L-Phenyl­alanine nitrate (4/1)

The asymmetric unit of the title compound, L-phenyl­alaninium nitrate tris(L-phenyl­alanine), C₉H₁₂NO₂⁺·NO₃⁻·3C₉H₁₁NO₂, contains a nitrate anion and a peculiar sequence of four L-phenyl­alanine mol­ecules. Three of them are present as zwitterions, while the last carries the positive charge and acts as donor in a –COOH...⁻OOC– hydrogen bond with an O...O distance of 2.443 (9) Å.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.113
• wR factor = 0.269
• Data-to-parameter ratio = 7.3

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



DIFMX_01  Alert C The maximum difference density is > 0.1*ZMAX*0.75
          _refine_diff_density_max given =      0.618
          Test value =      0.600

DIFMX_02  Alert C The minimum difference density is > 0.1*ZMAX*0.75
          The relevant atom site should be identified.

RFACG_01  Alert C The value of the R factor is > 0.10
          R factor given   0.113

RFACR_01  Alert C The value of the weighted R factor is > 0.25
          Weighted R factor given   0.269

PLAT_731  Alert C Bond    Calc   1.391(13), Rep    1.390(6) ....       2.17 s.u-Ratio
                     C7C  -C8C     1.555   1.555

PLAT_731  Alert C Bond    Calc   1.388(13), Rep    1.389(6) ....       2.17 s.u-Ratio
                     C5D  -C6D     1.555   1.555

PLAT_732  Alert C Angle   Calc    119.8(7), Rep    119.8(3) ....       2.33 s.u-Ratio
                     C7A  -C6A  -C5A     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.9(7), Rep    119.8(3) ....       2.33 s.u-Ratio
                     C6A  -C7A  -C8A     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.8(7), Rep    119.9(3) ....       2.33 s.u-Ratio
                     C7B  -C6B  -C5B     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.9(7), Rep    119.8(3) ....       2.33 s.u-Ratio
                     C6B  -C7B  -C8B     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.6(7), Rep    119.6(3) ....       2.33 s.u-Ratio
                     C4B  -C9B  -C8B     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    120.1(8), Rep    120.0(3) ....       2.67 s.u-Ratio
                     C7C  -C6C  -C5C     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.7(7), Rep    119.8(3) ....       2.33 s.u-Ratio
                     C6C  -C7C  -C8C     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.7(7), Rep    119.6(3) ....       2.33 s.u-Ratio
                     C4C  -C9C  -C8C     1.555   1.555   1.555

PLAT_732  Alert C Angle   Calc    119.5(8), Rep    119.6(3) ....       2.67 s.u-Ratio
                     C6D  -C7D  -C8D     1.555   1.555   1.555

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C9 H11.25 N1.25 O2.75
          Atom count from _chemical_formula_moiety:C36 H45 N5 O11

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.03
         From the CIF: _reflns_number_total               3450
         Count of symmetry unique reflns         3470
         Completeness (_total/calc)             99.42%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured         0
         Fraction of Friedel pairs measured     0.000
         Are heavy atom types Z>Si present           no
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 15 Alert Level C = Please check

---

S1. Comment

The title compound, (I), was studied as part of a search for good crystallization conditions for various peptides. Several nice-looking crystals were obtained, but the diffraction patterns revealed that the structure was probably divided into layers that were misaligned along one axis. This made the unit-cell determination difficult, and only after testing several specimens was it possible to find the third axis, collect diffraction data and integrate them successfully.

As a result of the poor crystal quality, the final R factor is high for a small molecule structure. Nevertheless, the structure proved to be interesting in having an odd sequence of four phenylalanine molecules in the asymmetric unit in addition to the nitrate anion (Fig. 1). Three of the phenylalanines (B, C and D) are in the zwitterionic form. The positive charge most likely (see below) resides with the last amino acid molecule A, which is connected to molecule B by a very short –COOH···^-OOC– hydrogen bond (Table 2). The shortness of this interaction can in part be attributed to the fact that the carboxylate group of molecule B participates in no other strong interactions, a most unusual incidence. The COOH group of molecule A is furthermore involved in only one additional hydrogen bond with an H···O distance less than 2.50 Å.

The molecular packing shown in Fig. 2 has, as suspected, thick hydrophobic layers of L-phenylalanine side chains, and also hydrophilic layers composed of two interconnected hydrogen-bonded sheets. This is a very persistent pattern, which occurs not only in the structure of phenylalanine itself (Weissbuch et al., 1990) and its complexes with mandelic acid (Okamura et al., 1997), but also in other salts such as L-phenylalanine hydrochloride (Al-Karaghouli & Koetzle, 1975), L-phenylalnine L-phenylalaninium formate (Görbitz & Etter, 1992) and L-phenylalanine L-phenylalaninium perchlorate (Srinivasan & Rajaram, 1997). It is noteworthy that the latter two structures include one L-phenylalanine zwitterion and one L-phenylalaninium cation in the asymmetric unit, which are in both cases connected by a very short hydrogen bond like the one seen in the title structure.

S2. Experimental

L-Phenylalanine was obtained from Sigma and used as received. Crystals in the shape of long flat needles were grown by slow evaporation of a dilute nitric acid solution of the amino acid at room temperature.

S3. Refinement

Three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 4.98 cm. Constrained H-atom refinement with U_iso values set to 1.2U_eq of the carrier atom or 1.5U_eq for the amino groups. The H atom in the shortest hydrogen bond could not be found in difference Fourier maps. It could therefore not be established with certainty whether it is actually bonded to O2A or O2B (a centered position was considered to be less likely). A combined geometric and force-field calculation with the program HYDROGEN (Nardelli, 1999) showed, however, that the H atom is most likely associated with O2A, and it was thus named HO2A. For a 2.44 Å O···O distance, the previously observed lengthening of the covalent O—H bond is about 0.15 Å (Steiner & Saenger, 1994). The HO2A position output by HYDROGEN was consequently adjusted so as to increase the O—H bond length from 0.85 (default) to 1.00 Å. Based on results from a survey of neutron diffraction structures with COOH groups from the Cambridge Structural Database (Allen & Kennard, 1993), the C—O—H angle was furthermore set to 111.5° and the the C—C—O—H torsion angle was increased to 175° (Görbitz, 2001). SAME 0.005 0.005 constraints were used for the four phenylalanine side chains. The absolute structure could not be determined, and Friedel pairs were merged in the final refinements.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of the title compound with the atomic numbering indicated. Displacement ellipsoids are shown at the 50% probability level and H atoms are shown as spheres of arbitrary size.
	Fig. 2. The unit cell and molecular packing viewed along the a axis. Hydrogen bonds have been dashed.

L-Phenylalanine nitrate (4/1)

Crystal data

C9H12NO2^+·NO3^−·3C9H11NO2	F(000) = 1536
Mr = 180.95	Dx = 1.373 Mg m^−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 30.285 (8) Å	Cell parameters from 3964 reflections
b = 5.3022 (13) Å	θ = 1.9–25.0°
c = 22.317 (6) Å	µ = 0.10 mm^−1
β = 102.263 (4)°	T = 150 K
V = 3501.9 (15) Å^3	Flat needle, colourless
Z = 16	0.55 × 0.20 × 0.07 mm

Data collection

Siemens SMART CCD diffractometer	3450 independent reflections
Radiation source: fine-focus sealed tube	2777 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.100
Detector resolution: 8.3 pixels mm^-1	θmax = 25.0°, θmin = 1.9°
sets of exposures each taken over 0.3° ω rotation scans	h = −36→34
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −6→6
Tmin = 0.945, Tmax = 0.993	l = −24→26
9411 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.113	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.269	w = 1/[σ^2(Fo^2) + (0.098P)^2 + 3.75P] where P = (Fo^2 + 2Fc^2)/3
S = 1.63	(Δ/σ)max = 0.005
3450 reflections	Δρmax = 0.62 e Å^−3
474 parameters	Δρmin = −0.54 e Å^−3
543 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0053 (14)

Special details

Refinement. Refinement of F² against ALL reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1A	0.3062 (2)	0.3387 (13)	0.0591 (3)	0.0298 (15)
O2A	0.3194 (2)	0.1777 (13)	0.1536 (3)	0.0335 (16)
HO2A	0.3151	0.3546	0.1674	0.050*
N1A	0.29139 (18)	−0.1575 (13)	0.0158 (3)	0.0210 (16)
H1A	0.2961	−0.3174	0.0037	0.032*
H2A	0.2935	−0.0477	−0.0149	0.032*
H3A	0.2634	−0.1465	0.0243	0.032*
C1A	0.3157 (2)	0.1668 (13)	0.0959 (3)	0.0178 (17)
C2A	0.32619 (19)	−0.0934 (13)	0.0718 (3)	0.0236 (19)
H21A	0.3246	−0.2220	0.1040	0.028*
C3A	0.37314 (18)	−0.1053 (15)	0.0571 (3)	0.033 (2)
H31A	0.3806	−0.2843	0.0514	0.039*
H32A	0.3721	−0.0177	0.0176	0.039*
C4A	0.4108 (2)	0.0093 (14)	0.1049 (3)	0.029 (2)
C5A	0.4215 (3)	−0.0852 (15)	0.1646 (3)	0.032 (2)
H51A	0.4056	−0.2277	0.1751	0.038*
C6A	0.4549 (3)	0.0266 (18)	0.2088 (3)	0.042 (3)
H61A	0.4621	−0.0404	0.2492	0.050*
C7A	0.4775 (3)	0.2355 (16)	0.1940 (3)	0.040 (3)
H71A	0.5001	0.3141	0.2243	0.048*
C8A	0.4673 (3)	0.3305 (16)	0.1347 (3)	0.043 (3)
H81A	0.4830	0.4739	0.1246	0.051*
C9A	0.4340 (3)	0.2178 (15)	0.0898 (3)	0.040 (3)
H91A	0.4273	0.2830	0.0492	0.048*
O1B	0.2901 (2)	0.3968 (13)	0.2706 (3)	0.0302 (15)
O2B	0.3250 (2)	0.5881 (14)	0.2045 (3)	0.0359 (17)
N1B	0.3060 (2)	0.7650 (15)	0.3540 (3)	0.0309 (19)
H1B	0.3121	0.9037	0.3784	0.046*
H2B	0.3223	0.6318	0.3726	0.046*
H3B	0.2760	0.7286	0.3477	0.046*
C1B	0.3115 (3)	0.5761 (14)	0.2543 (3)	0.023 (2)
C2B	0.3184 (2)	0.8158 (13)	0.2940 (3)	0.025 (2)
H21B	0.2974	0.9478	0.2724	0.030*
C3B	0.36626 (19)	0.9197 (12)	0.3036 (3)	0.028 (2)
H31B	0.3737	0.9430	0.2628	0.033*
H32B	0.3668	1.0883	0.3227	0.033*
C4B	0.4029 (2)	0.7602 (12)	0.3425 (2)	0.0198 (18)
C5B	0.4225 (3)	0.5587 (14)	0.3174 (3)	0.029 (2)
H51B	0.4136	0.5237	0.2748	0.035*
C6B	0.4551 (3)	0.4090 (14)	0.3541 (3)	0.033 (2)
H61B	0.4685	0.2735	0.3366	0.040*
C7B	0.4678 (3)	0.4571 (15)	0.4161 (3)	0.031 (2)
H71B	0.4898	0.3536	0.4414	0.037*
C8B	0.4485 (3)	0.6574 (15)	0.4415 (3)	0.033 (2)
H81B	0.4576	0.6913	0.4841	0.039*
C9B	0.4159 (3)	0.8092 (14)	0.4049 (3)	0.030 (2)
H91B	0.4027	0.9452	0.4226	0.036*
O1C	0.2980 (2)	0.0210 (13)	0.4784 (3)	0.0292 (15)
O2C	0.3302 (2)	0.2695 (14)	0.4186 (3)	0.0348 (17)
N1C	0.2911 (2)	0.3854 (14)	0.5580 (3)	0.0249 (17)
H1C	0.2992	0.4900	0.5908	0.037*
H2C	0.2966	0.2228	0.5703	0.037*
H3C	0.2612	0.4050	0.5414	0.037*
C1C	0.3156 (3)	0.2316 (14)	0.4652 (3)	0.0215 (19)
C2C	0.3179 (2)	0.4485 (13)	0.5112 (3)	0.0220 (19)
H21C	0.3036	0.5995	0.4881	0.026*
C3C	0.3661 (2)	0.5201 (12)	0.5420 (3)	0.026 (2)
H31C	0.3831	0.5539	0.5097	0.031*
H32C	0.3651	0.6793	0.5649	0.031*
C4C	0.3918 (2)	0.3257 (13)	0.5857 (2)	0.027 (2)
C5C	0.4210 (3)	0.1543 (14)	0.5665 (3)	0.028 (2)
H51C	0.4253	0.1609	0.5256	0.033*
C6C	0.4437 (3)	−0.0257 (15)	0.6068 (3)	0.039 (3)
H61C	0.4622	−0.1473	0.5928	0.047*
C7C	0.4395 (3)	−0.0277 (17)	0.6671 (3)	0.043 (3)
H71C	0.4558	−0.1470	0.6950	0.052*
C8C	0.4112 (3)	0.1455 (18)	0.6869 (3)	0.047 (3)
H81C	0.4080	0.1423	0.7283	0.056*
C9C	0.3876 (3)	0.3240 (15)	0.6465 (3)	0.037 (2)
H91C	0.3687	0.4437	0.6604	0.044*
O1D	0.2777 (2)	0.4577 (13)	0.9240 (3)	0.0289 (15)
O2D	0.3019 (3)	0.0734 (13)	0.9050 (3)	0.0343 (17)
N1D	0.2841 (2)	0.6584 (11)	0.8188 (3)	0.0273 (17)
H1D	0.2920	0.7192	0.7845	0.041*
H2D	0.2977	0.7516	0.8518	0.041*
H3D	0.2536	0.6680	0.8144	0.041*
C1D	0.2928 (3)	0.2989 (15)	0.8913 (3)	0.0235 (19)
C2D	0.29870 (19)	0.3903 (12)	0.8283 (3)	0.0209 (18)
H21D	0.2779	0.2876	0.7967	0.025*
C3D	0.34613 (19)	0.3540 (12)	0.8177 (3)	0.027 (2)
H31D	0.3452	0.3784	0.7735	0.033*
H32D	0.3551	0.1769	0.8277	0.033*
C4D	0.3827 (2)	0.5236 (14)	0.8534 (2)	0.025 (2)
C5D	0.3988 (3)	0.4946 (18)	0.9164 (3)	0.043 (3)
H51D	0.3859	0.3695	0.9379	0.052*
C6D	0.4334 (3)	0.6461 (19)	0.9480 (3)	0.046 (3)
H61D	0.4443	0.6228	0.9908	0.055*
C7D	0.4519 (3)	0.8308 (17)	0.9173 (3)	0.039 (2)
H71D	0.4753	0.9363	0.9388	0.047*
C8D	0.4361 (3)	0.8612 (17)	0.8546 (3)	0.044 (3)
H81D	0.4484	0.9906	0.8335	0.053*
C9D	0.4025 (3)	0.7039 (15)	0.8222 (2)	0.033 (2)
H91D	0.3931	0.7198	0.7789	0.040*
O1E	0.2868 (2)	−0.1140 (14)	0.6098 (3)	0.0385 (17)
O2E	0.2882 (3)	0.1299 (15)	0.6877 (3)	0.0401 (19)
O3E	0.3071 (3)	−0.2648 (19)	0.7011 (4)	0.060 (2)
N1E	0.2944 (3)	−0.0867 (17)	0.6663 (3)	0.0314 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.048 (3)	0.008 (3)	0.030 (3)	−0.001 (3)	0.000 (2)	0.000 (2)
O2A	0.057 (4)	0.008 (3)	0.033 (3)	−0.002 (3)	0.004 (3)	−0.003 (3)
N1A	0.030 (3)	0.008 (3)	0.023 (3)	0.000 (3)	0.001 (2)	−0.001 (2)
C1A	0.022 (4)	0.007 (4)	0.021 (3)	−0.001 (3)	−0.001 (3)	0.001 (3)
C2A	0.038 (4)	0.006 (4)	0.024 (3)	−0.002 (3)	0.001 (3)	0.001 (3)
C3A	0.040 (4)	0.023 (4)	0.034 (4)	0.003 (4)	0.005 (3)	−0.001 (4)
C4A	0.036 (4)	0.014 (4)	0.034 (4)	−0.001 (4)	0.005 (3)	0.000 (3)
C5A	0.041 (4)	0.024 (4)	0.032 (4)	−0.001 (4)	0.008 (3)	0.001 (4)
C6A	0.043 (5)	0.039 (5)	0.039 (4)	−0.002 (4)	0.002 (4)	−0.005 (4)
C7A	0.037 (4)	0.033 (5)	0.048 (4)	−0.001 (4)	0.006 (4)	−0.009 (4)
C8A	0.043 (5)	0.030 (5)	0.053 (5)	−0.005 (4)	0.006 (4)	−0.002 (4)
C9A	0.045 (5)	0.027 (5)	0.046 (4)	0.002 (4)	0.003 (4)	0.005 (4)
O1B	0.044 (3)	0.010 (3)	0.037 (3)	−0.007 (3)	0.009 (2)	−0.009 (3)
O2B	0.054 (3)	0.018 (3)	0.035 (3)	−0.006 (3)	0.007 (2)	−0.006 (2)
N1B	0.033 (4)	0.022 (4)	0.037 (4)	0.006 (3)	0.006 (3)	−0.008 (3)
C1B	0.029 (4)	0.009 (4)	0.029 (4)	0.002 (3)	−0.001 (3)	0.001 (3)
C2B	0.037 (4)	0.013 (4)	0.024 (4)	0.003 (4)	0.002 (3)	−0.002 (3)
C3B	0.038 (4)	0.012 (4)	0.032 (4)	0.004 (4)	0.004 (3)	−0.002 (3)
C4B	0.024 (4)	0.009 (4)	0.027 (4)	−0.005 (3)	0.006 (3)	−0.005 (3)
C5B	0.037 (4)	0.020 (4)	0.028 (4)	0.002 (4)	0.002 (3)	0.001 (3)
C6B	0.038 (4)	0.018 (4)	0.043 (4)	0.001 (4)	0.006 (3)	−0.006 (4)
C7B	0.029 (4)	0.026 (4)	0.036 (4)	0.005 (4)	0.003 (3)	0.001 (4)
C8B	0.034 (4)	0.027 (4)	0.035 (4)	−0.004 (4)	0.003 (3)	−0.002 (4)
C9B	0.029 (4)	0.025 (4)	0.035 (4)	0.000 (4)	0.007 (3)	−0.005 (4)
O1C	0.041 (3)	0.007 (3)	0.037 (3)	−0.004 (3)	0.001 (3)	−0.003 (3)
O2C	0.048 (4)	0.020 (3)	0.036 (3)	0.005 (3)	0.009 (3)	−0.005 (3)
N1C	0.033 (3)	0.009 (3)	0.031 (3)	−0.001 (3)	0.003 (3)	−0.002 (3)
C1C	0.029 (4)	0.008 (4)	0.024 (4)	−0.003 (3)	−0.001 (3)	−0.002 (3)
C2C	0.024 (4)	0.010 (4)	0.031 (4)	0.004 (3)	0.003 (3)	0.000 (3)
C3C	0.034 (4)	0.011 (4)	0.033 (4)	0.000 (4)	0.007 (3)	0.001 (3)
C4C	0.028 (4)	0.023 (4)	0.028 (4)	−0.008 (4)	0.002 (3)	−0.004 (3)
C5C	0.025 (4)	0.021 (4)	0.035 (4)	−0.001 (4)	0.001 (3)	0.000 (4)
C6C	0.044 (5)	0.023 (4)	0.047 (4)	−0.001 (4)	0.003 (4)	−0.007 (4)
C7C	0.047 (5)	0.032 (5)	0.048 (4)	0.004 (4)	0.005 (4)	0.006 (4)
C8C	0.049 (5)	0.049 (5)	0.041 (4)	0.004 (5)	0.007 (4)	0.006 (4)
C9C	0.044 (5)	0.027 (5)	0.038 (4)	0.004 (4)	0.008 (3)	0.003 (4)
O1D	0.042 (3)	0.017 (3)	0.030 (3)	−0.002 (3)	0.013 (2)	−0.003 (3)
O2D	0.058 (4)	0.008 (3)	0.036 (3)	−0.006 (3)	0.008 (3)	0.001 (3)
N1D	0.039 (4)	0.009 (3)	0.031 (3)	0.001 (3)	0.001 (3)	0.000 (3)
C1D	0.031 (4)	0.013 (4)	0.026 (4)	−0.005 (4)	0.004 (3)	−0.003 (3)
C2D	0.026 (3)	0.008 (3)	0.025 (3)	0.000 (3)	−0.001 (3)	−0.001 (3)
C3D	0.038 (4)	0.012 (4)	0.031 (4)	0.002 (4)	0.006 (3)	0.005 (3)
C4D	0.031 (4)	0.020 (4)	0.028 (4)	−0.002 (4)	0.009 (3)	0.000 (3)
C5D	0.050 (5)	0.038 (5)	0.041 (4)	−0.011 (4)	0.009 (4)	0.007 (4)
C6D	0.047 (5)	0.048 (5)	0.043 (4)	−0.005 (4)	0.011 (4)	0.002 (4)
C7D	0.037 (4)	0.027 (5)	0.049 (4)	−0.001 (4)	0.002 (4)	−0.003 (4)
C8D	0.042 (5)	0.035 (5)	0.052 (5)	−0.002 (4)	0.006 (4)	0.011 (4)
C9D	0.034 (4)	0.025 (4)	0.040 (4)	−0.001 (4)	0.004 (3)	0.008 (4)
O1E	0.061 (4)	0.016 (3)	0.037 (3)	0.001 (3)	0.009 (3)	0.000 (3)
O2E	0.048 (4)	0.028 (4)	0.044 (3)	−0.004 (3)	0.008 (3)	−0.015 (3)
O3E	0.072 (5)	0.046 (4)	0.062 (4)	0.016 (4)	0.015 (3)	0.025 (4)
N1E	0.040 (4)	0.019 (4)	0.035 (4)	0.006 (4)	0.007 (3)	0.003 (3)

Geometric parameters (Å, º)

O1A—C1A	1.219 (10)	O2C—C1C	1.230 (9)
O2A—C1A	1.271 (9)	N1C—C2C	1.489 (6)
O2A—HO2A	1.0042	N1C—H1C	0.9100
N1A—C2A	1.494 (6)	N1C—H2C	0.9100
N1A—H1A	0.9100	N1C—H3C	0.9100
N1A—H2A	0.9100	C1C—C2C	1.534 (7)
N1A—H3A	0.9100	C2C—C3C	1.523 (7)
C1A—C2A	1.538 (7)	C2C—H21C	1.0000
C2A—C3A	1.527 (7)	C3C—C4C	1.516 (6)
C2A—H21A	1.0000	C3C—H31C	0.9900
C3A—C4A	1.515 (6)	C3C—H32C	0.9900
C3A—H31A	0.9900	C4C—C9C	1.389 (7)
C3A—H32A	0.9900	C4C—C5C	1.397 (6)
C4A—C9A	1.389 (7)	C5C—C6C	1.389 (6)
C4A—C5A	1.395 (6)	C5C—H51C	0.9500
C5A—C6A	1.388 (6)	C6C—C7C	1.380 (8)
C5A—H51A	0.9500	C6C—H61C	0.9500
C6A—C7A	1.380 (8)	C7C—C8C	1.390 (6)
C6A—H61A	0.9500	C7C—H71C	0.9500
C7A—C8A	1.388 (6)	C8C—C9C	1.396 (6)
C7A—H71A	0.9500	C8C—H81C	0.9500
C8A—C9A	1.396 (6)	C9C—H91C	0.9500
C8A—H81A	0.9500	O1D—C1D	1.261 (10)
C9A—H91A	0.9500	O2D—C1D	1.250 (10)
O1B—C1B	1.247 (10)	N1D—C2D	1.491 (6)
O2B—C1B	1.265 (9)	N1D—H1D	0.9100
N1B—C2B	1.490 (6)	N1D—H2D	0.9100
N1B—H1B	0.9100	N1D—H3D	0.9100
N1B—H2B	0.9100	C1D—C2D	1.535 (6)
N1B—H3B	0.9100	C2D—C3D	1.516 (7)
C1B—C2B	1.538 (7)	C2D—H21D	1.0000
C2B—C3B	1.521 (7)	C3D—C4D	1.514 (6)
C2B—H21B	1.0000	C3D—H31D	0.9900
C3B—C4B	1.515 (6)	C3D—H32D	0.9900
C3B—H31B	0.9900	C4D—C9D	1.390 (7)
C3B—H32B	0.9900	C4D—C5D	1.396 (6)
C4B—C9B	1.389 (7)	C5D—C6D	1.389 (6)
C4B—C5B	1.396 (6)	C5D—H51D	0.9500
C5B—C6B	1.389 (6)	C6D—C7D	1.381 (8)
C5B—H51B	0.9500	C6D—H61D	0.9500
C6B—C7B	1.379 (8)	C7D—C8D	1.388 (6)
C6B—H61B	0.9500	C7D—H71D	0.9500
C7B—C8B	1.389 (6)	C8D—C9D	1.394 (6)
C7B—H71B	0.9500	C8D—H81D	0.9500
C8B—C9B	1.395 (6)	C9D—H91D	0.9500
C8B—H81B	0.9500	O1E—N1E	1.243 (9)
C9B—H91B	0.9500	O2E—N1E	1.272 (11)
O1C—C1C	1.298 (10)	O3E—N1E	1.230 (12)
C1A—O2A—HO2A	111.3	C2C—N1C—H2C	109.5
C2A—N1A—H1A	109.5	H1C—N1C—H2C	109.5
C2A—N1A—H2A	109.5	C2C—N1C—H3C	109.5
H1A—N1A—H2A	109.5	H1C—N1C—H3C	109.5
C2A—N1A—H3A	109.5	H2C—N1C—H3C	109.5
H1A—N1A—H3A	109.5	O2C—C1C—O1C	124.9 (6)
H2A—N1A—H3A	109.5	O2C—C1C—C2C	118.1 (6)
O1A—C1A—O2A	127.3 (7)	O1C—C1C—C2C	117.0 (5)
O1A—C1A—C2A	118.2 (6)	N1C—C2C—C3C	110.6 (4)
O2A—C1A—C2A	114.5 (6)	N1C—C2C—C1C	110.3 (5)
N1A—C2A—C3A	109.5 (4)	C3C—C2C—C1C	113.0 (4)
N1A—C2A—C1A	109.6 (4)	N1C—C2C—H21C	107.6
C3A—C2A—C1A	112.6 (4)	C3C—C2C—H21C	107.6
N1A—C2A—H21A	108.4	C1C—C2C—H21C	107.6
C3A—C2A—H21A	108.4	C4C—C3C—C2C	115.7 (4)
C1A—C2A—H21A	108.4	C4C—C3C—H31C	108.4
C4A—C3A—C2A	115.4 (4)	C2C—C3C—H31C	108.4
C4A—C3A—H31A	108.4	C4C—C3C—H32C	108.4
C2A—C3A—H31A	108.4	C2C—C3C—H32C	108.4
C4A—C3A—H32A	108.4	H31C—C3C—H32C	107.4
C2A—C3A—H32A	108.4	C9C—C4C—C5C	119.4 (3)
H31A—C3A—H32A	107.5	C9C—C4C—C3C	119.4 (4)
C9A—C4A—C5A	119.5 (3)	C5C—C4C—C3C	121.1 (4)
C9A—C4A—C3A	119.4 (4)	C6C—C5C—C4C	120.5 (4)
C5A—C4A—C3A	121.0 (4)	C6C—C5C—H51C	119.8
C6A—C5A—C4A	120.7 (4)	C4C—C5C—H51C	119.8
C6A—C5A—H51A	119.6	C7C—C6C—C5C	120.0 (3)
C4A—C5A—H51A	119.6	C7C—C6C—H61C	120.0
C7A—C6A—C5A	119.8 (3)	C5C—C6C—H61C	120.0
C7A—C6A—H61A	120.1	C6C—C7C—C8C	119.8 (3)
C5A—C6A—H61A	120.1	C6C—C7C—H71C	120.1
C6A—C7A—C8A	119.8 (3)	C8C—C7C—H71C	120.1
C6A—C7A—H71A	120.1	C7C—C8C—C9C	120.6 (4)
C8A—C7A—H71A	120.1	C7C—C8C—H81C	119.7
C7A—C8A—C9A	120.7 (4)	C9C—C8C—H81C	119.7
C7A—C8A—H81A	119.6	C4C—C9C—C8C	119.6 (3)
C9A—C8A—H81A	119.6	C4C—C9C—H91C	120.2
C4A—C9A—C8A	119.4 (3)	C8C—C9C—H91C	120.2
C4A—C9A—H91A	120.3	C2D—N1D—H1D	109.5
C8A—C9A—H91A	120.3	C2D—N1D—H2D	109.5
C2B—N1B—H1B	109.5	H1D—N1D—H2D	109.5
C2B—N1B—H2B	109.5	C2D—N1D—H3D	109.5
H1B—N1B—H2B	109.5	H1D—N1D—H3D	109.5
C2B—N1B—H3B	109.5	H2D—N1D—H3D	109.5
H1B—N1B—H3B	109.5	O2D—C1D—O1D	125.9 (6)
H2B—N1B—H3B	109.5	O2D—C1D—C2D	117.5 (7)
O1B—C1B—O2B	125.4 (6)	O1D—C1D—C2D	116.5 (6)
O1B—C1B—C2B	118.5 (6)	N1D—C2D—C3D	111.2 (4)
O2B—C1B—C2B	115.8 (6)	N1D—C2D—C1D	110.0 (4)
N1B—C2B—C3B	110.8 (4)	C3D—C2D—C1D	113.7 (4)
N1B—C2B—C1B	109.8 (5)	N1D—C2D—H21D	107.2
C3B—C2B—C1B	112.9 (4)	C3D—C2D—H21D	107.2
N1B—C2B—H21B	107.7	C1D—C2D—H21D	107.2
C3B—C2B—H21B	107.7	C2D—C3D—C4D	117.0 (4)
C1B—C2B—H21B	107.7	C2D—C3D—H31D	108.0
C4B—C3B—C2B	116.0 (4)	C4D—C3D—H31D	108.0
C4B—C3B—H31B	108.3	C2D—C3D—H32D	108.0
C2B—C3B—H31B	108.3	C4D—C3D—H32D	108.0
C4B—C3B—H32B	108.3	H31D—C3D—H32D	107.3
C2B—C3B—H32B	108.3	C9D—C4D—C5D	119.0 (3)
H31B—C3B—H32B	107.4	C9D—C4D—C3D	119.3 (4)
C9B—C4B—C5B	119.4 (3)	C5D—C4D—C3D	121.5 (4)
C9B—C4B—C3B	119.2 (3)	C6D—C5D—C4D	120.9 (4)
C5B—C4B—C3B	121.3 (4)	C6D—C5D—H51D	119.6
C6B—C5B—C4B	120.6 (4)	C4D—C5D—H51D	119.6
C6B—C5B—H51B	119.7	C7D—C6D—C5D	119.9 (3)
C4B—C5B—H51B	119.7	C7D—C6D—H61D	120.0
C7B—C6B—C5B	119.9 (3)	C5D—C6D—H61D	120.0
C7B—C6B—H61B	120.0	C6D—C7D—C8D	119.6 (3)
C5B—C6B—H61B	120.0	C6D—C7D—H71D	120.2
C6B—C7B—C8B	119.8 (3)	C8D—C7D—H71D	120.2
C6B—C7B—H71B	120.1	C7D—C8D—C9D	120.7 (4)
C8B—C7B—H71B	120.1	C7D—C8D—H81D	119.6
C7B—C8B—C9B	120.6 (4)	C9D—C8D—H81D	119.6
C7B—C8B—H81B	119.7	C4D—C9D—C8D	119.8 (3)
C9B—C8B—H81B	119.7	C4D—C9D—H91D	120.1
C4B—C9B—C8B	119.6 (3)	C8D—C9D—H91D	120.1
C4B—C9B—H91B	120.2	O3E—N1E—O1E	121.1 (9)
C8B—C9B—H91B	120.2	O3E—N1E—O2E	120.5 (8)
C2C—N1C—H1C	109.5	O1E—N1E—O2E	118.4 (8)
O1A—C1A—C2A—N1A	−46.3 (8)	O2C—C1C—C2C—N1C	169.3 (7)
O2A—C1A—C2A—N1A	135.9 (6)	O1C—C1C—C2C—N1C	−10.3 (9)
O1A—C1A—C2A—C3A	75.9 (8)	O2C—C1C—C2C—C3C	−66.3 (9)
O2A—C1A—C2A—C3A	−101.9 (7)	O1C—C1C—C2C—C3C	114.1 (7)
N1A—C2A—C3A—C4A	167.2 (6)	N1C—C2C—C3C—C4C	55.8 (7)
C1A—C2A—C3A—C4A	45.1 (8)	C1C—C2C—C3C—C4C	−68.4 (6)
C2A—C3A—C4A—C9A	−116.4 (8)	C2C—C3C—C4C—C9C	−86.2 (9)
C2A—C3A—C4A—C5A	61.0 (10)	C2C—C3C—C4C—C5C	96.2 (8)
C9A—C4A—C5A—C6A	−0.1 (14)	C9C—C4C—C5C—C6C	3.5 (13)
C3A—C4A—C5A—C6A	−177.5 (9)	C3C—C4C—C5C—C6C	−178.8 (8)
C4A—C5A—C6A—C7A	0.8 (16)	C4C—C5C—C6C—C7C	−3.4 (15)
C5A—C6A—C7A—C8A	−0.9 (16)	C5C—C6C—C7C—C8C	2.1 (16)
C6A—C7A—C8A—C9A	0.3 (16)	C6C—C7C—C8C—C9C	−0.9 (17)
C5A—C4A—C9A—C8A	−0.6 (15)	C5C—C4C—C9C—C8C	−2.3 (14)
C3A—C4A—C9A—C8A	176.9 (9)	C3C—C4C—C9C—C8C	−180.0 (9)
C7A—C8A—C9A—C4A	0.4 (16)	C7C—C8C—C9C—C4C	1.0 (17)
O1B—C1B—C2B—N1B	12.4 (9)	O2D—C1D—C2D—N1D	177.2 (7)
O2B—C1B—C2B—N1B	−173.5 (7)	O1D—C1D—C2D—N1D	−0.7 (9)
O1B—C1B—C2B—C3B	136.6 (7)	O2D—C1D—C2D—C3D	−57.4 (9)
O2B—C1B—C2B—C3B	−49.3 (9)	O1D—C1D—C2D—C3D	124.7 (7)
N1B—C2B—C3B—C4B	55.4 (7)	N1D—C2D—C3D—C4D	53.5 (7)
C1B—C2B—C3B—C4B	−68.2 (6)	C1D—C2D—C3D—C4D	−71.3 (6)
C2B—C3B—C4B—C9B	−93.8 (8)	C2D—C3D—C4D—C9D	−112.0 (8)
C2B—C3B—C4B—C5B	83.5 (8)	C2D—C3D—C4D—C5D	71.5 (10)
C9B—C4B—C5B—C6B	−0.5 (14)	C9D—C4D—C5D—C6D	1.3 (16)
C3B—C4B—C5B—C6B	−177.8 (8)	C3D—C4D—C5D—C6D	177.8 (9)
C4B—C5B—C6B—C7B	0.8 (15)	C4D—C5D—C6D—C7D	0.9 (18)
C5B—C6B—C7B—C8B	−0.8 (15)	C5D—C6D—C7D—C8D	−0.9 (18)
C6B—C7B—C8B—C9B	0.7 (15)	C6D—C7D—C8D—C9D	−1.4 (17)
C5B—C4B—C9B—C8B	0.3 (13)	C5D—C4D—C9D—C8D	−3.5 (15)
C3B—C4B—C9B—C8B	177.7 (8)	C3D—C4D—C9D—C8D	179.9 (9)
C7B—C8B—C9B—C4B	−0.4 (15)	C7D—C8D—C9D—C4D	3.6 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—HO2A···O2B	1.00	1.49	2.443 (9)	158
N1A—H1A···O1D^i	0.91	2.11	2.858 (8)	138
N1A—H1A···O1A^ii	0.91	2.19	2.844 (10)	128
N1A—H2A···O2D^iii	0.91	1.97	2.837 (9)	159
N1A—H3A···O1D^iv	0.91	1.95	2.785 (9)	152
N1A—H3A···O1A^v	0.91	2.50	3.071 (8)	121
N1B—H1B···O2C^vi	0.91	2.16	3.053 (10)	167
N1B—H2B···O2C	0.91	2.17	3.012 (10)	154
N1B—H3B···O2E^vii	0.91	2.01	2.898 (10)	166
N1C—H1C···O1E^vi	0.91	2.19	2.909 (10)	135
N1C—H2C···O1E	0.91	2.04	2.903 (10)	158
N1C—H3C···O1C^vii	0.91	1.86	2.744 (9)	164
N1D—H1D···O3E^vi	0.91	2.01	2.886 (10)	161
N1D—H2D···O2D^vi	0.91	2.07	2.896 (9)	151
N1D—H3D···O1B^vii	0.91	2.40	2.954 (9)	119
N1D—H3D···O2A^vii	0.91	2.46	3.322 (10)	157

Symmetry codes: (i) x, y−1, z−1; (ii) x, y−1, z; (iii) x, y, z−1; (iv) −x+1/2, y−1/2, −z+1; (v) −x+1/2, y−1/2, −z; (vi) x, y+1, z; (vii) −x+1/2, y+1/2, −z+1.