Crystal structures of cristobalite-type and coesite-type PON redetermined on the basis of single-crystal X-ray diffraction data

The crystal structures of two phospho­rus oxonitride polymorphs (cristobalite- and coesite-type) were redetermined by means of single-crystal X-ray diffraction data.

Key indicators

Structure: cri-PON

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma]() = 0.000 Å
• Disorder in main residue
• R factor = 0.016
• wR factor = 0.043
• Data-to-parameter ratio = 11.5

Structure: coe-PON

• Single-crystal synchrotron study
• T = 100 K
• Mean [sigma]() = 0.000 Å
• Disorder in main residue
• R factor = 0.037
• wR factor = 0.102
• Data-to-parameter ratio = 9.4

checkCIF/PLATON results

No syntax errors found



Datablock: cri-PON



Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.500
           From the CIF: _refine_ls_abs_structure_Flack_su    0.000

Author Response: An attempt to refine Flack parameter leads to a value 0.3(1), which does not allow to define the absolute structure of cri-PON unambiguously.

Alert level G
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O      is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N      is Constrained at      0.500 Check
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         44 Note
PLAT432_ALERT_2_G Short Inter X...Y Contact  P      ..  P       ..       2.90 Ang.
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          2 Note
PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by .       0.18 Check
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

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

   2 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
   5 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check




Datablock: coe-PON



Alert level B
PLAT395_ALERT_2_B Deviating  X-O-Y  Angle from 120 Deg for     *O2      180.0 Degree

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      1.408
            Test value =      1.125
DIFMX02_ALERT_1_C  The maximum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT088_ALERT_3_C Poor Data / Parameter Ratio ....................       9.39 Note
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.63 Report
PLAT097_ALERT_2_C Large Reported Max.  (Positive) Residual Density       1.41 eA-3
PLAT215_ALERT_3_C Disordered O5        has ADP max/min Ratio .....        3.3
PLAT215_ALERT_3_C Disordered N5        has ADP max/min Ratio .....        3.3
PLAT395_ALERT_2_C Deviating  X-O-Y  Angle from 120 Deg for     *O3      148.5 Degree
PLAT395_ALERT_2_C Deviating  X-O-Y  Angle from 120 Deg for     *O4      141.3 Degree
PLAT395_ALERT_2_C Deviating  X-O-Y  Angle from 120 Deg for     *O5      141.3 Degree
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          4 Report
PLAT926_ALERT_1_C Reported and Calculated   R1 Differ by .........    -0.0022 Check
PLAT927_ALERT_1_C Reported and Calculated  wR2 Differ by .........    -0.0030 Check

Alert level G
ABSMU01_ALERT_1_G  Calculation of _exptl_absorpt_correction_mu
                not performed for this radiation type.
PLAT004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          3 Info
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT045_ALERT_1_G Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          5 Report
PLAT300_ALERT_4_G Atom Site Occupancy of *O1     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O2     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O3     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O4     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *O5     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N1     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N2     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N3     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N4     is Constrained at      0.500 Check
PLAT300_ALERT_4_G Atom Site Occupancy of *N5     is Constrained at      0.500 Check
PLAT301_ALERT_3_G Main Residue  Disorder ............ Percentage =         57 Note
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         17 Note

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

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


checkCIF publication errors

Alert level A
PUBL024_ALERT_1_A The number of authors is greater than 5.
              Please specify the role of each of the co-authors
              for your paper.

Author Response: Maxim Bykov has solved and refined the crystal structure, Elena Bykova has selected the crystal, Vadim Dyadkin has performed the data collection, Dominik Baumann and Wolfgang Schnick have synthesized the crystal, Leonid Dubrovinsky and Natalia Dubrovinskaia have supervised the research.

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

---

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

(cri-PON) Phosphorus oxonitride

Crystal data

NOP	Dx = 2.719 Mg m^−3
Mr = 60.98	Mo Kα radiation, λ = 0.71069 Å
Tetragonal, I42d	Cell parameters from 431 reflections
a = 4.6135 (2) Å	θ = 5.3–28.2°
c = 6.9991 (5) Å	µ = 1.24 mm^−1
V = 148.97 (2) Å^3	T = 293 K
Z = 4	Prism, colourless
F(000) = 120	0.02 × 0.02 × 0.02 mm

Data collection

Three-circle diffractometer	92 independent reflections
Radiation source: rotating-anode X-ray tube, Rigaku Rotor Flex FR-D	92 reflections with I > 2σ(I)
Detector resolution: 16.6 pixels mm^-1	Rint = 0.016
ω scans	θmax = 28.3°, θmin = 5.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −5→5
Tmin = 0.791, Tmax = 1.000	k = −5→6
445 measured reflections	l = −5→9

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0229P)^2 + 0.0508P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.016	(Δ/σ)max < 0.001
wR(F^2) = 0.043	Δρmax = 0.21 e Å^−3
S = 1.45	Δρmin = −0.28 e Å^−3
92 reflections	Absolute structure: Refined as a perfect inversion twin.
8 parameters	Absolute structure parameter: 0.5

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refined as a 2-component perfect inversion twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P	0.5000	0.5000	0.0000	0.0106 (3)
N	0.3630 (5)	0.2500	0.1250	0.0155 (5)	0.5
O	0.3630 (5)	0.2500	0.1250	0.0155 (5)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0112 (4)	0.0112 (4)	0.0094 (4)	0.000	0.000	0.000
N	0.0151 (11)	0.0149 (12)	0.0165 (9)	0.000	0.000	0.0065 (10)
O	0.0151 (11)	0.0149 (12)	0.0165 (9)	0.000	0.000	0.0065 (10)

Geometric parameters (Å, º)

P—O^i	1.5796 (10)	P—O^iii	1.5796 (10)
P—N^i	1.5796 (10)	P—N^iii	1.5796 (10)
P—O^ii	1.5796 (10)	P—N	1.5796 (10)
P—N^ii	1.5796 (10)	N—P^iv	1.5796 (10)
O^i—P—N^i	0.0	N^i—P—N^iii	107.86 (2)
O^i—P—O^ii	107.86 (2)	O^ii—P—N^iii	112.7
N^i—P—O^ii	107.86 (2)	N^ii—P—N^iii	112.73 (5)
O^i—P—N^ii	107.9	O^iii—P—N^iii	0.0
N^i—P—N^ii	107.86 (2)	O^i—P—N	112.7
O^ii—P—N^ii	0.0	N^i—P—N	112.73 (5)
O^i—P—O^iii	107.86 (2)	O^ii—P—N	107.9
N^i—P—O^iii	107.86 (2)	N^ii—P—N	107.86 (2)
O^ii—P—O^iii	112.73 (5)	O^iii—P—N	107.9
N^ii—P—O^iii	112.73 (5)	N^iii—P—N	107.86 (2)
O^i—P—N^iii	107.9	P—N—P^iv	132.83 (16)

Symmetry codes: (i) −x+1, −y+1, z; (ii) y, −x+1, −z; (iii) −y+1, x, −z; (iv) x, −y+1/2, −z+1/4.

(coe-PON) Phosphorus oxonitride

Crystal data

NOP	F(000) = 480
Mr = 60.98	Dx = 3.219 Mg m^−3
Monoclinic, C2/c	Synchrotron radiation, λ = 0.69428 Å
a = 6.9464 (6) Å	Cell parameters from 1202 reflections
b = 12.0340 (4) Å	θ = 3.3–26.3°
c = 6.9463 (5) Å	µ = 1.35 mm^−1
β = 119.914 (10)°	T = 100 K
V = 503.30 (7) Å^3	Prism, colourless
Z = 16	0.02 × 0.02 × 0.02 mm

Data collection

PILATUS@SNBL diffractometer	535 independent reflections
Radiation source: Beamline BM1A, SNBL ESRF, Grenoble, France	469 reflections with I > 2σ(I)
Detector resolution: 5.8 pixels mm^-1	Rint = 0.038
φ scans	θmax = 26.4°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −8→8
Tmin = 0.949, Tmax = 1.000	k = −15→15
2415 measured reflections	l = −8→8

Refinement

Refinement on F^2	57 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.037	w = 1/[σ^2(Fo^2) + (0.054P)^2 + 4.3556P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.102	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 1.41 e Å^−3
535 reflections	Δρmin = −0.54 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.28266 (16)	0.09026 (8)	0.04006 (16)	0.0067 (4)
P2	0.31812 (17)	0.35749 (7)	0.42525 (17)	0.0084 (4)
N1	0.2117 (5)	0.4603 (2)	0.4818 (6)	0.0148 (8)	0.5
O1	0.2117 (5)	0.4603 (2)	0.4818 (6)	0.0148 (8)	0.5
N2	0.2500	0.2500	0.5000	0.0116 (10)	0.5
O2	0.2500	0.2500	0.5000	0.0116 (10)	0.5
N3	0.2322 (6)	0.3532 (3)	0.1704 (5)	0.0188 (8)	0.5
O3	0.2322 (6)	0.3532 (3)	0.1704 (5)	0.0188 (8)	0.5
N4	0.5000	0.1336 (3)	0.2500	0.0110 (10)	0.5
O4	0.5000	0.1336 (3)	0.2500	0.0110 (10)	0.5
N5	0.0792 (5)	0.1273 (3)	0.0656 (6)	0.0186 (8)	0.5
O5	0.0792 (5)	0.1273 (3)	0.0656 (6)	0.0186 (8)	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0054 (7)	0.0057 (6)	0.0070 (7)	0.0003 (3)	0.0016 (5)	0.0013 (3)
P2	0.0075 (7)	0.0071 (6)	0.0095 (7)	0.0000 (4)	0.0035 (5)	0.0011 (4)
N1	0.0191 (18)	0.0047 (15)	0.0250 (19)	0.0010 (12)	0.0142 (16)	−0.0018 (12)
O1	0.0191 (18)	0.0047 (15)	0.0250 (19)	0.0010 (12)	0.0142 (16)	−0.0018 (12)
N2	0.013 (2)	0.006 (2)	0.016 (2)	−0.0007 (16)	0.008 (2)	0.0032 (17)
O2	0.013 (2)	0.006 (2)	0.016 (2)	−0.0007 (16)	0.008 (2)	0.0032 (17)
N3	0.028 (2)	0.0177 (16)	0.0062 (18)	−0.0054 (14)	0.0048 (16)	0.0015 (13)
O3	0.028 (2)	0.0177 (16)	0.0062 (18)	−0.0054 (14)	0.0048 (16)	0.0015 (13)
N4	0.008 (2)	0.009 (2)	0.013 (2)	0.000	0.003 (2)	0.000
O4	0.008 (2)	0.009 (2)	0.013 (2)	0.000	0.003 (2)	0.000
N5	0.0034 (17)	0.0255 (18)	0.0213 (19)	0.0014 (13)	0.0020 (15)	−0.0079 (15)
O5	0.0034 (17)	0.0255 (18)	0.0213 (19)	0.0014 (13)	0.0020 (15)	−0.0079 (15)

Geometric parameters (Å, º)

P1—O3^i	1.568 (3)	P2—O5^iii	1.584 (3)
P1—N3^i	1.568 (3)	P2—N5^iii	1.584 (3)
P1—O1^ii	1.573 (3)	P2—N1	1.588 (3)
P1—N1^ii	1.573 (3)	N1—P1^iv	1.574 (3)
P1—N5	1.574 (3)	N2—P2^v	1.5530 (9)
P1—N4	1.5755 (17)	N3—P1^i	1.568 (3)
P2—N2	1.5530 (9)	N4—P1^vi	1.5755 (17)
P2—N3	1.562 (3)	N5—P2^vii	1.584 (3)
O3^i—P1—N3^i	0.0	N2—P2—N3	110.10 (13)
O3^i—P1—O1^ii	109.55 (17)	N2—P2—O5^iii	109.69 (13)
N3^i—P1—O1^ii	109.55 (17)	N3—P2—O5^iii	112.0 (2)
O3^i—P1—N1^ii	109.55 (17)	N2—P2—N5^iii	109.69 (13)
N3^i—P1—N1^ii	109.55 (17)	N3—P2—N5^iii	112.0 (2)
O1^ii—P1—N1^ii	0.0	O5^iii—P2—N5^iii	0.0
O3^i—P1—N5	109.7 (2)	N2—P2—N1	108.03 (12)
N3^i—P1—N5	109.7 (2)	N3—P2—N1	110.13 (18)
O1^ii—P1—N5	111.04 (17)	O5^iii—P2—N1	106.79 (19)
N1^ii—P1—N5	111.04 (17)	N5^iii—P2—N1	106.79 (19)
O3^i—P1—N4	107.83 (16)	P1^iv—N1—P2	135.5 (2)
N3^i—P1—N4	107.83 (16)	P2—N2—P2^v	180.0
O1^ii—P1—N4	111.09 (19)	P2—N3—P1^i	148.5 (2)
N1^ii—P1—N4	111.09 (19)	P1^vi—N4—P1	141.3 (3)
N5—P1—N4	107.57 (15)	P1—N5—P2^vii	141.3 (2)

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