Bis[bis(1-oxo-2-pyridyl)aminato]nickel(II) methanol solvate

The title complex, [Ni(C₁₀H₈N₃O₂)₂]·CH₃OH, is a mononuclear nickel(II) compound containing two di-2-pyridyl­amine N,N'-dioxide (dpa dioxide) ligands that are nearly perpendicular to each other. The Ni^II ion of the complex has a distorted octa­hedral environment with the equatorial plane formed by an N atom from each amine group and two O atoms of one ligand, while the axial positions are occupied by two O atoms of the second ligand. In the solid state, hydrogen-bonding inter­actions are dominant, with solvent mol­ecules also participating in hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.036
• wR factor = 0.097
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT410_ALERT_2_B Short Intra H...H Contact  H4     ..  H7      ..       1.81 Ang.

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O2      ..       5.92 su

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2; software used to prepare material for publication: APEX2.

Bis(di-2-pyridylaminato N,N'-dioxide)nickel(II) methanol solvate

Crystal data

[Ni(C10H8N3O2)2]·CH4O	F(000) = 2048
Mr = 495.14	Dx = 1.578 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5074 reflections
a = 11.3969 (17) Å	θ = 3.1–28.2°
b = 12.911 (2) Å	µ = 0.98 mm^−1
c = 28.337 (4) Å	T = 273 K
V = 4169.5 (11) Å^3	Block, green
Z = 8	0.30 × 0.22 × 0.20 mm

Data collection

Bruker APEX-II area-detector diffractometer	5108 independent reflections
Radiation source: fine-focus sealed tube	3665 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 28.2°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −15→15
Tmin = 0.77, Tmax = 0.82	k = −17→8
25649 measured reflections	l = −37→36

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0256P)^2 + 1.9608P] where P = (Fo^2 + 2Fc^2)/3
5108 reflections	(Δ/σ)max = 0.002
299 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Experimental. IR (cm^-1): 3456.19, 3095.32, 1605.30, 1505.23, 1189.7, 1125.5, 837.2, 745.8.

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
O5	0.69573 (18)	1.00149 (19)	0.55550 (6)	0.0754 (6)
Ni1	0.98722 (2)	0.94546 (2)	0.645413 (8)	0.03234 (9)
N2	0.89227 (14)	0.95019 (13)	0.70520 (5)	0.0326 (4)
N5	1.08692 (14)	0.94531 (13)	0.58717 (6)	0.0341 (4)
N3	0.77879 (14)	1.06151 (13)	0.66230 (6)	0.0333 (4)
N1	1.04182 (14)	0.84913 (14)	0.73287 (6)	0.0338 (4)
N4	0.95213 (15)	0.82940 (14)	0.56083 (6)	0.0344 (4)
O3	1.08610 (12)	0.85071 (12)	0.68902 (5)	0.0410 (4)
O2	0.91465 (12)	0.82313 (12)	0.60576 (5)	0.0400 (4)
C7	0.71763 (19)	1.03978 (18)	0.74087 (7)	0.0408 (5)
H7	0.7259	1.0099	0.7705	0.049*
C6	0.79815 (16)	1.01367 (16)	0.70532 (7)	0.0303 (4)
C5	0.93768 (17)	0.89957 (17)	0.74287 (7)	0.0344 (4)
C1	1.1028 (2)	0.79627 (18)	0.76608 (8)	0.0441 (5)
H1	1.1733	0.7648	0.7578	0.053*
C14	1.07853 (19)	0.89572 (18)	0.50188 (7)	0.0409 (5)
H14	1.1416	0.9369	0.4929	0.049*
C13	1.0199 (2)	0.8404 (2)	0.46819 (8)	0.0490 (6)
H13	1.0426	0.8446	0.4367	0.059*
C8	0.6272 (2)	1.1079 (2)	0.73332 (8)	0.0471 (6)
H8	0.5755	1.1235	0.7577	0.057*
C10	0.69029 (19)	1.12905 (18)	0.65493 (8)	0.0422 (5)
H10	0.6821	1.1596	0.6254	0.051*
C12	0.9267 (2)	0.7781 (2)	0.48119 (8)	0.0524 (6)
H12	0.8863	0.7396	0.4587	0.063*
C2	1.0634 (2)	0.7882 (2)	0.81112 (9)	0.0575 (7)
H2	1.1069	0.7530	0.8338	0.069*
C4	0.8957 (2)	0.8873 (2)	0.78927 (8)	0.0617 (8)
H4	0.8242	0.9169	0.7975	0.074*
C17	1.2821 (2)	1.0103 (2)	0.55931 (9)	0.0539 (6)
H17	1.2877	0.9649	0.5339	0.065*
C20	1.2710 (2)	1.1418 (2)	0.63444 (8)	0.0535 (6)
H20	1.2670	1.1861	0.6602	0.064*
C11	0.8948 (2)	0.77414 (19)	0.52761 (8)	0.0478 (6)
H11	0.8321	0.7324	0.5365	0.057*
C19	1.3648 (2)	1.1469 (2)	0.60520 (10)	0.0674 (8)
H19	1.4240	1.1951	0.6105	0.081*
C3	0.9572 (3)	0.8332 (3)	0.82259 (9)	0.0694 (9)
H3	0.9274	0.8267	0.8530	0.083*
C18	1.3711 (2)	1.0797 (3)	0.56759 (10)	0.0702 (9)
H18	1.4360	1.0812	0.5477	0.084*
C9	0.61292 (19)	1.15334 (18)	0.68967 (8)	0.0440 (5)
H9	0.5518	1.1995	0.6841	0.053*
C16	1.18302 (17)	1.00675 (17)	0.58842 (7)	0.0367 (5)
C15	1.04624 (17)	0.89225 (16)	0.54976 (7)	0.0324 (4)
O1	1.09420 (15)	1.07198 (13)	0.65728 (5)	0.0506 (4)
O4	0.85133 (14)	1.04278 (13)	0.62577 (5)	0.0465 (4)
N6	1.18306 (16)	1.07341 (15)	0.62689 (6)	0.0405 (4)
C21	0.6364 (3)	0.9134 (3)	0.56814 (15)	0.1051 (13)
H21	0.6916	0.8603	0.5765	0.158*
H23	0.5894	0.8902	0.5421	0.158*
H22	0.5867	0.9280	0.5947	0.158*
H5	0.7468	1.0130	0.5757	0.158*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O5	0.0815 (14)	0.0976 (17)	0.0472 (11)	−0.0174 (13)	−0.0027 (9)	0.0036 (11)
Ni1	0.03475 (14)	0.03698 (17)	0.02529 (14)	−0.00008 (11)	0.00279 (9)	0.00141 (11)
N2	0.0357 (8)	0.0364 (10)	0.0257 (8)	0.0052 (7)	0.0014 (6)	0.0057 (7)
N5	0.0366 (9)	0.0370 (10)	0.0289 (8)	−0.0038 (8)	0.0041 (6)	−0.0019 (7)
N3	0.0380 (9)	0.0358 (10)	0.0262 (8)	0.0037 (8)	0.0008 (6)	0.0032 (7)
N1	0.0360 (8)	0.0345 (10)	0.0308 (8)	0.0011 (7)	−0.0046 (7)	0.0006 (7)
N4	0.0412 (9)	0.0339 (10)	0.0280 (8)	−0.0024 (8)	−0.0011 (7)	0.0029 (7)
O3	0.0367 (7)	0.0519 (10)	0.0345 (8)	0.0083 (7)	0.0031 (6)	0.0018 (7)
O2	0.0454 (8)	0.0457 (9)	0.0289 (7)	−0.0106 (7)	0.0053 (6)	0.0043 (6)
C7	0.0441 (11)	0.0474 (14)	0.0309 (10)	0.0074 (10)	0.0072 (8)	0.0078 (9)
C6	0.0328 (9)	0.0296 (10)	0.0285 (9)	−0.0032 (8)	−0.0008 (7)	0.0014 (8)
C5	0.0387 (10)	0.0362 (11)	0.0282 (10)	0.0025 (9)	−0.0011 (8)	0.0024 (9)
C1	0.0454 (12)	0.0428 (13)	0.0440 (13)	0.0100 (10)	−0.0119 (9)	0.0018 (10)
C14	0.0490 (12)	0.0401 (13)	0.0336 (11)	−0.0009 (10)	0.0082 (9)	−0.0004 (10)
C13	0.0722 (16)	0.0452 (14)	0.0298 (11)	0.0021 (12)	0.0038 (10)	−0.0031 (10)
C8	0.0496 (13)	0.0542 (15)	0.0376 (12)	0.0141 (11)	0.0092 (10)	−0.0004 (11)
C10	0.0494 (12)	0.0434 (13)	0.0337 (11)	0.0109 (10)	−0.0069 (9)	0.0035 (10)
C12	0.0729 (17)	0.0483 (15)	0.0360 (12)	−0.0081 (13)	−0.0096 (11)	−0.0069 (11)
C2	0.0706 (16)	0.0609 (17)	0.0409 (13)	0.0184 (14)	−0.0137 (12)	0.0094 (12)
C4	0.0656 (16)	0.084 (2)	0.0353 (12)	0.0300 (15)	0.0102 (11)	0.0187 (13)
C17	0.0432 (13)	0.0705 (18)	0.0481 (13)	−0.0077 (12)	0.0100 (10)	−0.0029 (13)
C20	0.0620 (15)	0.0547 (16)	0.0438 (13)	−0.0210 (13)	−0.0129 (11)	0.0049 (12)
C11	0.0557 (14)	0.0449 (14)	0.0427 (13)	−0.0123 (11)	−0.0043 (10)	0.0012 (11)
C19	0.0579 (16)	0.086 (2)	0.0583 (17)	−0.0348 (15)	−0.0134 (13)	0.0160 (16)
C3	0.086 (2)	0.090 (2)	0.0324 (12)	0.0315 (18)	0.0044 (12)	0.0195 (14)
C18	0.0438 (14)	0.107 (3)	0.0603 (17)	−0.0213 (15)	0.0067 (12)	0.0094 (17)
C9	0.0476 (12)	0.0425 (14)	0.0420 (12)	0.0128 (10)	−0.0039 (9)	−0.0028 (10)
C16	0.0364 (10)	0.0412 (12)	0.0326 (10)	−0.0012 (9)	−0.0002 (8)	0.0034 (9)
C15	0.0366 (10)	0.0302 (11)	0.0302 (10)	0.0028 (9)	0.0025 (8)	0.0021 (8)
O1	0.0588 (10)	0.0549 (11)	0.0380 (8)	−0.0148 (8)	0.0103 (7)	−0.0123 (8)
O4	0.0501 (9)	0.0632 (11)	0.0264 (7)	0.0156 (8)	0.0088 (6)	0.0100 (7)
N6	0.0446 (10)	0.0451 (11)	0.0319 (9)	−0.0093 (8)	−0.0028 (7)	0.0034 (8)
C21	0.065 (2)	0.106 (3)	0.144 (4)	−0.016 (2)	0.000 (2)	0.021 (3)

Geometric parameters (Å, º)

Ni1—N5	2.0036 (16)	C13—H13	0.9300
Ni1—N2	2.0113 (16)	C8—C9	1.379 (3)
Ni1—O1	2.0659 (16)	C8—H8	0.9300
Ni1—O4	2.0705 (15)	C10—C9	1.358 (3)
Ni1—O3	2.0720 (15)	C10—H10	0.9300
Ni1—O2	2.1074 (15)	C12—C11	1.366 (3)
N2—C6	1.350 (2)	C12—H12	0.9300
N2—C5	1.354 (2)	C2—C3	1.381 (4)
N5—C15	1.345 (3)	C2—H2	0.9300
N5—C16	1.353 (3)	C4—C3	1.368 (3)
N3—O4	1.347 (2)	C4—H4	0.9300
N3—C10	1.350 (3)	C17—C18	1.374 (4)
N3—C6	1.384 (2)	C17—C16	1.399 (3)
N1—O3	1.341 (2)	C17—H17	0.9300
N1—C1	1.354 (3)	C20—N6	1.352 (3)
N1—C5	1.383 (3)	C20—C19	1.354 (4)
N4—O2	1.345 (2)	C20—H20	0.9300
N4—C11	1.350 (3)	C11—H11	0.9300
N4—C15	1.381 (3)	C19—C18	1.376 (4)
C7—C8	1.371 (3)	C19—H19	0.9300
C7—C6	1.404 (3)	C3—H3	0.9300
C7—H7	0.9300	C18—H18	0.9300
C5—C4	1.408 (3)	C9—H9	0.9300
C1—C2	1.357 (3)	C16—N6	1.389 (3)
C1—H1	0.9300	O1—N6	1.329 (2)
C14—C13	1.367 (3)	O5—C21	1.371 (4)
C14—C15	1.406 (3)	C21—H21	0.9600
C14—H14	0.9300	C21—H23	0.9600
C13—C12	1.382 (3)	C21—H22	0.9600
N5—Ni1—N2	177.40 (7)	N3—C10—C9	121.5 (2)
N5—Ni1—O1	78.47 (7)	N3—C10—H10	119.3
N2—Ni1—O1	99.00 (7)	C9—C10—H10	119.3
N5—Ni1—O4	101.73 (6)	C11—C12—C13	118.9 (2)
N2—Ni1—O4	78.79 (6)	C11—C12—H12	120.5
O1—Ni1—O4	90.31 (7)	C13—C12—H12	120.5
N5—Ni1—O3	100.50 (6)	C1—C2—C3	118.6 (2)
N2—Ni1—O3	78.94 (6)	C1—C2—H2	120.7
O1—Ni1—O3	92.79 (7)	C3—C2—H2	120.7
O4—Ni1—O3	157.72 (6)	C3—C4—C5	121.9 (2)
N5—Ni1—O2	77.45 (6)	C3—C4—H4	119.1
N2—Ni1—O2	105.12 (6)	C5—C4—H4	119.1
O1—Ni1—O2	155.64 (6)	C18—C17—C16	121.1 (3)
O4—Ni1—O2	91.03 (6)	C18—C17—H17	119.4
O3—Ni1—O2	95.11 (6)	C16—C17—H17	119.4
C6—N2—C5	126.49 (17)	N6—C20—C19	121.3 (3)
C6—N2—Ni1	116.61 (12)	N6—C20—H20	119.3
C5—N2—Ni1	116.34 (13)	C19—C20—H20	119.3
C15—N5—C16	126.75 (17)	N4—C11—C12	121.5 (2)
C15—N5—Ni1	117.03 (13)	N4—C11—H11	119.2
C16—N5—Ni1	115.92 (13)	C12—C11—H11	119.2
O4—N3—C10	117.13 (17)	C20—C19—C18	119.0 (2)
O4—N3—C6	119.93 (16)	C20—C19—H19	120.5
C10—N3—C6	122.93 (17)	C18—C19—H19	120.5
O3—N1—C1	117.26 (17)	C4—C3—C2	120.1 (2)
O3—N1—C5	120.37 (15)	C4—C3—H3	120.0
C1—N1—C5	122.36 (18)	C2—C3—H3	120.0
O2—N4—C11	118.33 (17)	C17—C18—C19	120.3 (2)
O2—N4—C15	119.80 (16)	C17—C18—H18	119.9
C11—N4—C15	121.86 (18)	C19—C18—H18	119.9
N1—O3—Ni1	110.91 (11)	C10—C9—C8	118.4 (2)
N4—O2—Ni1	109.57 (11)	C10—C9—H9	120.8
C8—C7—C6	122.2 (2)	C8—C9—H9	120.8
C8—C7—H7	118.9	N5—C16—N6	112.58 (17)
C6—C7—H7	118.9	N5—C16—C17	131.1 (2)
N2—C6—N3	113.29 (16)	N6—C16—C17	116.3 (2)
N2—C6—C7	131.83 (18)	N5—C15—N4	112.82 (16)
N3—C6—C7	114.88 (17)	N5—C15—C14	130.9 (2)
N2—C5—N1	113.17 (16)	N4—C15—C14	116.18 (18)
N2—C5—C4	131.3 (2)	N6—O1—Ni1	110.81 (12)
N1—C5—C4	115.47 (18)	N3—O4—Ni1	111.20 (11)
N1—C1—C2	121.5 (2)	O1—N6—C20	118.1 (2)
N1—C1—H1	119.3	O1—N6—C16	119.97 (17)
C2—C1—H1	119.3	C20—N6—C16	121.9 (2)
C13—C14—C15	122.0 (2)	O5—C21—H21	109.5
C13—C14—H14	119.0	O5—C21—H23	109.5
C15—C14—H14	119.0	H21—C21—H23	109.5
C14—C13—C12	119.6 (2)	O5—C21—H22	109.5
C14—C13—H13	120.2	H21—C21—H22	109.5
C12—C13—H13	120.2	H23—C21—H22	109.5
C7—C8—C9	120.1 (2)	H21—C21—H5	91.3
C7—C8—H8	119.9	H23—C21—H5	134.4
C9—C8—H8	119.9	H22—C21—H5	100.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O4	0.83	1.89	2.719 (3)	174