Direct determination of the configuration of a benzenediazotate: The crystal structure of sy2 -sodium benzenediazotate-4-sulphonate

Tetrahedron Letters No. 33, pp 3115 - 3116. @Pergamon Press Ltd. 1979.Printed in Great Britain.

DIRECT

DETERMINATION

OF THE CONFIGURATION

OF A BENZENEDIAZOTATE:

THE CRYSTAL

STRUCTURE OF SYN-SOD IUM BENZENED IAZOTATE-4-SULPHONATE N.W. Department

Summary

of

Chemistry

The

crystal

the

-cis-

Arenediazonium

not

the

trans-isomer

of

cations

Kemp*

in

solution

at

ArN OH + OH2 dlazohydroxide

structures

of

identified by

the

analogy

the

two

with transoid.

bearing

2-substituents,

sole

concerning

it

has e+

in

dilute

Warwick,

Coventry

been

accepted

from

that

anti

this

the

to

be

following

+ H20

-ArN20since

that that

they the

studies

the

to

syn-ArN20-

controversial

assumed

,3

shows

pH > 8 according

e

been

been

CV4 7AL

d iazotate

have

2.

1973

have

been

be

of

-syn-form

was

reported.

compound

used

150

K to

is

configuration.

arenediazon~um

at

The The

U.V.

Schraube

are

is

of

regarded

Schmidt’

isomers’

cisoid

reactions be

and

geometrical

syn-form the

should

shown

in

C(4)-N(I)

of

838

Fig.

I.

The 6

or

aromatic those

all

of

and six

as

and

the

diazotates trans

and

is

out

ring bearing

of is

the

for

study.

X-ray

except

colourless

evidence for

substituents

described,5

potassium

direct

diazotates

solutions

and

that

needles.

agreed

with

which

a more These

the

of

is

(which

confirmed

making the

ring

distorted, substituents.

The

analysis

crystal

was

was

extensive

have

a -cis

at

observed.

planar,

plane

3115

for

different

small

X-ray were

is

that

provide

diffractometer.

slightly

4-amino

as

syn-diazotate

the

not

arwnatic

suitable

their

is

C6H4N2S042Na.3H20.

reflections

group

does

with

prepared

during

The

this

salts

four-circle

decomposition

bond

As

a diazotate

examined

a formulation:

a Syntex-PZl

minimise

for

extremely

spectra

C(4)-N(I)-N(2)-O(4)

forces. salts

ultimately

the

A total

structure

lattice

several

was

indicated on

temperature).

plane.

determined

crystals

yielded but

collected

at

The

Of

gave

which

recrystallised,

were

maintained

been

configuration. 3 etar., we have

Sterba

Microanalysis

Data

has

a -cis

benzenediazotate-4-sulphonate

I iterature.*

ambient

title

that

has of

the

solution not

which

suggestion

I structures only

structure 4

w-sodium

to

long

Sterba

suggested

crystal

the

cations,

ring

has

compounds, However,

syn-methyldiazotate

could

It

of

as _CIS.

The

crysta

diazotates

isomers.

similar

anti-form

anti-form

resulting

Goodman

#

syn-ArN20The

P.D.

University

benzenediazotate-4-sulphonate

aqueous

+

and

Sciences,

syn-sodium

react + ZOH-

ArN2+

T.J.

Molecular

structure and

scheme:

Alcock,”

and

but 7

to

an

angle

by

5.6O

less

of

69.06

(+O.Z”). so

than

with

the

probably in

simple

no

Jill

N‘(2)

N(1)

FIG.

I

Crystal

structure

bond

(i)

lengths

Comparison

with

N(l)-N(2)

and

whereas

I .306

in

vary

of

syn-benzenediazotate-4-sulphonate

in

the

potassium

0.012

!

(N-N)

-syn-methyidiazotate

N(Z)-O(4)

the

range

in

al iphatic

the

title

A” respectively.

This

to

shows

compound

diazotate,

ion.

they

indicates

Standard

i

fairly

a delocalised

in

differences:-

similar,

substantially

deviations

(C-C).

significant

are

are

0.015

i.e -*

1.296

different, structure

for

is

to

-i.e.

and

I.318

1.246

the

title

pure

sp2

i,

and

canpound,

viz:

Ar \ (ii)

The

angle

C4-N,-N2

a I iphatic

This

(119.3’)

work

was

of

the

arcxnatic

compound

closer

than

in

the

( 116.2’).

diazotate

supported

by

Ozalid

(UK)

Ltd.

through

a CASE studentship.

REFERENCES I

C.

Schraube

2

H.

Zol

Chemistry

of

(19781, 3

J.

and

I inger,

Schmidt, and

Diazonium

chap.

Jahelka,

C.

“Azo

Chem.

Diazo and

Ber.,

2,

Chemistry”, Diazo

514

(1894).

Interscience

Groups,

Part

I,

K.

Valter,

(19611, ed.

S.

p.

Patai.

57; J.

S. Wiley,

Sorriso

in

“The

Chichester

3. 0.

Mazhackov;,

V.

ztgt-ba

and

Coil.

Czech.

Chem.

Ccmm.,

38,

3290

( 1973). 4.

R.Huber,

5.

R.J.W.

6.

C.

7.

N.W. the

(Received

R. Le

Rtiming,

Langer

Fevre Acta

Alcock,

and

and

T.J.

J.B.

Chem.

UK 18 May

Sousa, Stand.,

Greenhough,

press.

in

W. Hoppe,

1979)

Acta J. 26,

D.M.

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Chem. 523 Hirst,

I&

Sot.,

467

3155

(1965).

(1955).

(1972). T.J.

Kemp and

D.R.

Payne,

J.C.S.

Perkin

II,

in