Please note: I'm not sure whether this is an elegant solution and more whether this can become a performance bottle neck. But at least it looks like it works.
a.) Create test table
CREATE TABLE Tbl
(
EMPId integer,
DATEtiME DateTime
);
b.) Insert Test data
INSERT INTO Tbl(EMPId, DATEtiME)
VALUES(1, '2019-04-20 07:30:00.000'),
(1, '2019-04-20 07:30:00.000'),
(1, '2019-04-20 12:30:00.000'),
(1, '2019-04-20 13:00:00.000'),
(2, '2019-04-20 07:30:00.000'),
(2, '2019-04-20 07:30:00.000'),
(2, ' 2019-04-20 13:00:00.000'),
(3, '2019-04-20 07:30:00.000'),
(3, '2019-04-20 12:30:00.000'),
(4, '2019-04-20 00:30:00.000')
c.) Test query
SELECT DISTINCT
a.EMPId,
a.DATEtiME
FROM Tbl a
WHERE a.DATEtiME IN (SELECT MIN(minEmp.DATEtiME) FROM Tbl minEmp WHERE minEmp.EMPId = a.EMPId)
OR a.DATEtiME IN (SELECT MAX(maxEmp.DATEtiME) FROM Tbl maxEmp WHERE maxEmp.EMPId = a.EMPId)
d.) Result
1 2019-04-20 07:30:00.000
1 2019-04-20 13:00:00.000
2 2019-04-20 07:30:00.000
2 2019-04-20 13:00:00.000
3 2019-04-20 07:30:00.000
3 2019-04-20 12:30:00.000
4 2019-04-20 00:30:00.000
Most probably the SQL experts @CHill60 and @losmac can give you a better answer ;)