Bis(3-eth­oxy-4-hydroxy­benzaldehyde thio­semicarbazonato-κ²S,N)nickel(II) monohydrate

In the crystal structure of the title compound, [Ni(C₁₀H₁₂N₃O₂S)₂]·H₂O, the Ni^II atom is located on an inversion center and is chelated by two hydroxy­ethoxy­benzaldehyde thio­semicarbazonate anions in a square-planar geometry. The five-membered chelate ring assumes an envelope conformation, with the Ni atom lying at the flap position. The uncoordinated water mol­ecule is disordered over another inversion center and is hydrogen bonded to the Ni^II complex.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 93%
• R factor = 0.053
• wR factor = 0.142
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) .......         O3

Author Response: As the lattice water is located on an inversion center, H atoms of the water molecule were not resasonably located.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.28
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1B    ...          ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C20 H26 N6 Ni1 O5 S2
            Atom count from the _atom_site data:  C20 H24 N6 Ni1 O5 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    1
           From the CIF: _chemical_formula_sum  C20 H26 N6 Ni O5 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         20.00     20.00    0.00
           H         26.00     24.00    2.00
           N          6.00      6.00    0.00
           Ni         1.00      1.00    0.00
           O          5.00      5.00    0.00
           S          2.00      2.00    0.00

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

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Bis(3-ethoxy-4-hydroxybenzaldehyde thiosemicarbazonato-κ²S,N)nickel(II) monohydrate

Crystal data

[Ni(C10H12N3O2S)2]·H2O	Z = 1
Mr = 553.30	F(000) = 288
Triclinic, P1	Dx = 1.585 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.794 (3) Å	Cell parameters from 728 reflections
b = 10.222 (4) Å	θ = 2.5–21.7°
c = 10.227 (5) Å	µ = 1.06 mm^−1
α = 75.100 (7)°	T = 294 K
β = 87.398 (6)°	Prism, red
γ = 81.956 (6)°	0.27 × 0.13 × 0.04 mm
V = 579.6 (5) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2015 independent reflections
Radiation source: fine-focus sealed tube	1593 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −6→6
Tmin = 0.763, Tmax = 0.957	k = −12→9
2904 measured reflections	l = −11→12

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.082P)^2 + 0.1304P] where P = (Fo^2 + 2Fc^2)/3
2015 reflections	(Δ/σ)max = 0.002
158 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.42 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
Ni1	0.0000	1.0000	0.0000	0.0307 (3)
S1	−0.01427 (18)	1.14248 (11)	0.12612 (12)	0.0415 (3)
O1	1.1889 (6)	0.4528 (3)	0.3081 (3)	0.0552 (9)
H1C	1.2471	0.4987	0.3660	0.066*
O2	1.0857 (5)	0.6868 (3)	0.3832 (3)	0.0436 (8)
O3	0.5000	0.5000	0.5000	0.0858 (18)
N1	0.3615 (7)	1.1694 (4)	0.2502 (4)	0.0565 (12)
H1A	0.2740	1.2438	0.2584	0.068*
H1B	0.5075	1.1468	0.2849	0.068*
N2	0.3949 (6)	0.9844 (3)	0.1666 (4)	0.0380 (9)
N3	0.2803 (5)	0.9129 (3)	0.0951 (3)	0.0332 (8)
C1	0.9943 (7)	0.5400 (4)	0.2596 (5)	0.0423 (11)
C2	0.8559 (8)	0.5058 (4)	0.1719 (5)	0.0505 (13)
H2	0.8966	0.4250	0.1455	0.061*
C3	0.6577 (8)	0.5906 (4)	0.1232 (5)	0.0478 (12)
H3	0.5632	0.5652	0.0653	0.057*
C4	0.5941 (7)	0.7129 (4)	0.1577 (4)	0.0350 (10)
C5	0.3798 (7)	0.7927 (4)	0.0965 (4)	0.0382 (10)
H5	0.2994	0.7472	0.0491	0.046*
C6	0.7382 (7)	0.7487 (4)	0.2449 (4)	0.0357 (10)
H6	0.7017	0.8315	0.2679	0.043*
C7	0.9340 (7)	0.6617 (4)	0.2970 (4)	0.0347 (10)
C8	1.0290 (8)	0.8076 (4)	0.4286 (5)	0.0457 (11)
H8A	0.8844	0.8044	0.4802	0.055*
H8B	1.0099	0.8870	0.3519	0.055*
C9	1.2240 (9)	0.8159 (5)	0.5151 (5)	0.0602 (14)
H9A	1.2399	0.7375	0.5912	0.090*
H9B	1.1913	0.8974	0.5466	0.090*
H9C	1.3663	0.8182	0.4632	0.090*
C10	0.2682 (7)	1.0926 (4)	0.1823 (4)	0.0395 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0301 (4)	0.0304 (4)	0.0334 (5)	0.0018 (3)	−0.0087 (3)	−0.0131 (3)
S1	0.0378 (6)	0.0415 (7)	0.0498 (7)	0.0093 (5)	−0.0166 (5)	−0.0249 (5)
O1	0.0512 (19)	0.0416 (18)	0.077 (2)	0.0150 (15)	−0.0241 (17)	−0.0292 (17)
O2	0.0410 (17)	0.0397 (17)	0.0530 (19)	0.0115 (13)	−0.0238 (15)	−0.0221 (15)
O3	0.071 (4)	0.082 (4)	0.104 (5)	0.010 (3)	−0.025 (3)	−0.030 (4)
N1	0.049 (2)	0.050 (2)	0.080 (3)	0.0127 (19)	−0.036 (2)	−0.037 (2)
N2	0.0353 (19)	0.038 (2)	0.044 (2)	0.0012 (16)	−0.0154 (16)	−0.0180 (17)
N3	0.0308 (17)	0.0348 (19)	0.0361 (19)	0.0025 (15)	−0.0129 (15)	−0.0143 (15)
C1	0.040 (2)	0.033 (2)	0.054 (3)	0.0098 (19)	−0.011 (2)	−0.015 (2)
C2	0.053 (3)	0.035 (2)	0.070 (3)	0.008 (2)	−0.024 (3)	−0.028 (2)
C3	0.050 (3)	0.041 (3)	0.059 (3)	0.000 (2)	−0.023 (2)	−0.024 (2)
C4	0.035 (2)	0.027 (2)	0.042 (2)	0.0042 (17)	−0.0069 (19)	−0.0121 (19)
C5	0.043 (2)	0.038 (2)	0.038 (2)	−0.0033 (19)	−0.0087 (19)	−0.0160 (19)
C6	0.039 (2)	0.030 (2)	0.040 (2)	0.0033 (18)	−0.0097 (19)	−0.0159 (19)
C7	0.036 (2)	0.034 (2)	0.036 (2)	−0.0014 (18)	−0.0066 (19)	−0.0117 (19)
C8	0.052 (3)	0.041 (3)	0.047 (3)	0.005 (2)	−0.013 (2)	−0.019 (2)
C9	0.063 (3)	0.066 (3)	0.060 (3)	−0.001 (3)	−0.023 (3)	−0.031 (3)
C10	0.040 (2)	0.037 (2)	0.044 (3)	0.0031 (19)	−0.015 (2)	−0.016 (2)

Geometric parameters (Å, º)

Ni1—S1^i	2.1712 (12)	C1—C7	1.388 (5)
Ni1—S1	2.1712 (12)	C2—C3	1.367 (6)
Ni1—N3	1.916 (3)	C2—H2	0.9300
Ni1—N3^i	1.916 (3)	C3—C4	1.383 (5)
S1—C10	1.723 (4)	C3—H3	0.9300
O1—C1	1.361 (5)	C4—C6	1.396 (5)
O1—H1C	0.9432	C4—C5	1.457 (5)
O2—C7	1.366 (5)	C5—H5	0.9300
O2—C8	1.420 (5)	C6—C7	1.375 (5)
N1—C10	1.350 (5)	C6—H6	0.9300
N1—H1A	0.8741	C8—C9	1.491 (6)
N1—H1B	0.9082	C8—H8A	0.9700
N2—C10	1.282 (5)	C8—H8B	0.9700
N2—N3	1.402 (4)	C9—H9A	0.9600
N3—C5	1.279 (5)	C9—H9B	0.9600
C1—C2	1.369 (6)	C9—H9C	0.9600
N3—Ni1—N3^i	180.000 (1)	C3—C4—C5	115.3 (4)
N3—Ni1—S1^i	94.47 (10)	C6—C4—C5	126.6 (3)
N3^i—Ni1—S1^i	85.53 (10)	N3—C5—C4	132.7 (4)
N3—Ni1—S1	85.53 (10)	N3—C5—H5	113.7
N3^i—Ni1—S1	94.47 (10)	C4—C5—H5	113.7
S1^i—Ni1—S1	180.00 (4)	C7—C6—C4	120.1 (4)
C10—S1—Ni1	95.26 (14)	C7—C6—H6	119.9
C1—O1—H1C	101.2	C4—C6—H6	119.9
C7—O2—C8	117.4 (3)	O2—C7—C6	124.7 (4)
C10—N1—H1A	116.2	O2—C7—C1	114.9 (3)
C10—N1—H1B	122.8	C6—C7—C1	120.4 (4)
H1A—N1—H1B	121.0	O2—C8—C9	107.5 (3)
C10—N2—N3	112.4 (3)	O2—C8—H8A	110.2
C5—N3—N2	115.4 (3)	C9—C8—H8A	110.2
C5—N3—Ni1	125.1 (3)	O2—C8—H8B	110.2
N2—N3—Ni1	119.5 (2)	C9—C8—H8B	110.2
O1—C1—C2	118.7 (4)	H8A—C8—H8B	108.5
O1—C1—C7	121.6 (4)	C8—C9—H9A	109.5
C2—C1—C7	119.6 (4)	C8—C9—H9B	109.5
C1—C2—C3	120.0 (4)	H9A—C9—H9B	109.5
C1—C2—H2	120.0	C8—C9—H9C	109.5
C3—C2—H2	120.0	H9A—C9—H9C	109.5
C2—C3—C4	121.7 (4)	H9B—C9—H9C	109.5
C2—C3—H3	119.2	N2—C10—N1	117.4 (4)
C4—C3—H3	119.2	N2—C10—S1	123.9 (3)
C3—C4—C6	118.2 (4)	N1—C10—S1	118.7 (3)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1^ii	0.87	2.30	3.124 (5)	156
O1—H1C···O2	0.94	2.06	2.678 (5)	121
O1—H1C···O3^iii	0.94	2.05	2.896 (4)	148

Symmetry codes: (ii) x−1, y+1, z; (iii) x+1, y, z.