


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037166/bt2445sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037166/bt2445Isup2.hkl |
CCDC reference: 660050
5 ml me thanol solution of 2-[(pyridin-2-yl)methoxy]pyrazine (0.0468 g, 0.250 mmol) was added into 10 ml H2O solution containing Mn(ClO4)2.6H2O (0.1021 g, 0.282 mmol) and NaSCN (0.0459 g, 0.566 mmol), and the mixed soulution was stirred for a few minutes. Colourless single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.
The H atoms from H2O were found in a difference Fourier map, and placed in idealized positions with O—H = 0.894–0.895 Å. The C-bound H atom were placed in calculated positions, C—H = 0.93–0.97 Å. All H atoms were refined as riding, with Uiso(H) = 1.2–1.5Ueq(C,O).
Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of coordination chemistry, but the ligand molecules that consist of pyridyl and pyrazyl groups are very limited (McMorran et al. 2002; Zhao et al., 2007a,b).
The title compound is shown in Fig. 1. In the mono-nuclear complex atom Mn1 is in a distorted octahedral geometry and is located on a twofold ratation axis. Between adjacent complexes there is a weak π-π stacking interaction between pyrazyl and pyridyl rings; the relevant distances are Cg1···Cg2i = 3.7457 (13) Å and Cg1···Cg2iperp = 3.222 Å [symmetry codes: (i) X, 1-Y, 1/2+Z; Cg1 and Cg2 are the centroids of the N2,N3,C2,C3,C4,C5 and N4,C7,C8,C9,C10,C11 rings, respectively; Cg1···Cg2perp is the perpendicular distance from ring Cg1 to ring Cg2]. Fig. 2 shows the O—H···N and O—H···S hydrogen bonds and Table 1 lists the geometric parameters. The dihedral angle between the pyridyl ring and the pyrazyl ring in 2-[(pyridin-2-yl)methoxy]pyrazine is 85.82 (9)°.
For related structures, see: McMorran et al. (2002); Zhao et al. (2007a,b).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Mn(NCS)2(C10H9N3O)2(H2O)2] | F(000) = 1196 |
Mr = 581.54 | Dx = 1.480 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4687 reflections |
a = 20.060 (3) Å | θ = 2.2–28.3° |
b = 10.1381 (12) Å | µ = 0.71 mm−1 |
c = 13.7285 (17) Å | T = 298 K |
β = 110.844 (2)° | Block, colourless |
V = 2609.3 (6) Å3 | 0.26 × 0.18 × 0.16 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 2317 independent reflections |
Radiation source: fine-focus sealed tube | 2133 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −23→22 |
Tmin = 0.837, Tmax = 0.895 | k = −12→11 |
5374 measured reflections | l = −9→16 |
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)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.0425P)2 + 1.6969P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.010 |
2317 reflections | Δρmax = 0.44 e Å−3 |
169 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0033 (4) |
[Mn(NCS)2(C10H9N3O)2(H2O)2] | V = 2609.3 (6) Å3 |
Mr = 581.54 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.060 (3) Å | µ = 0.71 mm−1 |
b = 10.1381 (12) Å | T = 298 K |
c = 13.7285 (17) Å | 0.26 × 0.18 × 0.16 mm |
β = 110.844 (2)° |
Bruker SMART APEX CCD diffractometer | 2317 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2133 reflections with I > 2σ(I) |
Tmin = 0.837, Tmax = 0.895 | Rint = 0.022 |
5374 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.44 e Å−3 |
2317 reflections | Δρmin = −0.45 e Å−3 |
169 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 | ||
Mn1 | 1.0000 | 0.79418 (3) | 1.2500 | 0.03392 (15) | |
S1 | 1.03076 (5) | 0.77723 (7) | 0.91123 (5) | 0.0820 (2) | |
N2 | 0.92253 (7) | 0.61791 (14) | 1.18728 (11) | 0.0387 (3) | |
O1 | 0.80883 (7) | 0.47898 (12) | 0.94850 (9) | 0.0490 (3) | |
N4 | 0.67814 (8) | 0.44033 (15) | 0.74592 (11) | 0.0435 (4) | |
O2 | 0.91697 (7) | 0.94209 (13) | 1.17325 (9) | 0.0493 (3) | |
H1 | 0.8847 | 0.9782 | 1.1964 | 0.074* | |
H6 | 0.9331 | 1.0103 | 1.1468 | 0.074* | |
N1 | 1.02389 (9) | 0.79825 (16) | 1.10881 (13) | 0.0492 (4) | |
C5 | 0.84117 (9) | 0.49147 (17) | 1.05252 (13) | 0.0387 (4) | |
C8 | 0.76848 (10) | 0.28795 (18) | 0.74656 (16) | 0.0459 (4) | |
H8 | 0.8078 | 0.2371 | 0.7843 | 0.055* | |
N3 | 0.82651 (8) | 0.40955 (15) | 1.11682 (11) | 0.0429 (4) | |
C1 | 1.02672 (10) | 0.79049 (17) | 1.02685 (15) | 0.0423 (4) | |
C9 | 0.74294 (11) | 0.28611 (19) | 0.63920 (17) | 0.0515 (5) | |
H9 | 0.7643 | 0.2330 | 0.6034 | 0.062* | |
C7 | 0.73497 (9) | 0.36634 (16) | 0.79734 (13) | 0.0374 (4) | |
C3 | 0.86224 (10) | 0.43152 (19) | 1.21803 (14) | 0.0472 (4) | |
H3 | 0.8549 | 0.3748 | 1.2664 | 0.057* | |
C4 | 0.88960 (9) | 0.59529 (17) | 1.08683 (13) | 0.0385 (4) | |
H4 | 0.8988 | 0.6493 | 1.0383 | 0.046* | |
C6 | 0.76005 (10) | 0.36903 (18) | 0.91382 (14) | 0.0467 (4) | |
H6A | 0.7199 | 0.3801 | 0.9367 | 0.056* | |
H6B | 0.7840 | 0.2871 | 0.9424 | 0.056* | |
C2 | 0.90920 (10) | 0.53366 (19) | 1.25373 (14) | 0.0453 (4) | |
H2 | 0.9323 | 0.5450 | 1.3251 | 0.054* | |
C11 | 0.65489 (11) | 0.4379 (2) | 0.64193 (15) | 0.0511 (5) | |
H11 | 0.6156 | 0.4895 | 0.6054 | 0.061* | |
C10 | 0.68574 (11) | 0.3634 (2) | 0.58593 (15) | 0.0520 (5) | |
H10 | 0.6682 | 0.3655 | 0.5135 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0365 (2) | 0.0357 (2) | 0.0277 (2) | 0.000 | 0.00914 (15) | 0.000 |
S1 | 0.1351 (6) | 0.0759 (5) | 0.0542 (4) | 0.0111 (4) | 0.0571 (4) | 0.0012 (3) |
N2 | 0.0368 (7) | 0.0388 (8) | 0.0357 (7) | −0.0029 (6) | 0.0070 (6) | 0.0008 (6) |
O1 | 0.0611 (8) | 0.0431 (7) | 0.0324 (6) | −0.0182 (6) | 0.0040 (6) | 0.0015 (5) |
N4 | 0.0454 (8) | 0.0435 (8) | 0.0391 (8) | 0.0011 (6) | 0.0120 (7) | −0.0035 (6) |
O2 | 0.0534 (7) | 0.0538 (8) | 0.0419 (7) | 0.0150 (6) | 0.0185 (6) | 0.0082 (6) |
N1 | 0.0614 (10) | 0.0511 (10) | 0.0407 (9) | −0.0029 (7) | 0.0251 (8) | 0.0007 (7) |
C5 | 0.0408 (9) | 0.0359 (9) | 0.0345 (9) | −0.0011 (7) | 0.0076 (7) | 0.0002 (7) |
C8 | 0.0418 (10) | 0.0402 (10) | 0.0536 (11) | −0.0006 (7) | 0.0145 (8) | 0.0000 (8) |
N3 | 0.0469 (8) | 0.0399 (8) | 0.0380 (8) | −0.0081 (6) | 0.0103 (6) | 0.0010 (6) |
C1 | 0.0465 (10) | 0.0377 (10) | 0.0454 (11) | 0.0019 (7) | 0.0197 (8) | 0.0021 (7) |
C9 | 0.0604 (12) | 0.0501 (11) | 0.0518 (11) | −0.0081 (9) | 0.0295 (10) | −0.0130 (9) |
C7 | 0.0403 (9) | 0.0337 (9) | 0.0356 (9) | −0.0101 (7) | 0.0103 (7) | −0.0020 (7) |
C3 | 0.0535 (10) | 0.0476 (10) | 0.0371 (9) | −0.0105 (8) | 0.0119 (8) | 0.0050 (8) |
C4 | 0.0408 (9) | 0.0363 (9) | 0.0346 (9) | −0.0030 (7) | 0.0087 (7) | 0.0027 (7) |
C6 | 0.0537 (10) | 0.0423 (10) | 0.0377 (9) | −0.0153 (8) | 0.0083 (8) | −0.0003 (8) |
C2 | 0.0477 (10) | 0.0492 (11) | 0.0334 (9) | −0.0076 (8) | 0.0077 (8) | 0.0010 (8) |
C11 | 0.0512 (10) | 0.0523 (11) | 0.0411 (10) | 0.0046 (9) | 0.0058 (8) | 0.0026 (8) |
C10 | 0.0637 (12) | 0.0551 (12) | 0.0350 (9) | −0.0123 (10) | 0.0151 (9) | −0.0059 (8) |
Mn1—N1i | 2.1564 (16) | C5—C4 | 1.396 (2) |
Mn1—N1 | 2.1564 (16) | C8—C9 | 1.378 (3) |
Mn1—O2i | 2.2100 (13) | C8—C7 | 1.380 (3) |
Mn1—O2 | 2.2100 (12) | C8—H8 | 0.9300 |
Mn1—N2 | 2.3233 (14) | N3—C3 | 1.336 (2) |
Mn1—N2i | 2.3233 (14) | C9—C10 | 1.367 (3) |
S1—C1 | 1.623 (2) | C9—H9 | 0.9300 |
N2—C4 | 1.320 (2) | C7—C6 | 1.496 (2) |
N2—C2 | 1.344 (2) | C3—C2 | 1.368 (3) |
O1—C5 | 1.348 (2) | C3—H3 | 0.9300 |
O1—C6 | 1.448 (2) | C4—H4 | 0.9300 |
N4—C11 | 1.335 (2) | C6—H6A | 0.9700 |
N4—C7 | 1.337 (2) | C6—H6B | 0.9700 |
O2—H1 | 0.8947 | C2—H2 | 0.9300 |
O2—H6 | 0.8938 | C11—C10 | 1.372 (3) |
N1—C1 | 1.149 (3) | C11—H11 | 0.9300 |
C5—N3 | 1.319 (2) | C10—H10 | 0.9300 |
N1i—Mn1—N1 | 177.81 (9) | C5—N3—C3 | 115.22 (15) |
N1i—Mn1—O2i | 85.95 (6) | N1—C1—S1 | 179.17 (17) |
N1—Mn1—O2i | 92.56 (6) | C10—C9—C8 | 119.12 (18) |
N1i—Mn1—O2 | 92.56 (6) | C10—C9—H9 | 120.4 |
N1—Mn1—O2 | 85.95 (6) | C8—C9—H9 | 120.4 |
O2i—Mn1—O2 | 94.55 (7) | N4—C7—C8 | 122.25 (16) |
N1i—Mn1—N2 | 90.83 (6) | N4—C7—C6 | 116.96 (16) |
N1—Mn1—N2 | 90.85 (6) | C8—C7—C6 | 120.77 (17) |
O2i—Mn1—N2 | 171.83 (5) | N3—C3—C2 | 123.03 (17) |
O2—Mn1—N2 | 93.09 (5) | N3—C3—H3 | 118.5 |
N1i—Mn1—N2i | 90.85 (6) | C2—C3—H3 | 118.5 |
N1—Mn1—N2i | 90.83 (6) | N2—C4—C5 | 120.88 (16) |
O2i—Mn1—N2i | 93.09 (5) | N2—C4—H4 | 119.6 |
O2—Mn1—N2i | 171.83 (5) | C5—C4—H4 | 119.6 |
N2—Mn1—N2i | 79.44 (7) | O1—C6—C7 | 107.25 (14) |
C4—N2—C2 | 116.88 (15) | O1—C6—H6A | 110.3 |
C4—N2—Mn1 | 122.75 (11) | C7—C6—H6A | 110.3 |
C2—N2—Mn1 | 120.37 (11) | O1—C6—H6B | 110.3 |
C5—O1—C6 | 115.79 (13) | C7—C6—H6B | 110.3 |
C11—N4—C7 | 117.52 (16) | H6A—C6—H6B | 108.5 |
Mn1—O2—H1 | 128.8 | N2—C2—C3 | 121.05 (16) |
Mn1—O2—H6 | 113.5 | N2—C2—H2 | 119.5 |
H1—O2—H6 | 103.9 | C3—C2—H2 | 119.5 |
C1—N1—Mn1 | 169.40 (16) | N4—C11—C10 | 123.61 (18) |
N3—C5—O1 | 120.80 (15) | N4—C11—H11 | 118.2 |
N3—C5—C4 | 122.89 (15) | C10—C11—H11 | 118.2 |
O1—C5—C4 | 116.31 (15) | C9—C10—C11 | 118.41 (18) |
C9—C8—C7 | 119.06 (17) | C9—C10—H10 | 120.8 |
C9—C8—H8 | 120.5 | C11—C10—H10 | 120.8 |
C7—C8—H8 | 120.5 | ||
N1i—Mn1—N2—C4 | 152.48 (14) | C11—N4—C7—C6 | −179.46 (16) |
N1—Mn1—N2—C4 | −26.12 (14) | C9—C8—C7—N4 | 0.4 (3) |
O2—Mn1—N2—C4 | 59.87 (14) | C9—C8—C7—C6 | 178.70 (16) |
N2i—Mn1—N2—C4 | −116.80 (15) | C5—N3—C3—C2 | 1.9 (3) |
N1i—Mn1—N2—C2 | −27.27 (14) | C2—N2—C4—C5 | 2.5 (2) |
N1—Mn1—N2—C2 | 154.13 (14) | Mn1—N2—C4—C5 | −177.28 (12) |
O2—Mn1—N2—C2 | −119.88 (13) | N3—C5—C4—N2 | −1.3 (3) |
N2i—Mn1—N2—C2 | 63.44 (12) | O1—C5—C4—N2 | 178.14 (15) |
O2i—Mn1—N1—C1 | −165.5 (8) | C5—O1—C6—C7 | −175.36 (15) |
O2—Mn1—N1—C1 | −71.1 (8) | N4—C7—C6—O1 | −87.09 (19) |
N2—Mn1—N1—C1 | 22.0 (8) | C8—C7—C6—O1 | 94.48 (19) |
N2i—Mn1—N1—C1 | 101.4 (8) | C4—N2—C2—C3 | −1.6 (3) |
C6—O1—C5—N3 | −2.0 (2) | Mn1—N2—C2—C3 | 178.21 (14) |
C6—O1—C5—C4 | 178.54 (15) | N3—C3—C2—N2 | −0.7 (3) |
O1—C5—N3—C3 | 179.65 (16) | C7—N4—C11—C10 | 0.5 (3) |
C4—C5—N3—C3 | −1.0 (3) | C8—C9—C10—C11 | −1.5 (3) |
C7—C8—C9—C10 | 0.9 (3) | N4—C11—C10—C9 | 0.8 (3) |
C11—N4—C7—C8 | −1.1 (3) |
Symmetry code: (i) −x+2, y, −z+5/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H6···S1ii | 0.89 | 2.49 | 3.3776 (16) | 171 |
O2—H1···N4iii | 0.89 | 1.90 | 2.793 (2) | 176 |
Symmetry codes: (ii) −x+2, −y+2, −z+2; (iii) −x+3/2, −y+3/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(NCS)2(C10H9N3O)2(H2O)2] |
Mr | 581.54 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 20.060 (3), 10.1381 (12), 13.7285 (17) |
β (°) | 110.844 (2) |
V (Å3) | 2609.3 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.26 × 0.18 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.837, 0.895 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5374, 2317, 2133 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.083, 1.04 |
No. of reflections | 2317 |
No. of parameters | 169 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.45 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H6···S1i | 0.89 | 2.49 | 3.3776 (16) | 170.9 |
O2—H1···N4ii | 0.89 | 1.90 | 2.793 (2) | 175.7 |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+3/2, −y+3/2, −z+2. |
Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of coordination chemistry, but the ligand molecules that consist of pyridyl and pyrazyl groups are very limited (McMorran et al. 2002; Zhao et al., 2007a,b).
The title compound is shown in Fig. 1. In the mono-nuclear complex atom Mn1 is in a distorted octahedral geometry and is located on a twofold ratation axis. Between adjacent complexes there is a weak π-π stacking interaction between pyrazyl and pyridyl rings; the relevant distances are Cg1···Cg2i = 3.7457 (13) Å and Cg1···Cg2iperp = 3.222 Å [symmetry codes: (i) X, 1-Y, 1/2+Z; Cg1 and Cg2 are the centroids of the N2,N3,C2,C3,C4,C5 and N4,C7,C8,C9,C10,C11 rings, respectively; Cg1···Cg2perp is the perpendicular distance from ring Cg1 to ring Cg2]. Fig. 2 shows the O—H···N and O—H···S hydrogen bonds and Table 1 lists the geometric parameters. The dihedral angle between the pyridyl ring and the pyrazyl ring in 2-[(pyridin-2-yl)methoxy]pyrazine is 85.82 (9)°.