Aqua­(pyridine N-oxide-κO)[tris(2-hydroxy­amino­propyl)­amine-κ⁴N]­nickel(II) dinitrate

The title complex, [Ni(C₅H₅NO)(C₉H₁₈N₄O₃)(H₂O)](NO₃)₂, is a six-coordinate pseudo-octahedral nickel(II) complex containing a tripodal amine ligand framework with three oxime donors, as well as pyridine N-oxide and aqua ligands. This complex displays crystallographic mirror symmetry and O—H...O hydrogen bonding between the cation and anion.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.030
• wR factor = 0.071
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors  for         N4
PLAT243_ALERT_4_C High Solvent U(eq) as Compared to Neighbors  for        O5B
PLAT244_ALERT_4_C Low  Solvent U(eq) as Compared to Neighbors  for         N5
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      20.00 Perc.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           29.40
           From the CIF: _reflns_number_total               2547
           Count of symmetry unique reflns         1736
           Completeness (_total/calc)            146.72%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       811
           Fraction of Friedel pairs measured     0.467
           Are heavy atom types Z>Si present          yes

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Aqua(pyridine N-oxide-κO)[tris(2-hydroxyaminopropyl)amine-κ⁴N]nickel(II) dinitrate

Crystal data

[Ni(C5H5NO)(C9H18N4O3)(H2O)](NO3)2	F(000) = 1096
Mr = 526.12	Dx = 1.512 Mg m^−3
Orthorhombic, Cmc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 5192 reflections
a = 11.0671 (10) Å	θ = 2.7–29.4°
b = 14.0481 (10) Å	µ = 0.91 mm^−1
c = 14.8625 (12) Å	T = 294 K
V = 2310.7 (3) Å^3	Block, purple
Z = 4	0.54 × 0.45 × 0.30 mm

Data collection

Bruker SMART 1K CCD diffractometer	2547 independent reflections
Radiation source: sealed tube	2427 reflections with I > 2σ(I)'
Graphite monochromator	Rint = 0.031
ω scans	θmax = 29.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −14→15
Tmin = 0.634, Tmax = 0.765	k = −17→19
7484 measured reflections	l = −20→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0328P)^2 + 1.1661P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.007
2547 reflections	Δρmax = 0.27 e Å^−3
176 parameters	Δρmin = −0.49 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1736 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.065 (16)

Special details

Experimental. The crystal was mounted on the tip of a glass fiber with epoxy resin.

The first 50 frames of data were recollected for a decay correction. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program.

The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I).

Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely on absorption effects and crystal size.

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.

dihedral angle for the tilt of the pyridine-N-oxide ring is 90.0 (1)° for the planes defined as Ni/C4/O4 and N4/C7/C8/C9/C8A/C9A/O4

the least squares deviation for the pyridine-N-oxide ring defined as N4/C7/C8/C9/C8A/C9A/O4 is 0.0053 Å

symmetry operator to generate C8A and C9A = -x + 1, y, z

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)
Ni	0.5000	0.35562 (2)	0.75087 (2)	0.02989 (9)
O1	0.5000	0.4926 (2)	0.59124 (19)	0.0634 (8)
H1	0.5000	0.4299	0.5925	0.095*
O2	0.22213 (16)	0.33684 (14)	0.71756 (13)	0.0541 (5)
H2	0.2379	0.3611	0.6560	0.081*
O3	0.5000	0.22996 (19)	0.82726 (19)	0.0424 (6)
H3	0.4454	0.2194	0.8601	0.064*
O4	0.5000	0.28402 (17)	0.63440 (18)	0.0506 (7)
N1	0.5000	0.48143 (19)	0.6845 (2)	0.0377 (6)
N2	0.31744 (17)	0.36694 (13)	0.77257 (14)	0.0378 (5)
N3	0.5000	0.4471 (2)	0.8617 (2)	0.0348 (6)
N4	0.5000	0.1892 (2)	0.6360 (2)	0.0474 (8)
C1	0.3876 (2)	0.4239 (2)	0.91275 (18)	0.0448 (6)
H1A	0.3631	0.4788	0.9478	0.054*
H1B	0.4038	0.3720	0.9541	0.054*
C2	0.2870 (2)	0.39592 (19)	0.85031 (19)	0.0430 (6)
C3	0.1600 (3)	0.4009 (3)	0.8834 (3)	0.0750 (10)
H3A	0.1510	0.3605	0.9350	0.112*
H3B	0.1061	0.3802	0.8367	0.112*
H3C	0.1411	0.4654	0.8997	0.112*
C4	0.5000	0.5468 (3)	0.8296 (3)	0.0498 (9)
H4	0.5696	0.5734	0.8521	0.060*
C5	0.5000	0.5583 (2)	0.7298 (3)	0.0402 (9)
C6	0.5000	0.6567 (3)	0.6921 (4)	0.0687 (14)
H6A	0.4525	0.6975	0.7300	0.103*	0.50
H6B	0.4661	0.6557	0.6327	0.103*	0.50
H6C	0.5814	0.6801	0.6894	0.103*	0.50
C7	0.3958 (4)	0.1431 (2)	0.6374 (3)	0.0781 (12)
H7	0.3235	0.1769	0.6379	0.094*
C8	0.3946 (5)	0.0450 (2)	0.6380 (4)	0.0971 (15)
H8	0.3213	0.0126	0.6380	0.117*
C9	0.5000	−0.0045 (3)	0.6388 (5)	0.098 (2)
H9	0.5000	−0.0730	0.6402	0.118*
N5	0.2180 (2)	0.33290 (17)	0.48815 (19)	0.0564 (6)
O5A	0.1840 (9)	0.2617 (10)	0.5250 (11)	0.086 (3)	0.50
O5B	0.1328 (9)	0.2859 (11)	0.5225 (11)	0.106 (4)	0.50
O6	0.2124 (3)	0.3444 (2)	0.40607 (18)	0.0850 (9)
O7	0.2827 (3)	0.3821 (2)	0.5357 (2)	0.0854 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.03301 (16)	0.02940 (15)	0.02726 (17)	0.000	0.000	−0.00018 (19)
O1	0.107 (3)	0.0487 (15)	0.0348 (16)	0.000	0.000	0.0085 (12)
O2	0.0430 (10)	0.0636 (11)	0.0557 (12)	−0.0054 (8)	−0.0180 (8)	−0.0048 (8)
O3	0.0450 (14)	0.0481 (14)	0.0341 (13)	0.000	0.000	0.0098 (11)
O4	0.088 (2)	0.0319 (12)	0.0321 (14)	0.000	0.000	−0.0003 (10)
N1	0.0447 (15)	0.0351 (14)	0.0334 (16)	0.000	0.000	0.0037 (12)
N2	0.0340 (8)	0.0383 (9)	0.0410 (14)	−0.0008 (7)	−0.0064 (8)	−0.0005 (7)
N3	0.0343 (13)	0.0400 (14)	0.0300 (15)	0.000	0.000	−0.0023 (12)
N4	0.076 (2)	0.0337 (15)	0.0329 (17)	0.000	0.000	−0.0015 (12)
C1	0.0387 (12)	0.0584 (15)	0.0374 (13)	−0.0007 (11)	0.0042 (11)	−0.0065 (11)
C2	0.0292 (10)	0.0527 (14)	0.0470 (16)	0.0005 (9)	0.0015 (10)	−0.0017 (11)
C3	0.0358 (14)	0.114 (3)	0.075 (3)	−0.0015 (17)	0.0126 (15)	−0.018 (2)
C4	0.060 (2)	0.0391 (19)	0.050 (2)	0.000	0.000	−0.0093 (17)
C5	0.0408 (15)	0.0325 (14)	0.047 (3)	0.000	0.000	0.0040 (14)
C6	0.097 (4)	0.0339 (19)	0.075 (3)	0.000	0.000	0.0082 (19)
C7	0.079 (2)	0.0501 (17)	0.105 (3)	−0.0053 (15)	−0.021 (2)	0.0009 (18)
C8	0.109 (3)	0.0470 (18)	0.135 (4)	−0.0233 (19)	−0.029 (3)	0.005 (2)
C9	0.166 (7)	0.035 (2)	0.093 (4)	0.000	0.000	−0.003 (2)
N5	0.0644 (16)	0.0477 (12)	0.0570 (17)	−0.0072 (11)	−0.0101 (13)	−0.0054 (11)
O5A	0.095 (7)	0.075 (5)	0.089 (6)	−0.029 (5)	−0.018 (6)	0.014 (4)
O5B	0.106 (8)	0.125 (11)	0.088 (7)	−0.068 (7)	0.020 (7)	−0.021 (7)
O6	0.100 (2)	0.103 (2)	0.0521 (16)	−0.0283 (16)	−0.0134 (15)	−0.0024 (13)
O7	0.0850 (18)	0.1012 (19)	0.0701 (18)	−0.0322 (15)	−0.0292 (15)	−0.0021 (14)

Geometric parameters (Å, º)

Ni—O4	2.002 (3)	C2—C3	1.491 (4)
Ni—N1	2.024 (3)	C3—H3A	0.9600
Ni—N2	2.0521 (19)	C3—H3B	0.9600
Ni—N3	2.089 (3)	C3—H3C	0.9600
Ni—O3	2.099 (3)	C4—C5	1.492 (6)
O1—N1	1.395 (4)	C4—H4	0.9185
O1—H1	0.8804	C5—C6	1.491 (5)
O2—N2	1.400 (3)	C6—H6A	0.9600
O2—H2	0.9918	C6—H6B	0.9600
O3—H3	0.7908	C6—H6C	0.9600
O4—N4	1.333 (4)	C7—C8	1.379 (4)
N1—C5	1.273 (5)	C7—H7	0.9300
N2—C2	1.270 (3)	C8—C9	1.358 (5)
N3—C4	1.480 (5)	C8—H8	0.9300
N3—C1	1.493 (3)	C9—H9	0.9626
N4—C7	1.322 (4)	N5—O5A	1.201 (14)
C1—C2	1.501 (4)	N5—O7	1.220 (3)
C1—H1A	0.9700	N5—O6	1.232 (4)
C1—H1B	0.9700	N5—O5B	1.259 (13)
O4—Ni—N1	90.98 (11)	C2—C1—H1B	109.4
O4—Ni—N2^i	100.07 (6)	H1A—C1—H1B	108.0
N1—Ni—N2^i	90.51 (5)	N2—C2—C3	124.4 (3)
O4—Ni—N2	100.07 (6)	N2—C2—C1	116.7 (2)
N1—Ni—N2	90.51 (5)	C3—C2—C1	118.9 (3)
N2^i—Ni—N2	159.82 (11)	C2—C3—H3A	109.5
O4—Ni—N3	172.19 (11)	C2—C3—H3B	109.5
N1—Ni—N3	81.20 (13)	H3A—C3—H3B	109.5
N2^i—Ni—N3	80.12 (5)	C2—C3—H3C	109.5
N2—Ni—N3	80.12 (5)	H3A—C3—H3C	109.5
O4—Ni—O3	92.59 (11)	H3B—C3—H3C	109.5
N1—Ni—O3	176.43 (13)	N3—C4—C5	115.0 (3)
N2^i—Ni—O3	88.86 (6)	N3—C4—H4	105.5
N2—Ni—O3	88.87 (6)	C5—C4—H4	108.5
N3—Ni—O3	95.23 (11)	N1—C5—C6	125.9 (4)
N1—O1—H1	82.3	N1—C5—C4	115.8 (3)
N2—O2—H2	107.6	C6—C5—C4	118.3 (3)
Ni—O3—H3	119.4	C5—C6—H6A	109.5
N4—O4—Ni	119.1 (2)	C5—C6—H6B	109.5
C5—N1—O1	115.5 (3)	H6A—C6—H6B	109.5
C5—N1—Ni	118.9 (3)	C5—C6—H6C	109.5
O1—N1—Ni	125.6 (2)	H6A—C6—H6C	109.5
C2—N2—O2	115.4 (2)	H6B—C6—H6C	109.5
C2—N2—Ni	115.37 (16)	N4—C7—C8	119.9 (4)
O2—N2—Ni	128.80 (15)	N4—C7—H7	120.1
C4—N3—C1^i	111.75 (18)	C8—C7—H7	120.1
C4—N3—C1	111.75 (18)	C9—C8—C7	120.2 (4)
C1^i—N3—C1	112.8 (3)	C9—C8—H8	119.9
C4—N3—Ni	109.2 (2)	C7—C8—H8	119.9
C1^i—N3—Ni	105.43 (16)	C8^i—C9—C8	118.4 (4)
C1—N3—Ni	105.44 (16)	C8^i—C9—H9	120.8
C7—N4—C7^i	121.4 (4)	C8—C9—H9	120.8
C7—N4—O4	119.31 (19)	O5A—N5—O7	113.0 (8)
C7^i—N4—O4	119.31 (19)	O5A—N5—O6	123.0 (8)
N3—C1—C2	111.1 (2)	O7—N5—O6	122.0 (3)
N3—C1—H1A	109.4	O7—N5—O5B	120.1 (8)
C2—C1—H1A	109.4	O6—N5—O5B	115.6 (7)
N3—C1—H1B	109.4

Symmetry code: (i) −x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4	0.88	2.14	2.999 (4)	164
O2—H2···O7	0.99	1.88	2.856 (4)	168
O2—H2···O5A	0.99	2.47	3.080 (17)	119
O2—H2···O5B	0.99	2.53	3.146 (16)	120
O3—H3···O6^ii	0.79	2.08	2.826 (3)	158
O3—H3···O5B^ii	0.79	2.57	3.260 (15)	148

Symmetry code: (ii) −x+1/2, −y+1/2, z+1/2.