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Electronic Supplementary Data

Synthesis, DNA binding properties and antibacterial activity of lanthanide complexes with 2-benzoylpyridine isonicotinoylhydrazone

B Moksharagni, M Rishitha & K Hussain Reddy*

Department of Chemistry, Sri Krishnadevaraya University, Ananthapuramu 515 003 (AP), India

Email: khussainreddy@yahoo.co.in

No. Contents Pg No.

1 Table S1 – Crystal data and structure refinement for BPINH ligand 2

2 Table S2 – Bond lengths [A] and angles [deg.] for BPINH 3

3 Table S3 – Electronic spectral data (cm-1) of lanthanide(III) complexes in solution state 4

4 Table S4 – Infrared spectral data (cm-1) for the BPINH ligand and its lanthanide(III)

complexes

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5 Table S5 – Cyclic voltametric data of lanthanide(III) complexes 5

6 Table S6 – Antibacterial activity of BPINH ligand and its lanthanide metal complexes 6

7 Fig. S1 – GC-MS spectrum of the BPINH ligand 7

8 Fig. S2 – Mass spectrum of [La(BPINH)2(NO3)](NO3)2 complex 8

9 Fig. S3 – Mass spectrum of [Ce(BPINH)2(NO3)](NO3)2 complex 9

10 Fig. S4 – An ORTEP diagram of the BPINH ligand 10

11 Fig. S5 – Close packing diagram of the BPINH ligand 10

12 Fig. S6 – Cyclic voltammograms of [Nd(BPINH)2(NO3)](NO3)2 complex at different scan

rates 25, 50, 75, 100 mVs-1

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13 Fig. S7 – Typical photographs of agar plates showing antibacterial activity of BPINH 12

and its lanthanide metal complexes

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Experimental: Details of biological studies 15

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Table S1 – Crystal data and structure refinement for BPINH ligand

Identification code Shelxl

Empirical formula C18H14N4O

Formula weight 302.33

Temperature 293(2) K

Wavelength 0.71073 A

Crystal system, space group Triclinic, P-1

Unit cell dimensions

a 8.2889(2) A

b 8.6674(2) A

c 11.05870(10) A

alpha 91.5970(10) deg

beta 93.967(2) deg

gama 109.5120(10) deg

Volume 745.97(3)A^3

Z, Calculated density 2,1.346 Mg/ m^3

Absorption coefficient 0.088mm^-1

F (000) 316

Crystal size 0.35 × 0.30 × 0.30mm

Theta range for data collection

2.50 to 24.99 deg

Reflection collected / unique 16088/16088 [R (int) = 0.0000]

Completeness to theta 24.99 99.6%

Absorption correction Equivalents

Se Semi- empirical from

Max. and min. transmission 0.9845 and 0.9687

Refinement method on F^2 Full matrix least – squares

Data / restraints / parameters 16088/ 1/214

Goodness – of - fit on F^2 1.073

R indices ( all data) R1 = 0.0800, wR = 0.1924

Extinction coefficient 0.067 (4)

Largest diff. peak and hole 0.312 and -0.262e.A^-3

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Table S2 – Bond lengths [A] and angles [deg.] for BPINH

C(1)-N(1) 1.3261(17) C(3)-C(4)-H(4) 120.3

C(1)-C(2) 1.3818(18) N(1)-C(5)-C(4) 123.81(13)

C(1)-H(1) 0.93 N(1)-C(5)-H(5) 118.1

C(2)-C(3) 1.3792(16) C(4)-C(5)-H(5) 118.1

C(2)-H(2) 0.93 O(1)-C(6)-N(2) 124.56(12)

C(3)-C(4) 1.3832(17) O(1)-C(6)-C(3) 122.11(11)

C(3)-C(6) 1.4980(16) N(2)-C(6)-C(3) 113.33(11)

C(4)-C(5) 1.3811(17) N(3)-C(7)-C(8) 127.67(11)

C(4)-H(4) 0.93 N(3)-C(7)-C(13) 114.17(11)

C(5)-N(1) 1.3290(17) C(8)-C(7)-C(13) 118.12(10)

C(5)-H(5) 0.93 N(4)-C(8)-C(9) 120.74(11)

C(6)-O(1) 1.2127(14) N(4)-C(8)-C(7) 117.97(10)

C(6)-N(2) 1.3582(16) C(9)-C(8)-C(7) 121.27(11)

C(7)-N(3) 1.2958(15) C(10)-C(9)-C(8) 119.65(12)

C(7)-C(8) 1.4886(16) C(10)-C(9)-H(9) 120.2

C(7)-C(13) 1.4932(16) C(8)-C(9)-H(9) 120.2

C(8)-N(4) 1.3508(14) C(11)-C(10)-C(9) 119.80(12)

C(8)-C(9) 1.3803(16) C(11)-C(10)-H(10) 120.1

C(9)-C(10) 1.3749(17) C(9)-C(10)-H(10) 120.1

C(9)-H(9) 0.93 C(10)-C(11)-C(12) 117.87(12)

C(10)-C(11) 1.3641(17) C(10)-C(11)-H(11) 121.1

C(10)-H(10) 0.93 C(12)-C(11)-H(11) 121.1

C(11)-C(12) 1.3697(17) N(4)-C(12)-C(11) 123.73(12)

C(11)-H(11) 0.93 N(4)-C(12)-H(12) 118.1

C(12)-N(4) 1.3360(15) C(11)-C(12)-H(12) 118.1

C(12)-H(12) 0.93 C(14)-C(13)-C(18) 118.64(11)

C(13)-C(14) 1.3826(17) C(14)-C(13)-C(7) 120.09(11)

C(13)-C(18) 1.3910(17) C(18)-C(13)-C(7) 121.27(11)

C(14)-C(15) 1.3759(17) C(15)-C(14)-C(13) 120.50(13)

C(14)-H(14) 0.93 C(15)-C(14)-H(14) 119.7

C(15)-C(16) 1.379(2) C(13)-C(14)-H(14) 119.7

C(15)-H(15) 0.93 C(14)-C(15)-C(16) 120.31(14)

C(16)-C(17) 1.369(2) C(14)-C(15)-H(15) 119.8

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Table S2 – Bond lengths [A] and angles [deg.] for BPINH

C(16)-H(16) 0.93 C(16)-C(15)-H(15) 119.8

C(17)-C(18) 1.3788(18) C(17)-C(16)-C(15) 119.78(13)

C(17)-H(17) 0.93 C(17)-C(16)-H(16) 120.1

C(18)-H(18) 0.93 C(15)-C(16)-H(16) 120.1

N(2)-N(3) 1.3669(14) C(16)-C(17)-C(18) 120.18(15)

N(2)-H(2A) 0.883(12) C(16)-C(17)-H(17) 119.9

N(1)-C(1)-C(2) 124.39(13) C(18)-C(17)-H(17) 119.9

N(1)-C(1)-H(1) 117.8 C(17)-C(18)-C(13) 120.53(13)

C(2)-C(1)-H(1) 117.8 C(17)-C(18)-H(18) 119.7

C(3)-C(2)-C(1) 119.04(13) C(13)-C(18)-H(18) 119.7

C(3)-C(2)-H(2) 120.5 C(1)-N(1)-C(5) 116.13(12)

C(1)-C(2)-H(2) 120.5 C(6)-N(2)-N(3) 120.51(11)

C(2)-C(3)-C(4) 117.16(12) C(6)-N(2)-H(2A) 123.8(9)

C(2)-C(3)-C(6) 118.20(11) N(3)-N(2)-H(2A) 115.4(9)

C(4)-C(3)-C(6) 124.64(11) C(7)-N(3)-N(2) 117.79(11)

C(5)-C(4)-C(3) 119.46(12) C(12)-N(4)-C(8) 118.21(11)

Table S3 – Electronic spectral data (cm-1) of lanthanide(III) complexes in solution state

Complex λmax (nm) ε† Band assignment

BPINH (ligand) 328 (30490) 6200 π - π*

[La(BPINH)2(NO3)](NO3)2 307 (32580) 373 (26870)

1860 1200

π – π* CT

[Ce(BPINH)2(NO3)](NO3)2 291 (34370) 378 (26460)

1388 1250

π - π* CT

[Nd(BPINH)2(NO3)](NO3)2 340 (29420) 381 (26250)

600 640

π – π* CT

[Pr(BPINH)2(NO3)](NO3)2 296 (33790) 376 (27030)

1600 1300

π – π* CT

[Sm(BPINH)2(NO3)](NO3)2 281 (35590) 373 (26810)

900 1180

π – π* CT

*Spectra of the complexes were recorded in DMF solvent. † Molar absorptivity Units, L. mol-1 cm-1.

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Table S4 – Infrared spectral data (cm-1) for the BPINH ligand and its lanthanide(III) complexes

Complex ν(O-H) ν(N-H) ν(C=O) ν(C=N) ν(NO3)

ν1 ν2 ν3 ν4 ν1-ν4

BPINH (ligand) … 3062 1690 1546 … … … … …

[La(BPINH)2(NO3)](NO3)2 3407 3068 1680 1566 1429 1062 843 1252 177

[Ce(BPINH)2(NO3)](NO3)2 3407 3303 1632 1561 1424 1056 804 1260 164

[Nd(BPINH)2(NO3)](NO3)2 … 3065 1687 1566 1456 1063 843 1287 169

[Pr(BPINH)2(NO3)](NO3)2 3396 3073 1632 1566 1435 1188 793 1298 137

[Sm(BPINH)2(NO3)](NO3)2 3440 3095 1632 1593 1462 1100 848 1287 175

Table S5 – Cyclic voltametric data of lanthanide(III) complexes

Complex BPINH (ligand)

Redox couple Epc V

Epa V

ΔE (mv)

E1/2 log Kca

-ΔG⁰

b

… -0.90 -0.70 200 -0.80 … …

[La(BPINH)2(NO3)](NO3)2 III/II -1.021 -0.799 221 0.912 0.152 872

[Ce(BPINH)2(NO3)](NO3)2 III/II -1.106 -0.994 112 1.052 0.299 1716

[Nd(BPINH)2(NO3)](NO3)2 III/II -1.082 -0.705 377 0.893 0.891 510

[Pr(BPINH)2(NO3)](NO3)2 III/II -1.052 -0.842 253 0.947 0.132 1452

[Sm(BPINH)2(NO3)](NO3) III/II -1.412 -1.204 208 1.308 0.161 924

alog Kc = 0.434 ZF/RT ∆Ep; b∆Go = - 2.303 RT log Kc

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Table S6 – Antibacterial activity of BPINH ligand and its lanthanide metal complexes

Name of the compound/ organism

Gram positive Gram negative

Basillus subtilis Staphylococcus aurous Escherichia coli Salmonella typhi

Zone of inhibition (mm) Zone of inhibition (mm) Zone of inhibition (mm) Zone of inhibition (mm)

A1 A2 A3 A4 A1 A2 A3 A4 A1 A2 A3 A4 A1 A2 A3 A4

INH 01 02 04 04 03 04 04 05 01 02 03 05 02 02 04 06

BPINH 08 13 14 18 18 20 28 25 09 11 15 16 07 14 20 25

La complex 14 18 20 26 10 20 24 30 20 26 30 36 17 23 26 30

Ce complex 09 16 34 44 12 20 26 38 20 24 28 34 18 22 29 32

Pr complex 10 08 32 38 04 28 34 38 08 30 36 42 08 29 33 38

Nd complex 08 28 32 34 05 26 31 38 12 26 30 32 10 21 28 38

Sm complex 16 24 32 36 15 26 28 36 11 08 24 28 10 25 26 29

Here A1- 2mg/1ml DMF, A2-4mg/1ml DMF, A3-6mg/1ml DMF, A4- 8mg/1ml; INH is abbreviation of isonicotinyl hydrazide

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Fig. S1 – GC-MS spectrum of the BPINH ligand.

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Fig. S2 – Mass spectrum of [La(BPINH)2(NO3)](NO3)2 complex.

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Fig. S3 – Mass spectrum of [Ce(BPINH)2(NO3)](NO3)2 complex.

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Fig. S4 – An ORTEP diagram of the BPINH ligand

Fig. S5 – Close packing diagram of the BPINH ligand.

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Fig. S6 – Cyclic voltammograms of [Nd(BPINH)2(NO3)](NO3)2 complex at different scan rates 25, 50, 75, 100 mVs-1

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Name of

the

compound

Name of the organism

B. subtilis S. aurous E. coli S. typhi Isoniazid

BPINH

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La- complex

Ce- complex

Nd- complex

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Fig. S7 – Typical photographs of agar plates showing antibacterial activity of BPINH 12 and its lanthanide metal complexes.

Pr- complex

Sm- complex

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Experimental details of biological studies

With different concentrations of 5 mg, 10mg, 20mg, 40 mg/ml of each compound was prepared in DMF

that had no influence on the microbial growth. The bacteria Staphylococcus aurous(MTCC-3160),

Bacillus subtilis (MTCC-441) are Gram positive Salmonella typhi (MTCC-735) and Escherichia coli

(MTCC-1652) are Gram negative culture of human pathogens were used to test the antibacterial activity

our compounds. Here DMF is tested as reference to assess extent of pure inhibition of our compounds.

Muller Hinton Agar plates were prepared by test microorganisms with MC Furland standards (1 to 5 x

108cfu/ml) were inoculated by the spread plate method. Filter paper discs approximately 6 mm in

diameter were soaked indifferent concentrations of tested compounds and placed in the previously

prepared agar plates. Each disc was pressed down to ensure complete contact with the agar surface and

distributed evenly so that they are no closer than 24 mm from each other, center to center. The agar plates

were then incubated at 37ºC for 24 h. After incubation, each plate was examined. The resulting zones of

inhibition were uniformly circular with a confluent lawn of growth. The standard bacterial strains were

acquired from the Microbial Type Culture Collection (MTCC), Institute of Microbial Technology

(IMTECH), and Chandigarh, India. The pure bacterial cultures were maintained on Nutrient Agar Media

(NAM).