(NH₄)(Zn,Ga)₂(PO₄)₂, an open-framework structure

Ammonium di­(zinc, gallium) bis­(phosphate), (NH₄)(Zn,Ga)₂(PO₄)₂, has a zeolite-like open-framework structure. It contains channels of four- and eight-membered rings of alternating tetrahedra of (Zn,Ga)O₄ (Zn:Ga ≃ 1:1) and PO₄, in which the tetrahedra are connected via corners. The NH₄⁺ cations are located in the channels and provide weak hydrogen bonds to the framework O atoms. The average (Zn,Ga)—O bond lengths of the two non-equivalent (Zn,Ga)O₄ tetrahedra are 1.863 and 1.870 Å. All atoms are in general positions. The compound is isostructural with K(Co^II,Al)₂(PO₄)₂ and [(NH₄)_x(NH₃)_0.5−x]Co_xAl_1−xPO₄ (x = 0.38). Single-crystal Raman and IR spectra are discussed.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](P-O) = 0.002 Å
• R factor = 0.023
• wR factor = 0.059
• Data-to-parameter ratio = 17.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_420  Alert C D-H Without Acceptor       N      -   H(1)              ?

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   H4 Ga1 N1 O8 P2 Zn1
          Atom count from _chemical_formula_moiety:

ABSTM_02  When printed, the submitted absorption T values will be replaced
          by the scaled T values. Since the ratio of scaled T's is
          identical to the ratio of reported T values, the scaling does
          not imply a change to the absorption corrections used in the
          study.
          Ratio of Tmax expected/reported      0.904
          Tmax scaled      0.465 Tmin scaled      0.328


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

Ammonium di(zinc,gallium) diphosphate

Crystal data

(NH4)(Zn·Ga)2(PO4)2	F(000) = 1328
Mr = 343.07	Dx = 2.921 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2331 reflections
a = 13.370 (3) Å	θ = 2.3–30.0°
b = 13.190 (3) Å	µ = 6.95 mm^−1
c = 8.998 (2) Å	T = 150 K
β = 100.46 (3)°	Fragment, colourless
V = 1560.4 (6) Å^3	0.18 × 0.11 × 0.11 mm
Z = 8

Data collection

Nonius KappaCCD diffractometer	2287 independent reflections
Radiation source: fine-focus sealed tube	2207 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (HKL SCALEPACK; Otwinowski & Minor, 1997)	h = −18→18
Tmin = 0.363, Tmax = 0.515	k = −18→18
4483 measured reflections	l = −12→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.023	Only H-atom coordinates refined
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.011P)^2 + 9.80P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max = 0.001
2287 reflections	Δρmax = 1.00 e Å^−3
131 parameters	Δρmin = −0.59 e Å^−3
4 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00097 (13)

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. H atoms were constrained to have a U_iso of 0.05 Ų. N—H distances were restrained to a length of 0.9 (5) Å.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.37042 (2)	0.05625 (2)	0.11547 (3)	0.01214 (9)	0.50
Ga1	0.37042 (2)	0.05625 (2)	0.11547 (3)	0.01214 (9)	0.50
Zn2	0.58004 (2)	0.37567 (2)	0.06484 (3)	0.01230 (9)	0.50
Ga2	0.58004 (2)	0.37567 (2)	0.06484 (3)	0.01230 (9)	0.50
P1	0.35211 (5)	0.43822 (5)	0.08472 (7)	0.01297 (13)
P2	0.57660 (5)	0.13577 (5)	0.04242 (7)	0.01139 (13)
O1	0.6526 (2)	0.4051 (3)	0.2552 (3)	0.0491 (8)
O2	0.63921 (17)	0.44698 (16)	−0.0795 (3)	0.0257 (5)
O3	0.24507 (15)	0.10156 (17)	0.0141 (3)	0.0251 (5)
O4	0.43892 (16)	0.38788 (17)	0.0219 (3)	0.0293 (5)
O5	0.36881 (19)	0.0803 (2)	0.3189 (3)	0.0358 (6)
O6	0.61803 (19)	0.24192 (17)	0.0297 (4)	0.0370 (6)
O7	0.46198 (15)	0.14235 (15)	0.0414 (2)	0.0203 (4)
O8	0.40204 (17)	−0.07976 (17)	0.0977 (2)	0.0228 (4)
N	0.3244 (2)	0.2490 (3)	−0.2222 (3)	0.0294 (6)
H1	0.294 (4)	0.302 (3)	−0.250 (6)	0.050*
H2	0.265 (3)	0.217 (4)	−0.221 (6)	0.050*
H3	0.357 (4)	0.222 (4)	−0.287 (5)	0.050*
H4	0.371 (3)	0.270 (4)	−0.157 (5)	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00842 (13)	0.01667 (15)	0.01109 (14)	0.00092 (9)	0.00113 (9)	−0.00309 (10)
Ga1	0.00842 (13)	0.01667 (15)	0.01109 (14)	0.00092 (9)	0.00113 (9)	−0.00309 (10)
Zn2	0.00988 (14)	0.01168 (14)	0.01535 (15)	−0.00052 (9)	0.00234 (10)	−0.00154 (10)
Ga2	0.00988 (14)	0.01168 (14)	0.01535 (15)	−0.00052 (9)	0.00234 (10)	−0.00154 (10)
P1	0.0091 (3)	0.0163 (3)	0.0129 (3)	−0.0022 (2)	0.0002 (2)	0.0046 (2)
P2	0.0103 (3)	0.0106 (3)	0.0135 (3)	−0.0002 (2)	0.0029 (2)	0.0010 (2)
O1	0.0523 (18)	0.073 (2)	0.0190 (11)	0.0085 (16)	−0.0003 (11)	−0.0202 (13)
O2	0.0287 (11)	0.0188 (10)	0.0332 (12)	−0.0043 (8)	0.0155 (9)	−0.0028 (9)
O3	0.0132 (9)	0.0209 (10)	0.0374 (12)	0.0020 (7)	−0.0059 (8)	−0.0065 (9)
O4	0.0111 (9)	0.0226 (10)	0.0549 (15)	0.0019 (8)	0.0083 (9)	−0.0048 (10)
O5	0.0272 (12)	0.0629 (18)	0.0187 (10)	−0.0208 (12)	0.0079 (9)	−0.0154 (11)
O6	0.0267 (12)	0.0148 (10)	0.075 (2)	−0.0065 (9)	0.0246 (12)	−0.0068 (11)
O7	0.0134 (9)	0.0175 (9)	0.0311 (11)	−0.0003 (7)	0.0066 (8)	0.0027 (8)
O8	0.0274 (11)	0.0249 (10)	0.0176 (9)	0.0034 (8)	0.0083 (8)	−0.0005 (8)
N	0.0212 (13)	0.0418 (17)	0.0259 (14)	−0.0028 (12)	0.0059 (10)	−0.0108 (12)

Geometric parameters (Å, º)

Zn1—O3	1.855 (2)	O2—P1^v	1.520 (2)
Zn1—O8	1.857 (2)	O2—N^iv	3.250 (4)
Zn1—O5	1.862 (2)	O2—N^iii	4.501 (4)
Zn1—O7	1.878 (2)	O3—P1^i	1.528 (2)
Zn1—N^i	3.900 (3)	O3—N^i	2.980 (4)
Zn1—N	3.923 (3)	O3—N	3.200 (4)
Zn1—N^ii	4.364 (3)	O4—N	3.050 (4)
Zn2—O1	1.850 (3)	O4—N^i	4.604 (4)
Zn2—O4	1.863 (2)	O5—P2^vi	1.514 (2)
Zn2—O6	1.878 (2)	O5—N^i	3.418 (5)
Zn2—O2	1.889 (2)	O5—N^ii	4.391 (5)
Zn2—N^iii	3.843 (3)	O6—N^iv	3.005 (4)
Zn2—N^iv	3.920 (3)	O6—N^iii	3.221 (4)
Zn2—N	4.236 (3)	O6—N	4.163 (4)
Zn2—N^v	5.243 (3)	O7—N	3.067 (4)
P1—O1^vi	1.517 (3)	O7—N^iv	4.623 (4)
P1—O2^v	1.520 (2)	O7—N^i	4.649 (4)
P1—O3^i	1.528 (2)	O8—P2^viii	1.532 (2)
P1—O4	1.532 (2)	O8—N^ii	3.049 (4)
P1—N	3.691 (3)	O8—N^viii	4.258 (4)
P1—N^i	3.775 (3)	N—O3^i	2.980 (4)
P1—N^vii	4.518 (4)	N—O6^iv	3.005 (4)
P2—O5^vi	1.514 (2)	N—O1^ix	3.045 (4)
P2—O6	1.518 (2)	N—O8^x	3.049 (4)
P2—O8^viii	1.532 (2)	N—O6^ix	3.221 (4)
P2—O7	1.533 (2)	N—O2^iv	3.250 (4)
P2—N^iv	3.698 (3)	N—O5^i	3.418 (5)
P2—N^iii	3.902 (3)	N—P2^iv	3.698 (3)
P2—N	4.044 (3)	N—H1	0.82 (4)
O1—P1^vi	1.517 (3)	N—H2	0.90 (4)
O1—N^iii	3.045 (4)	N—H3	0.86 (4)
O1—N^v	4.587 (5)	N—H4	0.83 (4)
O1—N^vi	4.639 (4)
O3—Zn1—O8	117.93 (10)	O6^iv—N—O7	118.67 (12)
O3—Zn1—O5	104.93 (12)	O1^ix—N—O7	94.87 (12)
O8—Zn1—O5	107.04 (12)	O8^x—N—O7	82.01 (10)
O3—Zn1—O7	102.69 (10)	O4—N—O7	64.30 (9)
O8—Zn1—O7	112.36 (9)	O3^i—N—O3	78.82 (10)
O5—Zn1—O7	111.72 (10)	O6^iv—N—O3	139.82 (13)
O1—Zn2—O4	121.02 (13)	O1^ix—N—O3	45.76 (8)
O1—Zn2—O6	103.92 (14)	O8^x—N—O3	95.41 (11)
O4—Zn2—O6	109.93 (10)	O4—N—O3	94.03 (11)
O1—Zn2—O2	108.50 (13)	O7—N—O3	55.40 (8)
O4—Zn2—O2	110.42 (11)	O3^i—N—O6^ix	94.91 (10)
O6—Zn2—O2	101.07 (11)	O6^iv—N—O6^ix	72.14 (10)
O1^vi—P1—O2^v	109.44 (17)	O1^ix—N—O6^ix	55.82 (8)
O1^vi—P1—O3^i	106.02 (16)	O8^x—N—O6^ix	89.44 (10)
O2^v—P1—O3^i	112.69 (13)	O4—N—O6^ix	137.02 (13)
O1^vi—P1—O4	113.00 (17)	O7—N—O6^ix	150.63 (13)
O2^v—P1—O4	110.67 (13)	O3—N—O6^ix	97.93 (10)
O3^i—P1—O4	104.92 (13)	O3^i—N—O2^iv	84.73 (11)
O5^vi—P2—O6	112.32 (17)	O6^iv—N—O2^iv	55.26 (8)
O5^vi—P2—O8^viii	108.13 (14)	O1^ix—N—O2^iv	133.32 (12)
O6—P2—O8^viii	104.93 (14)	O8^x—N—O2^iv	101.35 (10)
O5^vi—P2—O7	111.32 (13)	O4—N—O2^iv	78.86 (10)
O6—P2—O7	108.99 (12)	O7—N—O2^iv	131.65 (11)
O8^viii—P2—O7	110.97 (13)	O3—N—O2^iv	162.54 (12)
O3^i—N—O6^iv	139.45 (14)	O6^ix—N—O2^iv	77.53 (10)
O3^i—N—O1^ix	99.58 (12)	O3^i—N—O5^i	54.35 (8)
O6^iv—N—O1^ix	103.53 (12)	O6^iv—N—O5^i	95.39 (11)
O3^i—N—O8^x	173.19 (14)	O1^ix—N—O5^i	84.08 (11)
O6^iv—N—O8^x	47.08 (7)	O8^x—N—O5^i	131.40 (11)
O1^ix—N—O8^x	78.55 (11)	O4—N—O5^i	92.59 (10)
O3^i—N—O4	47.43 (7)	O7—N—O5^i	144.95 (11)
O6^iv—N—O4	120.14 (12)	O3—N—O5^i	104.08 (10)
O1^ix—N—O4	136.30 (13)	O6^ix—N—O5^i	44.46 (7)
O8^x—N—O4	130.34 (12)	O2^iv—N—O5^i	60.81 (8)
O3^i—N—O7	91.67 (10)
O4—Zn2—O1—P1^vi	1.3 (5)	O8—Zn1—O3—P1^i	2.7 (3)
O6—Zn2—O1—P1^vi	−122.6 (4)	O5—Zn1—O3—P1^i	−116.3 (3)
O2—Zn2—O1—P1^vi	130.4 (4)	O7—Zn1—O3—P1^i	126.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H2···O1^ix	0.90 (4)	2.19 (4)	3.045 (4)	160 (5)
N—H3···O6^iv	0.86 (4)	2.28 (4)	3.005 (4)	141 (4)
N—H3···O8^x	0.86 (4)	2.28 (4)	3.049 (4)	148 (4)
N—H4···O4	0.83 (4)	2.30 (4)	3.050 (4)	151 (5)

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