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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): m85.
Published online 2009 December 19. doi:  10.1107/S1600536809039415
PMCID: PMC2980217

Poly[bis­[μ2-1,4-bis­(1,2,4-triazol-1-yl­meth­yl)benzene-κ2 N 4:N 4′]bis(nitrito-κO)cobalt(II)]

Abstract

The CoII atom in the title complex, [Co(NO2)2(C12H12N6)2]n, lies on an inversion center and is coordinated by four N atoms from the triazole rings of two symmetry-related pairs of 1,4-bis­(1,2,4-triazol-1-ylmeth­yl)benzene (bbtz) ligands and two O atoms from two symmetry-related monodentate nitrate ligands in a distorted octa­hedral geometry. The Co atoms are bridged by four bbtz ligands, forming a two-dimensional (4,4) network parallel to (102).

Related literature

The synthesis of the ligand 1,4-bis­(1,2,4-triazol-1-ylmeth­yl)-benzene (bbtz) was described by Peng et al. (2004 [triangle]). Several bbtz complexes have been synthesized and structurally characterized, see: Li et al. (2005 [triangle]); Wang et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-00m85-scheme1.jpg

Experimental

Crystal data

  • [Co(NO2)2(C12H12N6)2]
  • M r = 631.50
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-00m85-efi5.jpg
  • a = 8.3037 (13) Å
  • b = 20.376 (3) Å
  • c = 8.4261 (11) Å
  • β = 104.390 (4)°
  • V = 1380.9 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.68 mm−1
  • T = 193 K
  • 0.33 × 0.26 × 0.10 mm

Data collection

  • Rigaku Mercury CCD diffractometer
  • Absorption correction: multi-scan (REQAB; Jacobson, 1998 [triangle]) T min = 0.806, T max = 0.935
  • 15379 measured reflections
  • 3152 independent reflections
  • 2768 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.098
  • S = 1.07
  • 3152 reflections
  • 197 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: CrystalClear (Rigaku, 2000 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809039415/gk2227sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039415/gk2227Isup2.hkl

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

Acknowledgments

This work was supported by the funds of the Civil Aviation University of China (grant No. 08CAUC-S03).

supplementary crystallographic information

Comment

The title compound is isostructural with its azido NiII analog (Wang et al., 2007).

Fig. 1 shows the local coordination of the CoII atom. In the complex the CoII atom occupies an inversion center. The coordination geometry of the CoII atom is a distorted octahedron. Each CoII atom is coordinated equatorial by four nitrogen atoms from the triazole rings of four bbtz ligands [Co1—N3, 2.1530 (16) Å; Co1—N6 (-x + 1, y - 1/2, -z + 1/2), 2.1418 (16) Å], and axially by two oxygen atoms from two symmetry-related nitrite anions [Co1—O1, 2.1031 (15) Å]. The bbtz ligands shows the trans-gauche conformation, similar to the uncoordinated bbtz molecule (Peng et al., 2004).

As illustrated in Fig.2, each bbtz ligand coordinated to the CoII atoms through its two triazole nitrogen atoms, thus acting as a bridging bidentate ligand to form a two-dimensional (4,4) network. As a consequence of the symmetry of the crystal structure, the edge lengths are equal, with a vaule of 14.4182 (14) Å. The square-grid sheets are stacked in an offset fashion parallel to the c direction. The off-set half-cell superposition of each pair of adjacent networks divides the voids into smaller rectangle. The nitrile anions of one sheet project into the holes of the next sheet. In the superposition structure, the sheets are arranged in the sequence···A—B—A—B··· (Fig.3).

Experimental

A H2O/MeOH solution (20 ml, 1:1 v/v) of Co(ClO4)2.6H2O (0.50 mmol) and NaNO2 (2.0 mmol) was added to one leg of a "H-shaped" tube, and a H2O/MeOH solution (20 ml, 1:1 v/v) of bbtz (0.240 g, 1.00 mmol) was added to the other leg of the tube. After several weeks, the well shaped red single crystals were obtained. Found: C, 45.57; H, 3.79; N, 30.94%. Calcd. for C24H24CoN14O4: C, 45.65; H, 3.83; N, 31.06%.

Refinement

H atom were placed in idealized positions and refined as riding, with C—H distances of 0.95 (triazole and benzene) and 0.99Å (methyl), and with Uiso(H) = 1.2 times Ueq(C).

Figures

Fig. 1.
The coordination environment of the CoII atom in the title compound. Ellipsoids are drawn at the 30% probability level. [Symmetry codes # -x, -y + 1, -z + 1; $ -x + 1, y - 1/2, -z + 1/2; * x - 1, -y + 3/2, z + 1/2]. The hydrogen atoms have been omitted ...
Fig. 2.
View of the two-dimensional (4,4) network of the title compound along the c direction.
Fig. 3.
The cell packing of the title compound.

Crystal data

[Co(NO2)2(C12H12N6)2]F(000) = 650
Mr = 631.50Dx = 1.519 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.3037 (13) ÅCell parameters from 5616 reflections
b = 20.376 (3) Åθ = 3.1–27.5°
c = 8.4261 (11) ŵ = 0.68 mm1
β = 104.390 (4)°T = 193 K
V = 1380.9 (3) Å3Block, red
Z = 20.33 × 0.26 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer3152 independent reflections
Radiation source: fine-focus sealed tube2768 reflections with I > 2σ(I)
graphiteRint = 0.032
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (REQAB; Jacobson, 1998)h = −10→10
Tmin = 0.806, Tmax = 0.935k = −26→26
15379 measured reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0436P)2 + 0.7485P] where P = (Fo2 + 2Fc2)/3
3152 reflections(Δ/σ)max < 0.001
197 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.29 e Å3

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 (Å2)

xyzUiso*/Ueq
Co10.00000.50000.50000.02085 (12)
O10.25015 (18)0.50405 (7)0.6333 (2)0.0350 (4)
O20.48900 (19)0.54314 (9)0.7278 (2)0.0461 (4)
N10.1620 (2)0.57944 (8)0.0939 (2)0.0273 (4)
N2−0.0036 (2)0.58502 (11)0.0290 (2)0.0412 (5)
N30.0484 (2)0.54604 (8)0.2865 (2)0.0257 (3)
N40.8222 (2)0.83452 (8)0.2102 (2)0.0274 (4)
N50.9542 (2)0.80233 (9)0.1784 (2)0.0349 (4)
N60.93982 (19)0.90596 (8)0.08323 (19)0.0253 (3)
N70.3509 (2)0.54893 (10)0.6299 (2)0.0425 (5)
C10.3965 (2)0.65065 (10)0.0737 (2)0.0282 (4)
C20.5418 (3)0.63661 (11)0.1894 (3)0.0343 (5)
H2A0.56990.59230.21880.041*
C30.6470 (3)0.68667 (11)0.2632 (3)0.0339 (5)
H3A0.74710.67620.34190.041*
C40.6084 (3)0.75136 (10)0.2239 (2)0.0289 (4)
C50.4628 (3)0.76574 (11)0.1061 (3)0.0376 (5)
H5A0.43530.81010.07660.045*
C60.3576 (3)0.71570 (11)0.0315 (3)0.0364 (5)
H6A0.25850.7260−0.04880.044*
C70.2823 (3)0.59545 (11)−0.0029 (3)0.0333 (5)
H7A0.22140.6082−0.11510.040*
H7B0.34940.5560−0.01120.040*
C80.7201 (3)0.80549 (11)0.3108 (3)0.0370 (5)
H8A0.65080.84030.34250.044*
H8B0.79390.78770.41250.044*
C9−0.0655 (3)0.56403 (12)0.1496 (3)0.0371 (5)
H9A−0.18170.56180.14060.044*
C100.1907 (3)0.55662 (11)0.2456 (2)0.0312 (5)
H10A0.29790.54890.31530.037*
C111.0198 (3)0.84752 (10)0.1016 (3)0.0317 (5)
H11A1.11570.83970.06210.038*
C120.8157 (2)0.89541 (10)0.1543 (2)0.0269 (4)
H12A0.73440.92700.16350.032*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.01814 (19)0.02220 (19)0.0236 (2)−0.00012 (13)0.00787 (14)0.00201 (14)
O10.0210 (7)0.0348 (8)0.0459 (9)−0.0049 (6)0.0020 (6)0.0075 (7)
O20.0229 (8)0.0624 (11)0.0527 (10)−0.0088 (7)0.0087 (7)−0.0060 (9)
N10.0262 (9)0.0307 (9)0.0257 (8)−0.0063 (7)0.0079 (7)0.0017 (7)
N20.0296 (10)0.0549 (13)0.0378 (10)−0.0010 (9)0.0058 (8)0.0142 (9)
N30.0251 (8)0.0266 (8)0.0273 (8)0.0002 (6)0.0101 (6)0.0036 (7)
N40.0262 (8)0.0276 (8)0.0291 (9)−0.0053 (7)0.0083 (7)−0.0024 (7)
N50.0296 (9)0.0304 (9)0.0455 (11)0.0004 (7)0.0108 (8)0.0020 (8)
N60.0221 (8)0.0260 (8)0.0289 (8)−0.0026 (6)0.0084 (6)−0.0019 (7)
N70.0331 (10)0.0523 (12)0.0406 (11)−0.0124 (9)0.0061 (8)0.0041 (9)
C10.0274 (10)0.0323 (11)0.0283 (10)−0.0054 (8)0.0135 (8)0.0017 (8)
C20.0330 (11)0.0293 (11)0.0412 (12)−0.0004 (9)0.0101 (9)0.0087 (9)
C30.0288 (11)0.0365 (11)0.0342 (11)−0.0014 (9)0.0034 (9)0.0089 (9)
C40.0293 (10)0.0314 (10)0.0284 (10)−0.0053 (8)0.0118 (8)0.0013 (8)
C50.0344 (12)0.0282 (11)0.0499 (14)−0.0001 (9)0.0098 (10)0.0077 (10)
C60.0284 (11)0.0389 (12)0.0394 (12)0.0001 (9)0.0035 (9)0.0091 (10)
C70.0368 (12)0.0396 (12)0.0281 (10)−0.0116 (9)0.0167 (9)−0.0018 (9)
C80.0424 (13)0.0397 (12)0.0323 (11)−0.0137 (10)0.0154 (10)−0.0017 (10)
C90.0244 (11)0.0480 (13)0.0404 (12)0.0020 (9)0.0110 (9)0.0111 (10)
C100.0249 (10)0.0411 (12)0.0280 (10)−0.0036 (8)0.0069 (8)0.0064 (9)
C110.0244 (10)0.0303 (10)0.0414 (12)−0.0003 (8)0.0099 (9)−0.0019 (9)
C120.0242 (10)0.0267 (10)0.0309 (10)−0.0022 (8)0.0088 (8)−0.0022 (8)

Geometric parameters (Å, °)

Co1—O1i2.1031 (15)C1—C21.380 (3)
Co1—O12.1031 (15)C1—C61.389 (3)
Co1—N6ii2.1418 (16)C1—C71.509 (3)
Co1—N6iii2.1418 (16)C2—C31.385 (3)
Co1—N32.1530 (16)C2—H2A0.9500
Co1—N3i2.1530 (16)C3—C41.377 (3)
O1—N71.245 (2)C3—H3A0.9500
O2—N71.240 (2)C4—C51.391 (3)
N1—C101.325 (3)C4—C81.509 (3)
N1—N21.353 (2)C5—C61.387 (3)
N1—C71.475 (2)C5—H5A0.9500
N2—C91.319 (3)C6—H6A0.9500
N3—C101.328 (2)C7—H7A0.9900
N3—C91.348 (3)C7—H7B0.9900
N4—C121.324 (3)C8—H8A0.9900
N4—N51.360 (2)C8—H8B0.9900
N4—C81.465 (3)C9—H9A0.9500
N5—C111.319 (3)C10—H10A0.9500
N6—C121.331 (2)C11—H11A0.9500
N6—C111.353 (3)C12—H12A0.9500
N6—Co1iv2.1418 (16)
O1i—Co1—O1180.0C4—C3—C2120.9 (2)
O1i—Co1—N6ii94.01 (6)C4—C3—H3A119.6
O1—Co1—N6ii85.99 (6)C2—C3—H3A119.6
O1i—Co1—N6iii85.99 (6)C3—C4—C5118.83 (19)
O1—Co1—N6iii94.01 (6)C3—C4—C8120.3 (2)
N6ii—Co1—N6iii180.00 (8)C5—C4—C8120.85 (19)
O1i—Co1—N386.30 (6)C6—C5—C4120.4 (2)
O1—Co1—N393.70 (6)C6—C5—H5A119.8
N6ii—Co1—N390.52 (6)C4—C5—H5A119.8
N6iii—Co1—N389.48 (6)C5—C6—C1120.3 (2)
O1i—Co1—N3i93.70 (6)C5—C6—H6A119.8
O1—Co1—N3i86.30 (6)C1—C6—H6A119.8
N6ii—Co1—N3i89.48 (6)N1—C7—C1111.64 (17)
N6iii—Co1—N3i90.52 (6)N1—C7—H7A109.3
N3—Co1—N3i180.00 (8)C1—C7—H7A109.3
N7—O1—Co1126.67 (14)N1—C7—H7B109.3
C10—N1—N2109.92 (16)C1—C7—H7B109.3
C10—N1—C7128.82 (18)H7A—C7—H7B108.0
N2—N1—C7121.23 (17)N4—C8—C4112.87 (17)
C9—N2—N1102.28 (17)N4—C8—H8A109.0
C10—N3—C9102.35 (17)C4—C8—H8A109.0
C10—N3—Co1130.55 (14)N4—C8—H8B109.0
C9—N3—Co1126.63 (14)C4—C8—H8B109.0
C12—N4—N5110.21 (16)H8A—C8—H8B107.8
C12—N4—C8127.34 (18)N2—C9—N3115.02 (19)
N5—N4—C8122.01 (17)N2—C9—H9A122.5
C11—N5—N4102.19 (17)N3—C9—H9A122.5
C12—N6—C11102.66 (16)N3—C10—N1110.43 (18)
C12—N6—Co1iv124.14 (13)N3—C10—H10A124.8
C11—N6—Co1iv132.60 (13)N1—C10—H10A124.8
O2—N7—O1115.52 (19)N5—C11—N6114.82 (18)
C2—C1—C6119.04 (19)N5—C11—H11A122.6
C2—C1—C7119.60 (19)N6—C11—H11A122.6
C6—C1—C7121.36 (19)N4—C12—N6110.11 (17)
C1—C2—C3120.5 (2)N4—C12—H12A124.9
C1—C2—H2A119.7N6—C12—H12A124.9
C3—C2—H2A119.7
N6ii—Co1—O1—N7126.75 (19)C2—C1—C6—C5−0.6 (3)
N6iii—Co1—O1—N7−53.25 (19)C7—C1—C6—C5178.6 (2)
N3—Co1—O1—N736.48 (19)C10—N1—C7—C1−63.3 (3)
N3i—Co1—O1—N7−143.52 (19)N2—N1—C7—C1119.1 (2)
C10—N1—N2—C9−0.5 (2)C2—C1—C7—N188.2 (2)
C7—N1—N2—C9177.54 (19)C6—C1—C7—N1−91.0 (2)
O1i—Co1—N3—C10−165.51 (19)C12—N4—C8—C4115.1 (2)
O1—Co1—N3—C1014.49 (19)N5—N4—C8—C4−73.2 (3)
N6ii—Co1—N3—C10−71.53 (19)C3—C4—C8—N4104.3 (2)
N6iii—Co1—N3—C10108.47 (19)C5—C4—C8—N4−77.4 (3)
O1i—Co1—N3—C95.24 (18)N1—N2—C9—N30.5 (3)
O1—Co1—N3—C9−174.76 (18)C10—N3—C9—N2−0.3 (3)
N6ii—Co1—N3—C999.22 (18)Co1—N3—C9—N2−173.14 (16)
N6iii—Co1—N3—C9−80.78 (18)C9—N3—C10—N10.0 (2)
C12—N4—N5—C11−0.5 (2)Co1—N3—C10—N1172.41 (13)
C8—N4—N5—C11−173.46 (18)N2—N1—C10—N30.3 (3)
Co1—O1—N7—O2175.00 (14)C7—N1—C10—N3−177.51 (18)
C6—C1—C2—C30.3 (3)N4—N5—C11—N60.4 (2)
C7—C1—C2—C3−178.94 (19)C12—N6—C11—N5−0.1 (2)
C1—C2—C3—C40.6 (3)Co1iv—N6—C11—N5170.93 (14)
C2—C3—C4—C5−1.2 (3)N5—N4—C12—N60.5 (2)
C2—C3—C4—C8177.2 (2)C8—N4—C12—N6172.95 (18)
C3—C4—C5—C60.9 (3)C11—N6—C12—N4−0.2 (2)
C8—C4—C5—C6−177.4 (2)Co1iv—N6—C12—N4−172.27 (12)
C4—C5—C6—C10.0 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2227).

References

  • Jacobson, R. (1998). REQAB Private communication to Rigaku Corporation, Tokyo, Japan.
  • Li, B. L., Peng, Y. F., Li, B. Z. & Zhang, Y. (2005). Chem. Commun. pp. 2333–2335. [PubMed]
  • Peng, Y. F., Li, B. Z., Zzhou, J. H., Li, B. L. & Zhang, Y. (2004). Chin. J. Struct. Chem.23, 985–988.
  • Rigaku (2000). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, L.-Y., Peng, Y.-F., Zhang, Y.-P., Li, B.-L. & Zhang, Y. (2007). Acta Cryst. C63, m297–m299. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography