organic compounds
D-(−)-2-Azaniumyl-2-(4-hydroxyphenyl)acetate: an orthorhombic polymorph
aSchool of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, People's Republic of China, and bSchool of Pharmaceutical Sciences, Zhengzhou University, Zhengzhou 450001, People's Republic of China
*Correspondence e-mail: confidencezzu@139.com
The title compound, C8H9NO3, is the zwitterionic form of D-(−)-4-hydroxyphenylglycine. The plane of the hydroxybenzene ring is inclined at an angle of 88.89 (5)° to the best-fit plane through the five non-H atoms of the aminoacetate substituent. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link adjacent molecules, forming a three-dimensional network. Weak C—H⋯π interactions are also observed.
Keywords: crystal structure; D-(−)-2-azaniumyl-2-(4-hydroxyphenyl)acetate; D-(−)-4-hydroxyphenylglycine; hydrogen bonding.
CCDC reference: 1478148
Structure description
D-(−)-4-hydroxyphenylglycine (D-HPG) is a key intermediate in the preparation of semi-synthetic antibiotics (Rudolph et al., 2001). The of a monoclinic polymorph of D-(−)-amino-(4-hydroxyphenyl) acetate has been reported previously in the P21 (Báthori & Bourne, 2009). For the crystal structures of other related compounds, see for example the structures of (p-hydroxyphenyl)glycine(−)-4-(2-chloro-phenyl)-5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphorinane 2-oxide (Ten Hoeve & Wynberg, 1985) and D-p-hydroxyphenylglycine (−)-1-phenylethanesulfonate (Yoshioka et al., 1994). Here we report the of D-(−)-amino-(4-hydroxyphenyl)acetate in the orthorhombic P212121. Although there is no heavy atom in the structure, the could be well determined by the [0.03 (11)]. However, crystals were grown from a commercial sample of D-(−)-4-hydroxyphenylglycine and the assigned on that basis.
As shown in Fig. 1, the reported compound is a zwitterion with the carboxylic acid of the glycine moiety deprotonated and the amino group protonated. The hydroxybenzene ring plane approximately bisects the N1—C7—C8 angle and the plane of the hydroxybenzene ring is inclined at an angle of 88.89 (5) ° to the best fit plane through the five non-hydrogen atoms of the aminoacetate substituent.
In the crystal, adjacent molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, and a weak C—H⋯π interaction into a three-dimensional network, Fig. 2 and Table 1.
Synthesis and crystallization
1.2 g D-(−)-4-hydroxyphenylglycine (Aldrich, 22818–40-2) was stirred into 40 ml of water at 55°C to prepare a Colourless block-like crystals of the title compound were grown by slow evaporation of this solution at 1°C.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1478148
10.1107/S2414314616007689/sj4032sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616007689/sj4032Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616007689/sj4032Isup3.cml
1.2 g D-(-)-4-hydroxyphenylglycine (Aldrich, 22818–40-2) was stirred into 40 ml of water at 55°C to prepare a
Colourless block-like crystals of the title compound were grown by slow evaporation of this solution at 1°C.D-(-)-4-hydroxyphenylglycine (D-HPG) is a key intermediate in the preparation of semi-synthetic antibiotics (Rudolph et al., 2001). The
of a monoclinic polymorph of D-(-)-amino-(4-hydroxyphenyl) acetate has been reported previously in the P21 (Báthori & Bourne, 2009). For the crystal structures of other related compounds, see for example the structures of (p-hydroxyphenyl)glycine(-)-4-(2-chloro-phenyl)-5,5-dimethyl-2- hydroxy-1,3,2-dioxaphosphorinane 2-oxide (Ten Hoeve & Wynberg, 1985) and D-p-hydroxyphenylglycine (-)-1-phenylethanesulfonate (Yoshioka et al., 1994). Here we report the of D-(-)-amino-(4-hydroxyphenyl)acetate in the orthorhombic spacegroup P212121. With no heavy atom in the structure the could not be clearly established from effects. However, crystals were grown from a commercial sample of D-(-)-4-hydroxyphenylglycine and the assigned on that basis.As shown in Fig.1, the reported compound is a zwitterion with the carboxylic acid of the glycine moiety deprotonated and the amino group protonated. The hydroxybenzene ring plane approximately bisects the N1—C7—C8 angle and the plane of the hydroxybenzene ring is inclined at an angle of 88.89 (5) ° to the best fit plane through the five non-hydrogen atoms of the aminoacetate substituent.
In the crystal, adjacent molecules are linked by N—H···O and O—H···O hydrogen bonds, and a weak C—H···π interaction into a three-dimensional network, Fig. 2 and Table 1.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).Fig. 1. View of the title compound, showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. | |
Fig. 2. The packing diagram of the title compound, viewed along the b axis. |
C8H9NO3 | Dx = 1.325 Mg m−3 |
Mr = 167.16 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 2415 reflections |
a = 5.83624 (17) Å | θ = 5.2–70.8° |
b = 8.4245 (3) Å | µ = 0.86 mm−1 |
c = 17.0381 (5) Å | T = 293 K |
V = 837.72 (4) Å3 | Block, colourless |
Z = 4 | 0.2 × 0.19 × 0.16 mm |
F(000) = 352 |
Agilent Xcalibur Eos Gemini diffractometer | 1613 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 1570 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 16.2312 pixels mm-1 | θmax = 70.9°, θmin = 5.2° |
ω scans | h = −7→6 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −10→10 |
Tmin = 0.861, Tmax = 1.000 | l = −17→20 |
3647 measured reflections |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0615P)2 + 0.1107P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.033 | (Δ/σ)max < 0.001 |
wR(F2) = 0.096 | Δρmax = 0.34 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
1613 reflections | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
112 parameters | Extinction coefficient: 0.076 (5) |
0 restraints | Absolute structure: Flack x determined using 616 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (11) |
Hydrogen site location: inferred from neighbouring sites |
C8H9NO3 | V = 837.72 (4) Å3 |
Mr = 167.16 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 5.83624 (17) Å | µ = 0.86 mm−1 |
b = 8.4245 (3) Å | T = 293 K |
c = 17.0381 (5) Å | 0.2 × 0.19 × 0.16 mm |
Agilent Xcalibur Eos Gemini diffractometer | 1613 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 1570 reflections with I > 2σ(I) |
Tmin = 0.861, Tmax = 1.000 | Rint = 0.031 |
3647 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.096 | Δρmax = 0.34 e Å−3 |
S = 1.05 | Δρmin = −0.17 e Å−3 |
1613 reflections | Absolute structure: Flack x determined using 616 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
112 parameters | Absolute structure parameter: 0.03 (11) |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8218 (4) | 0.6736 (2) | 0.67248 (12) | 0.0355 (5) | |
H1 | 0.8643 | 0.7484 | 0.6351 | 0.043* | |
C2 | 0.7995 (4) | 0.7195 (3) | 0.75027 (12) | 0.0369 (5) | |
H2 | 0.8267 | 0.8242 | 0.7648 | 0.044* | |
C3 | 0.7367 (4) | 0.6088 (3) | 0.80590 (11) | 0.0329 (5) | |
C4 | 0.6892 (5) | 0.4543 (3) | 0.78378 (12) | 0.0424 (6) | |
H4 | 0.6415 | 0.3806 | 0.8210 | 0.051* | |
C5 | 0.7130 (4) | 0.4097 (2) | 0.70566 (12) | 0.0355 (5) | |
H5 | 0.6822 | 0.3055 | 0.6911 | 0.043* | |
C6 | 0.7817 (3) | 0.5177 (2) | 0.64934 (10) | 0.0264 (4) | |
C7 | 0.8146 (3) | 0.4675 (2) | 0.56526 (10) | 0.0250 (4) | |
H7 | 0.7981 | 0.3519 | 0.5622 | 0.030* | |
C8 | 1.0554 (3) | 0.5127 (2) | 0.53564 (11) | 0.0270 (4) | |
N1 | 0.6394 (3) | 0.5416 (2) | 0.51327 (9) | 0.0276 (4) | |
H1A | 0.6596 | 0.5079 | 0.4642 | 0.033* | |
H1B | 0.6540 | 0.6467 | 0.5148 | 0.033* | |
H1C | 0.5000 | 0.5145 | 0.5296 | 0.033* | |
O1 | 0.7186 (4) | 0.6457 (2) | 0.88365 (8) | 0.0478 (5) | |
H1D | 0.7565 | 0.7384 | 0.8905 | 0.072* | |
O2 | 1.0735 (3) | 0.62801 (19) | 0.49116 (10) | 0.0396 (4) | |
O3 | 1.2178 (3) | 0.4283 (2) | 0.56048 (10) | 0.0445 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0467 (12) | 0.0325 (10) | 0.0274 (9) | −0.0062 (9) | 0.0064 (9) | 0.0043 (8) |
C2 | 0.0468 (12) | 0.0329 (10) | 0.0310 (10) | −0.0058 (9) | 0.0005 (9) | −0.0006 (8) |
C3 | 0.0358 (10) | 0.0425 (11) | 0.0205 (8) | −0.0008 (8) | −0.0037 (8) | 0.0010 (8) |
C4 | 0.0586 (14) | 0.0416 (12) | 0.0268 (10) | −0.0122 (11) | 0.0024 (9) | 0.0069 (8) |
C5 | 0.0447 (11) | 0.0325 (10) | 0.0293 (9) | −0.0092 (9) | 0.0017 (8) | 0.0014 (8) |
C6 | 0.0216 (8) | 0.0330 (9) | 0.0244 (9) | −0.0005 (7) | 0.0003 (7) | 0.0028 (7) |
C7 | 0.0216 (8) | 0.0274 (8) | 0.0260 (8) | −0.0022 (7) | 0.0014 (7) | 0.0022 (7) |
C8 | 0.0232 (9) | 0.0317 (9) | 0.0261 (9) | −0.0017 (7) | 0.0027 (7) | 0.0011 (7) |
N1 | 0.0235 (7) | 0.0347 (8) | 0.0247 (7) | −0.0002 (6) | 0.0002 (6) | 0.0000 (6) |
O1 | 0.0744 (12) | 0.0473 (9) | 0.0216 (7) | −0.0069 (9) | −0.0020 (8) | 0.0002 (6) |
O2 | 0.0347 (8) | 0.0366 (8) | 0.0474 (9) | −0.0045 (7) | 0.0063 (7) | 0.0119 (6) |
O3 | 0.0237 (7) | 0.0589 (10) | 0.0510 (9) | 0.0039 (7) | 0.0020 (6) | 0.0199 (7) |
C1—H1 | 0.9300 | C6—C7 | 1.506 (3) |
C1—C2 | 1.387 (3) | C7—H7 | 0.9800 |
C1—C6 | 1.391 (3) | C7—C8 | 1.541 (2) |
C2—H2 | 0.9300 | C7—N1 | 1.490 (2) |
C2—C3 | 1.379 (3) | C8—O2 | 1.237 (2) |
C3—C4 | 1.383 (3) | C8—O3 | 1.258 (3) |
C3—O1 | 1.365 (2) | N1—H1A | 0.8900 |
C4—H4 | 0.9300 | N1—H1B | 0.8900 |
C4—C5 | 1.390 (3) | N1—H1C | 0.8900 |
C5—H5 | 0.9300 | O1—H1D | 0.8200 |
C5—C6 | 1.382 (3) | ||
C2—C1—H1 | 119.4 | C5—C6—C7 | 120.84 (18) |
C2—C1—C6 | 121.21 (19) | C6—C7—H7 | 108.5 |
C6—C1—H1 | 119.4 | C6—C7—C8 | 111.00 (15) |
C1—C2—H2 | 120.2 | C8—C7—H7 | 108.5 |
C3—C2—C1 | 119.6 (2) | N1—C7—C6 | 111.12 (16) |
C3—C2—H2 | 120.2 | N1—C7—H7 | 108.5 |
C2—C3—C4 | 120.14 (18) | N1—C7—C8 | 109.12 (14) |
O1—C3—C2 | 122.26 (19) | O2—C8—C7 | 118.21 (16) |
O1—C3—C4 | 117.60 (18) | O2—C8—O3 | 125.84 (18) |
C3—C4—H4 | 120.2 | O3—C8—C7 | 115.94 (16) |
C3—C4—C5 | 119.67 (19) | C7—N1—H1A | 109.5 |
C5—C4—H4 | 120.2 | C7—N1—H1B | 109.5 |
C4—C5—H5 | 119.5 | C7—N1—H1C | 109.5 |
C6—C5—C4 | 121.1 (2) | H1A—N1—H1B | 109.5 |
C6—C5—H5 | 119.5 | H1A—N1—H1C | 109.5 |
C1—C6—C7 | 120.89 (17) | H1B—N1—H1C | 109.5 |
C5—C6—C1 | 118.26 (18) | C3—O1—H1D | 109.5 |
C1—C2—C3—C4 | −2.0 (4) | C4—C5—C6—C7 | 178.0 (2) |
C1—C2—C3—O1 | 178.0 (2) | C5—C6—C7—C8 | −126.0 (2) |
C1—C6—C7—C8 | 53.4 (2) | C5—C6—C7—N1 | 112.4 (2) |
C1—C6—C7—N1 | −68.2 (2) | C6—C1—C2—C3 | 0.1 (4) |
C2—C1—C6—C5 | 1.6 (3) | C6—C7—C8—O2 | −104.3 (2) |
C2—C1—C6—C7 | −177.8 (2) | C6—C7—C8—O3 | 74.7 (2) |
C2—C3—C4—C5 | 2.3 (4) | N1—C7—C8—O2 | 18.4 (2) |
C3—C4—C5—C6 | −0.6 (4) | N1—C7—C8—O3 | −162.55 (18) |
C4—C5—C6—C1 | −1.4 (4) | O1—C3—C4—C5 | −177.8 (2) |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.89 | 2.02 | 2.838 (2) | 153 |
N1—H1B···O2ii | 0.89 | 1.96 | 2.811 (2) | 160 |
N1—H1C···O3iii | 0.89 | 1.87 | 2.759 (2) | 172 |
O1—H1D···O3iv | 0.82 | 1.81 | 2.591 (2) | 158 |
C2—H2···Cgv | 0.93 | 3.17 | 3.913 (2) | 139 |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1, y, z; (iv) −x+2, y+1/2, −z+3/2; (v) −x, y+1/2, −z+3/2. |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.89 | 2.02 | 2.838 (2) | 153.0 |
N1—H1B···O2ii | 0.89 | 1.96 | 2.811 (2) | 160.0 |
N1—H1C···O3iii | 0.89 | 1.87 | 2.759 (2) | 172.0 |
O1—H1D···O3iv | 0.82 | 1.81 | 2.591 (2) | 158.3 |
C2—H2···Cgv | 0.93 | 3.165 | 3.913 (2) | 138.8 |
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x−1/2, −y+3/2, −z+1; (iii) x−1, y, z; (iv) −x+2, y+1/2, −z+3/2; (v) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C8H9NO3 |
Mr | 167.16 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 5.83624 (17), 8.4245 (3), 17.0381 (5) |
V (Å3) | 837.72 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.86 |
Crystal size (mm) | 0.2 × 0.19 × 0.16 |
Data collection | |
Diffractometer | Agilent Xcalibur Eos Gemini |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.861, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3647, 1613, 1570 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.096, 1.05 |
No. of reflections | 1613 |
No. of parameters | 112 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.17 |
Absolute structure | Flack x determined using 616 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Absolute structure parameter | 0.03 (11) |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), OLEX2 (Dolomanov et al., 2009).
Acknowledgements
The authors are grateful to the Analysis and Testing Center of Zhengzhou University for use of the single-crystal X-ray diffractometer. This work was supported by the Science and Technology Bureau of Henan through the Cooperation Research Project fund (No. 152107000043 for WL), the Education Bureau of Henan for Major Research Project fund (No. 14 A530007 for WL), National Natural Science Foundation of China (project Nos. 81430085, 21372206 and 81172937 for HML), a PhD Educational Award from the Ministry of Education (No. 20134101130001 for HML), and the Graduate Student Science Research Foundation of Zhengzhou University.
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