Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044066/ng2325sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044066/ng2325Isup2.hkl |
CCDC reference: 663605
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.035
- wR factor = 0.076
- Data-to-parameter ratio = 12.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for N6 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.11 Ratio
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C24 H16 Mn2 N16 Atom count from _chemical_formula_moiety:C2400 H1600 Mn400 N1000 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.99 From the CIF: _reflns_number_total 2337 Count of symmetry unique reflns 1521 Completeness (_total/calc) 153.65% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 816 Fraction of Friedel pairs measured 0.536 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.04 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 7 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 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of manganese sulfate monohydrate (0.169 g, 1 mmol), sodium azide (0.065 g, 1 mmol) 3,5-bis(pyridin-2-yl)-1,2,4-triazole (0.223 g, 1 mmol) and methanol (10 ml) was heated in a Teflon-lined stainless steel autoclave (25 ml) for 120 h at 393 K, after which the autoclave was cooled to room temperature over a period of 8 h at a rate of 10 K h-1. Pale yellow block single crystals of (I) were collected in about 15% yield. Elemental analysis, calcd (%) for C12H8MnN8: C, 45.16; H, 2.53; N, 35.11; found (%): C, 45.19; H, 2.50; N, 35.07.
All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93 Å and Uiso(H) = 1.2 Ueq(C).
1,2,4-triazole derivatives are a class of azole compounds that can act as either 2,4- or 1,2-bridging nitrogen donor ligands. 3,5-bis(pyridin-2-yl)-1,2,4-triazole can act as tetradentate ligands and are therefore very suitable for studying exchange-coupled pairs of transition-metal ions. (Prins et al., 1995; Chen et al., 2006). However, only small part of mononuclear and dinuclear complexes were characterized by X-ray crystallography. On the other hand, azide was widely used to connect metal ions, and the correlation between the structure and magnetic properties of different coordination modes was observed (Wang et al., 2006). In this paper, solvothermal technique has been successfully applied in the Mn2+/bpt-/N3- system to synthesize the title compound.
There are one MnII atom, one bpt- ligand and one azide ligand in the asymmetric unit. The MnII atom has an octahedral environment, formed by four N atoms from two different bpt- ligand and two N atoms belonging to two azide ligands. The bpt- ligand binds to manganese in a cis-bis(chelate) mode, through two pyridine and two triazole nitrogen atoms, linking the MnII atoms into a helical chain that runs along the b axis. Each pair of MnII ions from adjacent chains are additionally bridged by two azide lingds in the EE mode and further linked the [Mn(bpt)]+ chains into a two-dimensional (4,4) net.
For related literature, see: Prins et al. (1995); Chen et al. (2006); Wang et al. (2006).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Mn2(N3)2(C12H8N5)2] | F(000) = 322 |
Mr = 638.38 | Dx = 1.660 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6965 (9) Å | Cell parameters from 2337 reflections |
b = 6.5597 (7) Å | θ = 1.8–27.0° |
c = 11.8601 (13) Å | µ = 1.04 mm−1 |
β = 109.245 (2)° | T = 293 K |
V = 638.77 (12) Å3 | Block, pale yellow |
Z = 1 | 0.31 × 0.26 × 0.22 mm |
Bruker APEX area-detector diffractometer | 2337 independent reflections |
Radiation source: fine-focus sealed tube | 2207 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 27.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→11 |
Tmin = 0.732, Tmax = 0.796 | k = −6→8 |
3598 measured reflections | l = −15→11 |
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)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.076 | w = 1/[σ2(Fo2) + (0.0334P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2337 reflections | Δρmax = 0.40 e Å−3 |
190 parameters | Δρmin = −0.23 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 825 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (2) |
[Mn2(N3)2(C12H8N5)2] | V = 638.77 (12) Å3 |
Mr = 638.38 | Z = 1 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.6965 (9) Å | µ = 1.04 mm−1 |
b = 6.5597 (7) Å | T = 293 K |
c = 11.8601 (13) Å | 0.31 × 0.26 × 0.22 mm |
β = 109.245 (2)° |
Bruker APEX area-detector diffractometer | 2337 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2207 reflections with I > 2σ(I) |
Tmin = 0.732, Tmax = 0.796 | Rint = 0.019 |
3598 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.076 | Δρmax = 0.40 e Å−3 |
S = 1.05 | Δρmin = −0.23 e Å−3 |
2337 reflections | Absolute structure: Flack (1983), with 825 Friedel pairs |
190 parameters | Absolute structure parameter: 0.02 (2) |
1 restraint |
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 | ||
Mn1 | 0.20518 (4) | 0.28461 (8) | 0.01852 (3) | 0.02671 (12) | |
C1 | 0.2386 (4) | −0.0499 (5) | −0.1771 (3) | 0.0378 (8) | |
H1A | 0.2845 | −0.1357 | −0.1123 | 0.045* | |
C2 | 0.2498 (4) | −0.1043 (6) | −0.2863 (3) | 0.0432 (9) | |
H2A | 0.3023 | −0.2240 | −0.2948 | 0.052* | |
C3 | 0.1817 (4) | 0.0222 (6) | −0.3828 (3) | 0.0433 (9) | |
H3A | 0.1896 | −0.0090 | −0.4572 | 0.052* | |
C4 | 0.1025 (4) | 0.1938 (6) | −0.3673 (3) | 0.0398 (8) | |
H4A | 0.0545 | 0.2800 | −0.4316 | 0.048* | |
C5 | 0.0938 (3) | 0.2397 (5) | −0.2553 (3) | 0.0301 (8) | |
C6 | 0.0090 (3) | 0.4189 (5) | −0.2304 (2) | 0.0279 (6) | |
C7 | −0.1260 (4) | 0.6830 (5) | −0.2408 (3) | 0.0271 (6) | |
C8 | −0.2227 (4) | 0.8677 (5) | −0.2788 (3) | 0.0298 (7) | |
C9 | −0.2739 (4) | 0.9397 (6) | −0.3957 (3) | 0.0412 (8) | |
H9A | −0.2508 | 0.8674 | −0.4556 | 0.049* | |
C10 | −0.3587 (5) | 1.1186 (6) | −0.4209 (3) | 0.0492 (10) | |
H10A | −0.3943 | 1.1689 | −0.4985 | 0.059* | |
C11 | −0.3914 (4) | 1.2242 (6) | −0.3312 (3) | 0.0475 (9) | |
H11A | −0.4469 | 1.3477 | −0.3463 | 0.057* | |
C12 | −0.3394 (4) | 1.1413 (6) | −0.2185 (3) | 0.0418 (8) | |
H12A | −0.3627 | 1.2112 | −0.1579 | 0.050* | |
N1 | 0.0114 (3) | 0.4542 (4) | −0.1192 (2) | 0.0277 (6) | |
N2 | −0.0767 (3) | 0.6266 (4) | −0.1258 (2) | 0.0272 (6) | |
N3 | −0.0742 (3) | 0.5565 (4) | −0.3107 (2) | 0.0311 (6) | |
N4 | 0.1652 (3) | 0.1196 (4) | −0.1599 (2) | 0.0305 (6) | |
N5 | −0.2582 (3) | 0.9683 (4) | −0.1913 (2) | 0.0315 (6) | |
N6 | 0.3757 (3) | 0.4973 (5) | −0.0301 (3) | 0.0504 (8) | |
N7 | 0.4788 (3) | 0.5367 (4) | −0.0680 (2) | 0.0302 (6) | |
N8 | 0.5818 (3) | 0.5817 (5) | −0.1066 (3) | 0.0400 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0275 (2) | 0.0289 (2) | 0.0258 (2) | 0.0011 (2) | 0.01163 (15) | 0.0022 (2) |
C1 | 0.0392 (18) | 0.0314 (19) | 0.0395 (18) | 0.0030 (16) | 0.0084 (15) | 0.0001 (15) |
C2 | 0.0461 (19) | 0.035 (2) | 0.048 (2) | 0.0058 (17) | 0.0147 (16) | −0.0104 (17) |
C3 | 0.053 (2) | 0.048 (2) | 0.0321 (18) | 0.0030 (18) | 0.0171 (16) | −0.0110 (16) |
C4 | 0.0419 (18) | 0.046 (2) | 0.0304 (17) | 0.0092 (16) | 0.0112 (15) | 0.0016 (15) |
C5 | 0.0306 (14) | 0.032 (2) | 0.0277 (14) | 0.0035 (13) | 0.0100 (12) | −0.0002 (12) |
C6 | 0.0285 (15) | 0.0312 (18) | 0.0261 (15) | 0.0018 (13) | 0.0119 (12) | −0.0001 (13) |
C7 | 0.0259 (14) | 0.0311 (17) | 0.0256 (15) | 0.0003 (13) | 0.0104 (12) | −0.0005 (12) |
C8 | 0.0281 (15) | 0.0306 (16) | 0.0317 (16) | −0.0023 (13) | 0.0113 (13) | 0.0007 (13) |
C9 | 0.049 (2) | 0.042 (2) | 0.0333 (17) | 0.0043 (18) | 0.0149 (15) | 0.0046 (16) |
C10 | 0.055 (2) | 0.049 (2) | 0.040 (2) | 0.008 (2) | 0.0101 (18) | 0.0164 (17) |
C11 | 0.050 (2) | 0.033 (2) | 0.057 (2) | 0.0087 (16) | 0.0147 (18) | 0.0102 (16) |
C12 | 0.0446 (19) | 0.034 (2) | 0.048 (2) | 0.0056 (16) | 0.0171 (17) | −0.0014 (16) |
N1 | 0.0283 (13) | 0.0302 (15) | 0.0286 (13) | 0.0021 (11) | 0.0148 (10) | 0.0009 (11) |
N2 | 0.0248 (12) | 0.0300 (15) | 0.0282 (13) | 0.0021 (11) | 0.0106 (10) | 0.0027 (11) |
N3 | 0.0363 (14) | 0.0314 (15) | 0.0275 (13) | 0.0038 (12) | 0.0133 (11) | 0.0021 (11) |
N4 | 0.0329 (13) | 0.0275 (15) | 0.0305 (14) | 0.0015 (12) | 0.0098 (11) | 0.0016 (11) |
N5 | 0.0350 (14) | 0.0289 (15) | 0.0326 (14) | 0.0023 (12) | 0.0140 (12) | 0.0003 (12) |
N6 | 0.0377 (16) | 0.050 (2) | 0.068 (2) | −0.0082 (15) | 0.0233 (15) | 0.0086 (17) |
N7 | 0.0313 (13) | 0.0225 (13) | 0.0353 (14) | 0.0001 (11) | 0.0089 (12) | 0.0024 (11) |
N8 | 0.0380 (15) | 0.0431 (19) | 0.0441 (17) | −0.0086 (13) | 0.0207 (13) | −0.0045 (14) |
Mn1—N2i | 2.208 (2) | C7—N2 | 1.340 (4) |
Mn1—N1 | 2.221 (2) | C7—N3 | 1.351 (4) |
Mn1—N8ii | 2.240 (3) | C7—C8 | 1.459 (4) |
Mn1—N6 | 2.245 (3) | C8—N5 | 1.348 (4) |
Mn1—N5i | 2.289 (3) | C8—C9 | 1.392 (4) |
Mn1—N4 | 2.299 (3) | C9—C10 | 1.365 (5) |
C1—N4 | 1.331 (4) | C9—H9A | 0.9300 |
C1—C2 | 1.377 (5) | C10—C11 | 1.375 (5) |
C1—H1A | 0.9300 | C10—H10A | 0.9300 |
C2—C3 | 1.380 (5) | C11—C12 | 1.374 (5) |
C2—H2A | 0.9300 | C11—H11A | 0.9300 |
C3—C4 | 1.363 (5) | C12—N5 | 1.319 (4) |
C3—H3A | 0.9300 | C12—H12A | 0.9300 |
C4—C5 | 1.389 (4) | N1—N2 | 1.354 (3) |
C4—H4A | 0.9300 | N2—Mn1iii | 2.208 (2) |
C5—N4 | 1.351 (4) | N5—Mn1iii | 2.289 (3) |
C5—C6 | 1.468 (4) | N6—N7 | 1.157 (4) |
C6—N1 | 1.333 (4) | N7—N8 | 1.170 (4) |
C6—N3 | 1.339 (4) | N8—Mn1iv | 2.240 (3) |
N2i—Mn1—N1 | 104.67 (9) | N2—C7—C8 | 120.1 (3) |
N2i—Mn1—N8ii | 87.13 (10) | N3—C7—C8 | 126.5 (3) |
N1—Mn1—N8ii | 162.01 (9) | N5—C8—C9 | 121.5 (3) |
N2i—Mn1—N6 | 160.37 (11) | N5—C8—C7 | 115.1 (3) |
N1—Mn1—N6 | 84.57 (10) | C9—C8—C7 | 123.5 (3) |
N8ii—Mn1—N6 | 88.54 (11) | C10—C9—C8 | 118.8 (3) |
N2i—Mn1—N5i | 73.88 (9) | C10—C9—H9A | 120.6 |
N1—Mn1—N5i | 105.95 (9) | C8—C9—H9A | 120.6 |
N8ii—Mn1—N5i | 90.21 (10) | C9—C10—C11 | 119.9 (3) |
N6—Mn1—N5i | 87.01 (11) | C9—C10—H10A | 120.1 |
N2i—Mn1—N4 | 110.94 (9) | C11—C10—H10A | 120.1 |
N1—Mn1—N4 | 73.20 (9) | C12—C11—C10 | 117.9 (3) |
N8ii—Mn1—N4 | 90.03 (10) | C12—C11—H11A | 121.1 |
N6—Mn1—N4 | 88.19 (11) | C10—C11—H11A | 121.1 |
N5i—Mn1—N4 | 175.18 (10) | N5—C12—C11 | 123.8 (3) |
N4—C1—C2 | 123.2 (3) | N5—C12—H12A | 118.1 |
N4—C1—H1A | 118.4 | C11—C12—H12A | 118.1 |
C2—C1—H1A | 118.4 | C6—N1—N2 | 105.3 (2) |
C1—C2—C3 | 118.7 (3) | C6—N1—Mn1 | 113.65 (19) |
C1—C2—H2A | 120.7 | N2—N1—Mn1 | 137.63 (19) |
C3—C2—H2A | 120.7 | C7—N2—N1 | 105.9 (2) |
C4—C3—C2 | 118.9 (3) | C7—N2—Mn1iii | 113.8 (2) |
C4—C3—H3A | 120.6 | N1—N2—Mn1iii | 137.99 (19) |
C2—C3—H3A | 120.6 | C6—N3—C7 | 100.9 (2) |
C3—C4—C5 | 119.8 (3) | C1—N4—C5 | 118.0 (3) |
C3—C4—H4A | 120.1 | C1—N4—Mn1 | 126.9 (2) |
C5—C4—H4A | 120.1 | C5—N4—Mn1 | 112.7 (2) |
N4—C5—C4 | 121.4 (3) | C12—N5—C8 | 118.2 (3) |
N4—C5—C6 | 114.9 (3) | C12—N5—Mn1iii | 127.3 (2) |
C4—C5—C6 | 123.7 (3) | C8—N5—Mn1iii | 113.7 (2) |
N1—C6—N3 | 114.5 (3) | N7—N6—Mn1 | 154.2 (3) |
N1—C6—C5 | 119.6 (3) | N6—N7—N8 | 178.3 (4) |
N3—C6—C5 | 125.9 (2) | N7—N8—Mn1iv | 126.1 (2) |
N2—C7—N3 | 113.3 (3) |
Symmetry codes: (i) −x, y−1/2, −z; (ii) −x+1, y−1/2, −z; (iii) −x, y+1/2, −z; (iv) −x+1, y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn2(N3)2(C12H8N5)2] |
Mr | 638.38 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6965 (9), 6.5597 (7), 11.8601 (13) |
β (°) | 109.245 (2) |
V (Å3) | 638.77 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.04 |
Crystal size (mm) | 0.31 × 0.26 × 0.22 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.732, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3598, 2337, 2207 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.076, 1.05 |
No. of reflections | 2337 |
No. of parameters | 190 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.23 |
Absolute structure | Flack (1983), with 825 Friedel pairs |
Absolute structure parameter | 0.02 (2) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
1,2,4-triazole derivatives are a class of azole compounds that can act as either 2,4- or 1,2-bridging nitrogen donor ligands. 3,5-bis(pyridin-2-yl)-1,2,4-triazole can act as tetradentate ligands and are therefore very suitable for studying exchange-coupled pairs of transition-metal ions. (Prins et al., 1995; Chen et al., 2006). However, only small part of mononuclear and dinuclear complexes were characterized by X-ray crystallography. On the other hand, azide was widely used to connect metal ions, and the correlation between the structure and magnetic properties of different coordination modes was observed (Wang et al., 2006). In this paper, solvothermal technique has been successfully applied in the Mn2+/bpt-/N3- system to synthesize the title compound.
There are one MnII atom, one bpt- ligand and one azide ligand in the asymmetric unit. The MnII atom has an octahedral environment, formed by four N atoms from two different bpt- ligand and two N atoms belonging to two azide ligands. The bpt- ligand binds to manganese in a cis-bis(chelate) mode, through two pyridine and two triazole nitrogen atoms, linking the MnII atoms into a helical chain that runs along the b axis. Each pair of MnII ions from adjacent chains are additionally bridged by two azide lingds in the EE mode and further linked the [Mn(bpt)]+ chains into a two-dimensional (4,4) net.