Ammonium bis­(tetra­ethyl­ammonium) hexa­cyanido­ferrate(III) trihydrate

In the structure of the title salt, (NH₄)(C₈H₂₀N)₂[Fe(CN)₆]·3H₂O, the O atom of one of the water mol­ecules shares its crystallographic site with the N atom of the ammonium cation in a 1:1 ratio. The second O atom from the two crystallographically independent water mol­ecules is disordered over two positions separated by 0.551 (1) Å. The water mol­ecules and ammonium cations form tetra­meric hydrogen-bonded units that, along with the complex anion, form the hydro­philic part of the structure. The hydro­phobic part of the structure, represented by the tetra­ethyl­ammonium cation, is located in cube-like cavities of the hydro­philic framework.

S1. Comment

The structural and compositional diversity of cyano complexes makes this class of compounds attractive from several aspects, but during the past two decades cyano complexes have been studied mainly because of their interesting magnetic properties (Dunbar & Heintz, 1997; Ohba & Okawa, 2000; Verdaguer et al., 1999; Bernhardt et al., 2005).

Within our broader programme on cyano complexes as model compounds for studies of physical phenomena associated with magnetism (Černák et al., 2002), we dealt, among others, with Cd^II complexes based on hexacyanoferrates(III) (Maľarová, Černák & Massa, 2006; Maľarová, Černák, Kuchár et al., 2006). Apart from their magnetic character (low spin Fe^III atom with S = 1/2), these Cd^II–Fe^III compounds may serve for the sake of structural comparision with hexacyanoferrates(III) containing paramagnetic cationic central atoms. Moreover, such complexes are suitable models for Moessbauer studies, for example, studies of line broadening on lowering the temperature (Iijima et al., 2003).

As a continuation of our studies we aimed to prepare a Cd^II–Fe^III compound built up of [Cd(NH₃)₆]²⁺ and [Fe(CN)₆]^3- building blocks. There are a few examples of structures containing a [Cd(NH₃)₆]²⁺ building block [e.g. [Cd(NH₃)₆][C₂₀H₁₂O₂]·2(C₂₀H₁₄O₂); Paul et al., 2004] but, to our knowledge, no structure with a complex cyano anion. On the other hand, other cyano complexes with amine-type complex cations have already been described (Escorihuela et al., 2001; Petříček et al., 2005).

In order to balance the different charges of the outgoing complex ions during synthesis, (NEt₄)Br (Et is ethyl) was added to the aqueous reaction mixture, which thus comprised (NEt₄)Br, CdCl₂, NH₃ and K₃[Fe(CN)₆]. Instead of the desired compound, we unexpectedly obtained the title compound, (NH₄)(Et₄N)₂{[Fe(CN)₆]}·3H₂O, (I), in low yield. Its composition was first checked chemically (see Experimental). A search in the Cambridge Structural Database (Allen, 2002) indicates that only one similar compound, exhibiting composition (NEt₄)₃[Fe(CN)₆]·5H₂O, has been structurally characterized up to now (Mascharak, 1986).

The X-ray structure analysis reveals that the structure of the title compound 1 is ionic and is built up of [NH₄]⁺ and [Et₄N]⁺ cations, Fe(CN)₆]^3-anions, and two crystallographically independent not coordinated water molecules. A view of the asymmetric unit with atomic numbering scheme is shown in Fig. 1 and selected bond lengths and angles are listed in Table 1.

The Fe^III atom in (I) is six-coordinated by C-bound terminal cyano groups in the form of a regular octahedron, with Fe—C bond lengths within the range 1.937 (2)–1.945 (2) Å. Similar distances ranging between 1.921 (4) and 1.952 (3) Å were found in (Hbet)₃[Fe(CN)₆]·4H₂O and (C₃₀H₅₁N₆)[Fe(CN)₆]·8H₂O [Hbet is (CH₃)₃N⁺CH₃CO₂^-; Yan et al., 2001; Christofi et al., 2002). The Fe—C—N angles are almost linear, with a maximum deviation of 1.1° from linearity (Table 1) accounting, for the presence of π-back donation. All remaining geometric parameters in the anion are normal.

In line with the terminal character of all cyano ligands in the complex anion, the measured IR spectrum displays only one strong absorption band, at 2115 cm^-1, due to the streching vibration of the cyano group.

The negative charge of the complex anion is counterbalanced by one ammonium and two tetraethylammonium cations. The geometric parameters of the organic cation exhibit usual values and are similar to those found in other compounds (Iijima et al., 2003; Maľarová et al., 2003).

Atom O2 of one of the uncoordinated water molecules shares its crystallographic site with atom N5 of the ammonium cation in a 1:1 ratio as required by stoichiometry. Moreover, the O1 water molecule is disordered over two positions (O1A and O1B), separated by 0.551 (1) Å, with site occupation factors of 0.5 (Fig. 2).

Owing to the presence of a symmetry centre, the uncoordinated water molecules and ammonium cations (O1 and O2/N5 atomic sites) form a cyclic {(NH₄)(H₂O)₃} tetrameric unit in which the building species are held by N—H···O and O—H···N,O hydrogen bonds (Table 2 and Fig. 2). These tetrameric units are linked with the N atoms of the terminal cyano ligands by further hydrogen bonds. As a consequence, deformed cubes can be distinguished in the structure; four of its corners are formed by Fe^III atoms and four others by the tetrameric units. The edges of the cubes are composed by an Fe—C—N···O,N arrangement of atoms (Fig. 3). The tetraethylammonium cations are placed in the holes of the cubes. Such a view of the structure leads to an alternative description of (I) as composed of a hydrophilic part (complex anions, water molecules and ammonium cations) which encloses a hydrophobic part of the structure represented by the Et₄N⁺ cation, as in a host–guest system. Certainly, electrostatic forces play an important role in this structure. A similar situation was already found in the structure of [Ni(bpy)₃]₂[Ag(CN)₂]₃Cl·9H₂O, in which the chloride anions and O atoms of uncoordinated water molecules share its crystallographic positions Černák et al., 1994) (bpy is 2,2^'-bipyridine).

Related literature

For related literature, see: Allen (2002); Bernhardt et al. (2005); Christofi et al. (2002); Dunbar & Heintz (1997); Escorihuela et al. (2001); Iijima et al. (2003); Maľarová et al. (2003); Maľarová, Černák & Massa (2006); Maľarová, Černák, Kuchár, Varret & Massa (2006); Mascharak (1986); Nardelli (1995); Ohba & Okawa (2000); Paul et al. (2004); Petříček et al. (2005); Verdaguer et al. (1999); Yan et al. (2001); Černák et al. (1994, 2002).

S2. Experimental

Yellow single crystals of [NH₄][Et₄N]₂[Fe(CN)₆]·3H₂O were prepared by slow addition of a 0.1 M aqueous solution (10 ml) of K₃[Fe(CN)₆] (1 mmol) to an aqueous solution composed of CdCl₂·2.5H₂O (1 mmol), (Et₄N)Br (1 mmol) and NH₃ (25%, 60 mmol) at 313 K. A yellow precipitate formed immediately and was dissolved by addition of 0.5 ml of concentrated aqueous ammonia. The resulting clear solution was filtered and left aside for crystallization at room temperature. Within one week, a few large yellow prismatic single crystals were formed with a green microcrystalline powder as an admixture. The mixture was filtered off, washed with a small portion of cold water and dried in air. The yellow crystals were separated mechanically (yield 10%). The green precipitate has not been further analyzed as it was inhomogeneous under the microscope. Analysis calculated for C₂₂H₅₀FeN₉O₃ (Mr = 544.15): C 48.6, H 9.1, N 23.1, Fe 10.3%; found: C 48.2, H 9.1, N 22.6, Fe 10.8%. IR (KBr disc, cm^-1): ν(NH₂): 3404 (s), 3275 (s), 3003 (m); ν(CH₃): 2955 (m); ν(CH₂): 2901 (w); ν(CN): 2119 (s); δ(NH₂): 1635 (s); δ(CH₂): 1481 (m), 1437 (m), 1367 (m); ν(Fe—C): 398 (m).

S3. Refinement

The alkyl H atoms were treated as riding on their parent atoms. The U_iso(H) parameters were set at 1.2 or 1.5 times U_eq of the parent C atoms. The H atoms of the water molecules and ammonium cation were found in a difference map and refined assuming rigid geometry. The H atoms of the ammonium cation and atom H13 of the water molecule were refined with fixed distances 0.9 Å (N—H) and 0.92 Å (O—H), respectively. [Please clarify treatment of these and the other water H atoms; if distance restraints were applied give distance and s.u. values] Around atoms O1A and O1B, three H-atom positions were found. Several models were tried; the best results were obtained assuming that the position of atom H11 is fully occupied and the remaining two H atoms exhibit half occupation. Possible hydrogen bonds were calculated using the program PARST (Nardelli, 1995) and are displayed in Table 2.

Computing details

Data collection: EXPOSE in IPDS Software (Stoe, 1999); cell refinement: CELL in IPDS Software; data reduction: INTEGRATE in IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the asymmetric part of (I), along with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The site occupied simultaneously by atoms O2 and N5 is labelled as O2/N5. The less occupied disordered position of O1 is shown in a paler colour. [See below. Also check atom relabelling.] H atoms have been omitted for the sake of clarity. [Symmetry codes: (i) -x, -y + 1, -z + 2.]
	Fig. 2. The centrosymmetric tetrameric unit {(NH4)(H2O)3}. For the sake of clarity, only one of the two possible orientations linked by a centre of symmetry placed in the middle of the tetrameric unit is displayed. The less occupied position of the O1 atom (O1B) is shown in a paler colour. [(i) Is `less occupied' correct; both occupancies are 0.5. (ii) The pink atom is labelled O1A for the top pair.] Hydrogen bonds are displayed as dashed lines. [Symmetry code: (ii) -x + 1, -y + 2, -z + 2.]
	Fig. 3. The deformed cube of the hydrophilic part of the structure. The position of the tetraethylammonium cations within the cube (N atom) is shown by the large ball at the centre of the figure (light violet in the online version of the journal).

Ammonium bis(tetraethylammonium) hexacyanoferrate(III) trihydrate

Crystal data

(NH4)(C8H20N)2[Fe(CN)6]·3H2O	F(000) = 590
Mr = 544.56	Dx = 1.177 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 3710 reflections
a = 10.472 (1) Å	θ = 2.2–28.0°
b = 10.2339 (7) Å	µ = 0.53 mm^−1
c = 14.518 (2) Å	T = 193 K
β = 99.051 (9)°	Block, yellow
V = 1536.5 (3) Å^3	0.35 × 0.3 × 0.2 mm
Z = 2

Data collection

Stoe IPDS diffractometer	3710 independent reflections
Radiation source: fine-focus sealed tube	2472 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 150 pixels mm^-1	θmax = 28.0°, θmin = 2.2°
ϕ scans	h = −13→13
Absorption correction: numerical (XPREP in SHELXTL; Sheldrick, 1996)	k = −12→13
Tmin = 0.055, Tmax = 0.146	l = −19→19
13143 measured reflections

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.052P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3710 reflections	Δρmax = 0.29 e Å^−3
187 parameters	Δρmin = −0.47 e Å^−3
5 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: 0.0070 (14)

Special details

Experimental. Elemental analysis performed on a Perkin-Elmer CHN 2400 elemental analyzer and atomic absorption spectrometer Varian Spectr AA-30.

IR spectroscopy performed with a Nicolet Magma 750 spectrometer.

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)
Fe	0.0000	0.5000	1.0000	0.04139 (13)
N1	0.2164 (2)	0.6885 (2)	0.96172 (15)	0.0695 (5)
N2	−0.2038 (2)	0.7145 (2)	0.93792 (16)	0.0778 (6)
N3	−0.0106 (2)	0.4126 (2)	0.79484 (13)	0.0734 (6)
N4	0.03025 (16)	0.97031 (16)	0.75234 (11)	0.0482 (4)
N5	0.59386 (16)	0.89807 (17)	0.89926 (11)	0.0490 (4)	0.50
O1A	0.3932 (11)	0.8885 (9)	0.9919 (6)	0.092 (3)	0.50
O1B	0.4149 (9)	0.8550 (8)	1.0214 (5)	0.0611 (15)	0.50
O2	0.59386 (16)	0.89807 (17)	0.89926 (11)	0.0490 (4)	0.50
C1	0.1356 (2)	0.6191 (2)	0.97752 (13)	0.0505 (5)
C2	−0.1280 (2)	0.6343 (2)	0.96091 (15)	0.0550 (5)
C3	−0.0083 (2)	0.4436 (2)	0.87127 (15)	0.0532 (5)
C4	−0.0567 (2)	1.0726 (2)	0.78508 (16)	0.0671 (6)
C5	−0.0700 (3)	1.0653 (3)	0.88739 (16)	0.0735 (7)
C6	0.1655 (2)	0.9750 (2)	0.80748 (16)	0.0581 (5)
C7	0.2358 (3)	1.1036 (3)	0.8045 (2)	0.0913 (9)
C8	−0.0189 (2)	0.8333 (2)	0.76597 (15)	0.0560 (5)
C9	−0.1534 (3)	0.8020 (4)	0.71731 (18)	0.0906 (9)
C10	0.0320 (2)	0.9988 (3)	0.64975 (14)	0.0673 (6)
C12	0.1120 (3)	0.9054 (3)	0.60155 (17)	0.0759 (7)
H4A	−0.1438	1.0645	0.7475	0.081*
H4B	−0.0228	1.1601	0.7725	0.081*
H5A	−0.1274	1.1353	0.9022	0.110*
H5B	0.0153	1.0756	0.9256	0.110*
H5C	−0.1065	0.9804	0.9005	0.110*
H6A	0.1603	0.9542	0.8734	0.070*
H6B	0.2177	0.9057	0.7838	0.070*
H7A	0.3221	1.0968	0.8417	0.137*
H7B	0.1870	1.1729	0.8300	0.137*
H7C	0.2438	1.1245	0.7397	0.137*
H8A	0.0418	0.7704	0.7443	0.067*
H8B	−0.0162	0.8187	0.8337	0.067*
H9A	−0.1748	0.7115	0.7309	0.136*
H9B	−0.1573	0.8128	0.6499	0.136*
H9C	−0.2154	0.8612	0.7395	0.136*
H10A	−0.0580	0.9970	0.6165	0.081*
H10B	0.0657	1.0883	0.6442	0.081*
H11A	0.348 (3)	0.826 (3)	0.9901 (13)	0.096 (9)*	0.50
H11B	0.348 (3)	0.826 (3)	0.9901 (13)	0.096 (9)*	0.50
H12	0.4013	0.9077	1.0545	0.096 (9)*	0.50
H12A	0.1075	0.9312	0.5361	0.114*
H12B	0.0781	0.8166	0.6048	0.114*
H12C	0.2021	0.9081	0.6325	0.114*
H13	0.4569	0.8762	0.9563	0.096 (9)*	0.50
H51	0.651 (2)	0.842 (2)	0.9107 (19)	0.078 (5)*
H52	0.568 (2)	0.902 (2)	0.8402 (12)	0.078 (5)*
H53	0.612 (5)	0.978 (3)	0.921 (4)	0.078 (5)*	0.50
H54	0.540 (4)	0.878 (5)	0.938 (3)	0.078 (5)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe	0.04151 (19)	0.0421 (2)	0.04155 (19)	−0.00761 (19)	0.00978 (13)	−0.00203 (18)
N1	0.0684 (12)	0.0706 (13)	0.0732 (12)	−0.0312 (11)	0.0226 (10)	−0.0063 (10)
N2	0.0691 (13)	0.0814 (15)	0.0893 (15)	0.0206 (12)	0.0316 (11)	0.0304 (12)
N3	0.0961 (15)	0.0780 (14)	0.0491 (11)	−0.0260 (12)	0.0203 (10)	−0.0140 (9)
N4	0.0476 (8)	0.0510 (11)	0.0463 (8)	0.0087 (7)	0.0079 (7)	0.0071 (6)
N5	0.0476 (8)	0.0529 (9)	0.0466 (8)	0.0057 (7)	0.0078 (7)	0.0000 (7)
O1A	0.100 (6)	0.069 (5)	0.114 (7)	−0.046 (4)	0.037 (5)	−0.013 (4)
O1B	0.060 (3)	0.056 (4)	0.073 (3)	−0.019 (2)	0.030 (3)	−0.013 (3)
O2	0.0476 (8)	0.0529 (9)	0.0466 (8)	0.0057 (7)	0.0078 (7)	0.0000 (7)
C1	0.0529 (11)	0.0539 (12)	0.0453 (10)	−0.0060 (10)	0.0095 (8)	−0.0053 (8)
C2	0.0530 (12)	0.0605 (13)	0.0552 (12)	−0.0049 (10)	0.0199 (9)	0.0061 (10)
C3	0.0558 (12)	0.0508 (11)	0.0546 (12)	−0.0144 (10)	0.0130 (9)	−0.0019 (9)
C4	0.0770 (16)	0.0689 (16)	0.0576 (13)	0.0296 (13)	0.0171 (11)	0.0076 (11)
C5	0.0848 (17)	0.0834 (17)	0.0552 (13)	0.0111 (14)	0.0199 (12)	−0.0068 (12)
C6	0.0480 (11)	0.0580 (14)	0.0664 (12)	−0.0033 (9)	0.0030 (9)	0.0050 (10)
C7	0.0856 (19)	0.0711 (17)	0.118 (2)	−0.0253 (15)	0.0190 (17)	−0.0035 (16)
C8	0.0509 (11)	0.0607 (13)	0.0573 (12)	−0.0079 (10)	0.0114 (9)	−0.0027 (10)
C9	0.0627 (15)	0.150 (3)	0.0595 (14)	−0.0337 (17)	0.0101 (11)	−0.0153 (16)
C10	0.0696 (13)	0.0851 (16)	0.0499 (10)	0.0225 (14)	0.0175 (9)	0.0174 (13)
C12	0.0741 (16)	0.098 (2)	0.0614 (14)	0.0180 (14)	0.0281 (12)	0.0054 (13)

Geometric parameters (Å, º)

Fe—C1^i	1.937 (2)	C12—H12A	0.9800
Fe—C1	1.937 (2)	C12—H12B	0.9800
Fe—C2	1.941 (2)	C12—H12C	0.9800
Fe—C2^i	1.941 (2)	C7—H7A	0.9800
Fe—C3	1.945 (2)	C7—H7B	0.9800
Fe—C3^i	1.945 (2)	C7—H7C	0.9800
N4—C4	1.512 (3)	C5—H5A	0.9800
N4—C6	1.514 (3)	C5—H5B	0.9800
N4—C8	1.517 (3)	C5—H5C	0.9800
N4—C10	1.520 (2)	C9—H9A	0.9800
C10—C12	1.512 (3)	C9—H9B	0.9800
C10—H10A	0.9900	C9—H9C	0.9800
C10—H10B	0.9900	O1A—H11A	0.79 (3)
N1—C1	1.156 (3)	O1A—H12	0.9202
C4—C5	1.515 (3)	O1A—H11B	0.79 (3)
C4—H4A	0.9900	O1A—H13	0.9139
C4—H4B	0.9900	O1B—H11A	0.83 (3)
C3—N3	1.151 (3)	O1B—H12	0.7514
C8—C9	1.507 (3)	O1B—H11B	0.83 (3)
C8—H8A	0.9900	O1B—H13	1.1230
C8—H8B	0.9900	N5—H53	0.89 (2)
C6—C7	1.512 (3)	N5—H54	0.88 (2)
C6—H6A	0.9900	N5—H51	0.827 (17)
C6—H6B	0.9900	N5—H52	0.859 (16)
C2—N2	1.153 (3)
C1^i—Fe—C1	180.00 (8)	N3—C3—Fe	178.10 (19)
C1^i—Fe—C2	90.24 (9)	N1—C1—Fe	178.09 (18)
C1—Fe—C2	89.76 (9)	N2—C2—Fe	179.7 (3)
C1^i—Fe—C2^i	89.76 (9)	C10—C12—H12A	109.5
C1—Fe—C2^i	90.24 (9)	C10—C12—H12B	109.5
C2—Fe—C2^i	180.000 (1)	H12A—C12—H12B	109.5
C1^i—Fe—C3	92.97 (8)	C10—C12—H12C	109.5
C1—Fe—C3	87.03 (8)	H12A—C12—H12C	109.5
C2—Fe—C3	90.27 (9)	H12B—C12—H12C	109.5
C2^i—Fe—C3	89.73 (9)	C6—C7—H7A	109.5
C1^i—Fe—C3^i	87.03 (8)	C6—C7—H7B	109.5
C1—Fe—C3^i	92.97 (8)	H7A—C7—H7B	109.5
C2—Fe—C3^i	89.73 (9)	C6—C7—H7C	109.5
C2^i—Fe—C3^i	90.27 (9)	H7A—C7—H7C	109.5
C3—Fe—C3^i	180.000 (1)	H7B—C7—H7C	109.5
C4—N4—C6	111.78 (17)	C4—C5—H5A	109.5
C4—N4—C8	111.46 (17)	C4—C5—H5B	109.5
C6—N4—C8	105.56 (15)	H5A—C5—H5B	109.5
C4—N4—C10	106.03 (15)	C4—C5—H5C	109.5
C6—N4—C10	110.93 (17)	H5A—C5—H5C	109.5
C8—N4—C10	111.19 (17)	H5B—C5—H5C	109.5
C12—C10—N4	115.17 (19)	C8—C9—H9A	109.5
C12—C10—H10A	108.5	C8—C9—H9B	109.5
N4—C10—H10A	108.5	H9A—C9—H9B	109.5
C12—C10—H10B	108.5	C8—C9—H9C	109.5
N4—C10—H10B	108.5	H9A—C9—H9C	109.5
H10A—C10—H10B	107.5	H9B—C9—H9C	109.5
N4—C4—C5	115.26 (19)	H11A—O1A—H12	99.8
N4—C4—H4A	108.5	H11A—O1A—H11B	0 (4)
C5—C4—H4A	108.5	H12—O1A—H11B	99.8
N4—C4—H4B	108.5	H11A—O1A—H13	110.4
C5—C4—H4B	108.5	H12—O1A—H13	128.7
H4A—C4—H4B	107.5	H11B—O1A—H13	110.4
C9—C8—N4	116.5 (2)	H11A—O1B—H12	112.7
C9—C8—H8A	108.2	H11A—O1B—H11B	0 (5)
N4—C8—H8A	108.2	H12—O1B—H11B	112.7
C9—C8—H8B	108.2	H11A—O1B—H13	90.9
N4—C8—H8B	108.2	H12—O1B—H13	122.5
H8A—C8—H8B	107.3	H11B—O1B—H13	90.9
C7—C6—N4	115.5 (2)	H53—N5—H54	97 (5)
C7—C6—H6A	108.4	H53—N5—H51	117 (4)
N4—C6—H6A	108.4	H54—N5—H51	103 (4)
C7—C6—H6B	108.4	H53—N5—H52	109 (4)
N4—C6—H6B	108.4	H54—N5—H52	121 (4)
H6A—C6—H6B	107.5	H51—N5—H52	110 (2)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H11B···N1	0.83 (3)	1.97 (3)	2.722 (10)	152 (3)
N5—H53···O1B^ii	0.89 (2)	1.94 (3)	2.785 (9)	158 (5)
N5—H53···O1A^ii	0.89 (2)	1.87 (3)	2.687 (11)	152 (5)
N5—H54···O1B	0.88 (2)	1.94 (2)	2.809 (8)	173 (5)
N5—H54···O1A	0.88 (2)	1.84 (3)	2.669 (11)	157 (5)
N5—H51···N2^iii	0.83 (2)	2.00 (2)	2.822 (3)	177 (3)
N5—H52···N3^iv	0.86 (2)	1.96 (2)	2.820 (2)	179 (3)

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