Q.Indicate the complex ion which shows geometrical isomerism.
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Coordination Compound Nomenclature: From Intuition to Precision
Imagine you're naming a person. You'd say "Ravi Sharma" — family name first, then given name. Coordination compounds have a similar logic, but the "family name" is the metal, and the "given names" are the groups attached to it. The rules are just a systematic way of writing that name so any chemist anywhere can draw the exact structure from it.
The Core Idea
A coordination compound has a central metal ion surrounded by molecules or ions called ligands. Think of the metal as the nucleus and ligands as planets orbiting it. The entire assembly (metal + ligands) is called the coordination sphere, and it's written inside square brackets: [Co(NH₃)₆]Cl₃.
The nomenclature rules tell you:
- What order to list things
- How to name each ligand
- How to indicate the metal's oxidation state
- How to handle the counter-ions outside the brackets
The Rules, Step by Step
1. Cation before anion (just like NaCl is sodium chloride)
If the complex ion is positive, it's named first. If it's negative, it's named last. Simple.
2. Within the coordination sphere: ligands first, then metal
This is the big rule. Ligands are named before the metal, in alphabetical order (ignoring prefixes like di-, tri-).
Alphabetical order is based on the ligand's name, not its formula. So NH₃ (ammine) comes before H₂O (aqua), even though N comes after H in the alphabet.
3. Naming ligands
| Ligand type | Name | Example |
|---|---|---|
| Neutral molecule (NH₃) | ammine | [Co(NH₃)₆]³⁺ → hexaamminecobalt(III) |
| Neutral molecule (H₂O) | aqua | [Cu(H₂O)₄]²⁺ → tetraaquacopper(II) |
| Neutral molecule (CO) | carbonyl | [Ni(CO)₄] → tetracarbonylnickel(0) |
| Negative ion (Cl⁻) | chloro | [PtCl₆]²⁻ → hexachloroplatinate(IV) |
| Negative ion (CN⁻) | cyano | [Fe(CN)₆]⁴⁻ → hexacyanoferrate(II) |
| Negative ion (OH⁻) | hydroxo | [Al(OH)₄]⁻ → tetrahydroxoaluminate(III) |
ammine (with two m's) is for NH₃ as a ligand. amine (one m) is for organic compounds like ethylamine. Don't mix them up — exam setters love this trap.
4. Prefixes for multiple ligands
Use Greek prefixes: di-, tri-, tetra-, penta-, hexa-, hepta-, octa-.
If the ligand name already contains a number (like ethylenediamine), use bis-, tris-, tetrakis- instead.
[Co(en)₃]³⁺ is tris(ethylenediamine)cobalt(III), not triethylenediaminecobalt(III). The parentheses around the ligand name are mandatory when using bis/tris/tetrakis.
5. Oxidation state of the metal
Write it in Roman numerals in parentheses right after the metal name. No space.
[Fe(CN)₆]³⁻ → hexacyanoferrate(III) (iron is in +3 state)
6. If the complex is an anion, change the metal's ending
| Metal | Anionic form |
|---|---|
| Cobalt | cobaltate |
| Copper | cuprate |
| Iron | ferrate |
| Nickel | nickelate |
| Platinum | platinate |
| Zinc | zincate |
General pattern:
[M(L)ₙ]Xₘ → cation name = [prefix-ligands]metal(oxidation state)
anion name = [prefix-ligands]metalate(oxidation state)
Worked Examples
Example 1: K₃[Fe(CN)₆]
- Cation: potassium (K⁺)
- Complex anion:
[Fe(CN)₆]³⁻ - Ligands: 6 cyano → hexacyano
- Metal: iron → ferrate (because it's an anion)
- Oxidation state: Fe is +3 (since 6 CN⁻ = -6, total charge -3, so Fe must be +3)
- Answer: Potassium hexacyanoferrate(III)
Example 2: [Co(NH₃)₅Cl]Cl₂
- Cation:
[Co(NH₃)₅Cl]²⁺ - Ligands: 5 ammine + 1 chloro → alphabetical: ammine before chloro → pentaamminechloro
- Metal: cobalt
- Oxidation state: Co is +3 (5 NH₃ neutral, 1 Cl⁻ = -1, total +2, so Co = +3) …
Why this formula?
Coordination Compound Nomenclature: Why the Rules Work
Coordination compound nomenclature isn't about a single formula — it's a system of rules built on a few core principles. Let's understand the why behind each major rule, so you never have to memorise blindly.
1. The Central Idea: Ligands as "Guests" Around a Metal "Host"
A coordination compound has a central metal atom/ion surrounded by ligands (molecules or ions that donate electron pairs). The naming reflects this relationship:
- Cation first, then anion (like normal ionic compounds)
- Ligands named before the metal (because they modify the metal's identity)
Why?
In chemistry, we name the more electropositive part first (cation). The metal-ligand complex is treated as a single unit — the ligands are "attached" to the metal, so they come first in the complex name.
2. Key Rule: Ligand Order — Alphabetical, Not by Charge
Rule: Ligands are named in alphabetical order (ignoring prefixes like di-, tri-).
Why?
- If we ordered by charge or size, the name would change every time a ligand is replaced.
- Alphabetical order is universal and unambiguous — it doesn't depend on the metal or oxidation state.
- Example:
[Co(NH₃)₄Cl₂]⁺is tetraamminedichlorocobalt(III) — "ammine" (a) before "chloro" (c).
3. Oxidation State: Why Roman Numerals?
Rule: The metal's oxidation state is written in Roman numerals in parentheses after the metal name.
Why?
- The oxidation state tells you the charge on the metal after accounting for ligand charges.
- Roman numerals avoid confusion with Arabic numbers (which are used for ligand counts).
- Example:
[Fe(CN)₆]³⁻→ hexacyanoferrate(III) — the iron is Fe³⁺, not Fe²⁺.
Derivation of oxidation state:
Let the complex charge = Q, ligand charges = sum of ligand charges L, number of ligands = n.
Then:
Metal oxidation state=Q−L
For [Fe(CN)₆]³⁻: CN⁻ has charge -1, so L=6×(−1)=−6, Q=−3.
Fe oxidation state=−3−(−6)=+3
4. Anionic Ligands: The "-o" Ending
Rule: Anionic ligands (negative ions) end in -o (e.g., Cl⁻ → chloro, CN⁻ → cyano, OH⁻ → hydroxo).
Why?
- This distinguishes them from neutral ligands (e.g., NH₃ → ammine, H₂O → aqua).
- The suffix -o signals "this ligand came from an anion" — crucial for charge balance.
Common examples:
| Anion | Ligand name |
|---|---|
| Cl⁻ | chloro |
| CN⁻ | cyano |
| OH⁻ | hydroxo |
| SO₄²⁻ | sulfato |
5. Neutral Ligands: Special Names
Rule: Neutral ligands keep their molecular name, except for a few with special names:
- NH₃ → ammine (not "ammonia")
- H₂O → aqua
- CO → carbonyl
- NO → nitrosyl
Why?
- "Ammine" avoids confusion with ammonia (NH₃) as a free molecule.
- These special names are historical but standardised — you must memorise them for exams.
6. Prefixes: di-, tri-, tetra-, etc.
Rule: Use Greek prefixes to indicate the number of each ligand:
- 2 → di, 3 → tri, 4 → tetra, 5 → penta, 6 → hexa
Why?
- Without prefixes,
[Co(NH₃)₆]³⁺would be "hexaamminecobalt(III)" — the "hexa" tells you there are six ammines. - For ligands with complex names (e.g., ethylenediamine), use bis-, tris-, tetrakis- to avoid confusion.
Example:
[Co(en)₃]³⁺ → tris(ethylenediamine)cobalt(III) — "tris" because "triethylenediamine" would sound like three ethylenediamine molecules (which is correct, but "tris" is clearer).
7. Anionic Complexes: The "-ate" Suffix …
The key idea is that geometrical isomerism occurs in coordination compounds with a coordination number of 4 (square planar) or 6 (octahedral) when two or more different ligands are arranged in distinct spatial positions (cis/trans or fac/mer).
Reasoning:
- Option (i): [Cr(H2O)4Cl2]+ is octahedral with two identical Cl ligands. These can be adjacent (cis) or opposite (trans), so geometrical isomers exist.
- Option (ii): [Pt(NH3)3Cl] is square planar with three identical NH₃ ligands — only one arrangement possible (no isomerism). …
Geometrical isomerism arises when ligands can occupy different spatial positions around a metal centre, typically in square planar or octahedral complexes with two different types of ligands. The complex [Cr(H2O)4Cl2]+ is octahedral with four identical water ligands and two identical chloride ligands, allowing cis and trans isomers — so option (i) is correct.
Geometrical isomerism in coordination compounds is a form of stereoisomerism where the same set of ligands can be arranged differently in space around the central metal ion. The key condition is that the complex must have at least two different types of ligands, and the geometry must allow distinct spatial arrangements — typically seen in square planar complexes of type [MA2B2] or [MA2BC], and octahedral complexes of type [MA4B2] or [MA3B3].
Let’s examine each option carefully.
-
Option (i): [Cr(H2O)4Cl2]+
This is an octahedral complex with chromium in the +3 oxidation state (since each water is neutral and each chloride is -1, total charge = +3 - 2 = +1). The coordination sphere has four identical water ligands and two identical chloride ligands. In an octahedral geometry, two identical ligands can be placed either adjacent to each other (cis, 90° apart) or opposite each other (trans, 180° apart). These are non-superimposable mirror images? No — cis and trans are diastereomers, not enantiomers, but they are distinct geometrical isomers. So this complex does show geometrical isomerism.
-
Option (ii): [Pt(NH3)3Cl]+ (the stem's printed formula omits the charge; charge balance requires it — three neutral NH3 plus one Cl− on Pt2+ gives a net +1 complex ion)
Platinum(II) with a coordination number of 4 is essentially always square planar. For a square-planar [MA3B] complex, the three identical A ligands and the single B ligand have only one possible spatial arrangement — every position is related to every other by a simple rotation, so there is no cis/trans distinction. No geometrical isomerism.
-
Option (iii): [Co(NH3)6]3+
This is an octahedral complex with six identical ammonia ligands. All positions are equivalent — there is only one possible arrangement. No geometrical isomerism possible.
-
Option (iv): [Co(CN)5(NC)]3− …
Method: Check for Coordination Number and Ligand Arrangement that Allows Cis–Trans Isomerism
Geometrical isomerism in coordination compounds occurs when ligands can occupy different spatial positions around the central metal ion. The key is to look for:
- Coordination number 4 (square planar) or 6 (octahedral)
- At least two different types of ligands (not all identical)
- Possibility of cis (adjacent) and trans (opposite) arrangements
Step-by-step analysis for each option
Option (i): [Cr(H2O)4Cl2]+
- Coordination number: 6 (octahedral)
- Ligands: 4 water molecules + 2 chloride ions → two different types
- Possible isomers:
- Cis: both Cl⁻ adjacent
- Trans: both Cl⁻ opposite
- ✓ Shows geometrical isomerism
Option (ii): [Pt(NH3)3Cl]
- Coordination number: 4 (square planar for Pt²⁺)
- Ligands: 3 ammonia + 1 chloride → only one chloride ligand
- No possibility of cis/trans because you need at least two identical ligands to swap positions
- ✗ No geometrical isomerism
Option (iii): [Co(NH3)6]3+
- Coordination number: 6 (octahedral) …
🧠 Step 1: Understand the Core Concept First
Geometrical isomerism (cis-trans or fac-mer) occurs when:
- The coordination number is 4 (square planar or tetrahedral) or 6 (octahedral).
- There are two or more different ligands arranged around the central metal.
- The spatial arrangement of identical ligands can be different.
Key rule: If all ligands are identical, no geometrical isomerism is possible.
✗ Common Mistake #1: Forgetting that [Pt(NH3)3Cl] is neutral and square planar
- What students do: They see 4 ligands and assume tetrahedral → no geometrical isomerism.
- Why it’s wrong: Pt2+ is d⁸, almost always square planar, not tetrahedral.
- How to avoid: Memorise:
- Pt2+, Pd2+, Au3+ → square planar (coordination number 4).
- Square planar complexes with formula [MA3B] do show geometrical isomerism (only one isomer exists here, but the possibility is there — actually [Pt(NH3)3Cl] has no geometrical isomers because all three NH₃ are identical; but if formula were [MA2B2], it would).
Correction for this exam: Option (ii) [Pt(NH3)3Cl] has no geometrical isomers because three NH₃ are identical — only one arrangement exists.
✗ Common Mistake #2: Ignoring the charge and coordination number
- What students do: They see [Cr(H2O)4Cl2]+ and think “Cr is +3, coordination number 6” but forget to check if it’s octahedral.
- Why it’s wrong: Cr³⁺ is d³, always octahedral. With 4 H₂O and 2 Cl, it’s [MA4B2] type.
- How to avoid:
- Always determine oxidation state and coordination number first.
- For octahedral [MA4B2]: cis and trans isomers exist.
✓ Option (i) shows geometrical isomerism.
✗ Common Mistake #3: Assuming [Co(NH3)6]3+ can show isomerism
- What students do: They see 6 ligands and think “octahedral → maybe isomers”.
- Why it’s wrong: All six ligands are identical (NH₃). No geometrical isomerism possible.
- How to avoid:
- Geometrical isomerism requires at least two different types of ligands.
✗ Option (iii) has no geometrical isomers.
✗ Common Mistake #4: Misidentifying linkage isomerism as geometrical isomerism
- What students do: They see [Co(CN)5(NC)]3− and think “CN and NC are different → geometrical isomers possible”. …
- KEAM 2026Set eng-2026-04184 marksMCQQ.The correct IUPAC name of the complex [Ag(NH3)2][Ag(CN)2] is named as (A) diamminesilver(II) dicyanoargentate(II) (B) diamminesilver(II) dicyanoargentate(I) (C) diamminesilver(I)dicyanidoargentate(I) (D) diaminesilver(I)dicyanoargentate(I) (E) diamminesilver(I)dicyanidoargentate(II)
›Reveal solutionSolution
Both silver centres are +1; use current IUPAC ligand names (ammine, cyanido) and the -ate suffix for the anion.
Cation [Ag(NH3)2]+: two NH3 = diammine, Ag oxidation state +1 ⇒ diamminesilver(I).
Anion [Ag(CN)2]−: two CN− = dicyanido (modern IUPAC), Ag +1, anionic complex takes -ate on the Latin stem argent ⇒ dicyanidoargentate(I). …
- KEAM 2026Set eng-2026-04204 marksMCQQ.IUPAC name of [CoCl2(en)2]Cl is (A) Bis(ethane-1,2-diamine)dichloridocobalt(III)chloride (B) Dichloridobis(ethane-1,2-diamine)cobalt(II)chloride (C) Dichloridobis(ethylenediamine)cobalt(III)chloride (D) Dichloridobis(ethane-1,2-diamine)cobalt(III)chloride (E) Dichloridobis(ethylenediamine)cobalt(II)chloride
›Reveal solutionSolution
Correct IUPAC name = Dichloridobis(ethane-1,2-diamine)cobalt(III)chloride.
Oxidation state of Co: complex [CoCl2(en)2]+ (charge +1 balancing the outer Cl−); with 2(−1) from chlorido and neutral en, Co =+3.
Naming rules:
- Ligands cited alphabetically: chlorido (c) before ethane-1,2-diamine (e), so "dichlorido" then "bis(ethane-1,2-diamine)". …
- KEAM 2026Set eng-2026-04214 marksMCQQ.The formula of Pentaamminecarbonatocobalt(III)chloride is (A) [Co(NH3)5(CO)]Cl2 (B) [Co(NH3)5(CO3)]Cl (C) [Co(NH3)5(CO)3]Cl2 (D) [Co(NH3)5(CO3)]Cl2 (E) [Co(NH3)5(CO3)]Cl3
›Reveal solutionSolution
Charge balance gives [Co(NH3)5(CO3)]Cl.
Co is +3, five neutral NH3, carbonato CO32−:
+3+5(0)+(−2)=+1. …
- KEAM 2026Set pha-2026-0420F4 marksMCQQ.The IUPAC name of the complex [Co(NH3)5ONO]Cl2 is (A) Pentaamminenitritocobalt (III) chloride (B) Pentaamminenitritocobalt (II) chloride (C) Pentaamminenitrocobalt (III) chloride (D) O-Nitritopentaamminecobalt (III) chloride (E) Pentaamminemononitritocobalt (III) chloride
›Reveal solutionSolution
Co is +3; O-bonded ONO is 'nitrito'; alphabetical ligand order gives Pentaamminenitritocobalt(III) chloride.
Determine the metal oxidation state: NH3 is neutral, the ONO ligand (bonded through oxygen) is nitrito with charge −1, and the two chlorides are counterions (−1 each). For overall neutrality the complex cation is +2, so
Co+5(0)+(−1)=+2⇒Co=+3. …
- KEAM 2025Set eng-2025-04254 marksMCQQ.The IUPAC name of [Co(en)3]2(SO4)3 is (A) tris(ethane-1,2-diamine)cobalt(III) sulphate (B) bis(ethane-1,2-diamine)cobalt(III) sulphate (C) bis(ethane-1,2-diamine)cobalt(II) sulphate (D) tris(ethane-1,2-diamine)cobaltate(II) sulphate (E) tris(ethylene-1,2-diamine)cobalt(III) sulphate
›Reveal solutionSolution
With three neutral en ligands and a sulphate counter-ion, cobalt is in the +3 state; the IUPAC name is tris(ethane-1,2-diamine)cobalt(III) sulphate.
In [Co(en)3]2(SO4)3:
- en (ethane-1,2-diamine) is a neutral bidentate ligand; there are three of them → prefix tris (as the ligand name contains 'di').
- Charge: three SO42− give −6 shared over two complex cations, so each [Co(en)3]3+, making cobalt +3. …
- KEAM 2025Set pha-2025-0424F4 marksMCQQ.The IUPAC name of the complex [Co(NH3)3(H2O)3]Cl3 is (A) triaquatriamminecobalt(III) chloride (B) triamminetriaquacobalt(III) chloride (C) triaquatriamminecobalt(II) chloride (D) triamminetriaquacobalt(II) chloride (E) triaquatriamminecobalt(III) trichloride
›Reveal solutionSolution
Name ligands alphabetically (ammine < aqua) and assign Co the +3 oxidation state, so the complex is triamminetriaquacobalt(III) chloride.
For [Co(NH3)3(H2O)3]Cl3:
- Ligands are named in alphabetical order using the ligand name (ignoring the multiplying prefix): ammine (a) comes before aqua (a-q) → "triammine" is cited before "triaqua".
- Oxidation state of cobalt: overall charge zero; three Cl− counter-ions give the complex ion a +3 charge; NH3 and H2O are neutral, so Co is +3.
- Anion: chloride. …
- KEAM 2025Set pha-2025-0424A4 marksMCQQ.The IUPAC name of the following complex [Cr(H2O)3(NH3)3]Cl3 is (A) Triamminetriaquachromium(III) chloride (B) Triaquatriamminechromium(III) chloride (C) Triaquatriamminechromium(II) chloride (D) Triamminetriaquachromium(II) chloride (E) Triaquatriamminechromium(III) trichloride
›Reveal solutionSolution
The IUPAC name is triamminetriaquachromium(III) chloride.
Naming [Cr(H2O)3(NH3)3]Cl3:
- Ligands are cited in alphabetical order of ligand name: ammine (a) comes before aqua (a-q), so 'triammine' precedes 'triaqua'.
- Oxidation state of Cr: the complex cation carries +3 (balanced by three Cl−), so chromium is Cr(III). …
- KEAM 2024Set eng-2024-06054 marksMCQQ.The IUPAC name of the co-ordination compound [Co(NH3)4(H2O)Cl]Cl2 is (A) Tetraammineaquachloridocobalt(III) chloride (B) Aquatetraamminechloridocobalt(III) chloride (C) Chloridotetraammineaquacobalt(II) chloride (D) Tetraamminechloridoaquacobalt(III) dichloride (E) Tetraamminechloridoaquacobalt(II) dichloride
›Reveal solutionSolution
Alphabetical ligand order ammine < aqua < chlorido, Co oxidation state +3, giving tetraammineaquachloridocobalt(III) chloride.
In [Co(NH3)4(H2O)Cl]Cl2 the two chloride counter-ions make the complex ion +2. Charge balance: x+4(0)+0+(−1)=+2⇒x=+3. …
- KEAM 2024Set eng-2024-06064 marksMCQQ.The IUPAC name of the complex [Cr(NH3)3(H2O)3]Cl3 is (A) triaquatriamminechromium(III) chloride (B) triamminetriaquachromium(III) chloride (C) triaquatriamminechromium(II) chloride (D) triamminetriaquachromium(II) chloride (E) triaquatriamminechromium(III) trichloride
›Reveal solutionSolution
In IUPAC nomenclature ligands are cited alphabetically (ammine < aqua), and the metal oxidation state is set by charge balance. For [Cr(NH3)3(H2O)3]Cl3, three chlorides outside give Cr = +3.
Working it out:
- Ligands: 3 NH3 (ammine) and 3 H2O (aqua). Alphabetical order → triammine then triaqua. …
- KEAM 2024Set eng-2024-06084 marksMCQQ.The IUPAC name of the coordination compound Hg[Co(SCN)4] is (A) Mercury (I) tetrathiocyanato-S-cobaltate (III) (B) Mercury (II) tetrathiocyanato-S-cobaltate(II) (C) Mercury (I) tetrathiocyanato-S-cobaltate (IV) (D) Mercury (II) tetraisocyanato-S-cobaltate (III) (E) Mercury (I) tetraisocyanato-N-cobaltate (III)
›Reveal solutionSolution
Hg[Co(SCN)4]: Hg is +2, so [Co(SCN)4]2− makes Co +2; thiocyanate binds via sulphur, giving Mercury(II) tetrathiocyanato-S-cobaltate(II).
Assign oxidation states. Mercury is Hg2+, so the complex anion carries a −2 charge:
[Co(SCN)4]2−
Each thiocyanate ligand is SCN−, so four contribute −4. Letting the cobalt state be x:
x+4(−1)=−2⇒x=+2 …
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