Pearls on a string: a Z' = 7 structure for glycyl-L-valine

The title peptide, C₇H₁₄N₂O₃, crystallizes with seven independent mol­ecules in the asymmetric unit. All have essentially the same overall conformation, but some flexibility is exhibited by the glycine residue. It appears that the high Z' value, observed only three times before for an organic compound, permits formation of shorter hydrogen bonds in one of the two head-to-tail chains involving the N-terminal amino groups and the C-terminal carboxyl­ate groups than found in a hypothetical model structure of glycyl-L-valine with Z' = 1, and that it furthermore alleviates strain associated with an eclipsed orientation of the amino group.

S1. Comment

Among dipeptides constructed from the 20 natural amino acids, the Gly–Xaa series of crystal structures, where Xaa is any amino acid, is the most complete for a specific N-terminal amino acid, with 13 entries in the Cambridge Structural Database (CSD, Version 5.27 of November 2005; Allen, 2002). In a student project, we sought to expand this group of structures towards completeness by crystallization of the title compound, Gly-L-Val, (I).

Thin flakes of (I) obtained by slow evaporation were generally of low quality, but a specimen usable for data collection was found after a number of tests. The initial observation of a 44 Å unit-cell axis indicated that this was an unusual dipeptide crystal, a suspicion that was subsequently verified when structure determination revealed seven independent peptide molecules in the asymmetric unit, labelled A to G (Fig. 1). All seven molecules have essentially the same conformation, but with some torsion angle variations, in particular for rotation about the C1—C2 bond (ψ₁) (Table 1 and Fig. 2). It is interesting to note that the main chain conformation of Gly-L-Leu [(II); Pattabhi et al., 1974] can be seen to represent an average of the seven Gly-L-Val conformations (Table 1), and the closely related monoclinic structure of (II) provides some clues as to why (I) has crystallized with Z' = 7.

As seen for (II), the crystal structure of (I) is divided into hydrophobic and hydrophilic layers (Fig. 3), and we first suspected that the side-chain modification going from Leu to Val rendered efficient packing of the side chain difficult with Z' limited to 1. To test this hypothesis, a molecular modelling program (SYBYL; Tripos, 2005) was used to construct a theoretical Gly-L-Val structure with Z' = 1, based on (II) but adapted to the correct space group, P2₁2₁2₁. This model showed no unfavourable short contacts or large voids compared with the structure of (I).

Our attention then turned to the hydrogen-bonding pattern, with contacts listed in Table 2. Atoms H1 and H3 are involved in head-to-tail chains within a hydrophilic sheet that also comprises the N2—H4···O3 interactions. Two such antiparallel sheets are interconnected by N1—H2···O3 hydrogen bonds and thus generate a hydrophilic layer (Fig. 3). A peculiarity of (II) is the eclipsed conformation of the amino group, as reflected by the H3—N1—C1—C2 torsion angle in Table 1, which is required to minimize the H···O distance in the N1—H3···O2 interaction (Table 2). In (I), two different rotational modes are observed for the amino group, one with H3—N1—C1—C2 < 0° for molecules B, C, E and F, and one with H3—N1—C1—C2 > 0° for molecules A, D and G. The fully eclipsed conformation is thus avoided, and at the same time the associated hydrogen bonds are significantly shorter overall than in (II) (while hydrogen bonds involving atoms H1 and H2 are unchanged).

A further effect of this rearrangement can be seen as a reduction of the structural periodicity along the head-to-tail chains from 6.369 Å for (II) (a axis) to 6.299 Å for (I) (c axis/7). On the other hand, the shorter N2—H4···O3 hydrogen bond in (I) compared with (II) is most probably attributable mainly to more efficient packing of Val than Leu side chains, indicated by a shorter cell axis [5.5238 (7) Å for (I) and 5.565 Å for (II)], as only molecules of the same kind (A···A etc.) are involved.

The monclinic C2 structure of L-Ala-L-Leu hemihydrate (Görbitz, 1999) is related to both (I) and (II) (Fig. 3), with essentially the same molecular conformation. Space for the extra methyl side chain at residue I is nicely provided by insertion of extra water molecules in the hydrophilic layers. Water thus replaces atom O3 as the acceptor in the N1—H2···O3 interaction, and at the same time the two hydrogen-bonded sheets in a single layer (see above) switch from antiparallel to parallel orientation to provide carboxylate acceptors for both water H atoms.

There are only three other structures in the CSD with Z' = 7. Two of these are peptides, viz. L-Met-L-Ala in space group P6₁ (Görbitz, 2003) and Boc-L-Phe-L-Leu-OBzl, a protected dipeptide fragment of enkephalin, in space group P2₁ (Antolić et al., 1999). In both cases, the seven molecules exhibit a mixture of conformations, particularly with regard to the side chains, but also with extensive flexibility for the peptide main chains. The third compound, 2-cyano-2-isonitroso-N-morpholinylacetamide [(III); Eddings et al., 2004], shares the P2₁2₁2₁ space group with (I) and, with its 7.3 × 14.4 × 54.8 Å unit cell, shows some of the same packing features, but not the division into hydrophobic and hydrophilic layers as seen for (I). In (III), there is a 4:3 distribution between two different chair conformations for the six-membered ring.

S2. Experimental

The title peptide was obtained from Bachem. Crystals in the shape of extremely thin plates were obtained by slow evaporation of an aqueous solution.

S3. Refinement

H atoms were positioned with idealized geometry, with amide H atoms in the peptide plane, and fixed C—H and N—H distances of 0.98–1.00 Å and 0.88–0.91 Å, respectively. [Please check added text] Rigid rotation was permitted for amino groups only. U_iso(H) values were 1.2U_eq of the carrier atom, or 1.5U_eq(parent) for amino and methyl groups. In the absence of significant anomalous scattering effects, 4887 Friedel pairs were merged. The absolute configuration was known for the purchased material.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. Atomic numbering is shown for molecule A only. The valyl side chain is shaded differently for molecules A, B, C, D, E, F and G.
	Fig. 2. Overlap diagram of the seven molecules in the asymmetric unit of (I) after best fit to the average structure (not shown).
	Fig. 3. (a) The molecular packing and unit cell of (I), viewed along the a axis. Hydrogen bonds are indicated by dashed lines. H atoms not involved in such interactions have been omitted for clarity. One half of the molecules are shown in a space-filling representation. The shading is similar to that in Fig. 1. (b) The crystal structure of Gly-L-Leu (Pattabhi et al., 1974), viewed along the b axis. (c) The crystal structure of L-Ala-L-Leu (Görbitz, 1999), viewed along the c axis.

glycyl-L-valine

Crystal data

C7H14N2O3	Dx = 1.251 Mg m^−3
Mr = 174.20	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4643 reflections
a = 5.5238 (7) Å	θ = 0.9–25.0°
b = 26.581 (3) Å	µ = 0.10 mm^−1
c = 44.093 (5) Å	T = 105 K
V = 6474.0 (14) Å^3	Plate, colourless
Z = 28	0.75 × 0.25 × 0.01 mm
F(000) = 2632

Data collection

Siemens SMART CCD area-detector diffractometer	4122 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.125
Graphite monochromator	θmax = 25.0°, θmin = 0.9°
Detector resolution: 8.3 pixels mm^-1	h = −6→6
ω scans	k = −31→31
35141 measured reflections	l = −52→39
6579 independent 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)] = 0.073	H-atom parameters constrained
wR(F^2) = 0.172	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 2.98P] where P = (Fo^2 + 2Fc^2)/3
S = 1.28	(Δ/σ)max = 0.009
6579 reflections	Δρmax = 0.34 e Å^−3
765 parameters	Δρmin = −0.35 e Å^−3
1101 restraints	Extinction correction: SHELXTL (Bruker, 2000), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00086 (13)

Special details

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. Data were collected by measuring three sets of exposures with the detector set at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F² against ALL reflections.

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

	x	y	z	Uiso*/Ueq
O1A	0.6208 (7)	0.69919 (15)	0.09435 (9)	0.0254 (11)
O2A	0.6337 (8)	0.70171 (15)	0.01811 (10)	0.0335 (12)
O3A	0.9653 (7)	0.65673 (17)	0.02741 (10)	0.0329 (12)
N1A	0.2233 (9)	0.73321 (17)	0.12486 (9)	0.0190 (12)
H1A	0.1215	0.7151	0.1369	0.029*
H2A	0.1854	0.7665	0.1262	0.029*
H3A	0.3787	0.7284	0.1311	0.029*
N2A	0.3894 (8)	0.65230 (15)	0.06289 (10)	0.0229 (13)
H4A	0.2414	0.6432	0.0579	0.027*
C1A	0.1975 (8)	0.7163 (2)	0.09304 (11)	0.0206 (15)
H11A	0.1729	0.7458	0.0797	0.025*
H12A	0.0546	0.6941	0.0911	0.025*
C2A	0.4222 (8)	0.68836 (18)	0.08358 (11)	0.0183 (15)
C3A	0.5944 (9)	0.62784 (14)	0.04847 (10)	0.0239 (16)
H31A	0.7009	0.6139	0.0648	0.029*
C4A	0.5012 (10)	0.58368 (17)	0.02936 (12)	0.0301 (18)
H41A	0.3785	0.5973	0.0148	0.036*
C5A	0.3745 (13)	0.5454 (2)	0.04936 (14)	0.0353 (18)
H51A	0.2457	0.5621	0.0609	0.053*
H52A	0.4917	0.5306	0.0634	0.053*
H53A	0.3041	0.5189	0.0367	0.053*
C6A	0.6993 (13)	0.5588 (2)	0.01082 (15)	0.048 (2)
H61A	0.7754	0.5839	−0.0024	0.072*
H62A	0.6292	0.5320	−0.0016	0.072*
H63A	0.8213	0.5446	0.0245	0.072*
C7A	0.7441 (8)	0.66531 (18)	0.02976 (13)	0.0278 (17)
O1B	0.5819 (8)	0.6690 (2)	0.23788 (10)	0.0408 (14)
O2B	0.6172 (7)	0.72008 (13)	0.16550 (9)	0.0219 (11)
O3B	0.9606 (6)	0.67655 (14)	0.16456 (10)	0.0230 (11)
N1B	0.1862 (10)	0.6993 (2)	0.26730 (9)	0.0272 (14)
H1B	0.0686	0.6861	0.2794	0.041*
H2B	0.1754	0.7335	0.2675	0.041*
H3B	0.3340	0.6898	0.2743	0.041*
N2B	0.3838 (8)	0.64530 (16)	0.19511 (8)	0.0235 (13)
H4B	0.2418	0.6405	0.1865	0.028*
C1B	0.1545 (9)	0.6808 (3)	0.23598 (12)	0.0359 (19)
H11B	0.0864	0.7080	0.2232	0.043*
H12B	0.0394	0.6523	0.2359	0.043*
C2B	0.3943 (9)	0.6641 (2)	0.22321 (10)	0.0252 (16)
C3B	0.6024 (8)	0.63273 (15)	0.17846 (10)	0.0200 (15)
H31B	0.7104	0.6131	0.1923	0.024*
C4B	0.5376 (10)	0.59910 (16)	0.15142 (11)	0.0219 (15)
H41B	0.4197	0.6180	0.1385	0.026*
C5B	0.4136 (13)	0.5512 (2)	0.16192 (15)	0.042 (2)
H51B	0.3705	0.5307	0.1442	0.063*
H52B	0.2667	0.5598	0.1732	0.063*
H53B	0.5237	0.5321	0.1750	0.063*
C6B	0.7551 (11)	0.5865 (2)	0.13178 (14)	0.0364 (19)
H61B	0.7033	0.5656	0.1147	0.055*
H62B	0.8748	0.5681	0.1439	0.055*
H63B	0.8275	0.6177	0.1241	0.055*
C7B	0.7386 (8)	0.68052 (15)	0.16885 (13)	0.0184 (15)
O1C	0.5635 (7)	0.63502 (15)	0.38021 (9)	0.0284 (11)
O2C	0.5706 (8)	0.68407 (14)	0.30779 (10)	0.0256 (11)
O3C	0.9152 (7)	0.64068 (15)	0.30723 (9)	0.0262 (11)
N1C	0.1991 (10)	0.68115 (17)	0.40870 (9)	0.0191 (12)
H1C	0.0914	0.6702	0.4229	0.029*
H2C	0.1874	0.7152	0.4068	0.029*
H3C	0.3519	0.6728	0.4146	0.029*
N2C	0.3436 (7)	0.61148 (16)	0.33923 (8)	0.0177 (12)
H4C	0.1971	0.6053	0.3323	0.021*
C1C	0.1449 (9)	0.6571 (2)	0.37919 (11)	0.0292 (17)
H11C	0.0816	0.6826	0.3649	0.035*
H12C	0.0193	0.6310	0.3820	0.035*
C2C	0.3708 (8)	0.63367 (19)	0.36633 (9)	0.0154 (14)
C3C	0.5534 (8)	0.59740 (15)	0.32105 (9)	0.0194 (15)
H31C	0.6621	0.5759	0.3337	0.023*
C4C	0.4684 (10)	0.56650 (18)	0.29373 (11)	0.0266 (17)
H41C	0.3518	0.5877	0.2820	0.032*
C5C	0.3346 (12)	0.5197 (2)	0.30412 (14)	0.0339 (18)
H51C	0.2010	0.5293	0.3175	0.051*
H52C	0.4464	0.4976	0.3151	0.051*
H53C	0.2700	0.5019	0.2864	0.051*
C6C	0.6753 (12)	0.5525 (3)	0.27258 (13)	0.0384 (19)
H61C	0.7588	0.5831	0.2660	0.058*
H62C	0.6108	0.5348	0.2549	0.058*
H63C	0.7897	0.5306	0.2833	0.058*
C7C	0.6940 (8)	0.64488 (16)	0.31159 (12)	0.0198 (15)
O1D	0.6089 (7)	0.68049 (15)	0.52337 (9)	0.0242 (11)
O2D	0.6016 (7)	0.68173 (13)	0.44650 (9)	0.0219 (10)
O3D	0.9414 (6)	0.64067 (14)	0.45755 (9)	0.0185 (10)
N1D	0.2257 (9)	0.72095 (17)	0.55292 (9)	0.0155 (12)
H1D	0.1221	0.7055	0.5660	0.023*
H2D	0.1965	0.7546	0.5529	0.023*
H3D	0.3809	0.7152	0.5589	0.023*
N2D	0.3688 (8)	0.63394 (15)	0.49262 (9)	0.0199 (12)
H4D	0.2196	0.6250	0.4882	0.024*
C1D	0.1889 (9)	0.7006 (2)	0.52198 (11)	0.0189 (15)
H11D	0.1643	0.7286	0.5075	0.023*
H12D	0.0432	0.6789	0.5216	0.023*
C2D	0.4084 (8)	0.67038 (18)	0.51292 (11)	0.0183 (14)
C3D	0.5715 (8)	0.60896 (13)	0.47787 (9)	0.0137 (13)
H31D	0.6786	0.5942	0.4938	0.016*
C4D	0.4742 (9)	0.56617 (15)	0.45784 (10)	0.0151 (14)
H41D	0.3579	0.5811	0.4430	0.018*
C5D	0.3380 (11)	0.52756 (19)	0.47671 (13)	0.0288 (17)
H51D	0.2761	0.5009	0.4634	0.043*
H52D	0.2024	0.5440	0.4871	0.043*
H53D	0.4477	0.5129	0.4918	0.043*
C6D	0.6770 (11)	0.5411 (2)	0.44002 (12)	0.0254 (16)
H61D	0.6093	0.5144	0.4272	0.038*
H62D	0.7946	0.5265	0.4541	0.038*
H63D	0.7576	0.5662	0.4272	0.038*
C7D	0.7193 (7)	0.64737 (16)	0.45933 (11)	0.0135 (14)
O1E	0.6001 (8)	0.68919 (17)	0.66735 (10)	0.0318 (12)
O2E	0.6311 (7)	0.71674 (12)	0.59262 (9)	0.0221 (11)
O3E	0.9679 (6)	0.67145 (14)	0.59615 (10)	0.0237 (11)
N1E	0.1973 (10)	0.71915 (19)	0.69669 (9)	0.0243 (14)
H1E	0.0843	0.7036	0.7084	0.036*
H2E	0.1751	0.7530	0.6975	0.036*
H3E	0.3479	0.7114	0.7036	0.036*
N2E	0.3910 (7)	0.65149 (15)	0.62945 (9)	0.0202 (12)
H4E	0.2467	0.6429	0.6228	0.024*
C1E	0.1725 (9)	0.7019 (3)	0.66506 (12)	0.0334 (18)
H11E	0.1238	0.7305	0.6520	0.040*
H12E	0.0451	0.6758	0.6638	0.040*
C2E	0.4093 (8)	0.6806 (2)	0.65404 (10)	0.0221 (15)
C3E	0.6045 (8)	0.63381 (14)	0.61355 (10)	0.0181 (14)
H31E	0.7121	0.6168	0.6286	0.022*
C4E	0.5274 (9)	0.59464 (16)	0.59005 (11)	0.0216 (15)
H41E	0.4027	0.6107	0.5767	0.026*
C5E	0.4101 (13)	0.5494 (2)	0.60510 (14)	0.0383 (19)
H51E	0.2773	0.5607	0.6182	0.057*
H52E	0.5308	0.5316	0.6173	0.057*
H53E	0.3465	0.5267	0.5895	0.057*
C6E	0.7344 (11)	0.5778 (2)	0.56980 (13)	0.0345 (18)
H61E	0.8081	0.6073	0.5601	0.052*
H62E	0.6725	0.5550	0.5542	0.052*
H63E	0.8562	0.5603	0.5820	0.052*
C7E	0.7460 (7)	0.67782 (16)	0.59960 (12)	0.0176 (15)
O1F	0.5668 (7)	0.63960 (17)	0.80719 (9)	0.0295 (12)
O2F	0.5873 (8)	0.70117 (14)	0.73716 (9)	0.0278 (11)
O3F	0.9299 (7)	0.65752 (16)	0.73459 (10)	0.0307 (12)
N1F	0.1901 (10)	0.67809 (17)	0.83745 (9)	0.0177 (12)
H1F	0.0838	0.6653	0.8512	0.026*
H2F	0.1723	0.7121	0.8365	0.026*
H3F	0.3440	0.6706	0.8433	0.026*
N2F	0.3564 (8)	0.62346 (17)	0.76419 (8)	0.0246 (13)
H4F	0.2116	0.6196	0.7562	0.030*
C1F	0.1421 (9)	0.6559 (3)	0.80735 (11)	0.0270 (17)
H11F	0.0616	0.6811	0.7942	0.032*
H12F	0.0322	0.6267	0.8095	0.032*
C2F	0.3760 (8)	0.6393 (2)	0.79288 (9)	0.0223 (15)
C3F	0.5689 (9)	0.61250 (15)	0.74594 (9)	0.0223 (15)
H31F	0.6776	0.5898	0.7578	0.027*
C4F	0.4914 (10)	0.58489 (18)	0.71692 (10)	0.0237 (16)
H41F	0.3786	0.6075	0.7056	0.028*
C5F	0.3552 (12)	0.5369 (2)	0.72437 (14)	0.0359 (19)
H51F	0.3079	0.5201	0.7055	0.054*
H52F	0.2101	0.5452	0.7362	0.054*
H53F	0.4597	0.5146	0.7363	0.054*
C6F	0.7050 (12)	0.5735 (2)	0.69633 (13)	0.0378 (19)
H61F	0.6476	0.5562	0.6781	0.057*
H62F	0.8204	0.5519	0.7071	0.057*
H63F	0.7849	0.6050	0.6906	0.057*
C7F	0.7081 (8)	0.66133 (16)	0.73877 (13)	0.0215 (16)
O1G	0.5927 (8)	0.65189 (18)	0.95235 (10)	0.0383 (13)
O2G	0.5846 (7)	0.67127 (12)	0.87620 (9)	0.0208 (10)
O3G	0.9293 (6)	0.62970 (14)	0.88348 (9)	0.0223 (10)
N1G	0.2217 (10)	0.6979 (2)	0.98004 (10)	0.0289 (14)
H1G	0.1280	0.6826	0.9943	0.043*
H2G	0.1848	0.7312	0.9792	0.043*
H3G	0.3806	0.6941	0.9850	0.043*
N2G	0.3571 (8)	0.61279 (16)	0.91741 (9)	0.0237 (13)
H4G	0.2085	0.6042	0.9124	0.028*
C1G	0.1755 (10)	0.6747 (3)	0.95012 (13)	0.0354 (19)
H11G	0.1399	0.7012	0.9350	0.043*
H12G	0.0333	0.6521	0.9514	0.043*
C2G	0.3946 (9)	0.6451 (2)	0.94031 (11)	0.0298 (17)
C3G	0.5620 (8)	0.59193 (14)	0.90086 (10)	0.0183 (14)
H31G	0.6695	0.5736	0.9154	0.022*
C4G	0.4703 (9)	0.55484 (16)	0.87672 (11)	0.0221 (15)
H41G	0.3565	0.5735	0.8631	0.027*
C5G	0.3311 (11)	0.51202 (19)	0.89109 (14)	0.0317 (17)
H51G	0.2744	0.4890	0.8752	0.048*
H52G	0.1917	0.5255	0.9022	0.048*
H53G	0.4369	0.4938	0.9051	0.048*
C6G	0.6773 (11)	0.5351 (2)	0.85726 (13)	0.0319 (17)
H61G	0.7664	0.5635	0.8485	0.048*
H62G	0.6119	0.5141	0.8409	0.048*
H63G	0.7869	0.5149	0.8698	0.048*
C7G	0.7070 (7)	0.63495 (16)	0.88592 (12)	0.0174 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.019 (2)	0.030 (2)	0.027 (2)	−0.003 (2)	−0.001 (2)	−0.0059 (19)
O2A	0.031 (3)	0.048 (3)	0.021 (2)	0.002 (2)	0.000 (2)	0.005 (2)
O3A	0.023 (3)	0.053 (3)	0.023 (2)	−0.002 (2)	0.002 (2)	−0.007 (2)
N1A	0.019 (3)	0.019 (2)	0.020 (3)	−0.003 (2)	0.000 (2)	−0.001 (2)
N2A	0.016 (3)	0.030 (3)	0.023 (3)	−0.002 (2)	−0.001 (2)	−0.012 (2)
C1A	0.016 (3)	0.027 (3)	0.019 (3)	−0.004 (3)	0.000 (3)	−0.004 (2)
C2A	0.020 (3)	0.020 (3)	0.015 (3)	−0.003 (3)	0.000 (3)	−0.001 (2)
C3A	0.022 (3)	0.028 (3)	0.021 (3)	0.006 (3)	−0.002 (3)	−0.009 (2)
C4A	0.027 (3)	0.033 (3)	0.030 (3)	−0.002 (3)	0.003 (3)	−0.009 (3)
C5A	0.040 (4)	0.030 (3)	0.036 (3)	−0.006 (3)	−0.002 (3)	−0.015 (3)
C6A	0.047 (4)	0.054 (4)	0.042 (4)	0.008 (3)	0.006 (3)	−0.018 (3)
C7A	0.024 (4)	0.041 (3)	0.018 (3)	0.000 (3)	−0.004 (3)	−0.006 (3)
O1B	0.027 (3)	0.069 (3)	0.027 (2)	0.004 (3)	0.002 (2)	0.000 (2)
O2B	0.022 (3)	0.022 (2)	0.022 (2)	−0.001 (2)	0.001 (2)	0.0002 (18)
O3B	0.021 (3)	0.027 (2)	0.021 (2)	−0.001 (2)	−0.001 (2)	0.0006 (19)
N1B	0.020 (3)	0.043 (3)	0.018 (3)	0.001 (3)	0.002 (2)	0.008 (2)
N2B	0.021 (3)	0.029 (3)	0.021 (3)	−0.002 (2)	0.002 (2)	0.002 (2)
C1B	0.033 (4)	0.052 (4)	0.022 (3)	0.002 (3)	0.000 (3)	−0.004 (3)
C2B	0.022 (3)	0.036 (3)	0.017 (3)	0.003 (3)	0.001 (3)	0.009 (3)
C3B	0.021 (3)	0.024 (3)	0.015 (3)	0.000 (3)	0.002 (3)	0.005 (2)
C4B	0.029 (3)	0.019 (3)	0.018 (3)	0.000 (3)	−0.003 (3)	−0.005 (2)
C5B	0.046 (4)	0.033 (3)	0.047 (4)	−0.008 (3)	−0.004 (3)	0.000 (3)
C6B	0.040 (4)	0.035 (3)	0.034 (3)	−0.004 (3)	0.006 (3)	−0.003 (3)
C7B	0.017 (3)	0.025 (3)	0.013 (3)	0.003 (3)	−0.002 (2)	−0.003 (2)
O1C	0.024 (3)	0.035 (2)	0.026 (2)	−0.001 (2)	−0.007 (2)	−0.012 (2)
O2C	0.024 (3)	0.033 (2)	0.020 (2)	−0.001 (2)	−0.002 (2)	0.0057 (19)
O3C	0.023 (3)	0.037 (2)	0.019 (2)	−0.003 (2)	−0.002 (2)	−0.0003 (19)
N1C	0.021 (3)	0.019 (2)	0.018 (3)	0.000 (2)	−0.002 (2)	0.001 (2)
N2C	0.016 (2)	0.023 (2)	0.014 (2)	−0.0025 (19)	−0.0015 (19)	−0.0031 (18)
C1C	0.028 (4)	0.040 (3)	0.019 (3)	−0.001 (3)	0.001 (3)	−0.007 (3)
C2C	0.014 (3)	0.018 (3)	0.014 (3)	−0.004 (2)	0.000 (2)	−0.001 (2)
C3C	0.018 (3)	0.030 (3)	0.011 (3)	0.002 (3)	−0.001 (3)	−0.003 (2)
C4C	0.026 (3)	0.038 (3)	0.016 (3)	−0.008 (3)	0.002 (3)	−0.012 (3)
C5C	0.037 (4)	0.041 (3)	0.023 (3)	−0.007 (3)	0.001 (3)	−0.018 (3)
C6C	0.039 (4)	0.050 (4)	0.026 (3)	−0.005 (3)	0.010 (3)	−0.018 (3)
C7C	0.019 (2)	0.027 (2)	0.014 (2)	−0.003 (2)	−0.003 (2)	−0.0007 (19)
O1D	0.016 (2)	0.031 (2)	0.025 (2)	0.000 (2)	−0.002 (2)	−0.0079 (19)
O2D	0.024 (2)	0.020 (2)	0.021 (2)	0.000 (2)	−0.007 (2)	0.0001 (17)
O3D	0.020 (2)	0.022 (2)	0.014 (2)	−0.0032 (19)	0.0026 (18)	0.0019 (17)
N1D	0.017 (3)	0.018 (2)	0.012 (2)	0.001 (2)	0.002 (2)	−0.001 (2)
N2D	0.020 (2)	0.026 (2)	0.014 (2)	0.0020 (19)	0.0010 (18)	−0.0055 (17)
C1D	0.021 (3)	0.021 (3)	0.015 (3)	0.004 (3)	−0.003 (3)	0.001 (2)
C2D	0.018 (3)	0.024 (2)	0.013 (2)	0.004 (2)	0.002 (2)	0.000 (2)
C3D	0.014 (2)	0.016 (2)	0.011 (2)	0.001 (2)	0.0001 (19)	−0.0033 (18)
C4D	0.016 (2)	0.018 (2)	0.011 (2)	0.0000 (18)	−0.0029 (18)	0.0005 (17)
C5D	0.029 (3)	0.024 (3)	0.033 (3)	−0.001 (3)	0.001 (3)	0.003 (3)
C6D	0.028 (3)	0.026 (3)	0.023 (3)	−0.001 (3)	0.005 (3)	−0.002 (3)
C7D	0.015 (2)	0.015 (2)	0.010 (2)	−0.0029 (18)	−0.0007 (18)	−0.0014 (17)
O1E	0.023 (3)	0.046 (3)	0.027 (2)	0.004 (2)	−0.003 (2)	−0.005 (2)
O2E	0.027 (3)	0.018 (2)	0.022 (2)	0.004 (2)	−0.004 (2)	0.0014 (17)
O3E	0.020 (2)	0.034 (2)	0.018 (2)	0.0015 (19)	0.0018 (19)	0.0086 (19)
N1E	0.020 (3)	0.032 (3)	0.021 (3)	0.005 (2)	0.005 (2)	−0.002 (2)
N2E	0.018 (3)	0.029 (2)	0.014 (2)	−0.002 (2)	−0.001 (2)	0.002 (2)
C1E	0.030 (4)	0.043 (3)	0.027 (3)	0.005 (3)	0.001 (3)	−0.007 (3)
C2E	0.019 (3)	0.028 (3)	0.020 (3)	0.003 (3)	−0.003 (3)	0.003 (3)
C3E	0.021 (3)	0.019 (3)	0.014 (3)	0.001 (3)	−0.005 (3)	0.001 (2)
C4E	0.024 (3)	0.019 (3)	0.021 (3)	0.000 (3)	−0.005 (3)	−0.001 (2)
C5E	0.048 (4)	0.033 (3)	0.034 (3)	−0.007 (3)	−0.003 (3)	−0.002 (3)
C6E	0.044 (4)	0.033 (3)	0.027 (3)	0.007 (3)	−0.001 (3)	−0.008 (3)
C7E	0.019 (3)	0.021 (2)	0.013 (2)	0.000 (2)	−0.002 (2)	0.002 (2)
O1F	0.023 (3)	0.047 (3)	0.018 (2)	0.010 (2)	−0.003 (2)	−0.002 (2)
O2F	0.026 (3)	0.038 (2)	0.020 (2)	−0.001 (2)	0.001 (2)	−0.0038 (19)
O3F	0.024 (3)	0.045 (3)	0.022 (2)	0.003 (2)	0.001 (2)	0.005 (2)
N1F	0.016 (2)	0.025 (2)	0.012 (2)	0.0011 (19)	0.0017 (19)	0.0013 (18)
N2F	0.024 (2)	0.032 (2)	0.018 (2)	0.001 (2)	0.000 (2)	−0.0019 (19)
C1F	0.026 (4)	0.031 (3)	0.024 (3)	0.000 (3)	−0.002 (3)	−0.011 (3)
C2F	0.019 (3)	0.031 (3)	0.016 (3)	0.002 (3)	0.000 (3)	0.000 (3)
C3F	0.023 (3)	0.030 (3)	0.013 (3)	0.005 (3)	0.000 (3)	0.002 (2)
C4F	0.028 (3)	0.033 (3)	0.010 (3)	0.008 (3)	−0.002 (3)	−0.001 (3)
C5F	0.046 (4)	0.035 (3)	0.027 (3)	−0.002 (3)	−0.001 (3)	0.001 (3)
C6F	0.042 (4)	0.043 (3)	0.029 (3)	0.010 (3)	0.003 (3)	−0.004 (3)
C7F	0.018 (3)	0.030 (3)	0.016 (2)	0.004 (2)	−0.003 (2)	−0.003 (2)
O1G	0.027 (3)	0.060 (3)	0.028 (2)	0.006 (2)	−0.006 (2)	−0.012 (2)
O2G	0.024 (2)	0.0181 (19)	0.021 (2)	0.0020 (19)	−0.004 (2)	0.0010 (17)
O3G	0.017 (2)	0.033 (2)	0.017 (2)	0.0005 (19)	−0.0003 (19)	0.0023 (18)
N1G	0.022 (3)	0.049 (3)	0.015 (3)	0.005 (3)	−0.001 (2)	−0.001 (2)
N2G	0.016 (3)	0.037 (3)	0.018 (2)	0.000 (2)	−0.002 (2)	0.000 (2)
C1G	0.036 (4)	0.046 (4)	0.024 (3)	0.008 (3)	−0.003 (3)	−0.002 (3)
C2G	0.024 (3)	0.048 (3)	0.018 (3)	0.000 (3)	0.001 (3)	0.001 (3)
C3G	0.018 (3)	0.021 (3)	0.016 (3)	−0.002 (3)	−0.003 (3)	0.006 (2)
C4G	0.023 (3)	0.017 (3)	0.026 (3)	0.000 (2)	−0.003 (3)	−0.003 (3)
C5G	0.033 (4)	0.030 (3)	0.032 (3)	−0.006 (3)	−0.007 (3)	0.009 (3)
C6G	0.032 (4)	0.035 (3)	0.028 (3)	−0.001 (3)	0.000 (3)	−0.011 (3)
C7G	0.018 (3)	0.020 (2)	0.014 (2)	−0.002 (2)	0.000 (2)	−0.003 (2)

Geometric parameters (Å, º)

O1A—C2A	1.230 (4)	C3D—C4D	1.537 (4)
O2A—C7A	1.254 (4)	C3D—C7D	1.542 (4)
O3A—C7A	1.247 (4)	C3D—H31D	1.0000
N1A—C1A	1.480 (5)	C4D—C6D	1.522 (5)
N1A—H1A	0.9100	C4D—C5D	1.520 (5)
N1A—H2A	0.9100	C4D—H41D	1.0000
N1A—H3A	0.9100	C5D—H51D	0.9800
N2A—C2A	1.335 (4)	C5D—H52D	0.9800
N2A—C3A	1.452 (4)	C5D—H53D	0.9800
N2A—H4A	0.8800	C6D—H61D	0.9800
C1A—C2A	1.506 (4)	C6D—H62D	0.9800
C1A—H11A	0.9900	C6D—H63D	0.9800
C1A—H12A	0.9900	O1E—C2E	1.228 (4)
C3A—C7A	1.535 (4)	O2E—C7E	1.252 (4)
C3A—C4A	1.534 (5)	O3E—C7E	1.246 (4)
C3A—H31A	1.0000	N1E—C1E	1.475 (5)
C4A—C6A	1.517 (5)	N1E—H1E	0.9100
C4A—C5A	1.517 (5)	N1E—H2E	0.9100
C4A—H41A	1.0000	N1E—H3E	0.9100
C5A—H51A	0.9800	N2E—C2E	1.336 (4)
C5A—H52A	0.9800	N2E—C3E	1.450 (4)
C5A—H53A	0.9800	N2E—H4E	0.8800
C6A—H61A	0.9800	C1E—C2E	1.506 (5)
C6A—H62A	0.9800	C1E—H11E	0.9900
C6A—H63A	0.9800	C1E—H12E	0.9900
O1B—C2B	1.228 (4)	C3E—C4E	1.529 (4)
O2B—C7B	1.256 (4)	C3E—C7E	1.536 (4)
O3B—C7B	1.245 (4)	C3E—H31E	1.0000
N1B—C1B	1.476 (5)	C4E—C6E	1.518 (5)
N1B—H1B	0.9100	C4E—C5E	1.519 (5)
N1B—H2B	0.9100	C4E—H41E	1.0000
N1B—H3B	0.9100	C5E—H51E	0.9800
N2B—C2B	1.337 (4)	C5E—H52E	0.9800
N2B—C3B	1.452 (4)	C5E—H53E	0.9800
N2B—H4B	0.8800	C6E—H61E	0.9800
C1B—C2B	1.507 (5)	C6E—H62E	0.9800
C1B—H11B	0.9900	C6E—H63E	0.9800
C1B—H12B	0.9900	O1F—C2F	1.229 (4)
C3B—C7B	1.536 (4)	O2F—C7F	1.254 (4)
C3B—C4B	1.532 (4)	O3F—C7F	1.243 (4)
C3B—H31B	1.0000	N1F—C1F	1.476 (5)
C4B—C6B	1.519 (5)	N1F—H1F	0.9100
C4B—C5B	1.518 (5)	N1F—H2F	0.9100
C4B—H41B	1.0000	N1F—H3F	0.9100
C5B—H51B	0.9800	N2F—C2F	1.338 (4)
C5B—H52B	0.9800	N2F—C3F	1.453 (4)
C5B—H53B	0.9800	N2F—H4F	0.8800
C6B—H61B	0.9800	C1F—C2F	1.508 (5)
C6B—H62B	0.9800	C1F—H11F	0.9900
C6B—H63B	0.9800	C1F—H12F	0.9900
O1C—C2C	1.228 (4)	C3F—C4F	1.536 (4)
O2C—C7C	1.256 (4)	C3F—C7F	1.542 (4)
O3C—C7C	1.242 (4)	C3F—H31F	1.0000
N1C—C1C	1.480 (5)	C4F—C6F	1.519 (5)
N1C—H1C	0.9100	C4F—C5F	1.516 (5)
N1C—H2C	0.9100	C4F—H41F	1.0000
N1C—H3C	0.9100	C5F—H51F	0.9800
N2C—C2C	1.341 (4)	C5F—H52F	0.9800
N2C—C3C	1.458 (4)	C5F—H53F	0.9800
N2C—H4C	0.8800	C6F—H61F	0.9800
C1C—C2C	1.506 (5)	C6F—H62F	0.9800
C1C—H11C	0.9900	C6F—H63F	0.9800
C1C—H12C	0.9900	O1G—C2G	1.230 (4)
C3C—C4C	1.531 (4)	O2G—C7G	1.254 (4)
C3C—C7C	1.539 (4)	O3G—C7G	1.241 (4)
C3C—H31C	1.0000	N1G—C1G	1.479 (5)
C4C—C6C	1.521 (5)	N1G—H1G	0.9100
C4C—C5C	1.519 (5)	N1G—H2G	0.9100
C4C—H41C	1.0000	N1G—H3G	0.9100
C5C—H51C	0.9800	N2G—C2G	1.341 (4)
C5C—H52C	0.9800	N2G—C3G	1.457 (4)
C5C—H53C	0.9800	N2G—H4G	0.8800
C6C—H61C	0.9800	C1G—C2G	1.507 (5)
C6C—H62C	0.9800	C1G—H11G	0.9900
C6C—H63C	0.9800	C1G—H12G	0.9900
O1D—C2D	1.229 (4)	C3G—C4G	1.537 (5)
O2D—C7D	1.256 (4)	C3G—C7G	1.544 (4)
O3D—C7D	1.242 (4)	C3G—H31G	1.0000
N1D—C1D	1.481 (5)	C4G—C5G	1.512 (5)
N1D—H1D	0.9100	C4G—C6G	1.524 (5)
N1D—H2D	0.9100	C4G—H41G	1.0000
N1D—H3D	0.9100	C5G—H51G	0.9800
N2D—C2D	1.337 (4)	C5G—H52G	0.9800
N2D—C3D	1.455 (4)	C5G—H53G	0.9800
N2D—H4D	0.8800	C6G—H61G	0.9800
C1D—C2D	1.508 (5)	C6G—H62G	0.9800
C1D—H11D	0.9900	C6G—H63G	0.9800
C1D—H12D	0.9900
C1A—N1A—H1A	109.5	C7D—C3D—H31D	108.7
C1A—N1A—H2A	109.5	C6D—C4D—C5D	110.5 (4)
H1A—N1A—H2A	109.5	C6D—C4D—C3D	111.3 (4)
C1A—N1A—H3A	109.5	C5D—C4D—C3D	111.0 (3)
H1A—N1A—H3A	109.5	C6D—C4D—H41D	107.9
H2A—N1A—H3A	109.5	C5D—C4D—H41D	107.9
C2A—N2A—C3A	121.0 (4)	C3D—C4D—H41D	107.9
C2A—N2A—H4A	119.5	C4D—C5D—H51D	109.5
C3A—N2A—H4A	119.5	C4D—C5D—H52D	109.5
N1A—C1A—C2A	109.4 (4)	H51D—C5D—H52D	109.5
N1A—C1A—H11A	109.8	C4D—C5D—H53D	109.5
C2A—C1A—H11A	109.8	H51D—C5D—H53D	109.5
N1A—C1A—H12A	109.8	H52D—C5D—H53D	109.5
C2A—C1A—H12A	109.8	C4D—C6D—H61D	109.5
H11A—C1A—H12A	108.2	C4D—C6D—H62D	109.5
O1A—C2A—N2A	123.6 (4)	H61D—C6D—H62D	109.5
O1A—C2A—C1A	120.8 (3)	C4D—C6D—H63D	109.5
N2A—C2A—C1A	115.6 (4)	H61D—C6D—H63D	109.5
N2A—C3A—C7A	111.4 (3)	H62D—C6D—H63D	109.5
N2A—C3A—C4A	108.7 (3)	O3D—C7D—O2D	126.0 (4)
C7A—C3A—C4A	112.5 (4)	O3D—C7D—C3D	117.5 (4)
N2A—C3A—H31A	108.0	O2D—C7D—C3D	116.5 (3)
C7A—C3A—H31A	108.0	C1E—N1E—H1E	109.5
C4A—C3A—H31A	108.0	C1E—N1E—H2E	109.5
C6A—C4A—C5A	110.8 (4)	H1E—N1E—H2E	109.5
C6A—C4A—C3A	112.8 (4)	C1E—N1E—H3E	109.5
C5A—C4A—C3A	110.4 (4)	H1E—N1E—H3E	109.5
C6A—C4A—H41A	107.6	H2E—N1E—H3E	109.5
C5A—C4A—H41A	107.6	C2E—N2E—C3E	121.3 (4)
C3A—C4A—H41A	107.6	C2E—N2E—H4E	119.4
C4A—C5A—H51A	109.5	C3E—N2E—H4E	119.4
C4A—C5A—H52A	109.5	N1E—C1E—C2E	110.0 (4)
H51A—C5A—H52A	109.5	N1E—C1E—H11E	109.7
C4A—C5A—H53A	109.5	C2E—C1E—H11E	109.7
H51A—C5A—H53A	109.5	N1E—C1E—H12E	109.7
H52A—C5A—H53A	109.5	C2E—C1E—H12E	109.7
C4A—C6A—H61A	109.5	H11E—C1E—H12E	108.2
C4A—C6A—H62A	109.5	O1E—C2E—N2E	124.1 (4)
H61A—C6A—H62A	109.5	O1E—C2E—C1E	121.5 (4)
C4A—C6A—H63A	109.5	N2E—C2E—C1E	114.5 (4)
H61A—C6A—H63A	109.5	N2E—C3E—C4E	108.8 (3)
H62A—C6A—H63A	109.5	N2E—C3E—C7E	111.1 (3)
O2A—C7A—O3A	125.7 (4)	C4E—C3E—C7E	112.9 (3)
O2A—C7A—C3A	117.3 (4)	N2E—C3E—H31E	108.0
O3A—C7A—C3A	117.0 (4)	C4E—C3E—H31E	108.0
C1B—N1B—H1B	109.5	C7E—C3E—H31E	108.0
C1B—N1B—H2B	109.5	C6E—C4E—C5E	110.2 (4)
H1B—N1B—H2B	109.5	C6E—C4E—C3E	112.9 (4)
C1B—N1B—H3B	109.5	C5E—C4E—C3E	111.2 (4)
H1B—N1B—H3B	109.5	C6E—C4E—H41E	107.4
H2B—N1B—H3B	109.5	C5E—C4E—H41E	107.4
C2B—N2B—C3B	121.2 (4)	C3E—C4E—H41E	107.4
C2B—N2B—H4B	119.4	C4E—C5E—H51E	109.5
C3B—N2B—H4B	119.4	C4E—C5E—H52E	109.5
N1B—C1B—C2B	110.1 (4)	H51E—C5E—H52E	109.5
N1B—C1B—H11B	109.6	C4E—C5E—H53E	109.5
C2B—C1B—H11B	109.6	H51E—C5E—H53E	109.5
N1B—C1B—H12B	109.6	H52E—C5E—H53E	109.5
C2B—C1B—H12B	109.6	C4E—C6E—H61E	109.5
H11B—C1B—H12B	108.2	C4E—C6E—H62E	109.5
O1B—C2B—N2B	124.3 (4)	H61E—C6E—H62E	109.5
O1B—C2B—C1B	120.9 (4)	C4E—C6E—H63E	109.5
N2B—C2B—C1B	114.7 (4)	H61E—C6E—H63E	109.5
N2B—C3B—C7B	110.9 (3)	H62E—C6E—H63E	109.5
N2B—C3B—C4B	109.4 (3)	O2E—C7E—O3E	125.5 (4)
C7B—C3B—C4B	112.5 (3)	O2E—C7E—C3E	118.0 (3)
N2B—C3B—H31B	108.0	O3E—C7E—C3E	116.5 (4)
C7B—C3B—H31B	108.0	C1F—N1F—H1F	109.5
C4B—C3B—H31B	108.0	C1F—N1F—H2F	109.5
C6B—C4B—C5B	110.2 (4)	H1F—N1F—H2F	109.5
C6B—C4B—C3B	112.8 (4)	C1F—N1F—H3F	109.5
C5B—C4B—C3B	111.0 (4)	H1F—N1F—H3F	109.5
C6B—C4B—H41B	107.5	H2F—N1F—H3F	109.5
C5B—C4B—H41B	107.5	C2F—N2F—C3F	121.4 (4)
C3B—C4B—H41B	107.5	C2F—N2F—H4F	119.3
C4B—C5B—H51B	109.5	C3F—N2F—H4F	119.3
C4B—C5B—H52B	109.5	N1F—C1F—C2F	110.1 (4)
H51B—C5B—H52B	109.5	N1F—C1F—H11F	109.6
C4B—C5B—H53B	109.5	C2F—C1F—H11F	109.6
H51B—C5B—H53B	109.5	N1F—C1F—H12F	109.6
H52B—C5B—H53B	109.5	C2F—C1F—H12F	109.6
C4B—C6B—H61B	109.5	H11F—C1F—H12F	108.2
C4B—C6B—H62B	109.5	O1F—C2F—N2F	123.9 (4)
H61B—C6B—H62B	109.5	O1F—C2F—C1F	121.1 (3)
C4B—C6B—H63B	109.5	N2F—C2F—C1F	115.0 (4)
H61B—C6B—H63B	109.5	N2F—C3F—C4F	109.4 (3)
H62B—C6B—H63B	109.5	N2F—C3F—C7F	110.3 (3)
O2B—C7B—O3B	125.4 (4)	C4F—C3F—C7F	111.7 (3)
O2B—C7B—C3B	117.6 (3)	N2F—C3F—H31F	108.4
O3B—C7B—C3B	117.0 (4)	C4F—C3F—H31F	108.4
C1C—N1C—H1C	109.5	C7F—C3F—H31F	108.4
C1C—N1C—H2C	109.5	C6F—C4F—C5F	110.3 (4)
H1C—N1C—H2C	109.5	C6F—C4F—C3F	112.1 (4)
C1C—N1C—H3C	109.5	C5F—C4F—C3F	111.1 (4)
H1C—N1C—H3C	109.5	C6F—C4F—H41F	107.7
H2C—N1C—H3C	109.5	C5F—C4F—H41F	107.7
C2C—N2C—C3C	120.9 (4)	C3F—C4F—H41F	107.7
C2C—N2C—H4C	119.5	C4F—C5F—H51F	109.5
C3C—N2C—H4C	119.5	C4F—C5F—H52F	109.5
N1C—C1C—C2C	110.0 (4)	H51F—C5F—H52F	109.5
N1C—C1C—H11C	109.7	C4F—C5F—H53F	109.5
C2C—C1C—H11C	109.7	H51F—C5F—H53F	109.5
N1C—C1C—H12C	109.7	H52F—C5F—H53F	109.5
C2C—C1C—H12C	109.7	C4F—C6F—H61F	109.5
H11C—C1C—H12C	108.2	C4F—C6F—H62F	109.5
O1C—C2C—N2C	123.6 (4)	H61F—C6F—H62F	109.5
O1C—C2C—C1C	121.2 (3)	C4F—C6F—H63F	109.5
N2C—C2C—C1C	115.1 (3)	H61F—C6F—H63F	109.5
N2C—C3C—C4C	109.1 (3)	H62F—C6F—H63F	109.5
N2C—C3C—C7C	109.9 (3)	O2F—C7F—O3F	125.8 (4)
C4C—C3C—C7C	112.4 (3)	O2F—C7F—C3F	117.2 (4)
N2C—C3C—H31C	108.5	O3F—C7F—C3F	117.0 (4)
C4C—C3C—H31C	108.5	C1G—N1G—H1G	109.5
C7C—C3C—H31C	108.5	C1G—N1G—H2G	109.5
C6C—C4C—C5C	110.5 (4)	H1G—N1G—H2G	109.5
C6C—C4C—C3C	112.5 (4)	C1G—N1G—H3G	109.5
C5C—C4C—C3C	110.6 (4)	H1G—N1G—H3G	109.5
C6C—C4C—H41C	107.7	H2G—N1G—H3G	109.5
C5C—C4C—H41C	107.7	C2G—N2G—C3G	120.0 (4)
C3C—C4C—H41C	107.7	C2G—N2G—H4G	120.0
C4C—C5C—H51C	109.5	C3G—N2G—H4G	120.0
C4C—C5C—H52C	109.5	N1G—C1G—C2G	109.6 (4)
H51C—C5C—H52C	109.5	N1G—C1G—H11G	109.7
C4C—C5C—H53C	109.5	C2G—C1G—H11G	109.7
H51C—C5C—H53C	109.5	N1G—C1G—H12G	109.7
H52C—C5C—H53C	109.5	C2G—C1G—H12G	109.7
C4C—C6C—H61C	109.5	H11G—C1G—H12G	108.2
C4C—C6C—H62C	109.5	O1G—C2G—N2G	123.8 (4)
H61C—C6C—H62C	109.5	O1G—C2G—C1G	120.9 (4)
C4C—C6C—H63C	109.5	N2G—C2G—C1G	115.2 (4)
H61C—C6C—H63C	109.5	N2G—C3G—C4G	109.6 (3)
H62C—C6C—H63C	109.5	N2G—C3G—C7G	109.6 (3)
O3C—C7C—O2C	126.0 (4)	C4G—C3G—C7G	110.5 (3)
O3C—C7C—C3C	117.7 (4)	N2G—C3G—H31G	109.0
O2C—C7C—C3C	116.2 (4)	C4G—C3G—H31G	109.0
C1D—N1D—H1D	109.5	C7G—C3G—H31G	109.0
C1D—N1D—H2D	109.5	C5G—C4G—C6G	111.0 (4)
H1D—N1D—H2D	109.5	C5G—C4G—C3G	111.1 (4)
C1D—N1D—H3D	109.5	C6G—C4G—C3G	111.3 (4)
H1D—N1D—H3D	109.5	C5G—C4G—H41G	107.7
H2D—N1D—H3D	109.5	C6G—C4G—H41G	107.7
C2D—N2D—C3D	120.3 (4)	C3G—C4G—H41G	107.7
C2D—N2D—H4D	119.9	C4G—C5G—H51G	109.5
C3D—N2D—H4D	119.9	C4G—C5G—H52G	109.5
N1D—C1D—C2D	109.2 (3)	H51G—C5G—H52G	109.5
N1D—C1D—H11D	109.8	C4G—C5G—H53G	109.5
C2D—C1D—H11D	109.8	H51G—C5G—H53G	109.5
N1D—C1D—H12D	109.8	H52G—C5G—H53G	109.5
C2D—C1D—H12D	109.8	C4G—C6G—H61G	109.5
H11D—C1D—H12D	108.3	C4G—C6G—H62G	109.5
O1D—C2D—N2D	123.8 (4)	H61G—C6G—H62G	109.5
O1D—C2D—C1D	120.6 (4)	C4G—C6G—H63G	109.5
N2D—C2D—C1D	115.6 (4)	H61G—C6G—H63G	109.5
N2D—C3D—C4D	109.0 (3)	H62G—C6G—H63G	109.5
N2D—C3D—C7D	110.0 (3)	O3G—C7G—O2G	126.2 (4)
C4D—C3D—C7D	111.8 (3)	O3G—C7G—C3G	117.8 (4)
N2D—C3D—H31D	108.7	O2G—C7G—C3G	115.9 (3)
C4D—C3D—H31D	108.7
C3A—N2A—C2A—O1A	−8.7 (9)	C7D—C3D—C4D—C6D	54.0 (5)
C3A—N2A—C2A—C1A	170.5 (5)	N2D—C3D—C4D—C5D	−60.6 (5)
N1A—C1A—C2A—O1A	−31.0 (8)	C7D—C3D—C4D—C5D	177.6 (4)
N1A—C1A—C2A—N2A	149.7 (5)	N2D—C3D—C7D—O3D	146.6 (5)
C2A—N2A—C3A—C7A	−63.3 (6)	C4D—C3D—C7D—O3D	−92.2 (6)
C2A—N2A—C3A—C4A	172.3 (5)	N2D—C3D—C7D—O2D	−35.8 (6)
N2A—C3A—C4A—C6A	174.2 (5)	C4D—C3D—C7D—O2D	85.4 (5)
C7A—C3A—C4A—C6A	50.4 (6)	C3E—N2E—C2E—O1E	−10.0 (9)
N2A—C3A—C4A—C5A	−61.3 (6)	C3E—N2E—C2E—C1E	171.4 (5)
C7A—C3A—C4A—C5A	174.8 (5)	N1E—C1E—C2E—O1E	−16.7 (9)
N2A—C3A—C7A—O2A	−30.5 (7)	N1E—C1E—C2E—N2E	161.9 (5)
C4A—C3A—C7A—O2A	91.9 (6)	C2E—N2E—C3E—C4E	170.5 (5)
N2A—C3A—C7A—O3A	149.7 (5)	C2E—N2E—C3E—C7E	−64.6 (6)
C4A—C3A—C7A—O3A	−87.9 (6)	N2E—C3E—C4E—C6E	173.8 (4)
C3B—N2B—C2B—O1B	−5.3 (10)	C7E—C3E—C4E—C6E	50.0 (6)
C3B—N2B—C2B—C1B	173.1 (5)	N2E—C3E—C4E—C5E	−61.7 (5)
N1B—C1B—C2B—O1B	−3.3 (10)	C7E—C3E—C4E—C5E	174.4 (4)
N1B—C1B—C2B—N2B	178.2 (5)	N2E—C3E—C7E—O2E	−27.5 (6)
C2B—N2B—C3B—C7B	−71.1 (6)	C4E—C3E—C7E—O2E	95.1 (5)
C2B—N2B—C3B—C4B	164.3 (5)	N2E—C3E—C7E—O3E	152.7 (5)
N2B—C3B—C4B—C6B	176.9 (5)	C4E—C3E—C7E—O3E	−84.8 (6)
C7B—C3B—C4B—C6B	53.2 (6)	C3F—N2F—C2F—O1F	−9.7 (9)
N2B—C3B—C4B—C5B	−58.9 (6)	C3F—N2F—C2F—C1F	171.8 (5)
C7B—C3B—C4B—C5B	177.4 (5)	N1F—C1F—C2F—O1F	8.3 (9)
N2B—C3B—C7B—O2B	−26.3 (6)	N1F—C1F—C2F—N2F	−173.3 (5)
C4B—C3B—C7B—O2B	96.6 (5)	C2F—N2F—C3F—C4F	168.1 (5)
N2B—C3B—C7B—O3B	154.8 (5)	C2F—N2F—C3F—C7F	−68.5 (6)
C4B—C3B—C7B—O3B	−82.3 (6)	N2F—C3F—C4F—C6F	178.5 (5)
C3C—N2C—C2C—O1C	−14.4 (8)	C7F—C3F—C4F—C6F	56.0 (6)
C3C—N2C—C2C—C1C	166.0 (5)	N2F—C3F—C4F—C5F	−57.6 (6)
N1C—C1C—C2C—O1C	1.5 (8)	C7F—C3F—C4F—C5F	179.9 (4)
N1C—C1C—C2C—N2C	−178.9 (5)	N2F—C3F—C7F—O2F	−29.3 (6)
C2C—N2C—C3C—C4C	172.1 (5)	C4F—C3F—C7F—O2F	92.7 (5)
C2C—N2C—C3C—C7C	−64.3 (6)	N2F—C3F—C7F—O3F	151.9 (5)
N2C—C3C—C4C—C6C	177.0 (5)	C4F—C3F—C7F—O3F	−86.1 (6)
C7C—C3C—C4C—C6C	54.9 (6)	C3G—N2G—C2G—O1G	−13.9 (10)
N2C—C3C—C4C—C5C	−58.9 (6)	C3G—N2G—C2G—C1G	164.2 (5)
C7C—C3C—C4C—C5C	179.0 (5)	N1G—C1G—C2G—O1G	−17.1 (10)
N2C—C3C—C7C—O3C	151.6 (5)	N1G—C1G—C2G—N2G	164.8 (6)
C4C—C3C—C7C—O3C	−86.8 (6)	C2G—N2G—C3G—C4G	178.0 (5)
N2C—C3C—C7C—O2C	−31.3 (6)	C2G—N2G—C3G—C7G	−60.6 (6)
C4C—C3C—C7C—O2C	90.3 (5)	N2G—C3G—C4G—C5G	−60.0 (5)
C3D—N2D—C2D—O1D	−10.0 (8)	C7G—C3G—C4G—C5G	179.1 (4)
C3D—N2D—C2D—C1D	168.1 (4)	N2G—C3G—C4G—C6G	175.7 (4)
N1D—C1D—C2D—O1D	−28.4 (8)	C7G—C3G—C4G—C6G	54.8 (5)
N1D—C1D—C2D—N2D	153.4 (5)	N2G—C3G—C7G—O3G	147.1 (5)
C2D—N2D—C3D—C4D	175.4 (5)	C4G—C3G—C7G—O3G	−92.1 (6)
C2D—N2D—C3D—C7D	−61.8 (6)	N2G—C3G—C7G—O2G	−35.9 (6)
N2D—C3D—C4D—C6D	175.8 (4)	C4G—C3G—C7G—O2G	85.0 (5)