Crystal structure of (3R)-3-benzyl-4-[(tert-but-oxy-carbon-yl)amino]-butanoic acid.

The characteristic feature of the title mol-ecule, C16H23NO4, is the syn configuration of the partially double amide C-N bond [C-N-C-O torsion angle = -14.8 (2)°]. The crystal packing is determined by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds, which link the mol-ecules into a double-chain structure extending along [010].

Related literature

The title enanti­omeric compound was synthesized according to Loukas et al. (2003 ▶) and Felluga et al. (2008 ▶). For related structures, see: Pihko & Koskinen (1998 ▶); Jimeno et al. (2011 ▶). For solution conformation of oligomers based on monosubstituted γ-amino acids, see: Guo et al. (2012 ▶); Kang & Byun (2012 ▶). For amino acid analysis by HPLC after derivatization with Marfey’s reagent, see: Marfey (1984 ▶).

Experimental

Crystal data

C16H23NO4

M = 293.35

Monoclinic,

a = 19.5872 (12) Å

b = 6.5263 (4) Å

c = 14.7598 (9) Å

β = 120.846 (2)°

V = 1619.89 (17) Å3

Z = 4

Cu Kα radiation

μ = 0.70 mm−1

T = 100 K

0.4 × 0.04 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.738, T max = 0.973

8769 measured reflections

2880 independent reflections

2805 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.073

S = 1.06

2880 reflections

197 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.16 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), 1138 Friedel pairs

Absolute structure parameter: 0.05 (15)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814019497/gk2614sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019497/gk2614Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814019497/gk2614Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814019497/gk2614fig1.tif

The mol­ecular structure with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S1600536814019497/gk2614fig2.tif

Packing of the title compound viewed along the [101] direction.

CCDC reference: 938020

Additional supporting information: crystallographic information; 3D view; checkCIF report

C16H23NO4	F(000) = 632
Mr = 293.35	Dx = 1.203 Mg m−3
Monoclinic, C2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: C 2y	Cell parameters from 3858 reflections
a = 19.5872 (12) Å	θ = 3.5–64.2°
b = 6.5263 (4) Å	µ = 0.70 mm−1
c = 14.7598 (9) Å	T = 100 K
β = 120.846 (2)°	Needle, colourless
V = 1619.89 (17) Å3	0.4 × 0.04 × 0.04 mm
Z = 4

Bruker SMART APEX CCD diffractometer	2880 independent reflections
Radiation source: fine-focus sealed tube	2805 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scan	θmax = 72.4°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −24→24
Tmin = 0.738, Tmax = 0.973	k = −7→8
8769 measured reflections	l = −18→18

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)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.0236P)2 + 0.6631P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2880 reflections	Δρmax = 0.16 e Å−3
197 parameters	Δρmin = −0.18 e Å−3
1 restraint	Absolute structure: Flack (1983), 1138 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (15)

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	0.89784 (7)	0.5954 (2)	0.40885 (10)	0.0213 (3)
C2	0.88937 (8)	0.3833 (2)	0.44237 (10)	0.0220 (3)
H2A	0.9309	0.2966	0.4459	0.026*
H2B	0.8386	0.3268	0.3891	0.026*
C3	0.89425 (7)	0.3775 (2)	0.54933 (10)	0.0211 (3)
H3	0.9405	0.4574	0.6005	0.025*
C4	0.90258 (7)	0.1581 (2)	0.58971 (10)	0.0226 (3)
H4A	0.8936	0.1582	0.6485	0.027*
H4B	0.8612	0.0753	0.5341	0.027*
C6	1.04195 (8)	0.0711 (2)	0.72350 (10)	0.0215 (3)
C8	1.08942 (8)	0.2534 (2)	0.89211 (11)	0.0285 (3)
C9	1.05139 (13)	0.4342 (4)	0.91403 (14)	0.0596 (6)
H9A	1.0502	0.5499	0.8731	0.089*
H9B	1.0818	0.4680	0.9877	0.089*
H9C	0.9981	0.3992	0.8952	0.089*
C10	1.09383 (10)	0.0664 (3)	0.95540 (12)	0.0392 (4)
H10A	1.0413	0.0302	0.9395	0.059*
H10B	1.1265	0.0960	1.0293	0.059*
H10C	1.1165	−0.0457	0.9375	0.059*
C11	1.17061 (10)	0.3096 (3)	0.90952 (12)	0.0390 (4)
H11A	1.1938	0.1918	0.8967	0.058*
H11B	1.2045	0.3549	0.9809	0.058*
H11C	1.1649	0.4176	0.8619	0.058*
C30	0.81864 (8)	0.4716 (2)	0.53904 (10)	0.0234 (3)
H30A	0.8038	0.5900	0.4930	0.028*
H30B	0.7760	0.3723	0.5048	0.028*
C31	0.82452 (7)	0.5377 (2)	0.64118 (10)	0.0212 (3)
C32	0.86972 (9)	0.7077 (2)	0.69501 (12)	0.0290 (3)
H32	0.9003	0.7720	0.6717	0.035*
C33	0.86995 (9)	0.7831 (3)	0.78276 (13)	0.0346 (3)
H33	0.9000	0.8985	0.8171	0.041*
C34	0.82581 (9)	0.6883 (3)	0.81985 (11)	0.0318 (3)
H34	0.8254	0.7405	0.8782	0.038*
C35	0.78253 (9)	0.5154 (3)	0.76924 (12)	0.0348 (4)
H35	0.7537	0.4484	0.7944	0.042*
C36	0.78199 (8)	0.4414 (3)	0.68080 (11)	0.0297 (3)
H36	0.7525	0.3247	0.6473	0.036*
N5	0.97942 (6)	0.06104 (18)	0.62403 (9)	0.0218 (2)
H5	0.9795 (9)	−0.034 (3)	0.5849 (12)	0.026*
O1	0.88632 (7)	0.59996 (17)	0.31251 (8)	0.0335 (3)
H1	0.8915	0.7177	0.2976	0.050*
O2	0.91355 (6)	0.74770 (16)	0.46349 (8)	0.0286 (2)
O6	1.10102 (6)	−0.03990 (16)	0.75856 (7)	0.0281 (2)
O7	1.03178 (5)	0.21689 (15)	0.77878 (7)	0.0261 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0191 (6)	0.0193 (7)	0.0236 (6)	−0.0012 (5)	0.0095 (5)	−0.0024 (5)
C2	0.0246 (6)	0.0160 (6)	0.0247 (6)	0.0011 (5)	0.0121 (5)	−0.0020 (5)
C3	0.0216 (6)	0.0175 (7)	0.0217 (6)	−0.0008 (5)	0.0093 (5)	−0.0006 (5)
C4	0.0227 (6)	0.0170 (7)	0.0256 (6)	−0.0016 (5)	0.0106 (5)	−0.0009 (5)
C6	0.0293 (7)	0.0125 (6)	0.0242 (6)	−0.0002 (5)	0.0147 (5)	−0.0012 (5)
C8	0.0341 (7)	0.0233 (8)	0.0208 (6)	0.0009 (6)	0.0088 (6)	−0.0044 (6)
C9	0.0666 (12)	0.0553 (13)	0.0349 (9)	0.0212 (10)	0.0103 (8)	−0.0206 (9)
C10	0.0449 (9)	0.0405 (10)	0.0286 (7)	−0.0090 (8)	0.0163 (7)	0.0027 (7)
C11	0.0421 (9)	0.0372 (10)	0.0275 (7)	−0.0131 (7)	0.0105 (7)	0.0005 (7)
C30	0.0237 (6)	0.0215 (7)	0.0233 (6)	0.0016 (5)	0.0107 (5)	0.0007 (5)
C31	0.0203 (6)	0.0167 (7)	0.0240 (6)	0.0037 (5)	0.0095 (5)	0.0021 (5)
C32	0.0345 (7)	0.0156 (7)	0.0400 (8)	−0.0024 (6)	0.0214 (7)	0.0001 (6)
C33	0.0384 (8)	0.0207 (8)	0.0414 (8)	−0.0041 (6)	0.0181 (7)	−0.0102 (6)
C34	0.0327 (7)	0.0338 (9)	0.0268 (7)	0.0042 (6)	0.0137 (6)	−0.0057 (6)
C35	0.0343 (7)	0.0409 (10)	0.0330 (8)	−0.0079 (7)	0.0201 (6)	−0.0033 (7)
C36	0.0296 (7)	0.0290 (8)	0.0308 (7)	−0.0097 (6)	0.0156 (6)	−0.0069 (6)
N5	0.0270 (6)	0.0122 (6)	0.0244 (5)	0.0004 (4)	0.0117 (5)	−0.0030 (4)
O1	0.0551 (7)	0.0190 (6)	0.0296 (5)	−0.0092 (5)	0.0241 (5)	−0.0031 (4)
O2	0.0384 (5)	0.0164 (5)	0.0290 (5)	−0.0035 (4)	0.0159 (4)	−0.0049 (4)
O6	0.0299 (5)	0.0220 (5)	0.0292 (5)	0.0074 (4)	0.0129 (4)	−0.0008 (4)
O7	0.0302 (5)	0.0195 (5)	0.0227 (5)	0.0052 (4)	0.0094 (4)	−0.0039 (4)

C1—O2	1.2159 (17)	C10—H10A	0.9600
C1—O1	1.3209 (16)	C10—H10B	0.9600
C1—C2	1.507 (2)	C10—H10C	0.9600
C2—C3	1.5322 (17)	C11—H11A	0.9600
C2—H2A	0.9700	C11—H11B	0.9600
C2—H2B	0.9700	C11—H11C	0.9600
C3—C4	1.5272 (19)	C30—C31	1.5144 (18)
C3—C30	1.5373 (18)	C30—H30A	0.9700
C3—H3	0.9800	C30—H30B	0.9700
C4—N5	1.4634 (17)	C31—C32	1.388 (2)
C4—H4A	0.9700	C31—C36	1.3894 (19)
C4—H4B	0.9700	C32—C33	1.383 (2)
C6—O6	1.2318 (16)	C32—H32	0.9300
C6—O7	1.3332 (16)	C33—C34	1.384 (2)
C6—N5	1.3476 (17)	C33—H33	0.9300
C8—O7	1.4809 (16)	C34—C35	1.379 (2)
C8—C10	1.512 (2)	C34—H34	0.9300
C8—C9	1.516 (2)	C35—C36	1.387 (2)
C8—C11	1.520 (2)	C35—H35	0.9300
C9—H9A	0.9600	C36—H36	0.9300
C9—H9B	0.9600	N5—H5	0.846 (18)
C9—H9C	0.9600	O1—H1	0.8200
O2—C1—O1	122.74 (13)	C8—C10—H10C	109.5
O2—C1—C2	124.47 (11)	H10A—C10—H10C	109.5
O1—C1—C2	112.79 (11)	H10B—C10—H10C	109.5
C1—C2—C3	113.68 (11)	C8—C11—H11A	109.5
C1—C2—H2A	108.8	C8—C11—H11B	109.5
C3—C2—H2A	108.8	H11A—C11—H11B	109.5
C1—C2—H2B	108.8	C8—C11—H11C	109.5
C3—C2—H2B	108.8	H11A—C11—H11C	109.5
H2A—C2—H2B	107.7	H11B—C11—H11C	109.5
C4—C3—C2	111.29 (11)	C31—C30—C3	115.96 (10)
C4—C3—C30	108.53 (11)	C31—C30—H30A	108.3
C2—C3—C30	109.89 (10)	C3—C30—H30A	108.3
C4—C3—H3	109.0	C31—C30—H30B	108.3
C2—C3—H3	109.0	C3—C30—H30B	108.3
C30—C3—H3	109.0	H30A—C30—H30B	107.4
N5—C4—C3	115.21 (11)	C32—C31—C36	117.71 (13)
N5—C4—H4A	108.5	C32—C31—C30	119.88 (12)
C3—C4—H4A	108.5	C36—C31—C30	122.28 (12)
N5—C4—H4B	108.5	C33—C32—C31	121.01 (14)
C3—C4—H4B	108.5	C33—C32—H32	119.5
H4A—C4—H4B	107.5	C31—C32—H32	119.5
O6—C6—O7	124.44 (12)	C32—C33—C34	120.58 (14)
O6—C6—N5	124.22 (12)	C32—C33—H33	119.7
O7—C6—N5	111.34 (11)	C34—C33—H33	119.7
O7—C8—C10	109.69 (12)	C35—C34—C33	119.14 (14)
O7—C8—C9	101.12 (11)	C35—C34—H34	120.4
C10—C8—C9	112.02 (15)	C33—C34—H34	120.4
O7—C8—C11	110.82 (12)	C34—C35—C36	120.05 (14)
C10—C8—C11	111.52 (13)	C34—C35—H35	120.0
C9—C8—C11	111.23 (16)	C36—C35—H35	120.0
C8—C9—H9A	109.5	C35—C36—C31	121.45 (14)
C8—C9—H9B	109.5	C35—C36—H36	119.3
H9A—C9—H9B	109.5	C31—C36—H36	119.3
C8—C9—H9C	109.5	C6—N5—C4	123.71 (11)
H9A—C9—H9C	109.5	C6—N5—H5	117.4 (11)
H9B—C9—H9C	109.5	C4—N5—H5	116.2 (11)
C8—C10—H10A	109.5	C1—O1—H1	109.5
C8—C10—H10B	109.5	C6—O7—C8	122.65 (10)
H10A—C10—H10B	109.5
O2—C1—C2—C3	5.74 (18)	C32—C33—C34—C35	1.1 (2)
O1—C1—C2—C3	−174.26 (11)	C33—C34—C35—C36	−1.6 (2)
C1—C2—C3—C4	−168.26 (10)	C34—C35—C36—C31	0.1 (2)
C1—C2—C3—C30	71.50 (14)	C32—C31—C36—C35	1.9 (2)
C2—C3—C4—N5	70.78 (14)	C30—C31—C36—C35	−174.09 (13)
C30—C3—C4—N5	−168.17 (11)	O6—C6—N5—C4	165.44 (13)
C4—C3—C30—C31	76.50 (15)	O7—C6—N5—C4	−14.81 (18)
C2—C3—C30—C31	−161.60 (11)	C3—C4—N5—C6	89.89 (15)
C3—C30—C31—C32	70.93 (17)	O6—C6—O7—C8	−3.7 (2)
C3—C30—C31—C36	−113.17 (15)	N5—C6—O7—C8	176.54 (11)
C36—C31—C32—C33	−2.4 (2)	C10—C8—O7—C6	−63.08 (17)
C30—C31—C32—C33	173.69 (14)	C9—C8—O7—C6	178.48 (15)
C31—C32—C33—C34	1.0 (2)	C11—C8—O7—C6	60.48 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O6i	0.82	1.83	2.6368 (15)	170
N5—H5···O2ii	0.846 (18)	2.131 (18)	2.8856 (16)	148.2 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6i	0.82	1.83	2.6368 (15)	170
N5—H5⋯O2ii	0.846 (18)	2.131 (18)	2.8856 (16)	148.2 (15)

Symmetry codes: (i) ; (ii) .