The azide-bridged mixed-valent cobalt(II,III) compound [(CH(3))(3)NH](2)[CoCo(2)(N(3))(10)].

The crystal structure of the title compound, poly[bis-(tri-methyl-ammonium) hexa-μ(1,1)-azido-tetra-azido-tricobalt-ate(II,III)], [(CH(3))(3)NH](2)[Co(II)Co(III) (2)(N(3))(10)], consists of anionic chains [Co(II)Co(III) (2)(N(3))(10)](2-) extending parallel to the c axis and [(CH(3))(3)NH](+) counter-cations situated between the chains. In the anionic chain, one tetra-hedrally coordinated Co(II) atom (site symmetry 2) and two octa-hedrally coordinated Co(III) atoms are arranged alternately and are linked by μ(1,1)-azide bridges. The anionic chains and cations are connected via N-H⋯N hydrogen bonding into a three-dimensional structure.

Related literature

For background to transition-metal azido-complexes templated by counter-cations of various sizes, see: Liu et al. (2006 ▶, 2008 ▶). For related cobalt complexes, see: Zhang et al. (2010 ▶).

Experimental

Crystal data

(C3H10N)2[Co3(N3)10]

M = 717.33

Monoclinic,

a = 21.7200 (6) Å

b = 11.3812 (4) Å

c = 12.1628 (4) Å

β = 115.524 (2)°

V = 2713.21 (15) Å3

Z = 4

Mo Kα radiation

μ = 1.88 mm−1

T = 293 K

0.10 × 0.06 × 0.05 mm

Data collection

Rigaku Saturn diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.708, T max = 0.823

22049 measured reflections

2389 independent reflections

1481 reflections with I > 2σ(I)

R int = 0.103

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.061

S = 0.98

2389 reflections

190 parameters

24 restraints

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.35 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); 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: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810049421/wm2430sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049421/wm2430Isup2.hkl

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

(C3H10N)2[Co3(N3)10]	F(000) = 1444
Mr = 717.33	Dx = 1.756 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 14377 reflections
a = 21.7200 (6) Å	θ = 3.4–25.0°
b = 11.3812 (4) Å	µ = 1.88 mm−1
c = 12.1628 (4) Å	T = 293 K
β = 115.524 (2)°	Pillar, red
V = 2713.21 (15) Å3	0.10 × 0.06 × 0.05 mm
Z = 4

Rigaku Saturn diffractometer	2389 independent reflections
Radiation source: fine-focus sealed tube	1481 reflections with I > 2σ(I)
graphite	Rint = 0.103
Detector resolution: 0.76 pixels mm-1	θmax = 25.0°, θmin = 3.6°
dtprofit.ref scans	h = −25→25
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −13→13
Tmin = 0.708, Tmax = 0.823	l = −14→14
22049 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H-atom parameters constrained
wR(F2) = 0.061	w = 1/[σ2(Fo2) + (0.0204P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max = 0.001
2389 reflections	Δρmax = 0.31 e Å−3
190 parameters	Δρmin = −0.35 e Å−3
24 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00084 (18)

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
Co1	0.04965 (2)	0.10300 (4)	0.05706 (4)	0.03529 (17)
Co2	0.0000	−0.04737 (5)	0.2500	0.0402 (2)
N1	0.06948 (14)	0.0409 (2)	0.2209 (3)	0.0428 (6)
N2	0.12002 (17)	0.0827 (3)	0.3042 (3)	0.0448 (6)
N3	0.16669 (18)	0.1210 (3)	0.3810 (3)	0.0740 (10)
N4	0.14720 (14)	0.1256 (2)	0.1097 (3)	0.0523 (7)
N5	0.16894 (15)	0.1348 (3)	0.0363 (3)	0.0540 (7)
N6	0.1925 (2)	0.1442 (4)	−0.0308 (4)	0.1069 (15)
N7	0.04578 (16)	0.2621 (2)	0.1120 (3)	0.0489 (8)
N8	−0.00656 (18)	0.3009 (3)	0.1097 (3)	0.0504 (8)
N9	−0.05415 (18)	0.3426 (3)	0.1100 (3)	0.0806 (12)
N10	0.02748 (13)	0.1593 (3)	−0.1084 (2)	0.0434 (6)
N11	0.04393 (15)	0.2609 (3)	−0.1156 (2)	0.0492 (6)
N12	0.0599 (2)	0.3555 (3)	−0.1195 (3)	0.0930 (13)
N13	−0.04827 (13)	0.0595 (2)	0.0083 (2)	0.0384 (6)
N14	−0.09288 (16)	0.1253 (3)	−0.0627 (3)	0.0425 (6)
N15	−0.13450 (17)	0.1858 (3)	−0.1255 (3)	0.0715 (10)
N16	0.16193 (14)	0.4179 (3)	0.2144 (3)	0.0539 (8)
H16	0.1336	0.3554	0.1828	0.065*
C1	0.2022 (2)	0.3949 (5)	0.3459 (4)	0.1044 (17)
H1A	0.2292	0.4628	0.3840	0.157*
H1B	0.2316	0.3287	0.3565	0.157*
H1C	0.1719	0.3783	0.3826	0.157*
C2	0.1190 (3)	0.5217 (4)	0.1950 (5)	0.1125 (19)
H2A	0.0852	0.5067	0.2242	0.169*
H2B	0.0970	0.5396	0.1096	0.169*
H2C	0.1468	0.5871	0.2384	0.169*
C3	0.2062 (2)	0.4251 (5)	0.1509 (4)	0.1121 (19)
H3A	0.1787	0.4379	0.0655	0.168*
H3B	0.2311	0.3529	0.1621	0.168*
H3C	0.2377	0.4891	0.1837	0.168*

	U11	U22	U33	U12	U13	U23
Co1	0.0382 (3)	0.0364 (3)	0.0331 (3)	−0.0041 (2)	0.0171 (2)	−0.0013 (2)
Co2	0.0487 (4)	0.0370 (4)	0.0412 (5)	0.000	0.0253 (4)	0.000
N1	0.0456 (15)	0.0502 (15)	0.0338 (16)	−0.0052 (12)	0.0181 (13)	0.0022 (12)
N2	0.0475 (15)	0.0518 (15)	0.0353 (16)	−0.0042 (13)	0.0180 (13)	0.0033 (13)
N3	0.065 (2)	0.095 (3)	0.052 (2)	−0.019 (2)	0.015 (2)	−0.006 (2)
N4	0.0449 (15)	0.0647 (16)	0.0528 (17)	−0.0104 (12)	0.0264 (12)	−0.0027 (13)
N5	0.0453 (15)	0.0637 (16)	0.0561 (18)	−0.0079 (12)	0.0249 (13)	−0.0055 (13)
N6	0.097 (3)	0.148 (4)	0.112 (4)	−0.027 (3)	0.079 (3)	−0.026 (3)
N7	0.061 (2)	0.0407 (19)	0.051 (2)	−0.0085 (16)	0.0293 (18)	−0.0088 (15)
N8	0.062 (2)	0.040 (2)	0.050 (2)	−0.0019 (17)	0.025 (2)	−0.0050 (15)
N9	0.071 (3)	0.068 (3)	0.103 (3)	0.009 (2)	0.037 (3)	−0.020 (2)
N10	0.0570 (15)	0.0435 (16)	0.0329 (14)	−0.0095 (13)	0.0222 (12)	0.0004 (13)
N11	0.0626 (15)	0.0478 (16)	0.0348 (15)	−0.0086 (14)	0.0186 (12)	0.0007 (13)
N12	0.150 (4)	0.054 (2)	0.064 (3)	−0.036 (2)	0.036 (3)	0.004 (2)
N13	0.0378 (15)	0.0388 (15)	0.0414 (17)	−0.0002 (10)	0.0197 (13)	−0.0025 (11)
N14	0.0408 (15)	0.0412 (16)	0.0447 (17)	−0.0017 (11)	0.0176 (13)	−0.0036 (11)
N15	0.058 (2)	0.058 (2)	0.081 (3)	0.0085 (19)	0.014 (2)	0.005 (2)
N16	0.0501 (19)	0.050 (2)	0.061 (2)	−0.0163 (15)	0.0234 (19)	−0.0118 (16)
C1	0.083 (3)	0.143 (5)	0.067 (4)	−0.039 (3)	0.013 (3)	0.007 (3)
C2	0.115 (4)	0.052 (3)	0.165 (6)	0.015 (3)	0.055 (4)	−0.001 (3)
C3	0.093 (4)	0.173 (5)	0.099 (4)	−0.055 (4)	0.069 (3)	−0.045 (4)

Co1—N7	1.944 (3)	N11—N12	1.139 (4)
Co1—N4	1.948 (3)	N13—N14	1.234 (4)
Co1—N10	1.964 (3)	N13—Co1i	2.008 (3)
Co1—N1	1.979 (3)	N14—N15	1.131 (4)
Co1—N13i	2.008 (3)	N16—C2	1.460 (5)
Co1—N13	2.008 (3)	N16—C3	1.473 (4)
Co2—N1ii	1.968 (3)	N16—C1	1.478 (5)
Co2—N1	1.968 (3)	N16—H16	0.9100
Co2—N10i	2.014 (3)	C1—H1A	0.9600
Co2—N10iii	2.014 (3)	C1—H1B	0.9600
N1—N2	1.224 (4)	C1—H1C	0.9600
N2—N3	1.129 (4)	C2—H2A	0.9600
N4—N5	1.181 (4)	C2—H2B	0.9600
N5—N6	1.140 (4)	C2—H2C	0.9600
N7—N8	1.209 (4)	C3—H3A	0.9600
N8—N9	1.139 (4)	C3—H3B	0.9600
N10—N11	1.225 (4)	C3—H3C	0.9600
N10—Co2i	2.014 (3)
N7—Co1—N4	88.05 (12)	Co1—N10—Co2i	121.43 (14)
N7—Co1—N10	91.18 (12)	N12—N11—N10	178.5 (4)
N4—Co1—N10	92.62 (12)	N14—N13—Co1i	114.1 (2)
N7—Co1—N1	90.55 (12)	N14—N13—Co1	118.0 (2)
N4—Co1—N1	88.97 (12)	Co1i—N13—Co1	100.22 (11)
N10—Co1—N1	177.69 (12)	N15—N14—N13	178.2 (4)
N7—Co1—N13i	176.56 (13)	C2—N16—C3	112.7 (4)
N4—Co1—N13i	94.61 (11)	C2—N16—C1	110.9 (4)
N10—Co1—N13i	86.53 (11)	C3—N16—C1	111.2 (3)
N1—Co1—N13i	91.67 (11)	C2—N16—H16	107.3
N7—Co1—N13	97.71 (11)	C3—N16—H16	107.3
N4—Co1—N13	173.16 (12)	C1—N16—H16	107.3
N10—Co1—N13	90.96 (11)	N16—C1—H1A	109.5
N1—Co1—N13	87.29 (11)	N16—C1—H1B	109.5
N13i—Co1—N13	79.78 (11)	H1A—C1—H1B	109.5
N1ii—Co2—N1	118.61 (16)	N16—C1—H1C	109.5
N1ii—Co2—N10i	120.58 (11)	H1A—C1—H1C	109.5
N1—Co2—N10i	97.86 (11)	H1B—C1—H1C	109.5
N1ii—Co2—N10iii	97.86 (11)	N16—C2—H2A	109.5
N1—Co2—N10iii	120.58 (11)	N16—C2—H2B	109.5
N10i—Co2—N10iii	101.58 (16)	H2A—C2—H2B	109.5
N2—N1—Co2	122.3 (2)	N16—C2—H2C	109.5
N2—N1—Co1	115.0 (2)	H2A—C2—H2C	109.5
Co2—N1—Co1	120.82 (15)	H2B—C2—H2C	109.5
N3—N2—N1	179.9 (5)	N16—C3—H3A	109.5
N5—N4—Co1	119.7 (3)	N16—C3—H3B	109.5
N6—N5—N4	177.2 (4)	H3A—C3—H3B	109.5
N8—N7—Co1	120.8 (2)	N16—C3—H3C	109.5
N9—N8—N7	176.5 (4)	H3A—C3—H3C	109.5
N11—N10—Co1	115.5 (2)	H3B—C3—H3C	109.5
N11—N10—Co2i	121.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N16—H16···N7	0.91	2.02	2.890	159.

Table 1

Selected bond lengths (Å)

Co1—N7	1.944 (3)
Co1—N4	1.948 (3)
Co1—N10	1.964 (3)
Co1—N1	1.979 (3)
Co1—N13i	2.008 (3)
Co1—N13	2.008 (3)
Co2—N1ii	1.968 (3)
Co2—N1	1.968 (3)
Co2—N10i	2.014 (3)
Co2—N10iii	2.014 (3)

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

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N16—H16⋯N7	0.91	2.02	2.890	159