  Water provides the driving force for the assembly and stability of many
cellular components. Despite its impact on biological functions, a nanoscale
understanding of the relationship between its structure and dynamics under soft
confinement has remained elusive. As expected, water in contact with biological
membranes recovers its bulk density and dynamics at $\sim 1$ nm from
phospholipid headgroups but surprisingly enhances its intermediate-range order
(IRO) over a distance, at least, twice as large. Here, we explore how the IRO
is related to the water's hydrogen bond network (HBN) and its coordination
defects. We characterize the increased IRO by an alteration of the HBN up to
more than eight coordination shells of hydration water. The HBN analysis
emphasizes the existence of a bound-unbound water interface at $\sim 0.8$ nm
from the membrane. The unbound water has a distribution of defects intermediate
between bound and bulk water, but with density and dynamics similar to bulk,
while bound water has reduced thermal energy and much more HBN defects than
low-temperature water. This observation could be fundamental for developing
nanoscale models of biological interactions and for understanding how
alteration of the water structure and topology, for example, due to changes in
extracellular ions concentration, could affect diseases and signaling. More
generally, it gives us a different perspective to study nanoconfined water.
