Tris(ethyl­enediamine)nickel(II) tetra­oxomolybdate(VI)

The crystal structure of the title compound, [Ni(C₂H₈N₂)₃][MoO₄], is composed of tetra­hedral [MoO₄]^2- anions and octa­hedral [Ni(en)₃]²⁺ cations (en is ethyl­enediamine), both ions lying on special positions of site symmetry 2. The components are held together in a three-dimensional network by hydrogen-bonding inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.153
• Data-to-parameter ratio = 21.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Ni     -   N2      ..      11.13 su

Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni     -   N1      ..       6.98 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni     -   N3      ..       9.42 su
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1D    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2D    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2D    ..  O1      ..       2.64 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          5
            N1  -NI  -N1  -C1    -28.01  0.18   4.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            N3  -NI  -N2  -C2    -25.60  0.60   4.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            N2  -NI  -N3  -C3    -36.30  0.60   4.555   1.555   1.555   1.555

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           27.99
           From the CIF: _reflns_number_total               1785
           From the CIF: _diffrn_reflns_limit_ max hkl   18.   21.   13.
           From the CIF: _diffrn_reflns_limit_ min hkl  -18.  -21.  -13.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   21.   21.   13.
           Calculated minimum hkl  -21.  -21.  -13.

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

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

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1987); cell refinement: TEXSAN (Molecular Structure Corporation, 1987); data reduction: TEXSAN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Tris(ethylenediamine)nickel(II) tetraoxomolybdate(VI)

Crystal data

[Ni(C2H8N2)3][MoO4]	Dx = 1.799 Mg m^−3
Mr = 398.96	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3c1	Cell parameters from 200 reflections
Hall symbol: -P 3 2"c	θ = 10–20°
a = 16.0024 (16) Å	µ = 2.15 mm^−1
c = 9.9608 (19) Å	T = 291 K
V = 2209.0 (5) Å^3	Block, violet
Z = 6	0.20 × 0.12 × 0.08 mm
F(000) = 1224

Data collection

Rigaku AFC-5R diffractometer	1538 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 28.0°, θmin = 2.6°
ω–2θ scans	h = −18→18
Absorption correction: ψ scan (North et al., 1968)	k = −21→21
Tmin = 0.674, Tmax = 0.847	l = −13→13
5355 measured reflections	3 standard reflections every 150 reflections
1785 independent reflections	intensity decay: 0.2%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0867P)^2 + 1.4958P] where P = (Fo^2 + 2Fc^2)/3
1785 reflections	(Δ/σ)max = 0.001
83 parameters	Δρmax = 0.94 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3

Special details

Experimental. crystal coated in epoxy glue

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
Ni	0.33135 (2)	0.33135 (2)	0.2500	0.0317 (2)
Mo	0.0000	0.334817 (15)	0.2500	0.0356 (2)
O1	0.07418 (13)	0.43261 (13)	0.15839 (17)	0.0483 (5)
O2	0.06951 (12)	0.31208 (13)	0.36123 (16)	0.0431 (4)
N1	0.40297 (17)	0.27074 (17)	0.3637 (3)	0.0428 (5)
H1C	0.3957	0.2761	0.4524	0.051*
H1D	0.3782	0.2079	0.3436	0.051*
N2	0.4603 (2)	0.38995 (19)	0.1322 (3)	0.0493 (6)
H2C	0.4458	0.3813	0.0442	0.059*
H2D	0.4977	0.4536	0.1481	0.059*
N3	0.25274 (18)	0.20474 (19)	0.1309 (3)	0.0475 (6)
H3C	0.2574	0.2206	0.0434	0.057*
H3D	0.2768	0.1650	0.1422	0.057*
C1	0.5037 (2)	0.3249 (3)	0.3269 (3)	0.0513 (7)
H1A	0.5372	0.2890	0.3553	0.062*
H1B	0.5369	0.3868	0.3691	0.062*
C2	0.5113 (2)	0.3377 (2)	0.1724 (3)	0.0460 (6)
H2A	0.5785	0.3742	0.1456	0.055*
H2B	0.4820	0.2751	0.1288	0.055*
C3	0.1560 (2)	0.1590 (2)	0.1721 (3)	0.0436 (6)
H3A	0.1204	0.0942	0.1356	0.052*
H3B	0.1255	0.1952	0.1427	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0324 (3)	0.0324 (3)	0.0306 (4)	0.01642 (19)	0.00001 (6)	−0.00001 (6)
Mo	0.0365 (2)	0.0363 (2)	0.0340 (3)	0.01827 (12)	−0.00001 (9)	0.00000 (4)
O1	0.0501 (10)	0.0460 (10)	0.0460 (9)	0.0219 (8)	−0.0011 (8)	0.0002 (7)
O2	0.0445 (9)	0.0446 (9)	0.0416 (8)	0.0233 (8)	−0.0011 (7)	−0.0006 (7)
N1	0.0439 (12)	0.0447 (11)	0.0417 (12)	0.0235 (10)	−0.0011 (9)	0.0007 (9)
N2	0.0506 (14)	0.0502 (13)	0.0481 (14)	0.0259 (11)	0.0026 (10)	0.0013 (10)
N3	0.0464 (12)	0.0460 (13)	0.0476 (13)	0.0213 (10)	−0.0018 (10)	−0.0021 (10)
C1	0.0492 (15)	0.0560 (17)	0.0506 (16)	0.0277 (13)	−0.0011 (12)	−0.0010 (13)
C2	0.0437 (14)	0.0510 (15)	0.0450 (15)	0.0249 (12)	0.0024 (11)	0.0003 (12)
C3	0.0413 (13)	0.0421 (13)	0.0443 (14)	0.0185 (11)	−0.0019 (11)	−0.0021 (10)

Geometric parameters (Å, º)

Ni—N1^i	2.156 (2)	N2—H2C	0.9000
Ni—N2^i	2.140 (3)	N2—H2D	0.9000
Ni—N3	2.132 (3)	N3—C3	1.403 (4)
Ni—N3^i	2.132 (3)	N3—H3C	0.9000
Ni—N2	2.140 (3)	N3—H3D	0.9000
Ni—N1	2.156 (2)	C1—C2	1.550 (5)
Mo—O1^ii	1.6832 (18)	C1—H1A	1.0022
Mo—O1	1.6832 (18)	C1—H1B	0.9560
Mo—O2^ii	1.7326 (17)	C2—H2A	0.9700
Mo—O2	1.7326 (17)	C2—H2B	0.9700
N1—C1	1.445 (4)	C3—C3^i	1.553 (5)
N1—H1C	0.9000	C3—H3A	0.9700
N1—H1D	0.9000	C3—H3B	0.9700
N2—C2	1.485 (4)
N3—Ni—N3^i	79.28 (14)	Ni—N2—H2C	110.4
N3—Ni—N2^i	170.85 (11)	C2—N2—H2D	110.4
N3^i—Ni—N2^i	95.32 (11)	Ni—N2—H2D	110.4
N3—Ni—N2	95.32 (11)	H2C—N2—H2D	108.6
N3^i—Ni—N2	170.85 (11)	C3—N3—Ni	107.80 (19)
N2^i—Ni—N2	90.95 (15)	C3—N3—H3C	110.1
N3—Ni—N1^i	90.24 (10)	Ni—N3—H3C	110.1
N3^i—Ni—N1^i	93.36 (11)	C3—N3—H3D	110.1
N2^i—Ni—N1^i	82.65 (12)	Ni—N3—H3D	110.1
N2—Ni—N1^i	94.05 (10)	H3C—N3—H3D	108.5
N3—Ni—N1	93.36 (11)	N1—C1—C2	108.7 (2)
N3^i—Ni—N1	90.24 (10)	N1—C1—H1A	109.9
N2^i—Ni—N1	94.05 (10)	C2—C1—H1A	109.1
N2—Ni—N1	82.65 (12)	N1—C1—H1B	112.6
N1^i—Ni—N1	175.32 (13)	C2—C1—H1B	109.5
O1^ii—Mo—O1	109.50 (13)	H1A—C1—H1B	107.0
O1^ii—Mo—O2^ii	108.27 (9)	N2—C2—C1	108.3 (2)
O1—Mo—O2^ii	107.42 (8)	N2—C2—H2A	110.0
O1^ii—Mo—O2	107.42 (8)	C1—C2—H2A	110.0
O1—Mo—O2	108.27 (9)	N2—C2—H2B	110.0
O2^ii—Mo—O2	115.85 (11)	C1—C2—H2B	110.0
C1—N1—Ni	106.35 (19)	H2A—C2—H2B	108.4
C1—N1—H1C	110.5	N3—C3—C3^i	105.4 (2)
Ni—N1—H1C	110.5	N3—C3—H3A	110.7
C1—N1—H1D	110.5	C3^i—C3—H3A	110.7
Ni—N1—H1D	110.5	N3—C3—H3B	110.7
H1C—N1—H1D	108.7	C3^i—C3—H3B	110.7
C2—N2—Ni	106.63 (18)	H3A—C3—H3B	108.8
C2—N2—H2C	110.4
N3—Ni—N1—C1	112.3 (2)	N3^i—Ni—N3—C3	18.12 (14)
N3^i—Ni—N1—C1	−168.41 (18)	N2^i—Ni—N3—C3	−36.3 (6)
N2^i—Ni—N1—C1	−73.1 (2)	N2—Ni—N3—C3	−169.35 (19)
N2—Ni—N1—C1	17.38 (17)	N1^i—Ni—N3—C3	−75.3 (2)
N1^i—Ni—N1—C1	−28.01 (18)	N1—Ni—N3—C3	107.7 (2)
N3—Ni—N2—C2	−79.0 (2)	Ni—N1—C1—C2	−44.5 (3)
N3^i—Ni—N2—C2	−25.6 (6)	Ni—N2—C2—C1	−41.0 (3)
N2^i—Ni—N2—C2	107.7 (2)	N1—C1—C2—N2	59.5 (4)
N1^i—Ni—N2—C2	−169.60 (18)	Ni—N3—C3—C3^i	−47.5 (3)
N1—Ni—N2—C2	13.74 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2^iii	0.90	2.19	3.028 (3)	154
N2—H2C···O1^iv	0.90	2.04	2.934 (3)	170
N2—H2D···O1^v	0.90	2.64	3.510 (3)	164
N3—H3C···O2^vi	0.90	2.42	3.236 (3)	152
N3—H3D···O2^i	0.90	1.88	2.765 (3)	169

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