(R)-1-[(S)-(3-Cyano-thio-morpholino)carbon-yl]-2-methyl-propyl-aminium chloride dihydrate.

In the title compound, C(10)H(18)N(3)OS(+)·Cl(-)·2H(2)O, the three C atoms of the isopropyl group are disordered and were refined using a split-site mode [occupancy ratio 0.53 (3):0.47 (3)]. In the crystal, the cations, anions and water mol-ecules are connected via O-H⋯O, O-H⋯Cl, N-H⋯Cl and N-H⋯O hydrogen bonding.

Related literature

For N-substituted thio­morpholine derivatives as potentialdipeptidyl peptidase IV(DPP-IV) inhibitors, see: Engel et al. (2003 ▶). For their biological activity, see: Mu et al. (2006 ▶); Proost et al. (1998 ▶). For the synthesis, see: Li et al. (2007 ▶)

Experimental

Crystal data

C10H18N3OS+·Cl−·2H2O

M = 299.82

Monoclinic,

a = 9.6425 (19) Å

b = 6.8180 (14) Å

c = 12.082 (2) Å

β = 99.25 (3)°

V = 784.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.38 mm−1

T = 113 K

0.24 × 0.20 × 0.16 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.914, T max = 0.942

6464 measured reflections

3554 independent reflections

2987 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.066

S = 1.00

3554 reflections

216 parameters

49 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.35 e Å−3

Absolute structure: Flack (1983 ▶), 1544 Friedel pairs

Flack parameter: −0.03 (4)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536809050624/nc2164sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809050624/nc2164Isup2.hkl

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

C10H18N3OS+·Cl−·2H2O	F(000) = 320
Mr = 299.82	Dx = 1.270 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.6425 (19) Å	Cell parameters from 2714 reflections
b = 6.8180 (14) Å	θ = 3.0–27.9°
c = 12.082 (2) Å	µ = 0.38 mm−1
β = 99.25 (3)°	T = 113 K
V = 784.0 (3) Å3	Block, colorless
Z = 2	0.24 × 0.20 × 0.16 mm

Rigaku Saturn CCD area-detector diffractometer	3554 independent reflections
Radiation source: rotating anode	2987 reflections with I > 2σ(I)
confocal	Rint = 0.028
Detector resolution: 7.31 pixels mm-1	θmax = 27.9°, θmin = 1.7°
ω and φ scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→8
Tmin = 0.914, Tmax = 0.942	l = −11→15
6464 measured reflections

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066	w = 1/[σ2(Fo2) + (0.0336P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
3554 reflections	Δρmax = 0.20 e Å−3
216 parameters	Δρmin = −0.35 e Å−3
49 restraints	Absolute structure: Flack (1983), 1535 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.03 (4)

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	Occ. (<1)
S1	−0.41733 (4)	0.64231 (8)	0.03966 (4)	0.03201 (12)
O1	−0.03965 (11)	0.5796 (2)	0.38313 (8)	0.0233 (3)
N1	−0.12007 (18)	0.2338 (3)	0.05250 (14)	0.0364 (4)
N2	−0.12711 (12)	0.6463 (2)	0.20239 (10)	0.0155 (3)
N3	0.10799 (15)	0.8983 (2)	0.42585 (11)	0.0158 (3)
H3A	0.186 (2)	0.986 (3)	0.4463 (14)	0.024*
H3B	0.1398 (19)	0.784 (3)	0.4706 (15)	0.024*
H3C	0.041 (2)	0.947 (3)	0.4483 (14)	0.024*
C1	−0.16317 (19)	0.3355 (3)	0.11428 (15)	0.0232 (4)
C2	−0.21136 (16)	0.4683 (3)	0.19675 (12)	0.0181 (3)
H2	−0.1927	0.4031	0.2718	0.022*
C3	−0.36913 (17)	0.5114 (3)	0.16917 (13)	0.0251 (4)
H3D	−0.3975	0.5895	0.2309	0.030*
H3E	−0.4214	0.3859	0.1648	0.030*
C4	−0.29541 (17)	0.8435 (3)	0.07232 (15)	0.0253 (4)
H4A	−0.3025	0.9325	0.0069	0.030*
H4B	−0.3208	0.9191	0.1361	0.030*
C5	−0.14514 (17)	0.7707 (3)	0.10221 (13)	0.0180 (3)
H5A	−0.1198	0.6951	0.0384	0.022*
H5B	−0.0809	0.8845	0.1156	0.022*
C6	−0.04067 (15)	0.6840 (2)	0.30047 (12)	0.0154 (3)
C7	0.06389 (15)	0.8528 (2)	0.30441 (11)	0.0148 (3)
H7A	0.0150	0.9647	0.2691	0.018*	0.53 (3)
H7B	0.0196	0.9649	0.2656	0.018*	0.47 (3)
C8	0.1874 (9)	0.8031 (14)	0.2407 (11)	0.024 (3)	0.53 (3)
H8	0.1468	0.7550	0.1642	0.028*	0.53 (3)
C9	0.2793 (11)	0.641 (2)	0.3005 (11)	0.041 (2)	0.53 (3)
H9A	0.3459	0.5962	0.2526	0.062*	0.53 (3)
H9B	0.2200	0.5310	0.3161	0.062*	0.53 (3)
H9C	0.3311	0.6917	0.3711	0.062*	0.53 (3)
C10	0.2733 (12)	0.9874 (18)	0.2277 (11)	0.047 (2)	0.53 (3)
H10A	0.3165	1.0345	0.3019	0.070*	0.53 (3)
H10B	0.2116	1.0893	0.1897	0.070*	0.53 (3)
H10C	0.3470	0.9566	0.1832	0.070*	0.53 (3)
C8'	0.1900 (8)	0.7874 (14)	0.2504 (11)	0.019 (3)	0.47 (3)
H8'	0.1524	0.7688	0.1690	0.023*	0.47 (3)
C9'	0.2515 (12)	0.5906 (16)	0.2911 (13)	0.034 (2)	0.47 (3)
H9D	0.3310	0.5595	0.2528	0.052*	0.47 (3)
H9E	0.1795	0.4887	0.2746	0.052*	0.47 (3)
H9F	0.2839	0.5964	0.3722	0.052*	0.47 (3)
C10'	0.3015 (10)	0.9447 (18)	0.2549 (12)	0.036 (2)	0.47 (3)
H10D	0.3581	0.9474	0.3299	0.053*	0.47 (3)
H10E	0.2564	1.0726	0.2385	0.053*	0.47 (3)
H10F	0.3622	0.9161	0.1992	0.053*	0.47 (3)
Cl1	0.21552 (4)	0.56119 (6)	0.61863 (3)	0.01970 (9)
O2	0.67759 (13)	0.6702 (2)	0.49074 (11)	0.0268 (3)
H2A	0.703 (2)	0.768 (4)	0.4543 (18)	0.040*
H2B	0.611 (2)	0.735 (4)	0.5235 (17)	0.040*
O3	0.47478 (13)	0.8267 (2)	0.59628 (12)	0.0324 (3)
H3F	0.407 (3)	0.756 (4)	0.6016 (18)	0.049*
H3G	0.436 (2)	0.934 (4)	0.5706 (18)	0.049*

	U11	U22	U33	U12	U13	U23
S1	0.0217 (2)	0.0299 (3)	0.0392 (3)	−0.00703 (19)	−0.01085 (17)	0.0057 (2)
O1	0.0302 (6)	0.0248 (7)	0.0141 (5)	−0.0081 (5)	0.0005 (4)	0.0054 (5)
N1	0.0515 (11)	0.0204 (10)	0.0419 (10)	−0.0008 (8)	0.0216 (8)	−0.0005 (7)
N2	0.0165 (6)	0.0134 (7)	0.0157 (6)	−0.0021 (6)	−0.0002 (5)	0.0013 (5)
N3	0.0151 (6)	0.0182 (8)	0.0143 (6)	−0.0016 (6)	0.0031 (5)	−0.0042 (5)
C1	0.0285 (9)	0.0151 (9)	0.0258 (8)	−0.0034 (7)	0.0040 (7)	0.0033 (7)
C2	0.0219 (8)	0.0168 (9)	0.0157 (7)	−0.0055 (6)	0.0031 (6)	0.0016 (6)
C3	0.0200 (8)	0.0262 (11)	0.0292 (9)	−0.0059 (7)	0.0045 (6)	−0.0007 (7)
C4	0.0210 (8)	0.0209 (10)	0.0309 (9)	−0.0011 (7)	−0.0046 (7)	0.0055 (8)
C5	0.0194 (8)	0.0163 (9)	0.0173 (8)	−0.0031 (6)	−0.0002 (6)	0.0055 (6)
C6	0.0159 (7)	0.0161 (9)	0.0145 (7)	0.0012 (6)	0.0029 (5)	−0.0016 (6)
C7	0.0149 (7)	0.0175 (9)	0.0115 (7)	−0.0009 (6)	0.0008 (5)	0.0001 (6)
C8	0.019 (4)	0.035 (4)	0.019 (4)	0.008 (3)	0.007 (3)	0.003 (3)
C9	0.022 (3)	0.065 (5)	0.039 (3)	0.015 (3)	0.011 (3)	0.006 (4)
C10	0.043 (4)	0.064 (5)	0.038 (4)	−0.028 (3)	0.021 (3)	−0.007 (3)
C8'	0.015 (4)	0.035 (5)	0.008 (3)	−0.011 (3)	0.000 (3)	−0.003 (3)
C9'	0.024 (3)	0.040 (4)	0.042 (4)	0.018 (3)	0.013 (3)	0.009 (3)
C10'	0.028 (3)	0.049 (4)	0.036 (4)	−0.012 (3)	0.022 (3)	−0.011 (3)
Cl1	0.01873 (17)	0.0176 (2)	0.02289 (18)	−0.00188 (16)	0.00372 (13)	0.00047 (16)
O2	0.0250 (6)	0.0215 (8)	0.0359 (7)	0.0045 (6)	0.0106 (5)	0.0060 (6)
O3	0.0219 (7)	0.0244 (8)	0.0526 (9)	−0.0029 (6)	0.0118 (6)	0.0001 (7)

S1—C3	1.7965 (17)	C7—H7A	0.9601
S1—C4	1.8085 (18)	C7—H7B	0.9601
O1—C6	1.2251 (18)	C8—C9	1.523 (8)
N1—C1	1.145 (2)	C8—C10	1.527 (7)
N2—C6	1.3594 (18)	C8—H8	1.0000
N2—C2	1.456 (2)	C9—H9A	0.9800
N2—C5	1.465 (2)	C9—H9B	0.9800
N3—C7	1.4931 (18)	C9—H9C	0.9800
N3—H3A	0.96 (2)	C10—H10A	0.9800
N3—H3B	0.97 (2)	C10—H10B	0.9800
N3—H3C	0.807 (18)	C10—H10C	0.9800
C1—C2	1.476 (2)	C8'—C10'	1.514 (7)
C2—C3	1.533 (2)	C8'—C9'	1.517 (8)
C2—H2	1.0000	C8'—H8'	1.0000
C3—H3D	0.9900	C9'—H9D	0.9800
C3—H3E	0.9900	C9'—H9E	0.9800
C4—C5	1.519 (2)	C9'—H9F	0.9800
C4—H4A	0.9900	C10'—H10D	0.9800
C4—H4B	0.9900	C10'—H10E	0.9800
C5—H5A	0.9900	C10'—H10F	0.9800
C5—H5B	0.9900	O2—H2A	0.85 (2)
C6—C7	1.525 (2)	O2—H2B	0.92 (2)
C7—C8'	1.535 (7)	O3—H3F	0.82 (2)
C7—C8	1.555 (7)	O3—H3G	0.86 (3)
C3—S1—C4	96.81 (8)	C6—C7—C8'	109.4 (4)
C6—N2—C2	117.26 (13)	N3—C7—C8	114.3 (5)
C6—N2—C5	125.82 (14)	C6—C7—C8	112.0 (4)
C2—N2—C5	116.91 (12)	C8'—C7—C8	5.8 (8)
C7—N3—H3A	118.0 (10)	N3—C7—H7A	108.3
C7—N3—H3B	113.3 (11)	C6—C7—H7A	108.1
H3A—N3—H3B	101.0 (15)	C8'—C7—H7A	114.1
C7—N3—H3C	107.4 (13)	C8—C7—H7A	108.3
H3A—N3—H3C	107.0 (17)	N3—C7—H7B	110.4
H3B—N3—H3C	109.8 (17)	C6—C7—H7B	110.2
N1—C1—C2	177.1 (2)	C8'—C7—H7B	110.1
N2—C2—C1	108.01 (12)	C8—C7—H7B	104.3
N2—C2—C3	112.16 (14)	H7A—C7—H7B	3.9
C1—C2—C3	112.35 (14)	C9—C8—C10	111.2 (6)
N2—C2—H2	108.1	C9—C8—C7	110.9 (7)
C1—C2—H2	108.1	C10—C8—C7	110.1 (6)
C3—C2—H2	108.1	C9—C8—H8	108.2
C2—C3—S1	113.17 (11)	C10—C8—H8	108.2
C2—C3—H3D	108.9	C7—C8—H8	108.2
S1—C3—H3D	108.9	C10'—C8'—C9'	112.1 (6)
C2—C3—H3E	108.9	C10'—C8'—C7	112.7 (6)
S1—C3—H3E	108.9	C9'—C8'—C7	114.5 (7)
H3D—C3—H3E	107.8	C10'—C8'—H8'	105.6
C5—C4—S1	111.44 (13)	C9'—C8'—H8'	105.6
C5—C4—H4A	109.3	C7—C8'—H8'	105.6
S1—C4—H4A	109.3	C8'—C9'—H9D	109.5
C5—C4—H4B	109.3	C8'—C9'—H9E	109.5
S1—C4—H4B	109.3	H9D—C9'—H9E	109.5
H4A—C4—H4B	108.0	C8'—C9'—H9F	109.5
N2—C5—C4	111.57 (13)	H9D—C9'—H9F	109.5
N2—C5—H5A	109.3	H9E—C9'—H9F	109.5
C4—C5—H5A	109.3	C8'—C10'—H10D	109.5
N2—C5—H5B	109.3	C8'—C10'—H10E	109.5
C4—C5—H5B	109.3	H10D—C10'—H10E	109.5
H5A—C5—H5B	108.0	C8'—C10'—H10F	109.5
O1—C6—N2	121.61 (15)	H10D—C10'—H10F	109.5
O1—C6—C7	119.60 (13)	H10E—C10'—H10F	109.5
N2—C6—C7	118.67 (13)	H2A—O2—H2B	97 (2)
N3—C7—C6	105.67 (11)	H3F—O3—H3G	103 (2)
N3—C7—C8'	111.0 (5)
C6—N2—C2—C1	−114.30 (15)	N2—C6—C7—N3	162.20 (13)
C5—N2—C2—C1	66.80 (17)	O1—C6—C7—C8'	97.7 (6)
C6—N2—C2—C3	121.36 (15)	N2—C6—C7—C8'	−78.2 (6)
C5—N2—C2—C3	−57.54 (17)	O1—C6—C7—C8	103.3 (5)
N1—C1—C2—N2	49 (4)	N2—C6—C7—C8	−72.7 (5)
N1—C1—C2—C3	173 (4)	N3—C7—C8—C9	52.9 (9)
N2—C2—C3—S1	57.51 (16)	C6—C7—C8—C9	−67.3 (10)
C1—C2—C3—S1	−64.39 (17)	C8'—C7—C8—C9	−3(8)
C4—S1—C3—C2	−54.02 (14)	N3—C7—C8—C10	−70.6 (9)
C3—S1—C4—C5	56.05 (13)	C6—C7—C8—C10	169.3 (7)
C6—N2—C5—C4	−118.33 (16)	C8'—C7—C8—C10	−127 (9)
C2—N2—C5—C4	60.48 (18)	N3—C7—C8'—C10'	−61.6 (9)
S1—C4—C5—N2	−61.99 (17)	C6—C7—C8'—C10'	−177.9 (8)
C2—N2—C6—O1	−4.4 (2)	C8—C7—C8'—C10'	64 (8)
C5—N2—C6—O1	174.41 (15)	N3—C7—C8'—C9'	68.0 (10)
C2—N2—C6—C7	171.52 (12)	C6—C7—C8'—C9'	−48.2 (11)
C5—N2—C6—C7	−9.7 (2)	C8—C7—C8'—C9'	−166 (9)
O1—C6—C7—N3	−21.81 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2i	0.96 (2)	1.89 (2)	2.838 (2)	169.3 (15)
N3—H3B···Cl1	0.97 (2)	2.37 (2)	3.3178 (16)	165.3 (15)
N3—H3C···O1ii	0.807 (18)	2.232 (18)	2.7891 (17)	126.6 (17)
N3—H3C···Cl1ii	0.807 (18)	2.599 (19)	3.2732 (16)	142.0 (16)
O2—H2A···Cl1i	0.85 (2)	2.37 (3)	3.2176 (15)	171 (2)
O2—H2B···O3	0.92 (2)	1.81 (2)	2.7186 (19)	171 (2)
O3—H3F···Cl1	0.82 (2)	2.31 (2)	3.1332 (15)	179 (2)
O3—H3G···O2i	0.86 (3)	2.02 (3)	2.873 (2)	173 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2i	0.96 (2)	1.89 (2)	2.838 (2)	169.3 (15)
N3—H3B⋯Cl1	0.97 (2)	2.37 (2)	3.3178 (16)	165.3 (15)
N3—H3C⋯O1ii	0.807 (18)	2.232 (18)	2.7891 (17)	126.6 (17)
N3—H3C⋯Cl1ii	0.807 (18)	2.599 (19)	3.2732 (16)	142.0 (16)
O2—H2A⋯Cl1i	0.85 (2)	2.37 (3)	3.2176 (15)	171 (2)
O2—H2B⋯O3	0.92 (2)	1.81 (2)	2.7186 (19)	171 (2)
O3—H3F⋯Cl1	0.82 (2)	2.31 (2)	3.1332 (15)	179 (2)
O3—H3G⋯O2i	0.86 (3)	2.02 (3)	2.873 (2)	173 (2)

Symmetry codes: (i) ; (ii) .