Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023707/kp2108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023707/kp2108Isup2.hkl |
CCDC reference: 651361
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.040
- wR factor = 0.116
- Data-to-parameter ratio = 18.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 - C8 .. 5.06 su PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.36 PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4B ... ?
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 1.99
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
1.0 mmol H-Pysc, 0.5 mmol Mn(Ac)2.4H2O and 1.0 mmol of (NH4)SCN were dissolved in a water-ethanol mixture (1:2 v/v; 20 ml), and the mixture was stirred for ca 2 h at 343 K. The mixture was further stirred for another 1 h at 333 K and filtered. The resultant filtrate was left to stand for slow evaporation at room temperature. Colourless single crystals of (I) suitable for X-ray structure analysis were obtained after a period of 15 days (yield 72%).
Hydrogen atoms attached to carbon atoms and nitrogen atoms were positioned geometrically and treated as riding, with C—H = 0.93 Å, N—H = 0.86 Å, and Uiso(H) = 1.2Ueq(C or N)]. Water H atoms were located in difference maps and constrained to ride at O—H distances (0.85 Å) with Uiso(H) = 1.5Ueq(O).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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, 1997); software used to prepare material for publication: SHELXTL.
Structurally characterized metal-organic complexes based on the Schiff base ligands derived from semicarbazone have been reported due to their antimicrobial, cytotoxic and antioxidant activities (Chen, Zhou, Liang et al., 2004; Chen, Zhou, Li et al., 2004; Beraldo et al., 2001). We report here the crystal structure of the title compound (I).
The Mn atom in compound (I) is six-coordinated by two O atoms of water molecules and four N atoms, two of which come from two thiocyanate anions and the rest from H-Pysc ligands (Fig. 1). The bond lengths and three trans angles at Mn1 suggests a slightly distorted octahedral geometry (Table 1).
The molecules are held together by intermolecular hydrogen bonding forming three-dimensional supramolecular network. The coordinated water molecules (O1W) donate H atoms to the terminal O1 atom and thiocyanate S atoms to form O—H···Oi and O—H···Sii hydrogen bonds, respectively (Table 2, Fig. 2) The O1 atoms also accept H atom from N3 to form N—H···Oiii hydrogen bonds (Table 2, Fig. 2).
For related literature, see: Beraldo et al. (2001); Chen, Zhou, Li et al. (2004); Chen, Zhou, Liang et al. (2004); Sheldrick (1997).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Mn(SCN)2(C7H8N4O)2(H2O)2] | Z = 1 |
Mr = 535.48 | F(000) = 275 |
Triclinic, P1 | Dx = 1.551 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6998 (19) Å | Cell parameters from 2857 reflections |
b = 9.329 (3) Å | θ = 2.2–28.4° |
c = 10.478 (3) Å | µ = 0.80 mm−1 |
α = 64.770 (3)° | T = 173 K |
β = 82.711 (3)° | Block, colourless |
γ = 75.384 (3)° | 0.56 × 0.46 × 0.35 mm |
V = 573.1 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 2738 independent reflections |
Radiation source: fine-focus sealed tube | 2010 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
phi and ω scans | θmax = 28.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −8→8 |
Tmin = 0.647, Tmax = 0.753 | k = −12→12 |
5162 measured reflections | l = −13→13 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0574P)2 + 0.0195P] where P = (Fo2 + 2Fc2)/3 |
2738 reflections | (Δ/σ)max < 0.001 |
151 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Mn(SCN)2(C7H8N4O)2(H2O)2] | γ = 75.384 (3)° |
Mr = 535.48 | V = 573.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.6998 (19) Å | Mo Kα radiation |
b = 9.329 (3) Å | µ = 0.80 mm−1 |
c = 10.478 (3) Å | T = 173 K |
α = 64.770 (3)° | 0.56 × 0.46 × 0.35 mm |
β = 82.711 (3)° |
Bruker SMART CCD area-detector diffractometer | 2738 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 2010 reflections with I > 2σ(I) |
Tmin = 0.647, Tmax = 0.753 | Rint = 0.068 |
5162 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.61 e Å−3 |
2738 reflections | Δρmin = −0.48 e Å−3 |
151 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 | 0.5000 | 0.0000 | 0.0000 | 0.03568 (17) | |
S1 | 0.11296 (10) | −0.42537 (8) | 0.10273 (8) | 0.0535 (2) | |
O1 | −0.5650 (3) | 0.1500 (2) | −0.67672 (18) | 0.0485 (4) | |
N2 | −0.1690 (3) | 0.1982 (2) | −0.5220 (2) | 0.0377 (4) | |
O1W | 0.2788 (3) | 0.1500 (2) | 0.09562 (18) | 0.0509 (5) | |
H1B | 0.1822 | 0.2316 | 0.0542 | 0.076* | |
H1A | 0.3169 | 0.1696 | 0.1592 | 0.076* | |
N1 | 0.3320 (3) | 0.1506 (2) | −0.21142 (19) | 0.0347 (4) | |
C1 | 0.1792 (3) | 0.1049 (3) | −0.2461 (2) | 0.0347 (5) | |
H1 | 0.1338 | 0.0120 | −0.1781 | 0.042* | |
C2 | 0.0843 (3) | 0.1862 (3) | −0.3759 (2) | 0.0327 (5) | |
N3 | −0.3197 (3) | 0.1331 (2) | −0.5403 (2) | 0.0413 (5) | |
H3A | −0.3478 | 0.0434 | −0.4733 | 0.050* | |
C8 | 0.2205 (3) | −0.2772 (3) | 0.0791 (2) | 0.0394 (5) | |
C3 | 0.1501 (3) | 0.3210 (3) | −0.4753 (2) | 0.0391 (5) | |
H3 | 0.0917 | 0.3774 | −0.5663 | 0.047* | |
C6 | −0.0808 (3) | 0.1251 (3) | −0.4029 (2) | 0.0377 (5) | |
H6 | −0.1216 | 0.0317 | −0.3321 | 0.045* | |
C5 | 0.3886 (3) | 0.2840 (3) | −0.3076 (2) | 0.0410 (5) | |
H5 | 0.4933 | 0.3205 | −0.2842 | 0.049* | |
N5 | 0.2998 (3) | −0.1731 (3) | 0.0611 (2) | 0.0514 (5) | |
C7 | −0.4251 (3) | 0.2080 (3) | −0.6625 (3) | 0.0410 (5) | |
C4 | 0.3025 (4) | 0.3718 (3) | −0.4394 (3) | 0.0481 (6) | |
H4 | 0.3479 | 0.4661 | −0.5046 | 0.058* | |
N4 | −0.3730 (4) | 0.3407 (3) | −0.7595 (2) | 0.0654 (7) | |
H4B | −0.4384 | 0.3936 | −0.8398 | 0.078* | |
H4A | −0.2728 | 0.3762 | −0.7438 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0336 (3) | 0.0431 (3) | 0.0360 (3) | −0.0139 (2) | −0.01144 (19) | −0.0156 (2) |
S1 | 0.0500 (4) | 0.0465 (4) | 0.0689 (5) | −0.0199 (3) | −0.0100 (3) | −0.0207 (3) |
O1 | 0.0491 (9) | 0.0577 (11) | 0.0472 (10) | −0.0107 (8) | −0.0229 (8) | −0.0242 (9) |
N2 | 0.0311 (9) | 0.0479 (11) | 0.0422 (11) | −0.0095 (8) | −0.0094 (8) | −0.0232 (9) |
O1W | 0.0520 (10) | 0.0606 (11) | 0.0473 (10) | −0.0018 (8) | −0.0200 (8) | −0.0298 (9) |
N1 | 0.0306 (8) | 0.0422 (10) | 0.0369 (10) | −0.0084 (7) | −0.0099 (7) | −0.0188 (8) |
C1 | 0.0311 (10) | 0.0422 (12) | 0.0344 (11) | −0.0119 (9) | −0.0062 (9) | −0.0156 (10) |
C2 | 0.0246 (9) | 0.0439 (12) | 0.0351 (11) | −0.0067 (8) | −0.0057 (8) | −0.0205 (10) |
N3 | 0.0385 (10) | 0.0475 (11) | 0.0434 (11) | −0.0132 (8) | −0.0183 (8) | −0.0170 (9) |
C8 | 0.0354 (11) | 0.0468 (13) | 0.0368 (12) | −0.0107 (9) | −0.0125 (9) | −0.0139 (10) |
C3 | 0.0329 (10) | 0.0501 (13) | 0.0353 (12) | −0.0093 (10) | −0.0095 (9) | −0.0159 (10) |
C6 | 0.0321 (10) | 0.0447 (12) | 0.0398 (13) | −0.0101 (9) | −0.0104 (9) | −0.0172 (10) |
C5 | 0.0347 (11) | 0.0498 (13) | 0.0443 (14) | −0.0171 (10) | −0.0101 (10) | −0.0180 (11) |
N5 | 0.0496 (12) | 0.0577 (13) | 0.0519 (13) | −0.0251 (10) | −0.0142 (10) | −0.0165 (11) |
C7 | 0.0404 (11) | 0.0497 (13) | 0.0396 (13) | −0.0062 (10) | −0.0142 (10) | −0.0231 (11) |
C4 | 0.0434 (12) | 0.0522 (15) | 0.0461 (15) | −0.0229 (11) | −0.0109 (11) | −0.0083 (12) |
N4 | 0.0730 (16) | 0.0786 (17) | 0.0439 (13) | −0.0333 (14) | −0.0224 (12) | −0.0097 (12) |
Mn1—N5 | 2.193 (2) | C1—H1 | 0.9500 |
Mn1—N5i | 2.193 (2) | C2—C3 | 1.381 (3) |
Mn1—O1Wi | 2.2203 (17) | C2—C6 | 1.471 (3) |
Mn1—O1W | 2.2203 (17) | N3—C7 | 1.358 (3) |
Mn1—N1 | 2.3085 (18) | N3—H3A | 0.8800 |
Mn1—N1i | 2.3085 (18) | C8—N5 | 1.158 (3) |
S1—C8 | 1.630 (2) | C3—C4 | 1.380 (3) |
O1—C7 | 1.246 (3) | C3—H3 | 0.9500 |
N2—C6 | 1.276 (3) | C6—H6 | 0.9500 |
N2—N3 | 1.372 (2) | C5—C4 | 1.383 (3) |
O1W—H1B | 0.8533 | C5—H5 | 0.9500 |
O1W—H1A | 0.8447 | C7—N4 | 1.320 (3) |
N1—C5 | 1.335 (3) | C4—H4 | 0.9500 |
N1—C1 | 1.345 (2) | N4—H4B | 0.8800 |
C1—C2 | 1.387 (3) | N4—H4A | 0.8800 |
N5—Mn1—N5i | 180.00 (9) | C3—C2—C6 | 122.49 (19) |
N5—Mn1—O1Wi | 88.84 (8) | C1—C2—C6 | 119.0 (2) |
N5i—Mn1—O1Wi | 91.16 (8) | C7—N3—N2 | 119.6 (2) |
N5—Mn1—O1W | 91.16 (8) | C7—N3—H3A | 120.2 |
N5i—Mn1—O1W | 88.84 (8) | N2—N3—H3A | 120.2 |
O1Wi—Mn1—O1W | 180.00 (13) | N5—C8—S1 | 178.8 (2) |
N5—Mn1—N1 | 90.01 (7) | C4—C3—C2 | 118.5 (2) |
N5i—Mn1—N1 | 89.99 (7) | C4—C3—H3 | 120.8 |
O1Wi—Mn1—N1 | 90.48 (6) | C2—C3—H3 | 120.8 |
O1W—Mn1—N1 | 89.52 (6) | N2—C6—C2 | 119.7 (2) |
N5—Mn1—N1i | 89.99 (7) | N2—C6—H6 | 120.1 |
N5i—Mn1—N1i | 90.01 (7) | C2—C6—H6 | 120.1 |
O1Wi—Mn1—N1i | 89.52 (6) | N1—C5—C4 | 123.3 (2) |
O1W—Mn1—N1i | 90.48 (6) | N1—C5—H5 | 118.4 |
N1—Mn1—N1i | 180.00 (6) | C4—C5—H5 | 118.4 |
C6—N2—N3 | 116.5 (2) | C8—N5—Mn1 | 167.3 (2) |
Mn1—O1W—H1B | 127.1 | O1—C7—N4 | 123.9 (2) |
Mn1—O1W—H1A | 120.4 | O1—C7—N3 | 119.1 (2) |
H1B—O1W—H1A | 104.6 | N4—C7—N3 | 117.1 (2) |
C5—N1—C1 | 116.89 (18) | C3—C4—C5 | 119.3 (2) |
C5—N1—Mn1 | 121.13 (13) | C3—C4—H4 | 120.4 |
C1—N1—Mn1 | 121.93 (15) | C5—C4—H4 | 120.4 |
N1—C1—C2 | 123.5 (2) | C7—N4—H4B | 120.0 |
N1—C1—H1 | 118.2 | C7—N4—H4A | 120.0 |
C2—C1—H1 | 118.2 | H4B—N4—H4A | 120.0 |
C3—C2—C1 | 118.52 (19) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O1ii | 0.84 | 1.90 | 2.724 (3) | 164 |
O1W—H1B···S1iii | 0.85 | 2.52 | 3.352 (2) | 164 |
N3—H3A···O1iv | 0.88 | 1.99 | 2.865 (3) | 175 |
N4—H4A···N2 | 0.88 | 2.28 | 2.637 (3) | 104 |
Symmetry codes: (ii) x+1, y, z+1; (iii) −x, −y, −z; (iv) −x−1, −y, −z−1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(SCN)2(C7H8N4O)2(H2O)2] |
Mr | 535.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.6998 (19), 9.329 (3), 10.478 (3) |
α, β, γ (°) | 64.770 (3), 82.711 (3), 75.384 (3) |
V (Å3) | 573.1 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.56 × 0.46 × 0.35 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.647, 0.753 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5162, 2738, 2010 |
Rint | 0.068 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.116, 1.06 |
No. of reflections | 2738 |
No. of parameters | 151 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.48 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Mn1—N5 | 2.193 (2) | Mn1—N1 | 2.3085 (18) |
Mn1—O1W | 2.2203 (17) | ||
N5—Mn1—N5i | 180.00 (9) | O1W—Mn1—N1 | 89.52 (6) |
N5—Mn1—O1Wi | 88.84 (8) | N5—Mn1—N1i | 89.99 (7) |
N5—Mn1—O1W | 91.16 (8) | O1W—Mn1—N1i | 90.48 (6) |
O1Wi—Mn1—O1W | 180.00 (13) | N1—Mn1—N1i | 180.00 (6) |
N5—Mn1—N1 | 90.01 (7) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O1ii | 0.84 | 1.90 | 2.724 (3) | 164 |
O1W—H1B···S1iii | 0.85 | 2.52 | 3.352 (2) | 164 |
N3—H3A···O1iv | 0.88 | 1.99 | 2.865 (3) | 175 |
N4—H4A···N2 | 0.88 | 2.28 | 2.637 (3) | 104 |
Symmetry codes: (ii) x+1, y, z+1; (iii) −x, −y, −z; (iv) −x−1, −y, −z−1. |
Structurally characterized metal-organic complexes based on the Schiff base ligands derived from semicarbazone have been reported due to their antimicrobial, cytotoxic and antioxidant activities (Chen, Zhou, Liang et al., 2004; Chen, Zhou, Li et al., 2004; Beraldo et al., 2001). We report here the crystal structure of the title compound (I).
The Mn atom in compound (I) is six-coordinated by two O atoms of water molecules and four N atoms, two of which come from two thiocyanate anions and the rest from H-Pysc ligands (Fig. 1). The bond lengths and three trans angles at Mn1 suggests a slightly distorted octahedral geometry (Table 1).
The molecules are held together by intermolecular hydrogen bonding forming three-dimensional supramolecular network. The coordinated water molecules (O1W) donate H atoms to the terminal O1 atom and thiocyanate S atoms to form O—H···Oi and O—H···Sii hydrogen bonds, respectively (Table 2, Fig. 2) The O1 atoms also accept H atom from N3 to form N—H···Oiii hydrogen bonds (Table 2, Fig. 2).