Suggested answer:
(1) Examples of married to and married with:
Her sister was married to William de Morgan.
She was married with four children.

(2) The two expressions differ in that married to is typically followed by the name of the person someone is married to, as in the above example married to Willieam de Morgan, while married with states that someone is married and has children. In the corpus married with is almost invariable followed by a phrase including "children".

In addition there is the following example, where the PP with such discretion functions as an adverbial of manner.
But twelve months after they had married with such discretion...

(3) In the examples cited under (1), the two expressions do not differ syntactically, both PPs function as adjectival complements. However, as already mentioned, in the example cited in (2) the PP functions as an adverbial in its own right, i.e. the PP is not an integral part of the adjective prase including married.

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Read about adjective + preposition combinations here and here
Terminology: (adjectival) complement, preposition, prepositional phrase (PP), adverbial, (adjunct) manner adverbial, adjective phrase