Poly[μ-(5,5′-diazenediyldi­tetra­zolido)-dicaesium]

The asymmetric unit of the title compound, [Cs₂(C₂N₁₀)]_n, comprises a Cs⁺ cation, and one-half of a 5,5′-diazenediylditetra­zolide anion. The Cs⁺ cation is six-coordinated by N atoms from six 5,5′-diazenediylditetra­zolide ligands. Each 5,5′-diazenediylditetra­zolide ligand is surrounded by 12 Cs⁺ cations, coordinating through ten N atoms. The Cs⁺ cations are arranged in a chain along the a-axis direction with a Cs⋯Cs separation of 4.4393 (10) Å. Such coordination leads to the formation of the three-dimensional framework.

Related literature

For applications of 5,5′-diazenediylditetra­zolide salts, see: Hammerl et al. (2001). For the synthesis of sodium 5,5′-diazenediylditetra­zolide, see: Thiele (1892). For the synthesis and characterization of alkali and alkaline earth metal salts of 5,5′-diazenediylditetra­zolide, see: Hammerl et al. (2002); Steinhauser et al. (2009). For Cs—N bond lengths, see: Ebespächer et al. (2009).

Experimental

Crystal data

• [Cs₂(C₂N₁₀)]

• M_r = 429.94

• Monoclinic, P 2₁ /c

• a = 4.4393 (9) Å

• b = 8.7151 (17) Å

• c = 11.860 (2) Å

• β = 93.83 (3)°

• V = 457.82 (16) ų

• Z = 2

• Mo Kα radiation

• μ = 7.94 mm⁻¹

• T = 293 K

• 0.42 × 0.26 × 0.07 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007) T_min = 0.135, T_max = 0.606

• 4146 measured reflections

• 842 independent reflections

• 747 reflections with I > 2σ(I)

• R_int = 0.047

Refinement

• R[F² > 2σ(F²)] = 0.031

• wR(F²) = 0.082

• S = 1.15

• 842 reflections

• 64 parameters

• Δρ_max = 1.36 e Å⁻³

• Δρ_min = −1.47 e Å⁻³

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010).

Supporting information

S1. Comment

Salts of 5,5'-diazenediylditetrazolide are powerful gas generation agents and can be used in gas generators for airbags and fire extinguishing systems (Hammerl et al., 2001). Thiele first prepared sodium 5,5'-diazenediylditetrazolide (Thiele, 1892), which is usually used as the starting material for other 5,5'-diazenediylditetrazolide compounds. Up to now, although many alkali-and alkaline earth metal salts of 5,5'-diazenediylditetrazolide have been prepared (Hammerl et al., 2002; Steinhauser et al.,2009), more work still needs to be done. In this paper, we report the crystal structure of the title compound, (I), a new Cs complex obtained by the reaction of sodium 5,5'-diazenediylditetrazolide and CsCl in water.

The asymmetric unit of the title compound comprises a Cs⁺ cation, and a half of 5,5'-diazenediylditetrazolide anion. The central cation is coordinated to six N atoms from six 5,5'-diazenediylditetrazolide ligands (Fig. 1) with the Cs—N distances ranging from 3.225 (6) Å to 3.341 (5) Å, which are well within the range reported in the literature (Ebespächer et al., 2009). The atom N2 from the tetrazole rings acts as µ₃-bridge. Thus, each 5,5'-diazenediylditetrazolide anion links twelve Cs⁺ cations through ten nitrogen atoms. The Cs⁺ cations are arranged in a one-dimensional chain along the a-axis direction with the Cs⁺ ··· Cs⁺ separation of 4.4393 (10) Å. Such linking mode leads to the formation of the three-dimensional framework of the title compound (Fig. 2).

Related literature

For applications of 5,5'-diazenediylditetrazolide salts, see: Hammerl et al. (2001). For the synthesis of sodium 5,5'-diazenediylditetrazolide, see: Thiele (1892). For the synthesis and characterization of alkali and alkaline earth metal salts of 5,5'-diazenediylditetrazolide, see: Hammerl et al. (2002); Steinhauser et al. (2009). For the Cs—N bond lengths, see: Ebespächer et al. (2009). Author: scheme should show the polymeric nature of the title compound

S2. Experimental

To a solution of sodium 5,5'-diazenediylditetrazolide in 20 ml bidistilled water, a solution of CsCl was added dropwise at room temperature. After stirring for 30 minutes a yellow solution was obtained after filtration. The filtrate was then set aside for crystallization at room temperature. Three weeks later, yellow block crystals of the title compound suitable for X-ray determination were isolated.

S3. Refinement

All atoms were refined anisotropically. The maximum residual electron density of 1.36 e Å^-3 is located 1.11 Å from Cs1 and the minimum density of -1.46 e Å^-3 lies 0.83 Å from Cs1.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The structure of (I), with 30% probability displacement ellipsoids. Symmetry code: (i) – x, – y + 1, – z + 1; (ii) x + 1, y, z; (iii) – x, y – 1/2, – z + 1/2; (iv) x + 1, – y + 1/2, z – 1/2; (v) – x – 1, y + 1/2, – z + 1/2;(vi) x, – y + 1/2, z – 1/2.
	Fig. 2. The three-dimensional framework of (I).

Poly[µ-(5,5'-diazenediylditetrazolido)-dicaesium]

Crystal data

[Cs2(C2N10)]	F(000) = 384
Mr = 429.94	Dx = 3.119 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1601 reflections
a = 4.4393 (9) Å	θ = 3.4–25.4°
b = 8.7151 (17) Å	µ = 7.94 mm^−1
c = 11.860 (2) Å	T = 293 K
β = 93.83 (3)°	Block, yellow
V = 457.82 (16) Å^3	0.42 × 0.26 × 0.07 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	842 independent reflections
Radiation source: fine-focus sealed tube	747 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 25.3°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −5→4
Tmin = 0.135, Tmax = 0.606	k = −10→10
4146 measured reflections	l = −12→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.031	Secondary atom site location: difference Fourier map
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0385P)^2 + 0.5977P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max < 0.001
842 reflections	Δρmax = 1.36 e Å^−3
64 parameters	Δρmin = −1.47 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.

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

	x	y	z	Uiso*/Ueq
Cs1	0.08959 (8)	0.47092 (5)	0.19017 (3)	0.0345 (2)
C1	−0.2743 (12)	0.3536 (7)	0.4829 (5)	0.0246 (13)
N1	−0.3813 (11)	0.3517 (6)	0.3756 (4)	0.0320 (12)
N2	−0.5901 (11)	0.2386 (6)	0.3729 (5)	0.0346 (13)
N3	−0.6023 (13)	0.1805 (6)	0.4744 (5)	0.0389 (14)
N4	−0.4029 (13)	0.2515 (7)	0.5477 (5)	0.0379 (14)
N5	−0.0545 (11)	0.4536 (6)	0.5334 (5)	0.0293 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.0288 (3)	0.0391 (3)	0.0354 (3)	−0.00007 (16)	0.0014 (2)	0.00540 (17)
C1	0.022 (3)	0.026 (3)	0.026 (3)	0.005 (3)	0.001 (2)	−0.001 (3)
N1	0.028 (3)	0.035 (3)	0.032 (3)	−0.004 (2)	−0.001 (2)	−0.007 (3)
N2	0.026 (3)	0.034 (3)	0.043 (3)	−0.002 (2)	0.001 (2)	−0.009 (3)
N3	0.031 (3)	0.029 (3)	0.057 (4)	0.003 (2)	0.004 (3)	0.008 (3)
N4	0.031 (3)	0.040 (3)	0.042 (3)	0.001 (3)	0.001 (3)	0.009 (3)
N5	0.025 (3)	0.032 (3)	0.031 (3)	0.002 (2)	0.003 (2)	−0.003 (2)

Geometric parameters (Å, º)

Cs1—N2^i	3.225 (6)	N1—N2	1.352 (7)
Cs1—N3^ii	3.260 (6)	N2—N3	1.311 (8)
Cs1—N2^iii	3.270 (5)	N2—Cs1^vi	3.225 (6)
Cs1—N4^iv	3.301 (6)	N2—Cs1^vii	3.270 (5)
Cs1—N1	3.301 (5)	N2—Cs1^viii	3.341 (5)
Cs1—N2^v	3.341 (5)	N3—N4	1.349 (8)
C1—N1	1.329 (7)	N3—Cs1^ix	3.260 (6)
C1—N4	1.329 (8)	N4—Cs1^x	3.301 (6)
C1—N5	1.411 (8)	N5—N5^xi	1.252 (10)
N2^i—Cs1—N3^ii	94.82 (14)	N4—C1—N5	118.7 (5)
N2^i—Cs1—N2^iii	149.65 (5)	C1—N1—N2	103.4 (5)
N3^ii—Cs1—N2^iii	115.02 (14)	C1—N1—Cs1	115.6 (4)
N3^ii—Cs1—N1^i	94.53 (14)	N2—N1—Cs1	132.6 (4)
N2^iii—Cs1—N1^i	145.48 (14)	N3—N2—N1	109.3 (5)
N2^i—Cs1—N4^iv	102.85 (14)	N3—N2—Cs1^vi	144.7 (4)
N3^ii—Cs1—N4^iv	70.05 (14)	N1—N2—Cs1^vi	80.2 (3)
N2^iii—Cs1—N4^iv	83.47 (14)	N3—N2—Cs1^vii	82.3 (4)
N2^i—Cs1—N1	68.00 (13)	N1—N2—Cs1^vii	168.2 (4)
N3^ii—Cs1—N1	135.48 (14)	N3—N2—Cs1^viii	90.3 (4)
N2^iii—Cs1—N1	85.81 (13)	N1—N2—Cs1^viii	92.8 (3)
N4^iv—Cs1—N1	74.28 (13)	N2—N3—N4	110.4 (5)
N2^i—Cs1—N2^v	108.58 (7)	N2—N3—Cs1^ix	157.3 (4)
N3^ii—Cs1—N2^v	77.69 (14)	N4—N3—Cs1^ix	88.4 (4)
N2^iii—Cs1—N2^v	84.36 (13)	C1—N4—N3	102.9 (5)
N4^iv—Cs1—N2^v	136.31 (13)	C1—N4—Cs1^x	113.2 (4)
N1—Cs1—N2^v	146.00 (14)	N3—N4—Cs1^x	116.4 (4)
N1—C1—N4	113.9 (5)	N5^xi—N5—C1	114.6 (7)
N1—C1—N5	127.4 (6)

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