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Two new one-dimensional coordination polymers, viz. the title compounds, [Co{C(CN)3}2(C6H5N3)2]n, (I), and [Mn{C(CN)3}2(C5H8N2)2]n, (II), have been synthesized and characterized by X-ray diffraction. Both complexes consist of linear chains with double 1,5-tricyanomethanide bridges between neighbouring divalent metal ions. The Co and Mn atoms are located on centres of inversion. In (I), the coordination environment of the CoII atom is that of an elongated octahedron. The CoII atom is coordinated in the equatorial plane by four nitrile N atoms of four bridging tricyanomethanide ions, with Co-N distances of 2.106 (2) and 2.110 (2) Å, and in the apical positions by two N atoms from the benzotriazole ligands, with a Co-N distance of 2.149 (2) Å. The [Co{C(CN)3}2(C6H5N3)2] units form infinite chains extending along the a axis. These chains are crosslinked via a hydrogen bond between the uncoordinated nitrile N atom of a tricyanomethanide anion and the H atom on the uncoordinated N atom of a benzotriazole ligand from an adjacent chain, thus forming a three-dimensional network structure. In (II), the MnII atom also adopts a slightly distorted octahedral geometry, with four nitrile N atoms of tricyanomethanide ligands [Mn-N = 2.226 (2) and 2.227 (2) Å] in equatorial positions and two N atoms of the monodentate 3,5-dimethylpyrazole ligands [Mn-N = 2.231 (2) Å] in the axial sites. In (II), one-dimensional polymeric chains extending along the b axis are formed, with tricyanomethanide anions acting as bidentate bridging ligands. A hydrogen bond between the uncoordinated nitrile N atom of the tricyanomethanide ligand and the H atom on the uncoordinated N atom of a 3,5-dimethylpyrazole group from a neighbouring chain links the molecule into a two-dimensional layered structure.
Supporting information
CCDC references: 243572; 243573
An aqueous solution (2 ml) of potassium tricyanomethanide (0.60 mmol, 77.4 mg) and an ethanol solution (4 ml) of benzotriazole (0.60 mmol, 71.4 mg) were mixed and stirred for 5 min; the resulting solution was colorless. To the mixture was added slowly an aqueous solution (2 ml) of cobalt nitrate (0.30 mmol, 87.3 mg). After stirred for another 5 min, the solution was filtered and the filtrate was evaporated slowly in air. After two weeks, pink block-shaped crystals of (I) were isolated in 35% yield. Complex (II) was prepared in a similar manner (40% yield).
All H atoms were treated using a riding model [Uiso(H) = 1.2Ueq(C)]. In (I), H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 Å and N—H distances of 0.86 Å. In (II), the position of the H atoms were constrained to an ideal geometry, with C–H distances in the range 0.93–0.96 Å and N—H distances of 0.86 Å.
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.
(I)
catena-Poly[[bis(1
H-benzotriazole-
κN3)cobalt(II)]-di-µ-tricyanomethanido-
κ2N:
N']
top
Crystal data top
[Co(C4N3)2(C6H5N3)2] | Z = 1 |
Mr = 477.33 | F(000) = 241 |
Triclinic, P1 | Dx = 1.514 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.287 (2) Å | Cell parameters from 719 reflections |
b = 7.962 (3) Å | θ = 5.7–27.0° |
c = 9.583 (3) Å | µ = 0.86 mm−1 |
α = 75.643 (4)° | T = 298 K |
β = 76.678 (4)° | Block, pink |
γ = 89.697 (4)° | 0.20 × 0.15 × 0.10 mm |
V = 523.4 (3) Å3 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2008 independent reflections |
Radiation source: fine-focus sealed tube | 1943 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.847, Tmax = 0.919 | k = −8→9 |
2401 measured reflections | l = −6→11 |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0926P)2 + 0.2599P] where P = (Fo2 + 2Fc2)/3 |
2008 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
Crystal data top
[Co(C4N3)2(C6H5N3)2] | γ = 89.697 (4)° |
Mr = 477.33 | V = 523.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.287 (2) Å | Mo Kα radiation |
b = 7.962 (3) Å | µ = 0.86 mm−1 |
c = 9.583 (3) Å | T = 298 K |
α = 75.643 (4)° | 0.20 × 0.15 × 0.10 mm |
β = 76.678 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2008 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1943 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 0.919 | Rint = 0.023 |
2401 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.60 e Å−3 |
2008 reflections | Δρmin = −0.88 e Å−3 |
151 parameters | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Co1 | 1.0000 | 1.0000 | 1.0000 | 0.0249 (2) | |
N1 | 0.1850 (3) | 0.8070 (3) | 1.0628 (3) | 0.0365 (5) | |
N2 | 0.7818 (3) | 0.8103 (3) | 1.0348 (3) | 0.0338 (5) | |
N3 | 0.4156 (4) | 0.3219 (3) | 1.2747 (3) | 0.0494 (7) | |
N4 | 1.1032 (3) | 0.9850 (3) | 0.7747 (2) | 0.0326 (5) | |
N5 | 1.1752 (4) | 1.1255 (3) | 0.6724 (3) | 0.0406 (6) | |
N6 | 1.2408 (4) | 1.0807 (3) | 0.5467 (3) | 0.0438 (6) | |
C1 | 0.3099 (4) | 0.7285 (3) | 1.0910 (3) | 0.0282 (5) | |
C2 | 0.6419 (4) | 0.7293 (3) | 1.0766 (3) | 0.0282 (5) | |
C3 | 0.4417 (4) | 0.4634 (3) | 1.2075 (3) | 0.0316 (6) | |
C4 | 0.4651 (4) | 0.6383 (3) | 1.1257 (3) | 0.0280 (5) | |
C5 | 1.1224 (4) | 0.8458 (3) | 0.7123 (3) | 0.0308 (6) | |
C6 | 1.2128 (4) | 0.9075 (4) | 0.5638 (3) | 0.0374 (6) | |
C7 | 1.2561 (6) | 0.8002 (5) | 0.4669 (4) | 0.0527 (9) | |
C8 | 1.2058 (6) | 0.6287 (5) | 0.5274 (4) | 0.0566 (9) | |
C9 | 1.1145 (5) | 0.5629 (4) | 0.6782 (4) | 0.0481 (8) | |
C10 | 1.0719 (4) | 0.6682 (4) | 0.7726 (3) | 0.0372 (6) | |
H6 | 1.2945 | 1.1524 | 0.4642 | 0.053* | |
H7 | 1.3157 | 0.8432 | 0.3673 | 0.063* | |
H8 | 1.2324 | 0.5521 | 0.4671 | 0.068* | |
H9 | 1.0826 | 0.4446 | 0.7142 | 0.058* | |
H10 | 1.0123 | 0.6244 | 0.8721 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0224 (3) | 0.0212 (3) | 0.0279 (3) | −0.00011 (17) | −0.00236 (19) | −0.00382 (19) |
C2 | 0.0317 (14) | 0.0241 (12) | 0.0280 (12) | 0.0044 (10) | −0.0055 (10) | −0.0065 (10) |
C3 | 0.0264 (13) | 0.0334 (14) | 0.0297 (13) | 0.0007 (10) | −0.0021 (10) | −0.0025 (11) |
C4 | 0.0258 (12) | 0.0252 (12) | 0.0294 (13) | 0.0002 (9) | −0.0034 (10) | −0.0033 (10) |
C5 | 0.0329 (14) | 0.0286 (13) | 0.0291 (13) | 0.0014 (10) | −0.0036 (11) | −0.0075 (10) |
C6 | 0.0429 (16) | 0.0345 (14) | 0.0313 (14) | −0.0009 (12) | −0.0037 (12) | −0.0062 (11) |
C7 | 0.066 (2) | 0.055 (2) | 0.0336 (16) | −0.0002 (17) | 0.0019 (15) | −0.0174 (15) |
C8 | 0.071 (2) | 0.0499 (19) | 0.053 (2) | 0.0012 (17) | −0.0027 (18) | −0.0301 (16) |
C9 | 0.056 (2) | 0.0316 (15) | 0.055 (2) | −0.0007 (13) | −0.0061 (16) | −0.0159 (14) |
C10 | 0.0415 (16) | 0.0271 (13) | 0.0377 (15) | −0.0013 (11) | −0.0012 (12) | −0.0060 (11) |
N2 | 0.0273 (11) | 0.0292 (11) | 0.0413 (13) | −0.0025 (9) | −0.0052 (10) | −0.0050 (10) |
N3 | 0.0509 (16) | 0.0354 (14) | 0.0479 (16) | −0.0025 (11) | −0.0040 (13) | 0.0082 (12) |
N4 | 0.0401 (13) | 0.0239 (10) | 0.0296 (12) | 0.0005 (9) | −0.0024 (10) | −0.0047 (9) |
N5 | 0.0536 (15) | 0.0258 (11) | 0.0341 (13) | −0.0017 (10) | 0.0002 (11) | −0.0022 (10) |
N6 | 0.0608 (17) | 0.0328 (13) | 0.0268 (12) | −0.0047 (11) | 0.0032 (11) | −0.0001 (10) |
C1 | 0.0275 (13) | 0.0252 (12) | 0.0281 (12) | −0.0024 (10) | −0.0012 (10) | −0.0050 (10) |
N1 | 0.0320 (12) | 0.0302 (12) | 0.0414 (13) | 0.0018 (9) | −0.0049 (10) | −0.0017 (10) |
Geometric parameters (Å, º) top
Co1—N1i | 2.106 (2) | C6—C7 | 1.396 (4) |
Co1—N2 | 2.110 (2) | C7—C8 | 1.360 (5) |
Co1—N4 | 2.149 (2) | C7—H7 | 0.9300 |
C2—N2 | 1.143 (4) | C8—C9 | 1.411 (5) |
C2—C4 | 1.403 (4) | C8—H8 | 0.9300 |
C3—N3 | 1.143 (4) | C9—C10 | 1.365 (4) |
C3—C4 | 1.408 (4) | C9—H9 | 0.9300 |
C4—C1 | 1.397 (4) | C10—H10 | 0.9300 |
C5—N4 | 1.376 (3) | N4—N5 | 1.309 (3) |
C5—C6 | 1.387 (4) | N5—N6 | 1.324 (4) |
C5—C10 | 1.405 (4) | N6—H6 | 0.8600 |
C6—N6 | 1.358 (4) | C1—N1 | 1.147 (4) |
| | | |
N1i—Co1—N1ii | 180.00 (14) | C8—C7—C6 | 115.7 (3) |
N1i—Co1—N2iii | 88.84 (10) | C8—C7—H7 | 122.1 |
N1ii—Co1—N2iii | 91.16 (9) | C6—C7—H7 | 122.1 |
N1i—Co1—N2 | 91.16 (9) | C7—C8—C9 | 122.4 (3) |
N1i—Co1—N4iii | 91.63 (9) | C7—C8—H8 | 118.8 |
N1ii—Co1—N4iii | 88.37 (9) | C9—C8—H8 | 118.8 |
N2iii—Co1—N4iii | 91.16 (9) | C10—C9—C8 | 121.8 (3) |
N2—Co1—N4iii | 88.84 (9) | C10—C9—H9 | 119.1 |
N1i—Co1—N4 | 88.37 (9) | C8—C9—H9 | 119.1 |
N1ii—Co1—N4 | 91.63 (9) | C9—C10—C5 | 116.8 (3) |
N2—Co1—N4 | 91.16 (9) | C9—C10—H10 | 121.6 |
N4iii—Co1—N4 | 180.000 (1) | C5—C10—H10 | 121.6 |
N2—C2—C4 | 176.8 (3) | C2—N2—Co1 | 163.6 (2) |
N3—C3—C4 | 177.5 (3) | N5—N4—C5 | 108.8 (2) |
C1—C4—C2 | 117.3 (2) | N5—N4—Co1 | 119.40 (18) |
C1—C4—C3 | 120.5 (2) | C5—N4—Co1 | 131.58 (18) |
C2—C4—C3 | 122.2 (2) | N4—N5—N6 | 107.9 (2) |
N4—C5—C6 | 107.6 (2) | N5—N6—C6 | 111.7 (2) |
N4—C5—C10 | 131.9 (3) | N5—N6—H6 | 124.1 |
C6—C5—C10 | 120.5 (3) | C6—N6—H6 | 124.1 |
N6—C6—C5 | 103.9 (2) | N1—C1—C4 | 178.0 (3) |
N6—C6—C7 | 133.2 (3) | C1—N1—Co1iv | 166.9 (2) |
C5—C6—C7 | 122.9 (3) | | |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+2, −z+2; (iii) −x+2, −y+2, −z+2; (iv) x−1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3v | 0.86 | 1.99 | 2.849 (4) | 179 |
Symmetry code: (v) x+1, y+1, z−1. |
(II)
catena-poly[[bis(3,5-dimethyl-1
H-pyrazole-
κN2)manganese(II)-di-µ- tricyanomethanido-
κ2N:
N']
top
Crystal data top
[Mn(C4N3)2(C5H8N2)2] | F(000) = 876 |
Mr = 427.35 | Dx = 1.339 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 936 reflections |
a = 16.107 (9) Å | θ = 0.7–23.6° |
b = 7.547 (4) Å | µ = 0.65 mm−1 |
c = 17.437 (10) Å | T = 298 K |
V = 2120 (2) Å3 | Block, colourless |
Z = 4 | 0.25 × 0.15 × 0.10 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1853 independent reflections |
Radiation source: fine-focus sealed tube | 1226 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→19 |
Tmin = 0.855, Tmax = 0.938 | k = −8→8 |
4692 measured reflections | l = −20→12 |
Refinement top
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3 |
1853 reflections | (Δ/σ)max = 0.003 |
135 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
[Mn(C4N3)2(C5H8N2)2] | V = 2120 (2) Å3 |
Mr = 427.35 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 16.107 (9) Å | µ = 0.65 mm−1 |
b = 7.547 (4) Å | T = 298 K |
c = 17.437 (10) Å | 0.25 × 0.15 × 0.10 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1853 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1226 reflections with I > 2σ(I) |
Tmin = 0.855, Tmax = 0.938 | Rint = 0.029 |
4692 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.17 e Å−3 |
1853 reflections | Δρmin = −0.20 e Å−3 |
135 parameters | |
Special details top
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) top | x | y | z | Uiso*/Ueq | |
Mn1 | 1.0000 | 0.0000 | 0.5000 | 0.03964 (17) | |
N1 | 0.90209 (12) | 0.2061 (3) | 0.48651 (12) | 0.0548 (6) | |
N2 | 0.91420 (12) | 0.7795 (3) | 0.46990 (12) | 0.0553 (6) | |
N3 | 0.71276 (12) | 0.4929 (3) | 0.35013 (15) | 0.0668 (6) | |
N4 | 1.02980 (11) | 0.0326 (2) | 0.37587 (11) | 0.0471 (5) | |
N5 | 0.96772 (12) | 0.0324 (2) | 0.32351 (11) | 0.0477 (5) | |
C1 | 0.87257 (13) | 0.3349 (3) | 0.46441 (13) | 0.0404 (6) | |
C2 | 0.87933 (13) | 0.6515 (3) | 0.45566 (13) | 0.0410 (6) | |
C3 | 0.76882 (14) | 0.4932 (3) | 0.39012 (15) | 0.0455 (6) | |
C4 | 0.83836 (12) | 0.4941 (3) | 0.43843 (13) | 0.0391 (5) | |
C5 | 1.18246 (15) | 0.0637 (5) | 0.37143 (19) | 0.0915 (11) | |
C6 | 1.09825 (15) | 0.0568 (4) | 0.33526 (16) | 0.0602 (7) | |
C7 | 1.07907 (17) | 0.0729 (4) | 0.25863 (17) | 0.0757 (9) | |
C8 | 0.99481 (16) | 0.0556 (4) | 0.25272 (16) | 0.0586 (7) | |
C9 | 0.93761 (18) | 0.0582 (4) | 0.18576 (16) | 0.0837 (10) | |
H5 | 0.9162 | 0.0188 | 0.3351 | 0.057* | |
H5A | 1.1854 | 0.1633 | 0.4056 | 0.137* | |
H5B | 1.2239 | 0.0759 | 0.3322 | 0.137* | |
H5C | 1.1921 | −0.0435 | 0.3997 | 0.137* | |
H7 | 1.1162 | 0.0919 | 0.2186 | 0.091* | |
H9A | 0.9458 | −0.0470 | 0.1557 | 0.126* | |
H9B | 0.9489 | 0.1607 | 0.1549 | 0.126* | |
H9C | 0.8812 | 0.0624 | 0.2035 | 0.126* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0463 (3) | 0.0281 (3) | 0.0446 (3) | 0.0004 (2) | −0.0044 (2) | 0.0025 (2) |
C1 | 0.0381 (13) | 0.0379 (15) | 0.0450 (14) | −0.0037 (11) | −0.0029 (11) | −0.0064 (11) |
C2 | 0.0395 (13) | 0.0375 (14) | 0.0459 (15) | 0.0055 (11) | −0.0039 (11) | 0.0041 (11) |
C3 | 0.0388 (13) | 0.0391 (13) | 0.0587 (15) | −0.0022 (11) | 0.0021 (12) | 0.0049 (12) |
C4 | 0.0363 (11) | 0.0316 (12) | 0.0494 (13) | −0.0009 (11) | −0.0065 (10) | 0.0002 (12) |
C5 | 0.0429 (16) | 0.136 (3) | 0.096 (2) | −0.0024 (17) | 0.0040 (17) | 0.006 (2) |
C6 | 0.0418 (15) | 0.0723 (19) | 0.0665 (19) | 0.0001 (12) | 0.0101 (14) | 0.0007 (15) |
C7 | 0.0568 (18) | 0.114 (3) | 0.0565 (19) | −0.0065 (17) | 0.0209 (15) | 0.0046 (18) |
C8 | 0.0623 (17) | 0.0678 (18) | 0.0456 (16) | −0.0006 (13) | 0.0076 (14) | 0.0055 (13) |
C9 | 0.088 (2) | 0.110 (3) | 0.0532 (18) | −0.0109 (19) | −0.0085 (16) | 0.0110 (17) |
N1 | 0.0595 (13) | 0.0381 (12) | 0.0669 (15) | 0.0082 (10) | −0.0120 (11) | −0.0005 (10) |
N2 | 0.0635 (13) | 0.0349 (12) | 0.0674 (14) | −0.0058 (11) | −0.0162 (11) | 0.0040 (10) |
N3 | 0.0421 (12) | 0.0763 (17) | 0.0819 (16) | −0.0031 (11) | −0.0155 (12) | 0.0075 (13) |
N4 | 0.0391 (10) | 0.0533 (13) | 0.0491 (12) | 0.0010 (9) | 0.0028 (10) | 0.0040 (9) |
N5 | 0.0372 (10) | 0.0588 (14) | 0.0471 (13) | −0.0020 (9) | 0.0035 (10) | 0.0054 (10) |
Geometric parameters (Å, º) top
Mn1—N2i | 2.226 (2) | C5—H5C | 0.9600 |
Mn1—N1 | 2.227 (2) | C6—N4 | 1.323 (3) |
Mn1—N4 | 2.231 (2) | C6—C7 | 1.377 (4) |
C1—N1 | 1.149 (3) | C7—C8 | 1.367 (3) |
C1—C4 | 1.397 (3) | C7—H7 | 0.9300 |
C2—N2 | 1.145 (3) | C8—N5 | 1.321 (3) |
C2—C4 | 1.392 (3) | C8—C9 | 1.487 (4) |
C3—N3 | 1.141 (3) | C9—H9A | 0.9600 |
C3—C4 | 1.402 (3) | C9—H9B | 0.9600 |
C5—C6 | 1.497 (3) | C9—H9C | 0.9600 |
C5—H5A | 0.9600 | N4—N5 | 1.354 (3) |
C5—H5B | 0.9600 | N5—H5 | 0.8600 |
| | | |
N2i—Mn1—N1 | 86.70 (9) | C7—C6—C5 | 127.5 (2) |
N2ii—Mn1—N1 | 93.30 (9) | C8—C7—C6 | 106.7 (2) |
N2ii—Mn1—N1iii | 86.70 (9) | C8—C7—H7 | 126.6 |
N2i—Mn1—N4iii | 89.26 (7) | C6—C7—H7 | 126.6 |
N2ii—Mn1—N4iii | 90.74 (7) | N5—C8—C7 | 105.7 (2) |
N1—Mn1—N4iii | 91.55 (7) | N5—C8—C9 | 122.1 (2) |
N1iii—Mn1—N4iii | 88.45 (7) | C7—C8—C9 | 132.3 (3) |
N1—Mn1—N4 | 88.45 (7) | C8—C9—H9A | 109.5 |
N1—C1—C4 | 178.5 (2) | C8—C9—H9B | 109.5 |
N2—C2—C4 | 178.9 (2) | H9A—C9—H9B | 109.5 |
N3—C3—C4 | 179.2 (3) | C8—C9—H9C | 109.5 |
C2—C4—C1 | 118.48 (19) | H9A—C9—H9C | 109.5 |
C2—C4—C3 | 120.9 (2) | H9B—C9—H9C | 109.5 |
C1—C4—C3 | 120.4 (2) | C1—N1—Mn1 | 156.8 (2) |
C6—C5—H5A | 109.5 | C2—N2—Mn1iv | 170.64 (19) |
C6—C5—H5B | 109.5 | C6—N4—N5 | 104.7 (2) |
H5A—C5—H5B | 109.5 | C6—N4—Mn1 | 135.55 (17) |
C6—C5—H5C | 109.5 | N5—N4—Mn1 | 119.69 (14) |
H5A—C5—H5C | 109.5 | C8—N5—N4 | 112.7 (2) |
H5B—C5—H5C | 109.5 | C8—N5—H5 | 123.6 |
N4—C6—C7 | 110.2 (2) | N4—N5—H5 | 123.6 |
N4—C6—C5 | 122.3 (3) | | |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+2, −y, −z+1; (iv) x, y+1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N3v | 0.86 | 2.10 | 2.959 (3) | 173 |
Symmetry code: (v) −x+3/2, y−1/2, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Co(C4N3)2(C6H5N3)2] | [Mn(C4N3)2(C5H8N2)2] |
Mr | 477.33 | 427.35 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, Pbca |
Temperature (K) | 298 | 298 |
a, b, c (Å) | 7.287 (2), 7.962 (3), 9.583 (3) | 16.107 (9), 7.547 (4), 17.437 (10) |
α, β, γ (°) | 75.643 (4), 76.678 (4), 89.697 (4) | 90, 90, 90 |
V (Å3) | 523.4 (3) | 2120 (2) |
Z | 1 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.86 | 0.65 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 | 0.25 × 0.15 × 0.10 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.847, 0.919 | 0.855, 0.938 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2401, 2008, 1943 | 4692, 1853, 1226 |
Rint | 0.023 | 0.029 |
(sin θ/λ)max (Å−1) | 0.617 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.131, 1.05 | 0.035, 0.086, 0.94 |
No. of reflections | 2008 | 1853 |
No. of parameters | 151 | 135 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.88 | 0.17, −0.20 |
Selected geometric parameters (Å, º) for (I) topCo1—N1i | 2.106 (2) | C3—N3 | 1.143 (4) |
Co1—N2 | 2.110 (2) | C3—C4 | 1.408 (4) |
Co1—N4 | 2.149 (2) | C4—C1 | 1.397 (4) |
C2—N2 | 1.143 (4) | C1—N1 | 1.147 (4) |
C2—C4 | 1.403 (4) | | |
| | | |
N1i—Co1—N2ii | 88.84 (10) | N2—Co1—N4 | 91.16 (9) |
N1iii—Co1—N2ii | 91.16 (9) | N2—C2—C4 | 176.8 (3) |
N1i—Co1—N2 | 91.16 (9) | N3—C3—C4 | 177.5 (3) |
N1i—Co1—N4ii | 91.63 (9) | C1—C4—C2 | 117.3 (2) |
N1iii—Co1—N4ii | 88.37 (9) | C1—C4—C3 | 120.5 (2) |
N2ii—Co1—N4ii | 91.16 (9) | C2—C4—C3 | 122.2 (2) |
N2—Co1—N4ii | 88.84 (9) | C2—N2—Co1 | 163.6 (2) |
N1i—Co1—N4 | 88.37 (9) | N1—C1—C4 | 178.0 (3) |
N1iii—Co1—N4 | 91.63 (9) | C1—N1—Co1iv | 166.9 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+2, −z+2; (iii) −x+1, −y+2, −z+2; (iv) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N6—H6···N3v | 0.86 | 1.99 | 2.849 (4) | 179 |
Symmetry code: (v) x+1, y+1, z−1. |
Selected geometric parameters (Å, º) for (II) topMn1—N2i | 2.226 (2) | C2—N2 | 1.145 (3) |
Mn1—N1 | 2.227 (2) | C2—C4 | 1.392 (3) |
Mn1—N4 | 2.231 (2) | C3—N3 | 1.141 (3) |
C1—N1 | 1.149 (3) | C3—C4 | 1.402 (3) |
C1—C4 | 1.397 (3) | | |
| | | |
N2i—Mn1—N1 | 86.70 (9) | N1—C1—C4 | 178.5 (2) |
N2ii—Mn1—N1 | 93.30 (9) | N2—C2—C4 | 178.9 (2) |
N2ii—Mn1—N1iii | 86.70 (9) | N3—C3—C4 | 179.2 (3) |
N2i—Mn1—N4iii | 89.26 (7) | C2—C4—C1 | 118.48 (19) |
N2ii—Mn1—N4iii | 90.74 (7) | C2—C4—C3 | 120.9 (2) |
N1—Mn1—N4iii | 91.55 (7) | C1—C4—C3 | 120.4 (2) |
N1iii—Mn1—N4iii | 88.45 (7) | C1—N1—Mn1 | 156.8 (2) |
N1—Mn1—N4 | 88.45 (7) | C2—N2—Mn1iv | 170.64 (19) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+2, −y, −z+1; (iv) x, y+1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···N3v | 0.86 | 2.10 | 2.959 (3) | 173 |
Symmetry code: (v) −x+3/2, y−1/2, z. |
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The tricyanomethanide anion [C(CN)3−, tcm] has proved to be a versatile ligand for the construction of coordination polymers. It has been found that tcm can coordinate to metal ions in various modes, such as monodentate bonding through a nitrile N atom (Potočňák et al., 1997), bridging through the two nitrile N atoms (Batten et al., 2000; Hvastijová et al., 1995), and triple or quadraple coordination through all of three terminal N atoms (Manson et al., 1998; Batten et al., 1991, 1999; Chow & Britton, 1975). Therefore, tcm complexes continue to attract considerable interest, especially in the preparation of magnetic materials assembled by this ligand (Miller & Manson, 2001; Batten & Murray, 2003). Many investigation results indicate that the network topologies and the magnetic properties of the tcm-containing coordination polymers depend on the co-ligands. For example, the structure of the Ag(tcm)-type complex changes from two- to three-dimensional with the introduction of the pyrazine co-ligand (Batten et al., 1998). Notably, although metal–tcm coordination polymers with nitrogen-containing co-ligands, such as pyrazole (Kožíšek et al., 1991), 2-methylimidazole (Hvastijová et al., 1995, 1998), bipyridine (Batten et al., 2000) and tetramethylpyrazine (Abrahams et al., 2003; Batten et al., 2001), have been studied extensively, no tcm complexes with benzotriazole or 3,5-dimethylpyrazole as co-ligands have been characterized crystallographically so far. In order to further study how the nature of the co-ligands affects the stuctures and properties of tcm complexes, we report here the syntheses and crystal structures of two novel transition metal–tcm complexes with benzotriazole or 3,5-dimethylpyrazole as co-ligands, namely [Co(tcm)2(benzotriazole)2]n (I) and [Mn(tcm)2(3,5-dimethylpyrazole)2]n (II).
Complex (I) is composed of linear chains of CoII ions bridged by tcm ligands and coordinated by benzotriazole ligands (Fig. 1). Each CoII ion is connected to two neighbours by four equatorially bound tcm ligands, which participate in two successive Co(tcm)2Co units. Two nitrile N atoms in one tcm ligand are involved in coordination, so that the tcm ligands act as bridges in a µ–1,5 mode; a similar trend has been observed in Co(tcm)2(H2O)2 (Batten et al., 2001). The slightly distorted octahedral coordination environment of the Co atoms is completed by the coordination of two N atoms from the trans benzotriazole ligands, which only act as monodentate ligands. The Co—Ntcm equatorial distances [2.106 (2) and 2.110 (2) Å; mean 2.108 (2) Å] are slightly shorter than the Co—N(benzotriazole) axial lengths of 2.149 (2) Å; these distances are comparable to those in Co(tcm)2(2-methylimidazole)2 (Hvastijová et al., 1995). The CoN6 octahedron is only slightly distorted, as shown by the values (near 90°) of the cis N—Co—N' angles, which range from 88.37 (9) to 91.79 (6)°.
Polymeric one-dimensional chains lie along the a axis and are crosslinked by a hydrogen-bonding interaction between one H atom on a uncoordinated N atom (3-position) of the benzotriazole ligand and the uncoordinated nitrile N atom of the bridging tcm ligand from an adjacent chain [N····N = 2.849 (4) Å, H···N = 1.99 Å and N—H···N = 179°], thus forming a three-dimensional structure (Fig. 2). The shortest Co···Co intrachain length [7.287 (2) Å] is very similar to that in Co(tcm)2(H2O)2 (7.308 Å; Batten et al., 2001), and the shortest Co···Co interchain distance [7.962 (3) Å] in (I) is shorter than that in Co(tcm)2(2-methylimidazole)2 (Hvastijová et al., 1995). As the adjacent chains are not staggered, there are no π–π interactions between the adjacent benzotriazole rings. It is only the hydrogen bond that holds the crystal in the three-dimensional structure.
The structure of (II) also consists of polymeric one-dimensional chains, formed by Mn(3,5-dimethylpyrazole)22+ cations linked together by two bridging tcm anions (Fig. 3). The MnII atom is pseudo-octahedrally coordinated by four tcm nitrile atoms [N1, N1i, N2ii and N1iii; symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) x, y − 1, z; (iii) 2 − x, −y, 1 − z] in the equatorial plane and two N atoms [N4 and N4iii; symmetry code: (iii) 2 − x, −y, 1 − z] from the two trans monodentate 3,5-dimethylpyrazole ligands in the axial positions. In (II), the equatorial Mn—Ntcm bond lengths are in the normal range and are comparable to the Mn—N bond lengths in Mn(tcm)2 (Manson et al., 1998), while the axial Mn—N(3,5-dimethylpyrazole) is a little shorter than those observed in Mn(pydazine)2(dca)2 (Escuer et al., 2002) and Mn(2,5-Me2pyz)2(dca)2(H2O)2 (2,5-Me2pyz is 2,5-dimethylpyrazine; Manson et al., 2001).
In (II), polymetric one-dimensional chains are generated parallel to the b axis. An intermolecular hydrogen-bonding interaction between the uncoordinated terminal N atom of the tcm ligand and the H atom of the 3,5-dimethylpyrazole ligand in an adjacted chain [N····N = 2.959 (3) Å, H···N = 2.10 Å and N—H···N = 173°] results in the construction of a two-dimensional network (Fig. 4). The interchain Mn···Mn distance [8.053 (5) Å] is slightly longer than the intrachain Mn···Mn distance [7.547 (4) Å].
In (I) and (II), each tcm group is almost planar [the largest deviation of atoms from the mean plane is 0.026 (5) Å], and the bond lengths and angles of the tcm ions are in the normal range (Potočňák et al., 1997). The benzotriazole and 3,5-dimethylpyrazole ligands are also almost planar [the largest deviations of atoms from the mean planes are 0.031 (5) and 0.002 (7) Å, respectively].