Inter­molecular dihydrogen- and hydrogen-bonding inter­actions in diammonium closo-deca­hydro­deca­borate sesquihydrate

The asymmetric unit of the title salt, 2NH₄⁺·B₁₀H₁₀^2-·1.5H₂O or (NH₄)₂B₁₀H₁₀·1.5H₂O, (I), contains two B₁₀H₁₀^2- anions, four NH₄⁺ cations and three water mol­ecules. (I) was converted to the anhydrous compound (NH₄)₂B₁₀H₁₀, (II), by heating to 343 K and its X-ray powder pattern was obtained. The extended structure of (I) shows two types of hydrogen-bonding interactions (N-H...O and O-H...O) and two types of dihydrogen-bonding interactions (N-H...H-B and O-H...H-B). The N-H...H-B dihydrogen bonding forms a two-dimensional sheet structure, and hydrogen bonding (N-H...O and O-H...O) and O-H...H-B dihydrogen bonding link the respective sheets to form a three-dimensional polymeric network structure. Compound (II) has been shown to form a polymer with the accompanying loss of H₂ at a faster rate than (NH₄)₂B₁₂H₁₂ and we believe that this is due to the stronger dihydrogen-bonding inter­actions shown in the hydrate (I).

S1. Comment

Dihydrogen-bonded compounds such as NH₃BH₃ (Klooster et al.,1999) and (NH₃)₂Mg(BH₄)₂ (Soloveichik et al., 2008) give off H₂ when heated. Since the ammonium cation in (NH₄)₂B₁₀H₁₀ has protonic hydrogen and the B—H hydrogen on the boron cage (B₁₀H₁₀²⁻) is hydridic, it is a potential material for hydrogen storage. (NH₄)₂B₁₀H₁₀ has been mentioned in the literature as an additive in rocket fuel (Goddard et al., 1978), a hydrogen generator for a fuel cell (Kelly et al., 2005; Goddard et al., 1978), and its polymeric product as a neutron shield material (Yolles et al., 1969). The syntheses of anhydrous (NH₄)₂B₁₀H₁₀ (Muetterties et al., 1964) and dihydrate (NH₄)₂B₁₀H₁₀·2H₂O (Ivanov et al., 1992) have been reported but their structures remain unknown. The reported synthesis of anhydrous (NH₄)₂B₁₀H₁₀ involves a sulfur-containing precursor (B₁₀H₁₂·2SMe₂) which is undesirable for hydrogen-storage materials because the sulfur poisons the fuel cell catalyst. The single-crystal X-ray structure of the reported B₁₂ analogue, (NH₄)₂B₁₂H₁₂, has weak N—H···H—B dihydrogen-bonding interactions (Titritis & Schleid, 2003). We report here the synthesis of the sulfur-free dihydrogen-bonded compound (NH₄)₂B₁₀H₁₀·1.5H₂O, (I), and its anhydrous analogue (NH₄)₂B₁₀H₁₀, (II), and their characterization by NMR, IR, single-crystal X-ray diffraction analysis, powder X-ray diffraction analysis, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).

To determine whether the single-crystal structure of (I) is representative of the bulk sample, X-ray powder diffraction of (I) was done. The experimental and the calculated powder patterns are similar. The small difference in 2θ values is attributed to the temperature difference between the single-crystal collection temperature (150 K) and powder diffraction (297 K) (see supplementary files). The water molecules in (I) were removed by heating to 343 K for 2 h to form (II) where the loss of water was confirmed by IR, DSC and ¹HNMR. ¹H and ¹¹BNMR also confirmed that no hydrogen was lost as a result of heating of (I) to 343 K. The powder X-ray diffraction pattern of (II) is different from that of (I).

The asymmetric unit of (I) contains two crystallographically independent B₁₀H₁₀²⁻anions, four NH₄⁺ cations and three water molecules (Fig. 1) and the unit cell contains four asymmetric units (Fig. 2). There are nine different N—H···H—B dihydrogen-bonding interactions (Table 2) that lead to the formation of a two-dimensional dihydrogen-bonded sheet which lies parallel to the ab plane (Fig. 3, supplementary figures S3 and S4). The range of H···H distances in these interactions is 1.99 (3)–2.27 (3) Å and either two (N2) or three (N1 and N3) of the four H atoms of the ammonium cation are involved. In addition, four different O—H···H—B interactions are observed, with H···H distances in the range 2.06 (3)–2.23 (3) Å. An examination of 18 X-ray structures from the Cambridge Structural Database (CSD, Version 5.30, November 2008 release; Allen, 2002) containing either substituted ammonium ions or open-cage boron compounds found that the H···H distances in the N—H···H—B dihydrogen bonds are in the range of 1.7–2.2 Å, and H—H—B and H—H—N bond angles are clustered in the ranges 95–115° and 150–170°, respectively. The H—H—B and H—H—N bond angles of the nine dihydrogen-bonded interactions in (I) are similarly clustered in the ranges 90–110° and 130–160° with 5° (H—H—B) and 15° (H—H—N) shifts to smaller angles compared to the 18 X-ray structures from the CSD organic structure database. In comparison with the closely related cage compound (NH₄)₂B₁₂H₁₂, the N—H···H—B dihydrogen-bond distances in (I) are much shorter than those in (NH₄)₂B₁₂H₁₂, which are all the same by symmetry (2.36 Å) and close to the sum of the van der Waals radii of H atoms (~2.4 Å) (Titritis et al., 2003).

In the two-dimensional sheet (Fig. 3), two B₁₀H₁₀²⁻anions and two ammonium cations form a dihydrogen-bonded 14-membered ring and this unit is repeated in the two-dimensional sheet. The third dihydrogen bond on N1, H1B···H13, extends the two-dimensional sheet parallel to the a axis and connects two two-dimensional sheets together. The H2C proton on N2 has a bifurcated dihydrogen bond to two B—H protons (H2 and H5, Fig. 3) on the same B₁₀H₁₀²⁻. Two sets of N—H···H—B dihydrogen-bonded two-dimensional sheets are connected to another two sets of two-dimensional sheets by four different (O—H···H—B) dihydrogen-bonding interactions combined with six hydrogen-bonding interactions (four N—H···O and two O—H···H) (Tables 1 and 2) to form a three-dimensional extended network (Fig. S4). The B15—H15 hydridic protons have a bifurcated dihydrogen bond with two different water molecules and the O—H···H—B dihydrogen bonds form a one-dimensional zigzag chain (B—H···H—O—H···H—B) connecting the bottom and upper two-dimensional layers (Fig. S4). The hydrogen bonds also form a continuous one-dimensional chain of H—N—H···O···H—O···H—N—H···O along the b axis. Along the hydrogen-bonded one-dimensional chain (Fig. 4), additional ammonium ions and water molecules hydrogen bond with water on the main chain (O···H—N and O—H···O···H—N) and the end-group ammonium protons link the two two-dimensional sheets from above and below by dihydrogen bonding with B—H. The significance of this study is that since the dihydrogen bonds in (I) are stronger than those in (NH₄)₂B₁₂H₁₂, the kinetics of hydrogen release should be faster. In fact, Yolles et al.(1969) has reported that (NH₄)₂B₁₀H₁₀ releases hydrogen much faster than (NH₄)₂B₁₂H₁₂ when heated under the same conditions.

Related literature

For related literature, see: Goddard et al. (1978); Hawthorne & Pilling (1967); Kelly et al. (2005); Klooster et al. (1999); Macrae et al. (2006); Muetterties et al. (1964); Nonius (2000); Otwinowski & Minor (1997); Sheldrick (2008); Soloveichik et al. (2008); Yolles (1969).

S2. Experimental

Infrared spectra were recorded on a BrukerTensor 27 spectrometer. ¹H and ¹¹B NMR spectroscopy were performed on a DPX-400 spectrometer (at 250.1/400.1 and 62.9/100.6 MHz, respectively) or a Bruker DPX-250 spectrometer at 80.25 MHz [pls check spectrometer details are given correctly - different to previous version]. Boron spectra were externally referenced to BF₃·OEt₂ in C₆D₆ (d = 0 p.p.m.). Thermogravimetric analysis was done using a Perkin Elmer TGA 7 analyzer with a TAC 7/DS thermal analysis instrument controller and samples were loaded on a quartz crucible. Powder X-ray diffraction patterns were collected on a Bruker D8 Advanced X-ray diffractometer (40 kV, 50 mA, Cu Kα₁ radiation) equipped with an incident beam Ge 1 1 1 vario monochromator and a Lynxeye super speed detector. The sample of (I) was loaded in a sealed 1 mm capillary tube in a glove box. Mercury version 2.2 (Macrae et al., 2006) was used to generate one-, two- and three-dimensional structures.

For the synthesis of (I), (NEt₃H)₂B₁₀H₁₀ (synthesized from decaborane according to Hawthorne & Pilling, 1967) (5.0 g, 15.51 mmol) was passed through an acid exchange resin to form the acidic (H₃O)₂B₁₀H₁₀. To the water solution of (H₃O)₂B₁₀H₁₀, excess ammonia gas was bubbled for 2 min and (NH₄)₂B₁₀H₁₀·1.5H₂O was crystallized from water by evaporation to give colorless plate-shaped crystals. For the synthesis of (II), compound (I) (NH₄)₂B₁₀H₁₀·1.5H₂O) was heated at 343 K for 2 h to give the anhydrous compound (II) [(NH₄)₂B₁₀H_10]. Spectroscopic (IR and ¹H and ¹¹B NMR) and thermogravimetric analysis data are available in the archived CIF.

S3. Refinement

The structure of (I) was solved by direct methods and refined using SHELXS97 (Sheldrick, 2008) and SHELXL97 (Sheldrick, 2008) (difference electron-density calculations and full-matrix least-squares refinements). Non-H atoms were located and refined anisotropically. H atoms were also located and refined isotropically.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures

	Fig. 1. ORTEP diagram of the asymmetric unit of (I) with 25% probability displacement ellipsoids.
	Fig. 2. Packing diagram of (I) viewed along the b axis. (In the electronic version of this paper, the dotted green and dotted red lines represent dihydrogen bonding and hydrogen bonding, respectively.)
	Fig. 3. The two-dimensional sheet structure of (I) showing N—H···H—B dihydrogen-bonding interactions. (In the electronic version of this paper, the red dotted lines show the contacts for the extended structure.) Symmmetry codes: (i) 1/2 − x, 1/2 + y, 1/2 − z; (ii) 1.5 − x, 1/2 + y, 1/2 − z; (iii) 1/2 + x, 1.5 − y, −0.5 - z; (iv) x, 1 + y, z; (v) 1/2 − x, 1.5 + y, 1/2 − z; (vi) 1.5 − x, 1.5 + y, 1/2 − z; (vii) 1/2 + x, 2.5 − y, −1/2 + z.
	Fig. 4. A one-dimensional chain of O–H···O and N–H···O hydrogen bonding. (In the electronic version of this paper, the dotted red line represents the main chain of hydrogen bonding and dotted green lines represent hydrogen bonding branching from the main chain.) Symmetry codes: (i) 1.5 − x, −1/2 + y, 1/2 − z; (ii) 1/2 − x, 1/2 + y, 1/2 − z; (iii) x − 1, y, z; (iv) x, 1 + y, z; (v) 1,5 − x, 1/2 + y, 1/2 − z; (vi) 1/2 − x, 1.5 + y, 1/2 − z; (vii) x − 1, 1 + y, z.

diammonium closo-decahydrodecaborate sesquihydrate

Crystal data

2NH4^+·B10H10^2^−·1.5H2O	F(000) = 776
Mr = 181.29	Dx = 1.039 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 10211 reflections
a = 11.674 (2) Å	θ = 2.5–27.5°
b = 8.6230 (17) Å	µ = 0.06 mm^−1
c = 23.318 (5) Å	T = 150 K
β = 98.97 (3)°	Plate, colorless
V = 2318.6 (8) Å^3	0.38 × 0.31 × 0.12 mm
Z = 8

Data collection

Nonius Kappa CCD diffractometer	5318 independent reflections
Radiation source: fine-focus sealed tube	3637 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ϕ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	h = −15→15
Tmin = 0.978, Tmax = 0.993	k = −10→11
10211 measured reflections	l = −30→30

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0677P)^2] where P = (Fo^2 + 2Fc^2)/3
5318 reflections	(Δ/σ)max < 0.001
412 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.26 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.

Infrared spectra were recorded on a BrukerTensor 27 spectrometer. ¹H and ¹¹B NMR spectroscopy were performed on a DPX-400 spectrometer (at 250.1/400.1 and 62.9/100.6 MHz, respectively) or a Bruker DPX-250 spectrometer at 80.25 MHz [pls check spectrometer details are given correctly - different to previous version]. Boron spectra were externally referenced to BF₃·OEt₂ in C₆D₆ (d = 0 p.p.m.). Thermogravimetric analysis was done using a Perkin Elmer TGA 7 analyzer with a TAC 7/DS thermal analysis instrument controller and samples were loaded on a quartz crucible. Powder X-ray diffraction patterns were collected on a Bruker D8 Advanced X-ray diffractometer (40 kV, 50 mA, Cu Kα₁ radiation) equipped with an incident beam Ge 1 1 1 vario monochromator and a Lynxeye super speed detector. The sample of (I) was loaded in a sealed 1 mm capillary tube in a glove box. Mercury version 2.2 (Macrae et al., 2006) was used to generate one-, two- and three-dimensional structures.

¹HNMR (D₂O, p.p.m.) 4.5 (s, H₂O + NH₄), 3.2 (q, axial B—H), 0.03 (q, B—H equatorial B—H) ¹¹BNMR (D₂O, p.p.m.) −1.3 (d, axial B), −30.2 (d, equatorial B) IR (KBr, cm⁻¹) 3552 (sh, OH), 3164 (s, N—H), 2539 (m, B—H), 2482 (s, B—H), 1632 (OH), 1401 (s, N—H), 1030 (m, v-B—B), 663 (m, B—B) PXRD [2θ(°), %I] 7.63 (5), 12.1, 14.29 (61),15.31 (58),15.38 (76), 15.48 (100), 16.12 (24), 17.92 (12), 18.16(14.2), 19.06 (39),19.32 (9), 19.53 (28), 20.03 (25), 20.46 (49), 20.79 (10), 21.69 (14), 21.87 (15),22.02 (21), 22.89 (21), 22.92 (12), 23.32 (12), 23.56 (11), 24.01 (11), 25.34 (18),25.63 (16), 26.12 (13), 26.19 (8), 27.36 (8), 27.78 (8), 30.83 (12), 31.17 (9), 31.84 (9), 32.34 (8), 32.52 (11),33.09 (16), 34.41 (10), 34.48 (11), 35.6 (8), 37.24 (9), 38.59 (7), 40.49 (5),41.67 (6), 42.36 (5). PXRD (calcd) [(2θ(°), %I] 7.69 (4), 12.85 (3), 14.34 (38), 15.4 (85), 15.6 (100), 16.1 (20), 18.1 (10), 18.28 (13), 19.16 (39), 19.44 (21), 19.64 (40), 20.06 (25), 20.64 (55), 21 (10), 21.9 (16), 22.18 (28), 22.9 (31), 23.16 (9), 23.52 (6), 23.78 (7), 24.24 (9), 25.5 (21), 25.86 (13), 26.28 (9), 27.66 (7), 27.86 (5), 31.24 (10),31.48 (7), 31.74 (3), 32.14 (8), 32.46 (4), 32.62 (5), 32.82 (10), 33.3 (13), 34.68 (13), 34.92 (16), 35.44 (3), 35.68 (9), 35.98 (7), 37.38 (9), 38.94 (6), 40.88 (6), 41.84 (6), 42.76 (6) T GA (K) 343–375 (−1.5H₂O), 563–579 (−2H₂) DSC (K) 353 (–H₂O), 376 (endotherm), 563, 593, 653 (exotherm).

¹HNMR (CD₃CN, p.p.m.) 5.98 (s, NH₄), 3.2 (q, ax B—H), 0.01 (q, B—H eqB-H) ¹¹BNMR (D₂O, p.p.m.) −1.3 (d, ax B), −30.2 (d,eq B) IR (KBr, cm⁻¹) 3223 (s, N—H), 2555 (m, B—H), 2471 (s, B—H),1399 (s, N—H), 1025 (m, B—B) PXRD [2θ(°), %I] 13.366 (11), 13.83 (16), 14.81 (37),15.48 (100), 16.70 (10), 19.35 (13), 20.07 (21), 20.78 (17), 21.51 (29), 23.03 (13), 24.21 (10), 24.29 (10), 25.47 (10), 26.94 (9), 27.80 (8), 29.007(0.8), 28.91 (8),30.81 (7), 33.79 (7), 34.21 (8), 35.03 (8), 37.38 (5), 38.62 (4) DSC (K) 563(exotherm).

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

	x	y	z	Uiso*/Ueq
N1	0.50260 (12)	0.74496 (17)	0.50414 (6)	0.0224 (3)
H1B	0.546 (2)	0.811 (3)	0.5238 (10)	0.082 (8)*
H1A	0.475 (2)	0.686 (3)	0.5291 (11)	0.086 (8)*
H1C	0.545 (2)	0.693 (3)	0.4826 (10)	0.090 (8)*
H1D	0.441 (2)	0.789 (3)	0.4804 (10)	0.099 (8)*
N3	0.09434 (13)	0.49302 (16)	0.41548 (6)	0.0243 (3)
H3D	0.1127 (15)	0.4749 (19)	0.3770 (8)	0.044 (5)*
H3C	0.022 (2)	0.506 (2)	0.4165 (9)	0.066 (7)*
H3B	0.1221 (19)	0.424 (3)	0.4387 (10)	0.073 (7)*
H3A	0.1320 (19)	0.585 (3)	0.4274 (9)	0.076 (7)*
N4	0.37466 (13)	0.35786 (18)	0.28534 (6)	0.0262 (3)
H4D	0.3669 (15)	0.373 (2)	0.2488 (9)	0.045 (5)*
H4C	0.423 (2)	0.436 (3)	0.3002 (9)	0.072 (7)*
H4B	0.4110 (16)	0.261 (2)	0.2927 (8)	0.053 (6)*
H4A	0.3079 (18)	0.364 (2)	0.2985 (8)	0.055 (6)*
O5	0.48361 (11)	0.05537 (13)	0.29082 (5)	0.0293 (3)
H5A	0.4597 (19)	0.002 (2)	0.3169 (10)	0.065 (7)*
H5B	0.554 (2)	0.039 (2)	0.2934 (9)	0.062 (7)*
O6	0.77673 (10)	0.48608 (16)	0.19975 (5)	0.0313 (3)
H6B	0.753 (2)	0.524 (3)	0.2294 (11)	0.077 (8)*
H6A	0.7755 (17)	0.392 (3)	0.2051 (9)	0.063 (7)*
B11	0.59525 (14)	0.61791 (18)	0.32814 (7)	0.0210 (4)
H11	0.5276 (12)	0.6772 (16)	0.2966 (6)	0.029 (4)*
B12	0.66991 (13)	0.68148 (18)	0.39249 (7)	0.0188 (3)
H12	0.6538 (12)	0.8008 (16)	0.4079 (6)	0.026 (4)*
B13	0.57921 (14)	0.50808 (18)	0.38701 (7)	0.0184 (3)
H13	0.4923 (13)	0.4908 (15)	0.3982 (6)	0.022 (4)*
B14	0.65159 (13)	0.43552 (18)	0.32726 (7)	0.0192 (3)
H14	0.6197 (11)	0.3572 (15)	0.2901 (6)	0.023 (4)*
B15	0.74202 (14)	0.60926 (18)	0.33330 (7)	0.0195 (3)
H15	0.7870 (12)	0.6688 (17)	0.3005 (6)	0.030 (4)*
B16	0.70005 (13)	0.52662 (18)	0.44566 (7)	0.0184 (3)
H16	0.6824 (12)	0.5459 (15)	0.4905 (6)	0.023 (4)*
B17	0.68552 (13)	0.35330 (18)	0.39961 (7)	0.0187 (3)
H17	0.6537 (12)	0.2342 (16)	0.4071 (6)	0.023 (4)*
B18	0.80128 (13)	0.42475 (18)	0.36154 (7)	0.0191 (3)
H18	0.8672 (12)	0.3660 (16)	0.3377 (6)	0.029 (4)*
B19	0.81446 (13)	0.59910 (18)	0.40780 (7)	0.0193 (3)
H19	0.8879 (12)	0.6788 (15)	0.4207 (6)	0.025 (4)*
B20	0.81566 (14)	0.41657 (19)	0.43527 (7)	0.0206 (3)
H20	0.8839 (12)	0.3602 (17)	0.4678 (6)	0.031 (4)*
B1	0.34250 (14)	0.61601 (19)	0.05067 (7)	0.0199 (3)
H1	0.3760 (12)	0.6951 (16)	0.0201 (6)	0.031 (4)*
B2	0.38720 (13)	0.57238 (18)	0.12155 (7)	0.0183 (3)
H2	0.4672 (13)	0.6272 (17)	0.1452 (6)	0.031 (4)*
B3	0.24181 (13)	0.64555 (17)	0.09475 (6)	0.0174 (3)
H3	0.1986 (11)	0.7642 (16)	0.0974 (5)	0.022 (4)*
B4	0.22521 (13)	0.49764 (17)	0.03766 (6)	0.0175 (3)
H4	0.1658 (12)	0.4946 (14)	−0.0064 (6)	0.021 (4)*
B5	0.37022 (13)	0.42424 (19)	0.06443 (7)	0.0189 (3)
H5	0.4349 (11)	0.3652 (15)	0.0417 (6)	0.020 (4)*
B6	0.26794 (13)	0.52766 (18)	0.16009 (7)	0.0180 (3)
H6	0.2688 (12)	0.5862 (16)	0.2031 (6)	0.024 (4)*
B7	0.15265 (13)	0.47462 (18)	0.10038 (6)	0.0176 (3)
H7	0.0562 (12)	0.4875 (15)	0.0939 (6)	0.022 (4)*
B8	0.24402 (13)	0.31905 (18)	0.07939 (7)	0.0185 (3)
H8	0.2222 (11)	0.2078 (15)	0.0556 (5)	0.016 (3)*
B9	0.35908 (14)	0.37127 (18)	0.13857 (7)	0.0200 (3)
H9	0.4276 (12)	0.3014 (16)	0.1631 (6)	0.028 (4)*
B10	0.21909 (14)	0.34163 (19)	0.14876 (7)	0.0210 (4)
H10	0.1825 (11)	0.2580 (16)	0.1779 (6)	0.021 (3)*
N2	0.65139 (12)	0.52968 (17)	0.08650 (6)	0.0222 (3)
H2D	0.6859 (15)	0.5115 (18)	0.1246 (9)	0.042 (5)*
H2C	0.572 (2)	0.515 (2)	0.0842 (9)	0.071 (7)*
H2B	0.682 (2)	0.471 (2)	0.0635 (10)	0.073 (7)*
H2A	0.6631 (17)	0.628 (3)	0.0755 (9)	0.064 (6)*
O7	0.13364 (10)	0.40354 (14)	0.30424 (5)	0.0309 (3)
H7A	0.1079 (19)	0.308 (3)	0.3030 (10)	0.088 (8)*
H7B	0.093 (2)	0.453 (3)	0.2734 (11)	0.078 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0185 (7)	0.0228 (7)	0.0256 (7)	0.0011 (6)	0.0024 (6)	0.0002 (6)
N3	0.0186 (7)	0.0232 (7)	0.0309 (8)	0.0002 (6)	0.0036 (6)	0.0005 (6)
N4	0.0222 (7)	0.0341 (9)	0.0211 (7)	−0.0022 (7)	0.0001 (6)	0.0040 (6)
O5	0.0260 (7)	0.0349 (7)	0.0281 (6)	−0.0049 (5)	0.0077 (5)	0.0019 (5)
O6	0.0410 (7)	0.0292 (7)	0.0245 (6)	−0.0042 (5)	0.0078 (5)	−0.0032 (5)
B11	0.0218 (8)	0.0223 (8)	0.0189 (8)	0.0007 (7)	0.0030 (7)	0.0026 (7)
B12	0.0190 (8)	0.0171 (8)	0.0208 (8)	0.0005 (7)	0.0052 (6)	0.0002 (6)
B13	0.0155 (8)	0.0197 (8)	0.0206 (8)	0.0005 (6)	0.0051 (6)	−0.0008 (6)
B14	0.0183 (8)	0.0218 (8)	0.0182 (8)	−0.0030 (7)	0.0050 (6)	−0.0024 (7)
B15	0.0214 (8)	0.0180 (8)	0.0204 (8)	−0.0010 (7)	0.0070 (6)	−0.0001 (6)
B16	0.0178 (8)	0.0208 (8)	0.0171 (8)	0.0009 (6)	0.0043 (6)	−0.0002 (6)
B17	0.0185 (8)	0.0170 (8)	0.0213 (8)	0.0000 (6)	0.0052 (6)	0.0008 (6)
B18	0.0181 (8)	0.0176 (8)	0.0224 (8)	0.0000 (6)	0.0058 (6)	−0.0022 (6)
B19	0.0172 (8)	0.0191 (8)	0.0220 (8)	−0.0016 (7)	0.0045 (6)	−0.0052 (7)
B20	0.0173 (8)	0.0221 (8)	0.0225 (8)	0.0024 (7)	0.0028 (6)	0.0001 (7)
B1	0.0207 (8)	0.0199 (8)	0.0197 (8)	−0.0025 (7)	0.0047 (6)	−0.0022 (6)
B2	0.0147 (8)	0.0201 (8)	0.0202 (8)	0.0000 (6)	0.0029 (6)	−0.0062 (6)
B3	0.0185 (8)	0.0162 (8)	0.0171 (8)	0.0006 (6)	0.0011 (6)	−0.0013 (6)
B4	0.0169 (8)	0.0195 (8)	0.0158 (7)	0.0010 (6)	0.0020 (6)	−0.0022 (6)
B5	0.0141 (8)	0.0229 (8)	0.0195 (8)	0.0003 (7)	0.0025 (6)	−0.0063 (7)
B6	0.0167 (8)	0.0215 (8)	0.0155 (7)	0.0030 (6)	0.0017 (6)	−0.0013 (6)
B7	0.0153 (8)	0.0188 (8)	0.0189 (8)	−0.0004 (6)	0.0027 (6)	−0.0020 (6)
B8	0.0156 (8)	0.0174 (8)	0.0212 (8)	0.0019 (6)	−0.0009 (6)	−0.0019 (7)
B9	0.0173 (8)	0.0207 (8)	0.0205 (8)	0.0031 (7)	−0.0020 (6)	−0.0023 (7)
B10	0.0210 (8)	0.0207 (8)	0.0213 (8)	−0.0012 (7)	0.0030 (7)	0.0016 (7)
N2	0.0170 (7)	0.0245 (7)	0.0258 (7)	−0.0017 (6)	0.0052 (5)	−0.0019 (6)
O7	0.0312 (6)	0.0308 (7)	0.0311 (6)	0.0040 (5)	0.0057 (5)	0.0069 (5)

Geometric parameters (Å, º)

N1—H1B	0.85 (2)	B18—B19	1.843 (2)
N1—H1A	0.87 (3)	B18—H18	1.137 (15)
N1—H1C	0.88 (3)	B19—B20	1.699 (2)
N1—H1D	0.92 (3)	B19—H19	1.103 (14)
N3—H3D	0.968 (19)	B20—H20	1.122 (15)
N3—H3C	0.86 (2)	B1—B2	1.696 (2)
N3—H3B	0.84 (2)	B1—B4	1.697 (2)
N3—H3A	0.93 (2)	B1—B3	1.697 (2)
N4—H4D	0.85 (2)	B1—B5	1.706 (2)
N4—H4C	0.91 (2)	B1—H1	1.101 (15)
N4—H4B	0.94 (2)	B2—B6	1.812 (2)
N4—H4A	0.88 (2)	B2—B9	1.820 (2)
O5—H5A	0.84 (2)	B2—B3	1.827 (2)
O5—H5B	0.82 (2)	B2—B5	1.834 (2)
O6—H6B	0.85 (2)	B2—H2	1.113 (14)
O6—H6A	0.82 (2)	B3—B6	1.817 (2)
B11—B15	1.700 (2)	B3—B7	1.821 (2)
B11—B13	1.702 (2)	B3—B4	1.832 (2)
B11—B12	1.704 (2)	B3—H3	1.147 (14)
B11—B14	1.706 (2)	B4—B7	1.812 (2)
B11—H11	1.116 (14)	B4—B8	1.817 (2)
B12—B19	1.814 (2)	B4—B5	1.824 (2)
B12—B16	1.819 (2)	B4—H4	1.146 (14)
B12—B13	1.825 (2)	B5—B8	1.810 (2)
B12—B15	1.834 (2)	B5—B9	1.812 (2)
B12—H12	1.115 (14)	B5—H5	1.111 (13)
B13—B16	1.812 (2)	B6—B10	1.709 (2)
B13—B17	1.815 (2)	B6—B9	1.835 (2)
B13—B14	1.848 (2)	B6—B7	1.837 (2)
B13—H13	1.097 (15)	B6—H6	1.122 (14)
B14—B18	1.807 (2)	B7—B10	1.708 (2)
B14—B17	1.816 (2)	B7—B8	1.827 (2)
B14—B15	1.825 (2)	B7—H7	1.119 (14)
B14—H14	1.116 (13)	B8—B10	1.699 (2)
B15—B19	1.812 (2)	B8—B9	1.826 (2)
B15—B18	1.817 (2)	B8—H8	1.118 (13)
B15—H15	1.117 (15)	B9—B10	1.707 (2)
B16—B20	1.698 (2)	B9—H9	1.090 (14)
B16—B19	1.822 (2)	B10—H10	1.121 (14)
B16—B17	1.833 (2)	N2—H2D	0.93 (2)
B16—H16	1.109 (14)	N2—H2C	0.93 (2)
B17—B20	1.704 (2)	N2—H2B	0.86 (2)
B17—B18	1.835 (2)	N2—H2A	0.90 (2)
B17—H17	1.115 (14)	O7—H7A	0.87 (2)
B18—B20	1.703 (2)	O7—H7B	0.90 (3)
H1B—N1—H1A	107 (2)	B19—B20—B17	99.11 (11)
H1B—N1—H1C	108 (2)	B18—B20—B17	65.19 (10)
H1A—N1—H1C	112 (2)	B16—B20—H20	129.9 (8)
H1B—N1—H1D	113 (2)	B19—B20—H20	128.3 (7)
H1A—N1—H1D	108 (2)	B18—B20—H20	130.5 (8)
H1C—N1—H1D	109 (2)	B17—B20—H20	132.6 (7)
H3D—N3—H3C	114.1 (18)	B2—B1—B4	99.09 (11)
H3D—N3—H3B	111.5 (17)	B2—B1—B3	65.16 (9)
H3C—N3—H3B	111 (2)	B4—B1—B3	65.34 (9)
H3D—N3—H3A	104.6 (17)	B2—B1—B5	65.24 (9)
H3C—N3—H3A	107.9 (18)	B4—B1—B5	64.82 (9)
H3B—N3—H3A	107 (2)	B3—B1—B5	99.24 (11)
H4D—N4—H4C	103.2 (17)	B2—B1—H1	133.0 (7)
H4D—N4—H4B	107.0 (16)	B4—B1—H1	128.0 (7)
H4C—N4—H4B	110.9 (17)	B3—B1—H1	130.4 (7)
H4D—N4—H4A	112.0 (16)	B5—B1—H1	130.3 (7)
H4C—N4—H4A	110.5 (18)	B1—B2—B6	112.77 (11)
H4B—N4—H4A	112.8 (17)	B1—B2—B9	112.66 (11)
H5A—O5—H5B	107 (2)	B6—B2—B9	60.70 (9)
H6B—O6—H6A	103.9 (19)	B1—B2—B3	57.44 (9)
B15—B11—B13	98.91 (11)	B6—B2—B3	59.91 (8)
B15—B11—B12	65.19 (10)	B9—B2—B3	102.36 (10)
B13—B11—B12	64.80 (9)	B1—B2—B5	57.64 (9)
B15—B11—B14	64.81 (10)	B6—B2—B5	101.98 (10)
B13—B11—B14	65.66 (9)	B9—B2—B5	59.46 (9)
B12—B11—B14	99.32 (11)	B3—B2—B5	90.15 (10)
B15—B11—H11	131.9 (7)	B1—B2—H2	119.7 (8)
B13—B11—H11	129.2 (8)	B6—B2—H2	119.6 (8)
B12—B11—H11	130.2 (7)	B9—B2—H2	117.5 (8)
B14—B11—H11	130.4 (7)	B3—B2—H2	133.3 (8)
B11—B12—B19	112.31 (11)	B5—B2—H2	130.0 (8)
B11—B12—B16	112.47 (11)	B1—B3—B6	112.47 (11)
B19—B12—B16	60.21 (9)	B1—B3—B7	112.33 (11)
B11—B12—B13	57.54 (9)	B6—B3—B7	60.66 (9)
B19—B12—B13	101.81 (10)	B1—B3—B2	57.40 (9)
B16—B12—B13	59.65 (9)	B6—B3—B2	59.64 (9)
B11—B12—B15	57.31 (9)	B7—B3—B2	101.93 (10)
B19—B12—B15	59.55 (9)	B1—B3—B4	57.32 (9)
B16—B12—B15	101.59 (10)	B6—B3—B4	101.81 (10)
B13—B12—B15	89.91 (10)	B7—B3—B4	59.47 (8)
B11—B12—H12	119.5 (7)	B2—B3—B4	89.74 (10)
B19—B12—H12	119.7 (7)	B1—B3—H3	121.2 (7)
B16—B12—H12	118.8 (7)	B6—B3—H3	118.2 (7)
B13—B12—H12	130.8 (7)	B7—B3—H3	117.2 (7)
B15—B12—H12	132.6 (7)	B2—B3—H3	133.1 (6)
B11—B13—B16	112.89 (11)	B4—B3—H3	131.5 (6)
B11—B13—B17	112.41 (11)	B1—B4—B7	112.79 (11)
B16—B13—B17	60.70 (9)	B1—B4—B8	112.79 (11)
B11—B13—B12	57.66 (9)	B7—B4—B8	60.48 (9)
B16—B13—B12	60.00 (8)	B1—B4—B5	57.83 (9)
B17—B13—B12	102.51 (10)	B7—B4—B5	102.21 (10)
B11—B13—B14	57.28 (9)	B8—B4—B5	59.62 (8)
B16—B13—B14	101.84 (10)	B1—B4—B3	57.34 (9)
B17—B13—B14	59.43 (8)	B7—B4—B3	59.96 (8)
B12—B13—B14	90.10 (10)	B8—B4—B3	102.16 (10)
B11—B13—H13	119.3 (7)	B5—B4—B3	90.31 (10)
B16—B13—H13	118.2 (7)	B1—B4—H4	122.2 (7)
B17—B13—H13	119.8 (7)	B7—B4—H4	115.3 (7)
B12—B13—H13	130.0 (7)	B8—B4—H4	117.8 (6)
B14—B13—H13	133.0 (7)	B5—B4—H4	134.3 (7)
B11—B14—B18	112.96 (11)	B3—B4—H4	130.4 (6)
B11—B14—B17	112.18 (11)	B1—B5—B8	112.70 (11)
B18—B14—B17	60.87 (9)	B1—B5—B9	112.59 (11)
B11—B14—B15	57.44 (9)	B8—B5—B9	60.54 (9)
B18—B14—B15	60.02 (9)	B1—B5—B4	57.35 (9)
B17—B14—B15	102.06 (10)	B8—B5—B4	60.00 (8)
B11—B14—B13	57.06 (9)	B9—B5—B4	102.31 (11)
B18—B14—B13	102.02 (10)	B1—B5—B2	57.13 (9)
B17—B14—B13	59.39 (8)	B8—B5—B2	102.02 (11)
B15—B14—B13	89.47 (10)	B9—B5—B2	59.90 (9)
B11—B14—H14	119.0 (7)	B4—B5—B2	89.79 (10)
B18—B14—H14	119.7 (7)	B1—B5—H5	118.5 (7)
B17—B14—H14	118.9 (7)	B8—B5—H5	119.8 (7)
B15—B14—H14	132.5 (7)	B9—B5—H5	119.6 (7)
B13—B14—H14	130.8 (7)	B4—B5—H5	131.3 (7)
B11—B15—B19	112.62 (11)	B2—B5—H5	131.3 (7)
B11—B15—B18	112.75 (11)	B10—B6—B2	112.75 (11)
B19—B15—B18	61.04 (9)	B10—B6—B3	112.77 (11)
B11—B15—B14	57.75 (9)	B2—B6—B3	60.45 (9)
B19—B15—B14	102.25 (11)	B10—B6—B9	57.44 (9)
B18—B15—B14	59.49 (9)	B2—B6—B9	59.86 (9)
B11—B15—B12	57.50 (9)	B3—B6—B9	102.15 (10)
B19—B15—B12	59.69 (9)	B10—B6—B7	57.44 (8)
B18—B15—B12	102.60 (11)	B2—B6—B7	101.88 (10)
B14—B15—B12	90.52 (10)	B3—B6—B7	59.77 (8)
B11—B15—H15	120.5 (7)	B9—B6—B7	89.84 (10)
B19—B15—H15	118.6 (7)	B10—B6—H6	121.1 (7)
B18—B15—H15	117.2 (8)	B2—B6—H6	116.6 (7)
B14—B15—H15	130.7 (7)	B3—B6—H6	118.4 (7)
B12—B15—H15	132.7 (8)	B9—B6—H6	130.6 (7)
B20—B16—B13	112.68 (11)	B7—B6—H6	133.9 (7)
B20—B16—B12	112.75 (11)	B10—B7—B4	112.68 (11)
B13—B16—B12	60.34 (9)	B10—B7—B3	112.67 (11)
B20—B16—B19	57.57 (9)	B4—B7—B3	60.57 (8)
B13—B16—B19	101.99 (10)	B10—B7—B8	57.32 (9)
B12—B16—B19	59.77 (9)	B4—B7—B8	59.89 (9)
B20—B16—B17	57.56 (9)	B3—B7—B8	102.17 (11)
B13—B16—B17	59.72 (8)	B10—B7—B6	57.52 (9)
B12—B16—B17	102.05 (10)	B4—B7—B6	101.83 (10)
B19—B16—B17	90.21 (10)	B3—B7—B6	59.58 (8)
B20—B16—H16	119.1 (7)	B8—B7—B6	89.80 (10)
B13—B16—H16	119.2 (7)	B10—B7—H7	120.0 (7)
B12—B16—H16	119.2 (7)	B4—B7—H7	117.9 (7)
B19—B16—H16	131.5 (7)	B3—B7—H7	119.0 (7)
B17—B16—H16	131.3 (7)	B8—B7—H7	130.9 (7)
B20—B17—B13	112.25 (11)	B6—B7—H7	132.9 (7)
B20—B17—B14	112.16 (11)	B10—B8—B5	113.06 (11)
B13—B17—B14	61.18 (9)	B10—B8—B4	112.87 (11)
B20—B17—B16	57.24 (9)	B5—B8—B4	60.39 (9)
B13—B17—B16	59.58 (9)	B10—B8—B9	57.80 (9)
B14—B17—B16	102.29 (10)	B5—B8—B9	59.80 (9)
B20—B17—B18	57.37 (9)	B4—B8—B9	102.07 (10)
B13—B17—B18	102.20 (10)	B10—B8—B7	57.79 (9)
B14—B17—B18	59.34 (9)	B5—B8—B7	102.15 (10)
B16—B17—B18	90.10 (10)	B4—B8—B7	59.63 (8)
B20—B17—H17	120.8 (7)	B9—B8—B7	90.45 (10)
B13—B17—H17	117.8 (7)	B10—B8—H8	120.7 (7)
B14—B17—H17	118.4 (7)	B5—B8—H8	117.7 (7)
B16—B17—H17	131.5 (7)	B4—B8—H8	117.6 (6)
B18—B17—H17	132.3 (7)	B9—B8—H8	132.1 (6)
B20—B18—B14	112.65 (11)	B7—B8—H8	131.7 (6)
B20—B18—B15	111.97 (11)	B10—B9—B5	112.53 (11)
B14—B18—B15	60.49 (9)	B10—B9—B2	112.46 (11)
B20—B18—B17	57.44 (9)	B5—B9—B2	60.64 (9)
B14—B18—B17	59.80 (9)	B10—B9—B8	57.37 (9)
B15—B18—B17	101.64 (10)	B5—B9—B8	59.66 (9)
B20—B18—B19	57.09 (9)	B2—B9—B8	101.92 (10)
B14—B18—B19	101.75 (10)	B10—B9—B6	57.56 (9)
B15—B18—B19	59.34 (9)	B5—B9—B6	101.91 (11)
B17—B18—B19	89.50 (10)	B2—B9—B6	59.44 (9)
B20—B18—H18	120.5 (7)	B8—B9—B6	89.90 (10)
B14—B18—H18	119.2 (7)	B10—B9—H9	119.0 (8)
B15—B18—H18	117.5 (7)	B5—B9—H9	119.0 (8)
B17—B18—H18	133.9 (7)	B2—B9—H9	119.9 (7)
B19—B18—H18	130.5 (7)	B8—B9—H9	130.9 (7)
B20—B19—B15	112.43 (11)	B6—B9—H9	132.2 (7)
B20—B19—B12	112.94 (11)	B8—B10—B9	64.83 (10)
B15—B19—B12	60.76 (9)	B8—B10—B7	64.88 (9)
B20—B19—B16	57.53 (9)	B9—B10—B7	98.83 (11)
B15—B19—B16	102.32 (10)	B8—B10—B6	98.75 (11)
B12—B19—B16	60.02 (8)	B9—B10—B6	65.00 (9)
B20—B19—B18	57.30 (9)	B7—B10—B6	65.04 (9)
B15—B19—B18	59.62 (8)	B8—B10—H10	130.0 (7)
B12—B19—B18	102.36 (10)	B9—B10—H10	130.2 (7)
B16—B19—B18	90.18 (10)	B7—B10—H10	131.0 (7)
B20—B19—H19	120.9 (7)	B6—B10—H10	131.3 (7)
B15—B19—H19	117.2 (7)	H2D—N2—H2C	108.1 (16)
B12—B19—H19	118.0 (7)	H2D—N2—H2B	109.9 (18)
B16—B19—H19	132.8 (7)	H2C—N2—H2B	113.0 (19)
B18—B19—H19	131.1 (7)	H2D—N2—H2A	111.6 (16)
B16—B20—B19	64.90 (9)	H2C—N2—H2A	108.0 (16)
B16—B20—B18	99.53 (11)	H2B—N2—H2A	106.4 (19)
B19—B20—B18	65.61 (9)	H7A—O7—H7B	106.2 (19)
B16—B20—B17	65.20 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···O6	0.93 (2)	1.91 (2)	2.837 (2)	171.7 (15)
N3—H3D···O7	0.968 (19)	1.855 (19)	2.8117 (19)	168.8 (15)
N4—H4B···O5	0.94 (2)	1.96 (2)	2.896 (2)	168.5 (16)
N4—H4A···O7	0.88 (2)	2.09 (2)	2.942 (2)	162.7 (17)
O5—H5B···O6^i	0.82 (2)	2.01 (2)	2.8357 (18)	176.5 (19)
O7—H7B···O5^ii	0.90 (3)	1.85 (3)	2.7487 (18)	177 (2)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.