N-Methyl-l-leucyl-l-leucine hydro-chloride monohydrate.

In the title compound C(13)H(27)N(2)O(3) (+)·Cl(-)·H(2)O, obtained by deprotecting the amino and carboxyl groups of an inter-mediate in the synthesis of the cyclic penta-peptide Galaxamide, a number of hydrogen-bonding inter-actions occur including aminium N-H⋯Cl, amide-carboxyl N-H⋯O, water O-H⋯Cl and carbox-yl-water O-H⋯O associations. The aminium N-H⋯Cl⋯H-N bridging extensions give rise to zigzag chains extending along the a axis, the overall two-dimensional structure lying in the (110) plane.

Related literature

For general background to peptides, see: Humphrey & Chamberlin (1997 ▶). For the synthesis of Galaxamide, see: Xu, Liao, Xu et al. (2008 ▶); Rodriguez et al. (2007 ▶). For related structures, see: Liao et al. (2007 ▶); Xu, Liao, Diao et al. (2008 ▶).

Experimental

Crystal data

C13H27N2O3 +·Cl−·H2O

M = 312.83

Monoclinic,

a = 5.2212 (2) Å

b = 9.6032 (5) Å

c = 18.4081 (8) Å

β = 96.329 (4)°

V = 917.36 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 295 K

0.45 × 0.32 × 0.17 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 Gemini Ultra CCD diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T min = 0.990, T max = 1.000

3703 measured reflections

2616 independent reflections

2271 reflections with I > 2sI)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.114

S = 1.01

2616 reflections

186 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.22 e Å−3

Absolute structure: Flack (1983 ▶), 686 Friedel pairs

Flack parameter: −0.01 (8)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031126/zs2126sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031126/zs2126Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811031126/zs2126Isup3.cml

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

C13H27N2O3+·Cl−·H2O	F(000) = 340
Mr = 312.83	Dx = 1.133 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.7107 Å
a = 5.2212 (2) Å	Cell parameters from 1351 reflections
b = 9.6032 (5) Å	θ = 3.1–29.1°
c = 18.4081 (8) Å	µ = 0.22 mm−1
β = 96.329 (4)°	T = 295 K
V = 917.36 (7) Å3	Block, colourless
Z = 2	0.45 × 0.32 × 0.17 mm

Oxford Diffraction Xcalibur Sapphire3 Gemini Ultra CCD diffractometer	2616 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2271 reflections with I > 2s˘I)
graphite	Rint = 0.015
Detector resolution: 16.0288 pixels mm-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −7→11
Tmin = 0.990, Tmax = 1.000	l = −19→22
3703 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)] = 0.042	H-atom parameters constrained
wR(F2) = 0.114	w = 1/[σ2(Fo2) + (0.065P)2 + 0.1023P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
2616 reflections	Δρmax = 0.37 e Å−3
186 parameters	Δρmin = −0.22 e Å−3
1 restraint	Absolute structure: Flack (1983), 686 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (8)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O1	0.9159 (3)	0.8611 (2)	0.21026 (11)	0.0456 (7)
O2	1.1446 (4)	1.1632 (3)	0.27116 (12)	0.0647 (9)
O3	0.8114 (4)	1.1739 (3)	0.18571 (12)	0.0609 (8)
N1	0.5270 (4)	0.7595 (3)	0.09916 (12)	0.0467 (8)
N2	0.5803 (4)	0.9650 (3)	0.25512 (13)	0.0422 (8)
C1	0.4995 (5)	0.7609 (3)	0.17896 (15)	0.0407 (9)
C2	0.6837 (5)	0.8673 (3)	0.21552 (14)	0.0376 (8)
C3	0.7383 (5)	1.0686 (3)	0.29656 (15)	0.0429 (9)
C4	0.9252 (5)	1.1384 (3)	0.24936 (15)	0.0451 (9)
C5	0.5595 (5)	0.6146 (4)	0.20897 (15)	0.0460 (8)
C6	0.8781 (6)	1.0087 (4)	0.36714 (16)	0.0538 (10)
C7	0.5536 (5)	0.5991 (4)	0.29136 (15)	0.0477 (9)
C8	0.7036 (7)	0.9642 (5)	0.42373 (18)	0.0648 (13)
C9	0.6292 (8)	0.4502 (4)	0.3139 (2)	0.0718 (14)
C10	0.2924 (7)	0.6351 (6)	0.3153 (2)	0.0761 (14)
C11	0.8619 (12)	0.8836 (9)	0.4839 (3)	0.124 (3)
C12	0.5709 (8)	1.0854 (7)	0.4543 (2)	0.0883 (19)
C13	0.4878 (8)	0.8963 (5)	0.06236 (19)	0.0701 (14)
O4	1.0969 (8)	1.2934 (4)	0.09741 (19)	0.1200 (16)
Cl1	0.01614 (13)	0.60884 (9)	0.04716 (4)	0.0580 (3)
H1	0.32240	0.78610	0.18640	0.0490*
H1A	0.68570	0.72850	0.09280	0.0560*
H1B	0.41260	0.69860	0.07710	0.0560*
H2	0.41610	0.96640	0.25610	0.0510*
H3	0.62160	1.14120	0.31070	0.0520*
H3A	0.90570	1.21190	0.15680	0.0730*
H5A	0.43590	0.55010	0.18430	0.0550*
H5B	0.72900	0.58780	0.19700	0.0550*
H6A	0.97830	0.92880	0.35480	0.0640*
H6B	0.99780	1.07820	0.38890	0.0640*
H7	0.68190	0.66260	0.31610	0.0570*
H8	0.57160	0.90170	0.40000	0.0780*
H9A	0.50160	0.38660	0.29190	0.1070*
H9B	0.64010	0.44200	0.36620	0.1070*
H9C	0.79340	0.42830	0.29790	0.1070*
H10A	0.24780	0.72890	0.30110	0.1140*
H10B	0.29980	0.62660	0.36750	0.1140*
H10C	0.16460	0.57240	0.29260	0.1140*
H11A	0.94290	0.80570	0.46310	0.1850*
H11B	0.75120	0.85070	0.51860	0.1850*
H11C	0.99160	0.94350	0.50820	0.1850*
H12A	0.69730	1.14720	0.47860	0.1330*
H12B	0.45900	1.05260	0.48870	0.1330*
H12C	0.47140	1.13420	0.41540	0.1330*
H13A	0.50050	0.88560	0.01100	0.1050*
H13B	0.61720	0.96040	0.08280	0.1050*
H13C	0.32020	0.93160	0.06940	0.1050*
H4A	1.14740	1.23240	0.06880	0.1440*
H4B	1.01050	1.35560	0.07270	0.1440*

	U11	U22	U33	U12	U13	U23
O1	0.0316 (9)	0.0457 (13)	0.0607 (12)	0.0060 (9)	0.0102 (8)	−0.0027 (11)
O2	0.0421 (11)	0.0755 (19)	0.0769 (14)	−0.0069 (12)	0.0078 (10)	0.0094 (14)
O3	0.0645 (13)	0.0608 (16)	0.0567 (12)	−0.0036 (13)	0.0038 (11)	0.0162 (12)
N1	0.0420 (12)	0.0530 (17)	0.0443 (13)	−0.0020 (12)	0.0011 (10)	0.0028 (12)
N2	0.0325 (11)	0.0422 (15)	0.0526 (13)	0.0089 (11)	0.0075 (10)	0.0002 (12)
C1	0.0340 (12)	0.0426 (17)	0.0462 (15)	0.0045 (13)	0.0077 (11)	0.0011 (14)
C2	0.0342 (12)	0.0355 (16)	0.0434 (14)	0.0058 (13)	0.0059 (11)	0.0057 (13)
C3	0.0397 (13)	0.0399 (18)	0.0499 (15)	0.0089 (13)	0.0081 (12)	−0.0017 (13)
C4	0.0446 (15)	0.0358 (18)	0.0555 (16)	0.0064 (14)	0.0083 (13)	0.0016 (14)
C5	0.0427 (13)	0.0393 (16)	0.0551 (15)	−0.0006 (15)	0.0019 (11)	0.0009 (16)
C6	0.0487 (16)	0.062 (2)	0.0497 (17)	0.0062 (16)	0.0009 (13)	0.0009 (16)
C7	0.0475 (14)	0.0412 (17)	0.0535 (15)	0.0020 (16)	0.0022 (12)	0.0052 (16)
C8	0.073 (2)	0.071 (3)	0.0502 (17)	−0.022 (2)	0.0056 (16)	0.0017 (18)
C9	0.076 (2)	0.050 (2)	0.088 (3)	0.004 (2)	0.003 (2)	0.018 (2)
C10	0.0628 (19)	0.092 (3)	0.077 (2)	0.008 (2)	0.0236 (17)	0.025 (3)
C11	0.151 (5)	0.144 (6)	0.077 (3)	0.009 (5)	0.018 (3)	0.054 (4)
C12	0.079 (2)	0.130 (5)	0.060 (2)	−0.009 (3)	0.0255 (18)	−0.015 (3)
C13	0.078 (2)	0.071 (3)	0.059 (2)	−0.003 (2)	−0.0021 (18)	0.018 (2)
O4	0.165 (3)	0.099 (3)	0.099 (2)	−0.003 (3)	0.028 (2)	0.015 (2)
Cl1	0.0507 (4)	0.0606 (5)	0.0630 (4)	−0.0075 (4)	0.0081 (3)	−0.0114 (5)

O1—C2	1.228 (3)	C1—H1	0.9800
O2—C4	1.195 (3)	C3—H3	0.9800
O3—C4	1.300 (4)	C5—H5B	0.9700
O3—H3A	0.8500	C5—H5A	0.9700
O4—H4B	0.8500	C6—H6A	0.9700
O4—H4A	0.8500	C6—H6B	0.9700
N1—C13	1.482 (5)	C7—H7	0.9800
N1—C1	1.492 (4)	C8—H8	0.9800
N2—C2	1.338 (4)	C9—H9C	0.9600
N2—C3	1.454 (4)	C9—H9B	0.9600
N1—H1A	0.9000	C9—H9A	0.9600
N1—H1B	0.9000	C10—H10B	0.9600
N2—H2	0.8600	C10—H10A	0.9600
C1—C5	1.529 (5)	C10—H10C	0.9600
C1—C2	1.510 (4)	C11—H11B	0.9600
C3—C4	1.531 (4)	C11—H11A	0.9600
C3—C6	1.531 (4)	C11—H11C	0.9600
C5—C7	1.528 (4)	C12—H12B	0.9600
C6—C8	1.519 (5)	C12—H12C	0.9600
C7—C10	1.519 (5)	C12—H12A	0.9600
C7—C9	1.529 (5)	C13—H13C	0.9600
C8—C12	1.496 (7)	C13—H13A	0.9600
C8—C11	1.519 (8)	C13—H13B	0.9600
C4—O3—H3A	116.00	C3—C6—H6B	108.00
H4A—O4—H4B	110.00	C8—C6—H6A	109.00
C1—N1—C13	114.8 (3)	C3—C6—H6A	109.00
C2—N2—C3	121.7 (2)	H6A—C6—H6B	108.00
C1—N1—H1B	109.00	C8—C6—H6B	109.00
C13—N1—H1A	108.00	C5—C7—H7	108.00
H1A—N1—H1B	108.00	C9—C7—H7	108.00
C1—N1—H1A	109.00	C10—C7—H7	108.00
C13—N1—H1B	109.00	C6—C8—H8	108.00
C2—N2—H2	119.00	C11—C8—H8	108.00
C3—N2—H2	119.00	C12—C8—H8	108.00
N1—C1—C2	108.6 (2)	C7—C9—H9B	109.00
N1—C1—C5	108.0 (2)	C7—C9—H9C	110.00
C2—C1—C5	111.5 (2)	H9A—C9—H9B	109.00
O1—C2—C1	121.2 (2)	H9A—C9—H9C	109.00
N2—C2—C1	116.2 (2)	H9B—C9—H9C	109.00
O1—C2—N2	122.6 (3)	C7—C9—H9A	110.00
N2—C3—C6	112.2 (3)	C7—C10—H10A	109.00
C4—C3—C6	111.9 (2)	C7—C10—H10B	109.00
N2—C3—C4	111.2 (2)	H10A—C10—H10B	110.00
O2—C4—C3	123.0 (3)	H10A—C10—H10C	110.00
O3—C4—C3	111.7 (2)	H10B—C10—H10C	109.00
O2—C4—O3	125.2 (3)	C7—C10—H10C	110.00
C1—C5—C7	115.0 (3)	C8—C11—H11B	109.00
C3—C6—C8	115.0 (3)	C8—C11—H11C	109.00
C5—C7—C10	112.5 (2)	C8—C11—H11A	110.00
C9—C7—C10	110.3 (3)	H11A—C11—H11C	109.00
C5—C7—C9	109.1 (3)	H11B—C11—H11C	109.00
C6—C8—C12	112.1 (4)	H11A—C11—H11B	109.00
C11—C8—C12	111.1 (4)	C8—C12—H12A	109.00
C6—C8—C11	108.9 (3)	C8—C12—H12B	109.00
C2—C1—H1	110.00	H12A—C12—H12B	109.00
C5—C1—H1	110.00	H12A—C12—H12C	109.00
N1—C1—H1	110.00	C8—C12—H12C	110.00
C4—C3—H3	107.00	H12B—C12—H12C	109.00
C6—C3—H3	107.00	N1—C13—H13B	109.00
N2—C3—H3	107.00	N1—C13—H13C	109.00
C1—C5—H5B	109.00	N1—C13—H13A	110.00
C7—C5—H5A	108.00	H13A—C13—H13C	109.00
C7—C5—H5B	109.00	H13B—C13—H13C	109.00
H5A—C5—H5B	107.00	H13A—C13—H13B	109.00
C1—C5—H5A	109.00
C13—N1—C1—C2	−56.0 (3)	C2—C1—C5—C7	57.8 (3)
C13—N1—C1—C5	−177.1 (2)	N2—C3—C4—O2	−138.2 (3)
C3—N2—C2—O1	−1.8 (4)	N2—C3—C4—O3	45.8 (3)
C3—N2—C2—C1	176.3 (2)	C6—C3—C4—O2	−11.8 (4)
C2—N2—C3—C4	49.6 (3)	C6—C3—C4—O3	172.1 (3)
C2—N2—C3—C6	−76.5 (3)	N2—C3—C6—C8	−66.0 (4)
N1—C1—C2—O1	−56.6 (3)	C4—C3—C6—C8	168.1 (3)
N1—C1—C2—N2	125.2 (3)	C1—C5—C7—C9	−177.4 (3)
C5—C1—C2—O1	62.3 (3)	C1—C5—C7—C10	59.8 (4)
C5—C1—C2—N2	−115.9 (3)	C3—C6—C8—C11	169.8 (4)
N1—C1—C5—C7	177.1 (2)	C3—C6—C8—C12	−66.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.90	2.31	3.174 (2)	161
N1—H1B···Cl1	0.90	2.25	3.092 (2)	155
N2—H2···O2ii	0.86	2.40	3.006 (3)	128
O3—H3A···O4	0.85	1.74	2.591 (5)	179
O4—H4A···Cl1iii	0.85	2.51	3.198 (4)	139
O4—H4B···Cl1iv	0.85	2.48	3.182 (4)	141
C1—H1···O1ii	0.98	2.33	3.306 (3)	175
C3—H3···O2ii	0.98	2.53	3.215 (3)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.90	2.31	3.174 (2)	161
N1—H1B⋯Cl1	0.90	2.25	3.092 (2)	155
N2—H2⋯O2ii	0.86	2.40	3.006 (3)	128
O3—H3A⋯O4	0.85	1.74	2.591 (5)	179
O4—H4A⋯Cl1iii	0.85	2.51	3.198 (4)	139
O4—H4B⋯Cl1iv	0.85	2.48	3.182 (4)	141

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