Valyl benzyl ester chloride.

IN THE TITLE COMPOUND (SYSTEMATIC NAME: 1-benz-yloxy-3-methyl-1-oxobutan-2-aminium chloride), C(12)H(18)NO(2) (+)·Cl(-), the ester group is approximately planar, with a maximum deviation of 0.040 (2) Å from the least-squares plane, and makes a dihedral angle of 28.92 (16)° with the phenyl ring. The crystal structure is organized by N-H⋯Cl hydrogen bonds which join the two components into a chain along the b axis. Pairs of chains arranged anti-parallel are inter-connected by further N-H⋯Cl hydrogen bonds, forming eight-membered rings. Similar packing modes have been observed in a number of amino acid ester halides with a short unit-cell parameter of ca 5.5 Å along the direction in which the chains run.

Related literature

For valsartan, see: Black et al. (1997 ▶); Buhlmayer et al. (1994 ▶). For related structures, see: Bryndal et al. (2006 ▶); Jaeger et al. (2003 ▶); Nastopoulos et al. (1987 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H18NO2 +·Cl−

M = 243.72

Monoclinic,

a = 9.705 (1) Å

b = 5.406 (1) Å

c = 13.116 (2) Å

β = 96.58 (1)°

V = 683.60 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.27 mm−1

T = 295 K

0.4 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.741, T max = 0.948

2649 measured reflections

2010 independent reflections

1652 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.077

S = 1.06

2010 reflections

159 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.24 e Å−3

Absolute structure: Flack (1983 ▶), 530 Friedel pairs

Flack parameter: 0.02 (8)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810000176/is2507sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000176/is2507Isup2.hkl

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

C12H18NO2+·Cl−	F(000) = 260
Mr = 243.72	Dx = 1.184 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1449 reflections
a = 9.705 (1) Å	θ = 2.1–26.9°
b = 5.406 (1) Å	µ = 0.27 mm−1
c = 13.116 (2) Å	T = 295 K
β = 96.58 (1)°	Prism, colourless
V = 683.60 (18) Å3	0.4 × 0.2 × 0.2 mm
Z = 2

Oxford Diffraction Xcalibur Sapphire2 diffractometer	2010 independent reflections
Radiation source: Nova (Mo) X-ray Source	1652 reflections with I > 2σ(I)
graphite	Rint = 0.023
Detector resolution: 5.2679 pixels mm-1	θmax = 26.9°, θmin = 2.1°
ω scan	h = −10→12
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −4→6
Tmin = 0.741, Tmax = 0.948	l = −15→11
2649 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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.077	w = 1/[σ2(Fo2) + (0.040P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2010 reflections	Δρmax = 0.17 e Å−3
159 parameters	Δρmin = −0.24 e Å−3
1 restraint	Absolute structure: Flack (1983), 530 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.02 (8)

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
C1	0.6929 (3)	1.0154 (5)	0.2145 (2)	0.0492 (6)
O11	0.7115 (2)	0.9397 (3)	0.31112 (13)	0.0744 (6)
C12	0.6987 (5)	1.1297 (7)	0.3890 (2)	0.0963 (12)
H12A	0.6100	1.2132	0.3756	0.116*
H12B	0.7719	1.2516	0.3878	0.116*
C13	0.7099 (4)	1.0030 (7)	0.4919 (2)	0.0766 (10)
C14	0.6351 (4)	1.0998 (9)	0.5647 (2)	0.1010 (13)
H14	0.5791	1.2380	0.5506	0.121*
C15	0.6452 (6)	0.9849 (14)	0.6612 (3)	0.128 (2)
H15	0.5947	1.0479	0.7114	0.154*
C16	0.7258 (7)	0.7875 (13)	0.6824 (4)	0.137 (3)
H16	0.7314	0.7146	0.7469	0.165*
C17	0.7994 (6)	0.6933 (11)	0.6098 (4)	0.1375 (18)
H17	0.8544	0.5539	0.6243	0.165*
C18	0.7931 (5)	0.8035 (8)	0.5143 (3)	0.1053 (14)
H18	0.8459	0.7411	0.4653	0.126*
O1	0.6602 (2)	1.2196 (4)	0.18837 (14)	0.0702 (6)
C2	0.7212 (2)	0.8078 (4)	0.14310 (17)	0.0454 (6)
H2	0.6851	0.6536	0.1691	0.054*
N2	0.6429 (2)	0.8642 (6)	0.04138 (15)	0.0476 (5)
H2A	0.678 (3)	1.021 (7)	0.013 (2)	0.071 (10)*
H2B	0.649 (3)	0.740 (6)	−0.0041 (19)	0.049 (8)*
H2C	0.546 (3)	0.867 (7)	0.0479 (16)	0.064 (7)*
C3	0.8749 (3)	0.7732 (5)	0.1324 (2)	0.0558 (7)
H3	0.8806	0.6464	0.0796	0.067*
C4	0.9422 (3)	1.0029 (7)	0.0953 (3)	0.0886 (11)
H4A	0.9374	1.1335	0.1444	0.124*
H4B	0.8945	1.0526	0.0304	0.124*
H4C	1.0375	0.9688	0.0876	0.124*
C5	0.9560 (3)	0.6756 (7)	0.2299 (3)	0.0844 (10)
H5A	1.0481	0.6321	0.2163	0.118*
H5B	0.9103	0.5321	0.2530	0.118*
H5C	0.9609	0.8010	0.2820	0.118*
Cl1	0.33538 (6)	0.86692 (12)	0.08481 (4)	0.05096 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0545 (16)	0.0364 (15)	0.0597 (15)	−0.0021 (13)	0.0201 (12)	0.0033 (13)
O11	0.1207 (16)	0.0510 (14)	0.0542 (10)	0.0173 (11)	0.0221 (10)	0.0029 (8)
C12	0.171 (4)	0.060 (2)	0.0638 (19)	0.016 (3)	0.040 (2)	−0.0077 (17)
C13	0.107 (3)	0.068 (2)	0.0550 (17)	−0.004 (2)	0.0097 (17)	−0.0008 (16)
C14	0.117 (3)	0.125 (4)	0.062 (2)	−0.008 (3)	0.019 (2)	−0.018 (2)
C15	0.146 (5)	0.179 (6)	0.063 (3)	−0.054 (4)	0.025 (3)	−0.021 (3)
C16	0.181 (6)	0.160 (6)	0.064 (3)	−0.083 (5)	−0.015 (3)	0.021 (3)
C17	0.190 (5)	0.123 (4)	0.089 (3)	0.000 (4)	−0.030 (3)	0.027 (3)
C18	0.143 (4)	0.094 (4)	0.078 (2)	0.013 (3)	0.011 (2)	0.013 (2)
O1	0.1138 (17)	0.0358 (12)	0.0648 (12)	0.0101 (11)	0.0265 (11)	0.0051 (9)
C2	0.0508 (14)	0.0325 (16)	0.0541 (13)	−0.0006 (11)	0.0122 (10)	0.0044 (10)
N2	0.0450 (12)	0.0398 (12)	0.0593 (11)	−0.0043 (17)	0.0117 (9)	−0.0056 (15)
C3	0.0524 (16)	0.0503 (16)	0.0659 (16)	0.0095 (13)	0.0117 (13)	−0.0058 (13)
C4	0.055 (2)	0.090 (3)	0.123 (3)	−0.002 (2)	0.0227 (18)	0.021 (2)
C5	0.066 (2)	0.082 (3)	0.100 (2)	0.0181 (19)	−0.0083 (17)	0.0045 (19)
Cl1	0.0535 (3)	0.0506 (4)	0.0506 (3)	0.0008 (4)	0.0137 (2)	0.0006 (3)

C1—O1	1.188 (3)	C18—H18	0.9300
C1—O11	1.324 (3)	C2—N2	1.489 (3)
C1—C2	1.507 (3)	C2—C3	1.526 (3)
O11—C12	1.464 (4)	C2—H2	0.9800
C12—C13	1.506 (4)	N2—H2A	1.00 (3)
C12—H12A	0.9700	N2—H2B	0.90 (3)
C12—H12B	0.9700	N2—H2C	0.96 (3)
C13—C18	1.359 (5)	C3—C4	1.509 (4)
C13—C14	1.368 (5)	C3—C5	1.518 (4)
C14—C15	1.403 (6)	C3—H3	0.9800
C14—H14	0.9300	C4—H4A	0.9600
C15—C16	1.334 (7)	C4—H4B	0.9600
C15—H15	0.9300	C4—H4C	0.9600
C16—C17	1.353 (8)	C5—H5A	0.9600
C16—H16	0.9300	C5—H5B	0.9600
C17—C18	1.382 (6)	C5—H5C	0.9600
C17—H17	0.9300
O1—C1—O11	124.5 (3)	N2—C2—C3	110.25 (19)
O1—C1—C2	125.0 (2)	C1—C2—C3	113.5 (2)
O11—C1—C2	110.5 (2)	N2—C2—H2	108.6
C1—O11—C12	115.9 (2)	C1—C2—H2	108.6
O11—C12—C13	107.6 (3)	C3—C2—H2	108.6
O11—C12—H12A	110.2	C2—N2—H2A	110.6 (17)
C13—C12—H12A	110.2	C2—N2—H2B	112.0 (16)
O11—C12—H12B	110.2	H2A—N2—H2B	109.2 (19)
C13—C12—H12B	110.2	C2—N2—H2C	109.3 (13)
H12A—C12—H12B	108.5	H2A—N2—H2C	113 (3)
C18—C13—C14	120.1 (4)	H2B—N2—H2C	102 (3)
C18—C13—C12	122.4 (3)	C4—C3—C5	110.8 (3)
C14—C13—C12	117.5 (4)	C4—C3—C2	113.1 (2)
C13—C14—C15	118.2 (5)	C5—C3—C2	112.5 (2)
C13—C14—H14	120.9	C4—C3—H3	106.6
C15—C14—H14	120.9	C5—C3—H3	106.6
C16—C15—C14	121.4 (5)	C2—C3—H3	106.6
C16—C15—H15	119.3	C3—C4—H4A	109.5
C14—C15—H15	119.3	C3—C4—H4B	109.5
C15—C16—C17	119.9 (5)	H4A—C4—H4B	109.5
C15—C16—H16	120.0	C3—C4—H4C	109.5
C17—C16—H16	120.0	H4A—C4—H4C	109.5
C16—C17—C18	120.2 (6)	H4B—C4—H4C	109.5
C16—C17—H17	119.9	C3—C5—H5A	109.5
C18—C17—H17	119.9	C3—C5—H5B	109.5
C13—C18—C17	120.1 (4)	H5A—C5—H5B	109.5
C13—C18—H18	119.9	C3—C5—H5C	109.5
C17—C18—H18	119.9	H5A—C5—H5C	109.5
N2—C2—C1	107.1 (2)	H5B—C5—H5C	109.5
O1—C1—O11—C12	−4.1 (4)	C12—C13—C18—C17	−179.8 (4)
C2—C1—O11—C12	175.1 (3)	C16—C17—C18—C13	−1.8 (7)
C1—O11—C12—C13	174.8 (3)	O1—C1—C2—N2	−25.0 (4)
O11—C12—C13—C18	34.5 (5)	O11—C1—C2—N2	155.9 (2)
O11—C12—C13—C14	−147.1 (3)	O1—C1—C2—C3	96.9 (3)
C18—C13—C14—C15	−1.1 (6)	O11—C1—C2—C3	−82.2 (3)
C12—C13—C14—C15	−179.5 (4)	N2—C2—C3—C4	62.6 (3)
C13—C14—C15—C16	0.4 (6)	C1—C2—C3—C4	−57.6 (3)
C14—C15—C16—C17	−0.3 (7)	N2—C2—C3—C5	−170.9 (3)
C15—C16—C17—C18	1.1 (8)	C1—C2—C3—C5	69.0 (3)
C14—C13—C18—C17	1.9 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.98	2.38	3.301 (3)	157
N2—H2A···Cl1ii	1.00 (3)	2.26 (4)	3.201 (3)	156 (2)
N2—H2B···Cl1iii	0.90 (3)	2.29 (3)	3.177 (3)	166 (2)
N2—H2C···Cl1	0.96 (3)	2.15 (3)	3.101 (2)	172.1 (18)
C4—H4C···Cl1iv	0.96	2.95	3.904 (3)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.98	2.38	3.301 (3)	157
N2—H2A⋯Cl1ii	1.00 (3)	2.26 (4)	3.201 (3)	156 (2)
N2—H2B⋯Cl1iii	0.90 (3)	2.29 (3)	3.177 (3)	166 (2)
N2—H2C⋯Cl1	0.96 (3)	2.15 (3)	3.101 (2)	172.1 (18)
C4—H4C⋯Cl1iv	0.96	2.95	3.904 (3)	175

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