H4O	112 (4)	O3—C3—C4	110.9 (3)
C1—O5—C5	112.7 (3)	C2—C3—C4	113.9 (3)
C6—O6—H6O	106 (4)	O3—C3—H3	108.1
C2—N2—H2NC	112 (3)	C2—C3—H3	108.1
C2—N2—H2NB	102 (3)	C4—C3—H3	108.1
H2NC—N2—H2NB	114 (4)	O4—C4—C5	109.5 (3)
C2—N2—H2NA	110 (3)	O4—C4—C3	107.5 (3)
H2NC—N2—H2NA	110 (4)	C5—C4—C3	111.7 (3)
H2NB—N2—H2NA	108 (4)	O4—C4—H4	109.4
O1—C1—O5	108.3 (4)	C5—C4—H4	109.4
O1A—C1—O5	112.8 (5)	C3—C4—H4	109.4
O1—C1—C2	106.9 (4)	O5—C5—C6	105.9 (3)
O1A—C1—C2	106.1 (5)	O5—C5—C4	109.9 (3)
O5—C1—C2	109.8 (3)	C6—C5—C4	111.7 (3)
O1—C1—H1	110.6	O5—C5—H5	109.8
O5—C1—H1	110.6	C6—C5—H5	109.8
C2—C1—H1	110.6	C4—C5—H5	109.8
O1A—C1—H1A	109.4	O6—C6—C5	108.6 (3)
O5—C1—H1A	109.4	O6—C6—H6A	110.0
C2—C1—H1A	109.4	C5—C6—H6A	110.0
N2—C2—C1	108.6 (3)	O6—C6—H6B	110.0
N2—C2—C3	111.0 (3)	C5—C6—H6B	110.0
C1—C2—C3	110.7 (3)	H6A—C6—H6B	108.3
N2—C2—H2	108.8
C5—O5—C1—O1	178.1 (4)	O3—C3—C4—O4	−74.2 (4)
C5—O5—C1—O1A	52.6 (6)	C2—C3—C4—O4	164.3 (3)
C5—O5—C1—C2	−65.5 (4)	O3—C3—C4—C5	165.7 (3)
O1—C1—C2—N2	50.3 (5)	C2—C3—C4—C5	44.2 (5)
O1A—C1—C2—N2	170.9 (5)	C1—O5—C5—C6	−176.3 (3)
O5—C1—C2—N2	−67.0 (4)	C1—O5—C5—C4	62.9 (4)
O1—C1—C2—C3	172.4 (4)	O4—C4—C5—O5	−169.3 (3)
O1A—C1—C2—C3	−67.0 (5)	C3—C4—C5—O5	−50.4 (4)
O5—C1—C2—C3	55.1 (5)	O4—C4—C5—C6	73.5 (4)
N2—C2—C3—O3	−48.8 (4)	C3—C4—C5—C6	−167.6 (3)
C1—C2—C3—O3	−169.4 (3)	O5—C5—C6—O6	70.9 (4)
N2—C2—C3—C4	74.6 (4)	C4—C5—C6—O6	−169.5 (3)
C1—C2—C3—C4	−46.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···Cl1^i	0.78 (8)	2.38 (8)	3.151 (3)	173 (7)
O6—H6O···Cl1^ii	0.81 (6)	2.33 (6)	3.123 (3)	171 (6)
O1a—H1Oa···O3^iii	0.94 (17)	1.88 (17)	2.785 (6)	160 (14)
O1A—H1OA···Cl1^iv	0.90 (18)	2.70 (18)	3.247 (9)	120 (12)
O1A—H1OA···O4^iv	0.90 (18)	2.15 (17)	3.017 (10)	160 (15)
O4—H4O···Cl1	0.79 (6)	2.29 (6)	3.077 (3)	172 (6)
N2—H2NB···O6^v	0.84 (4)	1.92 (4)	2.762 (4)	172 (4)
N2—H2NC···O4^vi	0.90 (6)	2.11 (6)	2.960 (5)	157 (5)
N2—H2NA···Cl1^vii	0.98 (6)	2.27 (6)	3.179 (4)	153 (4)

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, y+1/2, −z+1/2; (iv) −x+1/2, −y+1, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) x+1/2, −y+1/2, −z+1; (vii) −x+3/2, −y+1, z−1/2.