metal-organic compounds
catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ2N1,O}copper(II)]-μ-dicyanamido-κ2N1:N5] monohydrate]
aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: seikweng@um.edu.my
The CuII atoms in the title coordination polymer, {[Cu(C13H11N4O)(C2N3)]·H2O}n, are N,N′,O-chelated by the deprotonated Schiff base ligands, and adjacent metal atoms are bridged by the dicyanamide ions, generating a polymeric chain that propagates along the b axis. The two independent metal atoms show a square-pyramidal N4O coordination. The two independent water molecules are disordered over two positions; each water molecule is a hydrogen-bond donor to a carbonyl O atom. Weak N—H⋯N hydrogen bonding is also observed.
Related literature
For the synthesis of the Schiff base ligand, see: de Lima et al. (2008). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536812035283/xu5601sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035283/xu5601Isup2.hkl
A methanol solution (20 ml) of 2-benzoylpyridine semicarbazone (0.240 g,1 mmol) (de Lima et al., 2008), copper acetate monohydrate (0.199 g, 1 mmol) and sodium dicyanamide (0.089 g, 1 mmol) was heated for 5 h. The dark green solid was collected and recrystallized from methanol.
Carbon-bound H-atoms were placed in calculated positions (C–H 0.93 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2U(C). The amino H-atoms were similarly treated (N–H 0.88 Å) and their temperature factors tied by a factor of 1.2 times.Omitted owing interference from the beam stop were (2 1 0), (0 0 2), (1 1 2), (1 1 4) and (1 2 1).
The presence of water was indicated by an infrared spectral measurement. The two independent water molecules are both disordered over two positions; the occupancy could not be refined, and was assumed as a 1:1 type of disorder. For one molecule, the disorder is such that two components are separated by about 2 Å, so that one hydrogen atom should be midway between two oxygen atoms. For the other, the two are separated by about 1 Å, so that one hydrogen atom should be occupying the site of the other oxygen atom. For both, hydrogen atoms were positioned on only one component oxygen atom so that each water molecule forms only one hydrogen bond. Furthermore, the hydrogen atoms were given full occupancy, i.e., hydrogen atoms were not placed on those atoms that do not engage in hydrogen bonding. The temperature factors of the primed atoms were set to those of the unprimed ones, and the anisotropic temperature factors were tightly restrained to be nearly isotropic.
Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).[Cu(C13H11N4O)(C2N3)]·H2O | F(000) = 3152 |
Mr = 386.86 | Dx = 1.477 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 9967 reflections |
a = 12.3996 (2) Å | θ = 2.7–26.5° |
b = 21.0115 (4) Å | µ = 1.28 mm−1 |
c = 26.7059 (5) Å | T = 293 K |
V = 6957.8 (2) Å3 | Prim, green |
Z = 16 | 0.40 × 0.30 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 7982 independent reflections |
Radiation source: fine-focus sealed tube | 5027 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→14 |
Tmin = 0.629, Tmax = 0.784 | k = −27→27 |
110924 measured reflections | l = −34→34 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0668P)2 + 9.8211P] where P = (Fo2 + 2Fc2)/3 |
7982 reflections | (Δ/σ)max = 0.001 |
457 parameters | Δρmax = 0.80 e Å−3 |
12 restraints | Δρmin = −0.46 e Å−3 |
[Cu(C13H11N4O)(C2N3)]·H2O | V = 6957.8 (2) Å3 |
Mr = 386.86 | Z = 16 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 12.3996 (2) Å | µ = 1.28 mm−1 |
b = 21.0115 (4) Å | T = 293 K |
c = 26.7059 (5) Å | 0.40 × 0.30 × 0.20 mm |
Bruker Kappa APEXII diffractometer | 7982 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5027 reflections with I > 2σ(I) |
Tmin = 0.629, Tmax = 0.784 | Rint = 0.054 |
110924 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 12 restraints |
wR(F2) = 0.166 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.80 e Å−3 |
7982 reflections | Δρmin = −0.46 e Å−3 |
457 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.74889 (4) | 0.32160 (2) | 0.591725 (16) | 0.03950 (15) | |
Cu2 | 0.51236 (4) | 0.06952 (2) | 0.406562 (15) | 0.03717 (15) | |
O1 | 0.6417 (2) | 0.38125 (13) | 0.61888 (10) | 0.0541 (8) | |
O2 | 0.6166 (2) | 0.13248 (12) | 0.38040 (10) | 0.0489 (7) | |
O1W | 0.4729 (16) | 0.4332 (10) | 0.5571 (8) | 0.269 (7) | 0.50 |
H1W1 | 0.5266 | 0.4228 | 0.5745 | 0.404* | |
H1W2 | 0.4808 | 0.4710 | 0.5475 | 0.404* | |
O2W | 0.8427 (16) | 0.1463 (9) | 0.4332 (7) | 0.234 (6) | 0.50 |
H2W1 | 0.7879 | 0.1336 | 0.4177 | 0.280* | |
H2W2 | 0.8367 | 0.1858 | 0.4373 | 0.280* | |
O1W' | 0.4691 (17) | 0.5292 (11) | 0.5296 (8) | 0.269 (7) | 0.50 |
O2W' | 0.7929 (19) | 0.1888 (10) | 0.4402 (8) | 0.234 (6) | 0.50 |
N1 | 0.8834 (3) | 0.26882 (16) | 0.58984 (12) | 0.0469 (8) | |
N2 | 0.7736 (3) | 0.31179 (14) | 0.66329 (11) | 0.0362 (7) | |
N3 | 0.7020 (3) | 0.33965 (15) | 0.69487 (11) | 0.0419 (7) | |
N4 | 0.5629 (3) | 0.41008 (19) | 0.69133 (14) | 0.0644 (11) | |
H41 | 0.5184 | 0.4351 | 0.6749 | 0.077* | |
H42 | 0.5586 | 0.4073 | 0.7241 | 0.077* | |
N5 | 0.3807 (3) | 0.01320 (15) | 0.40768 (10) | 0.0396 (7) | |
N6 | 0.4882 (2) | 0.06112 (14) | 0.33509 (11) | 0.0358 (7) | |
N7 | 0.5555 (3) | 0.09307 (15) | 0.30382 (11) | 0.0394 (7) | |
N8 | 0.6909 (3) | 0.16608 (17) | 0.30793 (13) | 0.0555 (9) | |
H81 | 0.7353 | 0.1909 | 0.3246 | 0.067* | |
H82 | 0.6936 | 0.1649 | 0.2750 | 0.067* | |
N9 | 0.6399 (4) | 0.2399 (2) | 0.58076 (14) | 0.0683 (12) | |
N10 | 0.5250 (4) | 0.1525 (2) | 0.55530 (14) | 0.0735 (13) | |
N11 | 0.5158 (3) | 0.09809 (17) | 0.47568 (12) | 0.0497 (8) | |
N12 | 0.7496 (3) | 0.35269 (18) | 0.52272 (13) | 0.0509 (9) | |
N13 | 0.7622 (4) | 0.3993 (2) | 0.43995 (14) | 0.0799 (15) | |
N14 | 0.8717 (3) | 0.48903 (18) | 0.41363 (13) | 0.0539 (9) | |
C1 | 0.9380 (4) | 0.2496 (2) | 0.54957 (17) | 0.0673 (14) | |
H1 | 0.9131 | 0.2611 | 0.5180 | 0.081* | |
C2 | 1.0297 (5) | 0.2132 (3) | 0.5532 (2) | 0.0814 (18) | |
H2 | 1.0658 | 0.1998 | 0.5246 | 0.098* | |
C3 | 1.0669 (5) | 0.1972 (2) | 0.6000 (2) | 0.0747 (16) | |
H3 | 1.1305 | 0.1741 | 0.6035 | 0.090* | |
C4 | 1.0095 (4) | 0.2154 (2) | 0.64189 (17) | 0.0546 (11) | |
H4 | 1.0326 | 0.2039 | 0.6737 | 0.066* | |
C5 | 0.9172 (3) | 0.25110 (17) | 0.63568 (14) | 0.0419 (9) | |
C6 | 0.8486 (3) | 0.27313 (16) | 0.67749 (13) | 0.0360 (8) | |
C7 | 0.8605 (3) | 0.24717 (17) | 0.72905 (13) | 0.0384 (8) | |
C8 | 0.7886 (4) | 0.2016 (2) | 0.74534 (17) | 0.0546 (11) | |
H8 | 0.7321 | 0.1890 | 0.7247 | 0.066* | |
C9 | 0.8002 (5) | 0.1745 (2) | 0.7924 (2) | 0.0696 (14) | |
H9 | 0.7519 | 0.1436 | 0.8032 | 0.084* | |
C10 | 0.8835 (5) | 0.1935 (3) | 0.82286 (19) | 0.0758 (16) | |
H10 | 0.8909 | 0.1758 | 0.8546 | 0.091* | |
C11 | 0.9552 (5) | 0.2379 (3) | 0.80682 (19) | 0.0831 (17) | |
H11 | 1.0119 | 0.2504 | 0.8275 | 0.100* | |
C12 | 0.9440 (4) | 0.2645 (2) | 0.76020 (17) | 0.0653 (13) | |
H12 | 0.9937 | 0.2947 | 0.7494 | 0.078* | |
C13 | 0.6370 (3) | 0.37643 (18) | 0.66655 (14) | 0.0427 (9) | |
C14 | 0.3281 (4) | −0.0096 (2) | 0.44722 (15) | 0.0527 (11) | |
H14 | 0.3484 | 0.0040 | 0.4790 | 0.063* | |
C15 | 0.2455 (4) | −0.0522 (3) | 0.44297 (19) | 0.0741 (16) | |
H15 | 0.2098 | −0.0671 | 0.4713 | 0.089* | |
C16 | 0.2161 (5) | −0.0725 (3) | 0.3959 (2) | 0.0832 (18) | |
H16 | 0.1602 | −0.1016 | 0.3920 | 0.100* | |
C17 | 0.2703 (4) | −0.0494 (2) | 0.35449 (17) | 0.0626 (13) | |
H17 | 0.2513 | −0.0627 | 0.3225 | 0.075* | |
C18 | 0.3520 (3) | −0.00673 (18) | 0.36126 (13) | 0.0403 (8) | |
C19 | 0.4168 (3) | 0.02092 (17) | 0.32052 (13) | 0.0368 (8) | |
C20 | 0.4045 (3) | −0.00038 (17) | 0.26745 (13) | 0.0369 (8) | |
C21 | 0.3209 (4) | 0.0214 (2) | 0.23788 (15) | 0.0562 (11) | |
H21 | 0.2697 | 0.0492 | 0.2508 | 0.067* | |
C22 | 0.3144 (4) | 0.0011 (3) | 0.18867 (17) | 0.0664 (13) | |
H22 | 0.2580 | 0.0154 | 0.1687 | 0.080* | |
C23 | 0.3888 (4) | −0.0392 (2) | 0.16898 (16) | 0.0644 (14) | |
H23 | 0.3844 | −0.0514 | 0.1356 | 0.077* | |
C24 | 0.4709 (4) | −0.0618 (2) | 0.19901 (19) | 0.0647 (14) | |
H24 | 0.5207 | −0.0906 | 0.1862 | 0.078* | |
C25 | 0.4789 (4) | −0.0417 (2) | 0.24776 (17) | 0.0521 (10) | |
H25 | 0.5354 | −0.0562 | 0.2676 | 0.062* | |
C26 | 0.6197 (3) | 0.13029 (17) | 0.33247 (14) | 0.0409 (9) | |
C27 | 0.5897 (4) | 0.1987 (2) | 0.56680 (14) | 0.0471 (10) | |
C28 | 0.5253 (3) | 0.12554 (19) | 0.51235 (14) | 0.0447 (9) | |
C29 | 0.7585 (3) | 0.3768 (2) | 0.48527 (16) | 0.0483 (10) | |
C30 | 0.8225 (3) | 0.4478 (2) | 0.42797 (13) | 0.0455 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0501 (3) | 0.0411 (3) | 0.0272 (2) | −0.00041 (19) | 0.00001 (19) | −0.00053 (18) |
Cu2 | 0.0476 (3) | 0.0394 (3) | 0.0245 (2) | −0.0023 (2) | −0.00390 (18) | −0.00204 (17) |
O1 | 0.070 (2) | 0.0597 (18) | 0.0327 (14) | 0.0195 (15) | −0.0050 (13) | 0.0012 (12) |
O2 | 0.0662 (19) | 0.0471 (16) | 0.0334 (14) | −0.0157 (14) | −0.0080 (13) | −0.0001 (11) |
O1W | 0.220 (9) | 0.323 (11) | 0.266 (10) | 0.038 (8) | −0.025 (8) | −0.002 (8) |
O2W | 0.247 (10) | 0.253 (11) | 0.201 (8) | 0.037 (8) | −0.069 (8) | −0.052 (8) |
O1W' | 0.220 (9) | 0.323 (11) | 0.266 (10) | 0.038 (8) | −0.025 (8) | −0.002 (8) |
O2W' | 0.247 (10) | 0.253 (11) | 0.201 (8) | 0.037 (8) | −0.069 (8) | −0.052 (8) |
N1 | 0.059 (2) | 0.0457 (18) | 0.0354 (17) | 0.0038 (16) | 0.0107 (15) | 0.0022 (14) |
N2 | 0.0452 (18) | 0.0354 (16) | 0.0281 (14) | 0.0019 (14) | −0.0007 (13) | −0.0020 (12) |
N3 | 0.046 (2) | 0.0472 (18) | 0.0323 (16) | 0.0081 (15) | −0.0028 (14) | −0.0045 (14) |
N4 | 0.075 (3) | 0.078 (3) | 0.0401 (19) | 0.036 (2) | 0.0021 (18) | 0.0022 (18) |
N5 | 0.0458 (19) | 0.0448 (17) | 0.0282 (15) | −0.0011 (14) | 0.0010 (13) | 0.0004 (13) |
N6 | 0.0418 (18) | 0.0395 (17) | 0.0261 (14) | −0.0010 (13) | −0.0031 (12) | −0.0002 (12) |
N7 | 0.0487 (19) | 0.0429 (17) | 0.0266 (14) | −0.0060 (15) | −0.0046 (13) | 0.0028 (13) |
N8 | 0.070 (3) | 0.054 (2) | 0.0427 (19) | −0.0245 (19) | −0.0014 (17) | 0.0026 (16) |
N9 | 0.090 (3) | 0.063 (2) | 0.052 (2) | −0.027 (2) | 0.001 (2) | −0.0150 (19) |
N10 | 0.097 (3) | 0.082 (3) | 0.041 (2) | −0.045 (3) | 0.021 (2) | −0.029 (2) |
N11 | 0.062 (2) | 0.055 (2) | 0.0321 (17) | −0.0067 (17) | −0.0025 (15) | −0.0054 (15) |
N12 | 0.058 (2) | 0.056 (2) | 0.0389 (19) | −0.0099 (17) | 0.0001 (16) | 0.0063 (16) |
N13 | 0.100 (3) | 0.096 (3) | 0.043 (2) | −0.056 (3) | −0.028 (2) | 0.030 (2) |
N14 | 0.061 (2) | 0.058 (2) | 0.0425 (19) | −0.0145 (19) | −0.0045 (17) | 0.0155 (16) |
C1 | 0.089 (4) | 0.068 (3) | 0.044 (2) | 0.022 (3) | 0.027 (2) | 0.007 (2) |
C2 | 0.101 (4) | 0.084 (4) | 0.060 (3) | 0.041 (3) | 0.036 (3) | 0.007 (3) |
C3 | 0.079 (4) | 0.069 (3) | 0.076 (4) | 0.035 (3) | 0.031 (3) | 0.011 (3) |
C4 | 0.062 (3) | 0.051 (2) | 0.051 (3) | 0.012 (2) | 0.007 (2) | 0.009 (2) |
C5 | 0.050 (2) | 0.0348 (19) | 0.041 (2) | 0.0007 (17) | 0.0088 (17) | 0.0028 (15) |
C6 | 0.043 (2) | 0.0308 (17) | 0.0345 (18) | −0.0025 (16) | 0.0010 (15) | 0.0002 (14) |
C7 | 0.043 (2) | 0.0394 (19) | 0.0326 (18) | 0.0044 (16) | 0.0035 (16) | 0.0042 (15) |
C8 | 0.062 (3) | 0.047 (2) | 0.056 (3) | −0.007 (2) | 0.004 (2) | 0.005 (2) |
C9 | 0.079 (4) | 0.056 (3) | 0.074 (3) | −0.002 (3) | 0.023 (3) | 0.020 (3) |
C10 | 0.088 (4) | 0.089 (4) | 0.051 (3) | 0.012 (3) | 0.002 (3) | 0.034 (3) |
C11 | 0.081 (4) | 0.121 (5) | 0.048 (3) | −0.013 (4) | −0.019 (3) | 0.025 (3) |
C12 | 0.064 (3) | 0.085 (3) | 0.047 (2) | −0.025 (3) | −0.011 (2) | 0.016 (2) |
C13 | 0.051 (2) | 0.042 (2) | 0.035 (2) | 0.0092 (18) | −0.0012 (17) | −0.0034 (16) |
C14 | 0.059 (3) | 0.065 (3) | 0.033 (2) | −0.002 (2) | 0.0065 (19) | 0.0007 (18) |
C15 | 0.066 (3) | 0.106 (4) | 0.051 (3) | −0.023 (3) | 0.011 (2) | 0.014 (3) |
C16 | 0.071 (4) | 0.118 (5) | 0.061 (3) | −0.043 (3) | −0.003 (3) | 0.013 (3) |
C17 | 0.064 (3) | 0.082 (3) | 0.042 (2) | −0.032 (3) | −0.006 (2) | 0.003 (2) |
C18 | 0.042 (2) | 0.048 (2) | 0.0305 (18) | −0.0046 (17) | −0.0027 (15) | −0.0003 (15) |
C19 | 0.042 (2) | 0.0369 (19) | 0.0314 (18) | −0.0001 (16) | −0.0041 (15) | 0.0008 (14) |
C20 | 0.042 (2) | 0.0375 (19) | 0.0307 (18) | −0.0070 (16) | −0.0029 (15) | −0.0030 (14) |
C21 | 0.059 (3) | 0.071 (3) | 0.038 (2) | 0.011 (2) | −0.011 (2) | −0.008 (2) |
C22 | 0.076 (3) | 0.084 (3) | 0.039 (2) | −0.002 (3) | −0.023 (2) | −0.008 (2) |
C23 | 0.086 (4) | 0.074 (3) | 0.034 (2) | −0.028 (3) | 0.004 (2) | −0.019 (2) |
C24 | 0.071 (3) | 0.055 (3) | 0.069 (3) | −0.007 (2) | 0.020 (3) | −0.032 (2) |
C25 | 0.053 (3) | 0.054 (3) | 0.049 (2) | −0.001 (2) | −0.003 (2) | −0.007 (2) |
C26 | 0.050 (2) | 0.037 (2) | 0.0356 (19) | 0.0002 (17) | −0.0006 (17) | 0.0036 (16) |
C27 | 0.060 (3) | 0.053 (2) | 0.0280 (18) | −0.007 (2) | 0.0055 (18) | −0.0048 (17) |
C28 | 0.052 (2) | 0.049 (2) | 0.033 (2) | −0.0117 (19) | 0.0037 (17) | −0.0062 (17) |
C29 | 0.047 (2) | 0.054 (2) | 0.043 (2) | −0.0148 (19) | −0.0113 (18) | 0.0046 (19) |
C30 | 0.050 (2) | 0.062 (3) | 0.0252 (18) | −0.008 (2) | −0.0133 (17) | 0.0066 (17) |
Cu1—N2 | 1.946 (3) | C1—H1 | 0.9300 |
Cu1—N12 | 1.955 (3) | C2—C3 | 1.376 (7) |
Cu1—O1 | 1.966 (3) | C2—H2 | 0.9300 |
Cu1—N1 | 2.004 (4) | C3—C4 | 1.380 (6) |
Cu1—N9 | 2.205 (4) | C3—H3 | 0.9300 |
Cu2—N6 | 1.940 (3) | C4—C5 | 1.377 (6) |
Cu2—N11 | 1.941 (3) | C4—H4 | 0.9300 |
Cu2—O2 | 1.977 (3) | C5—C6 | 1.479 (5) |
Cu2—N5 | 2.016 (3) | C6—C7 | 1.488 (5) |
Cu2—N14i | 2.228 (4) | C7—C8 | 1.378 (6) |
O1—C13 | 1.278 (4) | C7—C12 | 1.378 (6) |
O2—C26 | 1.281 (4) | C8—C9 | 1.387 (7) |
O1W—H1W1 | 0.8401 | C8—H8 | 0.9300 |
O1W—H1W2 | 0.8401 | C9—C10 | 1.375 (8) |
O2W—H2W1 | 0.8400 | C9—H9 | 0.9300 |
O2W—H2W2 | 0.8400 | C10—C11 | 1.359 (8) |
N1—C1 | 1.333 (5) | C10—H10 | 0.9300 |
N1—C5 | 1.346 (5) | C11—C12 | 1.371 (6) |
N2—C6 | 1.292 (5) | C11—H11 | 0.9300 |
N2—N3 | 1.358 (4) | C12—H12 | 0.9300 |
N3—C13 | 1.349 (5) | C14—C15 | 1.364 (7) |
N4—C13 | 1.334 (5) | C14—H14 | 0.9300 |
N4—H41 | 0.8800 | C15—C16 | 1.377 (7) |
N4—H42 | 0.8800 | C15—H15 | 0.9300 |
N5—C14 | 1.331 (5) | C16—C17 | 1.383 (7) |
N5—C18 | 1.356 (4) | C16—H16 | 0.9300 |
N6—C19 | 1.284 (5) | C17—C18 | 1.365 (6) |
N6—N7 | 1.358 (4) | C17—H17 | 0.9300 |
N7—C26 | 1.353 (5) | C18—C19 | 1.472 (5) |
N8—C26 | 1.332 (5) | C19—C20 | 1.494 (5) |
N8—H81 | 0.8800 | C20—C25 | 1.372 (6) |
N8—H82 | 0.8800 | C20—C21 | 1.381 (6) |
N9—C27 | 1.129 (5) | C21—C22 | 1.384 (6) |
N10—C28 | 1.280 (5) | C21—H21 | 0.9300 |
N10—C27 | 1.296 (6) | C22—C23 | 1.358 (7) |
N11—C28 | 1.143 (5) | C22—H22 | 0.9300 |
N12—C29 | 1.127 (5) | C23—C24 | 1.381 (7) |
N13—C29 | 1.300 (5) | C23—H23 | 0.9300 |
N13—C30 | 1.303 (6) | C24—C25 | 1.372 (6) |
N14—C30 | 1.127 (5) | C24—H24 | 0.9300 |
N14—Cu2ii | 2.228 (4) | C25—H25 | 0.9300 |
C1—C2 | 1.372 (7) | ||
N2—Cu1—N12 | 163.76 (14) | N2—C6—C7 | 125.0 (3) |
N2—Cu1—O1 | 79.14 (12) | C5—C6—C7 | 121.8 (3) |
N12—Cu1—O1 | 97.91 (14) | C8—C7—C12 | 118.6 (4) |
N2—Cu1—N1 | 80.51 (13) | C8—C7—C6 | 118.8 (4) |
N12—Cu1—N1 | 99.07 (14) | C12—C7—C6 | 122.4 (4) |
O1—Cu1—N1 | 157.69 (13) | C7—C8—C9 | 120.3 (5) |
N2—Cu1—N9 | 98.30 (14) | C7—C8—H8 | 119.9 |
N12—Cu1—N9 | 97.91 (15) | C9—C8—H8 | 119.9 |
O1—Cu1—N9 | 97.52 (15) | C10—C9—C8 | 119.6 (5) |
N1—Cu1—N9 | 94.37 (16) | C10—C9—H9 | 120.2 |
N6—Cu2—N11 | 165.22 (14) | C8—C9—H9 | 120.2 |
N6—Cu2—O2 | 79.29 (12) | C11—C10—C9 | 120.3 (4) |
N11—Cu2—O2 | 96.58 (13) | C11—C10—H10 | 119.8 |
N6—Cu2—N5 | 80.58 (12) | C9—C10—H10 | 119.8 |
N11—Cu2—N5 | 100.68 (13) | C10—C11—C12 | 120.0 (5) |
O2—Cu2—N5 | 158.01 (11) | C10—C11—H11 | 120.0 |
N6—Cu2—N14i | 96.54 (13) | C12—C11—H11 | 120.0 |
N11—Cu2—N14i | 98.04 (14) | C11—C12—C7 | 121.1 (4) |
O2—Cu2—N14i | 96.66 (13) | C11—C12—H12 | 119.5 |
N5—Cu2—N14i | 94.34 (14) | C7—C12—H12 | 119.5 |
C13—O1—Cu1 | 110.4 (2) | O1—C13—N4 | 118.9 (4) |
C26—O2—Cu2 | 110.4 (2) | O1—C13—N3 | 125.2 (3) |
H1W1—O1W—H1W2 | 108.7 | N4—C13—N3 | 115.9 (3) |
H2W1—O2W—H2W2 | 107.9 | N5—C14—C15 | 122.6 (4) |
C1—N1—C5 | 119.4 (4) | N5—C14—H14 | 118.7 |
C1—N1—Cu1 | 127.6 (3) | C15—C14—H14 | 118.7 |
C5—N1—Cu1 | 112.9 (3) | C14—C15—C16 | 118.6 (4) |
C6—N2—N3 | 124.0 (3) | C14—C15—H15 | 120.7 |
C6—N2—Cu1 | 117.9 (2) | C16—C15—H15 | 120.7 |
N3—N2—Cu1 | 117.5 (2) | C15—C16—C17 | 119.5 (5) |
C13—N3—N2 | 106.8 (3) | C15—C16—H16 | 120.3 |
C13—N4—H41 | 120.0 | C17—C16—H16 | 120.3 |
C13—N4—H42 | 120.0 | C18—C17—C16 | 119.1 (4) |
H41—N4—H42 | 120.0 | C18—C17—H17 | 120.5 |
C14—N5—C18 | 119.1 (4) | C16—C17—H17 | 120.5 |
C14—N5—Cu2 | 128.3 (3) | N5—C18—C17 | 121.2 (4) |
C18—N5—Cu2 | 112.3 (2) | N5—C18—C19 | 114.2 (3) |
C19—N6—N7 | 124.2 (3) | C17—C18—C19 | 124.5 (3) |
C19—N6—Cu2 | 117.7 (2) | N6—C19—C18 | 114.3 (3) |
N7—N6—Cu2 | 117.7 (2) | N6—C19—C20 | 123.7 (3) |
C26—N7—N6 | 107.4 (3) | C18—C19—C20 | 121.8 (3) |
C26—N8—H81 | 120.0 | C25—C20—C21 | 119.7 (4) |
C26—N8—H82 | 120.0 | C25—C20—C19 | 119.0 (3) |
H81—N8—H82 | 120.0 | C21—C20—C19 | 121.4 (3) |
C27—N9—Cu1 | 168.1 (4) | C20—C21—C22 | 119.0 (4) |
C28—N10—C27 | 122.9 (4) | C20—C21—H21 | 120.5 |
C28—N11—Cu2 | 166.7 (3) | C22—C21—H21 | 120.5 |
C29—N12—Cu1 | 170.9 (4) | C23—C22—C21 | 121.4 (5) |
C29—N13—C30 | 122.2 (4) | C23—C22—H22 | 119.3 |
C30—N14—Cu2ii | 164.2 (3) | C21—C22—H22 | 119.3 |
N1—C1—C2 | 122.2 (5) | C22—C23—C24 | 119.4 (4) |
N1—C1—H1 | 118.9 | C22—C23—H23 | 120.3 |
C2—C1—H1 | 118.9 | C24—C23—H23 | 120.3 |
C1—C2—C3 | 118.5 (4) | C25—C24—C23 | 119.9 (4) |
C1—C2—H2 | 120.7 | C25—C24—H24 | 120.1 |
C3—C2—H2 | 120.7 | C23—C24—H24 | 120.1 |
C2—C3—C4 | 119.7 (5) | C20—C25—C24 | 120.7 (4) |
C2—C3—H3 | 120.1 | C20—C25—H25 | 119.7 |
C4—C3—H3 | 120.1 | C24—C25—H25 | 119.7 |
C5—C4—C3 | 118.8 (4) | O2—C26—N8 | 119.4 (4) |
C5—C4—H4 | 120.6 | O2—C26—N7 | 124.6 (3) |
C3—C4—H4 | 120.6 | N8—C26—N7 | 116.0 (3) |
N1—C5—C4 | 121.2 (4) | N9—C27—N10 | 173.3 (5) |
N1—C5—C6 | 114.9 (3) | N11—C28—N10 | 172.7 (5) |
C4—C5—C6 | 123.9 (4) | N12—C29—N13 | 173.4 (5) |
N2—C6—C5 | 112.9 (3) | N14—C30—N13 | 174.2 (4) |
N2—Cu1—O1—C13 | −7.3 (3) | C3—C4—C5—N1 | −0.8 (7) |
N12—Cu1—O1—C13 | −171.1 (3) | C3—C4—C5—C6 | 179.6 (4) |
N1—Cu1—O1—C13 | −31.8 (5) | N3—N2—C6—C5 | −178.4 (3) |
N9—Cu1—O1—C13 | 89.8 (3) | Cu1—N2—C6—C5 | 10.5 (4) |
N6—Cu2—O2—C26 | −5.6 (3) | N3—N2—C6—C7 | 7.6 (6) |
N11—Cu2—O2—C26 | −171.2 (3) | Cu1—N2—C6—C7 | −163.6 (3) |
N5—Cu2—O2—C26 | −29.6 (5) | N1—C5—C6—N2 | −7.2 (5) |
N14i—Cu2—O2—C26 | 89.9 (3) | C4—C5—C6—N2 | 172.5 (4) |
N2—Cu1—N1—C1 | −178.0 (4) | N1—C5—C6—C7 | 167.1 (3) |
N12—Cu1—N1—C1 | −14.5 (4) | C4—C5—C6—C7 | −13.2 (6) |
O1—Cu1—N1—C1 | −153.6 (4) | N2—C6—C7—C8 | 72.8 (5) |
N9—Cu1—N1—C1 | 84.3 (4) | C5—C6—C7—C8 | −100.8 (5) |
N2—Cu1—N1—C5 | 3.5 (3) | N2—C6—C7—C12 | −110.7 (5) |
N12—Cu1—N1—C5 | 167.1 (3) | C5—C6—C7—C12 | 75.7 (5) |
O1—Cu1—N1—C5 | 28.0 (5) | C12—C7—C8—C9 | 0.6 (7) |
N9—Cu1—N1—C5 | −94.2 (3) | C6—C7—C8—C9 | 177.3 (4) |
N12—Cu1—N2—C6 | −98.0 (5) | C7—C8—C9—C10 | 0.3 (7) |
O1—Cu1—N2—C6 | −178.9 (3) | C8—C9—C10—C11 | −0.9 (9) |
N1—Cu1—N2—C6 | −8.1 (3) | C9—C10—C11—C12 | 0.6 (9) |
N9—Cu1—N2—C6 | 84.9 (3) | C10—C11—C12—C7 | 0.4 (9) |
N12—Cu1—N2—N3 | 90.3 (6) | C8—C7—C12—C11 | −1.0 (8) |
O1—Cu1—N2—N3 | 9.4 (3) | C6—C7—C12—C11 | −177.5 (5) |
N1—Cu1—N2—N3 | −179.8 (3) | Cu1—O1—C13—N4 | −175.2 (3) |
N9—Cu1—N2—N3 | −86.8 (3) | Cu1—O1—C13—N3 | 5.1 (5) |
C6—N2—N3—C13 | 180.0 (3) | N2—N3—C13—O1 | 2.2 (5) |
Cu1—N2—N3—C13 | −8.9 (4) | N2—N3—C13—N4 | −177.5 (4) |
N6—Cu2—N5—C14 | −179.3 (4) | C18—N5—C14—C15 | −0.4 (7) |
N11—Cu2—N5—C14 | −14.2 (4) | Cu2—N5—C14—C15 | −173.8 (4) |
O2—Cu2—N5—C14 | −155.3 (3) | N5—C14—C15—C16 | 0.4 (9) |
N14i—Cu2—N5—C14 | 84.8 (4) | C14—C15—C16—C17 | −0.2 (10) |
N6—Cu2—N5—C18 | 6.9 (3) | C15—C16—C17—C18 | 0.0 (9) |
N11—Cu2—N5—C18 | 172.0 (3) | C14—N5—C18—C17 | 0.2 (6) |
O2—Cu2—N5—C18 | 30.9 (5) | Cu2—N5—C18—C17 | 174.7 (4) |
N14i—Cu2—N5—C18 | −89.0 (3) | C14—N5—C18—C19 | −179.1 (4) |
N11—Cu2—N6—C19 | −104.8 (6) | Cu2—N5—C18—C19 | −4.7 (4) |
O2—Cu2—N6—C19 | −179.8 (3) | C16—C17—C18—N5 | 0.0 (8) |
N5—Cu2—N6—C19 | −8.7 (3) | C16—C17—C18—C19 | 179.2 (5) |
N14i—Cu2—N6—C19 | 84.7 (3) | N7—N6—C19—C18 | −178.9 (3) |
N11—Cu2—N6—N7 | 82.0 (6) | Cu2—N6—C19—C18 | 8.4 (4) |
O2—Cu2—N6—N7 | 7.0 (2) | N7—N6—C19—C20 | 5.5 (6) |
N5—Cu2—N6—N7 | 178.1 (3) | Cu2—N6—C19—C20 | −167.3 (3) |
N14i—Cu2—N6—N7 | −88.5 (3) | N5—C18—C19—N6 | −2.1 (5) |
C19—N6—N7—C26 | −179.3 (3) | C17—C18—C19—N6 | 178.6 (4) |
Cu2—N6—N7—C26 | −6.6 (4) | N5—C18—C19—C20 | 173.7 (3) |
N2—Cu1—N9—C27 | −157 (2) | C17—C18—C19—C20 | −5.7 (6) |
N12—Cu1—N9—C27 | 24 (2) | N6—C19—C20—C25 | 74.0 (5) |
O1—Cu1—N9—C27 | 123 (2) | C18—C19—C20—C25 | −101.3 (4) |
N1—Cu1—N9—C27 | −76 (2) | N6—C19—C20—C21 | −105.0 (5) |
N6—Cu2—N11—C28 | −52.0 (19) | C18—C19—C20—C21 | 79.7 (5) |
O2—Cu2—N11—C28 | 20.8 (16) | C25—C20—C21—C22 | −0.3 (7) |
N5—Cu2—N11—C28 | −145.5 (16) | C19—C20—C21—C22 | 178.7 (4) |
N14i—Cu2—N11—C28 | 118.5 (16) | C20—C21—C22—C23 | −0.5 (8) |
C5—N1—C1—C2 | −1.6 (8) | C21—C22—C23—C24 | 1.8 (8) |
Cu1—N1—C1—C2 | −179.9 (4) | C22—C23—C24—C25 | −2.3 (7) |
N1—C1—C2—C3 | −1.0 (9) | C21—C20—C25—C24 | −0.3 (6) |
C1—C2—C3—C4 | 2.7 (9) | C19—C20—C25—C24 | −179.3 (4) |
C2—C3—C4—C5 | −1.8 (8) | C23—C24—C25—C20 | 1.6 (7) |
C1—N1—C5—C4 | 2.5 (6) | Cu2—O2—C26—N8 | −175.3 (3) |
Cu1—N1—C5—C4 | −179.0 (3) | Cu2—O2—C26—N7 | 4.0 (5) |
C1—N1—C5—C6 | −177.8 (4) | N6—N7—C26—O2 | 1.5 (5) |
Cu1—N1—C5—C6 | 0.7 (4) | N6—N7—C26—N8 | −179.2 (3) |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+3/2, y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H42···N7iii | 0.88 | 2.13 | 3.006 (5) | 176 |
N8—H82···N3iv | 0.88 | 2.15 | 3.025 (5) | 179 |
O1w—H1w1···O1 | 0.84 | 2.05 | 2.88 (2) | 169 |
O2w—H2w1···O2 | 0.84 | 2.34 | 3.151 (19) | 161 |
Symmetry codes: (iii) x, −y+1/2, z+1/2; (iv) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C13H11N4O)(C2N3)]·H2O |
Mr | 386.86 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 12.3996 (2), 21.0115 (4), 26.7059 (5) |
V (Å3) | 6957.8 (2) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 1.28 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker Kappa APEXII diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.629, 0.784 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 110924, 7982, 5027 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.166, 1.12 |
No. of reflections | 7982 |
No. of parameters | 457 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.46 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H42···N7i | 0.88 | 2.13 | 3.006 (5) | 175.6 |
N8—H82···N3ii | 0.88 | 2.15 | 3.025 (5) | 178.9 |
O1w—H1w1···O1 | 0.84 | 2.05 | 2.88 (2) | 168.9 |
O2w—H2w1···O2 | 0.84 | 2.34 | 3.151 (19) | 161.0 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
Acknowledgements
RJK thanks the University Grants Commission (India) for a Junior Research Fellowship. We thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, for the diffraction measurements. We also thank the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.
References
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Lima, D. F. de, Pérez-Rebolledo, A., Ellena, J. & Beraldo, H. (2008). Acta Cryst. E64, o177. Web of Science CSD CrossRef IUCr Journals Google Scholar
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2-Benzoylpyridine semicarbazone (de Lima et al., 2008) is a Schiff base that is capable of N,N',O-chelation to transition metal ions. This feature has been documented a copper(II) dichloride adduct; in this, the Schiff base exists as a neutral molecule (Peŕez-Rebolledo et al., 2006). However, the CuII atom in the coordination polymer, [Cu(C2N3)(C13H11N4O).H2O]n (I), is N,N',O-chelated instead by the deprotonated Schiff base (Fig. 1). Adjacent metal atoms are bridged by the dicyanamide ion to generate a chain that propagates along the b axis of the orthorhombic unit cell (Fig. 2). The two independent metal atoms show square pyramidal coordination. The two independent water molecules are disordered over two positions; each water molecule is a hydrogen-bond donor to a carbonyl O atom.