Bis(L-proline) hydrogen(1+) perchlorate

In the title compound, 2C₅H₉NO₂·H⁺·ClO₄⁻, two proline residues are linked by a strong O—H...O hydrogen bond with an O...O distance of 2.474 (6) Å. Conformational disorder is observed in the pyrrolidine rings of the two proline residues. In one of the residues, both the major and minor conformers adopt conformations intermediate between half-chair and envelope, whereas in the other residue, they adopt envelope conformations. The crystal structure is stabilized by a number of N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in solvent or counterion
• R factor = 0.051
• wR factor = 0.145
• Data-to-parameter ratio = 7.0

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_202  Alert C Isotropic non-H Atoms in Anion/Solvent       =          1

PLAT_302  Alert C Anion/Solvent Disorder .......................       9.00 Perc.

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:   C10 H19 Cl1 N2 O8
          Atom count from _chemical_formula_moiety:C10 H18 Cl1 N2 O8

REFLT_03
         From the CIF: _diffrn_reflns_theta_max           24.97
         From the CIF: _reflns_number_total               1420
         Count of symmetry unique reflns         1422
         Completeness (_total/calc)             99.86%
         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          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

Proline is a very important amino acid due to its unique conformation, which may affect the structure of proteins, in particular, collagen. The crystal structures of L-proline monohydrate (Kayushina & Vainshtein, 1965), DL-proline hydrochloride (Mitsui et al., 1969), DL-homoproline tetrahydrate (Bhattacharjee & Chacko, 1979) and DL-proline monohydrate (Padmanabhan et al., 1995) have been reported. The crystal structure determination of L-proline perchloric acid was undertaken to study the effect of the inorganic acid on the conformation of the proline residue.

The asymmetric unit of the title compound, (I), consists of two crystallographically independent proline residues A and B, a H⁺ cation and a ClO₄^- ion. The conformation angles ψ¹ for A and B are 3.9 (6) and 7.8 (9)°, respectively. The twisting of the carboxyl plane away from the C—N bond is observed in various amino acids (Lakshminarayanan et al., 1967). The conformation angles χ¹, χ², χ³, χ⁴ and θ of the pyrrolidine ring for both A and B, respectively, are 33.3 (8) and 40.7 (10), -37.6 (10) and -31.8 (11), 26.8 (10) and 10.0 (10)°, -6.1 (8) and 16.8 (9), and -16.6 (7) and -35.5 (8)° (Prasad & Vijayan, 1993).

The conformation of the pyrrolidine ring, in general, is intermediate between half-chair and envelope (Prasad & Vijayan, 1993; Padmanabhan et al., 1995). In the present case, the C^γ atom of residue A and C^β of residue B are disordered. Both the major and minor conformers of the pyrrolidine ring adopt conformations intermediate between half-chair and envelope in residue A, whereas in residue B, they adopt half-chair conformations (Cremer & Pople, 1975; Nardelli, 1983).

The two proline residues in the asymmetric unit are linked through a strong O-==H···O hydrogen bond [2.474 (6) Å]. The equality of the C—O distances within significant limits [1.219 (7) and 1.184 (7), and 1.283 (6) and 1.280 (8) Å] indicates that atom H2B is equally shared by residues A and B. Hence, this hydrogen bond may be termed as a symmetric hydrogen bond. The O2B—H2B and O1B—H2B distances are 1.23 (10) and 1.34 (11) Å, respectively. This symmetrically hydrogen-bonded proline dimer is positively charged, as found in L-phenylalanine L-phenylalaninium perchlorate (Srinivasan & Rajaram, 1997) and L-lysine L-lysinium dichloride nitrate (Srinivasan et al., 2001).

The perchlorate anion form hydrogen bonds with the amino N atoms of both proline residues (Table 2). An intramolecular hydrogen bond, N11—H11A···O1A, is observed in residue A. The N atoms of both A and B are involved in three-centred hydrogen bonds with O atoms of the carbonyl groups and the perchlorate anion. Residues A and B are engaged in a head-to-tail sequence, since the N11—H11A···O1A(-x + 1, y + 1/2, -z + 1) (Z1 sequence), –N11–H11A···O2A(-x + 1, y + 1/2, -z + 1) (as a three-centred hydrogen bond) and N21—H21A···O1B(x, y - 1, z) hydrogen bonds connect them (Vijayan, 1988).

S2. Experimental

The title compound was crystallized by slow evaporation from an aqueous solution of L-proline and perchloric acid in a 2:1 stoichiometric ratio.

S3. Refinement

Atoms C14 and C23 were found to be disordered, suggesting conformational disorder in the pyrrolidine rings of both proline residues. The population of the major conformation was found to be 76% for proline residue A and 72% for residue B. The corresponding C—C distances in the major and minor conformers were restrained to be equal, with an effective standard deviation of 0.01 Å. Due to large ADP max/min ratio, the disordered positions C23 and C23' were isotropically refined. Atom H2B was located in a difference Fourier map and refined isotropically; all other H atoms were geometrically fixed and allowed to ride on their attached atoms. Since the crystal belongs to a non-centrosymmetric space group and the diffracted intensities are rather low, the data-to-parameter ratio (6.63) is poor.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I) showing the atomic numbering scheme and 50% probability displacement ellipsoids (Johnson, 1976). For clarity, only the major conformers (76 and 72%) of the pyrrolidine rings are shown.
	Fig. 2. Packing of the molecules viewed down the b axis (for clarity, only the major conformers of the pyrrolidine rings are shown).

Bis(L-proline) H + perchlorate

Crystal data

2C5H9NO2·H^+.ClO4^−	F(000) = 348
Mr = 330.72	Dx = 1.475 Mg m^−3 Dm = 1.472 Mg m^−3 Dm measured by flotation in a mixture of carbon tetrachloride and xylene
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 7.848 (6) Å	Cell parameters from 25 reflections
b = 7.3951 (14) Å	θ = 8.3–11.6°
c = 12.834 (5) Å	µ = 0.30 mm^−1
β = 90.95 (4)°	T = 293 K
V = 744.7 (5) Å^3	Needle, colorless
Z = 2	0.5 × 0.3 × 0.2 mm

Data collection

Enraf-Nonius sealed tube diffractometer	1181 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.009
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω–2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
Tmin = 0.899, Tmax = 0.942	l = −15→15
1528 measured reflections	3 standard reflections every 60 min
1420 independent reflections	intensity decay: none

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)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.0739P)^2 + 0.4916P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.002
1420 reflections	Δρmax = 0.29 e Å^−3
204 parameters	Δρmin = −0.29 e Å^−3
19 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (17)

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	0.25414 (18)	0.3333 (2)	0.78695 (10)	0.0558 (4)
O1	0.1316 (7)	0.1989 (8)	0.8086 (4)	0.0846 (16)
O2	0.2853 (9)	0.4403 (12)	0.8744 (5)	0.117 (2)
O3	0.1820 (12)	0.4414 (14)	0.7083 (5)	0.155 (4)
O4	0.4024 (8)	0.2560 (12)	0.7501 (7)	0.143 (3)
O1A	0.3298 (5)	0.4238 (5)	0.4672 (3)	0.0534 (11)
O1B	0.2380 (5)	0.5672 (5)	0.3241 (3)	0.0503 (10)
C11	0.2930 (6)	0.5605 (8)	0.4187 (4)	0.0383 (11)
O2A	0.3390 (8)	0.1049 (8)	0.2919 (5)	0.104 (2)
O2B	0.1743 (7)	0.3035 (6)	0.2113 (4)	0.0757 (15)
H2B	0.229 (10)	0.402 (15)	0.281 (6)	0.114*
C21	0.2427 (7)	0.1478 (8)	0.2243 (4)	0.0465 (13)
C12	0.3080 (7)	0.7429 (8)	0.4713 (4)	0.0405 (12)
H12	0.3842	0.8199	0.4309	0.049*
C13	0.1430 (8)	0.8433 (11)	0.4895 (5)	0.0701 (19)
H13A	0.1112	0.9152	0.4290	0.084*	0.76 (2)
H13B	0.0514	0.7595	0.5041	0.084*	0.76 (2)
H13C	0.0492	0.7738	0.4620	0.084*	0.24 (2)
H13D	0.1442	0.9580	0.4544	0.084*	0.24 (2)
C14	0.1797 (14)	0.9616 (15)	0.5814 (6)	0.064 (4)	0.76 (2)
H14A	0.0754	0.9939	0.6164	0.077*	0.76 (2)
H14B	0.2376	1.0713	0.5605	0.077*	0.76 (2)
C14'	0.1192 (16)	0.857 (5)	0.6027 (8)	0.064 (9)	0.24 (2)
H14C	0.0494	0.7578	0.6273	0.077*	0.24 (2)
H14D	0.0641	0.9700	0.6202	0.077*	0.24 (2)
C15	0.2924 (8)	0.8481 (11)	0.6506 (4)	0.0610 (16)
H15A	0.2252	0.7825	0.7009	0.073*	0.76 (2)
H15B	0.3743	0.9232	0.6880	0.073*	0.76 (2)
H15C	0.2843	0.7986	0.7195	0.073*	0.24 (2)
H15D	0.3517	0.9616	0.6544	0.073*	0.24 (2)
N11	0.3818 (5)	0.7193 (6)	0.5794 (3)	0.0455 (11)
H11A	0.3666	0.6048	0.6011	0.055*
H11B	0.4943	0.7429	0.5796	0.055*
C22	0.1845 (8)	0.0128 (8)	0.1437 (5)	0.0515 (15)
H22	0.0609	0.0174	0.1322	0.062*	0.72 (3)
H22'	0.0613	0.0065	0.1544	0.062*	0.28 (3)
C23	0.2814 (18)	0.0425 (14)	0.0419 (7)	0.069 (4)*	0.72 (3)
H23A	0.2293	0.1380	0.0005	0.083*	0.72 (3)
H23B	0.3998	0.0730	0.0560	0.083*	0.72 (3)
C23'	0.183 (5)	0.034 (3)	0.0271 (8)	0.069 (10)*	0.28 (3)
H23C	0.2465	0.1399	0.0066	0.083*	0.28 (3)
H23D	0.0668	0.0446	0.0002	0.083*	0.28 (3)
C24	0.2662 (15)	−0.1378 (11)	−0.0128 (5)	0.104 (3)
H24A	0.1627	−0.1428	−0.0550	0.125*	0.72 (3)
H24B	0.3630	−0.1578	−0.0574	0.125*	0.72 (3)
H24C	0.1960	−0.1778	−0.0712	0.125*	0.28 (3)
H24D	0.3818	−0.1218	−0.0369	0.125*	0.28 (3)
C25	0.2621 (12)	−0.2753 (10)	0.0714 (5)	0.075 (2)
H25A	0.3667	−0.3451	0.0731	0.090*
H25B	0.1668	−0.3572	0.0608	0.090*
N21	0.2428 (7)	−0.1712 (8)	0.1701 (3)	0.0601 (13)
H21A	0.1663	−0.2258	0.2111	0.072*
H21B	0.3432	−0.1662	0.2049	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0636 (8)	0.0499 (8)	0.0541 (7)	−0.0035 (8)	0.0036 (6)	−0.0007 (8)
O1	0.092 (3)	0.074 (4)	0.087 (3)	−0.017 (3)	0.005 (3)	0.013 (3)
O2	0.147 (6)	0.117 (6)	0.086 (4)	−0.019 (5)	−0.006 (4)	−0.051 (4)
O3	0.225 (9)	0.131 (7)	0.107 (5)	−0.042 (7)	−0.054 (5)	0.059 (5)
O4	0.075 (3)	0.129 (6)	0.228 (8)	−0.010 (4)	0.037 (4)	−0.087 (6)
O1A	0.074 (3)	0.034 (2)	0.053 (2)	0.007 (2)	−0.0083 (19)	0.002 (2)
O1B	0.077 (3)	0.0305 (19)	0.0426 (19)	−0.001 (2)	−0.0133 (18)	−0.0051 (17)
C11	0.037 (2)	0.033 (3)	0.044 (3)	0.000 (2)	−0.004 (2)	0.000 (2)
O2A	0.133 (5)	0.070 (4)	0.106 (4)	0.040 (4)	−0.079 (4)	−0.042 (3)
O2B	0.119 (4)	0.037 (3)	0.069 (3)	0.015 (3)	−0.033 (3)	−0.012 (2)
C21	0.052 (3)	0.041 (3)	0.047 (3)	−0.002 (3)	−0.009 (3)	0.002 (3)
C12	0.047 (3)	0.034 (3)	0.039 (3)	−0.001 (2)	−0.010 (2)	−0.003 (2)
C13	0.067 (4)	0.062 (4)	0.081 (4)	0.029 (4)	−0.024 (3)	−0.022 (4)
C14	0.068 (6)	0.058 (6)	0.065 (6)	0.013 (5)	−0.003 (5)	−0.010 (5)
C14'	0.041 (12)	0.056 (19)	0.095 (18)	0.000 (13)	0.023 (11)	0.033 (16)
C15	0.074 (4)	0.065 (4)	0.045 (3)	0.012 (4)	0.006 (3)	−0.010 (4)
N11	0.048 (2)	0.041 (3)	0.048 (2)	0.001 (2)	−0.0103 (19)	−0.006 (2)
C22	0.055 (3)	0.037 (3)	0.062 (4)	0.004 (3)	−0.012 (3)	−0.009 (3)
C24	0.194 (10)	0.067 (6)	0.053 (4)	0.013 (6)	0.010 (5)	0.004 (4)
C25	0.111 (6)	0.054 (5)	0.061 (4)	0.014 (5)	−0.003 (4)	−0.014 (4)
N21	0.097 (4)	0.038 (2)	0.045 (2)	0.003 (4)	0.002 (2)	0.007 (3)

Geometric parameters (Å, º)

Cl1—O4	1.386 (6)	C15—H15A	0.97
Cl1—O2	1.391 (6)	C15—H15B	0.97
Cl1—O3	1.400 (7)	C15—H15C	0.96
Cl1—O1	1.414 (6)	C15—H15D	0.96
O1A—C11	1.219 (7)	N11—H11A	0.90
O1B—C11	1.283 (6)	N11—H11B	0.90
O1B—H2B	1.34 (11)	C22—N21	1.473 (8)
C11—C12	1.512 (7)	C22—C23'	1.504 (11)
O2A—C21	1.184 (7)	C22—C23	1.539 (9)
O2B—C21	1.280 (8)	C22—H22	0.98
O2B—H2B	1.23 (10)	C22—H22'	0.98
C21—C22	1.503 (8)	C23—C24	1.510 (9)
C12—C13	1.515 (8)	C23—H23A	0.97
C12—N11	1.504 (7)	C23—H23B	0.97
C12—H12	0.98	C23'—C24	1.522 (11)
C13—C14'	1.472 (10)	C23'—H23C	0.97
C13—C14	1.493 (8)	C23'—H23D	0.97
C13—H13A	0.97	C24—C25	1.484 (11)
C13—H13B	0.97	C24—H24A	0.97
C13—H13C	0.96	C24—H24B	0.97
C13—H13D	0.96	C24—H24C	0.97
C14—C15	1.500 (8)	C24—H24D	0.97
C14—H14A	0.97	C25—N21	1.493 (8)
C14—H14B	0.97	C25—H25A	0.97
C14'—C15	1.484 (10)	C25—H25B	0.97
C14'—H14C	0.97	N21—H21A	0.90
C14'—H14D	0.97	N21—H21B	0.90
C15—N11	1.502 (8)
O4—Cl1—O2	111.8 (4)	N11—C15—H15D	110.7
O4—Cl1—O3	108.7 (6)	H15A—C15—H15D	132.3
O2—Cl1—O3	108.6 (6)	H15B—C15—H15D	32.7
O4—Cl1—O1	110.8 (5)	H15C—C15—H15D	109.1
O2—Cl1—O1	110.7 (4)	C15—N11—C12	108.1 (4)
O3—Cl1—O1	106.0 (4)	C15—N11—H11A	110.1
C11—O1B—H2B	112 (4)	C12—N11—H11A	110.1
O1A—C11—O1B	126.0 (5)	C15—N11—H11B	110.1
O1A—C11—C12	119.7 (4)	C12—N11—H11B	110.1
O1B—C11—C12	114.3 (4)	H11A—N11—H11B	108.4
C21—O2B—H2B	107 (5)	N21—C22—C21	111.5 (5)
O2A—C21—O2B	126.7 (6)	N21—C22—C23'	108.8 (7)
O2A—C21—C22	120.6 (6)	C21—C22—C23'	127.9 (13)
O2B—C21—C22	112.7 (5)	N21—C22—C23	99.9 (6)
C13—C12—C11	116.5 (5)	C21—C22—C23	109.9 (6)
C13—C12—N11	103.4 (4)	C23'—C22—C23	30.4 (11)
C11—C12—N11	109.6 (4)	N21—C22—H22	111.7
C13—C12—H12	109.0	C21—C22—H22	111.7
C11—C12—H12	109.0	C23'—C22—H22	81.5
N11—C12—H12	109.0	C23—C22—H22	111.7
C14'—C13—C14	37.4 (12)	N21—C22—H22'	103.1
C14'—C13—C12	107.9 (9)	C21—C22—H22'	102.9
C14—C13—C12	104.8 (5)	C23'—C22—H22'	98.7
C14'—C13—H13A	135.9	C23—C22—H22'	128.9
C14—C13—H13A	110.8	H22—C22—H22'	17.4
C12—C13—H13A	110.8	C24—C23—C22	103.4 (7)
C14'—C13—H13B	75.3	C24—C23—H23A	111.1
C14—C13—H13B	110.8	C22—C23—H23A	111.1
C12—C13—H13B	110.8	C24—C23—H23B	111.1
H13A—C13—H13B	108.9	C22—C23—H23B	111.1
C14'—C13—H13C	106.8	H23A—C23—H23B	109.0
C14—C13—H13C	137.8	C22—C23'—C24	104.5 (9)
C12—C13—H13C	109.5	C22—C23'—H23C	110.8
H13A—C13—H13C	79.3	C24—C23'—H23C	110.8
H13B—C13—H13C	33.1	C22—C23'—H23D	110.8
C14'—C13—H13D	113.9	C24—C23'—H23D	110.8
C14—C13—H13D	81.3	H23C—C23'—H23D	108.9
C12—C13—H13D	110.2	C25—C24—C23	105.6 (6)
H13A—C13—H13D	31.3	C25—C24—C23'	108.2 (8)
H13B—C13—H13D	131.9	C23—C24—C23'	30.5 (11)
H13C—C13—H13D	108.3	C25—C24—H24A	110.6
C13—C14—C15	104.2 (6)	C23—C24—H24A	110.6
C13—C14—H14A	110.9	C23'—C24—H24A	81.8
C15—C14—H14A	110.9	C25—C24—H24B	110.6
C13—C14—H14B	110.9	C23—C24—H24B	110.6
C15—C14—H14B	110.9	C23'—C24—H24B	132.2
H14A—C14—H14B	108.9	H24A—C24—H24B	108.7
C13—C14'—C15	106.0 (9)	C25—C24—H24C	109.5
C13—C14'—H14C	110.5	C23—C24—H24C	131.9
C15—C14'—H14C	110.5	C23'—C24—H24C	105.8
C13—C14'—H14D	110.5	H24A—C24—H24C	25.3
C15—C14'—H14D	110.5	H24B—C24—H24C	86.4
H14C—C14'—H14D	108.7	C25—C24—H24D	110.3
C14'—C15—C14	37.2 (12)	C23—C24—H24D	88.5
C14'—C15—N11	102.1 (11)	C23'—C24—H24D	114.6
C14—C15—N11	105.7 (5)	H24A—C24—H24D	127.2
C14'—C15—H15A	78.0	H24B—C24—H24D	23.8
C14—C15—H15A	110.6	H24C—C24—H24D	108.2
N11—C15—H15A	110.6	C24—C25—N21	105.6 (6)
C14'—C15—H15B	140.8	C24—C25—H25A	110.6
C14—C15—H15B	110.6	N21—C25—H25A	110.6
N11—C15—H15B	110.6	C24—C25—H25B	110.6
H15A—C15—H15B	108.7	N21—C25—H25B	110.6
C14'—C15—H15C	108.9	H25A—C25—H25B	108.8
C14—C15—H15C	135.4	C22—N21—C25	108.5 (5)
N11—C15—H15C	110.9	C22—N21—H21A	110.0
H15A—C15—H15C	32.0	C25—N21—H21A	110.0
H15B—C15—H15C	79.4	C22—N21—H21B	110.0
C14'—C15—H15D	115.0	C25—N21—H21B	110.0
C14—C15—H15D	79.7	H21A—N21—H21B	108.4
O1A—C11—C12—C13	−112.9 (6)	O2B—C21—C22—N21	−170.7 (6)
O1B—C11—C12—C13	66.0 (7)	O2A—C21—C22—C23'	−130.3 (15)
O1A—C11—C12—N11	3.9 (6)	O2B—C21—C22—C23'	51.2 (16)
O1B—C11—C12—N11	−177.1 (4)	O2A—C21—C22—C23	−102.0 (9)
C11—C12—C13—C14'	114.6 (15)	O2B—C21—C22—C23	79.5 (8)
N11—C12—C13—C14'	−5.6 (16)	N21—C22—C23—C24	40.7 (10)
C11—C12—C13—C14	153.5 (7)	C21—C22—C23—C24	157.9 (8)
N11—C12—C13—C14	33.3 (8)	C23'—C22—C23—C24	−69.8 (11)
C14'—C13—C14—C15	62.8 (11)	N21—C22—C23'—C24	−8 (3)
C12—C13—C14—C15	−37.6 (10)	C21—C22—C23'—C24	131.2 (14)
C14—C13—C14'—C15	−65.1 (12)	C23—C22—C23'—C24	69.4 (11)
C12—C13—C14'—C15	26 (3)	C22—C23—C24—C25	−31.8 (11)
C13—C14'—C15—C14	65.1 (12)	C22—C23—C24—C23'	67.6 (10)
C13—C14'—C15—N11	−35 (2)	C22—C23'—C24—C25	18 (3)
C13—C14—C15—C14'	−62.5 (11)	C22—C23'—C24—C23	−71.8 (12)
C13—C14—C15—N11	26.8 (10)	C23—C24—C25—N21	10.0 (10)
C14'—C15—N11—C12	32.0 (14)	C23'—C24—C25—N21	−21.8 (18)
C14—C15—N11—C12	−6.1 (8)	C21—C22—N21—C25	−151.7 (6)
C13—C12—N11—C15	−16.6 (7)	C23'—C22—N21—C25	−5.5 (17)
C11—C12—N11—C15	−141.4 (5)	C23—C22—N21—C25	−35.5 (8)
O2A—C21—C22—N21	7.8 (9)	C24—C25—N21—C22	16.8 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2B—H2B···O1B	1.23 (10)	1.34 (11)	2.474 (6)	149 (8)
N11—H11B···O1A^i	0.90	2.02	2.795 (6)	143
N11—H11B···O2A^i	0.90	2.32	2.851 (7)	117
N11—H11A···O1A	0.90	2.19	2.645 (6)	110
N11—H11A···O3	0.90	2.35	3.083 (9)	139
N21—H21A···O1B^ii	0.90	2.18	2.766 (6)	123
N21—H21A···O1^iii	0.90	2.41	3.108 (8)	134
N21—H21B···O4^iv	0.90	2.15	3.000 (9)	158

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