Tetra­kis(1,3,4,6,7,9-hexa­aza-1H-phen­alen-6-ium) sodium(I) penta­kis(tetra­fluorido­borate)

Jiang, Y.; Hou, Y.; Chen, Y.

doi:10.1107/S1600536808030286

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1318

doi:10.1107/S1600536808030286

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Tetrakis(1,3,4,6,7,9-hexaaza-1H-phenalen-6-ium) sodium(I) pentakis(tetrafluoridoborate)

Yuqin Jiang,^a Yanhui Hou ^a and Yongsheng Chen ^a ^*

^aKey Laboratoy for Functional Polymer Materials and Center for Nanoscale Science and Technology, Institute of Polymer Chemistry, College of Chemistry, Nankai University, Tianjin, Weijin Road No. 94, Tianjin, People's Republic of China
^*Correspondence e-mail: jiangyuqin800520@mail.nankai.edu.cn

(Received 1 September 2008; accepted 20 September 2008; online 24 September 2008)

In the title compound, Na⁺·4C₇H₅N₆⁺·5BF₄⁻, the Na⁺ ion lies on a fourfold rotation axis and one of the tetrafluoridoborate ions lies on a site of symmetry $[\overline{4}]$ . Each Na⁺ ion is surrounded by four symmetry-related tetrafluoridoborate ions, and is eight-coordinated by F atoms, the Na⋯F separation being 2.3956 (15) or 2.4347 (17) Å. The hexaazaphenalenium ring system is essentially planar. In the crystal structure, the cations and anions are linked into a three-dimensional network by N—H⋯N and C—H⋯F hydrogen bonds.

Related literature

For general background, see: Goto et al. (1999 ); Haddon (1975 ); Koutentis et al. (2001 ). For related structures, see: Morita et al. (2002 , 2003 ); Tamaki et al. (1997 ); Zheng et al. (2003 , 2005 ). For related preparation, see: Suzuki et al. (2005 ).

Experimental

Crystal data

Na⁺·4C₇H₅N₆⁺·5BF₄⁻
M_r = 1149.72
Tetragonal, P 4/n
a = 15.0665 (6) Å
c = 8.9322 (5) Å
V = 2027.60 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 113 (2) K
0.14 × 0.12 × 0.12 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2005 ) T_min = 0.877, T_max = 0.977
21698 measured reflections
2423 independent reflections
2247 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.152
S = 1.19
2423 reflections
177 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.79 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N4ⁱ	0.88	2.05	2.930 (2)	176
N6—H6N⋯N5ⁱⁱ	0.88	2.09	2.866 (2)	146
C1—H1⋯F3ⁱⁱⁱ	0.95	2.47	3.179 (2)	132
C1—H1⋯F4ⁱⁱ	0.95	2.55	2.940 (3)	105
C3—H3⋯F2ⁱ	0.95	2.22	3.124 (2)	159
C5—H5⋯F3^iv	0.95	2.40	3.097 (2)	130
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) $[-y+1, x+{\script{1\over 2}}, -z+1]$ ; (iii) $[y, -x+{\script{3\over 2}}, z]$ ; (iv) $[-y+{\script{1\over 2}}, x, z]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030286/ci2666sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030286/ci2666Isup2.hkl

checkCIF report

Comment top

Phenalenyl, as a planar π system with D₃_h symmetry, has received much attention and still played an important role as a building block for spin-mediated molecular functional materials (Haddon 1975; Koutentis et al., 2001; Goto et al., 1999). Hexaazaphenalene (HAP) is a highly symmetric heterocycle with full nitrogen substitution in all of the α sites of phenalene (Morita et al., 2002; Morita et al., 2003; Suzuki et al., 2005; Tamaki et al., 1997; Zheng et al., 2003; Zheng et al., 2005). Because of the directionality of lone-pair electrons at the nitrogen sites, incorporation of nitrogen atoms into the phenalenyl skeleton was found to give substantial effects on its electronic structure. Suzuki et al. have reported the preparation and single cystal structure of the anion of hexaazaphenalene. Herein, we report the preparation and crystal structure of a hexaazaphenalene fluoroboric salt, the title compound.

In the title compound, the Na⁺ ion lies on a four-fold rotation axis and one of the tetrafluoridoborate ions lies on a 4 site symmetry. One of the remaining four BF₄^- ions and one of the four hexaazaphenalenium ions are symmetry independent, and they lie on general positions. Each Na⁺ ion is surrounded by four symmetry related tetrafluoridoborate ions, with the Na···F separation being 2.3956 (15) or 2.4347 (17) Å (Fig.1). The hexaazaphenalenium ring system is essentially planar, with a maximum deviation of 0.042 (2) Å for atom N6. The C—N distances lie in the range 1.310 (3)-1.363 (3) Å.

Two types of hydrogen bonds viz. N—H···N and C—H···F exist in the solid state of the title compound. These hydrogen bonds link the cationic and anionic units into a three-dimensional network (Fig. 2). There are no face to face π-π staking involving the hexaazaphenalenium units, which is a common packing mode in other phenalene compounds.

Related literature top

For related literature, see: Goto et al. (1999); Haddon (1975); Koutentis et al. (2001); Morita et al. (2002, 2003); Suzuki et al. (2005); Tamaki et al. (1997); Zheng et al. (2003, 2005). It would be much more useful to readers if the "Related literature" section had some kind of simple sub-division, so that, instead of just "For related literature, see···" it said, for example, "For general background, see···. For related structures, see···.? etc. Please revise this section as indicated.

Experimental top

The sodium salt of hexaazaphenalene was prepared according to the literature method (Suzuki et al., 2005). To a water (5 ml) solution of sodium salt of hexaazaphenalene (97 mg, 0.5 mmol) was added 40% HBF₄ (0.5 ml, 3.0 mmol). The reaction mixture was evaporated slowly for 7 d to afford colourless crystals of the title compound.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top

	Fig. 1. A view of the environment around the Na⁺ ion in the title compound. Displacement ellipsoids are drawn at the 50% probability level. Atoms labelled with the suffixes A, B, C, D, E and F are generated by the symmetry operations (y, 1/2-x, z), (1/2-x, 1/2-y, z), (1/2-y, x, z), (1-y, x-1/2, -z), (y+1/2, 1-x, -z) and (3/2-x, 1/2-y, z), respectively.
	Fig. 2. The crystal packing of the title compound.

Tetrakis(1,3,4,6,7,9-hexaaza-1H-phenalen-6-ium) sodium(I) pentakis(tetrafluoridoborate) top

Crystal data top

Na⁺·4C₇H₅N₆⁺·5BF₄⁻	D_x = 1.883 Mg m⁻³
M_r = 1149.72	Mo Kα radiation, λ = 0.71070 Å
Tetragonal, P4/n	Cell parameters from 4230 reflections
Hall symbol: -P 4a	θ = 1.9–27.9°
a = 15.0665 (6) Å	µ = 0.20 mm⁻¹
c = 8.9322 (5) Å	T = 113 K
V = 2027.60 (16) Å³	Block, colourless
Z = 2	0.14 × 0.12 × 0.12 mm
F(000) = 1144

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2423 independent reflections
Radiation source: rotating anode	2247 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.044
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 1.9°
ω and ϕ scans	h = −19→19
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2005)	k = −19→19
T_min = 0.878, T_max = 0.977	l = −11→11
21698 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0759P)² + 1.4095P] where P = (F_o² + 2F_c²)/3
2423 reflections	(Δ/σ)_max = 0.001
177 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.79 e Å⁻³

Crystal data top

Na⁺·4C₇H₅N₆⁺·5BF₄⁻	Z = 2
M_r = 1149.72	Mo Kα radiation
Tetragonal, P4/n	µ = 0.20 mm⁻¹
a = 15.0665 (6) Å	T = 113 K
c = 8.9322 (5) Å	0.14 × 0.12 × 0.12 mm
V = 2027.60 (16) Å³

Data collection top

Rigaku Saturn CCD area-detector diffractometer	2423 independent reflections
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2005)	2247 reflections with I > 2σ(I)
T_min = 0.878, T_max = 0.977	R_int = 0.044
21698 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.152	H-atom parameters constrained
S = 1.19	Δρ_max = 0.74 e Å⁻³
2423 reflections	Δρ_min = −0.79 e Å⁻³
177 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Na1	0.2500	0.2500	0.4845 (2)	0.0275 (4)
B1	0.42320 (16)	0.33819 (16)	0.5211 (3)	0.0204 (5)
F1	0.39625 (9)	0.28695 (10)	0.39963 (15)	0.0293 (4)
F2	0.35132 (8)	0.34700 (9)	0.61981 (15)	0.0241 (3)
F3	0.49388 (9)	0.29764 (9)	0.59536 (16)	0.0274 (3)
F4	0.44983 (10)	0.42159 (9)	0.47314 (19)	0.0346 (4)
F5	0.73061 (11)	0.17735 (10)	0.08990 (17)	0.0371 (4)
B2	0.7500	0.2500	0.0000	0.0203 (9)
C1	0.43924 (15)	0.86438 (14)	0.7069 (2)	0.0202 (4)
H1	0.4317	0.9205	0.6602	0.024*
C2	0.50050 (13)	0.78212 (13)	0.8918 (2)	0.0150 (4)
C3	0.56501 (13)	0.69463 (13)	1.0679 (2)	0.0164 (4)
H3	0.6034	0.6886	1.1517	0.020*
C4	0.47115 (12)	0.62292 (12)	0.8956 (2)	0.0126 (4)
C5	0.38121 (13)	0.56354 (13)	0.7195 (2)	0.0157 (4)
H5	0.3522	0.5127	0.6798	0.019*
C6	0.40548 (13)	0.71345 (12)	0.7050 (2)	0.0135 (4)
C7	0.45850 (12)	0.70676 (12)	0.8328 (2)	0.0124 (4)
N1	0.48868 (12)	0.86262 (11)	0.82849 (19)	0.0188 (4)
N2	0.55508 (11)	0.77454 (11)	1.01274 (19)	0.0166 (4)
N3	0.52553 (11)	0.61957 (11)	1.01648 (18)	0.0138 (3)
H3N	0.5353	0.5686	1.0617	0.017*
N4	0.43264 (11)	0.54996 (11)	0.83918 (18)	0.0146 (4)
N5	0.36565 (11)	0.64098 (11)	0.64850 (19)	0.0155 (4)
N6	0.39805 (12)	0.79459 (11)	0.64176 (19)	0.0181 (4)
H6N	0.3669	0.8019	0.5594	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Na1	0.0214 (6)	0.0214 (6)	0.0396 (11)	0.000	0.000	0.000
B1	0.0199 (11)	0.0185 (11)	0.0227 (12)	−0.0013 (9)	0.0011 (9)	0.0025 (9)
F1	0.0278 (7)	0.0369 (8)	0.0231 (7)	−0.0037 (6)	0.0034 (5)	−0.0066 (6)
F2	0.0218 (7)	0.0290 (7)	0.0214 (7)	0.0028 (5)	−0.0002 (5)	−0.0023 (5)
F3	0.0219 (7)	0.0271 (7)	0.0332 (8)	0.0028 (5)	−0.0018 (5)	0.0047 (6)
F4	0.0324 (8)	0.0248 (7)	0.0466 (9)	−0.0042 (6)	−0.0024 (7)	0.0124 (6)
F5	0.0538 (10)	0.0295 (8)	0.0279 (8)	−0.0065 (7)	0.0028 (7)	0.0055 (6)
B2	0.0219 (14)	0.0219 (14)	0.017 (2)	0.000	0.000	0.000
C1	0.0289 (11)	0.0151 (9)	0.0167 (9)	0.0048 (8)	0.0014 (8)	0.0023 (8)
C2	0.0178 (9)	0.0139 (9)	0.0134 (9)	0.0013 (7)	0.0007 (7)	0.0003 (7)
C3	0.0188 (9)	0.0164 (9)	0.0139 (9)	0.0011 (7)	−0.0035 (7)	−0.0004 (7)
C4	0.0115 (8)	0.0136 (9)	0.0126 (8)	0.0013 (7)	0.0004 (7)	0.0005 (7)
C5	0.0131 (8)	0.0185 (9)	0.0155 (9)	−0.0013 (7)	−0.0005 (7)	−0.0013 (7)
C6	0.0159 (9)	0.0147 (9)	0.0099 (8)	0.0026 (7)	0.0003 (7)	−0.0005 (7)
C7	0.0141 (8)	0.0123 (9)	0.0110 (8)	0.0005 (7)	0.0009 (7)	0.0006 (7)
N1	0.0253 (9)	0.0131 (8)	0.0181 (8)	0.0011 (6)	−0.0028 (7)	0.0016 (6)
N2	0.0205 (9)	0.0139 (8)	0.0155 (8)	−0.0003 (6)	−0.0044 (6)	−0.0005 (6)
N3	0.0165 (8)	0.0120 (8)	0.0130 (8)	0.0010 (6)	−0.0029 (6)	0.0023 (6)
N4	0.0144 (8)	0.0153 (8)	0.0141 (8)	−0.0017 (6)	−0.0012 (6)	−0.0001 (6)
N5	0.0143 (8)	0.0177 (8)	0.0146 (8)	0.0006 (6)	−0.0016 (6)	−0.0017 (6)
N6	0.0249 (9)	0.0171 (8)	0.0124 (8)	0.0045 (7)	−0.0018 (7)	0.0033 (6)

Geometric parameters (Å, º) top

Na1—F1ⁱ	2.3956 (15)	C1—H1	0.95
Na1—F1ⁱⁱ	2.3956 (15)	C2—N1	1.350 (3)
Na1—F1ⁱⁱⁱ	2.3956 (15)	C2—N2	1.363 (3)
Na1—F1	2.3957 (15)	C2—C7	1.403 (3)
Na1—F2	2.4347 (17)	C3—N2	1.310 (3)
Na1—F2ⁱ	2.4347 (17)	C3—N3	1.358 (3)
Na1—F2ⁱⁱ	2.4347 (17)	C3—H3	0.95
Na1—F2ⁱⁱⁱ	2.4347 (17)	C4—N4	1.341 (2)
B1—F4	1.387 (3)	C4—N3	1.356 (2)
B1—F1	1.392 (3)	C4—C7	1.395 (3)
B1—F3	1.395 (3)	C5—N4	1.336 (3)
B1—F2	1.403 (3)	C5—N5	1.349 (3)
F5—B2	1.3887 (14)	C5—H5	0.95
B2—F5^iv	1.3887 (14)	C6—N5	1.344 (3)
B2—F5^v	1.3887 (14)	C6—N6	1.351 (2)
B2—F5^vi	1.3887 (14)	C6—C7	1.397 (3)
C1—N1	1.317 (3)	N3—H3N	0.88
C1—N6	1.353 (3)	N6—H6N	0.88

F1ⁱ—Na1—F1ⁱⁱ	84.26 (3)	F1—Na1—B1ⁱⁱⁱ	104.13 (6)
F1ⁱ—Na1—F1ⁱⁱⁱ	143.12 (11)	F2—Na1—B1ⁱⁱⁱ	72.30 (6)
F1ⁱⁱ—Na1—F1ⁱⁱⁱ	84.26 (3)	F2ⁱ—Na1—B1ⁱⁱⁱ	140.43 (9)
F1ⁱ—Na1—F1	84.26 (3)	F2ⁱⁱ—Na1—B1ⁱⁱⁱ	101.17 (7)
F1ⁱⁱ—Na1—F1	143.12 (11)	F2ⁱⁱⁱ—Na1—B1ⁱⁱⁱ	28.22 (6)
F1ⁱⁱⁱ—Na1—F1	84.26 (3)	B1—Na1—B1ⁱⁱⁱ	89.293 (14)
F1ⁱ—Na1—F2	124.30 (5)	B1ⁱ—Na1—B1ⁱⁱⁱ	167.24 (13)
F1ⁱⁱ—Na1—F2	150.83 (6)	B1ⁱⁱ—Na1—B1ⁱⁱⁱ	89.292 (14)
F1ⁱⁱⁱ—Na1—F2	75.56 (5)	F4—B1—F1	110.24 (19)
F1—Na1—F2	56.00 (4)	F4—B1—F3	108.83 (18)
F1ⁱ—Na1—F2ⁱ	56.00 (4)	F1—B1—F3	110.49 (19)
F1ⁱⁱ—Na1—F2ⁱ	124.30 (5)	F4—B1—F2	109.39 (19)
F1ⁱⁱⁱ—Na1—F2ⁱ	150.83 (6)	F1—B1—F2	108.49 (18)
F1—Na1—F2ⁱ	75.56 (5)	F3—B1—F2	109.39 (18)
F2—Na1—F2ⁱ	75.73 (5)	F4—B1—Na1	129.09 (15)
F1ⁱ—Na1—F2ⁱⁱ	75.56 (5)	F1—B1—Na1	53.49 (10)
F1ⁱⁱ—Na1—F2ⁱⁱ	56.00 (4)	F3—B1—Na1	122.09 (14)
F1ⁱⁱⁱ—Na1—F2ⁱⁱ	124.30 (5)	F2—B1—Na1	55.16 (10)
F1—Na1—F2ⁱⁱ	150.84 (6)	B1—F1—Na1	98.66 (13)
F2—Na1—F2ⁱⁱ	120.46 (11)	B1—F2—Na1	96.62 (12)
F2ⁱ—Na1—F2ⁱⁱ	75.73 (5)	F5—B2—F5^iv	109.54 (6)
F1ⁱ—Na1—F2ⁱⁱⁱ	150.84 (6)	F5—B2—F5^v	109.54 (6)
F1ⁱⁱ—Na1—F2ⁱⁱⁱ	75.56 (5)	F5^iv—B2—F5^v	109.34 (13)
F1ⁱⁱⁱ—Na1—F2ⁱⁱⁱ	56.00 (4)	F5—B2—F5^vi	109.34 (13)
F1—Na1—F2ⁱⁱⁱ	124.29 (5)	F5^iv—B2—F5^vi	109.54 (6)
F2—Na1—F2ⁱⁱⁱ	75.73 (5)	F5^v—B2—F5^vi	109.54 (6)
F2ⁱ—Na1—F2ⁱⁱⁱ	120.46 (11)	N1—C1—N6	126.77 (19)
F2ⁱⁱ—Na1—F2ⁱⁱⁱ	75.73 (5)	N1—C1—H1	116.6
F1ⁱ—Na1—B1	104.13 (6)	N6—C1—H1	116.6
F1ⁱⁱ—Na1—B1	162.64 (8)	N1—C2—N2	119.14 (18)
F1ⁱⁱⁱ—Na1—B1	79.99 (6)	N1—C2—C7	120.70 (18)
F1—Na1—B1	27.85 (6)	N2—C2—C7	120.15 (18)
F2—Na1—B1	28.22 (6)	N2—C3—N3	126.03 (18)
F2ⁱ—Na1—B1	72.30 (6)	N2—C3—H3	117.0
F2ⁱⁱ—Na1—B1	140.43 (9)	N3—C3—H3	117.0
F2ⁱⁱⁱ—Na1—B1	101.16 (7)	N4—C4—N3	122.01 (17)
F1ⁱ—Na1—B1ⁱ	27.85 (6)	N4—C4—C7	122.11 (17)
F1ⁱⁱ—Na1—B1ⁱ	104.13 (6)	N3—C4—C7	115.87 (17)
F1ⁱⁱⁱ—Na1—B1ⁱ	162.64 (8)	N4—C5—N5	127.57 (18)
F1—Na1—B1ⁱ	79.99 (6)	N4—C5—H5	116.2
F2—Na1—B1ⁱ	101.16 (7)	N5—C5—H5	116.2
F2ⁱ—Na1—B1ⁱ	28.22 (6)	N5—C6—N6	122.77 (18)
F2ⁱⁱ—Na1—B1ⁱ	72.30 (6)	N5—C6—C7	120.22 (17)
F2ⁱⁱⁱ—Na1—B1ⁱ	140.43 (9)	N6—C6—C7	117.00 (17)
B1—Na1—B1ⁱ	89.292 (14)	C4—C7—C6	118.18 (17)
F1ⁱ—Na1—B1ⁱⁱ	79.99 (6)	C4—C7—C2	121.34 (18)
F1ⁱⁱ—Na1—B1ⁱⁱ	27.85 (6)	C6—C7—C2	120.43 (17)
F1ⁱⁱⁱ—Na1—B1ⁱⁱ	104.13 (6)	C1—N1—C2	115.98 (18)
F1—Na1—B1ⁱⁱ	162.64 (8)	C3—N2—C2	116.39 (17)
F2—Na1—B1ⁱⁱ	140.43 (9)	C4—N3—C3	120.21 (16)
F2ⁱ—Na1—B1ⁱⁱ	101.17 (7)	C4—N3—H3N	119.9
F2ⁱⁱ—Na1—B1ⁱⁱ	28.22 (6)	C3—N3—H3N	119.9
F2ⁱⁱⁱ—Na1—B1ⁱⁱ	72.30 (6)	C5—N4—C4	115.22 (17)
B1—Na1—B1ⁱⁱ	167.24 (13)	C6—N5—C5	116.66 (17)
B1ⁱ—Na1—B1ⁱⁱ	89.293 (14)	C6—N6—C1	119.05 (18)
F1ⁱ—Na1—B1ⁱⁱⁱ	162.64 (8)	C6—N6—H6N	120.5
F1ⁱⁱ—Na1—B1ⁱⁱⁱ	79.99 (6)	C1—N6—H6N	120.5
F1ⁱⁱⁱ—Na1—B1ⁱⁱⁱ	27.85 (6)

F1ⁱ—Na1—B1—F4	133.1 (2)	F2ⁱ—Na1—F1—B1	−79.36 (13)
F1ⁱⁱ—Na1—B1—F4	15.7 (4)	F2ⁱⁱ—Na1—F1—B1	−89.7 (2)
F1ⁱⁱⁱ—Na1—B1—F4	−9.4 (2)	F2ⁱⁱⁱ—Na1—F1—B1	37.90 (16)
F1—Na1—B1—F4	87.3 (2)	B1ⁱ—Na1—F1—B1	−107.90 (14)
F2—Na1—B1—F4	−87.5 (2)	B1ⁱⁱ—Na1—F1—B1	−160.5 (3)
F2ⁱ—Na1—B1—F4	179.8 (2)	B1ⁱⁱⁱ—Na1—F1—B1	59.75 (12)
F2ⁱⁱ—Na1—B1—F4	−142.58 (17)	F4—B1—F2—Na1	124.71 (16)
F2ⁱⁱⁱ—Na1—B1—F4	−61.5 (2)	F1—B1—F2—Na1	4.42 (17)
B1ⁱ—Na1—B1—F4	156.90 (17)	F3—B1—F2—Na1	−116.18 (16)
B1ⁱⁱ—Na1—B1—F4	−119.4 (2)	F1ⁱ—Na1—F2—B1	49.76 (16)
B1ⁱⁱⁱ—Na1—B1—F4	−35.8 (2)	F1ⁱⁱ—Na1—F2—B1	−143.4 (2)
F1ⁱ—Na1—B1—F1	45.78 (13)	F1ⁱⁱⁱ—Na1—F2—B1	−95.75 (12)
F1ⁱⁱ—Na1—B1—F1	−71.6 (4)	F1—Na1—F2—B1	−2.94 (12)
F1ⁱⁱⁱ—Na1—B1—F1	−96.70 (14)	F2ⁱ—Na1—F2—B1	79.09 (14)
F2—Na1—B1—F1	−174.8 (2)	F2ⁱⁱ—Na1—F2—B1	142.68 (12)
F2ⁱ—Na1—B1—F1	92.50 (13)	F2ⁱⁱⁱ—Na1—F2—B1	−153.72 (12)
F2ⁱⁱ—Na1—B1—F1	130.10 (12)	B1ⁱ—Na1—F2—B1	66.77 (10)
F2ⁱⁱⁱ—Na1—B1—F1	−148.85 (13)	B1ⁱⁱ—Na1—F2—B1	169.42 (10)
B1ⁱ—Na1—B1—F1	69.58 (15)	B1ⁱⁱⁱ—Na1—F2—B1	−124.56 (13)
B1ⁱⁱ—Na1—B1—F1	153.24 (12)	N4—C4—C7—C6	−1.5 (3)
B1ⁱⁱⁱ—Na1—B1—F1	−123.10 (13)	N3—C4—C7—C6	177.86 (16)
F1ⁱ—Na1—B1—F3	−47.1 (2)	N4—C4—C7—C2	−178.91 (18)
F1ⁱⁱ—Na1—B1—F3	−164.5 (2)	N3—C4—C7—C2	0.4 (3)
F1ⁱⁱⁱ—Na1—B1—F3	170.43 (18)	N5—C6—C7—C4	2.3 (3)
F1—Na1—B1—F3	−92.9 (2)	N6—C6—C7—C4	−176.63 (17)
F2—Na1—B1—F3	92.3 (2)	N5—C6—C7—C2	179.74 (18)
F2ⁱ—Na1—B1—F3	−0.36 (17)	N6—C6—C7—C2	0.8 (3)
F2ⁱⁱ—Na1—B1—F3	37.2 (2)	N1—C2—C7—C4	179.01 (18)
F2ⁱⁱⁱ—Na1—B1—F3	118.28 (17)	N2—C2—C7—C4	0.1 (3)
B1ⁱ—Na1—B1—F3	−23.3 (2)	N1—C2—C7—C6	1.7 (3)
B1ⁱⁱ—Na1—B1—F3	60.38 (17)	N2—C2—C7—C6	−177.25 (18)
B1ⁱⁱⁱ—Na1—B1—F3	144.04 (13)	N6—C1—N1—C2	1.5 (3)
F1ⁱ—Na1—B1—F2	−139.43 (13)	N2—C2—N1—C1	176.21 (19)
F1ⁱⁱ—Na1—B1—F2	103.2 (3)	C7—C2—N1—C1	−2.7 (3)
F1ⁱⁱⁱ—Na1—B1—F2	78.08 (12)	N3—C3—N2—C2	−0.6 (3)
F1—Na1—B1—F2	174.8 (2)	N1—C2—N2—C3	−179.00 (18)
F2ⁱ—Na1—B1—F2	−92.71 (14)	C7—C2—N2—C3	−0.1 (3)
F2ⁱⁱ—Na1—B1—F2	−55.11 (18)	N4—C4—N3—C3	178.34 (18)
F2ⁱⁱⁱ—Na1—B1—F2	25.93 (12)	C7—C4—N3—C3	−1.0 (3)
B1ⁱ—Na1—B1—F2	−115.63 (11)	N2—C3—N3—C4	1.1 (3)
B1ⁱⁱ—Na1—B1—F2	−31.97 (11)	N5—C5—N4—C4	1.6 (3)
B1ⁱⁱⁱ—Na1—B1—F2	51.69 (14)	N3—C4—N4—C5	−179.66 (17)
F4—B1—F1—Na1	−124.27 (16)	C7—C4—N4—C5	−0.3 (3)
F3—B1—F1—Na1	115.40 (16)	N6—C6—N5—C5	177.64 (18)
F2—B1—F1—Na1	−4.51 (18)	C7—C6—N5—C5	−1.2 (3)
F1ⁱ—Na1—F1—B1	−135.69 (13)	N4—C5—N5—C6	−0.8 (3)
F1ⁱⁱ—Na1—F1—B1	151.86 (13)	N5—C6—N6—C1	179.05 (18)
F1ⁱⁱⁱ—Na1—F1—B1	79.41 (15)	C7—C6—N6—C1	−2.1 (3)
F2—Na1—F1—B1	2.97 (12)	N1—C1—N6—C6	1.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4^vii	0.88	2.05	2.930 (2)	176
N6—H6N···N5^viii	0.88	2.09	2.866 (2)	146
C1—H1···F3^ix	0.95	2.47	3.179 (2)	132
C1—H1···F4^viii	0.95	2.55	2.940 (3)	105
C3—H3···F2^vii	0.95	2.22	3.124 (2)	159
C5—H5···F3ⁱⁱⁱ	0.95	2.40	3.097 (2)	130

Symmetry codes: (iii) −y+1/2, x, z; (vii) −x+1, −y+1, −z+2; (viii) −y+1, x+1/2, −z+1; (ix) y, −x+3/2, z.

Experimental details

Crystal data
Chemical formula	Na⁺·4C₇H₅N₆⁺·5BF₄⁻
M_r	1149.72
Crystal system, space group	Tetragonal, P4/n
Temperature (K)	113
a, c (Å)	15.0665 (6), 8.9322 (5)
V (Å³)	2027.60 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.14 × 0.12 × 0.12

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear, Rigaku/MSC, 2005)
T_min, T_max	0.878, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	21698, 2423, 2247
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.152, 1.19
No. of reflections	2423
No. of parameters	177
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.79

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku/MSC, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4ⁱ	0.88	2.05	2.930 (2)	176
N6—H6N···N5ⁱⁱ	0.88	2.09	2.866 (2)	146
C1—H1···F3ⁱⁱⁱ	0.95	2.47	3.179 (2)	132
C1—H1···F4ⁱⁱ	0.95	2.55	2.940 (3)	105
C3—H3···F2ⁱ	0.95	2.22	3.124 (2)	159
C5—H5···F3^iv	0.95	2.40	3.097 (2)	130

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC; grant Nos. 20644004 and 20774047), the Ministry of Science and Technology of China (MOST; grant No. 2006CB932702) and the NSF of Tianjin City (grant No. 07JCYBJC03000).

References

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Volume 64| Part 10| October 2008| Page m1318

doi:10.1107/S1600536808030286

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Tetra­kis(1,3,4,6,7,9-hexa­aza-1H-phen­alen-6-ium) sodium(I) penta­kis(tetra­fluorido­borate)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Tetrakis(1,3,4,6,7,9-hexaaza-1H-phenalen-6-ium) sodium(I) pentakis(tetrafluoridoborate)