(3S)-Benzyl N-(1-hydr­oxy-2,5-dioxopyrrolidin-3-yl)carbamate: two-dimensional sheets built from O—H...O, N—H...O, C=O...C=O and C—H...O inter­actions linked into a three-dimensional complex framework via C—H...π(arene) inter­actions

The title compound, C₁₀H₁₂O₅N₂, crystallizes with two independent mol­ecules in the asymmetric unit. The mol­ecules in the crystal structure are arranged into one-dimensional substructural ribbon motifs stabilized by a combination of two O—H...O and three N—H...O inter­molecular hydrogen bonds, and also augmented by short C=O...C=O carbon­yl–carbonyl inter­actions. Two inter­molecular C—H...O short contacts between adjacent ribbons generate complex two-dimensional sheets on the ab plane. Adjacent sheets are linked via C—H...π(arene) inter­actions, resulting in a complex three-dimensional framework.

S1. Comment

The title compound, (I), is a cyclic derivative of L-aspartic acid and belongs to the group of chiral N-hydroxysuccinimides. With the aim of synthesizing a new class of L-aspartic acid-based sulfonic esters of N-hydroxysuccinimides, we obtained (I) by reacting hydroxylamine with Cbz-L-aspartic acid anhydride (Cbz is carbobenzoxy) in a water–dioxane system. As part of our studies of N-oxysuccinimide ring geometry (Stefanowicz et al. 2005, 2006), we report here the molecular and supramolecular structure of (I), which offers a wide range of intermolecular interactions, such as classical N—H···O and O—H···O hydrogen bonds, short carbonyl–carbonyl O···C interactions, and C—H···O and C—H···π(arene) contacts.

Compound (I) crystallizes in the space group P2₁ with two independent molecules in the asymmetric unit, A and B (Fig. 1). Superposition of these two molecules is shown in Fig. 2. They differ mainly in the orientation of the benzyl moiety, with the O5—C6—C7—C8 torsion angles being 166.6 (2) and -117.6 (2)° for molecules A and B, respectively. Atoms N1 of molecules A and B are characterized by planar geometry, with deviations from the plane defined by atoms C1/C4/O2 of 0.023 (2) and 0.019 (2) Å, respectively. Comparison of these values with the data available for analogous compounds such as N-hydroxysuccinimide [0.061 (2) Å; Jones, 2003] and N-hydroxyphtalimide [0.108 (6) Å; Miao et al., 1995] indicates increased sp² character of the succinimide N atom for (I). The succinimide ring geometry of (I) is also slightly puckered compared with the virtually planar geometries of the N-hydroxyphtalimide and N-hydroxysuccinimide five-membered rings, which both have r.m.s. deviations of less than 0.02 Å. This difference can be explained by the substitution of atoms C2A/B by an aminobenzocarboxy moiety in (I), while in the other two compounds, both aromatic or methylene C atoms are geometrically equal. The puckering parameters (Cremer & Pople, 1975) for (I) are q₂ = 0.079 (2) Å and ψ₂ = 227 (1)° for molecule A, and q₂ = 0.081 (2) Å and ψ₂ = 251 (1)° for molecule B, indicating a twisted conformation on C1A—C2A and an approximate envelope conformation at C2B for the five-membered rings of molecules A and B, respectively.

The hydrogen-bond network is built up from the combination of three N—H···O and two O—H···O hydrogen bonds that link molecules A with neighbouring molecules B to form one-dimensional substructural ribbon motifs, augmented by short C═O···C═O carbonyl–carbonyl interactions between adjacent succinimide rings (Fig. 3). The strength of the C═ O···C═O interactions can be compared with medium-strength hydrogen bonds (Allen et al., 1998). Adjacent ribbons are linked via chains of C—H···O contacts between molecules of the same type to form two-dimensional sheets (Fig. 4). Only short C—H···π(arene) interactions link neighbouring sheets, generating a three-dimensional complex network (Fig. 5).

Atoms N2B and O2B from molecule B act as hydrogen-bond donors to atoms O2A and O4A from molecule A, respectively. The combination of these two hydrogen bonds gives an R²₂(14) ring (Bernstein et al., 1995). Atom O2A also acts as a hydrogen-bond donor to atom O4B of a neighbouring molecule at (x, y - 1, z), and atom N2A is a hydrogen-bond donor to atoms O1B and O2B, both at (x, y - 1, z), so R²₂(13), R²₂(14) and R²₁(5) ring motifs are generated (Fig. 3). Propagation of these motifs by simple translation along the b axis gives a one-dimensional substructural ribbon motif, which is additionally supported by C═O···C═O interactions between adjacent A and B molecules, e.g. O1A···C1B [2.848 (2) Å] and O1A···C4B [3.074 (2) Å], and O1Bⁱ···C1A [3.028 (2) Å] and O1Bⁱ···C4A [2.938 (2) Å] (Fig. 3). These contacts do not occur in the crystal structures of N-hydroxyphtalimide (Miao et al., 1995) and N-hydroxysuccinimide (Jones, 2003). Atoms C2A and C2B act as hydrogen-bond donors to atoms O3Aⁱⁱ and O3Bⁱⁱⁱ, respectively, both linking molecules of the same type from adjacent ribbons (Fig. 4). Propagation of these short C—H···O contacts by a 2₁ screw axis (1/2, y, 1/2) and translation along the a axis generate a two-dimensional sheet of C—H···O chains linked into ribbons in the ab plane. Adjacent sheets are linked via C—H···π (arene) interactions (Fig. 5), with C6A···π(arene)^iv and C6B···π(arene)^v distances of 3.401 (2) and 3.428 (2) Å, respectively, providing a complex three-dimensional framework.

It is worth mentioning that the characteristic C(5) motif of the O—H···O hydrogen-bonding combination in simple N-hydroxyimides (Miao et al., 1995; Jones, 2003) is absent from the structure of (I). The hydrogen-bonding geometry is listed in Table 1.

Related literature

For related literature, see: Allen et al. (1998); Bernstein et al. (1995); Cremer & Pople (1975); Jones (2003); Miao et al. (1995); Stefanowicz et al. (2005, 2006).

S2. Experimental

The synthesis of benzyl (3S)-1-hydroxy-2,5-dioxopyrrolidin-3-ylcarbamate was carried out according to the following procedure. Cbz-L-aspartic acid anhydride (1 g, 4 mmol) was added to a solution of hydroxylamine hydrochloride NH₃(OH)Cl (0.30 g, 4 mmol) and NaOH (0.16 g, 4 mmol) dissolved in a water–dioxane mixture (1:1 v/v; 4 ml). The solution was stirred for 15 min at room temperature and then for 1 h at 323 K. The water and dioxane were then evaporated under reduced pressure and the residue was heated at 398 K for 20 min in vacuo. The product was extracted with anhydrous ethyl acetate (30 ml). Single crystals of (I) were obtained by slow evaporation from an ethyl acetate solution (yield 77%; m.p. 413–414.5 K). The crystals of (I) are hygroscopic and not stable in air; on removal from the ethyl acetate solution they become matt and break. Analysis: [α]_D²⁴ = -39.7° (c = 1.40, MeOH); ESI–MS m/z 287 [MNa]⁺.

S3. Refinement

The absolute configuration of the chiral C atom was established in agreement with the absolute configuration of the L-enantiomer of aspartic acid, which was used for the synthesis of the compound (I). Friedel opposites were merged for the refinement. Other investigations showed the lack of racemization in the synthetic route of the present compound (Stefanowicz et al., 2006). Only the aliphatic and aromatic H atoms were positioned geometrically and refined as riding on their parent atoms, with C—H = 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C). Other H atoms were located in a difference Fourier map and their positions refined, with N—H = 0.84 (3) Å and O—H = 0.80 (3)–0.87 (3) Å; their U_iso(H) values were constrained to 1.2U_eq(parent atom). [Please check rephrasing]

Computing details

Data collection: KM-4 CCD Software (Oxford Diffraction, 2004); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The two molecules of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The superposition of molecules A and B. The reference atoms are N1A, C1A, C2A, C3A and C4A.
	Fig. 3. A view showing the formation of ribbons of alternately linked A and B molecules, with one R^22(13), two R^22(14) and one R^21(5) rings along the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Dashed lines indicate the various intermolecular interactions. (Symmetry code as in Table 2.)
	Fig. 4. A view showing the formation of two-dimensional sheets in the ab plane via C—H···O interactions (dashed lines) linking molecules of one type along the [010] direction. For the sake of clarity, H atoms not involved in the motif shown have been omitted. (Symmetry codes as in Table 2.)
	Fig. 5. The C—H···π(arene) interactions (thin lines) between adjacent sheets of (I). For the sake of clarity, H atoms not involved in the motif shown have been omitted. [Symmetry codes: (iv) x, 1 + y, -1 + z; (v) x, -1 + y, 1 + z.]

(3S)-Benzyl N-(1-hydroxy-2,5-dioxopyrrolidin-3-yl)carbamate

Crystal data

C12H12N2O5	F(000) = 552
Mr = 264.24	Dx = 1.477 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5987 reflections
a = 12.910 (3) Å	θ = 3.2–30.0°
b = 7.077 (4) Å	µ = 0.12 mm^−1
c = 14.001 (3) Å	T = 100 K
β = 111.67 (3)°	Plate, colourless
V = 1188.8 (8) Å^3	0.28 × 0.25 × 0.20 mm
Z = 4

Data collection

Oxford KM4 CCD area-detector diffractometer	3070 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 30.0°, θmin = 3.2°
Detector resolution: 0 pixels mm^-1	h = −18→14
ω scans	k = −9→9
17662 measured reflections	l = −19→19
3640 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0473P)^2] where P = (Fo^2 + 2Fc^2)/3
3640 reflections	(Δ/σ)max < 0.001
355 parameters	Δρmax = 0.22 e Å^−3
1 restraint	Δρmin = −0.22 e Å^−3

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 > 2σ(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
O1A	0.70860 (12)	0.2164 (2)	0.48559 (12)	0.0289 (4)
O2A	0.79722 (13)	0.1400 (2)	0.33584 (11)	0.0243 (3)
H1A	0.766 (2)	0.032 (4)	0.3117 (19)	0.029*
O3A	1.00027 (13)	−0.0542 (2)	0.42948 (13)	0.0320 (4)
O4A	0.79080 (12)	0.2630 (2)	0.74929 (11)	0.0214 (3)
O5A	0.74498 (12)	−0.0335 (2)	0.78135 (11)	0.0205 (3)
N1A	0.84965 (14)	0.1030 (2)	0.43960 (13)	0.0193 (4)
N2A	0.83702 (15)	0.0016 (3)	0.67733 (14)	0.0210 (4)
H2NA	0.823 (2)	−0.114 (4)	0.6695 (18)	0.025*
C1A	0.80102 (16)	0.1503 (3)	0.50842 (15)	0.0192 (4)
C2A	0.88554 (16)	0.1060 (3)	0.61501 (15)	0.0196 (4)
H2A	0.9159	0.2278	0.6505	0.024*
C3A	0.98004 (16)	0.0006 (3)	0.59489 (16)	0.0223 (4)
H31A	1.0526	0.0631	0.6313	0.027*
H32A	0.9847	−0.1320	0.6186	0.027*
C4A	0.95052 (16)	0.0083 (3)	0.48021 (16)	0.0219 (4)
C5A	0.79084 (16)	0.0917 (3)	0.73619 (15)	0.0179 (4)
C6A	0.71173 (16)	0.0379 (3)	0.86245 (15)	0.0201 (4)
H61A	0.6525	−0.0440	0.8690	0.024*
H62A	0.6807	0.1667	0.8444	0.024*
C7A	0.80870 (16)	0.0439 (3)	0.96372 (15)	0.0180 (4)
C8A	0.79748 (17)	0.1455 (3)	1.04528 (16)	0.0218 (4)
H8A	0.7303	0.2120	1.0351	0.026*
C9A	0.88372 (18)	0.1498 (3)	1.14095 (16)	0.0248 (4)
H9A	0.8757	0.2199	1.1957	0.030*
C10A	0.98165 (18)	0.0513 (3)	1.15624 (17)	0.0266 (5)
H10A	1.0408	0.0536	1.2215	0.032*
C11A	0.99277 (17)	−0.0503 (3)	1.07613 (16)	0.0263 (5)
H11A	1.0596	−0.1181	1.0867	0.032*
C12A	0.90701 (16)	−0.0540 (3)	0.98037 (16)	0.0226 (4)
H12A	0.9157	−0.1240	0.9259	0.027*
O3B	0.51201 (12)	0.4240 (2)	0.56098 (12)	0.0296 (4)
O2B	0.72170 (13)	0.5982 (2)	0.65733 (11)	0.0238 (3)
H1B	0.741 (2)	0.494 (4)	0.6791 (19)	0.029*
O1B	0.79804 (12)	0.7224 (2)	0.50629 (12)	0.0271 (3)
O4B	0.69593 (12)	0.8229 (2)	0.24594 (11)	0.0238 (3)
O5B	0.74485 (11)	0.5468 (2)	0.19123 (11)	0.0199 (3)
N1B	0.66311 (13)	0.5835 (2)	0.55306 (12)	0.0187 (4)
N2B	0.66563 (14)	0.5380 (3)	0.30778 (13)	0.0197 (4)
H2NB	0.6846 (19)	0.424 (4)	0.3122 (17)	0.024*
C4B	0.56044 (16)	0.4951 (3)	0.51081 (16)	0.0206 (4)
C3B	0.52739 (16)	0.5038 (3)	0.39590 (16)	0.0221 (4)
H31B	0.4535	0.5645	0.3635	0.027*
H32B	0.5240	0.3753	0.3669	0.027*
C2B	0.61842 (16)	0.6223 (3)	0.37743 (15)	0.0198 (4)
H2B	0.5862	0.7482	0.3494	0.024*
C1B	0.70671 (16)	0.6509 (3)	0.48407 (15)	0.0183 (4)
C5B	0.70265 (16)	0.6496 (3)	0.24930 (14)	0.0181 (4)
C6B	0.77324 (16)	0.6497 (3)	0.11328 (15)	0.0209 (4)
H61B	0.8393	0.5908	0.1056	0.025*
H62B	0.7923	0.7820	0.1358	0.025*
C7B	0.67727 (16)	0.6474 (3)	0.01147 (15)	0.0190 (4)
C8B	0.68887 (17)	0.5607 (3)	−0.07384 (17)	0.0217 (4)
H8B	0.7580	0.5042	−0.0670	0.026*
C9B	0.60116 (17)	0.5559 (3)	−0.16815 (16)	0.0241 (4)
H9B	0.6103	0.4966	−0.2254	0.029*
C10B	0.50023 (17)	0.6379 (3)	−0.17846 (17)	0.0240 (4)
H10B	0.4395	0.6327	−0.2426	0.029*
C11B	0.48770 (17)	0.7279 (3)	−0.09499 (16)	0.0255 (5)
H11B	0.4188	0.7864	−0.1028	0.031*
C12B	0.57518 (16)	0.7325 (3)	−0.00050 (16)	0.0233 (4)
H12B	0.5659	0.7934	0.0563	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0275 (8)	0.0308 (9)	0.0296 (8)	0.0091 (7)	0.0119 (7)	0.0030 (7)
O2A	0.0360 (8)	0.0195 (8)	0.0161 (7)	−0.0004 (7)	0.0082 (6)	0.0005 (6)
O3A	0.0361 (8)	0.0307 (9)	0.0381 (9)	0.0067 (8)	0.0240 (8)	0.0012 (8)
O4A	0.0280 (7)	0.0175 (8)	0.0192 (7)	−0.0015 (6)	0.0093 (6)	−0.0004 (6)
O5A	0.0280 (7)	0.0173 (8)	0.0202 (7)	−0.0030 (6)	0.0138 (6)	−0.0005 (6)
N1A	0.0248 (9)	0.0188 (9)	0.0149 (8)	0.0006 (7)	0.0081 (7)	0.0014 (6)
N2A	0.0295 (9)	0.0153 (9)	0.0211 (9)	−0.0032 (8)	0.0130 (7)	−0.0005 (7)
C1A	0.0228 (10)	0.0160 (9)	0.0207 (10)	0.0003 (9)	0.0101 (8)	−0.0005 (8)
C2A	0.0234 (10)	0.0190 (10)	0.0175 (10)	−0.0014 (8)	0.0089 (8)	0.0003 (7)
C3A	0.0180 (9)	0.0233 (11)	0.0254 (11)	0.0002 (8)	0.0077 (8)	0.0007 (8)
C4A	0.0237 (10)	0.0177 (10)	0.0277 (11)	−0.0013 (8)	0.0136 (9)	0.0001 (8)
C5A	0.0189 (9)	0.0188 (10)	0.0143 (9)	−0.0007 (8)	0.0039 (8)	0.0010 (7)
C6A	0.0224 (9)	0.0215 (10)	0.0203 (10)	0.0011 (8)	0.0125 (8)	0.0022 (8)
C7A	0.0201 (9)	0.0169 (10)	0.0191 (10)	−0.0014 (8)	0.0097 (8)	0.0017 (8)
C8A	0.0271 (10)	0.0178 (10)	0.0241 (11)	0.0023 (9)	0.0138 (9)	0.0013 (8)
C9A	0.0367 (11)	0.0201 (10)	0.0185 (10)	−0.0024 (10)	0.0112 (9)	−0.0022 (8)
C10A	0.0285 (11)	0.0251 (12)	0.0229 (11)	−0.0051 (9)	0.0055 (9)	0.0037 (9)
C11A	0.0228 (10)	0.0285 (12)	0.0285 (12)	0.0026 (9)	0.0105 (9)	0.0058 (10)
C12A	0.0252 (10)	0.0228 (11)	0.0231 (11)	0.0035 (9)	0.0130 (9)	0.0020 (9)
O3B	0.0316 (8)	0.0315 (9)	0.0322 (8)	−0.0070 (7)	0.0194 (7)	−0.0013 (7)
O2B	0.0335 (8)	0.0198 (8)	0.0151 (7)	−0.0015 (7)	0.0053 (6)	0.0004 (6)
O1B	0.0249 (8)	0.0284 (8)	0.0287 (8)	−0.0088 (7)	0.0106 (7)	−0.0040 (7)
O4B	0.0313 (8)	0.0175 (8)	0.0228 (8)	0.0008 (6)	0.0103 (7)	0.0000 (6)
O5B	0.0254 (7)	0.0183 (7)	0.0192 (7)	0.0015 (6)	0.0121 (6)	0.0022 (6)
N1B	0.0223 (8)	0.0181 (9)	0.0153 (8)	−0.0005 (7)	0.0066 (7)	−0.0003 (7)
N2B	0.0262 (9)	0.0156 (9)	0.0195 (9)	0.0019 (7)	0.0112 (7)	−0.0003 (7)
C4B	0.0216 (10)	0.0173 (10)	0.0237 (10)	0.0008 (8)	0.0092 (9)	−0.0023 (8)
C3B	0.0192 (9)	0.0232 (11)	0.0232 (10)	−0.0006 (8)	0.0068 (8)	−0.0029 (8)
C2B	0.0234 (10)	0.0219 (11)	0.0165 (10)	0.0021 (8)	0.0101 (8)	−0.0009 (8)
C1B	0.0218 (10)	0.0145 (9)	0.0197 (10)	0.0007 (8)	0.0090 (8)	−0.0010 (8)
C5B	0.0192 (9)	0.0189 (10)	0.0135 (9)	0.0001 (8)	0.0030 (7)	−0.0014 (8)
C6B	0.0234 (10)	0.0209 (10)	0.0208 (10)	−0.0014 (9)	0.0108 (8)	0.0026 (8)
C7B	0.0227 (10)	0.0149 (10)	0.0208 (10)	−0.0011 (8)	0.0097 (8)	0.0025 (8)
C8B	0.0241 (10)	0.0189 (10)	0.0254 (11)	0.0028 (8)	0.0131 (9)	0.0034 (8)
C9B	0.0332 (11)	0.0202 (11)	0.0205 (11)	−0.0012 (9)	0.0117 (9)	0.0011 (8)
C10B	0.0247 (10)	0.0229 (11)	0.0218 (10)	−0.0054 (9)	0.0056 (8)	0.0037 (9)
C11B	0.0225 (10)	0.0279 (11)	0.0283 (11)	0.0035 (10)	0.0120 (9)	0.0081 (9)
C12B	0.0270 (10)	0.0249 (11)	0.0220 (10)	0.0036 (9)	0.0140 (9)	0.0038 (9)

Geometric parameters (Å, º)

O1A—C1A	1.210 (2)	O3B—C4B	1.209 (2)
O2A—N1A	1.382 (2)	O2B—N1B	1.378 (2)
O2A—H1A	0.87 (3)	O2B—H1B	0.80 (3)
O3A—C4A	1.204 (2)	O1B—C1B	1.213 (2)
O4A—C5A	1.226 (3)	O4B—C5B	1.229 (3)
O5A—C5A	1.346 (2)	O5B—C5B	1.347 (2)
O5A—C6A	1.445 (2)	O5B—C6B	1.467 (2)
N1A—C1A	1.372 (3)	N1B—C1B	1.371 (3)
N1A—C4A	1.386 (3)	N1B—C4B	1.385 (3)
N2A—C5A	1.343 (3)	N2B—C5B	1.346 (3)
N2A—C2A	1.450 (3)	N2B—C2B	1.455 (3)
N2A—H2NA	0.84 (3)	N2B—H2NB	0.84 (3)
C1A—C2A	1.521 (3)	C4B—C3B	1.506 (3)
C2A—C3A	1.542 (3)	C3B—C2B	1.541 (3)
C2A—H2A	1.0000	C3B—H31B	0.9900
C3A—C4A	1.508 (3)	C3B—H32B	0.9900
C3A—H31A	0.9900	C2B—C1B	1.521 (3)
C3A—H32A	0.9900	C2B—H2B	1.0000
C6A—C7A	1.506 (3)	C6B—C7B	1.504 (3)
C6A—H61A	0.9900	C6B—H61B	0.9900
C6A—H62A	0.9900	C6B—H62B	0.9900
C7A—C12A	1.388 (3)	C7B—C8B	1.399 (3)
C7A—C8A	1.401 (3)	C7B—C12B	1.402 (3)
C8A—C9A	1.390 (3)	C8B—C9B	1.387 (3)
C8A—H8A	0.9500	C8B—H8B	0.9500
C9A—C10A	1.390 (3)	C9B—C10B	1.384 (3)
C9A—H9A	0.9500	C9B—H9B	0.9500
C10A—C11A	1.384 (3)	C10B—C11B	1.392 (3)
C10A—H10A	0.9500	C10B—H10B	0.9500
C11A—C12A	1.388 (3)	C11B—C12B	1.387 (3)
C11A—H11A	0.9500	C11B—H11B	0.9500
C12A—H12A	0.9500	C12B—H12B	0.9500
N1A—O2A—H1A	102.6 (17)	N1B—O2B—H1B	107.9 (19)
C5A—O5A—C6A	116.66 (16)	C5B—O5B—C6B	116.67 (16)
C1A—N1A—O2A	121.23 (16)	C1B—N1B—O2B	120.84 (16)
C1A—N1A—C4A	115.74 (17)	C1B—N1B—C4B	115.69 (17)
O2A—N1A—C4A	122.95 (16)	O2B—N1B—C4B	123.42 (16)
C5A—N2A—C2A	121.06 (18)	C5B—N2B—C2B	119.85 (18)
C5A—N2A—H2NA	115.1 (17)	C5B—N2B—H2NB	116.7 (16)
C2A—N2A—H2NA	122.5 (17)	C2B—N2B—H2NB	121.9 (16)
O1A—C1A—N1A	124.86 (19)	O3B—C4B—N1B	123.95 (19)
O1A—C1A—C2A	128.27 (19)	O3B—C4B—C3B	129.37 (19)
N1A—C1A—C2A	106.86 (16)	N1B—C4B—C3B	106.66 (17)
N2A—C2A—C1A	112.50 (16)	C4B—C3B—C2B	105.59 (16)
N2A—C2A—C3A	114.23 (17)	C4B—C3B—H31B	110.6
C1A—C2A—C3A	104.48 (16)	C2B—C3B—H31B	110.6
N2A—C2A—H2A	108.5	C4B—C3B—H32B	110.6
C1A—C2A—H2A	108.5	C2B—C3B—H32B	110.6
C3A—C2A—H2A	108.5	H31B—C3B—H32B	108.8
C4A—C3A—C2A	105.74 (16)	N2B—C2B—C1B	111.41 (16)
C4A—C3A—H31A	110.6	N2B—C2B—C3B	115.06 (17)
C2A—C3A—H31A	110.6	C1B—C2B—C3B	104.44 (16)
C4A—C3A—H32A	110.6	N2B—C2B—H2B	108.6
C2A—C3A—H32A	110.6	C1B—C2B—H2B	108.6
H31A—C3A—H32A	108.7	C3B—C2B—H2B	108.6
O3A—C4A—N1A	124.09 (19)	O1B—C1B—N1B	125.28 (19)
O3A—C4A—C3A	129.41 (19)	O1B—C1B—C2B	127.77 (19)
N1A—C4A—C3A	106.49 (17)	N1B—C1B—C2B	106.94 (16)
O4A—C5A—N2A	125.86 (19)	O4B—C5B—N2B	124.96 (19)
O4A—C5A—O5A	123.79 (19)	O4B—C5B—O5B	123.67 (19)
N2A—C5A—O5A	110.35 (18)	N2B—C5B—O5B	111.33 (18)
O5A—C6A—C7A	111.40 (16)	O5B—C6B—C7B	110.78 (15)
O5A—C6A—H61A	109.3	O5B—C6B—H61B	109.5
C7A—C6A—H61A	109.3	C7B—C6B—H61B	109.5
O5A—C6A—H62A	109.3	O5B—C6B—H62B	109.5
C7A—C6A—H62A	109.3	C7B—C6B—H62B	109.5
H61A—C6A—H62A	108.0	H61B—C6B—H62B	108.1
C12A—C7A—C8A	118.85 (19)	C8B—C7B—C12B	118.59 (18)
C12A—C7A—C6A	122.31 (18)	C8B—C7B—C6B	120.21 (17)
C8A—C7A—C6A	118.79 (18)	C12B—C7B—C6B	121.19 (18)
C9A—C8A—C7A	120.62 (19)	C9B—C8B—C7B	121.10 (19)
C9A—C8A—H8A	119.7	C9B—C8B—H8B	119.4
C7A—C8A—H8A	119.7	C7B—C8B—H8B	119.4
C10A—C9A—C8A	119.8 (2)	C10B—C9B—C8B	119.7 (2)
C10A—C9A—H9A	120.1	C10B—C9B—H9B	120.2
C8A—C9A—H9A	120.1	C8B—C9B—H9B	120.2
C11A—C10A—C9A	119.8 (2)	C9B—C10B—C11B	120.1 (2)
C11A—C10A—H10A	120.1	C9B—C10B—H10B	120.0
C9A—C10A—H10A	120.1	C11B—C10B—H10B	120.0
C10A—C11A—C12A	120.5 (2)	C12B—C11B—C10B	120.4 (2)
C10A—C11A—H11A	119.7	C12B—C11B—H11B	119.8
C12A—C11A—H11A	119.7	C10B—C11B—H11B	119.8
C7A—C12A—C11A	120.4 (2)	C11B—C12B—C7B	120.2 (2)
C7A—C12A—H12A	119.8	C11B—C12B—H12B	119.9
C11A—C12A—H12A	119.8	C7B—C12B—H12B	119.9
O2A—N1A—C1A—O1A	4.3 (3)	C1B—N1B—C4B—O3B	178.1 (2)
C4A—N1A—C1A—O1A	−172.5 (2)	O2B—N1B—C4B—O3B	0.6 (3)
O2A—N1A—C1A—C2A	−174.98 (16)	C1B—N1B—C4B—C3B	−0.6 (2)
C4A—N1A—C1A—C2A	8.2 (2)	O2B—N1B—C4B—C3B	−178.04 (17)
C5A—N2A—C2A—C1A	−89.0 (2)	O3B—C4B—C3B—C2B	176.7 (2)
C5A—N2A—C2A—C3A	152.09 (18)	N1B—C4B—C3B—C2B	−4.7 (2)
O1A—C1A—C2A—N2A	48.1 (3)	C5B—N2B—C2B—C1B	−92.2 (2)
N1A—C1A—C2A—N2A	−132.62 (18)	C5B—N2B—C2B—C3B	149.15 (18)
O1A—C1A—C2A—C3A	172.6 (2)	C4B—C3B—C2B—N2B	130.09 (18)
N1A—C1A—C2A—C3A	−8.2 (2)	C4B—C3B—C2B—C1B	7.6 (2)
N2A—C2A—C3A—C4A	128.98 (18)	O2B—N1B—C1B—O1B	2.0 (3)
C1A—C2A—C3A—C4A	5.6 (2)	C4B—N1B—C1B—O1B	−175.6 (2)
C1A—N1A—C4A—O3A	174.9 (2)	O2B—N1B—C1B—C2B	−176.80 (16)
O2A—N1A—C4A—O3A	−1.9 (3)	C4B—N1B—C1B—C2B	5.7 (2)
C1A—N1A—C4A—C3A	−4.4 (2)	N2B—C2B—C1B—O1B	48.4 (3)
O2A—N1A—C4A—C3A	178.82 (17)	C3B—C2B—C1B—O1B	173.2 (2)
C2A—C3A—C4A—O3A	179.5 (2)	N2B—C2B—C1B—N1B	−132.85 (18)
C2A—C3A—C4A—N1A	−1.3 (2)	C3B—C2B—C1B—N1B	−8.0 (2)
C2A—N2A—C5A—O4A	−5.1 (3)	C2B—N2B—C5B—O4B	−3.3 (3)
C2A—N2A—C5A—O5A	175.89 (17)	C2B—N2B—C5B—O5B	179.04 (16)
C6A—O5A—C5A—O4A	−10.9 (3)	C6B—O5B—C5B—O4B	−6.3 (3)
C6A—O5A—C5A—N2A	168.10 (16)	C6B—O5B—C5B—N2B	171.47 (16)
C5A—O5A—C6A—C7A	−83.3 (2)	C5B—O5B—C6B—C7B	−93.0 (2)
O5A—C6A—C7A—C12A	−16.1 (3)	O5B—C6B—C7B—C8B	−117.6 (2)
O5A—C6A—C7A—C8A	166.63 (17)	O5B—C6B—C7B—C12B	62.9 (3)
C12A—C7A—C8A—C9A	0.7 (3)	C12B—C7B—C8B—C9B	−0.9 (3)
C6A—C7A—C8A—C9A	178.00 (18)	C6B—C7B—C8B—C9B	179.54 (19)
C7A—C8A—C9A—C10A	−0.6 (3)	C7B—C8B—C9B—C10B	−0.1 (3)
C8A—C9A—C10A—C11A	0.1 (3)	C8B—C9B—C10B—C11B	1.3 (3)
C9A—C10A—C11A—C12A	0.3 (3)	C9B—C10B—C11B—C12B	−1.4 (3)
C8A—C7A—C12A—C11A	−0.3 (3)	C10B—C11B—C12B—C7B	0.4 (3)
C6A—C7A—C12A—C11A	−177.5 (2)	C8B—C7B—C12B—C11B	0.8 (3)
C10A—C11A—C12A—C7A	−0.2 (3)	C6B—C7B—C12B—C11B	−179.72 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H1A···O4B^i	0.87 (3)	1.80 (3)	2.667 (2)	173 (3)
N2A—H2NA···O2B^i	0.84 (3)	2.39 (3)	3.184 (3)	158 (2)
N2A—H2NA···O1B^i	0.84 (3)	2.47 (2)	3.000 (3)	122 (2)
O2B—H1B···O4A	0.80 (3)	1.90 (3)	2.689 (2)	172 (3)
N2B—H2NB···O2A	0.84 (3)	2.43 (3)	3.237 (3)	162 (2)
C2A—H2A···O3A^ii	1.00	2.39	3.004 (3)	119
C2B—H2B···O3B^iii	1.00	2.43	3.035 (3)	118

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