l-Phenyl­alanine fumaric acid

Alagar, M.; Krishnakumar, R.V.; Rajagopal, K.; Subha Nandhini, M.; Natarajan, S.

doi:10.1107/S1600536803011942

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L-Phenylalanine fumaric acid

M. Alagar, R. V. Krishnakumar, K. Rajagopal, M. Subha Nandhini and S. Natarajan

In the title adduct, C₉H₁₁NO₂·C₄H₄O₄, the amino acid molecules exist as zwitterions and the fumaric acid molecules exist in the unionized state, a feature uncommon in similar crystal structures. The asymmetric unit is composed of two molecules of each species. The fumaric acid molecules are related to each other through a pseudo-inversion centre and are essentially planar. The phenylalanine and fumaric acid molecules form hydrogen-bonded double layers, linked together by hydrogen bonds and extending along [001]. These double layers are flanked, on either side, by the hydrophobic side chains of phenylalanine, leading to alternating hydrophilic and hydrophobic zones.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803011942/wn6164sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803011942/wn6164Isup2.hkl Contains datablock I

CCDC reference: 217455

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.006 Å
R factor = 0.032
wR factor = 0.085
Data-to-parameter ratio = 6.6

checkCIF results

No syntax errors found


 Alert Level B:



PLAT_111  Alert B ADDSYM Detects (Pseudo) Centre of Symmetry .....         95 PerFit

PLAT_113  Alert B ADDSYM Suggests Possible Pseudo/New Spacegroup .           P-1


 Alert Level C:



REFNR_01  Alert C Ratio of reflections to parameters is < 8 for a
          non-centrosymmetric structure, where ZMAX < 18
          sine(theta)/lambda                0.5942
          Proportion of unique data used    0.9488
          Ratio reflections to parameters   6.5847

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.98
         From the CIF: _reflns_number_total               2540
         Count of symmetry unique reflns         2417
         Completeness (_total/calc)            105.09%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       123
         Fraction of Friedel pairs measured     0.051
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

In view of the importance of non-covalent interactions in the aggregation and interaction patterns of biological molecules, we have been elucidating the X-ray crystal structures of simple complexes involving amino acids and dicarboxylic acids. Precise crystallographic data on such complexes are expected to provide useful insights into chemical evolution and self-assembly, processes that might have led to the emergence of primitive multi-molecular systems. Fumaric acid (trans-butenedioic acid) is among the organic compounds widely found in Nature, and is a key intermediate in the biosynthesis of organic acids. X-ray investigations of amino acid complexes with fumaric acid seem to have been first initiated in our laboratory. Such investigations have provided some interesting data regarding the ionization states and stoichiometry of these molecules. Recently, we have reported the crystal structures of complexes of maleic acid (cis-butenedioic acid) with DL-phenylalanine (Alagar, Subha Nandhini et al., 2003) and L-phenylalanine (Alagar et al., 2001). The present study reports the crystal structure of a complex of L-phenylalanine with fumaric acid.

Fig.1 shows the molecular structure of (I) with the atom-numbering scheme. There are two molecules of phenylalanine and two molecules of fumaric acid in the asymmetric unit. The ionization state exhibited in this structure is uncommon in similar crystal structures. The amino acid molecules exist as zwitterions and the two fumaric acid molecules exist in the unionized state. Usually, in the crystal structures of amino acid-carboyxlic acid complexes, the amino acid molecules prefer the cationic state and the carboxylic acids the anionic state, either as carboxylate(2-) or semicarboxylate(1-) anions. The two fumaric acid molecules in the asymmetric unit are related to each other through a psuedo-inversion centre, and are essentially planar.

Interestingly, if we exclude the N and O atoms, then the two independent amino acid molecules are also related by a pseudo-inversion centre. This is evident from the torsion angles ψ¹[−164.1 (2), −138.6 (3)°], ψ²[17.8 (4), 41.1 (3)°], χ¹[−69.4 (3), 166.3 (3)°], χ²¹[−96.9 (4), 99.2 (4)°], χ²²[83.2 (4), −79.1 (4)].

The phenylalanine and fumaric acid molecules form hydrogen-bonded double layers, linked together by N—H···O and O—H···O hydrogen bonds, and extending along [001]. These double layers are flanked, on either side, by the hydrophobic side chains of phenylalanine, leading to alternating hydrophilic and hydrophobic zones (Fig.2). In addition to van der Waals interactions, a short carbonyl contact C1'···O2 (x + 1, y, z − 1) = 2.998 (3) Å is also observed (Allen et al., 1998).

In the present structure there are no direct hydrogen-bonded interactions between the fumaric acid molecules. This situation is also observed for the non-amino-acid components of the following complexes: L-phenylalanine L-phenylalaninium formate (Görbitz & Etter, 1992), L-phenylalaninium maleate (Alagar et al., 2001), DL-phenylalaninium maleate (Alagar, Subha Nandhini et al.,2003), DL– valine fumaric acid 2/1 (Alagar, Krishnakumar et al., 2003), and DL-valinium maleate (Alagar et al., 2001).

Experimental top

Colourless, single crystals of (I) were grown as transparent prisms, from a saturated aqueous solution containing L-phenylalanine and fumaric acid in a 1:1 stoichiometric ratio.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the molecules of (I), viewed down the a axis.

(I) top

Crystal data top

C₉H₁₁NO₂·C₄H₄O₄	Z = 2
M_r = 281.26	F(000) = 296
Triclinic, P1	D_x = 1.361 Mg m⁻³ D_m = 1.35 (2) Mg m⁻³ D_m measured by flotation in a mixture of xylene and bromoform
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7016 (10) Å	Cell parameters from 25 reflections
b = 11.4864 (15) Å	θ = 2–7°
c = 11.5542 (17) Å	µ = 0.11 mm⁻¹
α = 67.953 (11)°	T = 293 K
β = 81.158 (13)°	Prism, colorless
γ = 79.379 (15)°	0.28 × 0.23 × 0.18 mm
V = 686.37 (19) Å³

Data collection top

Enraf Nonius CAD4 diffractometer	2154 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.013
Graphite monochromator	θ_max = 25.0°, θ_min = 2.2°
non–profiled ω/2θ scans	h = −6→6
Absorption correction: ψ scan [North et al., 1968]	k = 0→13
T_min = 0.960, T_max = 0.975	l = −12→13
2541 measured reflections	2 standard reflections every 100 reflections
2540 independent reflections	intensity decay: <1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0551P)² + 0.0393P] where P = (F_o² + 2F_c²)/3
2410 reflections	(Δ/σ)_max < 0.001
366 parameters	Δρ_max = 0.18 e Å⁻³
3 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₉H₁₁NO₂·C₄H₄O₄	γ = 79.379 (15)°
M_r = 281.26	V = 686.37 (19) Å³
Triclinic, P1	Z = 2
a = 5.7016 (10) Å	Mo Kα radiation
b = 11.4864 (15) Å	µ = 0.11 mm⁻¹
c = 11.5542 (17) Å	T = 293 K
α = 67.953 (11)°	0.28 × 0.23 × 0.18 mm
β = 81.158 (13)°

Data collection top

Enraf Nonius CAD4 diffractometer	2154 reflections with I > 2σ(I)
Absorption correction: ψ scan [North et al., 1968]	R_int = 0.013
T_min = 0.960, T_max = 0.975	2 standard reflections every 100 reflections
2541 measured reflections	intensity decay: <1%
2540 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	3 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.03	Δρ_max = 0.18 e Å⁻³
2410 reflections	Δρ_min = −0.14 e Å⁻³
366 parameters

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. 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.2177 (3)	0.5907 (2)	0.15771 (18)	0.0444 (6)
O2	1.0094 (3)	0.64490 (19)	0.31153 (16)	0.0334 (4)
O3	0.8382 (4)	0.5849 (2)	0.54851 (19)	0.0491 (6)
H3	0.8806	0.5960	0.4745	0.074*
O4	0.4730 (4)	0.6316 (2)	0.48204 (18)	0.0435 (5)
O5	0.3373 (4)	0.5769 (3)	0.9349 (2)	0.0646 (8)
H5	0.2763	0.5919	0.9978	0.097*
O6	−0.0355 (4)	0.6312 (3)	0.8789 (2)	0.0744 (9)
O1'	−0.2517 (3)	−0.08448 (19)	0.13858 (17)	0.0387 (5)
O2'	−0.3549 (3)	−0.0946 (2)	0.33444 (18)	0.0435 (5)
O3'	−0.0096 (4)	0.9407 (3)	0.9166 (2)	0.0583 (7)
H3'	−0.0619	0.9322	0.9891	0.087*
O4'	0.3397 (4)	0.8650 (2)	0.99990 (19)	0.0576 (7)
O5'	0.5047 (4)	0.9449 (3)	0.5405 (2)	0.0668 (8)
H5'	0.5739	0.9506	0.4713	0.100*
O6'	0.8757 (4)	0.8889 (3)	0.5960 (2)	0.0570 (7)
N1	0.5858 (4)	0.6716 (2)	0.21939 (19)	0.0316 (5)
H1A	0.4555	0.6652	0.1897	0.047*
H1B	0.6013	0.7531	0.1971	0.047*
H1C	0.5721	0.6360	0.3027	0.047*
N1'	0.1311 (4)	−0.1469 (2)	0.3734 (2)	0.0367 (5)
H1'1	0.2788	−0.1348	0.3777	0.055*
H1'2	0.1312	−0.2274	0.3825	0.055*
H1'3	0.0328	−0.1291	0.4341	0.055*
C1	1.0254 (5)	0.6161 (3)	0.2165 (2)	0.0297 (6)
C2	0.8006 (4)	0.6057 (3)	0.1671 (2)	0.0309 (6)
H2	0.8155	0.6490	0.0758	0.037*
C3	0.7768 (5)	0.4663 (3)	0.1947 (3)	0.0431 (7)
H3A	0.6263	0.4634	0.1672	0.052*
H3B	0.9049	0.4327	0.1453	0.052*
C4	0.7852 (6)	0.3813 (3)	0.3305 (3)	0.0469 (8)
C5	0.9960 (7)	0.3078 (4)	0.3747 (4)	0.0651 (11)
H5A	1.1347	0.3112	0.3200	0.078*
C6	1.0033 (10)	0.2292 (4)	0.4992 (5)	0.0872 (16)
H6	1.1463	0.1793	0.5269	0.105*
C7	0.8036 (12)	0.2240 (5)	0.5817 (5)	0.0909 (16)
H7	0.8100	0.1718	0.6655	0.109*
C8	0.5908 (10)	0.2975 (5)	0.5391 (4)	0.0829 (13)
H8	0.4536	0.2950	0.5946	0.100*
C9	0.5819 (7)	0.3741 (4)	0.4150 (4)	0.0622 (10)
H9	0.4374	0.4219	0.3872	0.075*
C10	0.6026 (5)	0.6082 (3)	0.5643 (3)	0.0359 (7)
C11	0.5129 (5)	0.6016 (3)	0.6938 (2)	0.0377 (7)
H11	0.6204	0.5928	0.7504	0.045*
C12	0.2810 (5)	0.6082 (3)	0.7287 (3)	0.0411 (7)
H12	0.1775	0.6139	0.6713	0.049*
C13	0.1762 (6)	0.6070 (3)	0.8556 (3)	0.0444 (8)
C1'	−0.2059 (5)	−0.0818 (3)	0.2398 (2)	0.0307 (6)
C2'	0.0482 (5)	−0.0623 (3)	0.2493 (2)	0.0321 (6)
H2'	0.1559	−0.0847	0.1838	0.039*
C3'	0.0625 (6)	0.0752 (3)	0.2302 (3)	0.0455 (8)
H3'1	−0.0641	0.1037	0.2839	0.055*
H3'2	0.2148	0.0802	0.2545	0.055*
C4'	0.0386 (6)	0.1612 (3)	0.0959 (3)	0.0475 (8)
C5'	−0.1791 (7)	0.2338 (3)	0.0585 (4)	0.0628 (10)
H5'1	−0.3109	0.2318	0.1173	0.075*
C6'	−0.1996 (10)	0.3090 (4)	−0.0661 (6)	0.0899 (17)
H6'	−0.3459	0.3567	−0.0908	0.108*
C7'	−0.0076 (12)	0.3139 (4)	−0.1529 (5)	0.0903 (17)
H7'	−0.0228	0.3652	−0.2364	0.108*
C8'	0.2109 (10)	0.2424 (5)	−0.1171 (4)	0.0885 (15)
H8'	0.3424	0.2455	−0.1763	0.106*
C9'	0.2316 (8)	0.1668 (4)	0.0068 (4)	0.0662 (10)
H9'	0.3780	0.1187	0.0308	0.079*
C10'	0.2233 (6)	0.9046 (3)	0.9116 (3)	0.0411 (7)
C11'	0.3249 (6)	0.9177 (3)	0.7809 (3)	0.0432 (7)
H11'	0.2207	0.9369	0.7198	0.052*
C12'	0.5558 (6)	0.9031 (3)	0.7497 (3)	0.0461 (8)
H12'	0.6583	0.8867	0.8110	0.055*
C13'	0.6629 (6)	0.9112 (3)	0.6226 (3)	0.0415 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0214 (10)	0.0850 (16)	0.0390 (11)	−0.0062 (10)	0.0017 (8)	−0.0384 (11)
O2	0.0288 (10)	0.0518 (12)	0.0259 (9)	−0.0084 (8)	−0.0007 (7)	−0.0203 (9)
O3	0.0349 (12)	0.0846 (17)	0.0295 (10)	−0.0066 (11)	0.0023 (9)	−0.0248 (12)
O4	0.0383 (11)	0.0658 (14)	0.0257 (10)	0.0002 (10)	−0.0044 (9)	−0.0185 (9)
O5	0.0410 (13)	0.125 (2)	0.0379 (13)	−0.0009 (14)	−0.0006 (10)	−0.0463 (15)
O6	0.0396 (15)	0.136 (3)	0.0395 (13)	0.0061 (15)	0.0027 (10)	−0.0331 (15)
O1'	0.0364 (11)	0.0551 (12)	0.0281 (10)	−0.0076 (9)	−0.0051 (8)	−0.0174 (9)
O2'	0.0308 (11)	0.0737 (14)	0.0320 (11)	−0.0111 (10)	0.0006 (8)	−0.0252 (10)
O3'	0.0423 (13)	0.107 (2)	0.0307 (11)	−0.0080 (13)	0.0003 (9)	−0.0326 (13)
O4'	0.0548 (15)	0.0835 (18)	0.0320 (12)	0.0068 (13)	−0.0071 (10)	−0.0243 (12)
O5'	0.0401 (13)	0.128 (2)	0.0357 (12)	−0.0035 (14)	−0.0003 (10)	−0.0382 (15)
O6'	0.0384 (14)	0.0931 (19)	0.0406 (13)	0.0020 (12)	−0.0008 (10)	−0.0315 (13)
N1	0.0207 (10)	0.0502 (13)	0.0267 (11)	−0.0040 (9)	−0.0010 (8)	−0.0180 (10)
N1'	0.0291 (12)	0.0482 (14)	0.0327 (12)	−0.0009 (10)	−0.0048 (10)	−0.0155 (11)
C1	0.0270 (14)	0.0392 (15)	0.0239 (12)	−0.0039 (11)	−0.0022 (10)	−0.0128 (11)
C2	0.0224 (12)	0.0495 (16)	0.0241 (12)	−0.0054 (11)	−0.0004 (10)	−0.0173 (12)
C3	0.0304 (15)	0.059 (2)	0.0532 (18)	−0.0069 (14)	−0.0043 (13)	−0.0345 (16)
C4	0.0449 (18)	0.0426 (18)	0.063 (2)	−0.0090 (14)	−0.0119 (15)	−0.0262 (16)
C5	0.058 (2)	0.049 (2)	0.091 (3)	−0.0016 (18)	−0.023 (2)	−0.024 (2)
C6	0.094 (4)	0.050 (3)	0.110 (4)	−0.002 (2)	−0.049 (3)	−0.008 (3)
C7	0.126 (5)	0.068 (3)	0.074 (3)	−0.035 (3)	−0.035 (3)	0.001 (2)
C8	0.092 (3)	0.083 (3)	0.065 (3)	−0.029 (3)	−0.002 (2)	−0.010 (2)
C9	0.054 (2)	0.065 (2)	0.061 (2)	−0.0142 (18)	−0.0051 (18)	−0.0135 (19)
C10	0.0363 (16)	0.0427 (17)	0.0263 (14)	−0.0044 (13)	−0.0005 (12)	−0.0112 (12)
C11	0.0416 (17)	0.0505 (18)	0.0211 (13)	−0.0048 (14)	−0.0025 (12)	−0.0138 (13)
C12	0.0396 (18)	0.0572 (19)	0.0276 (14)	−0.0042 (14)	−0.0020 (12)	−0.0181 (14)
C13	0.0399 (18)	0.063 (2)	0.0295 (15)	−0.0041 (14)	0.0005 (13)	−0.0186 (14)
C1'	0.0300 (14)	0.0339 (15)	0.0294 (14)	−0.0032 (12)	−0.0043 (11)	−0.0126 (11)
C2'	0.0314 (14)	0.0401 (15)	0.0264 (13)	−0.0050 (11)	−0.0011 (10)	−0.0143 (11)
C3'	0.0489 (18)	0.0450 (18)	0.0489 (18)	−0.0091 (14)	−0.0125 (14)	−0.0195 (15)
C4'	0.0521 (19)	0.0384 (17)	0.055 (2)	−0.0104 (14)	−0.0132 (15)	−0.0148 (15)
C5'	0.061 (2)	0.042 (2)	0.081 (3)	−0.0008 (17)	−0.017 (2)	−0.0161 (19)
C6'	0.093 (4)	0.053 (3)	0.108 (4)	−0.005 (2)	−0.054 (3)	0.003 (3)
C7'	0.128 (5)	0.066 (3)	0.062 (3)	−0.027 (3)	−0.038 (3)	0.011 (2)
C8'	0.111 (4)	0.083 (3)	0.057 (3)	−0.035 (3)	−0.002 (3)	−0.001 (2)
C9'	0.059 (2)	0.071 (3)	0.058 (2)	−0.0121 (19)	−0.0060 (18)	−0.0087 (19)
C10'	0.0461 (18)	0.0507 (19)	0.0316 (16)	−0.0065 (14)	−0.0020 (14)	−0.0210 (14)
C11'	0.0444 (19)	0.057 (2)	0.0303 (15)	−0.0056 (14)	−0.0051 (13)	−0.0183 (14)
C12'	0.046 (2)	0.067 (2)	0.0307 (15)	−0.0052 (16)	−0.0036 (13)	−0.0243 (15)
C13'	0.0410 (18)	0.0550 (19)	0.0321 (15)	−0.0051 (14)	−0.0044 (12)	−0.0198 (14)

Geometric parameters (Å, º) top

O1—C1	1.245 (3)	C4—C9	1.390 (5)
O2—C1	1.247 (3)	C5—C6	1.384 (7)
N1—C2	1.488 (3)	C5—H5A	0.9300
C1—C2	1.521 (3)	C6—C7	1.363 (8)
C2—C3	1.539 (4)	C6—H6	0.9300
C3—C4	1.508 (5)	C7—C8	1.386 (8)
O3—C10	1.318 (4)	C7—H7	0.9300
O3—H3	0.8200	C8—C9	1.375 (6)
O4—C10	1.214 (4)	C8—H8	0.9300
O5—C13	1.307 (4)	C9—H9	0.9300
O5—H5	0.8200	C10—C11	1.483 (4)
O6—C13	1.200 (4)	C11—C12	1.319 (4)
O1'—C1'	1.249 (3)	C11—H11	0.9300
O2'—C1'	1.257 (3)	C12—C13	1.491 (4)
N1'—C2'	1.488 (3)	C12—H12	0.9300
C1'—C2'	1.533 (4)	C2'—H2'	0.9800
C2'—C3'	1.526 (4)	C3'—H3'1	0.9700
C3'—C4'	1.506 (4)	C3'—H3'2	0.9700
O3'—C10'	1.315 (4)	C4'—C9'	1.379 (5)
O3'—H3'	0.8200	C4'—C5'	1.391 (5)
O4'—C10'	1.199 (4)	C5'—C6'	1.384 (7)
O5'—C13'	1.313 (4)	C5'—H5'1	0.9300
O5'—H5'	0.8200	C6'—C7'	1.360 (8)
O6'—C13'	1.209 (4)	C6'—H6'	0.9300
N1—H1A	0.8900	C7'—C8'	1.387 (8)
N1—H1B	0.8900	C7'—H7'	0.9300
N1—H1C	0.8900	C8'—C9'	1.379 (6)
N1'—H1'1	0.8900	C8'—H8'	0.9300
N1'—H1'2	0.8900	C9'—H9'	0.9300
N1'—H1'3	0.8900	C10'—C11'	1.493 (4)
C2—H2	0.9800	C11'—C12'	1.307 (5)
C3—H3A	0.9700	C11'—H11'	0.9300
C3—H3B	0.9700	C12'—C13'	1.477 (4)
C4—C5	1.381 (5)	C12'—H12'	0.9300

C10—O3—H3	109.5	C12—C11—H11	119.9
C13—O5—H5	109.5	C10—C11—H11	119.9
C10'—O3'—H3'	109.5	C11—C12—C13	123.3 (3)
C13'—O5'—H5'	109.5	C11—C12—H12	118.3
C2—N1—H1A	109.5	C13—C12—H12	118.3
C2—N1—H1B	109.5	O6—C13—O5	125.2 (3)
H1A—N1—H1B	109.5	O6—C13—C12	121.7 (3)
C2—N1—H1C	109.5	O5—C13—C12	113.1 (3)
H1A—N1—H1C	109.5	O1'—C1'—O2'	124.1 (3)
H1B—N1—H1C	109.5	O1'—C1'—C2'	118.0 (2)
C2'—N1'—H1'1	109.5	O2'—C1'—C2'	117.9 (2)
C2'—N1'—H1'2	109.5	N1'—C2'—C1'	110.4 (2)
H1'1—N1'—H1'2	109.5	N1'—C2'—C3'	109.5 (2)
C2'—N1'—H1'3	109.5	C1'—C2'—C3'	111.8 (2)
H1'1—N1'—H1'3	109.5	N1'—C2'—H2'	108.4
H1'2—N1'—H1'3	109.5	C3'—C2'—H2'	108.4
O1—C1—O2	124.6 (2)	C1'—C2'—H2'	108.4
O1—C1—C2	115.2 (2)	C4'—C3'—C2'	111.7 (2)
O2—C1—C2	120.2 (2)	C4'—C3'—H3'1	109.3
N1—C2—C1	110.2 (2)	C2'—C3'—H3'1	109.3
N1—C2—C3	112.0 (2)	C4'—C3'—H3'2	109.3
C1—C2—C3	111.1 (2)	C2'—C3'—H3'2	109.3
N1—C2—H2	107.8	H3'1—C3'—H3'2	107.9
C1—C2—H2	107.8	C9'—C4'—C5'	118.8 (3)
C3—C2—H2	107.8	C9'—C4'—C3'	120.3 (3)
C4—C3—C2	114.9 (2)	C5'—C4'—C3'	120.9 (3)
C4—C3—H3A	108.5	C6'—C5'—C4'	120.0 (4)
C2—C3—H3A	108.5	C6'—C5'—H5'1	120.0
C4—C3—H3B	108.5	C4'—C5'—H5'1	120.0
C2—C3—H3B	108.5	C7'—C6'—C5'	120.6 (4)
H3A—C3—H3B	107.5	C7'—C6'—H6'	119.7
C5—C4—C9	117.9 (4)	C5'—C6'—H6'	119.7
C5—C4—C3	120.8 (3)	C6'—C7'—C8'	120.1 (4)
C9—C4—C3	121.2 (3)	C6'—C7'—H7'	120.0
C4—C5—C6	120.8 (4)	C8'—C7'—H7'	120.0
C4—C5—H5A	119.6	C9'—C8'—C7'	119.5 (5)
C6—C5—H5A	119.6	C9'—C8'—H8'	120.2
C7—C6—C5	120.8 (4)	C7'—C8'—H8'	120.2
C7—C6—H6	119.6	C8'—C9'—C4'	121.0 (4)
C5—C6—H6	119.6	C8'—C9'—H9'	119.5
C6—C7—C8	119.1 (5)	C4'—C9'—H9'	119.5
C6—C7—H7	120.4	O4'—C10'—O3'	124.9 (3)
C8—C7—H7	120.4	O4'—C10'—C11'	124.1 (3)
C9—C8—C7	120.3 (5)	O3'—C10'—C11'	111.0 (3)
C9—C8—H8	119.9	C12'—C11'—C10'	122.1 (3)
C7—C8—H8	119.9	C12'—C11'—H11'	119.0
C8—C9—C4	121.1 (4)	C10'—C11'—H11'	119.0
C8—C9—H9	119.5	C11'—C12'—C13'	123.6 (3)
C4—C9—H9	119.5	C11'—C12'—H12'	118.2
O4—C10—O3	123.6 (3)	C13'—C12'—H12'	118.2
O4—C10—C11	123.6 (3)	O6'—C13'—O5'	122.8 (3)
O3—C10—C11	112.7 (2)	O6'—C13'—C12'	123.6 (3)
C12—C11—C10	120.1 (3)	O5'—C13'—C12'	113.6 (3)

O1—C1—C2—N1	−164.1 (2)	O1'—C1'—C2'—N1'	−138.6 (2)
O2—C1—C2—N1	17.8 (4)	O2'—C1'—C2'—N1'	41.1 (3)
O1—C1—C2—C3	71.2 (3)	O1'—C1'—C2'—C3'	99.3 (3)
O2—C1—C2—C3	−106.9 (3)	O2'—C1'—C2'—C3'	−81.0 (3)
N1—C2—C3—C4	−69.4 (3)	N1'—C2'—C3'—C4'	166.3 (2)
C1—C2—C3—C4	54.3 (3)	C1'—C2'—C3'—C4'	−71.1 (3)
C2—C3—C4—C5	−96.9 (4)	C2'—C3'—C4'—C5'	99.2 (4)
C2—C3—C4—C9	83.2 (4)	C2'—C3'—C4'—C9'	−79.1 (4)
C9—C4—C5—C6	0.3 (6)	C9'—C4'—C5'—C6'	0.5 (6)
C3—C4—C5—C6	−179.6 (4)	C3'—C4'—C5'—C6'	−177.8 (4)
C4—C5—C6—C7	−1.1 (7)	C4'—C5'—C6'—C7'	−0.6 (7)
C5—C6—C7—C8	0.8 (8)	C5'—C6'—C7'—C8'	0.4 (8)
C6—C7—C8—C9	0.3 (8)	C6'—C7'—C8'—C9'	0.0 (8)
C7—C8—C9—C4	−1.1 (7)	C7'—C8'—C9'—C4'	−0.1 (7)
C5—C4—C9—C8	0.8 (6)	C5'—C4'—C9'—C8'	−0.1 (6)
C3—C4—C9—C8	−179.3 (4)	C3'—C4'—C9'—C8'	178.2 (4)
O4—C10—C11—C12	7.2 (5)	O4'—C10'—C11'—C12'	−9.7 (5)
O3—C10—C11—C12	−172.2 (3)	O3'—C10'—C11'—C12'	171.1 (3)
C10—C11—C12—C13	−177.7 (3)	C10'—C11'—C12'—C13'	177.9 (3)
C11—C12—C13—O6	169.1 (4)	C11'—C12'—C13'—O6'	−174.6 (4)
C11—C12—C13—O5	−11.1 (5)	C11'—C12'—C13'—O5'	5.3 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.83	2.633 (3)	168
O5—H5···O1ⁱ	0.82	1.82	2.616 (3)	163
O3′—H3′···O1′ⁱⁱ	0.82	1.86	2.659 (3)	166
O5′—H5′···O2′ⁱⁱⁱ	0.82	1.81	2.570 (3)	154
N1—H1A···O1^iv	0.89	1.88	2.730 (3)	160
N1—H1B···O1′ⁱⁱⁱ	0.89	2.02	2.882 (3)	162
N1—H1C···O4	0.89	2.05	2.880 (3)	156
N1′—H1′1···O2′^v	0.89	2.16	3.032 (3)	165
N1′—H1′2···O2^vi	0.89	2.18	2.959 (3)	146
N1′—H1′2···O4^vii	0.89	2.42	2.894 (3)	113
N1′—H1′3···O6′^vi	0.89	2.01	2.886 (3)	166

Symmetry codes: (i) x−1, y, z+1; (ii) x, y+1, z+1; (iii) x+1, y+1, z; (iv) x−1, y, z; (v) x+1, y, z; (vi) x−1, y−1, z; (vii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO₂·C₄H₄O₄
M_r	281.26
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.7016 (10), 11.4864 (15), 11.5542 (17)
α, β, γ (°)	67.953 (11), 81.158 (13), 79.379 (15)
V (Å³)	686.37 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.23 × 0.18

Data collection
Diffractometer	Enraf Nonius CAD4 diffractometer
Absorption correction	ψ scan [North et al., 1968]
T_min, T_max	0.960, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	2541, 2540, 2154
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.085, 1.03
No. of reflections	2410
No. of parameters	366
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.

Selected geometric parameters (Å, º) top

O1—C1	1.245 (3)	O1'—C1'	1.249 (3)
O2—C1	1.247 (3)	O2'—C1'	1.257 (3)
N1—C2	1.488 (3)	N1'—C2'	1.488 (3)
C1—C2	1.521 (3)	C1'—C2'	1.533 (4)
C2—C3	1.539 (4)	C2'—C3'	1.526 (4)
C3—C4	1.508 (5)	C3'—C4'	1.506 (4)
O3—C10	1.318 (4)	O3'—C10'	1.315 (4)
O4—C10	1.214 (4)	O4'—C10'	1.199 (4)
O5—C13	1.307 (4)	O5'—C13'	1.313 (4)
O6—C13	1.200 (4)	O6'—C13'	1.209 (4)

O1—C1—O2	124.6 (2)	O1'—C1'—O2'	124.1 (3)
N1—C2—C1	110.2 (2)	N1'—C2'—C1'	110.4 (2)
N1—C2—C3	112.0 (2)	N1'—C2'—C3'	109.5 (2)
C1—C2—C3	111.1 (2)	C1'—C2'—C3'	111.8 (2)
O4—C10—O3	123.6 (3)	O4'—C10'—O3'	124.9 (3)
C12—C11—C10	120.1 (3)	C12'—C11'—C10'	122.1 (3)
O6—C13—O5	125.2 (3)	O6'—C13'—O5'	122.8 (3)

O1—C1—C2—N1	−164.1 (2)	O1'—C1'—C2'—N1'	−138.6 (2)
O2—C1—C2—N1	17.8 (4)	O2'—C1'—C2'—N1'	41.1 (3)
O1—C1—C2—C3	71.2 (3)	O1'—C1'—C2'—C3'	99.3 (3)
O2—C1—C2—C3	−106.9 (3)	O2'—C1'—C2'—C3'	−81.0 (3)
N1—C2—C3—C4	−69.4 (3)	N1'—C2'—C3'—C4'	166.3 (2)
C1—C2—C3—C4	54.3 (3)	C1'—C2'—C3'—C4'	−71.1 (3)
C2—C3—C4—C5	−96.9 (4)	C2'—C3'—C4'—C5'	99.2 (4)
C2—C3—C4—C9	83.2 (4)	C2'—C3'—C4'—C9'	−79.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.83	2.633 (3)	168
O5—H5···O1ⁱ	0.82	1.82	2.616 (3)	163
O3'—H3'···O1'ⁱⁱ	0.82	1.86	2.659 (3)	166
O5'—H5'···O2'ⁱⁱⁱ	0.82	1.81	2.570 (3)	154
N1—H1A···O1^iv	0.89	1.88	2.730 (3)	160
N1—H1B···O1'ⁱⁱⁱ	0.89	2.02	2.882 (3)	162
N1—H1C···O4	0.89	2.05	2.880 (3)	156
N1'—H1'1···O2'^v	0.89	2.16	3.032 (3)	165
N1'—H1'2···O2^vi	0.89	2.18	2.959 (3)	146
N1'—H1'2···O4^vii	0.89	2.42	2.894 (3)	113
N1'—H1'3···O6'^vi	0.89	2.01	2.886 (3)	166

Symmetry codes: (i) x−1, y, z+1; (ii) x, y+1, z+1; (iii) x+1, y+1, z; (iv) x−1, y, z; (v) x+1, y, z; (vi) x−1, y−1, z; (vii) x, y−1, z.

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