Crystal structure of hydrazine iron(III) phosphate, the first transition metal phosphate containing hydrazine

The structure of the title compound can be described as a three-dimensional network of FePO₄N₂ octa­hedra resulting from corner-sharing with four PO₄ tetra­hedra and bonding with two trans-arranged hydrazine mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-N) = 0.002 Å
• R factor = 0.020
• wR factor = 0.027
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT374_ALERT_2_A Long   N - N         Bond  N      -   N_b    ...       1.46 Ang.

Author Response: it's typical distance for hydrazine molecule

Alert level B
PLAT920_ALERT_1_B Theta(Max)  in CIF and FCF Differ by ...........       0.81 Degree

Alert level C
PLAT416_ALERT_2_C Short Intra D-H..H-D       H1     ..  H1      ..       1.94 Ang.

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT793_ALERT_4_G The Model has Chirality at P       (Centro SPGR)          R Verify
PLAT794_ALERT_5_G Tentative Bond Valency for Fe      (IX)    .....       3.04 Note
PLAT808_ALERT_5_G No Parseable SHELXL Style Weighting Scheme Found     Please Check
PLAT929_ALERT_5_G No Weight Pars,Obs and Calc R1,wR2,S not checked          ! Info
PLAT953_ALERT_1_G Reported (CIF) and Actual (FCF) Hmax Differ by .          1 Units
PLAT960_ALERT_3_G Number of Intensities with I  <   - 2*sig(I) ...          2 Check

   1 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   5 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petrićek et al., 2014); molecular graphics: DIAMOND (Brandenburg & Putz, 2010); software used to prepare material for publication: JANA2006 (Petrićek et al., 2014).

Poly[(µ₂-hydrazine)(µ₄-phosphato)iron(III)]

Crystal data

[Fe(PO4)(N2H4)]	F(000) = 364
Mr = 182.87	Dx = 2.902 Mg m^−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 2128 reflections
a = 6.3114 (13) Å	θ = 4.2–26.9°
b = 7.6680 (15) Å	µ = 3.89 mm^−1
c = 8.6485 (18) Å	T = 293 K
V = 418.55 (15) Å^3	Parallelepiped, orange
Z = 4	0.05 × 0.03 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer	457 reflections with I > 3σ(I)
Radiation source: X-ray tube	Rint = 0.065
phi scan	θmax = 30.6°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −9→8
Tmin = 0.668, Tmax = 0.746	k = −10→10
13820 measured reflections	l = −12→12
601 independent reflections

Refinement

Refinement on F	0 constraints
R[F > 3σ(F)] = 0.020	All H-atom parameters refined
wR(F) = 0.027	Weighting scheme based on measured s.u.'s w = 1/(σ^2(F) + 0.0001F^2)
S = 1.46	(Δ/σ)max = 0.006
601 reflections	Δρmax = 0.40 e Å^−3
47 parameters	Δρmin = −0.33 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.0604 (2)	0.30096 (17)	0.36016 (16)	0.0093 (4)
Fe	0	0	0	0.00652 (11)
P	−0.25	0.25	0.25868 (8)	0.00567 (17)
O2	−0.1898 (2)	0.09269 (19)	0.15978 (16)	0.0111 (4)
N	0.2656 (3)	0.1556 (2)	0.0781 (2)	0.0103 (5)
H1	0.306 (4)	0.132 (3)	0.169 (3)	0.024 (7)*
H2	0.364 (4)	0.139 (3)	0.012 (3)	0.020 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0089 (6)	0.0090 (7)	0.0099 (7)	0.0001 (5)	−0.0032 (5)	−0.0013 (5)
Fe	0.00692 (19)	0.0059 (2)	0.00678 (19)	−0.00013 (13)	0.00010 (16)	−0.00054 (16)
P	0.0059 (3)	0.0053 (3)	0.0057 (3)	−0.0001 (3)	0	0
O2	0.0135 (6)	0.0096 (7)	0.0101 (7)	0.0003 (5)	0.0030 (6)	−0.0033 (6)
N	0.0110 (8)	0.0074 (8)	0.0123 (9)	−0.0017 (7)	−0.0012 (8)	0.0010 (7)

Geometric parameters (Å, º)

O1—Fe^i	1.9843 (14)	P—O2^iii	1.5268 (15)
O1—P	1.5346 (15)	N—N^iv	1.461 (2)
Fe—O2	1.9621 (15)	N—H1	0.85 (3)
Fe—O2^ii	1.9621 (15)	N—H2	0.85 (3)
P—O2	1.5268 (15)
Fe^i—O1—P	133.97 (8)	O1—P—O2^iii	108.25 (7)
O1^v—Fe—O1^vi	180.0 (5)	O1^iii—P—O2	108.25 (7)
O1^v—Fe—O2	88.09 (6)	O1^iii—P—O2^iii	109.13 (7)
O1^v—Fe—O2^ii	91.91 (6)	O2—P—O2^iii	111.85 (9)
O1^vi—Fe—O2	91.91 (6)	Fe—O2—P	146.37 (9)
O1^vi—Fe—O2^ii	88.09 (6)	N^iv—N—H1	104.6 (18)
O2—Fe—O2^ii	180.0 (5)	N^iv—N—H2	104.2 (18)
O1—P—O1^iii	110.23 (8)	H1—N—H2	112 (2)
O1—P—O2	109.13 (7)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y, −z; (iii) −x−1/2, −y+1/2, z; (iv) −x+1/2, −y+1/2, z; (v) −x, y−1/2, −z+1/2; (vi) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H1···O1^iv	0.85 (3)	2.36 (2)	3.086 (2)	144 (2)
N—H1···O2^vii	0.85 (3)	2.27 (3)	2.974 (2)	141 (2)
N—H2···O1^viii	0.85 (3)	2.19 (3)	2.873 (2)	137 (2)

Symmetry codes: (iv) −x+1/2, −y+1/2, z; (vii) x+1/2, −y, −z+1/2; (viii) −x+1/2, y, z−1/2.