Poly[bis­(μ₂-azido-κ²N¹:N³)(μ₂-3,5-di-2-pyridyl-1,2,4-triazole-κ⁴N¹,N⁵:N²,N³)mangan­ese(II)]

In the crystal structure of the polymeric title compound, [Mn₂(N₃)₂(C₁₂H₈N₅)₂]_n, the Mn^II atom exists in an octa­hedral geometry owing to coordination by four N atoms from two 3,5-bis­(pyridin-2-yl)-1,2,4-triazolate ligands and by two azide ligands. The heterocyclic ligand binds in a chelating mode. The bidentate bridging mode of both anions leads to a linear ribbon motif.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

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S1. Comment

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 Mn^II atom, one bpt^- ligand and one azide ligand in the asymmetric unit. The Mn^II 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 Mn^II atoms into a helical chain that runs along the b axis. Each pair of Mn^II 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.

Related literature

For related literature, see: Prins et al. (1995); Chen et al. (2006); Wang et al. (2006).

S2. Experimental

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.

S3. Refinement

All other H atoms were positioned geometrically and refined as riding, with C–H distances of 0.93 Å and U_iso(H) = 1.2 U_eq(C).

Computing details

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).

Figures

	Fig. 1. The asymmetric unit of (I), showing displacement ellipsoids drawn at the 30% probability level for non-H atoms. Hydrogen atoms have been omitted. Symmetry codes: (i) -x, y - 1/2, -z; (ii) 1 - x, y-1/2,-z.
	Fig. 2. 3-D Packing diagram of title complex; Hydrogen atoms have been omitted.

Poly[bis(µ₂-azido-κ²N¹:N³)(µ₂-3,5-di-2-pyridyl- 1,2,4-triazole-κ⁴N¹,N⁵:N²,N³)manganese(II)]

Crystal data

[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) Å^3	Block, pale yellow
Z = 1	0.31 × 0.26 × 0.22 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0334P)^2] where P = (Fo^2 + 2Fc^2)/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)

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
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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Mn1—N2^i	2.208 (2)	C7—N2	1.340 (4)
Mn1—N1	2.221 (2)	C7—N3	1.351 (4)
Mn1—N8^ii	2.240 (3)	C7—C8	1.459 (4)
Mn1—N6	2.245 (3)	C8—N5	1.348 (4)
Mn1—N5^i	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—Mn1^iii	2.208 (2)
C5—N4	1.351 (4)	N5—Mn1^iii	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—Mn1^iv	2.240 (3)
N2^i—Mn1—N1	104.67 (9)	N2—C7—C8	120.1 (3)
N2^i—Mn1—N8^ii	87.13 (10)	N3—C7—C8	126.5 (3)
N1—Mn1—N8^ii	162.01 (9)	N5—C8—C9	121.5 (3)
N2^i—Mn1—N6	160.37 (11)	N5—C8—C7	115.1 (3)
N1—Mn1—N6	84.57 (10)	C9—C8—C7	123.5 (3)
N8^ii—Mn1—N6	88.54 (11)	C10—C9—C8	118.8 (3)
N2^i—Mn1—N5^i	73.88 (9)	C10—C9—H9A	120.6
N1—Mn1—N5^i	105.95 (9)	C8—C9—H9A	120.6
N8^ii—Mn1—N5^i	90.21 (10)	C9—C10—C11	119.9 (3)
N6—Mn1—N5^i	87.01 (11)	C9—C10—H10A	120.1
N2^i—Mn1—N4	110.94 (9)	C11—C10—H10A	120.1
N1—Mn1—N4	73.20 (9)	C12—C11—C10	117.9 (3)
N8^ii—Mn1—N4	90.03 (10)	C12—C11—H11A	121.1
N6—Mn1—N4	88.19 (11)	C10—C11—H11A	121.1
N5^i—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—Mn1^iii	113.8 (2)
C4—C3—H3A	120.6	N1—N2—Mn1^iii	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—Mn1^iii	127.3 (2)
C4—C5—C6	123.7 (3)	C8—N5—Mn1^iii	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—Mn1^iv	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.