Dichloro­tetrapyridine­nickel(II) 0.76-hydrate

In the title compound, [NiCl₂(C₅H₅N)₄]·0.76H₂O, the nickel(II) ion is coordinated in a trans fashion by two Cl⁻ ions and four pyridine molecules. The molecule possesses crystallographic 222 symmetry. The Ni atom has a distorted octahedral geometry, with long Ni—Cl bonds. In the crystal structure, O—H...Cl hydrogen bonding forms a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in solvent or counterion
• R factor = 0.022
• wR factor = 0.049
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      38.00 Perc.

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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2003) and ATOMS (Dowty, 2002); software used to prepare material for publication: SHELXTL.

Dichlorotetrapyridinenickel(II) 0.76-hydrate

Crystal data

[NiCl2(C5H5N)4]·0.76H2O	Dx = 1.456 Mg m^−3
Mr = 459.68	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/acd	Cell parameters from 26814 reflections
Hall symbol: -I 4bd 2c	θ = 2.6–28.4°
a = 15.815 (6) Å	µ = 1.20 mm^−1
c = 16.773 (9) Å	T = 110 K
V = 4195 (3) Å^3	Prism, blue
Z = 8	0.21 × 0.15 × 0.13 mm
F(000) = 1900.8

Data collection

Bruker APEX CCD area-detector diffractometer	1324 independent reflections
Radiation source: fine-focus sealed tube	860 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 28.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
Tmin = 0.801, Tmax = 0.857	k = −21→21
26814 measured reflections	l = −22→22

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 0.83	w = 1/[σ^2(Fo^2) + (0.0235P)^2] where P = (Fo^2 + 2Fc^2)/3
1324 reflections	(Δ/σ)max < 0.001
72 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.25 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	Occ. (<1)
Ni1	0.5000	0.2500	0.8750	0.01753 (9)
Cl1	0.39171 (2)	0.35829 (2)	0.8750	0.02491 (12)
O1	0.2500	0.1001 (3)	0.5000	0.0339 (11)	0.38
H1	0.280 (3)	0.128 (3)	0.464 (3)	0.076 (19)*	0.38
N1	0.43412 (7)	0.18264 (7)	0.78621 (6)	0.0203 (2)
C2	0.47463 (10)	0.14468 (10)	0.72598 (8)	0.0257 (4)
H2	0.5345	0.1488	0.7235	0.031*
C3	0.43294 (11)	0.09986 (10)	0.66740 (9)	0.0322 (4)
H3	0.4637	0.0739	0.6253	0.039*
C4	0.34681 (11)	0.09319 (10)	0.67057 (9)	0.0344 (4)
H4	0.3169	0.0624	0.6309	0.041*
C5	0.30423 (10)	0.13175 (10)	0.73208 (9)	0.0297 (4)
H5	0.2444	0.1280	0.7358	0.036*
C6	0.34981 (9)	0.17583 (9)	0.78796 (9)	0.0235 (3)
H6	0.3200	0.2029	0.8300	0.028*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.01897 (12)	0.01897 (12)	0.01466 (16)	−0.00102 (16)	0.000	0.000
Cl1	0.02456 (17)	0.02456 (17)	0.0256 (3)	0.0045 (2)	−0.00158 (19)	−0.00158 (19)
O1	0.037 (3)	0.032 (3)	0.033 (3)	0.000	0.009 (2)	0.000
N1	0.0211 (7)	0.0215 (7)	0.0184 (6)	−0.0009 (5)	0.0003 (5)	−0.0006 (5)
C2	0.0271 (8)	0.0281 (8)	0.0219 (8)	−0.0012 (7)	0.0050 (6)	−0.0029 (7)
C3	0.0410 (10)	0.0316 (9)	0.0239 (9)	−0.0045 (8)	0.0044 (8)	−0.0100 (7)
C4	0.0432 (11)	0.0355 (11)	0.0245 (8)	−0.0140 (7)	−0.0062 (8)	−0.0055 (8)
C5	0.0275 (9)	0.0334 (9)	0.0280 (9)	−0.0072 (8)	−0.0043 (7)	0.0027 (7)
C6	0.0232 (8)	0.0258 (8)	0.0215 (8)	−0.0012 (7)	0.0019 (7)	0.0015 (7)

Geometric parameters (Å, º)

Ni1—N1	2.1067 (13)	C2—C3	1.379 (2)
Ni1—N1^i	2.1067 (13)	C2—H2	0.9500
Ni1—N1^ii	2.1067 (13)	C3—C4	1.367 (2)
Ni1—N1^iii	2.1067 (13)	C3—H3	0.9500
Ni1—Cl1	2.4219 (10)	C4—C5	1.375 (2)
Ni1—Cl1^iii	2.4219 (10)	C4—H4	0.9500
O1—H1	0.89 (5)	C5—C6	1.373 (2)
N1—C6	1.3380 (18)	C5—H5	0.9500
N1—C2	1.3384 (18)	C6—H6	0.9500
N1—Ni1—N1^i	179.10 (7)	C2—N1—Ni1	121.58 (10)
N1—Ni1—N1^ii	89.98 (7)	N1—C2—C3	122.64 (15)
N1^i—Ni1—N1^ii	90.03 (7)	N1—C2—H2	118.7
N1—Ni1—N1^iii	90.03 (7)	C3—C2—H2	118.7
N1^i—Ni1—N1^iii	89.98 (7)	C4—C3—C2	119.22 (15)
N1^ii—Ni1—N1^iii	179.10 (7)	C4—C3—H3	120.4
N1—Ni1—Cl1	90.45 (3)	C2—C3—H3	120.4
N1^i—Ni1—Cl1	90.45 (3)	C3—C4—C5	118.87 (14)
N1^ii—Ni1—Cl1	89.55 (3)	C3—C4—H4	120.6
N1^iii—Ni1—Cl1	89.55 (3)	C5—C4—H4	120.6
N1—Ni1—Cl1^iii	89.55 (3)	C6—C5—C4	118.73 (14)
N1^i—Ni1—Cl1^iii	89.55 (3)	C6—C5—H5	120.6
N1^ii—Ni1—Cl1^iii	90.45 (3)	C4—C5—H5	120.6
N1^iii—Ni1—Cl1^iii	90.45 (3)	N1—C6—C5	123.31 (14)
Cl1—Ni1—Cl1^iii	180.0	N1—C6—H6	118.3
C6—N1—C2	117.23 (12)	C5—C6—H6	118.3
C6—N1—Ni1	121.20 (9)
N1^iii—Ni1—N1—C6	−129.91 (13)	Ni1—N1—C2—C3	179.65 (12)
Cl1—Ni1—N1—C6	−40.36 (11)	N1—C2—C3—C4	−0.3 (3)
Cl1^iii—Ni1—N1—C6	139.64 (11)	C2—C3—C4—C5	0.2 (3)
N1^ii—Ni1—N1—C2	−130.56 (13)	C3—C4—C5—C6	0.2 (2)
N1^iii—Ni1—N1—C2	50.34 (10)	C2—N1—C6—C5	0.6 (2)
Cl1—Ni1—N1—C2	139.89 (11)	Ni1—N1—C6—C5	−179.14 (11)
Cl1^iii—Ni1—N1—C2	−40.11 (11)	C4—C5—C6—N1	−0.7 (2)
C6—N1—C2—C3	−0.1 (2)

Symmetry codes: (i) −y+3/4, −x+3/4, −z+7/4; (ii) y+1/4, x−1/4, −z+7/4; (iii) −x+1, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1^iv	0.89 (5)	2.32 (5)	3.1388 (14)	153 (4)

Symmetry code: (iv) −y+3/4, x−1/4, −z+5/4.