Thermal-induced transformation of glutamic acid to pyroglutamic acid is well known. However, confusion remains over the exact temperature at which this happens. Moreover, no diffraction data are available to support the transition. In this article, we make a systematic investigation involving thermal analysis, hot-stage microscopy and single-crystal X-ray diffraction to study a one-pot thermal transition of glutamic acid to pyroglutamic acid and subsequent self-cocrystallization between the product (hydrated pyroglutamic acid) and the unreacted precursor (glutamic acid). The melt upon cooling gave a robust cocrystal, namely, glutamic acid–pyroglutamic acid–water (1/1/1), C5H7NO3·C5H9NO4·H2O, whose structure has been elucidated from single-crystal X-ray diffraction data collected at room temperature. A three-dimensional network of strong hydrogen bonds has been found. A Hirshfeld surface analysis was carried out to make a quantitative estimation of the intermolecular interactions. In order to gain insight into the strength and stability of the cocrystal, the transferability principle was utilized to make a topological analysis and to study the electron-density-derived properties. The transferred model has been found to be superior to the classical independent atom model (IAM). The experimental results have been compared with results from a multipolar refinement carried out using theoretical structure factors generated from density functional theory (DFT) calculations. Very strong classical hydrogen bonds drive the cocrystallization and lend stability to the resulting cocrystal. Important conclusions have been drawn about this transition.
Supporting information
CCDC references: 2097833; 2097831
Cell refinement: SAINT (Bruker, 2016) for IAM_SHELX. Data reduction: SAINT (Bruker, 2016) for IAM_SHELX. Program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015) for IAM_SHELX. Program(s) used to refine structure: olex2.refine (Bourhis et al., 2015) for IAM_SHELX; MoPro (Jelsch et al., 2005) for ELMAM2_MoPro. Molecular graphics: OLEX2 (Dolomanov et al., 2009) for IAM_SHELX. Software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) for IAM_SHELX.
2-Aminopentanedioic acid–5-oxopyrrolidine-2-carboxylic acid–water (1/1/1) (IAM_SHELX)
top
Crystal data top
C5H7NO3·C5H9NO4·H2O | F(000) = 312.231 |
Mr = 294.26 | Dx = 1.450 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.1153 (3) Å | Cell parameters from 3695 reflections |
b = 7.1849 (4) Å | θ = 3.1–25.3° |
c = 18.4639 (9) Å | µ = 0.13 mm−1 |
β = 96.817 (2)° | T = 298 K |
V = 673.80 (6) Å3 | Plate-like, colourless |
Z = 2 | 0.5 × 0.29 × 0.07 mm |
Data collection top
Bruker D8 Venture diffractometer | 1905 reflections with I ≥ 2u(I) |
φ and ω scans | Rint = 0.055 |
Absorption correction: multi-scan (SADABS; Bruker, 2016; Krause et al., 2015) | θmax = 25.3°, θmin = 2.2° |
Tmin = 0.487, Tmax = 0.745 | h = −6→6 |
7139 measured reflections | k = −8→8 |
2442 independent reflections | l = −22→22 |
Refinement top
Refinement on F2 | 23 constraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.0331P)2 + 0.2123P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.116 | (Δ/σ)max = 0.0003 |
S = 1.12 | Δρmax = 0.27 e Å−3 |
2442 reflections | Δρmin = −0.27 e Å−3 |
199 parameters | Absolute structure: Flack (1983) |
1 restraint | Absolute structure parameter: 0.0 (19) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O2 | −0.1942 (5) | −0.6634 (4) | −0.70646 (12) | 0.0468 (7) | |
O3 | −0.5490 (5) | −0.5139 (4) | −0.67679 (12) | 0.0454 (7) | |
O4 | −0.3070 (4) | −0.4779 (4) | −0.54825 (10) | 0.0379 (6) | |
O5 | −0.6743 (4) | −0.5020 (3) | −0.49491 (11) | 0.0343 (6) | |
O6 | −0.3416 (5) | −0.4878 (4) | −0.25593 (12) | 0.0482 (7) | |
O7 | 0.0386 (5) | −0.5644 (4) | −0.19112 (12) | 0.0506 (8) | |
O8 | −0.1419 (9) | −0.4677 (7) | −0.07159 (18) | 0.0867 (12) | |
N1 | −0.4011 (8) | −0.7027 (5) | −0.84719 (15) | 0.0520 (10) | |
N2 | −0.0595 (5) | −0.2985 (4) | −0.42950 (13) | 0.0265 (6) | |
H2a | 0.018 (3) | −0.264 (2) | −0.38588 (13) | 0.0397 (9)* | |
H2b | 0.058 (2) | −0.3540 (9) | −0.4541 (9) | 0.0397 (9)* | |
H2c | −0.1242 (7) | −0.1988 (13) | −0.4541 (10) | 0.0397 (9)* | |
O1 | −0.2102 (7) | −0.6781 (4) | −0.95192 (14) | 0.0793 (11) | |
C1 | −0.3373 (9) | −0.6116 (6) | −0.9046 (2) | 0.0511 (11) | |
C2 | −0.4415 (13) | −0.4213 (7) | −0.9039 (3) | 0.0831 (18) | |
H2d | −0.3007 (13) | −0.3313 (7) | −0.9051 (3) | 0.100 (2)* | |
H2e | −0.5711 (13) | −0.4007 (7) | −0.9459 (3) | 0.100 (2)* | |
C3 | −0.5660 (10) | −0.4021 (6) | −0.8346 (2) | 0.0565 (12) | |
H3a | −0.4714 (10) | −0.3116 (6) | −0.8025 (2) | 0.0678 (14)* | |
H3b | −0.7479 (10) | −0.3625 (6) | −0.8450 (2) | 0.0678 (14)* | |
C4 | −0.5501 (7) | −0.5953 (5) | −0.79956 (16) | 0.0378 (9) | |
H4 | −0.7272 (7) | −0.6477 (5) | −0.80005 (16) | 0.0454 (11)* | |
C5 | −0.4099 (7) | −0.5955 (5) | −0.72237 (17) | 0.0337 (8) | |
C6 | −0.4334 (6) | −0.4712 (5) | −0.49441 (16) | 0.0275 (7) | |
C7 | −0.2773 (6) | −0.4305 (4) | −0.42022 (15) | 0.0244 (7) | |
H7a | −0.3944 (6) | −0.3754 (4) | −0.38777 (15) | 0.0293 (9)* | |
C8 | −0.1729 (7) | −0.6164 (5) | −0.38876 (16) | 0.0319 (8) | |
H8a | −0.3230 (7) | −0.6946 (5) | −0.38229 (16) | 0.0383 (9)* | |
H8b | −0.0782 (7) | −0.6763 (5) | −0.42487 (16) | 0.0383 (9)* | |
C9 | 0.0067 (7) | −0.6130 (5) | −0.31693 (15) | 0.0353 (8) | |
H9a | 0.0735 (7) | −0.7378 (5) | −0.30658 (15) | 0.0423 (10)* | |
H9b | 0.1562 (7) | −0.5335 (5) | −0.32252 (15) | 0.0423 (10)* | |
C10 | −0.1211 (8) | −0.5462 (5) | −0.25318 (17) | 0.0363 (9) | |
H7 | −0.042 (7) | −0.536 (6) | −0.152 (2) | 0.0544 (13)* | |
H1 | −0.339 (7) | −0.827 (6) | −0.832 (2) | 0.0544 (13)* | |
H3 | −0.467 (7) | −0.497 (7) | −0.628 (2) | 0.0544 (13)* | |
H8c | −0.126 (12) | −0.552 (11) | −0.031 (4) | 0.15 (3)* | |
H8d | 0.010 (12) | −0.395 (8) | −0.058 (3) | 0.10 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0454 (16) | 0.0587 (18) | 0.0343 (13) | 0.0148 (14) | −0.0034 (12) | −0.0035 (13) |
O3 | 0.0459 (14) | 0.0590 (18) | 0.0302 (12) | 0.0106 (15) | 0.0004 (11) | −0.0112 (13) |
O4 | 0.0310 (12) | 0.0594 (17) | 0.0228 (10) | −0.0007 (13) | 0.0010 (9) | −0.0082 (12) |
O5 | 0.0235 (12) | 0.0396 (15) | 0.0386 (12) | −0.0029 (12) | −0.0012 (9) | −0.0086 (12) |
O6 | 0.0520 (16) | 0.0563 (18) | 0.0369 (13) | 0.0077 (16) | 0.0073 (11) | −0.0001 (14) |
O7 | 0.0560 (17) | 0.065 (2) | 0.0288 (12) | −0.0069 (15) | −0.0021 (12) | 0.0038 (14) |
O8 | 0.117 (3) | 0.102 (3) | 0.0429 (18) | −0.029 (3) | 0.0159 (18) | −0.001 (2) |
N1 | 0.099 (3) | 0.0292 (19) | 0.0283 (16) | 0.0117 (19) | 0.0090 (17) | −0.0004 (15) |
N2 | 0.0283 (14) | 0.0246 (14) | 0.0257 (13) | −0.0054 (12) | −0.0003 (11) | 0.0011 (12) |
O1 | 0.133 (3) | 0.067 (2) | 0.0440 (16) | 0.024 (2) | 0.0347 (18) | 0.0022 (17) |
C1 | 0.077 (3) | 0.041 (2) | 0.0340 (19) | 0.004 (2) | 0.002 (2) | 0.003 (2) |
C2 | 0.147 (5) | 0.049 (3) | 0.058 (3) | 0.029 (3) | 0.031 (3) | 0.015 (2) |
C3 | 0.079 (3) | 0.046 (3) | 0.042 (2) | 0.021 (2) | −0.005 (2) | 0.004 (2) |
C4 | 0.049 (2) | 0.034 (2) | 0.0290 (16) | 0.0029 (18) | −0.0023 (16) | −0.0014 (17) |
C5 | 0.040 (2) | 0.0312 (19) | 0.0291 (16) | −0.0007 (17) | 0.0005 (15) | −0.0001 (16) |
C6 | 0.0288 (17) | 0.0223 (17) | 0.0310 (16) | 0.0018 (14) | 0.0018 (13) | −0.0009 (15) |
C7 | 0.0250 (17) | 0.0257 (18) | 0.0229 (15) | −0.0044 (13) | 0.0043 (13) | −0.0027 (14) |
C8 | 0.040 (2) | 0.0250 (18) | 0.0308 (17) | −0.0018 (16) | 0.0050 (14) | 0.0009 (16) |
C9 | 0.040 (2) | 0.034 (2) | 0.0302 (16) | 0.0059 (17) | −0.0030 (15) | 0.0044 (16) |
C10 | 0.047 (2) | 0.029 (2) | 0.0324 (18) | −0.0048 (17) | 0.0032 (16) | 0.0067 (16) |
Geometric parameters (Å, º) top
O2—C5 | 1.210 (4) | O1—C1 | 1.244 (5) |
O3—C5 | 1.304 (4) | C1—C2 | 1.468 (6) |
O4—C6 | 1.249 (3) | C2—C3 | 1.502 (6) |
O5—C6 | 1.251 (3) | C3—C4 | 1.530 (5) |
O6—C10 | 1.198 (4) | C4—C5 | 1.518 (5) |
O7—C10 | 1.333 (4) | C6—C7 | 1.530 (4) |
N1—C1 | 1.320 (5) | C7—C8 | 1.527 (4) |
N1—C4 | 1.452 (5) | C8—C9 | 1.521 (4) |
N2—C7 | 1.488 (4) | C9—C10 | 1.492 (4) |
| | | |
C4—N1—C1 | 114.9 (3) | O5—C6—O4 | 126.1 (3) |
O1—C1—N1 | 125.0 (4) | C7—C6—O4 | 117.1 (3) |
C2—C1—N1 | 109.3 (4) | C7—C6—O5 | 116.7 (3) |
C2—C1—O1 | 125.8 (4) | C6—C7—N2 | 109.7 (2) |
C3—C2—C1 | 106.5 (4) | C8—C7—N2 | 111.6 (2) |
C4—C3—C2 | 105.7 (3) | C8—C7—C6 | 107.2 (2) |
C3—C4—N1 | 103.4 (3) | C9—C8—C7 | 117.7 (3) |
C5—C4—N1 | 110.2 (3) | C10—C9—C8 | 114.6 (3) |
C5—C4—C3 | 113.2 (3) | O7—C10—O6 | 123.3 (3) |
O3—C5—O2 | 125.2 (3) | C9—C10—O6 | 125.3 (3) |
C4—C5—O2 | 122.9 (3) | C9—C10—O7 | 111.4 (3) |
C4—C5—O3 | 111.9 (3) | | |
| | | |
O2—C5—C4—N1 | 5.8 (4) | O7—C10—C9—C8 | 173.7 (3) |
O2—C5—C4—C3 | −109.3 (4) | N1—C1—C2—C3 | 3.6 (4) |
O3—C5—C4—N1 | −174.5 (3) | N1—C4—C3—C2 | 4.7 (4) |
O3—C5—C4—C3 | 70.3 (3) | N2—C7—C8—C9 | 55.7 (3) |
O4—C6—C7—N2 | 35.1 (3) | O1—C1—C2—C3 | −176.8 (6) |
O4—C6—C7—C8 | −86.2 (3) | C1—C2—C3—C4 | −5.1 (5) |
O5—C6—C7—N2 | −147.6 (3) | C2—C3—C4—C5 | 123.8 (4) |
O5—C6—C7—C8 | 91.0 (3) | C6—C7—C8—C9 | 175.8 (2) |
O6—C10—C9—C8 | −4.3 (4) | C7—C8—C9—C10 | 64.9 (3) |
2-Aminopentanedioic acid–5-oxopyrrolidine-2-carboxylic acid–water (1/1/1) (ELMAM2_MoPro)
top
Crystal data top
C5H7NO3·C5H9NO4·H2O | F(000) = 312 |
Mr = 294.25 | Dx = 1.451 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.1153 (3) Å | Cell parameters from 3695 reflections |
b = 7.1849 (4) Å | θ = 2.2–26.4° |
c = 18.4639 (9) Å | µ = 0.13 mm−1 |
β = 96.817 (2)° | T = 298 K |
V = 673.80 (6) Å3 | Plate-like, colourless |
Z = 2 | 0.5 × 0.29 × 0.07 mm |
Data collection top
Bruker D8 Venture diffractometer | 2373 independent reflections |
Radiation source: fine-focus sealed tube | 1855 reflections with I > 2 σ(I) |
Helios Mirror Optics monochromator | Rint = 0.055 |
ω and phi scan | θmax = 25.3°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −6→6 |
Tmin = 0.487, Tmax = 0.745 | k = −8→8 |
7139 measured reflections | l = 0→22 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.03314P)2 + 0.21229P] where P = (Fo2 + 2Fc2 |
S = 0.85 | (Δ/σ)max < 0.001 |
2373 reflections | Δρmax = 0.24 e Å−3 |
120 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.0 (19) |
Special details top
Refinement. Refinement of F2 against reflections.
The threshold expression of F2 > 2sigma(F2) is
used for calculating R-factors(gt) 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. The diffraction data was collected on a Bruker D8 Venture with PHOTON II
Detector single crystal
X-rays diffractometer at room temperature (298K) using source of Mo K
radiations (λ = 0.71073 Å). The data was processed using the SAINT (Bruker,
2016) program and absorption correction was done
with SADABS program (Krause
et al., 2015). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O2 | −0.1949 (5) | −0.66352 (4) | −0.70660 (12) | 0.0449 (8) | |
O3 | −0.5487 (4) | −0.5144 (5) | −0.67669 (11) | 0.0427 (7) | |
O4 | −0.3069 (4) | −0.4786 (6) | −0.54831 (10) | 0.0364 (6) | |
O5 | −0.6742 (4) | −0.5025 (5) | −0.49480 (11) | 0.0326 (6) | |
O6 | −0.3418 (5) | −0.4881 (5) | −0.25599 (11) | 0.0460 (8) | |
O7 | 0.0377 (5) | −0.5645 (5) | −0.19089 (10) | 0.0477 (8) | |
O8 | −0.1412 (7) | −0.4681 (7) | −0.07136 (14) | 0.0839 (13) | |
N1 | −0.4016 (7) | −0.7037 (6) | −0.84719 (14) | 0.0494 (13) | |
N2 | −0.0593 (5) | −0.2985 (5) | −0.42953 (13) | 0.0233 (7) | |
H2a | 0.02779 | −0.25631 | −0.37858 | 0.04989 | |
H2b | 0.08057 | −0.36351 | −0.45860 | 0.04642 | |
H2c | −0.13633 | −0.18110 | −0.45736 | 0.04816 | |
O1 | −0.2104 (7) | −0.6786 (6) | −0.95178 (13) | 0.0762 (14) | |
C1 | −0.3381 (9) | −0.6124 (7) | −0.90487 (19) | 0.0475 (14) | |
C2 | −0.4439 (12) | −0.4228 (8) | −0.9039 (3) | 0.080 (2) | |
H2d | −0.28769 | −0.31874 | −0.90416 | 0.08108 | |
H2e | −0.59363 | −0.39729 | −0.95040 | 0.08615 | |
C3 | −0.5665 (9) | −0.4022 (7) | −0.8348 (2) | 0.0525 (15) | |
H3a | −0.46015 | −0.29823 | −0.79972 | 0.06485 | |
H3b | −0.77012 | −0.35761 | −0.84797 | 0.07379 | |
C4 | −0.5502 (7) | −0.5963 (6) | −0.79962 (15) | 0.0354 (11) | |
H4 | −0.74871 | −0.65370 | −0.80134 | 0.06309 | |
C5 | −0.4105 (7) | −0.5959 (6) | −0.72228 (16) | 0.0303 (10) | |
C6 | −0.4335 (6) | −0.4713 (6) | −0.49452 (15) | 0.0234 (8) | |
C7 | −0.2771 (6) | −0.4300 (6) | −0.42021 (15) | 0.0214 (8) | |
H7a | −0.40471 | −0.36785 | −0.38373 | 0.04695 | |
C8 | −0.1734 (7) | −0.6172 (6) | −0.38898 (15) | 0.0285 (10) | |
H8a | −0.34072 | −0.70475 | −0.38055 | 0.05197 | |
H8b | −0.06218 | −0.68294 | −0.42869 | 0.04922 | |
C9 | 0.0074 (6) | −0.6141 (6) | −0.31685 (16) | 0.0328 (10) | |
H9a | 0.08318 | −0.75514 | −0.30609 | 0.06088 | |
H9b | 0.17297 | −0.52254 | −0.32425 | 0.05664 | |
C10 | −0.1217 (7) | −0.5464 (6) | −0.25300 (16) | 0.0330 (11) | |
H7 | −0.05506 | −0.53002 | −0.14644 | 0.06872 | |
H1 | −0.33635 | −0.83244 | −0.83096 | 0.07025 | |
H3 | −0.46134 | −0.49295 | −0.62412 | 0.04348 | |
H8c | −0.12148 | −0.55508 | −0.02919 | 0.09454 | |
H8d | 0.01745 | −0.39122 | −0.05805 | 0.08796 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0455 (16) | 0.0563 (18) | 0.0309 (13) | 0.0140 (14) | −0.0042 (11) | −0.0056 (13) |
O3 | 0.0422 (14) | 0.0569 (18) | 0.0278 (11) | 0.0102 (14) | −0.0008 (10) | −0.0109 (13) |
O4 | 0.0285 (12) | 0.0594 (17) | 0.0206 (10) | −0.0011 (13) | 0.0010 (9) | −0.0084 (12) |
O5 | 0.0214 (12) | 0.0394 (14) | 0.0358 (11) | −0.0032 (12) | −0.0008 (9) | −0.0096 (12) |
O6 | 0.0495 (15) | 0.0554 (18) | 0.0334 (12) | 0.0109 (15) | 0.0066 (11) | −0.0002 (14) |
O7 | 0.0542 (16) | 0.062 (2) | 0.0248 (11) | −0.0085 (14) | −0.0041 (11) | 0.0060 (13) |
O8 | 0.115 (3) | 0.099 (3) | 0.0394 (14) | −0.029 (2) | 0.0157 (14) | −0.0012 (18) |
N1 | 0.095 (3) | 0.0280 (18) | 0.0262 (14) | 0.0110 (18) | 0.0092 (16) | −0.0009 (14) |
N2 | 0.0244 (14) | 0.0219 (14) | 0.0231 (12) | −0.0059 (11) | 0.0006 (11) | 0.0018 (12) |
H2a | 0.05087 | 0.05550 | 0.04111 | −0.01113 | −0.00365 | −0.00304 |
H2b | 0.03792 | 0.05235 | 0.04969 | −0.00147 | 0.00812 | −0.00037 |
H2c | 0.05304 | 0.04055 | 0.04939 | −0.00055 | −0.00012 | 0.00437 |
O1 | 0.131 (3) | 0.063 (2) | 0.0399 (14) | 0.026 (2) | 0.0335 (17) | 0.0030 (16) |
C1 | 0.074 (3) | 0.036 (2) | 0.0323 (18) | 0.007 (2) | 0.0065 (19) | 0.0039 (19) |
C2 | 0.146 (5) | 0.043 (3) | 0.056 (3) | 0.028 (3) | 0.033 (3) | 0.017 (2) |
H2d | 0.12095 | 0.06835 | 0.05501 | 0.00304 | 0.01489 | 0.00477 |
H2e | 0.13176 | 0.07920 | 0.04270 | 0.02152 | −0.00958 | 0.00158 |
C3 | 0.079 (3) | 0.040 (2) | 0.036 (2) | 0.022 (2) | −0.003 (2) | 0.0054 (19) |
H3a | 0.09291 | 0.05398 | 0.04521 | 0.00519 | −0.00192 | −0.00064 |
H3b | 0.08819 | 0.07377 | 0.05443 | 0.02321 | −0.01218 | 0.00286 |
C4 | 0.050 (2) | 0.030 (2) | 0.0232 (15) | 0.0033 (18) | −0.0058 (16) | −0.0006 (16) |
H4 | 0.07224 | 0.06272 | 0.05093 | 0.00216 | −0.00676 | −0.00713 |
C5 | 0.033 (2) | 0.0333 (19) | 0.0233 (15) | 0.0042 (16) | −0.0015 (15) | −0.0023 (16) |
C6 | 0.0216 (16) | 0.0231 (17) | 0.0251 (15) | 0.0000 (14) | 0.0014 (13) | −0.0046 (14) |
C7 | 0.0225 (16) | 0.0237 (18) | 0.0178 (14) | −0.0032 (13) | 0.0010 (12) | −0.0022 (13) |
H7a | 0.04382 | 0.05340 | 0.04476 | 0.00260 | 0.01002 | −0.00766 |
C8 | 0.039 (2) | 0.0205 (18) | 0.0258 (15) | −0.0007 (15) | 0.0020 (14) | 0.0028 (15) |
H8a | 0.05005 | 0.05407 | 0.05201 | −0.01213 | 0.00700 | 0.00516 |
H8b | 0.05035 | 0.05360 | 0.04430 | 0.00986 | 0.00809 | 0.00146 |
C9 | 0.037 (2) | 0.033 (2) | 0.0265 (15) | 0.0068 (17) | −0.0009 (14) | 0.0034 (16) |
H9a | 0.07445 | 0.05545 | 0.05063 | 0.00968 | −0.00136 | 0.00914 |
H9b | 0.04913 | 0.06761 | 0.05163 | −0.00999 | −0.00042 | 0.00391 |
C10 | 0.041 (2) | 0.032 (2) | 0.0256 (17) | −0.0015 (17) | 0.0002 (16) | 0.0059 (15) |
H7 | 0.08678 | 0.07925 | 0.03919 | −0.00823 | 0.00352 | −0.00048 |
H1 | 0.10913 | 0.05286 | 0.04978 | 0.02096 | 0.01363 | −0.00102 |
H3 | 0.04304 | 0.04725 | 0.03882 | 0.00719 | −0.00062 | −0.00379 |
H8c | 0.13941 | 0.10077 | 0.04272 | −0.01619 | 0.00776 | 0.00748 |
H8d | 0.11437 | 0.09487 | 0.05149 | −0.02124 | −0.00321 | −0.00610 |
Geometric parameters (Å, º) top
O2—C5 | 1.208 (4) | C1—C2 | 1.466 (6) |
O3—C5 | 1.301 (4) | C2—C3 | 1.493 (6) |
O3—H3 | 1.0310 | C2—H2d | 1.0948 |
O4—C6 | 1.249 (3) | C2—H2e | 1.0962 |
O5—C6 | 1.251 (3) | C3—C4 | 1.536 (5) |
O6—C10 | 1.196 (4) | C3—H3b | 1.0894 |
O7—C10 | 1.332 (4) | C3—H3a | 1.0913 |
O7—H7 | 1.0260 | C4—C5 | 1.519 (4) |
O8—H8d | 0.9880 | C4—H4 | 1.0931 |
O8—H8c | 0.9943 | C6—C7 | 1.533 (4) |
N1—C1 | 1.324 (5) | C7—C8 | 1.533 (4) |
N1—C4 | 1.451 (4) | C7—H7a | 1.0879 |
N1—H1 | 1.0161 | C8—C9 | 1.529 (4) |
N2—C7 | 1.486 (4) | C8—H8b | 1.0880 |
N2—H2a | 1.0373 | C8—H8a | 1.0881 |
N2—H2c | 1.0409 | C9—C10 | 1.499 (4) |
N2—H2b | 1.0529 | C9—H9b | 1.0940 |
O1—C1 | 1.240 (5) | C9—H9a | 1.0944 |
| | | |
C5—O3—H3 | 117.9 | C5—C4—C3 | 113.1 (3) |
C10—O7—H7 | 111.8 | C5—C4—H4 | 111.1 |
H8d—O8—H8c | 98.8 | C3—C4—H4 | 109.1 |
C1—N1—C4 | 114.8 (3) | O3—C5—O2 | 125.2 (3) |
C1—N1—H1 | 125.8 | O3—C5—C4 | 112.2 (2) |
C4—N1—H1 | 118.9 | O2—C5—C4 | 122.6 (3) |
C7—N2—H2a | 109.1 | O4—C6—O5 | 126.3 (2) |
C7—N2—H2c | 109.1 | O4—C6—C7 | 117.1 (2) |
C7—N2—H2b | 110.0 | O5—C6—C7 | 116.6 (2) |
H2a—N2—H2c | 107.9 | N2—C7—C6 | 109.8 (2) |
H2a—N2—H2b | 110.3 | N2—C7—C8 | 111.7 (2) |
H2c—N2—H2b | 110.4 | N2—C7—H7a | 108.9 |
O1—C1—N1 | 124.8 (3) | C6—C7—C8 | 106.7 (2) |
O1—C1—C2 | 126.2 (3) | C6—C7—H7a | 110.2 |
N1—C1—C2 | 108.9 (3) | C8—C7—H7a | 109.5 |
C1—C2—C3 | 107.2 (3) | C7—C8—C9 | 117.5 (2) |
C1—C2—H2d | 111.3 | C7—C8—H8b | 108.2 |
C1—C2—H2e | 111.7 | C7—C8—H8a | 108.6 |
C3—C2—H2d | 108.5 | C9—C8—H8b | 106.4 |
C3—C2—H2e | 109.1 | C9—C8—H8a | 106.8 |
H2d—C2—H2e | 108.9 | H8b—C8—H8a | 109.2 |
C4—C3—C2 | 105.3 (3) | C10—C9—C8 | 114.3 (2) |
C4—C3—H3b | 111.3 | C10—C9—H9b | 108.8 |
C4—C3—H3a | 111.8 | C10—C9—H9a | 109.7 |
C2—C3—H3b | 109.1 | C8—C9—H9b | 107.3 |
C2—C3—H3a | 110.2 | C8—C9—H9a | 108.0 |
H3b—C3—H3a | 109.1 | H9b—C9—H9a | 108.5 |
N1—C4—C5 | 110.4 (2) | O7—C10—O6 | 123.4 (3) |
N1—C4—C3 | 103.5 (3) | O7—C10—C9 | 111.3 (2) |
N1—C4—H4 | 109.5 | O6—C10—C9 | 125.3 (3) |
| | | |
O2—C5—O3—H3 | 6.84 | O1—C1—C2—H2e | 64.34 |
O2—C5—C4—N1 | 6.0 (6) | C1—N1—C4—C5 | −124.1 (6) |
O2—C5—C4—C3 | −109.4 (6) | C1—N1—C4—C3 | −2.8 (5) |
O2—C5—C4—H4 | 127.60 | C1—N1—C4—H4 | 113.39 |
O3—C5—C4—N1 | −174.5 (7) | C1—C2—C3—C4 | −5.5 (7) |
O3—C5—C4—C3 | 70.2 (7) | C1—C2—C3—H3b | −125.05 |
O3—C5—C4—H4 | −52.86 | C1—C2—C3—H3a | 115.27 |
O4—C6—C7—N2 | 35.1 (7) | C2—C1—N1—C4 | −0.7 (7) |
O4—C6—C7—C8 | −86.1 (7) | C2—C1—N1—H1 | −172.48 |
O4—C6—C7—H7a | 155.06 | C2—C3—C4—C5 | 124.4 (8) |
O5—C6—C7—N2 | −148.0 (7) | C2—C3—C4—H4 | −111.51 |
O5—C6—C7—C8 | 90.8 (7) | H2d—C2—C3—C4 | −125.80 |
O5—C6—C7—H7a | −28.01 | H2d—C2—C3—H3b | 114.63 |
O6—C10—O7—H7 | 3.40 | H2d—C2—C3—H3a | −5.05 |
O6—C10—C9—C8 | −4.2 (7) | H2e—C2—C3—C4 | 115.66 |
O6—C10—C9—H9b | 115.73 | H2e—C2—C3—H3b | −3.91 |
O6—C10—C9—H9a | −125.74 | H2e—C2—C3—H3a | −123.59 |
O7—C10—C9—C8 | 173.8 (7) | C3—C4—N1—H1 | 169.63 |
O7—C10—C9—H9b | −66.28 | H3a—C3—C4—C5 | 4.69 |
O7—C10—C9—H9a | 52.25 | H3a—C3—C4—H4 | 128.83 |
N1—C1—C2—C3 | 4.0 (6) | H3b—C3—C4—C5 | −117.58 |
N1—C1—C2—H2d | 122.48 | H3b—C3—C4—H4 | 6.55 |
N1—C1—C2—H2e | −115.47 | C4—C5—O3—H3 | −172.69 |
N1—C4—C3—C2 | 4.9 (6) | H4—C4—N1—H1 | −74.20 |
N1—C4—C3—H3b | 123.00 | C5—C4—N1—H1 | 48.37 |
N1—C4—C3—H3a | −114.73 | C6—C7—C8—C9 | 175.7 (5) |
N2—C7—C8—C9 | 55.8 (5) | C6—C7—C8—H8b | 55.30 |
N2—C7—C8—H8b | −64.68 | C6—C7—C8—H8a | −63.09 |
N2—C7—C8—H8a | 176.93 | C7—C8—C9—C10 | 64.8 (5) |
H2a—N2—C7—C6 | 171.68 | C7—C8—C9—H9b | −56.00 |
H2a—N2—C7—C8 | −70.14 | C7—C8—C9—H9a | −172.76 |
H2a—N2—C7—H7a | 50.93 | H7a—C7—C8—C9 | −64.98 |
H2b—N2—C7—C6 | −67.16 | H7a—C7—C8—H8b | 174.58 |
H2b—N2—C7—C8 | 51.02 | H7a—C7—C8—H8a | 56.20 |
H2b—N2—C7—H7a | 172.09 | H8a—C8—C9—C10 | −57.33 |
H2c—N2—C7—C6 | 54.02 | H8a—C8—C9—H9b | −178.11 |
H2c—N2—C7—C8 | 172.19 | H8a—C8—C9—H9a | 65.13 |
H2c—N2—C7—H7a | −66.74 | H8b—C8—C9—C10 | −173.83 |
O1—C1—N1—C4 | 179.5 (6) | H8b—C8—C9—H9b | 65.39 |
O1—C1—N1—H1 | 7.71 | H8b—C8—C9—H9a | −51.37 |
O1—C1—C2—C3 | −176.2 (7) | C9—C10—O7—H7 | −174.64 |
O1—C1—C2—H2d | −57.72 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8a···O3i | 1.09 | 2.56 | 3.471 (4) | 141 |
C2—H2e···O1ii | 1.10 | 2.51 | 3.491 (6) | 148 |
N2—H2c···O5iii | 1.04 | 1.78 | 2.808 (3) | 169 |
N1—H1···O7iv | 1.02 | 2.27 | 3.220 (4) | 156 |
N2—H2a···O2v | 1.04 | 1.83 | 2.859 (3) | 175 |
O8—H8d···O1v | 0.99 | 1.82 | 2.749 (5) | 156 |
C7—H7a···O6 | 1.09 | 2.50 | 3.117 (3) | 115 |
O7—H7···O8 | 1.03 | 1.57 | 2.582 (4) | 169 |
O3—H3···O4 | 1.03 | 1.53 | 2.553 (3) | 173 |
O3—H3···C6 | 1.03 | 2.38 | 3.360 (3) | 157 |
O8—H8c···O1vi | 0.99 | 1.79 | 2.734 (4) | 158 |
O8—H8c···C1vi | 0.99 | 2.70 | 3.504 (4) | 139 |
N2—H2b···O5vii | 1.05 | 1.79 | 2.836 (3) | 170 |
Symmetry codes: (i) −x−1, y−1/2, −z−1; (ii) −x−1, y+1/2, −z−2; (iii) −x−1, y+1/2, −z−1; (iv) −x, y−1/2, −z−1; (v) −x, y+1/2, −z−1; (vi) x, y, z+1; (vii) x+1, y, z. |
Hydrogen-bond geometry (Å, °) of I for the ELMAM2 model arranged on the
basis of increasing hydrogen-bond distance topD—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4 | 1.03 | 1.53 | 2.5535 | 173 |
O7—H7···O8 | 1.03 | 1.57 | 2.5825 | 169 |
N2—H2c···O5iii | 1.04 | 1.78 | 2.8087 | 169 |
O8—H8c···O1vi | 0.99 | 1.79 | 2.7346 | 158 |
N2—H2b···O5vii | 1.05 | 1.79 | 2.8369 | 170 |
N2—H2a···O2v | 1.04 | 1.82 | 2.8566 | 174 |
O8—H8d···O1v | 0.99 | 1.82 | 2.7485 | 156 |
N1—H1···O7iv | 1.02 | 2.27 | 3.2218 | 156 |
O3—H3···C6 | 1.03 | 2.39 | 3.3599 | 157 |
C7—H7a···O6 | 1.09 | 2.50 | 3.1153 | 115 |
C2—H2e···O1ii | 1.10 | 2.51 | 3.4914 | 148 |
C8—H8a···O3i | 1.09 | 2.56 | 3.4705 | 141 |
O8—H8c···C1vi | 0.99 | 2.70 | 3.5045 | 139 |
Symmetry codes: (i) -x-1, y-1/2, -z-1;
(ii) -x-1, y+1/2, -z-2;
(iii) -x-1, y+1/2, -z-1;
(iv) -x, y-1/2, -z-1;
(v) -x, y+1/2, -z-1;
(vi) x, y, z+1;
(vii) x+1, y, z. |
Topological properties of (3,-1) CPs in the intermolecular interactions of
cocrystal (I), ELMAM2 values (upper) and theoretical values (below): distances
(Å), electron density (e Å-3), Laplacian (e Å-5), GCP = bond
kinetic-energy density (kJ mol-1 Bohr-3) and VCP = bond potential-energy
density (kJ mol-1 Bohr-3) topNo | Bonds | d12 | d1CP | d2BCP | ρBCP(r) | Nabla2ρBCP(r) | GCP | VCP |
1 | O3—H3···O4 | 1.527 | 1.059 | 0.468 | 0.480 | 1.533 | 119.9 | -198.1 |
1.527 | 1.041 | 0.486 | 0.555 | 0.51 | 126.4 | -239.0 | | |
2 | O7—H7···O8 | 1.569 | 1.076 | 0.493 | 0.435 | 1.571 | 106.7 | -170.7 |
1.566 | 1.063 | 0.504 | 0.485 | 0.916 | 110.2 | -195.5 | | |
3 | O8—H8c···O1vi | 1.787 | 0.643 | 1.148 | 0.287 | 1.558 | 67.45 | -92.47 |
1.789 | 0.603 | 1.186 | 0.266 | 1.974 | 70.21 | -86.65 | | |
4 | O8—H8d···O1v | 1.815 | 0.662 | 1.158 | 0.268 | 1.551 | 63.1 | -83.97 |
1.814 | 0.620 | 1.196 | 0.242 | 2.16 | 68.68 | -78.52 | | |
5 | N2—H2c···O5iii | 1.780 | 0.624 | 1.156 | 0.266 | 2.042 | 71.48 | -87.33 |
1.779 | 0.631 | 1.148 | 0.292 | 1.444 | 66.5 | -93.67 | | |
6 | N2—H2b···O5vii | 1.794 | 0.633 | 1.161 | 0.255 | 1.956 | 67.49 | -81.71 |
1.795 | 0.640 | 1.156 | 0.270 | 1.804 | 68.15 | -87.15 | | |
7 | N2—H2a···O2v | 1.822 | 0.647 | 1.176 | 0.243 | 1.836 | 62.97 | -75.95 |
1.822 | 0.656 | 1.167 | 0.268 | 1.323 | 58.84 | -81.64 | | |
8 | N1—H1···O7iv | 2.267 | 0.909 | 1.363 | 0.092 | 0.86 | 21.49 | -19.56 |
2.266 | 0.873 | 1.394 | 0.072 | 1.062 | 23.16 | -17.4 | | |
9 | C2—H2e···O1ii | 2.512 | 1.049 | 1.465 | 0.052 | 0.689 | 14.76 | -10.76 |
2.509 | 1.032 | 1.480 | 0.047 | 0.655 | 13.84 | -9.84 | | |
10 | C8—H8a···O3i | 2.556 | 1.067 | 1.497 | 0.048 | 0.679 | 14.29 | -10.08 |
2.555 | 1.057 | 1.501 | 0.045 | 0.678 | 14.13 | -9.78 | | |
Symmetry codes:
(i) -x-1, y-1/2, -z-1;
(ii) -x-1, y+1/2, -z-2;
(iii) -x-1, y+1/2, -z-1;
(iv) -x, y-1/2, -z-1;
(v) -x, y+1/2, -z-1;
(vi) x, y, z+1;
(vii) x+1, y, z. |