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The two new title complexes, [Mn(C5H3N6)2(H2O)2] and [Zn(C5H3N6)2(H2O)2], are isomorphous. In both compounds, the metal atom is located on an inversion center and is coordinated by four N atoms from two 5-(pyrazin-2-yl)-1H-tetrazolate anions in the basal plane and by two O atoms of water ligands in the apical positions to form a distorted octahedral geometry. Intermolecular hydrogen-bond interactions between the uncoordinated N atoms of the tetrazolate anions and the H atoms of the water molecules lead to the formation of a three-dimensional network.
Supporting information
CCDC references: 632928; 632929
A 4 ml e thanol solution of pyrazine-2-carbonitrile (0.20 mmol, 21.02 mg) and a 4 ml aqueous solution of manganese acetate (0.20 mmol, 49.02 mg) were mixed and stirred for 5 min; a 2 ml aqueous solution of sodium azide (0.20 mmol, 13.01 mg) was added to the mixture. After being stirred for another 5 min, the solution was filtered and the filtrate was slowly evaporated in air. After one week, colourless block crystals of (I) were isolated in 55% yield. Analysis calculated for C10H10MnN12O2: C 31.18, H 2.62, N 43.63%; found C 30.89, H 2.71, N 43.76%. Complex (II) was prepared by a similar procedure in 47% yield. Analysis calculated for C10H10N12O2Zn: C 30.36, H 2.55, N 42.48%; found C 30.09, H 2.41, N 42.65%.
In both complexes, the position of the water H atom was found from a difference Fourier map and refined freely along with an isotropic displacement parameter; all other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).
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 (Bruker, 2000); software used to prepare material for publication: SHELXTL.
(I) Diaquabis[5-(pyrazin-2-yl-
κN1)-1
H-tetrazolato-
κN1]manganese(II)
top
Crystal data top
[Mn(C5H3N6)2(H2O)2] | F(000) = 390 |
Mr = 385.24 | Dx = 1.745 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 722 reflections |
a = 5.9642 (19) Å | θ = 2.6–27.1° |
b = 11.715 (4) Å | µ = 0.94 mm−1 |
c = 10.853 (4) Å | T = 293 K |
β = 104.817 (4)° | Block, colourless |
V = 733.1 (4) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1455 independent reflections |
Radiation source: fine-focus sealed tube | 1235 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→6 |
Tmin = 0.705, Tmax = 0.799 | k = −8→14 |
3288 measured reflections | l = −12→13 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.089P)2] where P = (Fo2 + 2Fc2)/3 |
1455 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.62 e Å−3 |
3 restraints | Δρmin = −0.62 e Å−3 |
Crystal data top
[Mn(C5H3N6)2(H2O)2] | V = 733.1 (4) Å3 |
Mr = 385.24 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.9642 (19) Å | µ = 0.94 mm−1 |
b = 11.715 (4) Å | T = 293 K |
c = 10.853 (4) Å | 0.40 × 0.30 × 0.25 mm |
β = 104.817 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1455 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1235 reflections with I > 2σ(I) |
Tmin = 0.705, Tmax = 0.799 | Rint = 0.042 |
3288 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 3 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.62 e Å−3 |
1455 reflections | Δρmin = −0.62 e Å−3 |
123 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 | 0.0000 | 0.0000 | 1.0000 | 0.0361 (2) | |
N1 | 0.1366 (3) | 0.18434 (15) | 0.99557 (15) | 0.0352 (4) | |
N2 | 0.2347 (4) | 0.41445 (18) | 0.9712 (3) | 0.0596 (6) | |
N3 | −0.4259 (3) | 0.25931 (17) | 0.78875 (18) | 0.0427 (5) | |
N4 | −0.5894 (3) | 0.17956 (19) | 0.7549 (2) | 0.0487 (5) | |
N5 | −0.5126 (3) | 0.08293 (17) | 0.8089 (2) | 0.0462 (5) | |
N6 | −0.2960 (3) | 0.09646 (15) | 0.88000 (18) | 0.0395 (5) | |
C1 | 0.3427 (4) | 0.2294 (2) | 1.0515 (2) | 0.0418 (5) | |
H1 | 0.4579 | 0.1824 | 1.0999 | 0.050* | |
C2 | 0.3900 (4) | 0.3431 (2) | 1.0400 (3) | 0.0521 (6) | |
H2 | 0.5356 | 0.3710 | 1.0817 | 0.063* | |
C3 | 0.0290 (4) | 0.3704 (2) | 0.9159 (3) | 0.0501 (6) | |
H3 | −0.0854 | 0.4179 | 0.8679 | 0.060* | |
C4 | −0.0218 (3) | 0.25603 (17) | 0.92695 (19) | 0.0348 (5) | |
C5 | −0.2472 (3) | 0.20629 (19) | 0.86497 (19) | 0.0353 (5) | |
O1 | 0.1025 (4) | −0.04281 (18) | 0.83085 (19) | 0.0563 (5) | |
H1A | 0.219 (4) | −0.016 (2) | 0.811 (3) | 0.065 (11)* | |
H1B | 0.048 (4) | −0.0985 (17) | 0.784 (2) | 0.054 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0436 (3) | 0.0235 (3) | 0.0400 (3) | 0.00143 (16) | 0.0082 (2) | 0.00348 (17) |
N1 | 0.0377 (9) | 0.0316 (9) | 0.0361 (9) | 0.0004 (7) | 0.0089 (7) | 0.0022 (7) |
N2 | 0.0541 (13) | 0.0357 (11) | 0.0817 (16) | −0.0108 (9) | 0.0041 (11) | 0.0006 (11) |
N3 | 0.0383 (10) | 0.0401 (11) | 0.0464 (10) | 0.0022 (8) | 0.0044 (8) | 0.0080 (9) |
N4 | 0.0385 (10) | 0.0501 (12) | 0.0520 (11) | −0.0031 (9) | 0.0012 (8) | 0.0041 (10) |
N5 | 0.0382 (10) | 0.0435 (12) | 0.0527 (12) | −0.0074 (8) | 0.0039 (8) | −0.0011 (9) |
N6 | 0.0378 (9) | 0.0313 (10) | 0.0464 (10) | −0.0032 (7) | 0.0055 (8) | 0.0004 (8) |
C1 | 0.0368 (11) | 0.0430 (13) | 0.0419 (12) | 0.0025 (9) | 0.0033 (9) | 0.0015 (10) |
C2 | 0.0430 (12) | 0.0495 (14) | 0.0590 (15) | −0.0092 (11) | 0.0043 (11) | −0.0062 (12) |
C3 | 0.0471 (13) | 0.0310 (12) | 0.0664 (16) | 0.0002 (10) | 0.0038 (11) | 0.0068 (11) |
C4 | 0.0379 (11) | 0.0281 (11) | 0.0376 (11) | 0.0010 (8) | 0.0080 (9) | 0.0009 (8) |
C5 | 0.0371 (10) | 0.0318 (11) | 0.0367 (11) | 0.0022 (9) | 0.0088 (8) | 0.0024 (9) |
O1 | 0.0677 (12) | 0.0510 (11) | 0.0573 (11) | −0.0235 (10) | 0.0290 (9) | −0.0199 (10) |
Geometric parameters (Å, º) top
Mn1—N1 | 2.313 (2) | N4—N5 | 1.303 (3) |
Mn1—N1i | 2.313 (2) | N5—N6 | 1.334 (2) |
Mn1—N6 | 2.217 (2) | N6—C5 | 1.338 (3) |
Mn1—N6i | 2.217 (2) | C1—C2 | 1.375 (3) |
Mn1—O1 | 2.138 (2) | C1—H1 | 0.9300 |
Mn1—O1i | 2.138 (2) | C2—H2 | 0.9300 |
N1—C1 | 1.332 (3) | C3—C4 | 1.386 (3) |
N1—C4 | 1.339 (3) | C3—H3 | 0.9300 |
N2—C3 | 1.325 (3) | C4—C5 | 1.462 (3) |
N2—C2 | 1.327 (3) | O1—H1A | 0.84 (3) |
N3—C5 | 1.325 (3) | O1—H1B | 0.84 (3) |
N3—N4 | 1.332 (3) | | |
| | | |
N6—Mn1—N1 | 75.15 (7) | N5—N6—Mn1 | 141.9 (2) |
N6i—Mn1—N1i | 75.15 (7) | C5—N6—Mn1 | 113.3 (1) |
N6—Mn1—N1i | 104.85 (7) | N1—C1—C2 | 121.9 (2) |
N6i—Mn1—N1 | 104.85 (7) | N1—C1—H1 | 119.0 |
O1—Mn1—N1 | 91.23 (7) | C2—C1—H1 | 119.0 |
O1i—Mn1—N1i | 91.23 (7) | N2—C2—C1 | 122.1 (2) |
O1—Mn1—N6 | 88.56 (8) | N2—C2—H2 | 118.9 |
O1i—Mn1—N6i | 88.56 (8) | C1—C2—H2 | 118.9 |
O1—Mn1—N1i | 88.77 (7) | N2—C3—C4 | 122.4 (2) |
O1i—Mn1—N1 | 88.77 (7) | N2—C3—H3 | 118.8 |
O1—Mn1—N6i | 91.44 (8) | C4—C3—H3 | 118.8 |
O1i—Mn1—N6 | 91.44 (8) | N1—C4—C3 | 121.0 (2) |
C1—N1—C4 | 116.3 (2) | N1—C4—C5 | 116.2 (2) |
C1—N1—Mn1 | 130.5 (1) | C3—C4—C5 | 122.8 (2) |
C4—N1—Mn1 | 113.3 (1) | N3—C5—N6 | 111.2 (2) |
C3—N2—C2 | 116.2 (2) | N3—C5—C4 | 126.8 (2) |
C5—N3—N4 | 105.0 (2) | N6—C5—C4 | 122.0 (2) |
N5—N4—N3 | 109.7 (2) | Mn1—O1—H1A | 124 (2) |
N4—N5—N6 | 109.5 (2) | Mn1—O1—H1B | 124 (2) |
N5—N6—C5 | 104.6 (2) | H1A—O1—H1B | 111 (2) |
Symmetry code: (i) −x, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···N4ii | 0.84 (1) | 2.66 (2) | 3.378 (3) | 145 (2) |
O1—H1B···N3ii | 0.84 (1) | 1.91 (1) | 2.733 (3) | 168 (3) |
O1—H1A···N4iii | 0.84 (3) | 2.70 (2) | 3.408 (3) | 144 (3) |
O1—H1A···N5iii | 0.84 (3) | 1.98 (1) | 2.788 (3) | 162 (3) |
Symmetry codes: (ii) −x−1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
(II) diaquabis[5-(pyrazin-2-yl-
κN1)-1
H-tetrazolato-
κN1]zinc(II)
top
Crystal data top
[Zn(C5H3N6)2(H2O)2] | F(000) = 400 |
Mr = 395.67 | Dx = 1.830 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 904 reflections |
a = 6.0906 (18) Å | θ = 2.7–26.6° |
b = 11.456 (3) Å | µ = 1.75 mm−1 |
c = 10.686 (3) Å | T = 293 K |
β = 105.634 (4)° | Block, colourless |
V = 718.0 (3) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1406 independent reflections |
Radiation source: fine-focus sealed tube | 1161 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→7 |
Tmin = 0.541, Tmax = 0.669 | k = −14→12 |
3206 measured reflections | l = −12→13 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.04P)2] where P = (Fo2 + 2Fc2)/3 |
1406 reflections | (Δ/σ)max < 0.001 |
123 parameters | Δρmax = 0.43 e Å−3 |
3 restraints | Δρmin = −0.37 e Å−3 |
Crystal data top
[Zn(C5H3N6)2(H2O)2] | V = 718.0 (3) Å3 |
Mr = 395.67 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.0906 (18) Å | µ = 1.75 mm−1 |
b = 11.456 (3) Å | T = 293 K |
c = 10.686 (3) Å | 0.40 × 0.30 × 0.25 mm |
β = 105.634 (4)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1406 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1161 reflections with I > 2σ(I) |
Tmin = 0.541, Tmax = 0.669 | Rint = 0.034 |
3206 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.027 | 3 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.43 e Å−3 |
1406 reflections | Δρmin = −0.37 e Å−3 |
123 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 | |
Zn1 | 0.0000 | 0.0000 | 1.0000 | 0.03186 (14) | |
N1 | 0.1349 (3) | 0.17741 (15) | 0.99843 (15) | 0.0305 (4) | |
N2 | 0.2365 (3) | 0.41201 (18) | 0.9749 (2) | 0.0530 (6) | |
N3 | −0.4229 (3) | 0.25458 (17) | 0.79147 (17) | 0.0381 (4) | |
N4 | −0.5842 (3) | 0.17241 (18) | 0.7606 (2) | 0.0446 (5) | |
N5 | −0.5051 (3) | 0.07431 (17) | 0.81860 (18) | 0.0405 (5) | |
N6 | −0.2893 (3) | 0.09058 (15) | 0.88836 (17) | 0.0339 (4) | |
C1 | 0.3408 (4) | 0.2215 (2) | 1.0550 (2) | 0.0372 (5) | |
H1 | 0.4538 | 0.1727 | 1.1038 | 0.045* | |
C2 | 0.3896 (4) | 0.3377 (2) | 1.0427 (2) | 0.0457 (6) | |
H2 | 0.5351 | 0.3649 | 1.0835 | 0.055* | |
C3 | 0.0318 (4) | 0.3683 (2) | 0.9193 (2) | 0.0443 (6) | |
H3 | −0.0807 | 0.4178 | 0.8712 | 0.053* | |
C4 | −0.0205 (3) | 0.25227 (18) | 0.9300 (2) | 0.0299 (5) | |
C5 | −0.2450 (3) | 0.20180 (18) | 0.8694 (2) | 0.0306 (5) | |
O1 | 0.0823 (3) | −0.03652 (17) | 0.82549 (18) | 0.0465 (4) | |
H1A | 0.208 (3) | −0.0164 (19) | 0.817 (3) | 0.056 (9)* | |
H1B | 0.039 (4) | −0.0986 (14) | 0.785 (2) | 0.058 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.0328 (2) | 0.0222 (2) | 0.0381 (2) | 0.00033 (14) | 0.00524 (15) | 0.00323 (14) |
N1 | 0.0317 (10) | 0.0275 (10) | 0.0316 (9) | 0.0004 (7) | 0.0074 (7) | 0.0006 (7) |
N2 | 0.0477 (13) | 0.0330 (12) | 0.0705 (14) | −0.0098 (10) | 0.0029 (11) | 0.0000 (10) |
N3 | 0.0318 (10) | 0.0360 (11) | 0.0430 (10) | 0.0012 (8) | 0.0042 (8) | 0.0077 (9) |
N4 | 0.0338 (10) | 0.0455 (12) | 0.0491 (11) | −0.0017 (9) | 0.0019 (9) | 0.0055 (10) |
N5 | 0.0319 (10) | 0.0388 (12) | 0.0475 (11) | −0.0058 (9) | 0.0050 (8) | −0.0006 (9) |
N6 | 0.0291 (9) | 0.0280 (10) | 0.0417 (10) | −0.0019 (8) | 0.0046 (8) | 0.0018 (8) |
C1 | 0.0313 (12) | 0.0401 (14) | 0.0366 (12) | 0.0012 (10) | 0.0028 (10) | −0.0019 (10) |
C2 | 0.0361 (13) | 0.0428 (15) | 0.0534 (14) | −0.0080 (11) | 0.0034 (11) | −0.0046 (12) |
C3 | 0.0397 (13) | 0.0276 (13) | 0.0603 (16) | 0.0013 (10) | 0.0044 (12) | 0.0052 (11) |
C4 | 0.0301 (11) | 0.0258 (11) | 0.0332 (11) | 0.0005 (9) | 0.0073 (9) | 0.0011 (9) |
C5 | 0.0317 (11) | 0.0264 (11) | 0.0322 (11) | 0.0022 (9) | 0.0062 (9) | 0.0019 (9) |
O1 | 0.0492 (12) | 0.0437 (11) | 0.0521 (11) | −0.0157 (9) | 0.0233 (9) | −0.0153 (9) |
Geometric parameters (Å, º) top
Zn1—N1 | 2.194 (2) | N4—N5 | 1.311 (3) |
Zn1—N1i | 2.194 (2) | N5—N6 | 1.338 (2) |
Zn1—N6 | 2.115 (2) | N6—C5 | 1.329 (3) |
Zn1—N6i | 2.115 (2) | C1—C2 | 1.377 (3) |
Zn1—O1 | 2.099 (2) | C1—H1 | 0.9300 |
Zn1—O1i | 2.099 (2) | C2—H2 | 0.9300 |
N1—C1 | 1.336 (3) | C3—C4 | 1.379 (3) |
N1—C4 | 1.339 (3) | C3—H3 | 0.9300 |
N2—C2 | 1.325 (3) | C4—C5 | 1.465 (3) |
N2—C3 | 1.326 (3) | O1—H1A | 0.83 (1) |
N3—C5 | 1.322 (3) | O1—H1B | 0.84 (1) |
N3—N4 | 1.336 (3) | | |
| | | |
N6—Zn1—N1 | 78.34 (7) | C5—N6—Zn1 | 112.6 (1) |
N6i—Zn1—N1i | 78.34 (7) | N5—N6—Zn1 | 142.2 (1) |
N6—Zn1—N1i | 101.66 (7) | N1—C1—C2 | 121.5 (2) |
N6i—Zn1—N1 | 101.66 (7) | N1—C1—H1 | 119.3 |
O1—Zn1—N1 | 89.90 (7) | C2—C1—H1 | 119.3 |
O1i—Zn1—N1i | 89.90 (7) | N2—C2—C1 | 122.4 (2) |
O1—Zn1—N6 | 87.63 (8) | N2—C2—H2 | 118.8 |
O1i—Zn1—N6i | 87.63 (8) | C1—C2—H2 | 118.8 |
O1—Zn1—N1i | 90.10 (7) | N2—C3—C4 | 122.5 (2) |
O1i—Zn1—N1 | 90.10 (7) | N2—C3—H3 | 118.8 |
O1—Zn1—N6i | 92.37 (8) | C4—C3—H3 | 118.8 |
O1i—Zn1—N6 | 92.37 (8) | N1—C4—C3 | 121.2 (2) |
C1—N1—C4 | 116.4 (2) | N1—C4—C5 | 115.3 (2) |
C1—N1—Zn1 | 130.9 (2) | C3—C4—C5 | 123.6 (2) |
C4—N1—Zn1 | 112.7 (1) | N3—C5—N6 | 111.6 (2) |
C2—N2—C3 | 116.1 (2) | N3—C5—C4 | 127.4 (2) |
C5—N3—N4 | 104.9 (2) | N6—C5—C4 | 121.0 (2) |
N5—N4—N3 | 109.6 (2) | Zn1—O1—H1A | 119 (2) |
N4—N5—N6 | 108.9 (2) | Zn1—O1—H1B | 121 (2) |
C5—N6—N5 | 105.0 (2) | H1A—O1—H1B | 111 (2) |
Symmetry code: (i) −x, −y, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···N4ii | 0.84 (1) | 2.70 (2) | 3.460 (3) | 153 (2) |
O1—H1B···N3ii | 0.84 (1) | 1.92 (1) | 2.753 (3) | 173 (2) |
O1—H1A···N4iii | 0.83 (1) | 2.66 (2) | 3.331 (3) | 140 (2) |
O1—H1A···N5iii | 0.83 (1) | 2.03 (1) | 2.834 (3) | 164 (2) |
Symmetry codes: (ii) −x−1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Mn(C5H3N6)2(H2O)2] | [Zn(C5H3N6)2(H2O)2] |
Mr | 385.24 | 395.67 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 5.9642 (19), 11.715 (4), 10.853 (4) | 6.0906 (18), 11.456 (3), 10.686 (3) |
β (°) | 104.817 (4) | 105.634 (4) |
V (Å3) | 733.1 (4) | 718.0 (3) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.94 | 1.75 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 | 0.40 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.705, 0.799 | 0.541, 0.669 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3288, 1455, 1235 | 3206, 1406, 1161 |
Rint | 0.042 | 0.034 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.120, 1.00 | 0.027, 0.071, 0.99 |
No. of reflections | 1455 | 1406 |
No. of parameters | 123 | 123 |
No. of restraints | 3 | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.62, −0.62 | 0.43, −0.37 |
Selected geometric parameters (Å, º) for (I) topMn1—N1 | 2.313 (2) | Mn1—O1 | 2.138 (2) |
Mn1—N6 | 2.217 (2) | | |
| | | |
N6—Mn1—N1 | 75.15 (7) | O1—Mn1—N6 | 88.56 (8) |
N6—Mn1—N1i | 104.85 (7) | O1—Mn1—N1i | 88.77 (7) |
O1—Mn1—N1 | 91.23 (7) | O1—Mn1—N6i | 91.44 (8) |
Symmetry code: (i) −x, −y, −z+2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···N4ii | 0.84 (1) | 2.66 (2) | 3.378 (3) | 145 (2) |
O1—H1B···N3ii | 0.84 (1) | 1.91 (1) | 2.733 (3) | 168 (3) |
O1—H1A···N4iii | 0.84 (3) | 2.70 (2) | 3.408 (3) | 144 (3) |
O1—H1A···N5iii | 0.84 (3) | 1.98 (1) | 2.788 (3) | 162 (3) |
Symmetry codes: (ii) −x−1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
Selected geometric parameters (Å, º) for (II) topZn1—N1 | 2.194 (2) | Zn1—O1 | 2.099 (2) |
Zn1—N6 | 2.115 (2) | | |
| | | |
N6—Zn1—N1 | 78.34 (7) | O1—Zn1—N6 | 87.63 (8) |
N6—Zn1—N1i | 101.66 (7) | O1—Zn1—N1i | 90.10 (7) |
O1—Zn1—N1 | 89.90 (7) | O1—Zn1—N6i | 92.37 (8) |
Symmetry code: (i) −x, −y, −z+2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···N4ii | 0.84 (1) | 2.70 (2) | 3.460 (3) | 153 (2) |
O1—H1B···N3ii | 0.84 (1) | 1.92 (1) | 2.753 (3) | 173 (2) |
O1—H1A···N4iii | 0.83 (1) | 2.66 (2) | 3.331 (3) | 140 (2) |
O1—H1A···N5iii | 0.83 (1) | 2.03 (1) | 2.834 (3) | 164 (2) |
Symmetry codes: (ii) −x−1/2, y−1/2, −z+3/2; (iii) x+1, y, z. |
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Tetrazoles have attracted considerable interest because of their popular functionality and variety of applications (Butler, 1996). It is well known that tetrazoles have been used in many fields, including pharmaceuticals (Singh et al., 1980), speciality explosives (Ostrovskii et al., 1999), photography and information recording systems (Koldobskii & Ostrovskii, 1994), and as precursors to nitrogen-containing heterocycles (Huisgen et al., 1960). Simple heating of an azide salt with a nitrile in an aqueous solution could produce the corresponding tetrazolate (Dimroth & Fester, 1910). In contrast to the previous synthetic methods, the tetrazoles are easily prepared in high yield by addition of sodium azide to a nitrile in water, with the catalysis of Lewis acids such as zinc salts (Demko & Sharpless, 2001). Although the synthetic method has been improved, the role of Lewis acids in the synthesis reaction and the exact intermediates are rarely known (Lin et al., 2005; Wu et al., 2005; Yu et al., 2004). In order to better understand the influence of Lewis acids on the tetrazole synthesis reaction and to get obtain a deeper insight into the intermediates, we report here the syntheses and structures of two isomorphous complexes [Mn(5-PYZTZ)2(H2O)2], (I), and [Zn(5-PYZTZ)2(H2O)2], (II) [5-PYZTZ is 5-(pyrazin-2-yl)-1H-tetrazolate].
In (I), the MnII ion, located on an inversion center, is coordinated to two 5-(pyrazinyl)tetrazolate anions and two aqua ligands to give a distorted octahedral geometry, in which the basal plane is formed by two pyrazine N atoms and two tetrazolate N atoms (atoms N1, N6, N1i and N6i) of two 5-PYZTZ anions (Fig. 1). The apical positions are occupied by two O atoms (O1 and O1i) from two water molecules [symmetry codes: (i) −x, −y, −z + 2]. Intermolecular hydrogen-bonding interactions between the uncoordinated N atoms of the tetrazolate anions and the H atoms of the water molecules result in the formation of a three-dimensional network (Fig. 2, and Table 2).
In (II), the ZnII atom has the same coordination environment as the Mn atom in (I). The three-dimensional structure is also formed by intermolecular hydrogen bonds involving uncoordinated N atoms of the tetrazolate anions and the H atoms of the water molecules.
In (I) and (II), the Mn—N(5-PYZTZ) and Zn—N(5-PYZTZ) distances (Tables 1 and 3) are comparable to the corresponding distances in related manganese (Lin et al., 2005) and zinc complexes (Wang et al., 2005; Zhang et al., 2005), and the Mn—O and Zn—O distances are similar to the corresponding distances in water-coordinated manganese (Mautner et al., 2004) and zinc complexes (Zhang et al., 2005), respectively.
In (I), the N—Mn—N angles (two neighbouring atoms) are in the range 75.15 (7)–104.85 (7)°. The corresponding N—Zn—N angles are in the range 78.34 (7)–101.66 (7)°, indicating that the geometry in (I) is more distorted than that of (II).
In both complexes, the bond distances and angles of tetrazole ring [1.303 (3)–1.338 (3) Å and 104.6 (2)–111.6 (2)°] and pyrazine ring [1.325 (3)–1.386 (3) Å and 116.1 (2)–122.5 (2)°] are in the normal ranges observed in pyrazine- or tetrazole-containing complexes (Mautner et al., 2004; Ferigo et al., 1994).