A new compound, [Ni(pic)2{CO(NH2)2}2]·2[CO(NH2)2]·H2O (Hpic is picolinic acid) or [Ni(C6H4NO2)2(CH4N2O)2]·2CH4N2O·H2O, has been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. The structure shows that the Ni atom has an octahedral environment in which it is coordinated by two N and two O atoms of two picolinate ligands and two O atoms of two urea molecules. The Ni atom lies at an inversion center, with Ni—N = 2.0531 (18) Å, Ni—O(pic) = 2.0349 (15) Å and Ni—O(urea) = 2.1255 (15) Å. Both urea solvent molecules lie on mirror planes and have approximate C2v symmetry, and the water molecule has exact mirror symmetry. π–π stacking and hydrogen-bonding interactions result in a three-dimensional network.
Supporting information
CCDC reference: 239054
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.042
- wR factor = 0.109
- Data-to-parameter ratio = 11.6
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.583 0.803
Tmin' and Tmax expected: 0.685 0.803
RR' = 0.851
Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.83
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .... C21
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 18.00 Perc.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1
C14 H16 N6 Ni O6
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
C H4 N2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3
C H4 N2 O
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4
H2 O
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
10 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
2 ALERT type 3 Indicator that the structure quality may be low
7 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Crystal data top
[Ni(C6H4NO2)2(CH4N2O)2]·2CH4N2O·H2O | Dx = 1.554 Mg m−3 |
Mr = 561.18 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 3906 reflections |
a = 7.4562 (5) Å | θ = 3.0–25.1° |
b = 20.3619 (14) Å | µ = 0.88 mm−1 |
c = 15.8017 (10) Å | T = 293 K |
V = 2399.1 (3) Å3 | Prism, pale blue |
Z = 4 | 0.42 × 0.38 × 0.25 mm |
F(000) = 1168 | |
Data collection top
Siemens SMART CCD diffractometer | 2167 independent reflections |
Radiation source: fine-focus sealed tube | 1564 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 25.1°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→8 |
Tmin = 0.583, Tmax = 0.803 | k = −18→24 |
7104 measured reflections | l = −8→18 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0391P)2 + 4.0512P] where P = (Fo2 + 2Fc2)/3 |
2167 reflections | (Δ/σ)max < 0.001 |
187 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ni1 | 0.5000 | 0.5000 | −0.5000 | 0.03140 (10) | |
N2 | 1.0168 (3) | 0.40515 (11) | −0.49250 (14) | 0.0509 (6) | |
H2A | 1.0840 | 0.4391 | −0.4860 | 0.061* | |
H2B | 1.0636 | 0.3665 | −0.4932 | 0.061* | |
O1 | 0.7718 (2) | 0.46854 (7) | −0.50045 (10) | 0.0373 (4) | |
N1 | 0.7445 (3) | 0.35788 (10) | −0.51424 (15) | 0.0565 (7) | |
H1A | 0.6306 | 0.3606 | −0.5222 | 0.068* | |
H1B | 0.7963 | 0.3202 | −0.5145 | 0.068* | |
C1 | 0.8408 (3) | 0.41231 (11) | −0.50144 (14) | 0.0362 (6) | |
O11 | 0.6232 (3) | 0.64791 (9) | −0.65844 (12) | 0.0655 (6) | |
O12 | 0.5905 (2) | 0.58854 (7) | −0.54174 (9) | 0.0359 (4) | |
N11 | 0.4842 (2) | 0.48409 (9) | −0.62809 (12) | 0.0367 (5) | |
C11 | 0.5876 (3) | 0.59598 (11) | −0.62147 (15) | 0.0407 (6) | |
C12 | 0.5330 (3) | 0.53724 (12) | −0.67318 (14) | 0.0379 (6) | |
C13 | 0.5346 (4) | 0.53706 (13) | −0.76025 (16) | 0.0520 (7) | |
H13A | 0.5675 | 0.5745 | −0.7901 | 0.062* | |
C14 | 0.4865 (4) | 0.48050 (16) | −0.80267 (18) | 0.0626 (9) | |
H14A | 0.4881 | 0.4793 | −0.8615 | 0.075* | |
C15 | 0.4364 (4) | 0.42598 (14) | −0.75717 (17) | 0.0588 (8) | |
H15A | 0.4035 | 0.3875 | −0.7847 | 0.071* | |
C16 | 0.4356 (4) | 0.42939 (12) | −0.66985 (16) | 0.0474 (7) | |
H16A | 0.4004 | 0.3927 | −0.6390 | 0.057* | |
O21 | 0.7111 (4) | 0.7500 | −0.23655 (18) | 0.0736 (10) | |
N21 | 0.8593 (5) | 0.7500 | −0.3613 (2) | 0.0756 (12) | |
H21A | 0.9619 | 0.7500 | −0.3365 | 0.091* | |
H21B | 0.8535 | 0.7500 | −0.4157 | 0.091* | |
N22 | 0.5522 (5) | 0.7500 | −0.3572 (2) | 0.0637 (11) | |
H22A | 0.4520 | 0.7500 | −0.3303 | 0.076* | |
H22B | 0.5529 | 0.7500 | −0.4117 | 0.076* | |
C21 | 0.7064 (6) | 0.7500 | −0.3147 (3) | 0.0553 (11) | |
O31 | 0.0379 (3) | 0.7500 | −0.55338 (14) | 0.0467 (7) | |
N31 | 0.2038 (8) | 0.7150 (3) | −0.6644 (3) | 0.0860 (19) | 0.50 |
H31A | 0.2739 | 0.6932 | −0.6317 | 0.103* | 0.50 |
H31B | 0.2216 | 0.7150 | −0.7182 | 0.103* | 0.50 |
N32 | −0.0456 (7) | 0.7826 (2) | −0.6841 (3) | 0.0661 (15) | 0.50 |
H32A | −0.1358 | 0.8042 | −0.6647 | 0.079* | 0.50 |
H32B | −0.0252 | 0.7819 | −0.7377 | 0.079* | 0.50 |
C31 | 0.0634 (6) | 0.7500 | −0.6308 (3) | 0.0587 (12) | |
O1W | 0.5744 (5) | 0.7500 | −0.53977 (19) | 0.0709 (9) | |
H1C | 0.607 (3) | 0.7114 (6) | −0.5698 (12) | 0.085* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.03151 (19) | 0.02755 (18) | 0.03513 (19) | −0.00091 (18) | −0.00072 (19) | 0.00035 (17) |
N2 | 0.0328 (10) | 0.0386 (10) | 0.0813 (15) | 0.0044 (9) | −0.0054 (11) | 0.0028 (11) |
O1 | 0.0303 (7) | 0.0293 (7) | 0.0523 (9) | 0.0006 (7) | −0.0010 (8) | 0.0040 (8) |
N1 | 0.0371 (11) | 0.0304 (10) | 0.1019 (18) | 0.0009 (9) | −0.0025 (12) | −0.0052 (12) |
C1 | 0.0380 (12) | 0.0307 (11) | 0.0399 (12) | 0.0020 (10) | 0.0008 (11) | 0.0054 (11) |
O11 | 0.1033 (16) | 0.0403 (9) | 0.0529 (11) | −0.0157 (10) | −0.0007 (11) | 0.0120 (9) |
O12 | 0.0368 (8) | 0.0312 (8) | 0.0397 (8) | −0.0038 (7) | −0.0004 (7) | 0.0008 (7) |
N11 | 0.0358 (10) | 0.0363 (10) | 0.0380 (10) | −0.0001 (9) | −0.0047 (9) | −0.0004 (8) |
C11 | 0.0393 (13) | 0.0353 (12) | 0.0475 (13) | 0.0026 (11) | −0.0011 (12) | 0.0036 (11) |
C12 | 0.0355 (13) | 0.0391 (12) | 0.0389 (12) | 0.0052 (10) | −0.0022 (10) | 0.0007 (11) |
C13 | 0.0617 (17) | 0.0529 (15) | 0.0414 (13) | 0.0015 (13) | −0.0012 (13) | 0.0064 (13) |
C14 | 0.074 (2) | 0.0736 (19) | 0.0405 (14) | 0.0060 (17) | −0.0064 (14) | −0.0057 (14) |
C15 | 0.0668 (17) | 0.0586 (15) | 0.0509 (15) | 0.0018 (15) | −0.0099 (14) | −0.0196 (14) |
C16 | 0.0510 (15) | 0.0381 (13) | 0.0531 (14) | −0.0039 (12) | −0.0023 (13) | −0.0044 (12) |
O21 | 0.0576 (18) | 0.108 (2) | 0.0550 (17) | 0.000 | −0.0003 (15) | 0.000 |
N21 | 0.058 (2) | 0.105 (3) | 0.064 (2) | 0.000 | 0.0058 (19) | 0.000 |
N22 | 0.061 (2) | 0.076 (2) | 0.0540 (19) | 0.000 | −0.0041 (17) | 0.000 |
C21 | 0.058 (2) | 0.047 (2) | 0.061 (2) | 0.000 | 0.000 (2) | 0.000 |
O31 | 0.0556 (16) | 0.0454 (13) | 0.0393 (13) | 0.000 | 0.0017 (12) | 0.000 |
N31 | 0.085 (3) | 0.122 (4) | 0.051 (3) | 0.038 (3) | 0.012 (3) | 0.010 (3) |
N32 | 0.065 (3) | 0.087 (3) | 0.047 (2) | 0.013 (3) | 0.002 (2) | 0.017 (2) |
C31 | 0.043 (2) | 0.083 (3) | 0.051 (2) | 0.000 | −0.0008 (19) | 0.000 |
O1W | 0.096 (2) | 0.0523 (16) | 0.0643 (17) | 0.000 | 0.0219 (17) | 0.000 |
Geometric parameters (Å, º) top
Ni1—O12i | 2.0349 (15) | C14—H14A | 0.9300 |
Ni1—O12 | 2.0349 (15) | C15—C16 | 1.382 (4) |
Ni1—N11 | 2.0531 (18) | C15—H15A | 0.9300 |
Ni1—N11i | 2.0531 (18) | C16—H16A | 0.9300 |
Ni1—O1 | 2.1255 (15) | O21—C21 | 1.235 (5) |
Ni1—O1i | 2.1255 (15) | N21—C21 | 1.357 (5) |
N2—C1 | 1.328 (3) | N21—H21A | 0.8600 |
N2—H2A | 0.8600 | N21—H21B | 0.8600 |
N2—H2B | 0.8600 | N22—C21 | 1.332 (5) |
O1—C1 | 1.255 (3) | N22—H22A | 0.8600 |
N1—C1 | 1.336 (3) | N22—H22B | 0.8600 |
N1—H1A | 0.8600 | O31—C31 | 1.238 (5) |
N1—H1B | 0.8600 | N31—C31 | 1.373 (6) |
O11—C11 | 1.237 (3) | N31—N32ii | 1.886 (7) |
O12—C11 | 1.269 (3) | N31—H31A | 0.8600 |
N11—C16 | 1.344 (3) | N31—H31B | 0.8600 |
N11—C12 | 1.346 (3) | N32—C31 | 1.346 (6) |
C11—C12 | 1.504 (3) | N32—N31ii | 1.886 (7) |
C12—C13 | 1.376 (3) | N32—H32A | 0.8600 |
C13—C14 | 1.380 (4) | N32—H32B | 0.8600 |
C13—H13A | 0.9300 | O1W—H1C | 0.950 (9) |
C14—C15 | 1.374 (4) | | |
| | | |
O12i—Ni1—O12 | 180 | C12—C13—H13A | 120.5 |
O12i—Ni1—N11 | 99.24 (7) | C14—C13—H13A | 120.5 |
O12—Ni1—N11 | 80.76 (7) | C15—C14—C13 | 119.4 (2) |
O12i—Ni1—N11i | 80.76 (7) | C15—C14—H14A | 120.3 |
O12—Ni1—N11i | 99.24 (7) | C13—C14—H14A | 120.3 |
N11—Ni1—N11i | 180 | C14—C15—C16 | 118.9 (3) |
O12i—Ni1—O1 | 92.88 (6) | C14—C15—H15A | 120.6 |
O12—Ni1—O1 | 87.12 (6) | C16—C15—H15A | 120.6 |
N11—Ni1—O1 | 90.22 (7) | N11—C16—C15 | 122.1 (2) |
N11i—Ni1—O1 | 89.78 (7) | N11—C16—H16A | 119.0 |
O12i—Ni1—O1i | 87.12 (6) | C15—C16—H16A | 119.0 |
O12—Ni1—O1i | 92.88 (6) | C21—N21—H21A | 120.0 |
N11—Ni1—O1i | 89.78 (7) | C21—N21—H21B | 120.0 |
N11i—Ni1—O1i | 90.22 (7) | H21A—N21—H21B | 120.0 |
O1—Ni1—O1i | 180 | C21—N22—H22A | 120.0 |
C1—N2—H2A | 120.0 | C21—N22—H22B | 120.0 |
C1—N2—H2B | 120.0 | H22A—N22—H22B | 120.0 |
H2A—N2—H2B | 120.0 | O21—C21—N22 | 122.0 (4) |
C1—O1—Ni1 | 131.75 (14) | O21—C21—N21 | 121.2 (4) |
C1—N1—H1A | 120.0 | N22—C21—N21 | 116.8 (4) |
C1—N1—H1B | 120.0 | C31—N31—N32ii | 45.5 (3) |
H1A—N1—H1B | 120.0 | C31—N31—H31A | 120.0 |
O1—C1—N2 | 120.3 (2) | N32ii—N31—H31A | 135.4 |
O1—C1—N1 | 122.5 (2) | C31—N31—H31B | 120.0 |
N2—C1—N1 | 117.1 (2) | N32ii—N31—H31B | 89.4 |
C11—O12—Ni1 | 114.95 (14) | H31A—N31—H31B | 120.0 |
C16—N11—C12 | 118.6 (2) | C31—N32—N31ii | 46.7 (3) |
C16—N11—Ni1 | 129.06 (16) | C31—N32—H32A | 120.0 |
C12—N11—Ni1 | 112.30 (15) | N31ii—N32—H32A | 134.3 |
O11—C11—O12 | 124.6 (2) | C31—N32—H32B | 120.0 |
O11—C11—C12 | 118.8 (2) | N31ii—N32—H32B | 89.3 |
O12—C11—C12 | 116.7 (2) | H32A—N32—H32B | 120.0 |
N11—C12—C13 | 122.0 (2) | O31—C31—N32 | 121.7 (4) |
N11—C12—C11 | 115.14 (19) | O31—C31—N31 | 119.9 (4) |
C13—C12—C11 | 122.9 (2) | N32—C31—N31 | 118.3 (4) |
C12—C13—C14 | 119.1 (2) | | |
Symmetry codes: (i) −x+1, −y+1, −z−1; (ii) x, −y+3/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O12i | 0.86 | 2.19 | 2.866 (3) | 135 |
N1—H1B···O31i | 0.86 | 2.17 | 2.932 (3) | 147 |
N2—H2A···O1iii | 0.86 | 2.18 | 3.019 (3) | 166 |
N2—H2A···O12iii | 0.86 | 2.53 | 2.980 (3) | 114 |
N21—H21A···O21iv | 0.86 | 2.19 | 3.045 (5) | 175 |
N22—H22B···O1W | 0.86 | 2.03 | 2.889 (5) | 176 |
N22—H22A···O21v | 0.86 | 2.08 | 2.944 (5) | 179 |
N31—H31B···N32vi | 0.86 | 2.32 | 3.036 (7) | 141 |
N32—H32A···O11vii | 0.86 | 2.05 | 2.874 (5) | 161 |
O1W—H1C···O11 | 0.95 (1) | 1.91 (1) | 2.823 (3) | 161 (2) |
Symmetry codes: (i) −x+1, −y+1, −z−1; (iii) −x+2, −y+1, −z−1; (iv) x+1/2, y, −z−1/2; (v) x−1/2, y, −z−1/2; (vi) x+1/2, −y+3/2, −z−3/2; (vii) x−1, −y+3/2, z. |