Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010201586X/jz1514sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010201586X/jz1514Isup2.hkl |
CCDC reference: 197323
The pyridoxal 3-methylisothiosemicarbazone ligand, H2L, was prepared by the reaction of an ethanolic solution of 3-methylisothiosemicarbazide hydroiodide with pyridoxal hydrochloride and subsequent neutralization with an aqueous solution of Na2CO3. Green single crystals of (I) were obtained by the reaction of a hot ethanolic solution of the ligand with Cu(NO3)2·3H2O (molar ratio 1:1).
All H atoms were found in difference Fourier maps, and they were refined isotropically. A Gaussian-type absorption correction based on the crystal morphology was applied (Spek, 1990, 1998).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 EXPRESS (Enraf-Nonius, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).
[Cu(C10H14N4O2S)(H2O)(NO3)](NO3) | Z = 2 |
Mr = 459.89 | F(000) = 470 |
Triclinic, P1 | Dx = 1.806 Mg m−3 |
a = 7.945 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.262 (3) Å | Cell parameters from 23 reflections |
c = 11.701 (3) Å | θ = 12.0–16.8° |
α = 85.13 (2)° | µ = 1.48 mm−1 |
β = 89.34 (3)° | T = 293 K |
γ = 80.35 (3)° | Prismatic, green |
V = 845.8 (5) Å3 | 0.40 × 0.26 × 0.14 mm |
Enraf-Nonius CAD-4 diffractometer | 2853 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 26.0°, θmin = 1.8° |
ω/2θ scans | h = 0→9 |
Absorption correction: gaussian (PLATON; Spek, 1990, 1998) | k = −11→11 |
Tmin = 0.675, Tmax = 0.815 | l = −14→14 |
3570 measured reflections | 2 standard reflections every 60 min |
3316 independent reflections | intensity decay: none |
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)] = 0.034 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0554P)2 + 0.3428P] where P = (Fo2 + 2Fc2)/3 |
3316 reflections | (Δ/σ)max < 0.001 |
308 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
[Cu(C10H14N4O2S)(H2O)(NO3)](NO3) | γ = 80.35 (3)° |
Mr = 459.89 | V = 845.8 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.945 (3) Å | Mo Kα radiation |
b = 9.262 (3) Å | µ = 1.48 mm−1 |
c = 11.701 (3) Å | T = 293 K |
α = 85.13 (2)° | 0.40 × 0.26 × 0.14 mm |
β = 89.34 (3)° |
Enraf-Nonius CAD-4 diffractometer | 2853 reflections with I > 2σ(I) |
Absorption correction: gaussian (PLATON; Spek, 1990, 1998) | Rint = 0.017 |
Tmin = 0.675, Tmax = 0.815 | 2 standard reflections every 60 min |
3570 measured reflections | intensity decay: none |
3316 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.46 e Å−3 |
3316 reflections | Δρmin = −0.38 e Å−3 |
308 parameters |
x | y | z | Uiso*/Ueq | ||
Cu | 0.33859 (4) | 0.34981 (3) | 0.28580 (3) | 0.02925 (12) | |
N1 | 0.3748 (3) | 0.5560 (2) | 0.28256 (17) | 0.0262 (4) | |
N2 | 0.5257 (3) | 0.5654 (2) | 0.3339 (2) | 0.0313 (5) | |
N3 | 0.5546 (3) | 0.3181 (3) | 0.3660 (2) | 0.0318 (5) | |
C1 | 0.6166 (3) | 0.4347 (3) | 0.3781 (2) | 0.0267 (5) | |
S | 0.80801 (8) | 0.45089 (7) | 0.44462 (6) | 0.03355 (17) | |
C2 | 0.8933 (4) | 0.2620 (4) | 0.4817 (3) | 0.0454 (8) | |
C3 | 0.2762 (3) | 0.6745 (3) | 0.2444 (2) | 0.0268 (5) | |
C4 | 0.1121 (3) | 0.6728 (3) | 0.1916 (2) | 0.0261 (5) | |
O1 | 0.1211 (2) | 0.40805 (19) | 0.21801 (17) | 0.0339 (4) | |
C5 | 0.0485 (3) | 0.5391 (3) | 0.1815 (2) | 0.0269 (5) | |
C6 | −0.1105 (3) | 0.5485 (3) | 0.1242 (2) | 0.0293 (5) | |
C7 | −0.1857 (4) | 0.4156 (4) | 0.1077 (3) | 0.0379 (6) | |
N4 | −0.1926 (3) | 0.6794 (3) | 0.0836 (2) | 0.0352 (5) | |
C8 | −0.1379 (4) | 0.8075 (3) | 0.0956 (2) | 0.0370 (6) | |
C9 | 0.0133 (3) | 0.8076 (3) | 0.1490 (2) | 0.0303 (5) | |
C10 | 0.0633 (4) | 0.9555 (3) | 0.1639 (2) | 0.0351 (6) | |
O2 | 0.0595 (3) | 0.9869 (2) | 0.28084 (19) | 0.0400 (5) | |
O1W | 0.2854 (3) | 0.1573 (2) | 0.3405 (3) | 0.0512 (6) | |
N5 | 0.6603 (3) | 0.8926 (2) | 0.3716 (2) | 0.0345 (5) | |
O3 | 0.7314 (3) | 0.9994 (2) | 0.38660 (19) | 0.0452 (5) | |
O4 | 0.5026 (3) | 0.9011 (3) | 0.3794 (2) | 0.0569 (6) | |
O5 | 0.7465 (3) | 0.7739 (2) | 0.3501 (2) | 0.0512 (6) | |
N6 | 0.5481 (3) | 0.1934 (3) | 0.0690 (2) | 0.0437 (6) | |
O6 | 0.6451 (4) | 0.1266 (3) | 0.1421 (3) | 0.0759 (9) | |
O7 | 0.5632 (4) | 0.1712 (4) | −0.0324 (2) | 0.0858 (10) | |
O8 | 0.4293 (3) | 0.2938 (3) | 0.09494 (19) | 0.0523 (6) | |
H1N3 | 0.609 (5) | 0.244 (4) | 0.395 (3) | 0.050 (10)* | |
H2C0 | 0.183 (4) | 0.962 (3) | 0.134 (2) | 0.037 (8)* | |
H1C3 | 0.315 (4) | 0.761 (3) | 0.255 (2) | 0.033 (7)* | |
H1C8 | −0.211 (4) | 0.898 (4) | 0.064 (3) | 0.048 (9)* | |
H1C0 | −0.009 (4) | 1.030 (4) | 0.121 (3) | 0.044 (9)* | |
H1N4 | −0.271 (4) | 0.686 (4) | 0.044 (3) | 0.042 (9)* | |
H1N2 | 0.563 (4) | 0.648 (4) | 0.335 (3) | 0.041 (9)* | |
H3C7 | −0.268 (5) | 0.430 (4) | 0.063 (3) | 0.053 (10)* | |
H1C2 | 0.918 (5) | 0.217 (4) | 0.421 (3) | 0.055 (11)* | |
H1O2 | −0.026 (5) | 0.984 (4) | 0.311 (3) | 0.049 (11)* | |
H2C2 | 0.815 (5) | 0.218 (4) | 0.530 (3) | 0.055 (10)* | |
H3C2 | 0.984 (6) | 0.253 (4) | 0.520 (3) | 0.062 (11)* | |
H2C7 | −0.205 (5) | 0.367 (5) | 0.178 (4) | 0.067 (12)* | |
H1C7 | −0.102 (6) | 0.352 (5) | 0.070 (4) | 0.089 (15)* | |
H1W | 0.362 (6) | 0.101 (5) | 0.355 (3) | 0.063 (13)* | |
H2W | 0.208 (7) | 0.130 (6) | 0.315 (4) | 0.092 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.02403 (18) | 0.01951 (17) | 0.0448 (2) | −0.00529 (12) | −0.00772 (13) | −0.00197 (12) |
N1 | 0.0241 (10) | 0.0235 (10) | 0.0320 (11) | −0.0058 (8) | −0.0022 (8) | −0.0031 (8) |
N2 | 0.0290 (11) | 0.0216 (11) | 0.0448 (13) | −0.0080 (9) | −0.0091 (9) | −0.0031 (9) |
N3 | 0.0281 (11) | 0.0227 (11) | 0.0437 (13) | −0.0030 (9) | −0.0093 (9) | 0.0000 (9) |
C1 | 0.0231 (12) | 0.0269 (12) | 0.0307 (12) | −0.0043 (10) | −0.0008 (9) | −0.0046 (9) |
S | 0.0276 (3) | 0.0299 (3) | 0.0442 (4) | −0.0069 (3) | −0.0106 (3) | −0.0031 (3) |
C2 | 0.0379 (17) | 0.0333 (16) | 0.063 (2) | −0.0008 (13) | −0.0201 (16) | −0.0011 (15) |
C3 | 0.0291 (13) | 0.0210 (12) | 0.0310 (12) | −0.0055 (10) | 0.0004 (10) | −0.0041 (9) |
C4 | 0.0262 (12) | 0.0242 (12) | 0.0278 (12) | −0.0033 (10) | 0.0016 (9) | −0.0042 (9) |
O1 | 0.0254 (9) | 0.0209 (9) | 0.0552 (11) | −0.0030 (7) | −0.0090 (8) | −0.0025 (8) |
C5 | 0.0245 (12) | 0.0277 (12) | 0.0280 (12) | −0.0016 (10) | 0.0012 (9) | −0.0049 (9) |
C6 | 0.0268 (13) | 0.0324 (13) | 0.0293 (12) | −0.0055 (11) | 0.0006 (10) | −0.0050 (10) |
C7 | 0.0315 (15) | 0.0404 (16) | 0.0446 (17) | −0.0119 (13) | −0.0041 (13) | −0.0065 (13) |
N4 | 0.0278 (12) | 0.0367 (13) | 0.0404 (13) | −0.0039 (10) | −0.0114 (10) | −0.0002 (10) |
C8 | 0.0336 (14) | 0.0314 (14) | 0.0433 (15) | 0.0000 (12) | −0.0052 (12) | 0.0026 (12) |
C9 | 0.0308 (13) | 0.0276 (13) | 0.0318 (13) | −0.0026 (11) | 0.0005 (10) | −0.0021 (10) |
C10 | 0.0341 (15) | 0.0260 (13) | 0.0434 (15) | −0.0026 (11) | −0.0026 (12) | 0.0021 (11) |
O2 | 0.0357 (11) | 0.0356 (11) | 0.0525 (12) | −0.0129 (9) | 0.0038 (10) | −0.0121 (9) |
O1W | 0.0344 (12) | 0.0268 (11) | 0.0922 (19) | −0.0107 (10) | −0.0171 (12) | 0.0090 (11) |
N5 | 0.0343 (12) | 0.0270 (12) | 0.0422 (12) | −0.0074 (10) | −0.0040 (9) | 0.0017 (9) |
O3 | 0.0444 (12) | 0.0277 (10) | 0.0662 (14) | −0.0120 (9) | −0.0042 (10) | −0.0071 (9) |
O4 | 0.0337 (12) | 0.0391 (12) | 0.0970 (19) | −0.0078 (9) | −0.0041 (11) | 0.0025 (12) |
O5 | 0.0460 (13) | 0.0292 (11) | 0.0798 (16) | −0.0058 (9) | 0.0045 (11) | −0.0144 (10) |
N6 | 0.0319 (13) | 0.0408 (14) | 0.0598 (16) | −0.0066 (11) | −0.0038 (11) | −0.0114 (12) |
O6 | 0.0642 (17) | 0.0517 (15) | 0.105 (2) | 0.0174 (13) | −0.0394 (16) | −0.0127 (14) |
O7 | 0.073 (2) | 0.120 (3) | 0.0632 (18) | −0.0048 (19) | 0.0201 (15) | −0.0299 (17) |
O8 | 0.0375 (12) | 0.0617 (15) | 0.0535 (13) | 0.0104 (11) | −0.0121 (10) | −0.0167 (11) |
Cu—O1 | 1.8849 (19) | C6—N4 | 1.329 (4) |
Cu—N3 | 1.932 (2) | C6—C7 | 1.483 (4) |
Cu—O1W | 1.955 (2) | C7—H3C7 | 0.83 (4) |
Cu—N1 | 1.975 (2) | C7—H2C7 | 0.92 (4) |
Cu—O8 | 2.410 (2) | C7—H1C7 | 0.94 (5) |
N1—C3 | 1.286 (3) | N4—C8 | 1.348 (4) |
N1—N2 | 1.366 (3) | N4—H1N4 | 0.77 (3) |
N2—C1 | 1.365 (3) | C8—C9 | 1.361 (4) |
N2—H1N2 | 0.87 (4) | C8—H1C8 | 0.98 (3) |
N3—C1 | 1.278 (3) | C9—C10 | 1.513 (4) |
N3—H1N3 | 0.80 (4) | C10—O2 | 1.422 (4) |
C1—S | 1.751 (3) | C10—H2C0 | 1.02 (3) |
S—C2 | 1.786 (3) | C10—H1C0 | 0.93 (3) |
C2—H1C2 | 0.86 (4) | O2—H1O2 | 0.76 (4) |
C2—H2C2 | 0.95 (4) | O1W—H1W | 0.74 (5) |
C2—H3C2 | 0.84 (4) | O1W—H2W | 0.77 (6) |
C3—C4 | 1.452 (4) | N5—O5 | 1.238 (3) |
C3—H1C3 | 0.92 (3) | N5—O3 | 1.243 (3) |
C4—C9 | 1.413 (4) | N5—O4 | 1.245 (3) |
C4—C5 | 1.428 (3) | N6—O6 | 1.214 (4) |
O1—C5 | 1.293 (3) | N6—O7 | 1.223 (4) |
C5—C6 | 1.423 (3) | N6—O8 | 1.263 (3) |
O1—Cu—N3 | 171.27 (9) | O1—C5—C4 | 126.9 (2) |
O1—Cu—O1W | 91.87 (10) | C6—C5—C4 | 117.6 (2) |
N3—Cu—O1W | 93.71 (11) | N4—C6—C5 | 119.2 (2) |
O1—Cu—N1 | 91.49 (9) | N4—C6—C7 | 119.2 (2) |
N3—Cu—N1 | 81.12 (9) | C5—C6—C7 | 121.6 (2) |
O1W—Cu—N1 | 161.43 (11) | C6—C7—H3C7 | 114 (3) |
O1—Cu—O8 | 84.54 (8) | C6—C7—H2C7 | 110 (3) |
N3—Cu—O8 | 101.30 (9) | H3C7—C7—H2C7 | 115 (4) |
O1W—Cu—O8 | 98.09 (11) | C6—C7—H1C7 | 106 (3) |
N1—Cu—O8 | 100.41 (9) | H3C7—C7—H1C7 | 104 (4) |
C3—N1—N2 | 119.4 (2) | H2C7—C7—H1C7 | 107 (4) |
C3—N1—Cu | 129.40 (18) | C6—N4—C8 | 124.3 (2) |
N2—N1—Cu | 111.19 (16) | C6—N4—H1N4 | 121 (3) |
C1—N2—N1 | 115.1 (2) | C8—N4—H1N4 | 115 (3) |
C1—N2—H1N2 | 122 (2) | N4—C8—C9 | 120.0 (3) |
N1—N2—H1N2 | 122 (2) | N4—C8—H1C8 | 117 (2) |
C1—N3—Cu | 114.87 (19) | C9—C8—H1C8 | 123 (2) |
C1—N3—H1N3 | 115 (3) | C8—C9—C4 | 119.6 (2) |
Cu—N3—H1N3 | 130 (3) | C8—C9—C10 | 117.2 (2) |
N3—C1—N2 | 117.7 (2) | C4—C9—C10 | 123.2 (2) |
N3—C1—S | 128.4 (2) | O2—C10—C9 | 112.0 (2) |
N2—C1—S | 113.95 (19) | O2—C10—H2C0 | 107.5 (17) |
C1—S—C2 | 100.70 (14) | C9—C10—H2C0 | 112.0 (17) |
S—C2—H1C2 | 111 (3) | O2—C10—H1C0 | 110 (2) |
S—C2—H2C2 | 110 (2) | C9—C10—H1C0 | 110 (2) |
H1C2—C2—H2C2 | 112 (3) | H2C0—C10—H1C0 | 105 (3) |
S—C2—H3C2 | 111 (3) | C10—O2—H1O2 | 114 (3) |
H1C2—C2—H3C2 | 107 (3) | Cu—O1W—H1W | 114 (3) |
H2C2—C2—H3C2 | 106 (3) | Cu—O1W—H2W | 120 (4) |
N1—C3—C4 | 122.3 (2) | H1W—O1W—H2W | 117 (5) |
N1—C3—H1C3 | 115.6 (19) | O5—N5—O3 | 120.2 (2) |
C4—C3—H1C3 | 122.1 (19) | O5—N5—O4 | 118.4 (2) |
C9—C4—C5 | 119.3 (2) | O3—N5—O4 | 121.4 (2) |
C9—C4—C3 | 118.8 (2) | O6—N6—O7 | 122.4 (3) |
C5—C4—C3 | 121.8 (2) | O6—N6—O8 | 120.6 (3) |
C5—O1—Cu | 127.94 (17) | O7—N6—O8 | 116.9 (3) |
O1—C5—C6 | 115.5 (2) | N6—O8—Cu | 126.43 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O4 | 0.87 (4) | 2.41 (4) | 3.174 (3) | 147 (3) |
N2—H1N2···O5 | 0.87 (4) | 2.03 (4) | 2.837 (3) | 154 (3) |
N3—H1N3···O3i | 0.80 (4) | 2.32 (4) | 3.040 (3) | 151 (3) |
O1W—H1W···O4i | 0.74 (5) | 2.00 (5) | 2.698 (3) | 158 (5) |
O1W—H2W···O2i | 0.77 (6) | 1.98 (6) | 2.714 (3) | 157 (5) |
C2—H3C2···O5ii | 0.84 (4) | 2.61 (4) | 3.446 (4) | 177 (3) |
C10—H2C0···O7iii | 1.02 (3) | 2.52 (3) | 3.404 (4) | 145 (2) |
O2—H1O2···O3iv | 0.76 (4) | 2.10 (4) | 2.862 (3) | 174 (4) |
N4—H1N4···O7v | 0.77 (3) | 2.47 (4) | 3.078 (4) | 137 (3) |
N4—H1N4···O8v | 0.77 (3) | 2.05 (4) | 2.795 (3) | 164 (3) |
C8—H1C8···O6vi | 0.98 (3) | 2.47 (3) | 3.248 (4) | 135 (2) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x−1, y, z; (v) −x, −y+1, −z; (vi) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C10H14N4O2S)(H2O)(NO3)](NO3) |
Mr | 459.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.945 (3), 9.262 (3), 11.701 (3) |
α, β, γ (°) | 85.13 (2), 89.34 (3), 80.35 (3) |
V (Å3) | 845.8 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.48 |
Crystal size (mm) | 0.40 × 0.26 × 0.14 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Gaussian (PLATON; Spek, 1990, 1998) |
Tmin, Tmax | 0.675, 0.815 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3570, 3316, 2853 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.095, 1.05 |
No. of reflections | 3316 |
No. of parameters | 308 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.46, −0.38 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, CAD-4 EXPRESS (Enraf-Nonius, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97, PARST (Nardelli, 1995) and WinGX (Farrugia, 1999).
Cu—O1 | 1.8849 (19) | N2—C1 | 1.365 (3) |
Cu—N3 | 1.932 (2) | N3—C1 | 1.278 (3) |
Cu—O1W | 1.955 (2) | C1—S | 1.751 (3) |
Cu—N1 | 1.975 (2) | S—C2 | 1.786 (3) |
Cu—O8 | 2.410 (2) | C3—C4 | 1.452 (4) |
N1—C3 | 1.286 (3) | C4—C5 | 1.428 (3) |
N1—N2 | 1.366 (3) | O1—C5 | 1.293 (3) |
O1—Cu—N3 | 171.27 (9) | O1W—Cu—N1 | 161.43 (11) |
O1—Cu—O1W | 91.87 (10) | O1—Cu—O8 | 84.54 (8) |
N3—Cu—O1W | 93.71 (11) | N3—Cu—O8 | 101.30 (9) |
O1—Cu—N1 | 91.49 (9) | O1W—Cu—O8 | 98.09 (11) |
N3—Cu—N1 | 81.12 (9) | N1—Cu—O8 | 100.41 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···O4 | 0.87 (4) | 2.41 (4) | 3.174 (3) | 147 (3) |
N2—H1N2···O5 | 0.87 (4) | 2.03 (4) | 2.837 (3) | 154 (3) |
N3—H1N3···O3i | 0.80 (4) | 2.32 (4) | 3.040 (3) | 151 (3) |
O1W—H1W···O4i | 0.74 (5) | 2.00 (5) | 2.698 (3) | 158 (5) |
O1W—H2W···O2i | 0.77 (6) | 1.98 (6) | 2.714 (3) | 157 (5) |
C2—H3C2···O5ii | 0.84 (4) | 2.61 (4) | 3.446 (4) | 177 (3) |
C10—H2C0···O7iii | 1.02 (3) | 2.52 (3) | 3.404 (4) | 145 (2) |
O2—H1O2···O3iv | 0.76 (4) | 2.10 (4) | 2.862 (3) | 174 (4) |
N4—H1N4···O7v | 0.77 (3) | 2.47 (4) | 3.078 (4) | 137 (3) |
N4—H1N4···O8v | 0.77 (3) | 2.05 (4) | 2.795 (3) | 164 (3) |
C8—H1C8···O6vi | 0.98 (3) | 2.47 (3) | 3.248 (4) | 135 (2) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x−1, y, z; (v) −x, −y+1, −z; (vi) x−1, y+1, z. |
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Transition metal complexes with ligands based on thiosemicarbazides (TSC) have been studied for many years because of their interesting structural properties and biological activity (West et al., 1991; Casas et al., 2000). The CuII metal centre is especially interesting as an essential ion, since its complexes with TSC-based ligands possess a wide range of biological effects, such as antiviral, antitumour and anti-inflammatory activity (West et al., 1993). Isothiosemicarbazones can also act as biologically active agents with antibacterial activity (Cardia et al., 2000).
A number of metal complexes with pyridoxal thiosemicarbazone (PxTSC), always coordinated through the ONS atoms, have been synthesized and structurally characterized to date, namely [MnIICl(PxTSC)(H2O)]Cl and [CuII(PxTSC)(H2O)]Cl·H2O (Ferrari et al., 1987), [ZnIICl(PxTSC)]·H2O (Ferrari et al., 1992), [CuIICl(PxTSC)(H2O)]Cl (Belicchi et al., 1994), [CoIII(PxTSC)2]Cl·EtOH (Ferrari et al., 1995), [CuII(PxTSC)(H2O)2]SO4·H2O (Ferrari et al., 1998) and [AuIIICl(PxTSC)]Cl2·MeOH (Abram et al., 2000). The title complex, [CuII(H2L)(H2O)NO3]NO3 (H2L is pyridoxal 3-methylisothiosemicarbazone), (I), represents the first example of a transition metal complex with a pyridoxal isothiosemicarbazone (PxITSC) that has been synthesized and characterized by X-ray analysis. The H2L ligand is coordinated to the CuII atom through three atoms (ONN), forming two fused chelate rings (Fig. 1), one five-membered (ITSC) and one six-membered (Px). \sch
The coordination around the CuII atom in (I) is square pyramidal, as in all CuII complexes with PxTSC. The apical Cu—O bond is significantly longer than the other bonds in the coordination sphere, as also observed in the other complexes. The different mode of coordination in the complexes involving PxTSC (ONS) compared with (I) (ONN) leads to a difference in bond lengths in the TSC fragment, associated with a different π-electron delocalization in the N2—C3—N4 fragment (the superscript numbering is shown in the scheme and is in accordance with IUPAC rules).
The N2—C3 and C3—N4 distances in complexes involving the TSC moiety are approximately equal (Bogdanović et al., 2001), whereas in complexes with ITSC-based ligands, and also in (I), the C3—N4 bond is significantly shorter (by about 0.08 Å) than the N2—C3 bond. As a consequence of the alkylation of the S atom, the C3—S bond is longer in (I) than in complexes involving PxTSC, whereas all bonds in the Px part of the ligand are of similar length in all complexes.
In the crystal structures reported to date, PxTSC has been coordinated as a neutral molecule only in the CuII complexes, whereas in the cited complexes of MnII, ZnII, CoIII and AuIII, it is coordinated as the monoanion. In (I), the ligand is coordinated as a neutral molecule and, as with PxTSC, the pyridoxal moiety of the ITSC is in the form of a zwitterion, formed by migration of the phenolic OH H atom to the pyridine N atom. Further, the ITSC moiety, as in isothiosemicarbazides and other isothiosemicarbazones (Bogdanović et al., 2001; Novaković et al., 2002), exists in its imido form.
The chelate rings in (I), with an interplanar angle of 3.2 (1)°, are almost coplanar and, together with the water molecule, form the equatorial coordination plane. All non-H atoms from the equatorial PxITSC ligands are approximately coplanar, except for the OH of the –CH2—OH group, which is almost orthogonally directed out of the coordination plane. The CuII atom is displaced from this plane towards the apically coordinated NO3 group by 0.202 (1) Å; the donor atom O8 is displaced from the plane by 2.586 (3) Å. The interplanar angle between the coordinated nitrate and the equatorial plane is 78.6 (1)°.
The complex cation has five hydrogen-bond donor groups (atoms N2, N3, N4, O1W and O2), whereas the two nitrate groups have six O atoms as hydrogen acceptors. Consequently, numerous strong intermolecular O—H···O and N—H···O hydrogen bonds, plus weak C—H···O bonds (Table 2) and intermolecular C—H···π interactions (see below), give a three-dimensional supramolecular structure.
The crystal packing consists of tapes of molecules parallel to the y axis, which form layers parallel to (103) and to the coordination plane (Fig. 2). Within the tapes, residues are connected by direct O1W—H···O2 hydrogen bonds and by hydrogen bonds that involve uncoordinated NO3 groups within the tapes. Although all the tapes are crystallographically equivalent, they are connected in two different ways. Tapes A and B are connected by hydrogen bonds (two per molecule) which involve coordinated N6O3 groups (situated between neighbouring A and B tapes), and tapes B and C are connected by weak C2—H···O5 hydrogen bonds.
The layers are interconnected in several ways: (i) via O2—H···O3 hydrogen bonds, (ii) by direct Cu—O8 bonds from the N6O3 groups to the CuII atoms from adjacent layers (the boundary of the reference layer is represented by dashed lines in Fig. 2), (iii) the coordinated nitrate is also hydrogen bonded to atoms N4, C10 and C8 of two tapes (A and B) in the adjacent layer, and (iv) by C—H···π interactions (Desiraju & Steiner, 1999; see below) with the neighbouring layers, in such a way that each molecule is involved in two intermolecular C7—H···π interactions, as donor and acceptor. In such a three-dimensional network of hydrogen bonds, each formula unit forms 18 intermolecular hydrogen bonds with its neighbours, with two additional hydrogen bonds between the complex cation and the NO3 anion within the formula unit (Table 2). It may be concluded that the presence of two NO3 groups in (I) is of crucial significance for the manifestation of the three-dimensional supramolecular crystal structure of this compound.
The intermolecular C—H···π interactions are such that the C7 methyl group lies above the pyridine ring of the neighbouring ligand at (-x, 1 - y, -z), so that one of the H atoms is directed to the centre of the pyridine ring. Geometric parameters for these C—H···π interactions are as follows: (i) the distance between the H atom bonded to atom C7 and the centre (Cg) of the C4/C5/C6/N4/C8/C9 aromatic ring is 2.69 (3) Å, (ii) the γ angle between the line connecting the H atom and Cg, and the normal to the C4/C5/C6/N4/C8/C9 plane, is 3(2)°, and (iii) the C7—H···Cg angle is 140 (2)°.