Actually the best way to determine if the NCS is N- or S-bound is using IR spectroscopy. The are two bands to be aware of the CN stretch and the C-S stretch. For a terminal N bound NCS these should be at 2050-2090 cm-1 for CN and 800-825 cm-1 for the C-S stretch. If the NCS is S bound it should be at 2100-2120 cm-1 for CN and 710-730 cm-1 for the C-S stretch. For bridging NCS the CN stretch is a real give away being usually greater than 2140 cm-1, the C-S stretch is in the middle about 780-790 cm-1. There's an excellent paper on this in the Journal of Chemical Education (doi: 10.1021/ed100284z).

Actually the best way to determine if the NCS is N- or S-bound is using IR spectroscopy. The are two bands to be aware of the CN stretch and the C-S stretch. For a terminal N bound NCS these should be at 2050-2090 cm-1 for CN and 800-825 cm-1 for the C-S stretch. If the NCS is S bound it should be at 2100-2120 cm-1 for CN and 710-730 cm-1 for the C-S stretch. For bridging NCS the CN stretch is a real give away being usually greater than 2140 cm-1, the C-S stretch is in the middle about 780-790 cm-1. There's an excellent paper on this in the Journal of Chemical Education (doi: 10.1021/ed100284z).

I checked the mentioned article, As you said it was excellent.Thanks for your nice answer...

In complex, the M-NCS group is linear or bent, while M-SCN group is always bent .CN -Streching frequency will lower in M-NCS. complex then M-SCN complex.In UV -Visible,also M-SCN band in case of Rh(SCN)6 will appear at19600 cm-1, whereas, in

Rh(NCS)6, it appears at around 34700cm-1, and also on the basis of M-NCS , Streching frequency and M-SCN, stretching frequency in IR, can easily explain interaction between metal and nitrogen of NCS and Metal and sulphur of SCN group.

For more details, you can refer ,Inorganic Electronic Spectroscopy by A.B.P.Lever and Infrared Spectra of Inorganic and Coordination Compounds by KAZUO NAKAMOTO,Second Edition,JOHN WILEY publication.juneja