Crystal structure of the acyclic form of 1-de­oxy-1-[(4-methoxyphenyl)(methyl)amino]-d-fructose

Mossine, V.V.; Barnes, C.L.; Mawhinney, T.P.

doi:10.1107/S2056989018000099

Crystal structure of the acyclic form of 1-deoxy-1-[(4-methoxyphenyl)(methyl)amino]-D-fructose

V. V. Mossine, C. L. Barnes and T. P. Mawhinney

The monoclinic unit contains a rare acyclic keto tautomer of the amino sugar involved in the extensive hydrogen-bonding patterns. The acyclic conformation is a minor species in the compound's solution.

Keywords: crystal structure; D-fructosamine; acyclic carbohydrate; Hirshfeld surface analysis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989018000099/qm2121sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989018000099/qm2121Isup2.hkl Contains datablock I

CCDC reference: 1811885

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.031
wR factor = 0.082
Data-to-parameter ratio = 14.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3O      ..O4               2.67 Ang.

Alert level G
PLAT032_ALERT_4_G Std. Uncertainty on Flack Parameter Value High .      0.500 Report
PLAT791_ALERT_4_G Model has Chirality at C3          (Chiral SPGR)          S Verify
PLAT791_ALERT_4_G Model has Chirality at C4          (Chiral SPGR)          R Verify
PLAT791_ALERT_4_G Model has Chirality at C5          (Chiral SPGR)          R Verify
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter Values Differ by .       0.39 Check
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   9 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL022_ALERT_1_A There is a mismatched ~ on line 1128
                  C:\Xtals\Mossine\FRUCTO~1\FRUCANIS.res
              If you require a ~ then it should be escaped
              with a \, i.e. \~
              Otherwise there must be a matching closing ~, e.g. C~2~H~4~

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: X-SEED (Barbour, 2001) and Mercury (Macrae et al., 2008); software used to prepare material for publication: CIFTAB (Sheldrick, 2008) and publCIF (Westrip, 2010).

1-Deoxy-1-[(4-methoxyphenyl)(methyl)amino]-D-fructose top

Crystal data top

C₁₄H₂₁NO₆	F(000) = 320
M_r = 299.32	D_x = 1.350 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 10.8002 (15) Å	Cell parameters from 3774 reflections
b = 5.1439 (7) Å	θ = 2.6–25.8°
c = 13.3931 (19) Å	µ = 0.11 mm⁻¹
β = 98.382 (1)°	T = 100 K
V = 736.11 (18) Å³	Prism, colourless
Z = 2	0.35 × 0.15 × 0.12 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	2788 reflections with I > 2σ(I)
ω scans	R_int = 0.026
Absorption correction: multi-scan (SADABS; Sheldrick (2003)	θ_max = 26.4°, θ_min = 1.9°
T_min = 0.88, T_max = 0.99	h = −13→13
8031 measured reflections	k = −6→6
2993 independent reflections	l = −16→16

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0443P)² + 0.0803P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.082	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.19 e Å⁻³
2993 reflections	Δρ_min = −0.15 e Å⁻³
208 parameters	Absolute structure: Flack x determined using 1149 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.3 (5)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.10655 (16)	0.5973 (4)	0.64477 (12)	0.0275 (4)
C1	0.15040 (19)	0.4862 (4)	0.74257 (15)	0.0267 (4)
H1A	0.189953	0.316322	0.732685	0.032*
H1B	0.077318	0.453299	0.777617	0.032*
O2	0.26415 (14)	0.8787 (3)	0.79127 (12)	0.0321 (4)
C2	0.24391 (18)	0.6543 (4)	0.81040 (15)	0.0240 (4)
O3	0.40317 (13)	0.6914 (3)	0.95778 (11)	0.0268 (3)
C3	0.31015 (18)	0.5253 (4)	0.90646 (15)	0.0229 (4)
H3	0.352434	0.364549	0.886440	0.027*
O4	0.13795 (14)	0.6653 (3)	0.99012 (12)	0.0281 (3)
C4	0.21360 (18)	0.4440 (4)	0.97432 (14)	0.0220 (4)
H4	0.159267	0.302656	0.940569	0.026*
O5	0.35348 (13)	0.1285 (3)	1.06292 (11)	0.0270 (3)
C5	0.27762 (17)	0.3493 (4)	1.07730 (15)	0.0231 (4)
H5	0.332604	0.491086	1.109907	0.028*
O6	0.09673 (13)	0.0803 (3)	1.10474 (11)	0.0285 (3)
C6	0.18494 (19)	0.2727 (5)	1.14715 (15)	0.0285 (5)
H6A	0.231641	0.204885	1.210924	0.034*
H6B	0.138815	0.429609	1.163615	0.034*
C7	0.18576 (18)	0.5977 (4)	0.57050 (15)	0.0250 (4)
C8	0.2825 (2)	0.4181 (5)	0.57062 (16)	0.0322 (5)
H8	0.300894	0.301939	0.625936	0.039*
C9	0.3529 (2)	0.4053 (5)	0.49151 (17)	0.0352 (5)
H9	0.417860	0.280262	0.493123	0.042*
O10	0.39239 (16)	0.5762 (4)	0.32846 (12)	0.0437 (4)
C10	0.3286 (2)	0.5736 (5)	0.41076 (16)	0.0319 (5)
C11	0.2348 (2)	0.7560 (5)	0.41043 (17)	0.0352 (5)
H11	0.218288	0.874400	0.355652	0.042*
C12	0.1644 (2)	0.7690 (5)	0.48871 (16)	0.0316 (5)
H12	0.100474	0.896471	0.486890	0.038*
C13	0.0158 (2)	0.8065 (5)	0.64424 (17)	0.0330 (5)
H13A	0.059076	0.974339	0.646201	0.050*
H13B	−0.027328	0.790523	0.703438	0.050*
H13C	−0.045390	0.795655	0.582714	0.050*
C14	0.4858 (2)	0.3812 (7)	0.3254 (2)	0.0474 (7)
H14A	0.551236	0.401318	0.383834	0.071*
H14B	0.522812	0.399739	0.263176	0.071*
H14C	0.447653	0.208769	0.327161	0.071*
H5O	0.430 (3)	0.175 (7)	1.061 (2)	0.050 (8)*
H4O	0.069 (3)	0.643 (7)	0.959 (2)	0.052 (9)*
H6O	0.133 (3)	−0.034 (6)	1.078 (2)	0.047 (8)*
H3O	0.368 (2)	0.835 (6)	0.974 (2)	0.041 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0270 (9)	0.0286 (9)	0.0267 (9)	0.0036 (8)	0.0032 (7)	0.0003 (7)
C1	0.0277 (11)	0.0254 (10)	0.0268 (10)	−0.0020 (9)	0.0032 (8)	0.0011 (8)
O2	0.0344 (8)	0.0240 (8)	0.0372 (9)	−0.0023 (7)	0.0026 (7)	0.0027 (7)
C2	0.0207 (9)	0.0242 (10)	0.0288 (10)	0.0003 (8)	0.0099 (8)	−0.0007 (8)
O3	0.0166 (7)	0.0272 (8)	0.0365 (8)	−0.0027 (6)	0.0038 (6)	−0.0025 (6)
C3	0.0180 (9)	0.0223 (10)	0.0287 (10)	−0.0003 (7)	0.0048 (8)	−0.0013 (8)
O4	0.0178 (7)	0.0281 (8)	0.0383 (8)	0.0029 (6)	0.0040 (6)	−0.0057 (6)
C4	0.0172 (9)	0.0220 (10)	0.0274 (10)	0.0011 (7)	0.0052 (8)	−0.0023 (8)
O5	0.0168 (7)	0.0276 (8)	0.0368 (8)	0.0007 (6)	0.0045 (6)	0.0031 (6)
C5	0.0164 (9)	0.0270 (10)	0.0261 (10)	−0.0009 (8)	0.0037 (8)	−0.0033 (8)
O6	0.0190 (7)	0.0306 (8)	0.0370 (8)	−0.0016 (6)	0.0081 (6)	−0.0033 (7)
C6	0.0229 (10)	0.0363 (12)	0.0266 (10)	−0.0059 (9)	0.0043 (8)	−0.0020 (10)
C7	0.0244 (9)	0.0235 (10)	0.0258 (10)	−0.0023 (8)	−0.0012 (8)	−0.0044 (8)
C8	0.0327 (11)	0.0344 (12)	0.0288 (11)	0.0070 (10)	0.0021 (9)	0.0038 (9)
C9	0.0313 (11)	0.0390 (14)	0.0353 (12)	0.0084 (10)	0.0054 (9)	−0.0012 (10)
O10	0.0399 (9)	0.0585 (11)	0.0354 (9)	0.0012 (9)	0.0143 (7)	−0.0009 (8)
C10	0.0281 (11)	0.0398 (13)	0.0283 (10)	−0.0043 (10)	0.0055 (8)	−0.0046 (10)
C11	0.0376 (13)	0.0344 (12)	0.0335 (12)	0.0000 (10)	0.0054 (10)	0.0080 (10)
C12	0.0326 (11)	0.0263 (11)	0.0355 (12)	0.0058 (9)	0.0033 (9)	0.0040 (10)
C13	0.0294 (11)	0.0350 (13)	0.0346 (11)	0.0058 (10)	0.0044 (9)	−0.0031 (10)
C14	0.0331 (12)	0.0692 (19)	0.0416 (14)	0.0003 (13)	0.0115 (10)	−0.0126 (13)

Geometric parameters (Å, º) top

N1—C7	1.403 (3)	O6—H6O	0.82 (3)
N1—C1	1.444 (3)	C6—H6A	0.9900
N1—C13	1.455 (3)	C6—H6B	0.9900
C1—C2	1.525 (3)	C7—C8	1.395 (3)
C1—H1A	0.9900	C7—C12	1.399 (3)
C1—H1B	0.9900	C8—C9	1.392 (3)
O2—C2	1.209 (3)	C8—H8	0.9500
C2—C3	1.529 (3)	C9—C10	1.380 (3)
O3—C3	1.418 (2)	C9—H9	0.9500
O3—H3O	0.87 (3)	O10—C10	1.382 (3)
C3—C4	1.538 (3)	O10—C14	1.428 (3)
C3—H3	1.0000	C10—C11	1.381 (3)
O4—C4	1.435 (2)	C11—C12	1.383 (3)
O4—H4O	0.80 (3)	C11—H11	0.9500
C4—C5	1.530 (3)	C12—H12	0.9500
C4—H4	1.0000	C13—H13A	0.9800
O5—C5	1.430 (2)	C13—H13B	0.9800
O5—H5O	0.86 (3)	C13—H13C	0.9800
C5—C6	1.518 (3)	C14—H14A	0.9800
C5—H5	1.0000	C14—H14B	0.9800
O6—C6	1.432 (3)	C14—H14C	0.9800

C7—N1—C1	119.35 (16)	C5—C6—H6A	108.9
C7—N1—C13	118.38 (17)	O6—C6—H6B	108.9
C1—N1—C13	115.40 (17)	C5—C6—H6B	108.9
N1—C1—C2	114.64 (18)	H6A—C6—H6B	107.7
N1—C1—H1A	108.6	C8—C7—C12	117.14 (18)
C2—C1—H1A	108.6	C8—C7—N1	122.18 (19)
N1—C1—H1B	108.6	C12—C7—N1	120.53 (19)
C2—C1—H1B	108.6	C9—C8—C7	121.5 (2)
H1A—C1—H1B	107.6	C9—C8—H8	119.3
O2—C2—C1	122.7 (2)	C7—C8—H8	119.3
O2—C2—C3	121.04 (19)	C10—C9—C8	120.3 (2)
C1—C2—C3	116.29 (17)	C10—C9—H9	119.9
C3—O3—H3O	109.2 (18)	C8—C9—H9	119.9
O3—C3—C2	110.97 (16)	C10—O10—C14	116.9 (2)
O3—C3—C4	111.77 (16)	C9—C10—C11	118.96 (19)
C2—C3—C4	109.93 (15)	C9—C10—O10	124.8 (2)
O3—C3—H3	108.0	C11—C10—O10	116.2 (2)
C2—C3—H3	108.0	C10—C11—C12	121.0 (2)
C4—C3—H3	108.0	C10—C11—H11	119.5
C4—O4—H4O	108 (2)	C12—C11—H11	119.5
O4—C4—C5	108.19 (15)	C11—C12—C7	121.1 (2)
O4—C4—C3	108.74 (16)	C11—C12—H12	119.4
C5—C4—C3	111.30 (15)	C7—C12—H12	119.4
O4—C4—H4	109.5	N1—C13—H13A	109.5
C5—C4—H4	109.5	N1—C13—H13B	109.5
C3—C4—H4	109.5	H13A—C13—H13B	109.5
C5—O5—H5O	111 (2)	N1—C13—H13C	109.5
O5—C5—C6	108.62 (17)	H13A—C13—H13C	109.5
O5—C5—C4	108.92 (15)	H13B—C13—H13C	109.5
C6—C5—C4	112.72 (16)	O10—C14—H14A	109.5
O5—C5—H5	108.8	O10—C14—H14B	109.5
C6—C5—H5	108.8	H14A—C14—H14B	109.5
C4—C5—H5	108.8	O10—C14—H14C	109.5
C6—O6—H6O	110 (2)	H14A—C14—H14C	109.5
O6—C6—C5	113.26 (17)	H14B—C14—H14C	109.5
O6—C6—H6A	108.9

C7—N1—C1—C2	75.2 (2)	C4—C5—C6—O6	55.7 (2)
C13—N1—C1—C2	−75.3 (2)	C1—N1—C7—C8	24.6 (3)
N1—C1—C2—O2	11.7 (3)	C13—N1—C7—C8	174.25 (19)
N1—C1—C2—C3	−169.53 (16)	C1—N1—C7—C12	−160.0 (2)
O2—C2—C3—O3	−7.0 (3)	C13—N1—C7—C12	−10.3 (3)
C1—C2—C3—O3	174.20 (16)	C12—C7—C8—C9	−1.6 (3)
O2—C2—C3—C4	117.2 (2)	N1—C7—C8—C9	174.0 (2)
C1—C2—C3—C4	−61.6 (2)	C7—C8—C9—C10	0.5 (4)
O3—C3—C4—O4	70.7 (2)	C8—C9—C10—C11	0.8 (4)
C2—C3—C4—O4	−53.0 (2)	C8—C9—C10—O10	−179.7 (2)
O3—C3—C4—C5	−48.3 (2)	C14—O10—C10—C9	3.2 (3)
C2—C3—C4—C5	−172.04 (16)	C14—O10—C10—C11	−177.2 (2)
O4—C4—C5—O5	180.00 (15)	C9—C10—C11—C12	−1.0 (4)
C3—C4—C5—O5	−60.6 (2)	O10—C10—C11—C12	179.5 (2)
O4—C4—C5—C6	59.4 (2)	C10—C11—C12—C7	−0.1 (4)
C3—C4—C5—C6	178.77 (18)	C8—C7—C12—C11	1.4 (3)
O5—C5—C6—O6	−65.1 (2)	N1—C7—C12—C11	−174.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O4	0.87 (3)	2.67 (3)	2.962 (2)	101 (3)
O3—H3O···O5ⁱ	0.87 (3)	1.94 (3)	2.747 (2)	153 (2)
O4—H4O···O6ⁱⁱ	0.80 (3)	1.90 (3)	2.700 (2)	176 (3)
O5—H5O···O3ⁱⁱⁱ	0.86 (3)	1.86 (3)	2.702 (2)	165 (3)
O6—H6O···O5	0.82 (3)	2.56 (3)	2.918 (2)	108 (3)
O6—H6O···O4^iv	0.82 (3)	1.95 (3)	2.704 (2)	154 (3)

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

Distribution (%) of cyclic and acyclic forms of some 1-amino-1-deoxy-D-fructose derivatives in D₂O/pyridine (1:1) at 293 K, as estimated from the ¹³C NMR spectra, and in the crystalline state top

Compound	α-pyranose	β-pyranose	α-furanose	β-furanose	acyclic, keto	Crystalline isomers
(I)	2.1	52.0	4.9	30.6	10.3	acyclic keto
FruNMpti^a	2.1	49.9	4.8	32.2	11.0	acyclic keto
FruNEpca^a	2.0	48.7	4.2	32.3	12.7	acyclic keto
Frupti^a^,^b	3.5	61.0	9.4	24.2	1.9	β-pyranose
FruAlla^c	2.2	47.4	4.5	33.6	12.3	β-pyranose
Fructosamine^d	5.0	70.8	11.2	12.3	0.8	β-pyranose
FruAib^e	3.0	75.6	10.1	10.4	<0.7	β-pyranose

Notes: (a) Mossine et al. (2009); (b) Gomez de Anderez et al. (1996); (c) Mossine et al. (2009a); (d) Mossine et al. (2009b); (e) Mossine et al. (2018).

Suspected C—H···A contacts (Å, °) top

C—H···A	C—H	H···A	C···A	C—H···A	Symmetry
C1—H1A···O2	0.99	2.48	3.386 (3)	152	x, y - 1, z
C14—H14B···O2	0.98	2.52	3.311 (3)	138	-x + 1, y - 1/2, -z + 1
C14—H14A···Cg1	0.98	2.95	3.747 (3)	139	-x + 1, y - 1/2, -z + 1
C13—H13C···Cg1	0.98	2.80	3.539 (2)	133	-x, y + 1/2, -z + 1

Contributions (%) of specific contact types to the Hirshfeld surfaces of 1-amino-1-deoxy-D-fructose derivatives top

Compound	Conformation	O···H	H···H	C···H	Other contacts
(I)	acyclic keto	32.3	52.8	13.2	N···H 1.6; C···C 0.1
FruNMpti^a	acyclic keto	26.5	59.8	11.8	N···H 1.6; C···C 0.3
FruNEpca^a	acyclic keto	23.1	50.1	8.6	N···C 0.5; C···C 1.3; Cl···H 13.1; Cl···C 3.4
FruNAlla^b	β-pyranose	15.2	67.7	16.9	C···C 0.1
FruNBn₂^c	β-pyranose	16.5	64.2	19.2	C···O 0.1
TagNMBn^d	α-pyranose	20.6	65.8	13.5	O···O 0.1

Notes: (a) Mossine et al. (2009); (b) Mossine et al. (2009a); (c) Hou et al. (2001); (d) Pérez et al. (1978).

Supplementary Table S1. Chemical shifts (ppm) of peaks for selected carbon atoms in a ¹³C NMR spectrum of (I) in D₂O/pyridine (1:1) at 293 K and in the solid state top

Carbon	α-pyranose	β-pyranose	α-furanose	β-furanose	acyclic keto	solid state
C1	60.97	63.21	61.28	61.28	62.41	57.23
C2	101.13	101.56	108.26	105.62	215.08	210.04
C3	73.62	71.99	84.62	79.73	78.93	77.80
C4	74.92	72.98	80.26	77.42	74.96	69.59
C5	66.66	71.99	85.64	83.77	73.45	69.59
C6	63.7	65.90	64.37	65.14	65.81	64.70
C13	n.r.	42.62	n.r.	42.09	41.85	39.56

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Crystal structure of the acyclic form of 1-de­oxy-1-[(4-methoxyphenyl)(methyl)amino]-D-fructose

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Crystal structure of the acyclic form of 1-deoxy-1-[(4-methoxyphenyl)(methyl)amino]-D-fructose