Bis­(ethylene­diammonium) diaqua­bis[hydrogen­diphosphato(3–)]nickelate(II): structure and vibrational spectroscopy

In the crystal structure of the title compound, (C₂N₂H₁₀)₂[Ni(HP₂O₇)₂(H₂O)₂], each Ni cation is surrounded by two symmetry-related diphosphate anions and two symmetry-related water mol­ecules within a distorted octa­hedron. The octa­hedra are connected via O—H...O hydrogen bonding into layers. The ethyl­enediammonium cations are located in the inter­layer space and are connected by N—H...O hydrogen bonds to the anionic layers. The Ni cation and the two crystallographically independent ethyl­enediammonium cations are located on centres of inversion, whereas the diphosphate anion and the water mol­ecule are located in general positions.

Key indicators

• Single-crystal X-ray study
• T = 301 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.089
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O1  -NI1 -O1  -P1      9.00  0.00   2.775   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            O3  -NI1 -O3  -P2     13.00  0.00   2.775   1.555   1.555   1.555

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

   2 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); 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.

bis(ethylenediammonium) diaquabis[hydrogendiphosphato(3-)]nickel(II)

Crystal data

(C2H10N2)2[Ni(HP2O7)2(H2O)2]	Z = 1
Mr = 568.88	F(000) = 294
Triclinic, P1	Dx = 1.946 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4898 (9) Å	Cell parameters from 1929 reflections
b = 7.5517 (7) Å	θ = 3.0–29.2°
c = 9.7780 (1) Å	µ = 1.42 mm^−1
α = 103.876 (9)°	T = 301 K
β = 111.190 (1)°	Prism, pale green
γ = 97.711 (8)°	0.18 × 0.10 × 0.06 mm
V = 485.48 (9) Å^3

Data collection

Oxford Xcalibur diffractometer with Sapphire CCD area detector	1930 independent reflections
Radiation source: fine-focus sealed tube	1662 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Rotation method data acquisition using ω scans	θmax = 26.4°, θmin = 4.1°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2002)	h = −9→9
Tmin = 0.785, Tmax = 0.920	k = −9→9
3240 measured reflections	l = −11→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0576P)^2] where P = (Fo^2 + 2Fc^2)/3
1930 reflections	(Δ/σ)max = 0.010
140 parameters	Δρmax = 0.53 e Å^−3
3 restraints	Δρmin = −0.72 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.

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
Ni1	1.0000	1.0000	0.0000	0.01252 (15)
P1	1.22608 (10)	0.71164 (9)	−0.14428 (8)	0.01438 (18)
P2	1.29920 (9)	0.77543 (9)	0.18040 (7)	0.01297 (17)
O1	1.0799 (3)	0.8340 (2)	−0.1601 (2)	0.0172 (4)
O2	1.3634 (3)	0.7589 (3)	0.0369 (2)	0.0185 (4)
O3	1.1686 (3)	0.9143 (2)	0.17600 (19)	0.0167 (4)
O4	1.1143 (3)	0.4999 (3)	−0.2013 (2)	0.0242 (5)
O5	1.3646 (3)	0.7375 (3)	−0.2194 (2)	0.0249 (5)
O6	1.4931 (3)	0.8490 (3)	0.3223 (2)	0.0204 (4)
O7	1.1921 (3)	0.5790 (3)	0.1580 (2)	0.0240 (5)
H7	1.1009	0.5848	0.1852	0.029*
O8	1.2352 (3)	1.2237 (3)	0.0447 (2)	0.0210 (4)
H8A	1.219 (4)	1.334 (2)	0.068 (3)	0.025*
H8B	1.3578 (18)	1.232 (4)	0.092 (3)	0.025*
N1	0.8384 (3)	0.8787 (3)	0.2869 (2)	0.0168 (5)
H1A	0.8695	0.9718	0.2521	0.020*
H1C	0.7220	0.8776	0.2921	0.020*
H1B	0.8314	0.7695	0.2229	0.020*
N4	0.5620 (3)	0.7615 (3)	0.5911 (2)	0.0196 (5)
H4A	0.6775	0.8459	0.6437	0.024*
H4B	0.4951	0.7630	0.6501	0.024*
H4C	0.4928	0.7895	0.5071	0.024*
C2	0.9937 (4)	0.9076 (4)	0.4447 (3)	0.0261 (7)
H2A	1.1205	0.9081	0.4392	0.031*
H2B	0.9615	0.8049	0.4820	0.031*
C3	0.5962 (4)	0.5730 (4)	0.5451 (3)	0.0256 (6)
H3A	0.6726	0.5429	0.6366	0.031*
H3B	0.6716	0.5721	0.4827	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0119 (3)	0.0121 (2)	0.0139 (3)	0.00482 (18)	0.00507 (19)	0.00399 (18)
P1	0.0149 (3)	0.0141 (3)	0.0159 (3)	0.0051 (3)	0.0083 (3)	0.0038 (3)
P2	0.0122 (3)	0.0124 (3)	0.0149 (3)	0.0041 (3)	0.0052 (3)	0.0052 (3)
O1	0.0190 (9)	0.0175 (9)	0.0163 (9)	0.0083 (7)	0.0075 (8)	0.0049 (7)
O2	0.0163 (9)	0.0239 (10)	0.0170 (9)	0.0062 (8)	0.0079 (8)	0.0067 (8)
O3	0.0181 (10)	0.0183 (9)	0.0171 (9)	0.0101 (8)	0.0082 (8)	0.0067 (8)
O4	0.0278 (11)	0.0125 (9)	0.0308 (11)	0.0039 (8)	0.0144 (9)	0.0011 (8)
O5	0.0237 (11)	0.0340 (12)	0.0236 (11)	0.0075 (9)	0.0154 (9)	0.0108 (9)
O6	0.0158 (9)	0.0267 (10)	0.0180 (10)	0.0058 (8)	0.0052 (8)	0.0084 (8)
O7	0.0231 (11)	0.0186 (10)	0.0364 (12)	0.0045 (8)	0.0180 (10)	0.0100 (9)
O8	0.0148 (10)	0.0152 (9)	0.0303 (11)	0.0029 (8)	0.0080 (9)	0.0045 (8)
N1	0.0131 (11)	0.0169 (11)	0.0208 (12)	0.0024 (9)	0.0101 (9)	0.0020 (9)
N4	0.0261 (13)	0.0151 (11)	0.0164 (11)	0.0029 (9)	0.0090 (10)	0.0037 (9)
C2	0.0265 (15)	0.0266 (16)	0.0265 (16)	0.0086 (12)	0.0122 (13)	0.0075 (13)
C3	0.0263 (16)	0.0206 (14)	0.0277 (15)	0.0069 (12)	0.0085 (13)	0.0071 (12)

Geometric parameters (Å, º)

Ni1—O3	2.0389 (17)	O8—H8B	0.851 (10)
Ni1—O3^i	2.0389 (17)	N1—C2	1.502 (4)
Ni1—O1^i	2.0780 (17)	N1—H1A	0.8900
Ni1—O1	2.0780 (17)	N1—H1C	0.8900
Ni1—O8^i	2.1070 (18)	N1—H1B	0.8900
Ni1—O8	2.1070 (18)	N4—C3	1.472 (3)
P1—O5	1.4901 (19)	N4—H4A	0.8900
P1—O1	1.5144 (19)	N4—H4B	0.8900
P1—O4	1.5632 (19)	N4—H4C	0.8900
P1—O2	1.6141 (19)	C2—C2^ii	1.515 (5)
P2—O7	1.5134 (19)	C2—H2A	0.9700
P2—O6	1.5163 (19)	C2—H2B	0.9700
P2—O3	1.5248 (18)	C3—C3^iii	1.503 (5)
P2—O2	1.6230 (18)	C3—H3A	0.9700
O7—H7	0.8200	C3—H3B	0.9700
O8—H8A	0.848 (10)
O3—Ni1—O3^i	180.0	P2—O3—Ni1	131.55 (10)
O3—Ni1—O1^i	86.68 (7)	P2—O7—H7	109.5
O3^i—Ni1—O1^i	93.32 (7)	Ni1—O8—H8A	117.5 (18)
O3—Ni1—O1	93.32 (7)	Ni1—O8—H8B	126.7 (19)
O3^i—Ni1—O1	86.68 (7)	H8A—O8—H8B	106.3 (15)
O1^i—Ni1—O1	180.00 (8)	C2—N1—H1A	109.5
O3—Ni1—O8^i	87.67 (8)	C2—N1—H1C	109.5
O3^i—Ni1—O8^i	92.33 (8)	H1A—N1—H1C	109.5
O1^i—Ni1—O8^i	88.94 (7)	C2—N1—H1B	109.5
O1—Ni1—O8^i	91.06 (7)	H1A—N1—H1B	109.5
O3—Ni1—O8	92.33 (8)	H1C—N1—H1B	109.5
O3^i—Ni1—O8	87.67 (8)	C3—N4—H4A	109.5
O1^i—Ni1—O8	91.06 (7)	C3—N4—H4B	109.5
O1—Ni1—O8	88.94 (7)	H4A—N4—H4B	109.5
O8^i—Ni1—O8	180.000 (1)	C3—N4—H4C	109.5
O5—P1—O1	116.41 (11)	H4A—N4—H4C	109.5
O5—P1—O4	109.98 (11)	H4B—N4—H4C	109.5
O1—P1—O4	109.98 (11)	N1—C2—C2^ii	110.1 (3)
O5—P1—O2	105.77 (10)	N1—C2—H2A	109.6
O1—P1—O2	108.27 (10)	C2^ii—C2—H2A	109.6
O4—P1—O2	105.81 (11)	N1—C2—H2B	109.6
O7—P2—O6	113.18 (11)	C2^ii—C2—H2B	109.6
O7—P2—O3	112.79 (11)	H2A—C2—H2B	108.2
O6—P2—O3	111.81 (10)	N4—C3—C3^iii	110.8 (3)
O7—P2—O2	106.21 (11)	N4—C3—H3A	109.5
O6—P2—O2	104.25 (10)	C3^iii—C3—H3A	109.5
O3—P2—O2	107.93 (10)	N4—C3—H3B	109.5
P1—O1—Ni1	132.24 (11)	C3^iii—C3—H3B	109.5
P1—O2—P2	129.18 (12)	H3A—C3—H3B	108.1
O5—P1—O1—Ni1	−131.40 (14)	O7—P2—O2—P1	67.87 (18)
O4—P1—O1—Ni1	102.69 (15)	O6—P2—O2—P1	−172.34 (15)
O2—P1—O1—Ni1	−12.48 (17)	O3—P2—O2—P1	−53.33 (18)
O3—Ni1—O1—P1	−5.38 (15)	O7—P2—O3—Ni1	−93.67 (16)
O3^i—Ni1—O1—P1	174.62 (15)	O6—P2—O3—Ni1	137.43 (13)
O1^i—Ni1—O1—P1	92 (100)	O2—P2—O3—Ni1	23.35 (17)
O8^i—Ni1—O1—P1	−93.10 (15)	O3^i—Ni1—O3—P2	−132 (100)
O8—Ni1—O1—P1	86.90 (15)	O1^i—Ni1—O3—P2	178.89 (15)
O5—P1—O2—P2	173.42 (14)	O1—Ni1—O3—P2	−1.11 (15)
O1—P1—O2—P2	47.97 (18)	O8^i—Ni1—O3—P2	89.82 (15)
O4—P1—O2—P2	−69.90 (17)	O8—Ni1—O3—P2	−90.18 (15)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7···O4^iv	0.82	1.73	2.501 (3)	156
O8—H8A···O7^v	0.85 (1)	1.92 (1)	2.756 (3)	169 (3)
O8—H8B···O5^vi	0.85 (1)	1.95 (1)	2.795 (3)	174 (3)
N1—H1A···O1^i	0.89	1.96	2.846 (3)	175
N1—H1C···O6^vii	0.89	1.84	2.718 (3)	170
N1—H1B···O4^iv	0.89	2.10	2.888 (3)	147
N4—H4A···O3^ii	0.89	2.04	2.816 (3)	145
N4—H4B···O5^viii	0.89	1.89	2.779 (3)	172
N4—H4C···O6^vii	0.89	1.96	2.748 (3)	146

Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+2, −y+2, −z+1; (iv) −x+2, −y+1, −z; (v) x, y+1, z; (vi) −x+3, −y+2, −z; (vii) x−1, y, z; (viii) x−1, y, z+1.