(NH₄)₇(HPO₄)₂(PO₄), hepta­ammonium bis­(hydrogenphosphate) phosphate

The asymmetric unit of the compound (NH₄)₇(HPO₄)₂(PO₄) consists of two hydrogen phosphate anions, one phosphate anion and seven ammonium cations, all of them located in general positions. The two [PO₃(OH)]²⁻ anions are linked to the PO₄³⁻ anion via an O—H...O hydrogen bond to form a three-anion unit, which is surrounded by the ammonium cations. The anions and cations are further connected via N—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](P-O) = 0.002 Å
• R factor = 0.031
• wR factor = 0.084
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.92

Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.95 Ratio
PLAT731_ALERT_1_C Bond    Calc     0.89(4), Rep   0.891(19) ......       2.11 su-Rat
              N2   -H24     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.86(4), Rep   0.866(19) ......       2.11 su-Rat
              N6   -H64     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.89(4), Rep   0.891(19) ......       2.11 su-Rat
              N2   -H24     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.86(4), Rep   0.866(19) ......       2.11 su-Rat
              N6   -H64     1.555   1.555
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H4 N
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          5
              H4 N
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          6
              H4 N
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          7
              H4 N
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #         10
              H4 N

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           28.13
           From the CIF: _reflns_number_total               4004
           Count of symmetry unique reflns         2401
           Completeness (_total/calc)            166.76%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1603
           Fraction of Friedel pairs measured     0.668
           Are heavy atom types Z>Si present        yes

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

   6 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
   2 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: IPDS (Stoe & Cie, 1996); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1996); software used to prepare material for publication: CIF-Editor (Wieczorrek, 2004).

heptaammonium bis(hydrogenphosphate) phosphate

Crystal data

(NH4)7(HPO4)2(PO4)	F(000) = 440
Mr = 413.22	Dx = 1.523 Mg m^−3
Monoclinic, P21	Melting point: unknown K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 10.4667 (17) Å	Cell parameters from 1206 reflections
b = 6.2976 (7) Å	θ = 1.9–28.2°
c = 14.072 (2) Å	µ = 0.39 mm^−1
β = 103.738 (19)°	T = 293 K
V = 901.0 (2) Å^3	Column, colourless
Z = 2	0.5 × 0.25 × 0.25 mm

Data collection

Stoe IPDS I diffractometer	4004 independent reflections
Radiation source: fine-focus sealed tube	3538 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Detector resolution: not measured pixels mm^-1	θmax = 28.1°, θmin = 2.8°
φ scans	h = −13→13
Absorption correction: numerical The absorption correction (X-RED; Stoe & Cie, 2001) was performed after optimizing the crystal shape using X-SHAPE (Stoe & Cie, 1999).	k = −7→7
Tmin = 0.902, Tmax = 0.962	l = −18→18
8608 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0526P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.084	(Δ/σ)max = 0.001
S = 1.06	Δρmax = 0.43 e Å^−3
4004 reflections	Δρmin = −0.45 e Å^−3
320 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
29 restraints	Extinction coefficient: 0.081 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (8)

Special details

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary. The scattering intensities were collected on an imaging plate diffractometer (IPDS I, Stoe & Cie) equipped with a fine focus sealed tube X-ray source (Mo Kα, λ = 0.71073 Å) operating at 50 kV and 40 mA. Intensity data for the title compound were collected at room temperature by φ-scans in 100 frames (0 < φ < 200°, Δφ = 2°, exposure time of 5 min) in the 2 Θ range 3.8 to 56.3°. Structure solution and refinement were carried out using the programs SIR92 (Altomare et al., 1993) and SHELXL97 (Sheldrick, 1997). A numerical absorption correction (X-RED (Stoe & Cie, 2001) was applied after optimization of the crystal shape (X-SHAPE (Stoe & Cie, 1999)). The last cycles of refinement included atomic positions for all atoms, anisotropic parameters for all non-hydrogen atoms and isotropic thermal parameters for all hydrogen atoms. The final difference maps were free of any chemically significant features. The refinement was based on F² for ALL reflections.

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 (Ų)

	x	y	z	Uiso*/Ueq
P1	0.06286 (5)	0.70682 (11)	0.69882 (4)	0.01697 (14)
P2	0.50392 (5)	0.20332 (11)	0.65964 (4)	0.01664 (14)
P3	0.73850 (6)	0.30542 (10)	0.97653 (4)	0.01667 (14)
O11	0.18639 (18)	0.8277 (4)	0.76074 (14)	0.0335 (5)
H111	0.189 (4)	0.847 (8)	0.822 (3)	0.066 (14)*
O12	−0.06103 (17)	0.7967 (4)	0.72264 (14)	0.0286 (4)
O13	0.06793 (16)	0.7483 (3)	0.59310 (12)	0.0265 (5)
O14	0.07606 (18)	0.4717 (3)	0.72402 (14)	0.0285 (4)
O21	0.49282 (19)	0.3334 (4)	0.75288 (15)	0.0307 (5)
H211	0.548 (6)	0.370 (11)	0.790 (4)	0.10 (2)*
O22	0.38360 (16)	0.2665 (3)	0.57963 (13)	0.0274 (5)
O23	0.63168 (16)	0.2661 (3)	0.63262 (12)	0.0240 (4)
O24	0.50188 (18)	−0.0326 (3)	0.68323 (13)	0.0268 (4)
O31	0.68406 (17)	0.4504 (3)	0.88660 (12)	0.0240 (4)
O32	0.85225 (17)	0.1739 (3)	0.95559 (13)	0.0269 (5)
O33	0.79062 (19)	0.4514 (3)	1.06460 (13)	0.0277 (4)
O34	0.63092 (18)	0.1584 (3)	0.99590 (13)	0.0272 (5)
N1	0.7063 (2)	0.8299 (5)	1.13488 (17)	0.0273 (5)
H11	0.646 (3)	0.805 (7)	1.168 (2)	0.049 (10)*
H12	0.716 (3)	0.706 (4)	1.106 (3)	0.041 (9)*
H13	0.678 (3)	0.929 (5)	1.092 (2)	0.037 (9)*
H14	0.777 (3)	0.859 (7)	1.181 (2)	0.043 (10)*
N2	0.5190 (2)	−0.1752 (5)	0.87680 (17)	0.0292 (5)
H21	0.456 (3)	−0.215 (7)	0.904 (2)	0.048 (10)*
H22	0.485 (4)	−0.165 (7)	0.8124 (15)	0.051 (11)*
H23	0.572 (3)	−0.286 (4)	0.882 (2)	0.032 (8)*
H24	0.560 (4)	−0.070 (6)	0.914 (3)	0.059 (12)*
N3	−0.1209 (2)	0.2149 (5)	0.76305 (15)	0.0260 (4)
H31	−0.201 (2)	0.228 (7)	0.724 (2)	0.048 (10)*
H32	−0.072 (3)	0.325 (4)	0.753 (2)	0.025 (8)*
H33	−0.125 (4)	0.211 (8)	0.8234 (15)	0.052 (10)*
H34	−0.094 (3)	0.091 (4)	0.749 (2)	0.035 (9)*
N4	0.3232 (2)	−0.2974 (5)	0.55885 (16)	0.0260 (4)
H41	0.244 (2)	−0.278 (6)	0.563 (2)	0.034 (8)*
H42	0.346 (3)	−0.430 (3)	0.576 (2)	0.034 (9)*
H43	0.323 (3)	−0.278 (7)	0.4968 (15)	0.047 (10)*
H44	0.368 (3)	−0.203 (5)	0.597 (2)	0.038 (9)*
N5	0.1203 (2)	0.1947 (5)	0.57987 (15)	0.0246 (4)
H51	0.2068 (18)	0.196 (6)	0.586 (2)	0.029 (7)*
H52	0.106 (3)	0.065 (3)	0.596 (2)	0.029 (9)*
H53	0.067 (2)	0.219 (6)	0.5208 (15)	0.028 (7)*
H54	0.107 (3)	0.282 (5)	0.624 (2)	0.034 (9)*
N6	0.32090 (19)	0.2056 (5)	0.37697 (16)	0.0260 (4)
H61	0.2386 (19)	0.230 (6)	0.350 (2)	0.028 (8)*
H62	0.337 (3)	0.218 (7)	0.4413 (14)	0.036 (8)*
H63	0.339 (3)	0.073 (3)	0.367 (2)	0.023 (8)*
H64	0.361 (4)	0.289 (6)	0.345 (3)	0.055 (12)*
N7	0.9065 (2)	−0.2428 (4)	0.91732 (19)	0.0291 (6)
H71	0.975 (2)	−0.274 (7)	0.9652 (19)	0.039 (9)*
H72	0.879 (3)	−0.117 (4)	0.934 (2)	0.021 (8)*
H73	0.851 (3)	−0.337 (5)	0.927 (3)	0.050 (11)*
H74	0.926 (5)	−0.241 (9)	0.859 (2)	0.083 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0166 (2)	0.0172 (3)	0.0174 (3)	−0.0006 (3)	0.00444 (18)	−0.0006 (3)
P2	0.0159 (2)	0.0166 (3)	0.0175 (2)	0.0001 (3)	0.00408 (18)	−0.0003 (3)
P3	0.0209 (3)	0.0131 (3)	0.0170 (3)	−0.0002 (2)	0.0065 (2)	−0.0007 (2)
O11	0.0271 (9)	0.0465 (14)	0.0268 (9)	−0.0146 (9)	0.0061 (7)	−0.0087 (9)
O12	0.0221 (8)	0.0324 (12)	0.0320 (9)	0.0040 (8)	0.0076 (7)	−0.0063 (8)
O13	0.0263 (8)	0.0341 (14)	0.0188 (8)	−0.0024 (7)	0.0047 (6)	0.0021 (7)
O14	0.0336 (9)	0.0195 (12)	0.0340 (10)	0.0037 (7)	0.0113 (8)	0.0057 (8)
O21	0.0224 (9)	0.0415 (14)	0.0282 (9)	−0.0007 (8)	0.0059 (7)	−0.0149 (9)
O22	0.0231 (8)	0.0316 (14)	0.0251 (9)	0.0018 (7)	0.0008 (6)	0.0017 (7)
O23	0.0196 (7)	0.0274 (14)	0.0259 (8)	−0.0012 (6)	0.0072 (6)	0.0006 (7)
O24	0.0332 (9)	0.0181 (11)	0.0299 (10)	0.0001 (7)	0.0090 (7)	0.0040 (8)
O31	0.0297 (9)	0.0196 (11)	0.0213 (8)	−0.0029 (7)	0.0032 (7)	0.0029 (7)
O32	0.0286 (8)	0.0244 (13)	0.0295 (9)	0.0070 (7)	0.0107 (7)	−0.0028 (8)
O33	0.0386 (10)	0.0225 (12)	0.0205 (8)	0.0005 (8)	0.0045 (7)	−0.0047 (7)
O34	0.0318 (9)	0.0239 (13)	0.0295 (9)	−0.0064 (7)	0.0144 (7)	0.0012 (7)
N1	0.0307 (11)	0.0232 (16)	0.0283 (12)	−0.0002 (10)	0.0075 (9)	0.0011 (10)
N2	0.0346 (12)	0.0249 (16)	0.0307 (12)	−0.0036 (10)	0.0127 (9)	−0.0016 (11)
N3	0.0274 (10)	0.0254 (14)	0.0278 (10)	0.0013 (11)	0.0114 (8)	0.0007 (12)
N4	0.0254 (10)	0.0253 (14)	0.0276 (10)	−0.0001 (11)	0.0073 (8)	0.0006 (12)
N5	0.0262 (9)	0.0231 (14)	0.0244 (10)	0.0002 (11)	0.0060 (7)	0.0020 (11)
N6	0.0240 (10)	0.0239 (14)	0.0298 (11)	0.0008 (11)	0.0062 (8)	−0.0001 (12)
N7	0.0259 (11)	0.0241 (18)	0.0398 (13)	−0.0015 (8)	0.0129 (10)	0.0026 (10)

Geometric parameters (Å, º)

P1—O14	1.521 (2)	N2—H24	0.891 (19)
P1—O12	1.5233 (18)	N3—H31	0.887 (18)
P1—O13	1.5237 (17)	N3—H32	0.893 (18)
P1—O11	1.573 (2)	N3—H33	0.859 (18)
P2—O24	1.523 (2)	N3—H34	0.868 (19)
P2—O23	1.5266 (17)	N4—H41	0.853 (18)
P2—O22	1.5292 (18)	N4—H42	0.886 (19)
P2—O21	1.574 (2)	N4—H43	0.882 (18)
P3—O34	1.5312 (18)	N4—H44	0.861 (19)
P3—O32	1.5352 (18)	N5—H51	0.888 (17)
P3—O33	1.5356 (19)	N5—H52	0.876 (19)
P3—O31	1.5548 (19)	N5—H53	0.896 (17)
O11—H111	0.87 (4)	N5—H54	0.863 (18)
O21—H211	0.72 (6)	N6—H61	0.868 (18)
N1—H11	0.879 (19)	N6—H62	0.883 (18)
N1—H12	0.899 (19)	N6—H63	0.873 (18)
N1—H13	0.864 (19)	N6—H64	0.866 (19)
N1—H14	0.882 (19)	N7—H71	0.884 (18)
N2—H21	0.881 (18)	N7—H72	0.893 (18)
N2—H22	0.894 (19)	N7—H73	0.864 (19)
N2—H23	0.880 (18)	N7—H74	0.885 (19)
O14—P1—O12	110.20 (12)	H23—N2—H24	109 (4)
O14—P1—O13	111.85 (11)	H31—N3—H32	109 (3)
O12—P1—O13	112.33 (11)	H31—N3—H33	111 (3)
O14—P1—O11	108.96 (12)	H32—N3—H33	110 (4)
O12—P1—O11	109.20 (12)	H31—N3—H34	105 (4)
O13—P1—O11	104.07 (11)	H32—N3—H34	115 (3)
O24—P2—O23	111.42 (11)	H33—N3—H34	106 (4)
O24—P2—O22	111.24 (11)	H41—N4—H42	109 (3)
O23—P2—O22	111.48 (10)	H41—N4—H43	106 (3)
O24—P2—O21	108.55 (12)	H42—N4—H43	110 (4)
O23—P2—O21	108.38 (11)	H41—N4—H44	105 (3)
O22—P2—O21	105.51 (11)	H42—N4—H44	114 (3)
O34—P3—O32	110.16 (11)	H43—N4—H44	113 (4)
O34—P3—O33	110.71 (11)	H51—N5—H52	103 (3)
O32—P3—O33	109.56 (11)	H51—N5—H53	119 (3)
O34—P3—O31	110.92 (11)	H52—N5—H53	108 (3)
O32—P3—O31	108.16 (11)	H51—N5—H54	105 (3)
O33—P3—O31	107.24 (11)	H52—N5—H54	110 (3)
P1—O11—H111	117 (3)	H53—N5—H54	112 (3)
P2—O21—H211	125 (5)	H61—N6—H62	111 (3)
H11—N1—H12	105 (4)	H61—N6—H63	109 (3)
H11—N1—H13	108 (3)	H62—N6—H63	104 (3)
H12—N1—H13	112 (3)	H61—N6—H64	103 (3)
H11—N1—H14	103 (3)	H62—N6—H64	119 (4)
H12—N1—H14	111 (4)	H63—N6—H64	110 (4)
H13—N1—H14	117 (4)	H71—N7—H72	105 (3)
H21—N2—H22	108 (3)	H71—N7—H73	101 (4)
H21—N2—H23	105 (4)	H72—N7—H73	107 (3)
H22—N2—H23	104 (4)	H71—N7—H74	113 (4)
H21—N2—H24	105 (3)	H72—N7—H74	113 (4)
H22—N2—H24	125 (4)	H73—N7—H74	118 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H111···O33^i	0.87 (4)	1.69 (5)	2.535 (3)	164 (5)
O21—H211···O31	0.72 (6)	1.79 (6)	2.510 (3)	177 (8)
N1—H11···O21^i	0.88 (2)	2.04 (2)	2.899 (3)	165 (4)
N1—H12···O33	0.90 (2)	1.93 (2)	2.802 (3)	163 (3)
N1—H13···O34^ii	0.86 (2)	1.97 (2)	2.828 (3)	174 (3)
N1—H14···O14^i	0.88 (2)	1.92 (2)	2.789 (3)	170 (4)
N2—H21···O34^iii	0.88 (2)	2.01 (2)	2.847 (3)	159 (3)
N2—H22···O24	0.89 (2)	2.05 (3)	2.833 (3)	146 (4)
N2—H23···O31^iv	0.88 (2)	2.03 (2)	2.907 (3)	176 (3)
N2—H24···O34	0.89 (2)	1.88 (2)	2.768 (3)	174 (4)
N3—H31···O23^v	0.89 (2)	1.93 (2)	2.814 (3)	176 (4)
N3—H32···O14	0.89 (2)	1.93 (2)	2.776 (3)	158 (3)
N3—H33···O32^v	0.86 (2)	1.95 (2)	2.801 (3)	173 (4)
N3—H34···O12^iv	0.87 (2)	1.94 (2)	2.797 (4)	170 (3)
N4—H41···O13^iv	0.85 (2)	1.99 (2)	2.840 (3)	172 (3)
N4—H42···O22^iv	0.89 (2)	1.95 (2)	2.818 (4)	166 (3)
N4—H43···O23^vi	0.88 (2)	2.01 (2)	2.872 (3)	167 (3)
N4—H44···O24	0.86 (2)	1.94 (2)	2.791 (3)	167 (4)
N5—H51···O22	0.89 (2)	1.93 (2)	2.794 (3)	165 (3)
N5—H52···O13^iv	0.88 (2)	2.03 (2)	2.879 (4)	163 (3)
N5—H53···O13^vii	0.90 (2)	1.88 (2)	2.764 (3)	169 (3)
N5—H54···O14	0.86 (2)	1.93 (2)	2.796 (3)	178 (4)
N6—H61···O12^vii	0.87 (2)	1.94 (2)	2.807 (3)	173 (3)
N6—H62···O22	0.88 (2)	1.92 (2)	2.797 (3)	174 (4)
N6—H63···O23^vi	0.87 (2)	1.96 (2)	2.821 (4)	169 (3)
N6—H64···O24^viii	0.87 (2)	1.93 (2)	2.761 (3)	160 (4)
N7—H71···O32^ix	0.88 (2)	1.91 (2)	2.776 (3)	166 (3)
N7—H72···O32	0.89 (2)	1.89 (2)	2.765 (3)	166 (3)
N7—H73···O31^iv	0.86 (2)	2.17 (2)	2.977 (3)	156 (3)
N7—H73···O33^iv	0.86 (2)	2.55 (3)	3.266 (3)	141 (3)
N7—H74···O12^x	0.89 (2)	1.97 (2)	2.850 (3)	169 (5)

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