1-(2,3,4,6-Tetra-O-acetyl-β-d-gluco-pyranos-yl)-3-thio-ureidothio-urea monohydrate.

In the title compound, C(16)H(24)N(4)O(9)S(2)·H(2)O, the hexopyranosyl ring adopts a chair conformation ((4)C(1)), and the five substituents are in equatorial positions. In the crystal structure, extensive O-H⋯O, N-H⋯S and N-H⋯O hydrogen bonding leads to the formation of a three-dimensional network.

Related literature

For cyclo­addition and nucleophilic addition, see: Pearson et al. (2003 ▶); Reitz et al. (1989 ▶). For the crystal structure of glycosyl isothio­syanate, see: Jiang et al. (2003 ▶). For the crystal structures of glycosyl isothio­syanate methanol and ethanol derivatives, see: Zhang et al. (2001 ▶).

Experimental

Crystal data

C16H24N4O9S2·H2O

M = 498.53

Monoclinic,

a = 22.286 (2) Å

b = 7.2005 (7) Å

c = 15.8772 (17) Å

β = 110.119 (2)°

V = 2392.3 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 293 (2) K

0.45 × 0.22 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: none

6322 measured reflections

3525 independent reflections

3021 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.141

S = 1.07

3525 reflections

289 parameters

7 restraints

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.27 e Å−3

Absolute structure: Flack (1983 ▶), 1229 Friedel pairs

Flack parameter: −0.16 (12)

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043833/su2088sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043833/su2088Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H24N4O9S2·H2O	F(000) = 1048
Mr = 498.53	Dx = 1.384 Mg m−3
Monoclinic, C2	Melting point: not measured K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 22.286 (2) Å	Cell parameters from 7141 reflections
b = 7.2005 (7) Å	θ = 1.4–27.7°
c = 15.8772 (17) Å	µ = 0.28 mm−1
β = 110.119 (2)°	T = 293 K
V = 2392.3 (4) Å3	Block, colorless
Z = 4	0.45 × 0.22 × 0.22 mm

Bruker SMART CCD area-detector diffractometer	3021 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 25.0°, θmin = 1.4°
φ scans, and ω scans	h = −25→26
6322 measured reflections	k = −8→8
3525 independent reflections	l = −18→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H-atom parameters constrained
wR(F2) = 0.141	w = 1/[σ2(Fo2) + (0.0808P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3525 reflections	Δρmax = 0.42 e Å−3
289 parameters	Δρmin = −0.27 e Å−3
7 restraints	Absolute structure: Flack (1983), 1229 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.16 (12)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1W	0.0457 (4)	0.2431 (10)	0.3624 (6)	0.193 (3)
H10	0.0696	0.2068	0.3324	0.232*
H20	0.0081	0.1989	0.3326	0.232*
S1	1.01347 (6)	0.9344 (2)	0.17559 (9)	0.0605 (4)
S2	1.09337 (7)	0.5527 (2)	0.56716 (9)	0.0720 (5)
O1	0.87014 (12)	0.9697 (4)	0.28332 (19)	0.0433 (7)
O2	0.79211 (13)	1.1140 (5)	0.37749 (19)	0.0493 (8)
O3	0.69458 (16)	1.2284 (7)	0.3502 (3)	0.0796 (12)
O4	0.69663 (12)	0.9277 (5)	0.18084 (19)	0.0467 (7)
O5	0.67103 (18)	0.7887 (8)	0.2901 (3)	0.0880 (14)
O6	0.73828 (13)	0.5785 (4)	0.14481 (18)	0.0455 (7)
O7	0.71021 (18)	0.5906 (6)	−0.0050 (2)	0.0732 (11)
O8	0.86480 (13)	0.5944 (4)	0.12682 (18)	0.0464 (7)
O9	0.9131 (2)	0.3601 (6)	0.2159 (3)	0.0902 (14)
N1	0.95480 (15)	0.7892 (5)	0.2819 (2)	0.0427 (9)
H1A	0.9581	0.7239	0.3287	0.051*
N2	1.06247 (16)	0.7629 (6)	0.3289 (2)	0.0490 (10)
H2A	1.0987	0.7961	0.3256	0.059*
N3	1.06233 (17)	0.6483 (6)	0.3986 (2)	0.0496 (10)
H3A	1.0510	0.5342	0.3874	0.060*
N4	1.0852 (2)	0.8905 (7)	0.4975 (3)	0.0695 (13)
H4B	1.0779	0.9645	0.4526	0.083*
H4C	1.0960	0.9345	0.5510	0.083*
C1	0.89174 (18)	0.8500 (6)	0.2278 (3)	0.0396 (10)
H1B	0.8940	0.9195	0.1759	0.047*
C2	0.84790 (19)	0.6840 (6)	0.1959 (3)	0.0387 (10)
H2B	0.8538	0.5977	0.2459	0.046*
C3	0.77758 (18)	0.7409 (6)	0.1562 (3)	0.0387 (10)
H3B	0.7693	0.8028	0.0983	0.046*
C4	0.76213 (18)	0.8694 (6)	0.2203 (3)	0.0396 (10)
H4A	0.7681	0.8044	0.2768	0.047*
C5	0.8067 (2)	1.0374 (6)	0.2378 (3)	0.0423 (10)
H5A	0.8048	1.0902	0.1800	0.051*
C6	0.7926 (2)	1.1884 (7)	0.2936 (3)	0.0487 (11)
H6A	0.8249	1.2848	0.3050	0.058*
H6B	0.7514	1.2436	0.2612	0.058*
C7	0.7401 (3)	1.1452 (8)	0.3977 (4)	0.0586 (13)
C8	0.7464 (4)	1.0653 (12)	0.4877 (5)	0.102 (2)
H8A	0.7080	1.0891	0.5004	0.153*
H8B	0.7820	1.1220	0.5331	0.153*
H8C	0.7532	0.9337	0.4872	0.153*
C9	0.6553 (2)	0.8752 (8)	0.2213 (4)	0.0534 (12)
C10	0.5887 (2)	0.9374 (11)	0.1689 (4)	0.0745 (16)
H10A	0.5601	0.8955	0.1984	0.112*
H10B	0.5758	0.8859	0.1096	0.112*
H10C	0.5874	1.0705	0.1653	0.112*
C11	0.7051 (2)	0.5239 (7)	0.0609 (3)	0.0499 (12)
C12	0.6616 (3)	0.3661 (9)	0.0615 (4)	0.0735 (17)
H12A	0.6389	0.3273	0.0011	0.110*
H12B	0.6316	0.4054	0.0892	0.110*
H12C	0.6864	0.2642	0.0948	0.110*
C13	0.8985 (2)	0.4365 (7)	0.1448 (3)	0.0495 (11)
C14	0.9150 (2)	0.3741 (8)	0.0673 (4)	0.0643 (14)
H14A	0.9387	0.2602	0.0819	0.096*
H14B	0.9405	0.4672	0.0523	0.096*
H14C	0.8765	0.3543	0.0170	0.096*
C15	1.00857 (19)	0.8254 (6)	0.2658 (3)	0.0418 (10)
C16	1.0796 (2)	0.7105 (7)	0.4844 (3)	0.0495 (12)

	U11	U22	U33	U12	U13	U23
O1W	0.265 (7)	0.099 (4)	0.166 (5)	0.007 (5)	0.012 (5)	−0.014 (4)
S1	0.0520 (7)	0.0731 (9)	0.0629 (8)	0.0127 (7)	0.0280 (6)	0.0215 (7)
S2	0.0840 (10)	0.0872 (11)	0.0403 (7)	0.0242 (8)	0.0154 (6)	0.0036 (7)
O1	0.0333 (14)	0.0484 (18)	0.0460 (17)	−0.0008 (13)	0.0109 (13)	−0.0055 (14)
O2	0.0468 (17)	0.053 (2)	0.0451 (18)	0.0115 (15)	0.0115 (14)	−0.0022 (15)
O3	0.050 (2)	0.104 (3)	0.088 (3)	0.024 (2)	0.029 (2)	0.003 (3)
O4	0.0344 (14)	0.0564 (19)	0.0471 (17)	0.0005 (15)	0.0112 (13)	−0.0011 (16)
O5	0.062 (2)	0.121 (4)	0.089 (3)	−0.011 (2)	0.036 (2)	0.022 (3)
O6	0.0445 (16)	0.0522 (19)	0.0344 (15)	−0.0082 (15)	0.0066 (13)	−0.0036 (14)
O7	0.092 (3)	0.079 (3)	0.0369 (19)	−0.017 (2)	0.0069 (18)	−0.0039 (19)
O8	0.0526 (17)	0.0488 (18)	0.0352 (15)	0.0105 (16)	0.0118 (13)	−0.0008 (14)
O9	0.132 (4)	0.073 (3)	0.081 (3)	0.047 (3)	0.056 (3)	0.023 (2)
N1	0.0352 (18)	0.051 (2)	0.041 (2)	0.0027 (17)	0.0117 (15)	0.0089 (17)
N2	0.0342 (19)	0.069 (3)	0.044 (2)	0.0034 (18)	0.0148 (17)	0.008 (2)
N3	0.046 (2)	0.052 (2)	0.040 (2)	0.0041 (18)	0.0019 (17)	−0.0040 (18)
N4	0.079 (3)	0.073 (3)	0.051 (3)	−0.007 (2)	0.016 (2)	−0.015 (2)
C1	0.038 (2)	0.042 (2)	0.039 (2)	0.0045 (19)	0.0128 (18)	0.0030 (19)
C2	0.041 (2)	0.047 (2)	0.028 (2)	0.0074 (19)	0.0111 (18)	0.0022 (18)
C3	0.036 (2)	0.044 (2)	0.033 (2)	−0.001 (2)	0.0078 (17)	0.0021 (19)
C4	0.031 (2)	0.051 (3)	0.035 (2)	0.0046 (19)	0.0101 (17)	0.0036 (19)
C5	0.042 (2)	0.042 (2)	0.041 (2)	0.001 (2)	0.0108 (19)	0.000 (2)
C6	0.049 (3)	0.041 (3)	0.056 (3)	−0.004 (2)	0.017 (2)	−0.002 (2)
C7	0.059 (3)	0.057 (3)	0.065 (3)	0.003 (3)	0.028 (3)	−0.008 (3)
C8	0.145 (6)	0.096 (5)	0.087 (5)	0.033 (5)	0.068 (4)	0.017 (4)
C9	0.044 (3)	0.060 (3)	0.059 (3)	−0.012 (2)	0.021 (2)	−0.012 (3)
C10	0.041 (3)	0.103 (5)	0.080 (4)	−0.006 (3)	0.022 (3)	−0.016 (4)
C11	0.046 (3)	0.052 (3)	0.045 (3)	0.003 (2)	0.007 (2)	−0.009 (2)
C12	0.068 (3)	0.075 (4)	0.062 (3)	−0.022 (3)	0.003 (3)	−0.018 (3)
C13	0.054 (3)	0.046 (3)	0.047 (3)	0.006 (2)	0.016 (2)	0.006 (3)
C14	0.062 (3)	0.067 (4)	0.070 (3)	0.014 (3)	0.031 (3)	−0.008 (3)
C15	0.037 (2)	0.045 (3)	0.043 (2)	0.007 (2)	0.0136 (19)	−0.005 (2)
C16	0.034 (2)	0.066 (3)	0.045 (3)	0.009 (2)	0.010 (2)	−0.011 (2)

O1W—H10	0.868 (10)	C1—C2	1.516 (6)
O1W—H20	0.867 (8)	C1—H1B	0.9800
S1—C15	1.669 (5)	C2—C3	1.530 (5)
S2—C16	1.684 (5)	C2—H2B	0.9800
O1—C1	1.430 (5)	C3—C4	1.501 (6)
O1—C5	1.434 (5)	C3—H3B	0.9800
O2—C7	1.324 (6)	C4—C5	1.528 (6)
O2—C6	1.439 (6)	C4—H4A	0.9800
O3—C7	1.196 (6)	C5—C6	1.503 (6)
O4—C9	1.345 (6)	C5—H5A	0.9800
O4—C4	1.439 (5)	C6—H6A	0.9700
O5—C9	1.200 (6)	C6—H6B	0.9700
O6—C11	1.342 (5)	C7—C8	1.501 (9)
O6—C3	1.435 (5)	C8—H8A	0.9600
O7—C11	1.192 (6)	C8—H8B	0.9600
O8—C13	1.338 (6)	C8—H8C	0.9600
O8—C2	1.430 (5)	C9—C10	1.500 (7)
O9—C13	1.195 (6)	C10—H10A	0.9600
N1—C15	1.335 (5)	C10—H10B	0.9600
N1—C1	1.440 (5)	C10—H10C	0.9600
N1—H1A	0.8600	C11—C12	1.496 (8)
N2—C15	1.349 (5)	C12—H12A	0.9600
N2—N3	1.382 (5)	C12—H12B	0.9600
N2—H2A	0.8600	C12—H12C	0.9600
N3—C16	1.358 (6)	C13—C14	1.471 (7)
N3—H3A	0.8600	C14—H14A	0.9600
N4—C16	1.312 (7)	C14—H14B	0.9600
N4—H4B	0.8600	C14—H14C	0.9600
N4—H4C	0.8600
H10—O1W—H20	104.6 (8)	O2—C6—C5	110.3 (4)
C1—O1—C5	112.1 (3)	O2—C6—H6A	109.6
C7—O2—C6	116.6 (4)	C5—C6—H6A	109.6
C9—O4—C4	117.9 (4)	O2—C6—H6B	109.6
C11—O6—C3	117.9 (3)	C5—C6—H6B	109.6
C13—O8—C2	119.8 (3)	H6A—C6—H6B	108.1
C15—N1—C1	125.6 (4)	O3—C7—O2	123.8 (5)
C15—N1—H1A	117.2	O3—C7—C8	124.9 (5)
C1—N1—H1A	117.2	O2—C7—C8	111.3 (5)
C15—N2—N3	123.2 (4)	C7—C8—H8A	109.5
C15—N2—H2A	118.4	C7—C8—H8B	109.5
N3—N2—H2A	118.4	H8A—C8—H8B	109.5
C16—N3—N2	121.9 (4)	C7—C8—H8C	109.5
C16—N3—H3A	119.0	H8A—C8—H8C	109.5
N2—N3—H3A	119.0	H8B—C8—H8C	109.5
C16—N4—H4B	120.0	O5—C9—O4	123.2 (5)
C16—N4—H4C	120.0	O5—C9—C10	125.6 (5)
H4B—N4—H4C	120.0	O4—C9—C10	111.2 (5)
O1—C1—N1	106.4 (3)	C9—C10—H10A	109.5
O1—C1—C2	111.5 (3)	C9—C10—H10B	109.5
N1—C1—C2	110.1 (4)	H10A—C10—H10B	109.5
O1—C1—H1B	109.6	C9—C10—H10C	109.5
N1—C1—H1B	109.6	H10A—C10—H10C	109.5
C2—C1—H1B	109.6	H10B—C10—H10C	109.5
O8—C2—C1	107.6 (3)	O7—C11—O6	124.5 (4)
O8—C2—C3	107.9 (3)	O7—C11—C12	124.8 (5)
C1—C2—C3	112.2 (3)	O6—C11—C12	110.7 (4)
O8—C2—H2B	109.7	C11—C12—H12A	109.5
C1—C2—H2B	109.7	C11—C12—H12B	109.5
C3—C2—H2B	109.7	H12A—C12—H12B	109.5
O6—C3—C4	108.4 (3)	C11—C12—H12C	109.5
O6—C3—C2	109.1 (3)	H12A—C12—H12C	109.5
C4—C3—C2	109.1 (3)	H12B—C12—H12C	109.5
O6—C3—H3B	110.1	O9—C13—O8	122.9 (4)
C4—C3—H3B	110.1	O9—C13—C14	125.8 (5)
C2—C3—H3B	110.1	O8—C13—C14	111.4 (4)
O4—C4—C3	108.7 (3)	C13—C14—H14A	109.5
O4—C4—C5	110.3 (3)	C13—C14—H14B	109.5
C3—C4—C5	109.0 (3)	H14A—C14—H14B	109.5
O4—C4—H4A	109.7	C13—C14—H14C	109.5
C3—C4—H4A	109.7	H14A—C14—H14C	109.5
C5—C4—H4A	109.7	H14B—C14—H14C	109.5
O1—C5—C6	108.5 (3)	N1—C15—N2	114.9 (4)
O1—C5—C4	106.8 (3)	N1—C15—S1	125.8 (3)
C6—C5—C4	115.2 (4)	N2—C15—S1	119.3 (3)
O1—C5—H5A	108.7	N4—C16—N3	117.6 (5)
C6—C5—H5A	108.7	N4—C16—S2	124.1 (4)
C4—C5—H5A	108.7	N3—C16—S2	118.2 (4)
C15—N2—N3—C16	−107.9 (5)	C1—O1—C5—C6	−169.4 (3)
C5—O1—C1—N1	−178.7 (3)	C1—O1—C5—C4	65.9 (4)
C5—O1—C1—C2	−58.6 (4)	O4—C4—C5—O1	175.5 (3)
C15—N1—C1—O1	−116.8 (4)	C3—C4—C5—O1	−65.3 (4)
C15—N1—C1—C2	122.3 (5)	O4—C4—C5—C6	54.9 (5)
C13—O8—C2—C1	103.9 (4)	C3—C4—C5—C6	174.1 (4)
C13—O8—C2—C3	−134.9 (4)	C7—O2—C6—C5	−125.6 (4)
O1—C1—C2—O8	168.0 (3)	O1—C5—C6—O2	−64.5 (4)
N1—C1—C2—O8	−74.2 (4)	C4—C5—C6—O2	55.1 (5)
O1—C1—C2—C3	49.5 (4)	C6—O2—C7—O3	0.8 (7)
N1—C1—C2—C3	167.3 (3)	C6—O2—C7—C8	−178.4 (5)
C11—O6—C3—C4	129.2 (4)	C4—O4—C9—O5	2.9 (7)
C11—O6—C3—C2	−112.1 (4)	C4—O4—C9—C10	−176.6 (4)
O8—C2—C3—O6	73.5 (4)	C3—O6—C11—O7	7.1 (7)
C1—C2—C3—O6	−168.1 (3)	C3—O6—C11—C12	−173.9 (4)
O8—C2—C3—C4	−168.2 (3)	C2—O8—C13—O9	3.6 (7)
C1—C2—C3—C4	−49.9 (4)	C2—O8—C13—C14	−175.8 (4)
C9—O4—C4—C3	115.1 (4)	C1—N1—C15—N2	176.3 (4)
C9—O4—C4—C5	−125.6 (4)	C1—N1—C15—S1	−5.0 (7)
O6—C3—C4—O4	−63.5 (4)	N3—N2—C15—N1	8.6 (6)
C2—C3—C4—O4	177.8 (3)	N3—N2—C15—S1	−170.2 (3)
O6—C3—C4—C5	176.4 (3)	N2—N3—C16—N4	12.4 (7)
C2—C3—C4—C5	57.7 (4)	N2—N3—C16—S2	−166.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H10···O5i	0.868 (10)	2.637 (4)	3.382 (11)	144.5 (5)
O1W—H20···O9ii	0.867 (8)	2.563 (4)	3.181 (9)	129.1 (5)
N1—H1A···S2iii	0.86	2.62	3.400 (4)	151
N2—H2A···O3iv	0.86	2.09	2.856 (5)	147
N3—H3A···O1Wv	0.86	2.13	2.973 (9)	167
N4—H4B···O1Wvi	0.86	2.43	3.244 (9)	159
N4—H4C···O1iii	0.86	2.49	3.323 (5)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H10⋯O5i	0.87	2.64	3.382 (11)	146
O1W—H20⋯O9ii	0.87	2.56	3.181 (9)	129
N1—H1A⋯S2iii	0.86	2.62	3.400 (4)	151
N2—H2A⋯O3iv	0.86	2.09	2.856 (5)	147
N3—H3A⋯O1Wv	0.86	2.13	2.973 (9)	167
N4—H4B⋯O1Wvi	0.86	2.43	3.244 (9)	159
N4—H4C⋯O1iii	0.86	2.49	3.323 (5)	164

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .