Hydro­gen bonding in 2-(hydroxy­methyl)-1,3-propane­diol and N,N'-bis­[2-hydroxy-1,1-bis­(hydroxy­methyl)­ethyl]­malon­amide

The mol­ecule of 2-(hydroxy­methyl)-1,3-propane­diol, C₄H₁₀O₃, lies across a mirror plane in space group P2₁/m, with disorder of both terminal hydroxyl H atoms. The molecules are linked by three O-H...O hydrogen bonds which combine to form sheets; in each O-H...O bond, the H atom resonates between the two O atoms. In the crystal structure of N,N'-­bis­[2-hydroxy-1,1-bis­(hydroxy­methyl)­ethyl]­malon­amide, C₁₁H₂₂N₂O₈, the molecule lies about a twofold axis and has four strong hydrogen bonds which form a mixture of chains and dimers; these combine to give a three-dimensional supramolecular framework.

S1. Comment

The supramolecular structure of N,N'-bis[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]ethanediamide, (HOCH₂)₃CNHCOCONHC(CH₂OH)₃, (I), was recently reported to be two-dimensional, despite the presence of six independent hydrogen bonds (Ross et al., 2001). The aminotriol parent of (I), namely H₂NC(CH₂OH)₃, (II) (Eilerman & Rudman, 1980; Castellari & Ottani, 1997), also has a two-dimensional supramolecular structure in the orthorhombic phase, as does pentaerythritol, C(CH₂OH)₄, (III) (Ladd, 1979; Eilerman & Rudman, 1979a; Hope & Nichols, 1981; Semmingsen, 1988; Katrusiak, 1995; Batten & Robson, 1998). In contrast, the hydrogen-bonding arrangements in 3-hydroxy-2,2-bis(hydroxymethyl)propanoic acid, HO₂CC(CH₂OH)₃, (IV) (Eilerman & Rudman, 1979b), and 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, CH₃CH₂C(CH₂OH)₃, (V) (Zakaria et al., 2001), produce a three-dimensional array. The supramolecular structures of 2-(hydroxymethyl)-1,3-propanediol, (VI), and N,N'-bis-[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]malonamide, (VII), have now been determined and compared to those of the structure of compounds (I)–(V).

A general view of the molecule of (VI) is shown in Fig. 1. Atoms C1, C2 and O1 lie on the mirror plane, leading to disorder of the hydroxyl H atom bonded to O1. Similarly, there is disorder of the second hydroxyl group, resulting in three strong hydrogen bonds (Table 1). In fact, it can be considered that the H atoms resonate between the O atoms, so that a continous network of hydrogen bonds forms. In Fig. 2, H atoms have been omitted to make this network clearer; the dashed lines represent O—H···O bonds where the H atom may be coordinated to either O atom. Two chains form: the first forms from O2—H2C···O1^iv [symmetry code: (iv) 1 - x, y - 1/2, 1 - z] leading to a C(8) chain along (010), which combine to form a series of R²₂(12) rings (Fig. 2). The second chain forms from a combination of the first hydrogen bond and O2—H2B···O2ⁱⁱⁱ [symmetry code: (iii) -x, -y, -z] to give C(8) chains and R⁴₄(12) rings; these combine to form a sheet (Fig. 2), shown normal to [100].

A sheet arrangement of molecules was also found for the trihydroxy compound, (V) (Zakaria et al., 2001). The framework in (V) consists of parallel molecular ladders, generated by two of the three O—H···O hydrogen bonds. The ladders are linked together by the third hydrogen bond (Zakaria et al., 2001). In the tetrahydroxy compound, (III), the two-dimensional (sheet) structure is created by each molecule linking to four others by O—H···O hydrogen bonds; all the hydroxyl groups in (III) act as hydrogen-bond acceptors and donors (Ladd, 1979; Eilerman & Rudman, 1979a; Hope & Nichols, 1981; Semmingsen, 1988; Katrusiak, 1995; Batten & Robson, 1998).

N,N'-Bis-2-hydroxy-1,1-bis(hydroxymethyl)ethyl]malonamide, (VII) (Fig. 3), crystallizes in spacegroup C2/c with atom C6 on the 4 e s pecial positions; the remainder of the atoms are located in general positions with the full molecule generated by the c-glide (symmetry code: -x, y, 1/2 - z).

Four strong hydrogen bonds form (Table 2); amide atom N1 donates to hydroxyl atom O3 [N1—H1···O3(x, y + 1, z)], to form a C(5) chain along [010]. The symmetry of the molecule leads to two parallel C(5) chains giving linked R²₂(18) rings (Fig. 4). The hydroxyl atoms O2 and O4 act as both donor and acceptor; O4—H4···O2(-1/2 + x, 1/2 + y, z) leads to a C(13) chain along [110] whilst O2—H2···O4(1/2 - x, 1/2 - y, 1 - z) gives rise to a dimer centred on the inversion at (1/4, 1/4, 1/2) leading to an R²₂(12) motif. The two combine to give a sheet containing adjacent R⁴₄(8) and R²₂(12) rings (Fig. 5) O2—H2···O4—H4···O2. The final hydrogen bond again has a hydroxyl O atom as donor, but with the C═O as acceptor; O3—H3···O1(1/2 + x, -1/2 + y, z), thus generating a C(7) chain along [110]. The four hydrogen bonds combine in a number of ways. In addition to the formation of the R⁴₄(8) ring shown in Fig. 5, C(5) and C(7) combine to form an R²₂(8) ring, whilst C(7) and C(13) combine to give an R²₂(13) motif; both of these are shown in Fig. 6. Finally, all hydrogen bonds combine via the linking dimer to form a three-dimensional framework (Fig. 7).

The additional methylene group in (VII) results in significant structural differences between (I) (Ross et al., 2001) and (VII), the most striking being the change from a two-dimensional supramolecular network in (I) to the three-dimensional arrangement in (VII). The amido NH units in (I) take no part in the supramolecular aggregation, being solely involved in intramolecular hydrogen bonding with the adjacent carbonyl O atoms (Ross et al., 2001). Each molecule of (I) acts as a fourfold donor and acceptor in intermolecular hydrogen bonding and each molecule of (I) is thereby linked to six others in the resulting two-dimensional array (Ross et al., 2001). In the aminotriol, (II), the amino group is involved in the intermolecular hydrogen bonding. However, despite there being four distinct hydrogen bonds [two O—H···O, one O—H···N and one N—H···O], the supramolecular structure is only two-dimensional (Eilerman & Rudman, 1980; Castellari & Ottani, 1997).

S2. Experimental

Compound (VI) was a commercial sample and was recrystallized from dry ethyl acetate. Compound (VII) was prepared from (II) (0.045 mol) and diethyl malonate (0.023 mol) in refluxing methanol for 2 h. On cooling, colourless crystals of (VII) slowly formed. The product was recrystallized from aqueous EtOH (yield 90%, m.p. 428 K). ¹H NMR (Me₂SO-d₆, p.p.m.): δ 3.15 (s, 2H, COCH₂), 3.539 (d, 12H, CH₂OH), 4.63 (t, 6H, OH), 7.55 (s, 2H, NH). ¹³C NMR (Me₂SO-d₆, p.p.m.): δ 44.4 (COCH₂), 60.6 (CH₂OH), 62.9 (C-quarternary), 168.8 (CO). IR (KBr): ν 3361 and 3308 (OH), 3217 (NH), 2970, 2953 and 2883 (CH), 1648 (CO).

S3. Refinement

All H atoms were placed in geometrical positions and refined using a riding model. PLATON (Spek, 2002) was used for analysis of hydrogen bonding.

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (VI); SMART (Bruker, 1998) for (VII). Cell refinement: DENZO and COLLECT for (VI); SAINT (Bruker, 2000) for (VII). Data reduction: DENZO and COLLECT for (VI); SAINT for (VII). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX in OSCAIL (McArdle, 1994, 2000) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecule of (VI), showing the atom-numbering scheme. The molecule lies across the mirror [symmetry code: (i) x, -y + 1/2, z]. Dashed lines indicate disorder of the terminal H atoms. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.
	Fig. 2. Arrangement of molecules of (VI) within the unit cell, showing formation of sheets normal to [100]. Dashed lines indicate O—H···O bonds in which H atoms resonate between the two O atoms, as indicated by the disorder as shown in Fig. 1.
	Fig. 3. A view of the molecule of (VII), showing the atom-numbering scheme, and the formation of the molecule via symmetry operation [symmetry code: (i) -x, y, -z + 1/2]. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres.
	Fig. 4. Part of the crystal structure of (VII), showing the C(5) chains formed from N1—H1···O3^ii hydrogen bonds [symmetry code: (ii) x, y + 1, z].
	Fig. 5. Part of the crystal structure of (VII), showing the sheets formed from two hydrogen bonds [O2—H2···O4^iv and O4—H4···O2^iii; symmetry codes: (iii) -1/2 + x, 1/2 + y, z; (iv) 1/2 - x, 1/2 - y, 1 - z] resulting in an R^44(8) ring, viz. O4—H4···O2^ii—H2^ii···O4^vi—H4^vi····O2^iii—H2^iii···O4 [symmetry codes: (ii) x, y + 1, z; (vi) -1/2 - x, 1/2 + y, 1/2 - z].
	Fig. 6. Combination of three hydrogen bonds in the structure of (VII), i.e. N1—H1···O3, O3—H3···O1 and O4—H4···O2. This gives C(5), C(7) and C(13) chains which combine to give R^22(8) and R^22(13) rings. [Symmetry codes: (iii) -1/2 + x, 1/2 + y, z; (vi) -1/2 - x, 1/2 + y, 1/2 - z].
	Fig. 7. The unit cell of (VII), showing the formation of a three-dimensional framework of hydrogen bonds.

(VI) 2-(hydroxymethyl)-1,2-propanediol

Crystal data

C4H10O3	F(000) = 116
Mr = 106.12	Dx = 1.320 Mg m^−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1123 reflections
a = 4.8066 (3) Å	θ = 2.9–27.5°
b = 9.5179 (6) Å	µ = 0.11 mm^−1
c = 6.1346 (4) Å	T = 292 K
β = 107.911 (4)°	Prism, colourless
V = 267.05 (3) Å^3	0.26 × 0.12 × 0.05 mm
Z = 2

Data collection

Enraf-Nonius KappaCCD diffractometer	629 independent reflections
Radiation source: fine-focus sealed tube	504 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ–ω scans	θmax = 27.4°, θmin = 3.5°
Absorption correction: empirical (using intensity measurements) (SORTAV; Blessing, 1995, 1997)	h = −5→6
Tmin = 0.949, Tmax = 0.994	k = −12→11
2166 measured reflections	l = −7→7

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.0278P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
629 reflections	Δρmax = 0.17 e Å^−3
46 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.21 (5)

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)
C2	0.2426 (3)	0.2500	0.2648 (3)	0.0329 (4)
H2A	0.0409	0.2500	0.1622	0.039*
C1	0.2268 (4)	0.2500	0.5080 (3)	0.0393 (5)
H1A	0.1200	0.3324	0.5304	0.047*
O1	0.5093 (3)	0.2500	0.6743 (2)	0.0468 (4)
H1	0.5682	0.1689	0.6998	0.062 (9)*	0.50
C3	0.3879 (3)	0.11876 (11)	0.21179 (19)	0.0381 (4)
H3A	0.4199	0.1288	0.0640	0.046*
H3B	0.5766	0.1062	0.3268	0.046*
O2	0.2094 (2)	−0.00105 (9)	0.20882 (17)	0.0518 (4)
H2B	0.094 (8)	−0.001 (4)	0.079 (7)	0.078*	0.50
H2C	0.293 (8)	−0.073 (5)	0.236 (6)	0.078*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0341 (8)	0.0254 (8)	0.0340 (8)	0.000	0.0029 (6)	0.000
C1	0.0408 (9)	0.0344 (9)	0.0435 (10)	0.000	0.0144 (7)	0.000
O1	0.0587 (8)	0.0382 (8)	0.0348 (7)	0.000	0.0016 (5)	0.000
C3	0.0466 (7)	0.0277 (6)	0.0380 (7)	0.0000 (5)	0.0102 (5)	−0.0030 (4)
O2	0.0667 (7)	0.0254 (5)	0.0535 (7)	−0.0061 (4)	0.0040 (5)	−0.0018 (4)

Geometric parameters (Å, º)

C2—C3	1.5146 (13)	C3—O2	1.4239 (14)
C2—C1	1.517 (2)	C3—H3A	0.9700
C2—H2A	0.9800	C3—H3B	0.9700
C1—O1	1.426 (2)	O2—H2B	0.82 (4)
C1—H1A	0.9700	O2—H2C	0.79 (4)
O1—H1	0.8200
C3—C2—C3^i	111.13 (12)	O2—C3—H3A	109.6
C3—C2—C1	112.15 (8)	C2—C3—H3A	109.6
C3—C2—H2A	107.0	O2—C3—H3B	109.6
C1—C2—H2A	107.0	C2—C3—H3B	109.6
O1—C1—C2	112.28 (13)	H3A—C3—H3B	108.1
O1—C1—H1A	109.1	C3—O2—H2B	104 (3)
C2—C1—H1A	109.1	C3—O2—H2C	115 (3)
C1—O1—H1	109.5	H2B—O2—H2C	110 (4)
O2—C3—C2	110.32 (10)
C3—C2—C1—O1	62.93 (9)	C1—C2—C3—O2	67.63 (13)
C3^i—C2—C3—O2	−165.95 (8)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^ii	0.82	1.91	2.7130 (11)	167
O2—H2B···O2^iii	0.82 (4)	1.91 (4)	2.729 (2)	173 (4)
O2—H2C···O1^iv	0.79 (4)	1.93 (4)	2.7130 (11)	175 (4)

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

(VII) N,N'-bis[2-hydroxy-1,1-bis(hydroxymethyl)ethyl]malonamide

Crystal data

C11H22N2O8	F(000) = 664
Mr = 310.31	Dx = 1.484 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3982 reflections
a = 11.6928 (11) Å	θ = 3.7–32.3°
b = 5.6610 (5) Å	µ = 0.13 mm^−1
c = 21.0034 (19) Å	T = 292 K
β = 92.700 (2)°	Plate, colourless
V = 1388.7 (2) Å^3	0.50 × 0.50 × 0.10 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	2473 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ϕ–ω scans	θmax = 32.5°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→17
Tmin = 0.817, Tmax = 0.928	k = −8→8
6754 measured reflections	l = −31→31

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.187	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.1186P)^2 + 0.6984P] where P = (Fo^2 + 2Fc^2)/3
2473 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.27 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 > 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.

Reflections 6 0 14 and 6 0 16 were omitted from the refinement as these gave an anomalously poor fit.

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

	x	y	z	Uiso*/Ueq
C1	0.18283 (10)	0.0069 (2)	0.37960 (5)	0.0214 (2)
C2	0.30828 (11)	0.0892 (2)	0.39066 (6)	0.0273 (3)
H2A	0.3471	0.0772	0.3510	0.033*
H2B	0.3092	0.2537	0.4035	0.033*
O2	0.36882 (10)	−0.0482 (2)	0.43840 (6)	0.0388 (3)
H2	0.3746	0.0272	0.4717	0.058*
C3	0.17427 (12)	−0.2557 (2)	0.36034 (7)	0.0284 (3)
H3A	0.2077	−0.3511	0.3948	0.034*
H3B	0.0941	−0.2984	0.3548	0.034*
O3	0.22973 (10)	−0.3107 (2)	0.30335 (5)	0.0345 (3)
H3	0.2950	−0.3568	0.3123	0.052*
C4	0.11605 (13)	0.0373 (2)	0.44108 (6)	0.0293 (3)
H4A	0.0442	−0.0478	0.4363	0.035*
H4B	0.1601	−0.0320	0.4766	0.035*
O4	0.09299 (10)	0.2793 (2)	0.45517 (5)	0.0353 (3)
H4	0.0298	0.3157	0.4396	0.053*
N1	0.13697 (9)	0.15798 (19)	0.32724 (5)	0.0230 (2)
H1	0.1850	0.2435	0.3078	0.028*
C5	0.02636 (11)	0.1730 (2)	0.30746 (6)	0.0234 (2)
O1	−0.05086 (9)	0.0641 (2)	0.33328 (6)	0.0406 (3)
C6	0.0000	0.3319 (3)	0.2500	0.0246 (3)
H6A	−0.0696 (18)	0.428 (4)	0.2556 (10)	0.034 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0242 (5)	0.0226 (5)	0.0172 (5)	0.0016 (4)	−0.0019 (4)	0.0007 (3)
C2	0.0242 (6)	0.0303 (6)	0.0267 (5)	0.0010 (4)	−0.0059 (4)	−0.0027 (4)
O2	0.0393 (6)	0.0394 (6)	0.0361 (5)	0.0150 (5)	−0.0149 (5)	−0.0085 (4)
C3	0.0305 (6)	0.0237 (5)	0.0311 (6)	−0.0004 (4)	0.0032 (5)	−0.0017 (4)
O3	0.0322 (5)	0.0374 (5)	0.0340 (5)	0.0045 (4)	0.0018 (4)	−0.0111 (4)
C4	0.0347 (7)	0.0326 (6)	0.0210 (5)	0.0055 (5)	0.0046 (5)	0.0034 (4)
O4	0.0385 (6)	0.0400 (6)	0.0271 (5)	0.0120 (4)	−0.0025 (4)	−0.0089 (4)
N1	0.0221 (5)	0.0256 (5)	0.0211 (4)	−0.0014 (3)	0.0000 (3)	0.0040 (3)
C5	0.0234 (5)	0.0263 (5)	0.0206 (5)	0.0008 (4)	0.0003 (4)	0.0002 (4)
O1	0.0242 (5)	0.0584 (7)	0.0392 (6)	−0.0039 (5)	0.0014 (4)	0.0191 (5)
C6	0.0294 (8)	0.0255 (7)	0.0184 (6)	0.000	−0.0054 (6)	0.000

Geometric parameters (Å, º)

C1—N1	1.4740 (15)	O3—H3	0.8200
C1—C3	1.5429 (17)	C4—O4	1.4301 (17)
C1—C2	1.5460 (18)	C4—H4A	0.9700
C1—C4	1.5496 (17)	C4—H4B	0.9700
C2—O2	1.4299 (16)	O4—H4	0.8200
C2—H2A	0.9700	N1—C5	1.3424 (16)
C2—H2B	0.9700	N1—H1	0.8600
O2—H2	0.8200	C5—O1	1.2392 (16)
C3—O3	1.4224 (17)	C5—C6	1.5251 (16)
C3—H3A	0.9700	C6—C5^i	1.5250 (16)
C3—H3B	0.9700	C6—H6A	0.99 (2)
N1—C1—C3	110.27 (10)	H3A—C3—H3B	107.7
N1—C1—C2	104.28 (10)	C3—O3—H3	109.5
C3—C1—C2	112.26 (10)	O4—C4—C1	112.71 (11)
N1—C1—C4	112.18 (10)	O4—C4—H4A	109.1
C3—C1—C4	107.24 (10)	C1—C4—H4A	109.1
C2—C1—C4	110.69 (10)	O4—C4—H4B	109.1
O2—C2—C1	112.11 (11)	C1—C4—H4B	109.1
O2—C2—H2A	109.2	H4A—C4—H4B	107.8
C1—C2—H2A	109.2	C4—O4—H4	109.5
O2—C2—H2B	109.2	C5—N1—C1	125.38 (10)
C1—C2—H2B	109.2	C5—N1—H1	117.3
H2A—C2—H2B	107.9	C1—N1—H1	117.3
C2—O2—H2	109.5	O1—C5—N1	122.98 (12)
O3—C3—C1	113.90 (11)	O1—C5—C6	121.04 (11)
O3—C3—H3A	108.8	N1—C5—C6	115.98 (10)
C1—C3—H3A	108.8	C5^i—C6—C5	107.69 (14)
O3—C3—H3B	108.8	C5^i—C6—H6A	106.3 (12)
C1—C3—H3B	108.8	C5—C6—H6A	111.4 (12)
N1—C1—C2—O2	−177.01 (10)	C2—C1—C4—O4	71.84 (14)
C3—C1—C2—O2	−57.64 (14)	C3—C1—N1—C5	69.30 (15)
C4—C1—C2—O2	62.15 (13)	C2—C1—N1—C5	−169.99 (12)
N1—C1—C3—O3	56.21 (14)	C4—C1—N1—C5	−50.16 (16)
C2—C1—C3—O3	−59.59 (14)	C1—N1—C5—O1	2.5 (2)
C4—C1—C3—O3	178.62 (11)	C1—N1—C5—C6	−176.91 (10)
N1—C1—C4—O4	−44.19 (15)	O1—C5—C6—C5^i	−73.77 (13)
C3—C1—C4—O4	−165.40 (11)	N1—C5—C6—C5^i	105.60 (11)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^ii	0.86	2.58	3.2445 (16)	135
O4—H4···O2^iii	0.82	2.03	2.8037 (16)	157
O2—H2···O4^iv	0.82	1.91	2.7238 (15)	172
O3—H3···O1^v	0.82	1.89	2.7069 (16)	175
C4—H4A···O1	0.97	2.47	2.9227 (19)	108

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