Synthesis, crystal structure and vibrational spectra of a new di­ammonium zinc(II) di­hydrogendiphosphate dihydrate, (NH4)2Zn(H2P2O7)2·2H2O

Essehli, R.; Lachkar, M.; Svoboda, I.; Fuess, H.; El Bali, B.

doi:10.1107/S1600536805004642

Synthesis, crystal structure and vibrational spectra of a new diammonium zinc(II) dihydrogendiphosphate dihydrate, (NH₄)₂Zn(H₂P₂O₇)₂·2H₂O

R. Essehli, M. Lachkar, I. Svoboda, H. Fuess and B. El Bali

(NH₄)₂Zn(H₂P₂O₇)₂·2H₂O is isostructural with its manganese homologue. Isolated almost-regular ZnO₆ octahedra form a layered structure. The IR and Raman spectra show bands characteristic of H₂P₂O₇ groups.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805004642/br6177sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805004642/br6177Isup2.hkl Contains datablock I

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Key indicators

Single-crystal X-ray study
T = 301 K
Mean (P-O) = 0.002 Å
R factor = 0.032
wR factor = 0.090
Data-to-parameter ratio = 11.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          4
            O1  -ZN1 -O1  -P1     52.00100.00   2.565   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         20
            O5  -ZN1 -O5  -P2    -12.00100.00   2.565   1.555   1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.896(10) ......       3.00 su-Rat
              O2   -H2      1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.90(3), Rep   0.895(10) ......       3.00 su-Rat
              O7   -H7      1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.84(3), Rep   0.842(10) ......       3.00 su-Rat
              O8   -H81     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.90(2), Rep    0.896(9) ......       2.22 su-Rat
              N1   -H13     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.90(2), Rep    0.894(9) ......       2.22 su-Rat
              N1   -H14     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.896(10) ......       3.00 su-Rat
              O2   -H2      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(3), Rep   0.895(10) ......       3.00 su-Rat
              O7   -H7      1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.84(3), Rep   0.842(10) ......       3.00 su-Rat
              O8   -H81     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(2), Rep    0.896(9) ......       2.22 su-Rat
              N1   -H13     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.90(2), Rep    0.894(9) ......       2.22 su-Rat
              N1   -H14     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.61(3), Rep   1.610(12) ......       2.50 su-Rat
              H2   -O6      1.555   1.655
PLAT736_ALERT_1_C H...A   Calc     1.95(3), Rep   1.948(10) ......       3.00 su-Rat
              H81  -O3      1.555   1.565
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              H4 N

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  17 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

  13 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis RED (Oxford Diffraction, 2001); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

diammonium zinc(II) dihydrogendiphosphate dihydrate top

Crystal data top

(NH₄)₂Zn(H₂P₂O₇)₂·2H₂O	Z = 1
M_r = 489.40	F(000) = 248
Triclinic, P1	D_x = 2.168 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0074 (9) Å	Cell parameters from 2048 reflections
b = 7.339 (1) Å	θ = 2.8–29.8°
c = 7.796 (1) Å	µ = 2.15 mm⁻¹
α = 81.240 (1)°	T = 301 K
β = 71.080 (1)°	Prism, colourless
γ = 88.150 (1)°	0.26 × 0.18 × 0.08 mm
V = 374.78 (9) Å³

Data collection top

Oxford Diffraction Xcalibur with Sapphire CCD detector diffractometer	1495 independent reflections
Radiation source: fine-focus sealed tube	1402 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Rotation method data acquisition using ω scans	θ_max = 26.4°, θ_min = 4.1°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003)	h = −8→8
T_min = 0.605, T_max = 0.847	k = −9→6
2491 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: difference Fourier map
wR(F²) = 0.090	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0631P)² + 0.1969P] where P = (F_o² + 2F_c²)/3
1495 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.78 e Å⁻³
14 restraints	Δρ_min = −0.72 e Å⁻³

Special details top

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.5000	0.0000	0.01777 (16)
P1	0.25823 (9)	0.21050 (8)	−0.25586 (8)	0.01649 (18)
P2	−0.15613 (9)	0.25890 (8)	−0.25619 (8)	0.01671 (18)
O1	0.2489 (3)	0.3567 (3)	−0.1397 (3)	0.0256 (4)
O2	0.4409 (3)	0.2373 (3)	−0.4346 (2)	0.0272 (4)
H2	0.552 (3)	0.269 (5)	−0.412 (5)	0.033*
O3	0.2456 (3)	0.0158 (3)	−0.1574 (3)	0.0321 (5)
O4	0.0814 (3)	0.2336 (3)	−0.3463 (3)	0.0237 (4)
O5	−0.1912 (3)	0.3815 (2)	−0.1113 (3)	0.0217 (4)
O6	−0.2283 (3)	0.3292 (3)	−0.4143 (3)	0.0263 (4)
O7	−0.2490 (3)	0.0646 (3)	−0.1662 (3)	0.0279 (4)
H7	−0.226 (6)	0.022 (5)	−0.061 (3)	0.033*
O8	0.0560 (3)	0.7172 (3)	−0.2218 (3)	0.0311 (5)
H81	0.118 (5)	0.805 (4)	−0.204 (4)	0.037*
H82	0.102 (5)	0.705 (4)	−0.3338 (19)	0.037*
N1	−0.4171 (4)	0.7101 (3)	−0.2020 (3)	0.0292 (5)
H11	−0.5452 (18)	0.685 (3)	−0.131 (3)	0.035*
H12	−0.408 (4)	0.715 (3)	−0.3199 (15)	0.035*
H13	−0.337 (3)	0.622 (3)	−0.172 (3)	0.035*
H14	−0.379 (4)	0.819 (3)	−0.184 (3)	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0194 (2)	0.0188 (2)	0.0169 (2)	−0.00129 (15)	−0.00712 (17)	−0.00460 (15)
P1	0.0152 (3)	0.0208 (3)	0.0138 (3)	−0.0008 (2)	−0.0047 (2)	−0.0035 (2)
P2	0.0155 (3)	0.0207 (3)	0.0155 (3)	−0.0014 (2)	−0.0067 (2)	−0.0035 (2)
O1	0.0221 (9)	0.0319 (10)	0.0272 (10)	0.0024 (7)	−0.0094 (8)	−0.0149 (8)
O2	0.0166 (9)	0.0490 (12)	0.0155 (9)	−0.0049 (8)	−0.0029 (7)	−0.0076 (8)
O3	0.0463 (12)	0.0248 (9)	0.0277 (11)	−0.0059 (8)	−0.0178 (10)	0.0024 (8)
O4	0.0169 (8)	0.0377 (10)	0.0200 (9)	0.0022 (7)	−0.0079 (7)	−0.0106 (8)
O5	0.0199 (8)	0.0241 (8)	0.0235 (9)	−0.0002 (7)	−0.0074 (7)	−0.0097 (7)
O6	0.0208 (9)	0.0402 (10)	0.0188 (9)	−0.0030 (8)	−0.0097 (8)	0.0012 (8)
O7	0.0363 (11)	0.0238 (9)	0.0251 (10)	−0.0098 (8)	−0.0120 (9)	−0.0016 (8)
O8	0.0458 (13)	0.0253 (9)	0.0190 (9)	−0.0076 (8)	−0.0063 (9)	−0.0009 (7)
N1	0.0338 (13)	0.0322 (12)	0.0227 (12)	0.0021 (10)	−0.0111 (10)	−0.0031 (10)

Geometric parameters (Å, º) top

Zn1—O1ⁱ	2.0816 (18)	P2—O5	1.5040 (17)
Zn1—O1	2.0816 (18)	P2—O7	1.5521 (19)
Zn1—O5ⁱ	2.0888 (17)	P2—O4	1.5997 (19)
Zn1—O5	2.0888 (17)	O2—H2	0.896 (10)
Zn1—O8	2.108 (2)	O7—H7	0.895 (10)
Zn1—O8ⁱ	2.108 (2)	O8—H81	0.842 (10)
P1—O1	1.4930 (18)	O8—H82	0.844 (10)
P1—O3	1.506 (2)	N1—H11	0.896 (9)
P1—O2	1.5476 (18)	N1—H12	0.897 (9)
P1—O4	1.6056 (19)	N1—H13	0.896 (9)
P2—O6	1.4950 (19)	N1—H14	0.894 (9)

O1ⁱ—Zn1—O1	180.0	O6—P2—O5	116.10 (11)
O1ⁱ—Zn1—O5ⁱ	92.85 (7)	O6—P2—O7	109.92 (11)
O1—Zn1—O5ⁱ	87.15 (7)	O5—P2—O7	109.59 (11)
O1ⁱ—Zn1—O5	87.15 (7)	O6—P2—O4	104.82 (10)
O1—Zn1—O5	92.85 (7)	O5—P2—O4	108.97 (10)
O5ⁱ—Zn1—O5	180.0	O7—P2—O4	106.97 (11)
O1ⁱ—Zn1—O8	88.23 (8)	P1—O1—Zn1	128.95 (11)
O1—Zn1—O8	91.77 (8)	P1—O2—H2	111 (2)
O5ⁱ—Zn1—O8	92.18 (8)	P2—O4—P1	130.82 (12)
O5—Zn1—O8	87.82 (8)	P2—O5—Zn1	133.31 (11)
O1ⁱ—Zn1—O8ⁱ	91.77 (8)	P2—O7—H7	114 (2)
O1—Zn1—O8ⁱ	88.23 (8)	Zn1—O8—H81	111 (2)
O5ⁱ—Zn1—O8ⁱ	87.82 (8)	Zn1—O8—H82	125 (2)
O5—Zn1—O8ⁱ	92.18 (8)	H81—O8—H82	108.8 (16)
O8—Zn1—O8ⁱ	180.0	H11—N1—H12	109.0 (13)
O1—P1—O3	114.88 (12)	H11—N1—H13	109.3 (14)
O1—P1—O2	112.54 (11)	H12—N1—H13	110.0 (14)
O3—P1—O2	111.10 (12)	H11—N1—H14	109.3 (14)
O1—P1—O4	111.00 (10)	H12—N1—H14	109.9 (14)
O3—P1—O4	107.63 (11)	H13—N1—H14	109 (3)
O2—P1—O4	98.36 (10)

O3—P1—O1—Zn1	−94.77 (17)	O1—P1—O4—P2	−50.1 (2)
O2—P1—O1—Zn1	136.75 (14)	O3—P1—O4—P2	76.37 (18)
O4—P1—O1—Zn1	27.61 (18)	O2—P1—O4—P2	−168.26 (16)
O1ⁱ—Zn1—O1—P1	52 (100)	O6—P2—O5—Zn1	−123.32 (15)
O5ⁱ—Zn1—O1—P1	174.21 (16)	O7—P2—O5—Zn1	111.43 (16)
O5—Zn1—O1—P1	−5.79 (16)	O4—P2—O5—Zn1	−5.31 (18)
O8—Zn1—O1—P1	−93.70 (16)	O1ⁱ—Zn1—O5—P2	173.00 (16)
O8ⁱ—Zn1—O1—P1	86.30 (16)	O1—Zn1—O5—P2	−7.00 (16)
O6—P2—O4—P1	163.32 (16)	O5ⁱ—Zn1—O5—P2	−12 (100)
O5—P2—O4—P1	38.41 (19)	O8—Zn1—O5—P2	84.66 (16)
O7—P2—O4—P1	−79.99 (17)	O8ⁱ—Zn1—O5—P2	−95.34 (16)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O6ⁱⁱ	0.90 (1)	1.61 (1)	2.495 (3)	169 (4)
O7—H7···O3ⁱⁱⁱ	0.90 (1)	1.64 (2)	2.510 (3)	162 (4)
O8—H81···O3^iv	0.84 (1)	1.95 (1)	2.788 (3)	176 (3)
O8—H82···O6^v	0.84 (1)	1.93 (1)	2.770 (3)	175 (4)
N1—H11···O5^vi	0.90 (1)	2.18 (1)	3.037 (3)	161 (2)
N1—H12···O2^v	0.90 (1)	1.98 (1)	2.859 (3)	167 (2)
N1—H13···O5	0.90 (1)	2.08 (1)	2.963 (3)	169 (3)
N1—H14···O7^iv	0.89 (1)	2.09 (1)	2.977 (3)	172 (2)

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

Brahim crystal Raman spectrum (cm^-1) top

Raman frequency	Mode assignment
3344.7	OH stretching
3220	NH stretching
2850	NH₄⁺ combination modes
1670	OH₂ bending
1340	OH₂ bending
1450	NH₄⁺ bending
1034.9-1192.4	P—O stretching
970.6	asymmetric P—O—P stretching
907.6	asymmetric P—O—P stretching
748.2	symmetric P—O—P stretching
473.6-578.5	P—O bending modes and NH₄⁺ torsional oscillation

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Synthesis, crystal structure and vibrational spectra of a new di­ammonium zinc(II) di­hydrogendiphosphate dihydrate, (NH4)2Zn(H2P2O7)2·2H2O

Supporting information

Key indicators

checkCIF/PLATON results

Synthesis, crystal structure and vibrational spectra of a new diammonium zinc(II) dihydrogendiphosphate dihydrate, (NH₄)₂Zn(H₂P₂O₇)₂·2H₂O