I am having some difficulty's locating an issue within some code I am working on.
It breaks when it runs the "if (AIwords->name == NULL)"

    // This is the struct which is located in the header(.h)
    struct AIstruc_word
    {
        char *name;
        bool controlStatement;
        struct AIstruc_word *next;
    };

    // This is the struct that contains the sub struct
    struct AIstruc_sentence
    {
         struct AIstruc_word word;
         ....
         ....
         ....

    // This is the function which is crashing the program
    int AI_sentenceProc(struct AIstruc_sentence *AIdatabase, char *word)
    {
        struct AIstruc_word *AIwords = (struct AIstruc_word*)&AIdatabase->word;
        ...
        ...
        ...
        for (; ; AIwords = AIwords->next)
        {
            printf("%d\r\n", iPosition++);
            /// When we reach an empty word slot
            if (AIwords->name == NULL)
            {
                /// Break out of this 'do{}while()' loop.
                break;
            }
            if (AIwords->next == NULL)
            {
                AIwords->next = (struct AIstruc_word *)calloc(1, sizeof(struct AIstruc_word));
                break;
            }
        }
        ...
        ...
        ...

        // This is the code that passes the parent struct
        int AI_sentenceRequestProcess(.....)
        {
            struct AIstruc_sentence AIdatabase;
            ....
            ....
            AI_sentenceProc(&AIdatabase, quickBuffer);

Does anyone have an idea what I'm doing wrong here....
Help would be greatly appreciated

Most likely cause is that AIwords is either NULL or invalid so when you dereference it to get the name member you get a SIGSEGV (memory error).

AIstruc_word

Add a constructor which initializes the two pointers to NULL

The problem is I have declared the AIstruc_word struct within the ASstruc_sentence structure, it is not a pointer so surely the first one should be allocated.... I'm thinking that shomehow struct AIstruc_word *AIwords = (struct AIstruc_word*)&AIdatabase->word; is wrong and it is pointing to an invalid pointer which means if I am putting data in it. It will not be put into the global structure but a local calloc'd struct.

Thank-you Banfa & Ancient Dragon.

I used memset(AIdatabase, '\0', sizeof(AIstruc_sentence)); in the calling function.

Just a small point but, in C++, you don't need to put the struct keyword before the typename when you're using your structs. Also, I don't think that you need to do all the casting that you're doing. I think that this would be fine:

struct AIstruc_word
{
    // Set the name pointer to NULL on construction
    AIstruct_word() : name( NULL ) {}

    char *name;
    bool controlStatement;
    struct AIstruc_word *next;
};

// This is the struct that contains the sub struct
struct AIstruc_sentence
{
     // Don't need `struct` here
     AIstruc_word word;
     ....
     ....
     ....
};

// This is the function which is crashing the program
int AI_sentenceProc(struct AIstruc_sentence *AIdatabase, char *word)
{
    // No `struct` and no cast
    AIstruc_word *AIwords = &AIdatabase->word;
    ...
    ...
    ...

    // Use a `while` here
    while ( AIwords = AIwords->next)
    {
        ...
        ...
    }
}
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