Tetra-kis(1,3,4,6,7,9-hexa-aza-1H-phen-alen-6-ium) sodium(I) penta-kis(tetra-fluorido-borate).

In the title compound, Na(+)·4C(7)H(5)N(6) (+)·5BF(4) (-), the Na(+) ion lies on a fourfold rotation axis and one of the tetra-fluoridoborate ions lies on a site of symmetry . Each Na(+) ion is surrounded by four symmetry-related tetra-fluoridoborate ions, and is eight-coordinated by F atoms, the Na⋯F separation being 2.3956 (15) or 2.4347 (17) Å. The hexa-azaphenalenium 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 = 1149.72

Tetragonal,

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[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.152

S = 1.19

2423 reflections

177 parameters

H-atom parameters constrained

Δρmax = 0.74 e Å−3

Δρmin = −0.79 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Na+·4C7H5N6+·5BF4−	Dx = 1.883 Mg m−3
Mr = 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

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

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(Fo2) + (0.0759P)2 + 1.4095P] where P = (Fo2 + 2Fc2)/3
2423 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −0.79 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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—F5iv	1.3887 (14)	C6—N5	1.344 (3)
B2—F5v	1.3887 (14)	C6—N6	1.351 (2)
B2—F5vi	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—F5iv	109.54 (6)
F1i—Na1—F2iii	150.84 (6)	F5—B2—F5v	109.54 (6)
F1ii—Na1—F2iii	75.56 (5)	F5iv—B2—F5v	109.34 (13)
F1iii—Na1—F2iii	56.00 (4)	F5—B2—F5vi	109.34 (13)
F1—Na1—F2iii	124.29 (5)	F5iv—B2—F5vi	109.54 (6)
F2—Na1—F2iii	75.73 (5)	F5v—B2—F5vi	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)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N4vii	0.88	2.05	2.930 (2)	176
N6—H6N···N5viii	0.88	2.09	2.866 (2)	146
C1—H1···F3ix	0.95	2.47	3.179 (2)	132
C1—H1···F4viii	0.95	2.55	2.940 (3)	105
C3—H3···F2vii	0.95	2.22	3.124 (2)	159
C5—H5···F3iii	0.95	2.40	3.097 (2)	130

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⋯F3iv	0.95	2.40	3.097 (2)	130

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .