

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809039415/gk2227sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536809039415/gk2227Isup2.hkl |
CCDC reference: 766691
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.041
- wR factor = 0.098
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for O1 -- N7 .. 5.22 su PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 4 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 12
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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%.
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).
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); 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: SHELXTL (Sheldrick, 2008).
[Co(NO2)2(C12H12N6)2] | F(000) = 650 |
Mr = 631.50 | Dx = 1.519 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3037 (13) Å | Cell parameters from 5616 reflections |
b = 20.376 (3) Å | θ = 3.1–27.5° |
c = 8.4261 (11) Å | µ = 0.68 mm−1 |
β = 104.390 (4)° | T = 193 K |
V = 1380.9 (3) Å3 | Block, red |
Z = 2 | 0.33 × 0.26 × 0.10 mm |
Rigaku Mercury CCD diffractometer | 3152 independent reflections |
Radiation source: fine-focus sealed tube | 2768 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | h = −10→10 |
Tmin = 0.806, Tmax = 0.935 | k = −26→26 |
15379 measured reflections | l = −10→10 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0436P)2 + 0.7485P] where P = (Fo2 + 2Fc2)/3 |
3152 reflections | (Δ/σ)max < 0.001 |
197 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
[Co(NO2)2(C12H12N6)2] | V = 1380.9 (3) Å3 |
Mr = 631.50 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.3037 (13) Å | µ = 0.68 mm−1 |
b = 20.376 (3) Å | T = 193 K |
c = 8.4261 (11) Å | 0.33 × 0.26 × 0.10 mm |
β = 104.390 (4)° |
Rigaku Mercury CCD diffractometer | 3152 independent reflections |
Absorption correction: multi-scan (REQAB; Jacobson, 1998) | 2768 reflections with I > 2σ(I) |
Tmin = 0.806, Tmax = 0.935 | Rint = 0.032 |
15379 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.28 e Å−3 |
3152 reflections | Δρmin = −0.29 e Å−3 |
197 parameters |
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 | 0.0000 | 0.5000 | 0.5000 | 0.02085 (12) | |
O1 | 0.25015 (18) | 0.50405 (7) | 0.6333 (2) | 0.0350 (4) | |
O2 | 0.48900 (19) | 0.54314 (9) | 0.7278 (2) | 0.0461 (4) | |
N1 | 0.1620 (2) | 0.57944 (8) | 0.0939 (2) | 0.0273 (4) | |
N2 | −0.0036 (2) | 0.58502 (11) | 0.0290 (2) | 0.0412 (5) | |
N3 | 0.0484 (2) | 0.54604 (8) | 0.2865 (2) | 0.0257 (3) | |
N4 | 0.8222 (2) | 0.83452 (8) | 0.2102 (2) | 0.0274 (4) | |
N5 | 0.9542 (2) | 0.80233 (9) | 0.1784 (2) | 0.0349 (4) | |
N6 | 0.93982 (19) | 0.90596 (8) | 0.08323 (19) | 0.0253 (3) | |
N7 | 0.3509 (2) | 0.54893 (10) | 0.6299 (2) | 0.0425 (5) | |
C1 | 0.3965 (2) | 0.65065 (10) | 0.0737 (2) | 0.0282 (4) | |
C2 | 0.5418 (3) | 0.63661 (11) | 0.1894 (3) | 0.0343 (5) | |
H2A | 0.5699 | 0.5923 | 0.2188 | 0.041* | |
C3 | 0.6470 (3) | 0.68667 (11) | 0.2632 (3) | 0.0339 (5) | |
H3A | 0.7471 | 0.6762 | 0.3419 | 0.041* | |
C4 | 0.6084 (3) | 0.75136 (10) | 0.2239 (2) | 0.0289 (4) | |
C5 | 0.4628 (3) | 0.76574 (11) | 0.1061 (3) | 0.0376 (5) | |
H5A | 0.4353 | 0.8101 | 0.0766 | 0.045* | |
C6 | 0.3576 (3) | 0.71570 (11) | 0.0315 (3) | 0.0364 (5) | |
H6A | 0.2585 | 0.7260 | −0.0488 | 0.044* | |
C7 | 0.2823 (3) | 0.59545 (11) | −0.0029 (3) | 0.0333 (5) | |
H7A | 0.2214 | 0.6082 | −0.1151 | 0.040* | |
H7B | 0.3494 | 0.5560 | −0.0112 | 0.040* | |
C8 | 0.7201 (3) | 0.80549 (11) | 0.3108 (3) | 0.0370 (5) | |
H8A | 0.6508 | 0.8403 | 0.3425 | 0.044* | |
H8B | 0.7939 | 0.7877 | 0.4125 | 0.044* | |
C9 | −0.0655 (3) | 0.56403 (12) | 0.1496 (3) | 0.0371 (5) | |
H9A | −0.1817 | 0.5618 | 0.1406 | 0.044* | |
C10 | 0.1907 (3) | 0.55662 (11) | 0.2456 (2) | 0.0312 (5) | |
H10A | 0.2979 | 0.5489 | 0.3153 | 0.037* | |
C11 | 1.0198 (3) | 0.84752 (10) | 0.1016 (3) | 0.0317 (5) | |
H11A | 1.1157 | 0.8397 | 0.0621 | 0.038* | |
C12 | 0.8157 (2) | 0.89541 (10) | 0.1543 (2) | 0.0269 (4) | |
H12A | 0.7344 | 0.9270 | 0.1635 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01814 (19) | 0.02220 (19) | 0.0236 (2) | −0.00012 (13) | 0.00787 (14) | 0.00201 (14) |
O1 | 0.0210 (7) | 0.0348 (8) | 0.0459 (9) | −0.0049 (6) | 0.0020 (6) | 0.0075 (7) |
O2 | 0.0229 (8) | 0.0624 (11) | 0.0527 (10) | −0.0088 (7) | 0.0087 (7) | −0.0060 (9) |
N1 | 0.0262 (9) | 0.0307 (9) | 0.0257 (8) | −0.0063 (7) | 0.0079 (7) | 0.0017 (7) |
N2 | 0.0296 (10) | 0.0549 (13) | 0.0378 (10) | −0.0010 (9) | 0.0058 (8) | 0.0142 (9) |
N3 | 0.0251 (8) | 0.0266 (8) | 0.0273 (8) | 0.0002 (6) | 0.0101 (6) | 0.0036 (7) |
N4 | 0.0262 (8) | 0.0276 (8) | 0.0291 (9) | −0.0053 (7) | 0.0083 (7) | −0.0024 (7) |
N5 | 0.0296 (9) | 0.0304 (9) | 0.0455 (11) | 0.0004 (7) | 0.0108 (8) | 0.0020 (8) |
N6 | 0.0221 (8) | 0.0260 (8) | 0.0289 (8) | −0.0026 (6) | 0.0084 (6) | −0.0019 (7) |
N7 | 0.0331 (10) | 0.0523 (12) | 0.0406 (11) | −0.0124 (9) | 0.0061 (8) | 0.0041 (9) |
C1 | 0.0274 (10) | 0.0323 (11) | 0.0283 (10) | −0.0054 (8) | 0.0135 (8) | 0.0017 (8) |
C2 | 0.0330 (11) | 0.0293 (11) | 0.0412 (12) | −0.0004 (9) | 0.0101 (9) | 0.0087 (9) |
C3 | 0.0288 (11) | 0.0365 (11) | 0.0342 (11) | −0.0014 (9) | 0.0034 (9) | 0.0089 (9) |
C4 | 0.0293 (10) | 0.0314 (10) | 0.0284 (10) | −0.0053 (8) | 0.0118 (8) | 0.0013 (8) |
C5 | 0.0344 (12) | 0.0282 (11) | 0.0499 (14) | −0.0001 (9) | 0.0098 (10) | 0.0077 (10) |
C6 | 0.0284 (11) | 0.0389 (12) | 0.0394 (12) | 0.0001 (9) | 0.0035 (9) | 0.0091 (10) |
C7 | 0.0368 (12) | 0.0396 (12) | 0.0281 (10) | −0.0116 (9) | 0.0167 (9) | −0.0018 (9) |
C8 | 0.0424 (13) | 0.0397 (12) | 0.0323 (11) | −0.0137 (10) | 0.0154 (10) | −0.0017 (10) |
C9 | 0.0244 (11) | 0.0480 (13) | 0.0404 (12) | 0.0020 (9) | 0.0110 (9) | 0.0111 (10) |
C10 | 0.0249 (10) | 0.0411 (12) | 0.0280 (10) | −0.0036 (8) | 0.0069 (8) | 0.0064 (9) |
C11 | 0.0244 (10) | 0.0303 (10) | 0.0414 (12) | −0.0003 (8) | 0.0099 (9) | −0.0019 (9) |
C12 | 0.0242 (10) | 0.0267 (10) | 0.0309 (10) | −0.0022 (8) | 0.0088 (8) | −0.0022 (8) |
Co1—O1i | 2.1031 (15) | C1—C2 | 1.380 (3) |
Co1—O1 | 2.1031 (15) | C1—C6 | 1.389 (3) |
Co1—N6ii | 2.1418 (16) | C1—C7 | 1.509 (3) |
Co1—N6iii | 2.1418 (16) | C2—C3 | 1.385 (3) |
Co1—N3 | 2.1530 (16) | C2—H2A | 0.9500 |
Co1—N3i | 2.1530 (16) | C3—C4 | 1.377 (3) |
O1—N7 | 1.245 (2) | C3—H3A | 0.9500 |
O2—N7 | 1.240 (2) | C4—C5 | 1.391 (3) |
N1—C10 | 1.325 (3) | C4—C8 | 1.509 (3) |
N1—N2 | 1.353 (2) | C5—C6 | 1.387 (3) |
N1—C7 | 1.475 (2) | C5—H5A | 0.9500 |
N2—C9 | 1.319 (3) | C6—H6A | 0.9500 |
N3—C10 | 1.328 (2) | C7—H7A | 0.9900 |
N3—C9 | 1.348 (3) | C7—H7B | 0.9900 |
N4—C12 | 1.324 (3) | C8—H8A | 0.9900 |
N4—N5 | 1.360 (2) | C8—H8B | 0.9900 |
N4—C8 | 1.465 (3) | C9—H9A | 0.9500 |
N5—C11 | 1.319 (3) | C10—H10A | 0.9500 |
N6—C12 | 1.331 (2) | C11—H11A | 0.9500 |
N6—C11 | 1.353 (3) | C12—H12A | 0.9500 |
N6—Co1iv | 2.1418 (16) | ||
O1i—Co1—O1 | 180.0 | C4—C3—C2 | 120.9 (2) |
O1i—Co1—N6ii | 94.01 (6) | C4—C3—H3A | 119.6 |
O1—Co1—N6ii | 85.99 (6) | C2—C3—H3A | 119.6 |
O1i—Co1—N6iii | 85.99 (6) | C3—C4—C5 | 118.83 (19) |
O1—Co1—N6iii | 94.01 (6) | C3—C4—C8 | 120.3 (2) |
N6ii—Co1—N6iii | 180.00 (8) | C5—C4—C8 | 120.85 (19) |
O1i—Co1—N3 | 86.30 (6) | C6—C5—C4 | 120.4 (2) |
O1—Co1—N3 | 93.70 (6) | C6—C5—H5A | 119.8 |
N6ii—Co1—N3 | 90.52 (6) | C4—C5—H5A | 119.8 |
N6iii—Co1—N3 | 89.48 (6) | C5—C6—C1 | 120.3 (2) |
O1i—Co1—N3i | 93.70 (6) | C5—C6—H6A | 119.8 |
O1—Co1—N3i | 86.30 (6) | C1—C6—H6A | 119.8 |
N6ii—Co1—N3i | 89.48 (6) | N1—C7—C1 | 111.64 (17) |
N6iii—Co1—N3i | 90.52 (6) | N1—C7—H7A | 109.3 |
N3—Co1—N3i | 180.00 (8) | C1—C7—H7A | 109.3 |
N7—O1—Co1 | 126.67 (14) | N1—C7—H7B | 109.3 |
C10—N1—N2 | 109.92 (16) | C1—C7—H7B | 109.3 |
C10—N1—C7 | 128.82 (18) | H7A—C7—H7B | 108.0 |
N2—N1—C7 | 121.23 (17) | N4—C8—C4 | 112.87 (17) |
C9—N2—N1 | 102.28 (17) | N4—C8—H8A | 109.0 |
C10—N3—C9 | 102.35 (17) | C4—C8—H8A | 109.0 |
C10—N3—Co1 | 130.55 (14) | N4—C8—H8B | 109.0 |
C9—N3—Co1 | 126.63 (14) | C4—C8—H8B | 109.0 |
C12—N4—N5 | 110.21 (16) | H8A—C8—H8B | 107.8 |
C12—N4—C8 | 127.34 (18) | N2—C9—N3 | 115.02 (19) |
N5—N4—C8 | 122.01 (17) | N2—C9—H9A | 122.5 |
C11—N5—N4 | 102.19 (17) | N3—C9—H9A | 122.5 |
C12—N6—C11 | 102.66 (16) | N3—C10—N1 | 110.43 (18) |
C12—N6—Co1iv | 124.14 (13) | N3—C10—H10A | 124.8 |
C11—N6—Co1iv | 132.60 (13) | N1—C10—H10A | 124.8 |
O2—N7—O1 | 115.52 (19) | N5—C11—N6 | 114.82 (18) |
C2—C1—C6 | 119.04 (19) | N5—C11—H11A | 122.6 |
C2—C1—C7 | 119.60 (19) | N6—C11—H11A | 122.6 |
C6—C1—C7 | 121.36 (19) | N4—C12—N6 | 110.11 (17) |
C1—C2—C3 | 120.5 (2) | N4—C12—H12A | 124.9 |
C1—C2—H2A | 119.7 | N6—C12—H12A | 124.9 |
C3—C2—H2A | 119.7 | ||
N6ii—Co1—O1—N7 | 126.75 (19) | C2—C1—C6—C5 | −0.6 (3) |
N6iii—Co1—O1—N7 | −53.25 (19) | C7—C1—C6—C5 | 178.6 (2) |
N3—Co1—O1—N7 | 36.48 (19) | C10—N1—C7—C1 | −63.3 (3) |
N3i—Co1—O1—N7 | −143.52 (19) | N2—N1—C7—C1 | 119.1 (2) |
C10—N1—N2—C9 | −0.5 (2) | C2—C1—C7—N1 | 88.2 (2) |
C7—N1—N2—C9 | 177.54 (19) | C6—C1—C7—N1 | −91.0 (2) |
O1i—Co1—N3—C10 | −165.51 (19) | C12—N4—C8—C4 | 115.1 (2) |
O1—Co1—N3—C10 | 14.49 (19) | N5—N4—C8—C4 | −73.2 (3) |
N6ii—Co1—N3—C10 | −71.53 (19) | C3—C4—C8—N4 | 104.3 (2) |
N6iii—Co1—N3—C10 | 108.47 (19) | C5—C4—C8—N4 | −77.4 (3) |
O1i—Co1—N3—C9 | 5.24 (18) | N1—N2—C9—N3 | 0.5 (3) |
O1—Co1—N3—C9 | −174.76 (18) | C10—N3—C9—N2 | −0.3 (3) |
N6ii—Co1—N3—C9 | 99.22 (18) | Co1—N3—C9—N2 | −173.14 (16) |
N6iii—Co1—N3—C9 | −80.78 (18) | C9—N3—C10—N1 | 0.0 (2) |
C12—N4—N5—C11 | −0.5 (2) | Co1—N3—C10—N1 | 172.41 (13) |
C8—N4—N5—C11 | −173.46 (18) | N2—N1—C10—N3 | 0.3 (3) |
Co1—O1—N7—O2 | 175.00 (14) | C7—N1—C10—N3 | −177.51 (18) |
C6—C1—C2—C3 | 0.3 (3) | N4—N5—C11—N6 | 0.4 (2) |
C7—C1—C2—C3 | −178.94 (19) | C12—N6—C11—N5 | −0.1 (2) |
C1—C2—C3—C4 | 0.6 (3) | Co1iv—N6—C11—N5 | 170.93 (14) |
C2—C3—C4—C5 | −1.2 (3) | N5—N4—C12—N6 | 0.5 (2) |
C2—C3—C4—C8 | 177.2 (2) | C8—N4—C12—N6 | 172.95 (18) |
C3—C4—C5—C6 | 0.9 (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—C1 | 0.0 (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. |
Experimental details
Crystal data | |
Chemical formula | [Co(NO2)2(C12H12N6)2] |
Mr | 631.50 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 8.3037 (13), 20.376 (3), 8.4261 (11) |
β (°) | 104.390 (4) |
V (Å3) | 1380.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.68 |
Crystal size (mm) | 0.33 × 0.26 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD diffractometer |
Absorption correction | Multi-scan (REQAB; Jacobson, 1998) |
Tmin, Tmax | 0.806, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15379, 3152, 2768 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.098, 1.07 |
No. of reflections | 3152 |
No. of parameters | 197 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.29 |
Computer programs: CrystalClear (Rigaku, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Co1—O1 | 2.1031 (15) | Co1—N3 | 2.1530 (16) |
Co1—N6i | 2.1418 (16) | ||
O1ii—Co1—O1 | 180.0 | O1—Co1—N3 | 93.70 (6) |
O1—Co1—N6i | 85.99 (6) | N6i—Co1—N3 | 90.52 (6) |
N6i—Co1—N6iii | 180.00 (8) | N3—Co1—N3ii | 180.00 (8) |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x, −y+1, −z+1; (iii) x−1, −y+3/2, z+1/2. |
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).