Molecular salts and cocrystals of amino acids have potential applications as molecular materials with nonlinear optical, ferroelectric, piezoelectric, and other various target physical properties. The wide choice of amino acids and coformers makes it possible to design various crystal structures. The amino acid–maleic acid system provides a perfect example of a rich variety of crystal structures with different stoichiometries, symmetries and packing motifs built from the molecular building blocks, which are either exactly the same, or differ merely by protonation or as optical isomers. The present paper reports the crystal structures of two new salts of the DL-norvaline–maleic acid system with 1:1 and 2:1 stoichiometries, namely DL-norvalinium hydrogen maleate, C5H12NO2+·C4H3O4−, (I), and DL-norvalinium hydrogen maleate–DL-norvaline, C5H12NO2+·C4H3O4−·C5H11NO2, (II). These are the first examples of molecular salts of DL-norvaline with an organic anion. The crystal structure of (I) has the same C22(12) structure-forming motif which is common for hydrogen maleates of amino acids. The structure of (II) has dimeric cations. Of special interest is that the single crystals of (I) which are originally formed on crystallization from aqueous solution transform into single crystals of (II) if stored in the mother liquor for several hours.
Supporting information
CCDC references: 1517422; 1519878
Data collection: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. Cell refinement: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. Data reduction: CrysAlis PRO (Agilent, 2014) for (I); CrysAlis PRO (Rigaku OD, 2015) for 2dl_nv_mal. For both compounds, program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b). Molecular graphics: OLEX2 (Dolomanov et al., 2009) for (I); Mercury (Macrae et al., 2008) for 2dl_nv_mal. For both compounds, software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
(I)
DL-Norvalinium hydrogen maleate
top
Crystal data top
C5H12NO2+·C4H3O4− | F(000) = 992 |
Mr = 233.22 | Dx = 1.247 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 19.6385 (15) Å | Cell parameters from 3032 reflections |
b = 5.62705 (18) Å | θ = 1.8–25.1° |
c = 23.6867 (10) Å | µ = 0.11 mm−1 |
β = 108.283 (6)° | T = 293 K |
V = 2485.4 (2) Å3 | Block, clear light colourless |
Z = 8 | 0.25 × 0.15 × 0.1 mm |
Data collection top
Agilent Xcalibur Ruby Gemini ultra diffractometer | 2198 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 1807 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 10.3457 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −23→23 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −6→6 |
Tmin = 0.866, Tmax = 1.000 | l = −28→28 |
13186 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.068 | H-atom parameters constrained |
wR(F2) = 0.166 | w = 1/[σ2(Fo2) + (0.0688P)2 + 1.2674P] where P = (Fo2 + 2Fc2)/3 |
S = 1.23 | (Δ/σ)max < 0.001 |
2198 reflections | Δρmax = 0.25 e Å−3 |
169 parameters | Δρmin = −0.15 e Å−3 |
12 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O2 | 0.30316 (12) | 0.1684 (3) | 0.75497 (7) | 0.0587 (6) | |
O4 | 0.33415 (13) | 0.3088 (3) | 0.45870 (8) | 0.0634 (6) | |
O6 | 0.34166 (13) | 0.3563 (3) | 0.56205 (8) | 0.0653 (6) | |
H6 | 0.3388 | 0.3428 | 0.5269 | 0.098* | |
O5 | 0.33741 (12) | 0.1258 (4) | 0.63532 (8) | 0.0640 (6) | |
O3 | 0.32140 (14) | 0.0195 (3) | 0.39432 (8) | 0.0733 (7) | |
O1 | 0.35365 (15) | 0.4538 (4) | 0.71650 (9) | 0.0797 (8) | |
H1 | 0.3461 | 0.3614 | 0.6884 | 0.120* | |
N1 | 0.29849 (14) | 0.4474 (4) | 0.84537 (9) | 0.0530 (6) | |
H1A | 0.2541 | 0.4754 | 0.8218 | 0.064* | |
H1B | 0.3073 | 0.5355 | 0.8781 | 0.064* | |
H1C | 0.3030 | 0.2943 | 0.8553 | 0.064* | |
C9 | 0.33889 (16) | 0.1511 (4) | 0.58407 (10) | 0.0472 (7) | |
C1 | 0.33256 (16) | 0.3576 (5) | 0.75847 (11) | 0.0493 (7) | |
C6 | 0.32998 (17) | 0.0889 (5) | 0.44513 (11) | 0.0517 (7) | |
C2 | 0.35023 (16) | 0.5090 (5) | 0.81368 (11) | 0.0513 (7) | |
H2 | 0.3446 | 0.6770 | 0.8022 | 0.062* | |
C8 | 0.33796 (19) | −0.0648 (5) | 0.54893 (11) | 0.0602 (9) | |
H8 | 0.3401 | −0.2063 | 0.5697 | 0.072* | |
C7 | 0.33452 (19) | −0.0911 (5) | 0.49233 (12) | 0.0637 (9) | |
H7 | 0.3350 | −0.2480 | 0.4802 | 0.076* | |
C3 | 0.4257 (2) | 0.4676 (7) | 0.85504 (15) | 0.0804 (11) | |
H3AA | 0.4303 | 0.5434 | 0.8928 | 0.097* | 0.865 (8) |
H3AB | 0.4325 | 0.2983 | 0.8623 | 0.097* | 0.865 (8) |
H3BC | 0.4217 | 0.3299 | 0.8784 | 0.097* | 0.135 (8) |
H3BD | 0.4525 | 0.4145 | 0.8292 | 0.097* | 0.135 (8) |
C4A | 0.4845 (3) | 0.5576 (11) | 0.8329 (2) | 0.1011 (19) | 0.865 (8) |
H4AA | 0.5301 | 0.5092 | 0.8608 | 0.121* | 0.865 (8) |
H4AB | 0.4800 | 0.4808 | 0.7952 | 0.121* | 0.865 (8) |
C4B | 0.473 (2) | 0.624 (7) | 0.8964 (16) | 0.114 (9) | 0.135 (8) |
H4BA | 0.4527 | 0.6638 | 0.9274 | 0.136* | 0.135 (8) |
H4BB | 0.5181 | 0.5409 | 0.9150 | 0.136* | 0.135 (8) |
C5A | 0.4863 (4) | 0.8168 (15) | 0.8244 (5) | 0.143 (3) | 0.865 (8) |
H5AA | 0.4440 | 0.8653 | 0.7934 | 0.214* | 0.865 (8) |
H5AB | 0.5280 | 0.8578 | 0.8135 | 0.214* | 0.865 (8) |
H5AC | 0.4881 | 0.8961 | 0.8607 | 0.214* | 0.865 (8) |
C5B | 0.488 (4) | 0.829 (11) | 0.872 (3) | 0.166 (18) | 0.135 (8) |
H5BA | 0.4471 | 0.8746 | 0.8392 | 0.249* | 0.135 (8) |
H5BB | 0.5285 | 0.8054 | 0.8581 | 0.249* | 0.135 (8) |
H5BC | 0.4988 | 0.9530 | 0.9014 | 0.249* | 0.135 (8) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0956 (16) | 0.0514 (12) | 0.0351 (10) | −0.0135 (11) | 0.0289 (9) | −0.0092 (8) |
O4 | 0.1220 (19) | 0.0344 (10) | 0.0397 (10) | −0.0056 (10) | 0.0336 (10) | 0.0026 (7) |
O6 | 0.1231 (19) | 0.0385 (11) | 0.0417 (11) | −0.0051 (11) | 0.0364 (12) | −0.0074 (8) |
O5 | 0.1054 (17) | 0.0600 (12) | 0.0355 (10) | 0.0015 (11) | 0.0350 (10) | −0.0014 (8) |
O3 | 0.139 (2) | 0.0517 (12) | 0.0381 (11) | −0.0037 (12) | 0.0405 (12) | −0.0057 (8) |
O1 | 0.129 (2) | 0.0787 (16) | 0.0470 (12) | −0.0372 (14) | 0.0501 (13) | −0.0171 (10) |
N1 | 0.0863 (18) | 0.0445 (13) | 0.0319 (11) | 0.0082 (11) | 0.0240 (11) | −0.0036 (9) |
C9 | 0.0698 (19) | 0.0395 (14) | 0.0354 (14) | 0.0031 (12) | 0.0208 (12) | 0.0009 (10) |
C1 | 0.0698 (19) | 0.0502 (17) | 0.0322 (13) | −0.0032 (14) | 0.0221 (12) | −0.0026 (11) |
C6 | 0.087 (2) | 0.0372 (14) | 0.0364 (14) | −0.0011 (13) | 0.0279 (13) | −0.0007 (11) |
C2 | 0.072 (2) | 0.0471 (15) | 0.0380 (14) | −0.0066 (13) | 0.0210 (13) | −0.0077 (11) |
C8 | 0.111 (3) | 0.0333 (14) | 0.0418 (15) | 0.0039 (15) | 0.0321 (15) | 0.0065 (11) |
C7 | 0.124 (3) | 0.0296 (13) | 0.0429 (15) | 0.0042 (15) | 0.0347 (16) | −0.0041 (11) |
C3 | 0.082 (3) | 0.088 (3) | 0.065 (2) | 0.002 (2) | 0.0144 (19) | −0.0186 (18) |
C4A | 0.072 (3) | 0.129 (5) | 0.096 (3) | −0.002 (3) | 0.019 (3) | −0.028 (3) |
C4B | 0.114 (16) | 0.106 (16) | 0.104 (16) | −0.005 (15) | 0.012 (14) | −0.044 (14) |
C5A | 0.112 (5) | 0.122 (6) | 0.195 (9) | −0.031 (4) | 0.050 (6) | −0.010 (6) |
C5B | 0.15 (3) | 0.15 (3) | 0.17 (3) | −0.03 (3) | 0.01 (3) | −0.05 (3) |
Geometric parameters (Å, º) top
O2—C1 | 1.202 (3) | C7—H7 | 0.9300 |
O4—C6 | 1.274 (3) | C3—H3AA | 0.9700 |
O6—H6 | 0.8200 | C3—H3AB | 0.9700 |
O6—C9 | 1.275 (3) | C3—H3BC | 0.9700 |
O5—C9 | 1.231 (3) | C3—H3BD | 0.9700 |
O3—C6 | 1.226 (3) | C3—C4A | 1.498 (6) |
O1—H1 | 0.8200 | C3—C4B | 1.43 (3) |
O1—C1 | 1.308 (3) | C4A—H4AA | 0.9700 |
N1—H1A | 0.8900 | C4A—H4AB | 0.9700 |
N1—H1B | 0.8900 | C4A—C5A | 1.474 (9) |
N1—H1C | 0.8900 | C4B—H4BA | 0.9700 |
N1—C2 | 1.482 (4) | C4B—H4BB | 0.9700 |
C9—C8 | 1.469 (4) | C4B—C5B | 1.36 (7) |
C1—C2 | 1.507 (4) | C5A—H5AA | 0.9600 |
C6—C7 | 1.490 (4) | C5A—H5AB | 0.9600 |
C2—H2 | 0.9800 | C5A—H5AC | 0.9600 |
C2—C3 | 1.517 (5) | C5B—H5BA | 0.9600 |
C8—H8 | 0.9300 | C5B—H5BB | 0.9600 |
C8—C7 | 1.329 (4) | C5B—H5BC | 0.9600 |
| | | |
C9—O6—H6 | 109.5 | H3AA—C3—H3AB | 107.5 |
C1—O1—H1 | 109.5 | H3BC—C3—H3BD | 105.7 |
H1A—N1—H1B | 109.5 | C4A—C3—C2 | 115.2 (3) |
H1A—N1—H1C | 109.5 | C4A—C3—H3AA | 108.5 |
H1B—N1—H1C | 109.5 | C4A—C3—H3AB | 108.5 |
C2—N1—H1A | 109.5 | C4B—C3—C2 | 130.3 (16) |
C2—N1—H1B | 109.5 | C4B—C3—H3BC | 104.7 |
C2—N1—H1C | 109.5 | C4B—C3—H3BD | 104.7 |
O6—C9—C8 | 120.8 (2) | C3—C4A—H4AA | 108.3 |
O5—C9—O6 | 121.7 (2) | C3—C4A—H4AB | 108.3 |
O5—C9—C8 | 117.6 (2) | H4AA—C4A—H4AB | 107.4 |
O2—C1—O1 | 125.0 (2) | C5A—C4A—C3 | 115.9 (5) |
O2—C1—C2 | 122.4 (2) | C5A—C4A—H4AA | 108.3 |
O1—C1—C2 | 112.6 (2) | C5A—C4A—H4AB | 108.3 |
O4—C6—C7 | 119.1 (2) | C3—C4B—H4BA | 108.7 |
O3—C6—O4 | 122.4 (2) | C3—C4B—H4BB | 108.7 |
O3—C6—C7 | 118.5 (2) | H4BA—C4B—H4BB | 107.6 |
N1—C2—C1 | 107.4 (2) | C5B—C4B—C3 | 114 (3) |
N1—C2—H2 | 109.3 | C5B—C4B—H4BA | 108.7 |
N1—C2—C3 | 108.9 (2) | C5B—C4B—H4BB | 108.7 |
C1—C2—H2 | 109.3 | C4A—C5A—H5AA | 109.5 |
C1—C2—C3 | 112.7 (3) | C4A—C5A—H5AB | 109.5 |
C3—C2—H2 | 109.3 | C4A—C5A—H5AC | 109.5 |
C9—C8—H8 | 114.7 | H5AA—C5A—H5AB | 109.5 |
C7—C8—C9 | 130.6 (2) | H5AA—C5A—H5AC | 109.5 |
C7—C8—H8 | 114.7 | H5AB—C5A—H5AC | 109.5 |
C6—C7—H7 | 114.6 | C4B—C5B—H5BA | 109.5 |
C8—C7—C6 | 130.8 (2) | C4B—C5B—H5BB | 109.5 |
C8—C7—H7 | 114.6 | C4B—C5B—H5BC | 109.5 |
C2—C3—H3AA | 108.5 | H5BA—C5B—H5BB | 109.5 |
C2—C3—H3AB | 108.5 | H5BA—C5B—H5BC | 109.5 |
C2—C3—H3BC | 104.7 | H5BB—C5B—H5BC | 109.5 |
C2—C3—H3BD | 104.7 | | |
| | | |
O2—C1—C2—N1 | −26.0 (4) | N1—C2—C3—C4A | −170.8 (3) |
O2—C1—C2—C3 | 93.9 (4) | N1—C2—C3—C4B | −90 (2) |
O4—C6—C7—C8 | 5.0 (6) | C9—C8—C7—C6 | −0.4 (7) |
O6—C9—C8—C7 | −5.4 (6) | C1—C2—C3—C4A | 70.1 (4) |
O5—C9—C8—C7 | 175.1 (4) | C1—C2—C3—C4B | 151 (2) |
O3—C6—C7—C8 | −174.1 (4) | C2—C3—C4A—C5A | 63.3 (7) |
O1—C1—C2—N1 | 154.9 (3) | C2—C3—C4B—C5B | −57 (5) |
O1—C1—C2—C3 | −85.1 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O4 | 0.82 | 1.60 | 2.421 (2) | 178 |
O1—H1···O5 | 0.82 | 1.80 | 2.612 (3) | 171 |
N1—H1A···O2i | 0.89 | 2.11 | 2.864 (3) | 142 |
N1—H1B···O4ii | 0.89 | 2.01 | 2.898 (3) | 172 |
N1—H1C···O3iii | 0.89 | 1.97 | 2.850 (3) | 168 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x, −y+1, z+1/2; (iii) x, −y, z+1/2. |
(2dl_nv_mal)
DL-Norvalinium hydrogen maleate–
DL-norvaline (1/1)
top
Crystal data top
C5H12NO2+·C4H3O4−·C5H11NO2 | Dx = 1.226 Mg m−3 |
Mr = 350.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 6447 reflections |
a = 8.8572 (4) Å | θ = 2.3–27.7° |
b = 27.3614 (11) Å | µ = 0.10 mm−1 |
c = 7.8306 (4) Å | T = 293 K |
V = 1897.71 (15) Å3 | Block, clear light colourless |
Z = 4 | 0.5 × 0.25 × 0.2 mm |
F(000) = 752 | |
Data collection top
Agilent Xcalibur Ruby Gemini ultra diffractometer | 1975 independent reflections |
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source | 1731 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 10.3457 pixels mm-1 | θmax = 26.4°, θmin = 3.0° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −34→34 |
Tmin = 0.948, Tmax = 1.000 | l = −9→9 |
21923 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.146 | w = 1/[σ2(Fo2) + 2.5627P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max < 0.001 |
1975 reflections | Δρmax = 0.15 e Å−3 |
216 parameters | Δρmin = −0.20 e Å−3 |
298 restraints | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.3996 (7) | 0.5283 (3) | 0.4353 (8) | 0.0588 (14) | 0.733 (5) |
O2 | 0.2253 (12) | 0.4842 (4) | 0.5382 (11) | 0.0673 (19) | 0.733 (5) |
N1 | 0.1895 (3) | 0.58452 (10) | 0.2864 (4) | 0.0436 (9) | 0.733 (5) |
H1A | 0.209236 | 0.566396 | 0.194754 | 0.052* | 0.733 (5) |
H1B | 0.271973 | 0.601006 | 0.316357 | 0.052* | 0.733 (5) |
H1C | 0.115546 | 0.605455 | 0.262507 | 0.052* | 0.733 (5) |
C1 | 0.2668 (10) | 0.5162 (3) | 0.486 (2) | 0.053 (2) | 0.733 (5) |
C6 | 0.4597 (4) | 0.69058 (10) | 0.2591 (5) | 0.0667 (9) | |
C3 | 0.0925 (9) | 0.5831 (2) | 0.5848 (10) | 0.0563 (15) | 0.733 (5) |
H3A | 0.015017 | 0.605821 | 0.547903 | 0.068* | 0.733 (5) |
H3B | 0.047697 | 0.561615 | 0.669252 | 0.068* | 0.733 (5) |
C2 | 0.1420 (5) | 0.55218 (16) | 0.4302 (6) | 0.0450 (10) | 0.733 (5) |
H2 | 0.054865 | 0.533011 | 0.392004 | 0.054* | 0.733 (5) |
O4 | 0.4852 (12) | 0.70580 (16) | 0.1052 (7) | 0.082 (3) | 0.532 (13) |
C4 | 0.2156 (11) | 0.6112 (4) | 0.6672 (11) | 0.078 (2) | 0.733 (5) |
H4A | 0.258051 | 0.633807 | 0.584784 | 0.093* | 0.733 (5) |
H4B | 0.295023 | 0.588785 | 0.701321 | 0.093* | 0.733 (5) |
C7 | 0.4209 (11) | 0.7257 (3) | 0.3969 (11) | 0.055 (2) | 0.532 (13) |
H7 | 0.391943 | 0.711475 | 0.499571 | 0.066* | 0.532 (13) |
O4B | 0.5932 (11) | 0.70603 (18) | 0.1975 (19) | 0.112 (5) | 0.468 (13) |
N1B | 0.0750 (11) | 0.5607 (3) | 0.3297 (13) | 0.054 (3) | 0.267 (5) |
H1BA | 0.116614 | 0.543114 | 0.246574 | 0.065* | 0.267 (5) |
H1BB | 0.034246 | 0.587671 | 0.285670 | 0.065* | 0.267 (5) |
H1BC | 0.003694 | 0.543223 | 0.381236 | 0.065* | 0.267 (5) |
O1B | 0.425 (2) | 0.5365 (8) | 0.503 (2) | 0.067 (5) | 0.267 (5) |
O2B | 0.229 (4) | 0.4803 (10) | 0.593 (3) | 0.066 (5) | 0.267 (5) |
C2B | 0.1906 (15) | 0.5742 (4) | 0.4535 (19) | 0.054 (3) | 0.267 (5) |
H2B | 0.259337 | 0.597557 | 0.399015 | 0.064* | 0.267 (5) |
C7B | 0.3551 (12) | 0.7257 (3) | 0.3272 (18) | 0.068 (3) | 0.468 (13) |
H7B | 0.271968 | 0.711838 | 0.381295 | 0.082* | 0.468 (13) |
C1B | 0.271 (3) | 0.5271 (8) | 0.473 (7) | 0.049 (4) | 0.267 (5) |
C3B | 0.117 (4) | 0.5995 (9) | 0.605 (4) | 0.086 (6) | 0.267 (5) |
H3BA | 0.052294 | 0.625599 | 0.563819 | 0.103* | 0.267 (5) |
H3BB | 0.053207 | 0.576156 | 0.664850 | 0.103* | 0.267 (5) |
C4B | 0.223 (4) | 0.6193 (12) | 0.723 (4) | 0.107 (7) | 0.267 (5) |
H4BA | 0.240324 | 0.596531 | 0.815453 | 0.129* | 0.267 (5) |
H4BB | 0.318602 | 0.625157 | 0.665381 | 0.129* | 0.267 (5) |
O3 | 0.453 (5) | 0.6486 (10) | 0.284 (6) | 0.073 (7) | 0.532 (13) |
O3B | 0.440 (5) | 0.6447 (12) | 0.290 (6) | 0.063 (5) | 0.468 (13) |
C5 | 0.1602 (13) | 0.6408 (3) | 0.8296 (14) | 0.096 (3) | 0.733 (5) |
H5A | 0.089387 | 0.665441 | 0.794706 | 0.145* | 0.733 (5) |
H5B | 0.245280 | 0.656078 | 0.883680 | 0.145* | 0.733 (5) |
H5C | 0.112409 | 0.618901 | 0.908534 | 0.145* | 0.733 (5) |
C5B | 0.170 (5) | 0.6600 (9) | 0.782 (5) | 0.129 (11) | 0.267 (5) |
H5BA | 0.103300 | 0.674308 | 0.698621 | 0.193* | 0.267 (5) |
H5BB | 0.251346 | 0.682068 | 0.804935 | 0.193* | 0.267 (5) |
H5BC | 0.114773 | 0.653731 | 0.885012 | 0.193* | 0.267 (5) |
H1 | 0.500000 | 0.500000 | 0.500000 | 0.193* | |
H4 | 0.483 (9) | 0.750000 | 0.115 (11) | 0.193* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.044 (3) | 0.052 (3) | 0.080 (4) | 0.016 (2) | 0.004 (2) | 0.021 (3) |
O2 | 0.058 (2) | 0.061 (4) | 0.083 (6) | 0.005 (2) | 0.002 (4) | 0.030 (4) |
N1 | 0.0397 (17) | 0.0352 (15) | 0.056 (2) | 0.0090 (13) | −0.0013 (15) | 0.0050 (14) |
C1 | 0.045 (3) | 0.051 (4) | 0.061 (5) | 0.023 (3) | 0.001 (3) | 0.019 (5) |
C6 | 0.064 (2) | 0.0354 (15) | 0.101 (3) | 0.0003 (13) | 0.0253 (19) | −0.0043 (17) |
C3 | 0.048 (3) | 0.052 (3) | 0.069 (4) | 0.018 (2) | 0.009 (3) | 0.006 (3) |
C2 | 0.040 (2) | 0.034 (2) | 0.061 (3) | 0.0051 (18) | 0.001 (2) | 0.008 (2) |
O4 | 0.115 (7) | 0.047 (2) | 0.084 (3) | 0.000 (3) | 0.028 (4) | −0.011 (2) |
C4 | 0.072 (4) | 0.080 (4) | 0.081 (5) | 0.010 (3) | 0.014 (4) | −0.023 (4) |
C7 | 0.066 (5) | 0.035 (3) | 0.065 (4) | −0.001 (3) | 0.007 (4) | 0.003 (3) |
O4B | 0.070 (5) | 0.043 (3) | 0.223 (12) | 0.004 (3) | 0.081 (7) | 0.000 (4) |
N1B | 0.050 (6) | 0.041 (5) | 0.070 (6) | 0.009 (4) | −0.002 (5) | 0.010 (4) |
O1B | 0.044 (6) | 0.057 (7) | 0.101 (14) | 0.013 (5) | 0.003 (7) | 0.017 (9) |
O2B | 0.074 (7) | 0.059 (6) | 0.064 (11) | 0.029 (5) | 0.017 (8) | 0.050 (7) |
C2B | 0.050 (6) | 0.029 (5) | 0.083 (8) | 0.012 (5) | −0.006 (6) | 0.008 (5) |
C7B | 0.048 (5) | 0.038 (3) | 0.119 (9) | 0.000 (4) | 0.027 (5) | −0.002 (5) |
C1B | 0.053 (7) | 0.035 (8) | 0.059 (10) | 0.006 (6) | 0.014 (6) | 0.026 (7) |
C3B | 0.084 (13) | 0.090 (14) | 0.083 (10) | 0.037 (11) | −0.002 (9) | −0.005 (9) |
C4B | 0.127 (15) | 0.103 (14) | 0.092 (15) | 0.041 (12) | −0.025 (13) | −0.013 (10) |
O3 | 0.071 (14) | 0.023 (4) | 0.124 (11) | 0.004 (5) | 0.026 (9) | 0.005 (5) |
O3B | 0.050 (6) | 0.032 (6) | 0.108 (12) | 0.002 (6) | 0.019 (7) | −0.007 (7) |
C5 | 0.098 (5) | 0.094 (7) | 0.097 (6) | 0.020 (5) | 0.004 (4) | −0.023 (5) |
C5B | 0.20 (3) | 0.071 (14) | 0.12 (2) | 0.029 (16) | 0.020 (18) | 0.002 (12) |
Geometric parameters (Å, º) top
O1—C1 | 1.286 (11) | N1B—H1BA | 0.8900 |
O1—H1 | 1.284 (6) | N1B—H1BB | 0.8900 |
O2—C1 | 1.034 (15) | N1B—H1BC | 0.8900 |
N1—H1A | 0.8900 | N1B—C2B | 1.457 (17) |
N1—H1B | 0.8900 | O1B—C1B | 1.41 (2) |
N1—H1C | 0.8900 | O1B—H1 | 1.20 (2) |
N1—C2 | 1.492 (6) | O2B—C1B | 1.63 (4) |
C1—C2 | 1.544 (7) | C2B—H2B | 0.9800 |
C6—O4 | 1.295 (6) | C2B—C1B | 1.481 (18) |
C6—C7 | 1.486 (8) | C2B—C3B | 1.52 (3) |
C6—O4B | 1.345 (6) | C7B—C7Bi | 1.331 (17) |
C6—C7B | 1.437 (9) | C7B—H7B | 0.9300 |
C6—O3 | 1.17 (3) | C3B—H3BA | 0.9700 |
C6—O3B | 1.29 (3) | C3B—H3BB | 0.9700 |
C3—H3A | 0.9700 | C3B—C4B | 1.42 (3) |
C3—H3B | 0.9700 | C4B—H4BA | 0.9700 |
C3—C2 | 1.541 (8) | C4B—H4BB | 0.9700 |
C3—C4 | 1.481 (10) | C4B—C5B | 1.29 (4) |
C2—H2 | 0.9800 | C5—H5A | 0.9600 |
O4—H4 | 1.212 (7) | C5—H5B | 0.9600 |
C4—H4A | 0.9700 | C5—H5C | 0.9600 |
C4—H4B | 0.9700 | C5B—H5BA | 0.9600 |
C4—C5 | 1.586 (12) | C5B—H5BB | 0.9600 |
C7—C7i | 1.327 (14) | C5B—H5BC | 0.9600 |
C7—H7 | 0.9300 | | |
| | | |
C1—O1—H1 | 110.8 (7) | C2B—N1B—H1BA | 109.5 |
H1A—N1—H1B | 109.5 | C2B—N1B—H1BB | 109.5 |
H1A—N1—H1C | 109.5 | C2B—N1B—H1BC | 109.5 |
H1B—N1—H1C | 109.5 | C1B—O1B—H1 | 112.4 (17) |
C2—N1—H1A | 109.5 | N1B—C2B—H2B | 108.1 |
C2—N1—H1B | 109.5 | N1B—C2B—C1B | 100.8 (18) |
C2—N1—H1C | 109.5 | N1B—C2B—C3B | 109.4 (15) |
O1—C1—C2 | 113.7 (8) | C1B—C2B—H2B | 108.1 |
O2—C1—O1 | 131.8 (9) | C1B—C2B—C3B | 121 (2) |
O2—C1—C2 | 113.5 (9) | C3B—C2B—H2B | 108.1 |
O4—C6—C7 | 120.5 (4) | C6—C7B—H7B | 114.0 |
O4B—C6—C7B | 119.3 (5) | C7Bi—C7B—C6 | 131.9 (4) |
O3—C6—O4 | 119 (2) | C7Bi—C7B—H7B | 114.0 |
O3—C6—C7 | 120 (2) | O1B—C1B—O2B | 106 (2) |
O3B—C6—O4B | 120 (2) | O1B—C1B—C2B | 109.0 (19) |
O3B—C6—C7B | 120 (2) | C2B—C1B—O2B | 129 (3) |
H3A—C3—H3B | 107.6 | C2B—C3B—H3BA | 109.0 |
C2—C3—H3A | 108.6 | C2B—C3B—H3BB | 109.0 |
C2—C3—H3B | 108.6 | H3BA—C3B—H3BB | 107.8 |
C4—C3—H3A | 108.6 | C4B—C3B—C2B | 113 (3) |
C4—C3—H3B | 108.6 | C4B—C3B—H3BA | 109.0 |
C4—C3—C2 | 114.7 (6) | C4B—C3B—H3BB | 109.0 |
N1—C2—C1 | 113.0 (6) | C3B—C4B—H4BA | 110.0 |
N1—C2—C3 | 110.3 (4) | C3B—C4B—H4BB | 110.0 |
N1—C2—H2 | 108.0 | H4BA—C4B—H4BB | 108.4 |
C1—C2—H2 | 108.0 | C5B—C4B—C3B | 108 (3) |
C3—C2—C1 | 109.3 (8) | C5B—C4B—H4BA | 110.0 |
C3—C2—H2 | 108.0 | C5B—C4B—H4BB | 110.0 |
C6—O4—H4 | 105 (4) | C4—C5—H5A | 109.5 |
C3—C4—H4A | 109.0 | C4—C5—H5B | 109.5 |
C3—C4—H4B | 109.0 | C4—C5—H5C | 109.5 |
C3—C4—C5 | 112.7 (8) | H5A—C5—H5B | 109.5 |
H4A—C4—H4B | 107.8 | H5A—C5—H5C | 109.5 |
C5—C4—H4A | 109.0 | H5B—C5—H5C | 109.5 |
C5—C4—H4B | 109.0 | C4B—C5B—H5BA | 109.5 |
C6—C7—H7 | 114.8 | C4B—C5B—H5BB | 109.5 |
C7i—C7—C6 | 130.4 (3) | C4B—C5B—H5BC | 109.5 |
C7i—C7—H7 | 114.8 | H5BA—C5B—H5BB | 109.5 |
H1BA—N1B—H1BB | 109.5 | H5BA—C5B—H5BC | 109.5 |
H1BA—N1B—H1BC | 109.5 | H5BB—C5B—H5BC | 109.5 |
H1BB—N1B—H1BC | 109.5 | | |
| | | |
O1—C1—C2—N1 | 17.9 (14) | N1B—C2B—C1B—O1B | 147 (3) |
O1—C1—C2—C3 | −105.4 (12) | N1B—C2B—C1B—O2B | −83 (4) |
O2—C1—C2—N1 | −151.9 (12) | N1B—C2B—C3B—C4B | −173 (2) |
O2—C1—C2—C3 | 84.9 (15) | C2B—C3B—C4B—C5B | 144 (3) |
C2—C3—C4—C5 | −177.9 (7) | C1B—C2B—C3B—C4B | 71 (3) |
O4—C6—C7—C7i | −7.7 (7) | C3B—C2B—C1B—O1B | −92 (3) |
C4—C3—C2—N1 | −67.1 (8) | C3B—C2B—C1B—O2B | 38 (4) |
C4—C3—C2—C1 | 57.7 (9) | O3—C6—C7—C7i | −180 (3) |
O4B—C6—C7B—C7Bi | 8.4 (9) | O3B—C6—C7B—C7Bi | 174 (3) |
Symmetry code: (i) x, −y+3/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2ii | 0.89 | 1.94 | 2.807 (8) | 165 |
N1—H1B···O3 | 0.89 | 2.08 | 2.92 (4) | 157 |
N1—H1C···O3iii | 0.89 | 1.90 | 2.79 (4) | 178 |
O1—H1···O1iv | 1.28 (1) | 1.28 (1) | 2.568 (13) | 180 (1) |
O4—H4···O4i | 1.21 (1) | 1.21 (1) | 2.418 (9) | 173 (8) |
Symmetry codes: (i) x, −y+3/2, z; (ii) −x+1/2, −y+1, z−1/2; (iii) x−1/2, y, −z+1/2; (iv) −x+1, −y+1, −z+1. |
Classification of hydrogen maleates according with their stoichiometry topBrutto formula | Stoichiometry class | CSD refcodes (references to original work) |
(GlyH+).M- | A+B- | RENBAN (Rajagopal, Krishnakumar, Mostad & Natarajan, 2001) |
(L-AlaH+).M- | | BOQTEG (Alagar, Krishnakumar, Nandhini & Natarajan, 2001) |
(L-PheH+).M- | | EDAXIQ (Alagar, Krishnakumar & Natarajan, 2001) |
(DL-PheH+).M- | | VAGVIJ (Alagar et al., 2003) |
(DL-ValH+).M- | | QURSUR (Alagar, Krishnakumar, Mostad & Natarajan, 2001) |
(L-SerH+).M- | | REZPET (Arkhipov et al., 2013) |
(DL-SerH+). M- | | REZPAP (Arkhipov et al., 2013) |
(DL-MetH+).M- | | MOCXUX (Alagar et al., 2002) |
(SarH+).M- | | MIYBAX01 (Ilczyszyn et al., 2003) |
(L-ValH+).M- | | NUZMIG (Rychkov et al., 2016) |
(DL-ThrH+).M- | | ETEYOR (Rajagopal et al., 2004) |
(β-AlaH+).M- | | EDASUX (Rajagopal, Krishnakumar & Natarajan, 2001) |
(BacH+).M- | | LUSXII (Báthori & Kilinkissa, 2015) |
(L-LysH+).M- | | XADTOL (Pratap et al., 2000) |
(DL-ArgH+).M- | | (Ravishankar et al., 1998) |
(BetH+).M- | | NASQED01 (Haussühl & Schreuer, 2001) |
(L-HisH22+).(M-)2 | An+nB- | TENVOZ (Fleck et al., 2013) |
L-Met.L-MetH+.M- | A2+B- | (Natarajan et al. 2010) |
L-Nva.L-NvaH+.M- | | VUKQID (Arkhipov et al., 2015) |
(L-HisH+)2.(M-)2 | nA+nB- | XADTIF (Pratap et al., 2000) |
(L-LeuH+)3.(M-)3 | | VUKQAV (Arkhipov et al., 2015) |
There are also two hydrates belonging to the A+B- class:
(L-ArgH+).M-.2H2O (CSD refcode GIHGEK; Sun
et al., 2007),
(L-HisH+).M-.H2O (CSD refcode TENVUF; Fleck et al.,
2013);
and two other hydrates related to the nA+nB- class:
(L-HisH+)2.(M-)2.3H2O (CSD refcode VAZJUD;
Gonsago et al., 2012),
(L-IleH+)2.(M-)2.H2O
(CSD refcode VUKQEZ; Arkhipov et al., 2015). |