Human collective tasks in teams and organizations increasingly require participation of members with diverse backgrounds working in networked social environments. However, little is known about how network structure and the functional diversity of member backgrounds would interact with each other and affect collective processes. Here we conducted three sets of human-subject experiments which involved 617 university students who collaborated anonymously in a collective ideation task on a custom-made online social network platform. We found that spatially clustered collectives with assortative background distribution tended to explore more diverse ideas than in other conditions, whereas collectives with random background distribution consistently generated ideas with the highest utility. We also found that higher network connectivity may improve individuals' overall experience but may not improve the collective performance regarding idea generation, idea diversity, and final idea quality.