Intermolecular hydrogen bonding of the two independent mol­ecules of N-3,5-di­nitro­benzoyl-L-leucine

The title compound, C₁₃H₁₅N₃O₇, crystallizes as two independent mol­ecules which differ in their conformation. Intermolecular hydrogen bonding between the amide and carboxyl­ic acid groups as N-H...O=C interactions results in the formation of one-dimensional chains with N...O distances of 2.967 (6) and 3.019 (6) Å. Neighbouring chains are linked by C=O...H-O interactions to form a two-dimensional network, with O...O distances of 2.675 (6) and 2.778 (6) Å.

S1. Comment

The study of biologically important molecules continues to be of primary importance in medicinal chemistry. Processes such as blood coagulation, hormone processing, viral replication and cancer-cell invasion are critically ependent on protease enzymes which are attractive target molecules in the design of specific and selective drugs. Important protease inhibitors are usually based on modified amino acids incorporating structural features which determine normal enzyme-substrate recognition processes. Structure-based drug design strategies to identify interactions between a potential inhibitor and target receptor require accurate inhibitor structures. We are currently studying structure–activity relationships and molecular-recognition processes in biologically important molecules such as the title compound N-3,5-dinitrobenzoyl-L-leucine, (I), for applications in drug design (Gallagher & Murphy, 1999; Gallagher et al., 1999, 2000).

In (I), two independent molecules are present which differ in conformation in space group P1 (No. 1). The bond lengths are largely in accord with anticipated values (Orpen et al., 1994). The molecules differ in conformation about the N1—C2 bond, with N1—C2—C4 angles of 115.9 (5) and 110.1 (5)°, and C1—N1—C2—C3 torsion angles of -56.1 (7) and 81.5 (7)° in A and B, respectively. The aromatic C1—C11—C12 and C1—C11—C16 angles are 123.1 (6)/116.7 (6)° in molecule A and 125.6 (5)/116.6 (5)° in molecule B. This results from the intramolecular contacts H16A···O5A 2.45 Å and H1A···H12A 2.08 Å in A, and H16B···O5B, 2.42 Å and H1B···H12B, 2.14 Å in B (O5B···H2B 2.48 Å). The aromatic ring planes are oriented at angles of 19.1 (4) (A) and 12.8 (6)° (B) to their respective amide groups (O5/C1/N1/C2) and the nitro groups are almost coplanar (<10° from the aromatic ring planes), with O4A deviating by 0.265 (11) Å from the C₆ ring plane. The carboxylate (C2/C3/O6/O7) groups are almost normal to the (C11/C1/O5/N1/C2) planes, with angles of 85.9 (2) and 79.1 (2)° in molecules A and B, respectively.

The molecules are aligned in one-dimensional chains as [A···]_n and [B···]_n with (amide)_[A/B]N—H···O═C_[A/B](acid) hydrogen bonds and partial overlap due to π–π stacking of the 3,5-dinitrobenzoyl groups. The N···O distances are 2.967 (6) Å along [A···]_n and 3.019 (6) Å along [B···]_n. Interactions between the neighbouring A and B chains arise as carboxylate (for A → B) and 2.778 (6) Å (for B → A) (where → indicates the direction of the hydrogen bonding). This association results in the formation of two 20-membered hydrogen-bonded ring systems each consisting of two A and two B molecules and differing by the direction of the hydrogen bonding, [B···]_n → [A..]_n and [A···]_n → [B···]_n (where → indicates the carboxylic acid to amide O═C hydrogen bonds). Both rings have graph-set R⁴₄(20) which repeats as a two-dimensional network in the lattice (rings J and K in the deposited figure). Examination of the structure with PLATON (Spek, 1998) showed that there were no solvent-accessible voids.

The structure of L-Leucine has been reported previously (Harding & Howieson, 1976; Coll et al., 1986; Görbitz & Dalhus, 1996) and contains two crystallographically independent zwitterions having similar conformations in the asymmetric unit, unlike (I) above, where the two molecules differ significantly in conformation.

S2. Experimental

N-3,5-Dinitrobenzoyl-L-leucine was synthesized by the reaction of 3,5-dinitrobenzoyl chloride with the parent L-leucine. Recrystallization from ethanol/water afforded colourless plate-like crystals suitable for X-ray analysis [m.p. 451–453 K (uncorrected); literature 187° (Vogel, 1989)]. IR ν_max(KBr): 3400, 1725, 1650, 1550, 1350 cm^{-1. 1}H NMR data (400 MHz, δ, DMSO): 0.87–0.94 [6H, d, J = 6.4 Hz, C(CH₃)₂], 1.59–1.82 (3H, m, CH₂CH), 4.47–4.53 (1H, m, NCHCO₂), 8.38 (1H, d, J = 7.9 Hz, NH), 8.96 (1H, t, J = 2 Hz, ArH-para), 9.10 (2H, d, J = 2 Hz, ArH-ortho).

S3. Refinement

Molecule (I) crystallized in the triclinic system, space group P1 or P1. The molecule is chiral and space group P1 was chosen and confirmed by the analysis. The absolute configuration is based on L-leucine. The crystal diffracted quite weakly but sufficient data (hemisphere) were collected to establish the structure and elucidate the hydrogen bonding interactions. The absolute structure is not reliably determined by this X-ray analysis, but is inferred from the known absolute configuration of the L-leucine used in the synthesis.

Computing details

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: SET4 and CELDIM (Enraf-Nonius, 1992); data reduction: DATRD2 in NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: NRCVAX96, SHELXL97 and PREP8 (Ferguson, 1998).

3,5-dinitro-N`-[(1R)-1,3-dimethylbutyl]benzamide

Crystal data

C13H15N3O7	F(000) = 340
Mr = 325.28	Dx = 1.471 Mg m^−3
Triclinic, P1	Melting point: 452 K
a = 5.8046 (3) Å	Mo Kα radiation, λ = 0.7107 Å
b = 10.6400 (17) Å	Cell parameters from 25 reflections
c = 12.9556 (14) Å	θ = 9.3–22.0°
α = 109.428 (11)°	µ = 0.12 mm^−1
β = 102.416 (7)°	T = 294 K
γ = 90.250 (8)°	Plate, colourless
V = 734.44 (15) Å^3	0.30 × 0.20 × 0.05 mm
Z = 2

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.00
Radiation source: X-ray tube	θmax = 25.0°, θmin = 1.7°
Graphite monochromator	h = 0→6
ω–2θ scans	k = −12→12
2621 measured reflections	l = −15→14
2621 independent reflections	3 standard reflections every 60 min
1326 reflections with I > 2σ(I)	intensity decay: <1%

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.045	Calculated w = 1/[σ^2(Fo^2) + (0.0242P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.079	(Δ/σ)max = 0.001
S = 0.94	Δρmax = 0.19 e Å^−3
2621 reflections	Δρmin = −0.18 e Å^−3
418 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.0111 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.1 (16)

Special details

Experimental. Molecule (I) crystallized in the triclinic system, space group P1 or P-1, the molecule is chiral, space group P1 chosen and confirmed by the analysis. The absolute configuration is based on L-leucine. The plate diffracted quite weakly but sufficient data were collected to establish the structure and elucidate the hydrogen bonding interactions in the crystal structure.

Geometry. ############################################################# Hydrogen bonds with H.·A < r(A) + 2.000 Angstroms and <DHA> 110 °.

D—H d(D—H) d(H.·A) <DHA d(D.·A) A symmetry code O6A—H1 0.82 1.858 173.4 2.675 O5B [x, y - 1, z] N1A—H1A 0.86 2.151 158.1 2.967 O7A [x - 1, y, z] O6B—H2 0.82 1.973 166.9 2.778 O5A N1B—H1B 0.86 2.171 168.2 3.018 O7B [x + 1, y, z]

The e.s.d's are provided in the hydrogen bonding table #############################################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

1.4324(0.0226)x - 8.4976(0.0147)y - 3.7862(0.0316)z = 3.8408(0.0171)

* -0.0176 (0.0017) O5A * -0.0326 (0.0032) N1A * 0.0355 (0.0035) C1A * 0.0148 (0.0015) C2A

Rms deviation of fitted atoms = 0.0267

3.1338(0.0123)x - 7.8681(0.0181)y - 3.1512(0.0293)z = 4.0784(0.0086)

Angle to previous plane (with approximate e.s.d.) = 19.1 (4)

* -0.0177 (0.0040) C11A * 0.0125 (0.0040) C12A * 0.0013 (0.0041) C13A * -0.0098 (0.0039) C14A * 0.0048 (0.0040) C15A * 0.0090 (0.0040) C16A

Rms deviation of fitted atoms = 0.0106

3.2357(0.0198)x + 7.3943(0.0383)y + 0.7900(0.0408)z = 3.7470(0.0266)

Angle to previous plane (with approximate e.s.d.) = 66.7 (3)

* 0.0032 (0.0017) C11B * -0.0068 (0.0035) C12B * 0.0069 (0.0036) C13B * -0.0033 (0.0017) C14B -0.0158 (0.0112) C15B -0.0073 (0.0108) C16B

Rms deviation of fitted atoms = 0.0054

2.0972(0.0252)x + 8.4695(0.0162)y + 1.2906(0.0425)z = 2.5986(0.0194)

Angle to previous plane (with approximate e.s.d.) = 12.8 (6)

* 0.0087 (0.0018) O5B * 0.0158 (0.0033) N1B * -0.0172 (0.0036) C1B * -0.0073 (0.0015) C2B

Rms deviation of fitted atoms = 0.0130

0.1321(0.0174)x - 6.1943(0.0298)y + 12.1178(0.0157)z = 6.9518(0.0191)

Angle to previous plane (with approximate e.s.d.) = 86.4 (2)

* 0.0027 (0.0014) C2A * -0.0095 (0.0050) C3A * 0.0030 (0.0016) O6A * 0.0038 (0.0020) O7A

Rms deviation of fitted atoms = 0.0055

1.9382(0.0158)x - 8.5511(0.0142)y - 3.3487(0.0252)z = 4.1706(0.0096)

Angle to previous plane (with approximate e.s.d.) = 85.9 (2)

* 0.0718 (0.0027) C11A * -0.0496 (0.0050) C1A * -0.0050 (0.0019) O5A * -0.1004 (0.0038) N1A * 0.0833 (0.0028) C2A 1.4275 (0.0080) C3A 2.4225 (0.0063) O6A 1.5840 (0.0087) O7A

Rms deviation of fitted atoms = 0.0702

3.0932(0.0577)x - 6.9842(0.0750)y - 5.0418(0.0556)z = 3.7619(0.0764)

Angle to previous plane (with approximate e.s.d.) = 14.5 (9)

* 0.0000 (0.0000) O1A * 0.0000 (0.0000) O2A * 0.0000 (0.0000) N13A

Rms deviation of fitted atoms = 0.0000

3.1338(0.0123)x - 7.8681(0.0181)y - 3.1512(0.0293)z = 4.0784(0.0086)

Angle to previous plane (with approximate e.s.d.) = 9(1)

* -0.0177 (0.0040) C11A * 0.0125 (0.0040) C12A * 0.0013 (0.0041) C13A * -0.0098 (0.0039) C14A * 0.0048 (0.0040) C15A * 0.0090 (0.0040) C16A 0.2337 (0.0115) O1A -0.0979 (0.0103) O2A 0.0742 (0.0102) O3A 0.2646 (0.0111) O4A

Rms deviation of fitted atoms = 0.0106

2.5273(0.0345)x - 8.6928(0.0806)y - 2.2350(0.1700)z = 4.3002(0.0146)

Angle to previous plane (with approximate e.s.d.) = 8(1)

* 0.0000 (0.0000) O3A * 0.0000 (0.0000) O4A * 0.0000 (0.0000) N15A

Rms deviation of fitted atoms = 0.0000

-0.1072(0.0170)x - 3.3152(0.0310)y + 12.6956(0.0080)z = 3.4061(0.0129)

Angle to previous plane (with approximate e.s.d.) = 83.3 (8)

* -0.0046 (0.0015) C2B * 0.0161 (0.0052) C3B * -0.0051 (0.0016) O6B * -0.0064 (0.0021) O7B

Rms deviation of fitted atoms = 0.0093

2.2650(0.0167)x + 8.4269(0.0167)y + 1.0323(0.0264)z = 2.7078(0.0151)

Angle to previous plane (with approximate e.s.d.) = 79.1 (2)

* -0.0241 (0.0029) C11B * 0.0110 (0.0052) C1B * 0.0057 (0.0019) O5B * 0.0376 (0.0040) N1B * -0.0302 (0.0030) C2B -1.4508 (0.0079) C3B -2.2726 (0.0070) O6B -1.8396 (0.0092) O7B

Rms deviation of fitted atoms = 0.0247

3.0500(0.0548)x + 7.0653(0.0761)y + 1.9481(0.0401)z = 3.4487(0.1058)

Angle to previous plane (with approximate e.s.d.) = 11 (1)

* 0.0000 (0.0000) O1B * 0.0000 (0.0000) O2B * 0.0000 (0.0000) N13B

Rms deviation of fitted atoms = 0.0000

3.2226(0.0115)x + 7.4322(0.0185)y + 0.7487(0.0306)z = 3.7300(0.0152)

Angle to previous plane (with approximate e.s.d.) = 5(1)

* 0.0056 (0.0040) C11B * -0.0094 (0.0041) C12B * 0.0057 (0.0039) C13B * 0.0019 (0.0040) C14B * -0.0056 (0.0039) C15B * 0.0017 (0.0037) C16B -0.0464 (0.0102) O1B 0.1540 (0.0101) O2B -0.0499 (0.0103) O3B -0.0760 (0.0111) O4B

Rms deviation of fitted atoms = 0.0056

3.1236(0.0237)x + 7.6903(0.0834)y + 0.4769(0.1366)z = 3.6761(0.0353)

Angle to previous plane (with approximate e.s.d.) = 2(1)

* 0.0000 (0.0001) O3B * 0.0000 (0.0000) O4B * 0.0000 (0.0000) N15B

Rms deviation of fitted atoms = 0.0000

0.1321(0.0174)x - 6.1943(0.0298)y + 12.1178(0.0157)z = 6.9518(0.0191)

Angle to previous plane (with approximate e.s.d.) = 86.5 (6)

* 0.0027 (0.0014) C2A * -0.0095 (0.0050) C3A * 0.0030 (0.0016) O6A * 0.0038 (0.0020) O7A

Rms deviation of fitted atoms = 0.0055

1.9382(0.0158)x - 8.5511(0.0142)y - 3.3487(0.0252)z = 4.1706(0.0096)

Angle to previous plane (with approximate e.s.d.) = 85.9 (2)

* 0.0718 (0.0027) C11A * -0.0496 (0.0050) C1A * -0.0050 (0.0019) O5A * -0.1004 (0.0038) N1A * 0.0833 (0.0028) C2A 1.4275 (0.0080) C3A 2.4225 (0.0063) O6A 1.5840 (0.0087) O7A

Rms deviation of fitted atoms = 0.0702

#############################################################

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

	x	y	z	Uiso*/Ueq
O1A	−0.4819 (9)	−0.7250 (5)	−0.0375 (5)	0.0719 (17)
O2A	−0.6294 (8)	−0.6808 (5)	−0.1891 (4)	0.0659 (15)
O3A	−0.1298 (10)	−0.4481 (6)	−0.3281 (4)	0.0735 (16)
O4A	0.2254 (10)	−0.3699 (5)	−0.2305 (4)	0.0773 (19)
O5A	0.5199 (7)	−0.4204 (4)	0.1304 (3)	0.0489 (12)
O6A	0.5216 (8)	−0.7293 (5)	0.1954 (4)	0.0577 (15)
O7A	0.8415 (8)	−0.5861 (5)	0.2652 (4)	0.0562 (14)
N1A	0.2786 (7)	−0.4975 (4)	0.2161 (4)	0.0332 (12)
N13A	−0.4699 (10)	−0.6702 (6)	−0.1061 (5)	0.0480 (16)
N15A	0.0309 (13)	−0.4234 (6)	−0.2424 (5)	0.0599 (18)
C1A	0.3212 (12)	−0.4608 (6)	0.1319 (5)	0.0371 (16)
C2A	0.4677 (10)	−0.5118 (6)	0.3072 (5)	0.0382 (16)
C3A	0.6341 (11)	−0.6104 (7)	0.2540 (5)	0.0373 (16)
C4A	0.6007 (10)	−0.3821 (6)	0.3917 (5)	0.0440 (17)
C5A	0.4494 (13)	−0.2787 (7)	0.4486 (6)	0.059 (2)
C6A	0.2926 (13)	−0.3303 (7)	0.5070 (6)	0.071 (2)
C7A	0.6157 (15)	−0.1592 (7)	0.5321 (6)	0.078 (3)
C11A	0.1181 (11)	−0.4819 (6)	0.0320 (5)	0.0295 (15)
C12A	−0.0895 (11)	−0.5607 (6)	0.0128 (6)	0.0429 (18)
C13A	−0.2542 (12)	−0.5850 (6)	−0.0868 (5)	0.0368 (17)
C14A	−0.2275 (11)	−0.5394 (6)	−0.1706 (5)	0.0422 (17)
C15A	−0.0151 (12)	−0.4648 (6)	−0.1501 (5)	0.0396 (17)
C16A	0.1583 (11)	−0.4360 (6)	−0.0511 (5)	0.0397 (17)
O1B	1.6660 (8)	−0.2243 (5)	−0.0248 (4)	0.0556 (14)
O2B	1.6924 (8)	−0.1932 (5)	−0.1787 (4)	0.0589 (14)
O3B	1.1084 (9)	0.0490 (5)	−0.3425 (4)	0.0609 (15)
O4B	0.8509 (9)	0.1480 (5)	−0.2506 (4)	0.0626 (15)
O5B	0.7998 (8)	0.0957 (4)	0.0924 (3)	0.0495 (13)
O6B	0.8681 (7)	−0.2087 (4)	0.2207 (4)	0.0542 (13)
O7B	0.5687 (8)	−0.0807 (5)	0.2515 (4)	0.0569 (14)
N1B	1.0817 (8)	0.0113 (5)	0.1938 (4)	0.0357 (13)
N13B	1.6006 (10)	−0.1758 (5)	−0.0983 (5)	0.0481 (16)
N15B	1.0197 (11)	0.0801 (6)	−0.2613 (5)	0.0482 (16)
C1B	0.9895 (11)	0.0440 (6)	0.1033 (5)	0.0333 (15)
C2B	0.9563 (10)	0.0261 (6)	0.2828 (5)	0.0384 (17)
C3B	0.7752 (11)	−0.0901 (7)	0.2526 (5)	0.0397 (17)
C4B	1.1331 (10)	0.0490 (7)	0.3946 (5)	0.0403 (17)
C5B	1.2654 (12)	0.1887 (7)	0.4399 (6)	0.0519 (19)
C6B	1.1159 (14)	0.2964 (7)	0.4946 (6)	0.083 (3)
C7B	1.4961 (13)	0.1931 (9)	0.5244 (7)	0.093 (3)
C11B	1.1189 (11)	0.0163 (6)	0.0119 (5)	0.0319 (15)
C12B	1.3046 (11)	−0.0650 (6)	−0.0003 (5)	0.0365 (17)
C13B	1.3967 (10)	−0.0937 (6)	−0.0917 (5)	0.0308 (15)
C14B	1.3120 (11)	−0.0488 (6)	−0.1787 (5)	0.0380 (17)
C15B	1.1246 (12)	0.0305 (6)	−0.1683 (5)	0.0351 (16)
C16B	1.0270 (10)	0.0645 (5)	−0.0764 (4)	0.0320 (16)
H1	0.6149	−0.7810	0.1687	0.069*
H1A	0.1339	−0.5135	0.2171	0.040*
H2A	0.3914	−0.5536	0.3495	0.046*
H4A1	0.7134	−0.4036	0.4492	0.053*
H4A2	0.6902	−0.3428	0.3533	0.053*
H5A	0.3486	−0.2491	0.3915	0.070*
H6A1	0.2011	−0.2603	0.5415	0.106*
H6A2	0.3888	−0.3594	0.5637	0.106*
H6A3	0.1883	−0.4042	0.4531	0.106*
H7A1	0.5242	−0.0914	0.5698	0.117*
H7A2	0.7054	−0.1237	0.4924	0.117*
H7A3	0.7216	−0.1876	0.5864	0.117*
H12A	−0.1161	−0.5962	0.0663	0.051*
H14A	−0.3432	−0.5569	−0.2367	0.051*
H16A	0.2990	−0.3866	−0.0410	0.048*
H2	0.7646	−0.2692	0.2047	0.065*
H1B	1.2190	−0.0194	0.1998	0.043*
H2B	0.8704	0.1066	0.2907	0.046*
H4B1	1.2465	−0.0182	0.3844	0.048*
H4B2	1.0497	0.0393	0.4492	0.048*
H5B	1.3044	0.2082	0.3765	0.062*
H6B1	0.9707	0.2937	0.4415	0.125*
H6B2	1.2011	0.3824	0.5180	0.125*
H6B3	1.0813	0.2811	0.5588	0.125*
H7B1	1.5909	0.1249	0.4899	0.140*
H7B2	1.4614	0.1778	0.5886	0.140*
H7B3	1.5812	0.2791	0.5478	0.140*
H12B	1.3665	−0.1003	0.0556	0.044*
H14B	1.3769	−0.0703	−0.2415	0.046*
H16B	0.9017	0.1187	−0.0723	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.057 (4)	0.078 (4)	0.079 (4)	−0.025 (3)	0.005 (3)	0.031 (3)
O2A	0.035 (3)	0.088 (4)	0.061 (3)	0.001 (3)	−0.005 (3)	0.018 (3)
O3A	0.085 (4)	0.089 (4)	0.048 (3)	0.009 (3)	0.008 (3)	0.030 (3)
O4A	0.093 (5)	0.083 (4)	0.058 (4)	−0.033 (4)	0.013 (3)	0.030 (3)
O5A	0.036 (3)	0.061 (3)	0.050 (3)	−0.012 (2)	0.008 (2)	0.021 (2)
O6A	0.043 (3)	0.048 (3)	0.071 (4)	0.006 (3)	0.021 (3)	−0.001 (3)
O7A	0.032 (3)	0.067 (4)	0.069 (4)	0.000 (3)	0.016 (3)	0.019 (3)
N1A	0.021 (3)	0.040 (3)	0.032 (3)	−0.003 (2)	0.003 (3)	0.006 (3)
N13A	0.030 (4)	0.055 (4)	0.050 (4)	0.001 (3)	0.005 (3)	0.008 (3)
N15A	0.077 (5)	0.056 (5)	0.039 (4)	0.005 (4)	0.012 (4)	0.008 (3)
C1A	0.038 (5)	0.030 (4)	0.037 (4)	−0.001 (3)	0.012 (4)	0.001 (3)
C2A	0.031 (4)	0.044 (4)	0.037 (4)	−0.002 (3)	0.007 (3)	0.011 (3)
C3A	0.036 (4)	0.057 (5)	0.020 (3)	−0.001 (4)	0.003 (3)	0.017 (3)
C4A	0.039 (4)	0.042 (4)	0.046 (4)	−0.003 (3)	0.008 (3)	0.010 (3)
C5A	0.060 (5)	0.052 (5)	0.057 (5)	−0.003 (4)	0.011 (4)	0.012 (4)
C6A	0.054 (5)	0.071 (6)	0.088 (6)	0.005 (4)	0.043 (5)	0.012 (5)
C7A	0.113 (7)	0.044 (5)	0.054 (5)	−0.023 (5)	0.014 (5)	−0.009 (4)
C11A	0.031 (4)	0.033 (4)	0.031 (4)	0.006 (3)	0.014 (3)	0.014 (3)
C12A	0.043 (5)	0.043 (4)	0.046 (5)	0.003 (4)	0.019 (4)	0.016 (4)
C13A	0.032 (4)	0.023 (4)	0.046 (4)	−0.003 (3)	0.006 (3)	0.001 (3)
C14A	0.041 (5)	0.033 (4)	0.046 (4)	0.010 (3)	0.006 (3)	0.007 (3)
C15A	0.055 (5)	0.040 (4)	0.027 (4)	0.013 (4)	0.014 (3)	0.013 (3)
C16A	0.042 (4)	0.025 (4)	0.041 (4)	0.003 (3)	0.007 (4)	−0.002 (3)
O1B	0.059 (4)	0.064 (4)	0.050 (3)	0.028 (3)	0.020 (3)	0.022 (3)
O2B	0.047 (3)	0.076 (4)	0.056 (3)	0.006 (3)	0.032 (3)	0.013 (3)
O3B	0.078 (4)	0.072 (4)	0.034 (3)	0.002 (3)	0.012 (3)	0.020 (3)
O4B	0.077 (4)	0.076 (4)	0.039 (3)	0.028 (3)	0.013 (3)	0.024 (3)
O5B	0.045 (3)	0.072 (3)	0.043 (3)	0.031 (3)	0.015 (2)	0.029 (3)
O6B	0.045 (3)	0.050 (3)	0.062 (3)	−0.006 (2)	0.009 (3)	0.015 (3)
O7B	0.027 (3)	0.081 (4)	0.064 (3)	0.008 (3)	0.013 (2)	0.026 (3)
N1B	0.026 (3)	0.057 (4)	0.029 (3)	0.016 (3)	0.011 (2)	0.018 (3)
N13B	0.042 (4)	0.044 (4)	0.049 (4)	0.006 (3)	0.013 (4)	0.001 (3)
N15B	0.060 (5)	0.046 (4)	0.038 (4)	−0.001 (3)	0.012 (3)	0.013 (3)
C1B	0.035 (4)	0.032 (4)	0.029 (4)	0.002 (3)	0.002 (3)	0.009 (3)
C2B	0.043 (4)	0.042 (4)	0.037 (4)	0.014 (3)	0.019 (3)	0.017 (3)
C3B	0.036 (4)	0.048 (5)	0.038 (4)	0.006 (4)	0.005 (3)	0.021 (3)
C4B	0.037 (4)	0.058 (4)	0.030 (4)	−0.002 (4)	0.005 (3)	0.021 (3)
C5B	0.060 (5)	0.048 (5)	0.046 (4)	−0.010 (4)	0.015 (4)	0.011 (4)
C6B	0.116 (8)	0.038 (5)	0.076 (6)	0.006 (5)	0.016 (5)	−0.001 (4)
C7B	0.059 (6)	0.121 (8)	0.070 (6)	−0.016 (5)	0.003 (5)	0.003 (5)
C11B	0.037 (4)	0.033 (4)	0.026 (4)	0.002 (3)	0.008 (3)	0.008 (3)
C12B	0.046 (4)	0.037 (4)	0.031 (4)	0.002 (3)	0.019 (3)	0.010 (3)
C13B	0.022 (4)	0.029 (4)	0.031 (4)	−0.002 (3)	0.001 (3)	−0.001 (3)
C14B	0.036 (4)	0.039 (4)	0.034 (4)	−0.007 (3)	0.014 (3)	0.002 (3)
C15B	0.045 (4)	0.040 (4)	0.022 (3)	−0.005 (3)	0.001 (3)	0.018 (3)
C16B	0.030 (4)	0.026 (4)	0.032 (4)	−0.001 (3)	0.003 (3)	0.002 (3)

Geometric parameters (Å, º)

O1A—N13A	1.226 (6)	O1B—N13B	1.220 (6)
O2A—N13A	1.232 (6)	O2B—N13B	1.230 (6)
O3A—N15A	1.237 (7)	O3B—N15B	1.218 (6)
O4A—N15A	1.218 (7)	O4B—N15B	1.224 (6)
O5A—C1A	1.235 (7)	O5B—C1B	1.235 (7)
O6A—C3A	1.321 (7)	O6B—C3B	1.345 (7)
O7A—C3A	1.198 (7)	O7B—C3B	1.201 (7)
N1A—C1A	1.343 (7)	N1B—C1B	1.337 (7)
N1A—C2A	1.478 (6)	N1B—C2B	1.458 (6)
N13A—C13A	1.468 (8)	N13B—C13B	1.474 (7)
N15A—C15A	1.477 (7)	N15B—C15B	1.487 (7)
C1A—C11A	1.505 (8)	C1B—C11B	1.486 (8)
C2A—C4A	1.523 (7)	C2B—C3B	1.509 (8)
C2A—C3A	1.524 (8)	C2B—C4B	1.528 (7)
C4A—C5A	1.507 (8)	C4B—C5B	1.536 (9)
C5A—C6A	1.507 (8)	C5B—C6B	1.517 (9)
C5A—C7A	1.531 (9)	C5B—C7B	1.526 (9)
C11A—C16A	1.382 (7)	C11B—C12B	1.387 (8)
C11A—C12A	1.393 (8)	C11B—C16B	1.409 (7)
C12A—C13A	1.375 (7)	C12B—C13B	1.347 (7)
C13A—C14A	1.365 (8)	C13B—C14B	1.365 (7)
C14A—C15A	1.389 (8)	C14B—C15B	1.381 (8)
C15A—C16A	1.390 (7)	C15B—C16B	1.369 (7)
C1A—N1A—C2A	123.3 (5)	C1B—N1B—C2B	121.9 (5)
O1A—N13A—O2A	123.9 (6)	O1B—N13B—O2B	123.8 (6)
O1A—N13A—C13A	118.0 (6)	O1B—N13B—C13B	118.2 (6)
O2A—N13A—C13A	118.1 (6)	O2B—N13B—C13B	118.0 (6)
O3A—N15A—O4A	124.2 (7)	O3B—N15B—O4B	125.3 (6)
O3A—N15A—C15A	117.6 (7)	O3B—N15B—C15B	117.1 (6)
O4A—N15A—C15A	118.2 (6)	O4B—N15B—C15B	117.6 (6)
O5A—C1A—N1A	122.9 (6)	O5B—C1B—N1B	122.5 (6)
O5A—C1A—C11A	120.0 (6)	O5B—C1B—C11B	118.7 (6)
N1A—C1A—C11A	116.9 (6)	N1B—C1B—C11B	118.8 (6)
N1A—C2A—C3A	108.3 (5)	N1B—C2B—C3B	111.6 (5)
N1A—C2A—C4A	115.9 (5)	N1B—C2B—C4B	110.1 (5)
C3A—C2A—C4A	112.1 (5)	C3B—C2B—C4B	113.0 (5)
O6A—C3A—O7A	123.5 (6)	O6B—C3B—O7B	122.7 (6)
O6A—C3A—C2A	111.2 (5)	O6B—C3B—C2B	112.3 (5)
O7A—C3A—C2A	125.2 (6)	O7B—C3B—C2B	124.9 (6)
C2A—C4A—C5A	115.7 (5)	C2B—C4B—C5B	111.5 (5)
C4A—C5A—C6A	113.3 (6)	C4B—C5B—C6B	112.0 (6)
C4A—C5A—C7A	107.5 (6)	C4B—C5B—C7B	110.8 (6)
C6A—C5A—C7A	110.8 (7)	C6B—C5B—C7B	109.4 (6)
C12A—C11A—C1A	123.1 (6)	C12B—C11B—C1B	125.6 (5)
C16A—C11A—C1A	116.7 (6)	C16B—C11B—C1B	116.6 (5)
C12A—C11A—C16A	119.5 (6)	C12B—C11B—C16B	117.3 (5)
C11A—C12A—C13A	118.6 (6)	C11B—C12B—C13B	121.1 (6)
C12A—C13A—C14A	124.6 (6)	C12B—C13B—C14B	123.0 (6)
C12A—C13A—N13A	117.7 (6)	C12B—C13B—N13B	119.0 (6)
C14A—C13A—N13A	117.7 (6)	C14B—C13B—N13B	117.9 (6)
C13A—C14A—C15A	115.2 (6)	C13B—C14B—C15B	116.3 (6)
C14A—C15A—N15A	117.2 (6)	C14B—C15B—C16B	123.1 (6)
C14A—C15A—C16A	123.2 (6)	C14B—C15B—N15B	119.1 (6)
C16A—C15A—N15A	119.6 (6)	C16B—C15B—N15B	117.8 (6)
C11A—C16A—C15A	118.9 (6)	C11B—C16B—C15B	119.1 (6)
C2A—N1A—C1A—O5A	−8.9 (9)	C2B—N1B—C1B—O5B	4.3 (9)
C2A—N1A—C1A—C11A	165.9 (5)	C2B—N1B—C1B—C11B	−175.2 (5)
C1A—N1A—C2A—C4A	70.8 (7)	C1B—N1B—C2B—C3B	81.5 (7)
C1A—N1A—C2A—C3A	−56.1 (7)	C1B—N1B—C2B—C4B	−152.2 (5)
N1A—C2A—C3A—O7A	120.7 (6)	N1B—C2B—C3B—O7B	−124.8 (7)
C4A—C2A—C3A—O7A	−8.4 (9)	C4B—C2B—C3B—O7B	110.5 (7)
N1A—C2A—C3A—O6A	−61.2 (6)	N1B—C2B—C3B—O6B	52.0 (7)
C4A—C2A—C3A—O6A	169.7 (5)	C4B—C2B—C3B—O6B	−72.7 (7)
N1A—C2A—C4A—C5A	55.1 (7)	N1B—C2B—C4B—C5B	71.3 (7)
C3A—C2A—C4A—C5A	−179.9 (5)	C3B—C2B—C4B—C5B	−163.2 (6)
C2A—C4A—C5A—C6A	55.5 (8)	C2B—C4B—C5B—C6B	78.4 (7)
C2A—C4A—C5A—C7A	178.2 (6)	C2B—C4B—C5B—C7B	−159.2 (6)
O5A—C1A—C11A—C16A	−9.1 (8)	O5B—C1B—C11B—C12B	−165.8 (6)
N1A—C1A—C11A—C16A	175.9 (5)	N1B—C1B—C11B—C12B	13.8 (9)
O5A—C1A—C11A—C12A	161.3 (6)	O5B—C1B—C11B—C16B	6.6 (8)
N1A—C1A—C11A—C12A	−13.7 (8)	N1B—C1B—C11B—C16B	−173.9 (5)
C16A—C11A—C12A—C13A	−3.2 (8)	C16B—C11B—C12B—C13B	1.6 (8)
C1A—C11A—C12A—C13A	−173.3 (6)	C1B—C11B—C12B—C13B	173.9 (6)
C11A—C12A—C13A—C14A	1.4 (9)	C11B—C12B—C13B—C14B	−1.7 (9)
C11A—C12A—C13A—N13A	179.0 (6)	C11B—C12B—C13B—N13B	177.4 (6)
O1A—N13A—C13A—C14A	171.1 (6)	O1B—N13B—C13B—C12B	6.1 (8)
O2A—N13A—C13A—C14A	−9.9 (8)	O2B—N13B—C13B—C12B	−175.1 (6)
O1A—N13A—C13A—C12A	−6.6 (9)	O1B—N13B—C13B—C14B	−174.8 (5)
O2A—N13A—C13A—C12A	172.3 (5)	O2B—N13B—C13B—C14B	4.0 (8)
C12A—C13A—C14A—C15A	0.6 (9)	C12B—C13B—C14B—C15B	0.6 (8)
N13A—C13A—C14A—C15A	−176.9 (5)	N13B—C13B—C14B—C15B	−178.5 (5)
C13A—C14A—C15A—C16A	−1.0 (8)	C13B—C14B—C15B—C16B	0.5 (8)
C13A—C14A—C15A—N15A	174.8 (5)	C13B—C14B—C15B—N15B	−178.5 (5)
O4A—N15A—C15A—C14A	−172.7 (6)	O3B—N15B—C15B—C16B	180.0 (5)
O3A—N15A—C15A—C14A	5.8 (8)	O4B—N15B—C15B—C16B	−0.4 (8)
O4A—N15A—C15A—C16A	3.2 (9)	O3B—N15B—C15B—C14B	−1.0 (8)
O3A—N15A—C15A—C16A	−178.3 (6)	O4B—N15B—C15B—C14B	178.7 (6)
C12A—C11A—C16A—C15A	2.9 (8)	C14B—C15B—C16B—C11B	−0.6 (8)
C1A—C11A—C16A—C15A	173.6 (5)	N15B—C15B—C16B—C11B	178.5 (5)
C14A—C15A—C16A—C11A	−0.8 (9)	C12B—C11B—C16B—C15B	−0.5 (8)
N15A—C15A—C16A—C11A	−176.4 (5)	C1B—C11B—C16B—C15B	−173.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6A—H1···O5B^i	0.82	1.86	2.675 (6)	173
N1A—H1A···O7A^ii	0.86	2.15	2.967 (6)	158
O6B—H2···O5A	0.82	1.97	2.778 (6)	167
N1B—H1B···O7B^iii	0.86	2.17	3.018 (6)	168

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