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Solvent-free (2S)-methyl 2-ammonio-3-(4-hydroxy­phenyl)­propionate chloride, C10H14NO3+·Cl, (I), and its methanol solvate, C10H14NO3+·Cl·CH3OH, (II), are obtained from different solvents: crystallization from ethanol or propan-2-ol gives the same solvent-free crystals of (I) in both cases, while crystals of (II) were obtained by crystallization from methanol. The structure of (I) is characterized by the presence of two-dimensional layers linked together by N—H...Cl and O—H...Cl hydrogen bonds and also by C—H...O contacts. Incorporation of the methanol solvent mol­ecule in (II) introduces additional O—H...O hydrogen bonds linking the two-dimensional layers, resulting in the formation of a three-dimensional network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106002137/bm1620sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106002137/bm1620Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106002137/bm1620IIsup3.hkl
Contains datablock II

CCDC references: 603187; 603188

Comment top

Although L-tyrosine is one of the twenty natural amino acids which are the basic building blocks of proteins, there are surprisingly few references in the literature to the structures of short peptides containing L-tyrosine methyl ester. The simplest of the peptides described, N-acetyl-L-leucyl-L-tyrosyl methyl ester, containing the two amino acids L-leucine and L-tyrosine, was reported by Karle & Flippen-Anderson (1989). Another paper (Claeys-Bruno et al., 2001) describes the structure of a cobalt(III) chiroporphyrin complex containing the methyl ester of D-tyrosine hydrochloride. [From the Co-Editor: Please approve substitution of `phorphirynoid' with `chiroporphyrin'.] The present paper describes the first solid-state study of L-tyrosine methyl ester hydrochloride, both solvent-free [compound (I)] and as a methanol monosolvate [compound (II)].

Crystals of (I) were obtained from ethanol or propan-2-ol, while crystals of (II) were isolated from methanol, crystallizing in space groups P212121 and P21, respectively (Figs. 1 and 2). We have compared the crystal structures of (I) and (II), principally by analysis of selected torsion angles and hydrogen-bond graph-set analysis (Bernstein et al., 1995). The superposition of the L-tyrosine methyl ester cations is shown in Fig. 3. The values of the C2—C3—C4—C9 (χ22) and C2—C3—C4—C5 (χ21) torsion angles [88.3 (2) and −90.8 (2)°, respectively, in (II), and 71.2 (2) and −111.3 (2)°, respectively, in (I)] show only small differences in the orientation of the aromatic rings towards the plane defined by atoms C1/C2/N. The angle between the plane defined by atoms C1/C2/N and that defined by atoms C4–C9 is 68.2 (1)° in (I) and 64.6 (2)° in (II). Previously reported values for the torsion angles of L-tyrosine sulfate (Sridhar et al., 2002) are noticeably different because of the possible rotation around the C2—C3 and C3—C4 bonds, showing their dependence on crystal-packing forces. The backbone conformation angles N—C2—C1—O2 (ψ1) are 0.9 (2) and −2.2 (3)° in (I) and (II), respectively. Previous reports of the structures of L-tyrosine (Mostad et al., 1972) and L-tyrosinamide hydrochloride monohydrate (Kolev et al., 2005) have noted that the backbone torsion angles can adopt very different values for similar compounds, depending on the molecules present and their arrangement in the solid state. Significant differences can also exist within one crystal structure, as reported for bis(L-tyrosinium) sulfate monohydrate, where two independent cations are present in the asymmetric unit (Sridhar et al., 2002).

The crystal structures of compounds (I) and (II) are characterized by the presence of Cl anions which engage in numerous interactions. The N···Cl distances are in the ranges 3.117 (2)–3.212 (2) and 3.166 (2)–3.207 (2) Å for (I) and (II), respectively, and are comparable with the average value of 3.207 (4) Å for this type of interaction (Steiner, 1998). In addition to strong N—H···Cl and O—H···Cl hydrogen bonds, both crystal structures also feature weak C—H···O interactions (Figs. 4 and 5).

In compound (I), the ester cations are indirectly linked via Cl anions through intermolecular N—H···Cl and O—H···Cl hydrogen bonds. Each Cl anion acts as an acceptor for three hydrogen bonds with protonated amino groups. Therefore, the N—H1···N···Cl hydrogen bond is common to two adjacent ring motifs, forming a ring motif of a `puckered ladder' of hydrogen bonds, which can be described as R42(8). The fourth hydrogen bond, O1—H1···Cl, exists between the Cl anion and the hydroxyl group of another ester cation. The participation of the hydroxyl group in the hydrogen-bonding network causes the formation of two-dimensional antiparallel molecular layers containing ester cations and Cl anions. Within these layers, the ester cations are linked directly by C2—H2···O2iv interactions [symmetry code: (iv) x, y + 1, z; Table 2] between the methyl and carboxyl groups of adjacent ester cations. Propagation of the hydrogen-bonding C(4) motif generates a chain running along the b axis (Fig. 4).

In compound (II), each Cl anion accepts four hydrogen bonds which can be divided into two groups. The first group is part of a group of hydrogen bonds linking each Cl anion with three different cations via their protonated amino groups and its arrangement is analogous to that seen in (I). The second type of hydrogen bond, in which the Cl anion is the acceptor, is a linkage between the methanol molecule and the Cl anion, consisting of a single O4—H4···Cl hydrogen bond only. The ester cations are linked via the ring of four hydrogen bonds between two different Cl anions and two amino groups of the ester cations, which can be described as R42(8). Thus a `puckered ladder' motif of hydrogen bonds analogous to that observed in (I) can be also be recognized. However, the presence of the methanol solvent molecule results in a different arrangement observed for (II), namely a three-dimensional network. Additionally, the ester cations of (II) are linked directly by C2—H2···O2iv interactions [symmetry code: (iv) x − 1, y, z], resulting in a C(4) hydrogen-bonding motif similar to that in (I), with the chains running along the a axis (Fig. 5).

Experimental top

The methyl ester of L-tyrosine hydrochloride was prepared according to the standard procedure of Wróbel et al. (1983). L-tyrosine (30 g, 0.166 mol) was suspended in absolute methanol (450 ml) and saturated with gaseous hydrogen chloride until it dissolved completely. The resulting solution was cooled in an ice bath for 3 h and left in a refrigerator overnight. After the solvent had been removed in vacuo, the product was isolated (yield 33.37 g, 0.144 mol, 87%). Single crystals of (I) suitable for X-ray diffraction studies were obtained by slow evaporation from solutions of L-tyrosine hydrochloride in either ethanol or propan-2-ol. Single crystals of (II) were obtained by slow evaporation from a methanolic solution of L-tyrosine hydrochloride.

Refinement top

The known absolute configuration of L-tyrosine was assumed and confirmed by refinement of the Flack (1983) parameter. All H atoms were located in difference Fourier maps, and in the final refinement cycles they were treated as riding on their parent atoms, with C—H = 0.95–1.00 Å, N—H = 0.91 Å and O—H = 0.84 Å, and with Uiso(H) = 1.2Ueq(parent atom), except for methyl H atoms where Uiso(H) = 1.5Ueq(C).

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The dashed line indicates the hydrogen bond.
[Figure 2] Fig. 2. A view of (II), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The dashed lines indicate the hydrogen bonds.
[Figure 3] Fig. 3. Superposition of the cations in (I) (dashed lines) and (II) (solid lines), using atoms C1, C2 and N as the common reference points.
[Figure 4] Fig. 4. A view of the two-dimensional arrangement of (I), viewed along the a axis. For clarity, H atoms not involved in the hydrogen bonds shown have been omitted. [Symmetry codes: (i) x, y, z − 1; (ii) −x, y − 1/2, −z + 1; (iii) −x, y + 1/2, −z + 1.]
[Figure 5] Fig. 5. A view of the three-dimensional network of (II), viewed along the b axis. For clarity, H atoms (except those of the methanol molecules) not involved in the hydrogen bonds shown have been omitted. [Symmetry codes: (i) −x + 1/2, −y + 1, z − 1/2; (ii) −x, y − 1/2, −z + 3/2; (iii) −x + 1, y − 1/2, −z + 3/2; (v) −x + 1, y + 1/2, −z + 3/2.]
(I) methyl 2-ammonio-3-(4-hydroxyphenyl)propionate chloride top
Crystal data top
C10H14NO3+·ClF(000) = 244
Mr = 231.67Dx = 1.345 Mg m3
Monoclinic, P21Melting point: 463 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 9.943 (3) ÅCell parameters from 8187 reflections
b = 5.351 (2) Åθ = 4.8–35°
c = 11.154 (3) ŵ = 0.32 mm1
β = 105.38 (3)°T = 100 K
V = 572.2 (3) Å3Plate, colourless
Z = 20.40 × 0.35 × 0.10 mm
Data collection top
Kuma KM4 CCD κ-geometry
diffractometer
3754 independent reflections
Radiation source: fine-focus sealed tube2890 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.054
Detector resolution: 0 pixels mm-1θmax = 35.0°, θmin = 4.8°
ω scansh = 1516
Absorption correction: numerical
(Clark & Reid, 1995)
k = 86
Tmin = 0.882, Tmax = 0.969l = 1818
13013 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.091 w = 1/[σ2(Fo2) + (0.0431P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
3754 reflectionsΔρmax = 0.62 e Å3
139 parametersΔρmin = 0.23 e Å3
1 restraintAbsolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.06 (5)
Crystal data top
C10H14NO3+·ClV = 572.2 (3) Å3
Mr = 231.67Z = 2
Monoclinic, P21Mo Kα radiation
a = 9.943 (3) ŵ = 0.32 mm1
b = 5.351 (2) ÅT = 100 K
c = 11.154 (3) Å0.40 × 0.35 × 0.10 mm
β = 105.38 (3)°
Data collection top
Kuma KM4 CCD κ-geometry
diffractometer
3754 independent reflections
Absorption correction: numerical
(Clark & Reid, 1995)
2890 reflections with I > 2σ(I)
Tmin = 0.882, Tmax = 0.969Rint = 0.054
13013 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.62 e Å3
S = 1.00Δρmin = 0.23 e Å3
3754 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs
139 parametersAbsolute structure parameter: 0.06 (5)
1 restraint
Special details top

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. Diffraction data for I were collected on a Xcalibur PX ω-geometry diffractometer equipped with an Oxford Cryosystems low-temperature device. The crystal structure was solved by direct methods using the SHELXS97 program (Sheldrick, 1990) and refined using SHELXL97 (Sheldrick, 1997). The full-matrix least-squares were completed, using anisotropic parameters for all non H-atoms. For I the analytical numeric absorption correction using a multifaced crystal model based on expressions derived by Clark (Clark et al., 1995). All Figures were made using XP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.03854 (4)0.40089 (8)0.83527 (3)0.01977 (9)
O10.20259 (14)0.0622 (3)0.69078 (11)0.0257 (3)
H10.15930.15250.72960.031*
O20.30256 (14)0.0529 (2)0.10206 (12)0.0245 (3)
O30.48734 (14)0.3073 (3)0.16742 (12)0.0251 (3)
N0.11903 (13)0.4057 (3)0.12501 (11)0.0173 (2)
H1N0.08950.37010.04240.021*
H2N0.06750.53380.14320.021*
H3N0.10850.26830.16980.021*
C10.35278 (19)0.2531 (3)0.13858 (15)0.0174 (3)
C20.26911 (18)0.4791 (3)0.15735 (15)0.0168 (3)
H20.28000.60970.09650.020*
C30.31368 (18)0.5958 (3)0.28748 (15)0.0173 (3)
H310.41560.62460.30920.021*
H320.26800.76100.28430.021*
C40.28019 (17)0.4442 (3)0.39032 (14)0.0172 (3)
C50.17951 (18)0.5313 (3)0.44590 (15)0.0193 (3)
H50.12950.67930.41500.023*
C60.15013 (16)0.4071 (4)0.54571 (13)0.0191 (3)
H60.08120.47040.58250.023*
C70.22214 (18)0.1909 (3)0.59084 (15)0.0186 (3)
C80.32103 (17)0.0968 (3)0.53435 (15)0.0180 (3)
H80.36870.05430.56360.022*
C90.34980 (18)0.2232 (3)0.43583 (15)0.0176 (3)
H90.41800.15860.39850.021*
C100.5808 (2)0.1090 (4)0.1513 (2)0.0319 (4)
H1010.55440.05290.06460.048*
H1020.57420.03150.20590.048*
H1030.67680.17170.17270.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.02294 (18)0.01974 (17)0.01706 (16)0.00036 (19)0.00605 (13)0.00079 (18)
O10.0320 (7)0.0254 (7)0.0238 (6)0.0060 (6)0.0149 (5)0.0075 (6)
O20.0299 (7)0.0140 (5)0.0306 (7)0.0004 (6)0.0097 (5)0.0017 (5)
O30.0228 (6)0.0232 (6)0.0298 (7)0.0023 (5)0.0079 (5)0.0060 (5)
N0.0205 (6)0.0158 (5)0.0147 (5)0.0003 (8)0.0028 (4)0.0017 (7)
C10.0235 (8)0.0164 (7)0.0131 (7)0.0016 (6)0.0061 (6)0.0019 (6)
C20.0200 (8)0.0145 (7)0.0157 (7)0.0008 (6)0.0043 (6)0.0006 (6)
C30.0201 (8)0.0152 (7)0.0163 (7)0.0022 (7)0.0040 (6)0.0011 (6)
C40.0172 (7)0.0193 (9)0.0140 (6)0.0005 (6)0.0021 (5)0.0008 (6)
C50.0218 (8)0.0170 (8)0.0168 (7)0.0029 (7)0.0012 (6)0.0002 (6)
C60.0186 (7)0.0219 (7)0.0179 (7)0.0027 (9)0.0066 (5)0.0002 (9)
C70.0203 (8)0.0198 (8)0.0160 (7)0.0028 (7)0.0057 (6)0.0014 (7)
C80.0181 (8)0.0158 (7)0.0194 (8)0.0024 (7)0.0039 (6)0.0004 (7)
C90.0170 (8)0.0180 (8)0.0171 (7)0.0004 (6)0.0031 (6)0.0029 (6)
C100.0264 (10)0.0337 (11)0.0373 (10)0.0065 (9)0.0115 (8)0.0070 (9)
Geometric parameters (Å, º) top
O1—C71.368 (2)C3—H320.9900
O1—H10.8400C4—C51.390 (2)
O2—C11.206 (2)C4—C91.396 (2)
O3—C11.323 (2)C5—C61.392 (2)
O3—C101.453 (2)C5—H50.9500
N—C21.492 (2)C6—C71.383 (3)
N—H1N0.9100C6—H60.9500
N—H2N0.9100C7—C81.395 (2)
N—H3N0.9100C8—C91.383 (2)
C1—C21.514 (2)C8—H80.9500
C2—C31.534 (2)C9—H90.9500
C2—H21.0000C10—H1010.9800
C3—C41.513 (2)C10—H1020.9800
C3—H310.9900C10—H1030.9800
C7—O1—H1109.5C5—C4—C3119.18 (15)
C1—O3—C10116.64 (15)C9—C4—C3122.85 (15)
C2—N—H1N109.5C4—C5—C6121.67 (17)
C2—N—H2N109.5C4—C5—H5119.2
H1N—N—H2N109.5C6—C5—H5119.2
C2—N—H3N109.5C7—C6—C5119.47 (15)
H1N—N—H3N109.5C7—C6—H6120.3
H2N—N—H3N109.5C5—C6—H6120.3
O2—C1—O3125.35 (16)O1—C7—C6123.11 (15)
O2—C1—C2124.26 (16)O1—C7—C8117.12 (16)
O3—C1—C2110.39 (14)C6—C7—C8119.76 (15)
N—C2—C1107.89 (14)C9—C8—C7120.08 (16)
N—C2—C3110.83 (13)C9—C8—H8120.0
C1—C2—C3115.14 (14)C7—C8—H8120.0
N—C2—H2107.6C8—C9—C4121.06 (16)
C1—C2—H2107.6C8—C9—H9119.5
C3—C2—H2107.6C4—C9—H9119.5
C4—C3—C2115.65 (14)O3—C10—H101109.5
C4—C3—H31108.4O3—C10—H102109.5
C2—C3—H31108.4H101—C10—H102109.5
C4—C3—H32108.4O3—C10—H103109.5
C2—C3—H32108.4H101—C10—H103109.5
H31—C3—H32107.4H102—C10—H103109.5
C5—C4—C9117.92 (15)
C10—O3—C1—O21.1 (3)C9—C4—C5—C61.4 (2)
C10—O3—C1—C2178.70 (14)C3—C4—C5—C6176.24 (16)
N—C2—C1—O20.9 (2)C4—C5—C6—C70.3 (3)
O3—C1—C2—N179.29 (12)C5—C6—C7—O1177.95 (16)
O2—C1—C2—C3125.26 (18)C5—C6—C7—C81.4 (3)
O3—C1—C2—C354.94 (19)O1—C7—C8—C9177.51 (16)
N—C2—C3—C452.0 (2)C6—C7—C8—C91.9 (3)
C1—C2—C3—C470.82 (19)C7—C8—C9—C40.7 (3)
C2—C3—C4—C5111.3 (2)C5—C4—C9—C80.9 (2)
C2—C3—C4—C971.2 (2)C3—C4—C9—C8176.63 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl0.842.313.1524 (15)180
N—H1N···Cli0.912.243.1166 (15)163
N—H3N···Clii0.912.443.2118 (19)142
N—H2N···Cliii0.912.273.1686 (19)168
C2—H2···O2iv1.002.383.166 (2)135
Symmetry codes: (i) x, y, z1; (ii) x, y1/2, z+1; (iii) x, y+1/2, z+1; (iv) x, y+1, z.
(II) methyl 2-ammonio-3-(4-hydroxyphenyl)propionate chloride methanol solvate top
Crystal data top
C10H14NO3+·Cl·CH4ODx = 1.346 Mg m3
Mr = 263.71Melting point: 463 K
Orthorhombic, P212121Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2abCell parameters from 11981 reflections
a = 5.424 (2) Åθ = 4.1–75.9°
b = 11.080 (3) ŵ = 2.65 mm1
c = 21.647 (5) ÅT = 100 K
V = 1300.9 (7) Å3Plate, colourless
Z = 40.52 × 0.15 × 0.06 mm
F(000) = 560
Data collection top
Kuma KM4 CCD κ-geometry
diffractometer
2563 independent reflections
Radiation source: fine-focus sealed tube2462 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
ω scansθmax = 75.9°, θmin = 4.1°
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
h = 64
Tmin = 0.339, Tmax = 0.857k = 1313
12812 measured reflectionsl = 2327
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040 w = 1/[σ2(Fo2) + (0.0765P)2 + 0.4385P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.48 e Å3
2563 reflectionsΔρmin = 0.34 e Å3
160 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0101 (11)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with how many Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (2)
Crystal data top
C10H14NO3+·Cl·CH4OV = 1300.9 (7) Å3
Mr = 263.71Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 5.424 (2) ŵ = 2.65 mm1
b = 11.080 (3) ÅT = 100 K
c = 21.647 (5) Å0.52 × 0.15 × 0.06 mm
Data collection top
Kuma KM4 CCD κ-geometry
diffractometer
2563 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
2462 reflections with I > 2σ(I)
Tmin = 0.339, Tmax = 0.857Rint = 0.046
12812 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.108Δρmax = 0.48 e Å3
S = 1.06Δρmin = 0.34 e Å3
2563 reflectionsAbsolute structure: Flack (1983), with how many Friedel pairs
160 parametersAbsolute structure parameter: 0.02 (2)
0 restraints
Special details top

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. Diffraction data for II were collected on a Xcalibur PX ω-geometry diffractometer equipped with an Oxford Cryosystems low-temperature device. The crystal structure was solved by direct methods using SHELXS97 (Sheldrick, 1990) and refined using SHELXL97 (Sheldrick, 1997).

The full-matrix least-squares were completed using anisotropic parameters for all non H-atoms. All figures and packing diagrams were made using XP.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.49594 (9)0.66526 (4)0.90812 (2)0.01987 (17)
O10.4936 (3)0.24977 (13)0.81774 (7)0.0258 (3)
H10.57360.30340.83640.031*
O20.4029 (3)0.43158 (14)0.52895 (7)0.0217 (3)
O30.2138 (3)0.60732 (14)0.55071 (7)0.0241 (4)
N0.0024 (4)0.29849 (15)0.55319 (7)0.0183 (3)
H1N0.01250.28360.51190.022*
H2N0.13220.26040.56900.022*
H3N0.14060.27060.57220.022*
C10.2246 (4)0.48728 (19)0.54612 (9)0.0179 (4)
C20.0202 (4)0.43061 (18)0.56370 (9)0.0188 (4)
H20.14880.46240.53490.023*
C30.1041 (4)0.4575 (2)0.63007 (10)0.0209 (5)
H310.10950.54610.63590.025*
H320.27380.42640.63550.025*
C40.0588 (4)0.4034 (2)0.67962 (10)0.0196 (4)
C50.0094 (5)0.28870 (18)0.70304 (9)0.0211 (4)
H50.12870.24490.68800.025*
C60.1593 (4)0.2374 (2)0.74811 (10)0.0232 (5)
H60.12500.15860.76320.028*
C70.3591 (4)0.3015 (2)0.77104 (9)0.0207 (4)
C80.4124 (4)0.41596 (19)0.74803 (9)0.0201 (5)
H80.54990.45970.76350.024*
C90.2634 (4)0.46629 (19)0.70221 (10)0.0201 (4)
H90.30120.54400.68620.024*
C100.4393 (4)0.6708 (2)0.53444 (11)0.0263 (5)
H1010.48850.64880.49240.039*
H1020.57050.64840.56340.039*
H1030.41090.75810.53660.039*
O40.7358 (3)0.41512 (14)0.88760 (7)0.0261 (4)
H40.64930.47670.89400.031*
C110.9791 (5)0.4510 (2)0.87049 (12)0.0325 (5)
H110.97850.47970.82770.049*
H121.09090.38190.87420.049*
H131.03490.51600.89780.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0151 (2)0.0227 (3)0.0218 (3)0.0011 (2)0.0001 (2)0.00282 (15)
O10.0310 (8)0.0210 (7)0.0252 (7)0.0018 (8)0.0091 (8)0.0010 (5)
O20.0158 (7)0.0235 (8)0.0259 (8)0.0011 (6)0.0024 (6)0.0002 (6)
O30.0224 (8)0.0187 (7)0.0310 (8)0.0004 (6)0.0042 (7)0.0011 (6)
N0.0140 (7)0.0223 (8)0.0188 (8)0.0025 (8)0.0001 (8)0.0006 (6)
C10.0174 (10)0.0177 (9)0.0185 (9)0.0003 (8)0.0037 (8)0.0010 (7)
C20.0128 (9)0.0224 (10)0.0213 (9)0.0013 (9)0.0005 (9)0.0001 (7)
C30.0167 (9)0.0249 (11)0.0211 (10)0.0011 (8)0.0007 (8)0.0000 (8)
C40.0160 (11)0.0234 (10)0.0195 (9)0.0012 (7)0.0034 (7)0.0029 (8)
C50.0195 (9)0.0239 (10)0.0198 (9)0.0032 (10)0.0011 (9)0.0023 (7)
C60.0264 (11)0.0226 (11)0.0205 (10)0.0032 (9)0.0011 (9)0.0007 (8)
C70.0200 (10)0.0226 (10)0.0194 (10)0.0027 (8)0.0009 (8)0.0004 (8)
C80.0177 (10)0.0221 (11)0.0205 (10)0.0011 (8)0.0002 (8)0.0026 (9)
C90.0168 (9)0.0204 (10)0.0232 (10)0.0002 (8)0.0028 (8)0.0000 (8)
C100.0233 (11)0.0224 (10)0.0331 (11)0.0057 (8)0.0022 (9)0.0011 (9)
O40.0243 (8)0.0219 (8)0.0321 (8)0.0023 (7)0.0010 (7)0.0026 (6)
C110.0268 (12)0.0355 (12)0.0351 (12)0.0034 (12)0.0053 (11)0.0003 (10)
Geometric parameters (Å, º) top
O1—C71.372 (3)C5—C61.392 (3)
O1—H10.8400C5—H50.9500
O2—C11.206 (3)C6—C71.388 (3)
O3—C11.335 (3)C6—H60.9500
O3—C101.454 (3)C7—C81.392 (3)
N—C21.487 (2)C8—C91.396 (3)
N—H1N0.9100C8—H80.9500
N—H2N0.9100C9—H90.9500
N—H3N0.9100C10—H1010.9800
C1—C21.517 (3)C10—H1020.9800
C2—C31.536 (3)C10—H1030.9800
C2—H21.0000O4—C111.427 (3)
C3—C41.513 (3)O4—H40.8400
C3—H310.9900C11—H110.9800
C3—H320.9900C11—H120.9800
C4—C51.394 (3)C11—H130.9800
C4—C91.399 (3)
C7—O1—H1109.5C6—C5—H5119.5
C1—O3—C10115.28 (17)C4—C5—H5119.5
C2—N—H1N109.5C7—C6—C5119.8 (2)
C2—N—H2N109.5C7—C6—H6120.1
H1N—N—H2N109.5C5—C6—H6120.1
C2—N—H3N109.5O1—C7—C6117.67 (19)
H1N—N—H3N109.5O1—C7—C8122.3 (2)
H2N—N—H3N109.5C6—C7—C8120.0 (2)
O2—C1—O3124.6 (2)C7—C8—C9119.9 (2)
O2—C1—C2124.56 (19)C7—C8—H8120.1
O3—C1—C2110.80 (18)C9—C8—H8120.1
N—C2—C1107.28 (17)C8—C9—C4120.6 (2)
N—C2—C3111.00 (16)C8—C9—H9119.7
C1—C2—C3114.44 (17)C4—C9—H9119.7
N—C2—H2108.0O3—C10—H101109.5
C1—C2—H2108.0O3—C10—H102109.5
C3—C2—H2108.0H101—C10—H102109.5
C4—C3—C2114.41 (17)O3—C10—H103109.5
C4—C3—H31108.7H101—C10—H103109.5
C2—C3—H31108.7H102—C10—H103109.5
C4—C3—H32108.7C11—O4—H4109.5
C2—C3—H32108.7O4—C11—H11109.5
H31—C3—H32107.6O4—C11—H12109.5
C5—C4—C9118.7 (2)H11—C11—H12109.5
C5—C4—C3120.45 (19)O4—C11—H13109.5
C9—C4—C3120.9 (2)H11—C11—H13109.5
C6—C5—C4121.0 (2)H12—C11—H13109.5
C10—O3—C1—O21.2 (3)C9—C4—C5—C60.2 (3)
C10—O3—C1—C2179.62 (17)C3—C4—C5—C6179.3 (2)
N—C2—C1—O22.2 (3)C4—C5—C6—C71.0 (3)
O3—C1—C2—N176.15 (16)C5—C6—C7—O1176.60 (19)
O2—C1—C2—C3121.4 (2)C5—C6—C7—C81.4 (3)
O3—C1—C2—C360.2 (2)O1—C7—C8—C9177.39 (19)
N—C2—C3—C455.8 (2)C6—C7—C8—C90.5 (3)
C1—C2—C3—C465.8 (2)C7—C8—C9—C40.8 (3)
C2—C3—C4—C590.8 (2)C5—C4—C9—C81.1 (3)
C2—C3—C4—C988.3 (2)C3—C4—C9—C8179.83 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.841.882.715 (2)173
O4—H4···Cl0.842.273.0938 (18)167
N—H1N···Cli0.912.323.1659 (18)155
N—H2N···Clii0.912.293.192 (2)170
N—H3N···Cliii0.912.333.207 (2)162
C2—H2···O2iv1.002.463.219 (3)132
C9—H9···O1v0.952.543.434 (3)157
C10—H103···O4v0.982.523.328 (3)140
Symmetry codes: (i) x+1/2, y+1, z1/2; (ii) x, y1/2, z+3/2; (iii) x+1, y1/2, z+3/2; (iv) x1, y, z; (v) x+1, y+1/2, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC10H14NO3+·ClC10H14NO3+·Cl·CH4O
Mr231.67263.71
Crystal system, space groupMonoclinic, P21Orthorhombic, P212121
Temperature (K)100100
a, b, c (Å)9.943 (3), 5.351 (2), 11.154 (3)5.424 (2), 11.080 (3), 21.647 (5)
α, β, γ (°)90, 105.38 (3), 9090, 90, 90
V3)572.2 (3)1300.9 (7)
Z24
Radiation typeMo KαCu Kα
µ (mm1)0.322.65
Crystal size (mm)0.40 × 0.35 × 0.100.52 × 0.15 × 0.06
Data collection
DiffractometerKuma KM4 CCD κ-geometry
diffractometer
Kuma KM4 CCD κ-geometry
diffractometer
Absorption correctionNumerical
(Clark & Reid, 1995)
Analytical
(CrysAlis RED; Oxford Diffraction, 2003)
Tmin, Tmax0.882, 0.9690.339, 0.857
No. of measured, independent and
observed [I > 2σ(I)] reflections
13013, 3754, 2890 12812, 2563, 2462
Rint0.0540.046
(sin θ/λ)max1)0.8070.629
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.091, 1.00 0.040, 0.108, 1.06
No. of reflections37542563
No. of parameters139160
No. of restraints10
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.230.48, 0.34
Absolute structureFlack (1983), with how many Friedel pairsFlack (1983), with how many Friedel pairs
Absolute structure parameter0.06 (5)0.02 (2)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 1997), SHELXL97.

Selected geometric parameters (Å, º) for (I) top
O1—C71.368 (2)C3—C41.513 (2)
O2—C11.206 (2)C4—C51.390 (2)
O3—C11.323 (2)C4—C91.396 (2)
O3—C101.453 (2)C5—C61.392 (2)
N—C21.492 (2)C6—C71.383 (3)
C1—C21.514 (2)C7—C81.395 (2)
C2—C31.534 (2)C8—C91.383 (2)
C10—O3—C1—O21.1 (3)N—C2—C3—C452.0 (2)
N—C2—C1—O20.9 (2)C2—C3—C4—C5111.3 (2)
O2—C1—C2—C3125.26 (18)C2—C3—C4—C971.2 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl0.842.313.1524 (15)180
N—H1N···Cli0.912.243.1166 (15)163
N—H3N···Clii0.912.443.2118 (19)142
N—H2N···Cliii0.912.273.1686 (19)168
C2—H2···O2iv1.002.383.166 (2)135
Symmetry codes: (i) x, y, z1; (ii) x, y1/2, z+1; (iii) x, y+1/2, z+1; (iv) x, y+1, z.
Selected geometric parameters (Å, º) for (II) top
O1—C71.372 (3)C2—C31.536 (3)
O2—C11.206 (3)C3—C41.513 (3)
O3—C11.335 (3)C6—C71.388 (3)
O3—C101.454 (3)C7—C81.392 (3)
N—C21.487 (2)C8—C91.396 (3)
C1—C21.517 (3)
C10—O3—C1—O21.2 (3)N—C2—C3—C455.8 (2)
N—C2—C1—O22.2 (3)C2—C3—C4—C590.8 (2)
O2—C1—C2—C3121.4 (2)C2—C3—C4—C988.3 (2)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.841.882.715 (2)173
O4—H4···Cl0.842.273.0938 (18)167
N—H1N···Cli0.912.323.1659 (18)155
N—H2N···Clii0.912.293.192 (2)170
N—H3N···Cliii0.912.333.207 (2)162
C2—H2···O2iv1.002.463.219 (3)132
C9—H9···O1v0.952.543.434 (3)157
C10—H103···O4v0.982.523.328 (3)140
Symmetry codes: (i) x+1/2, y+1, z1/2; (ii) x, y1/2, z+3/2; (iii) x+1, y1/2, z+3/2; (iv) x1, y, z; (v) x+1, y+1/2, z+3/2.
 

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