Synthesis, crystal structure, stereochemical and Hirshfeld surface analysis of trans-di­aqua­bis­(1-phenyl­propane-1,2-di­amine-κ²N,N′)nickel(II) dichloride dihydrate

The cation of the title compound exhibits point group symmetry , with the central Ni^II atom in a trans [N₄O₂] coordination environment.

Key indicators

Structure: I

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• H-atom completeness 89%
• R factor = 0.061
• wR factor = 0.140
• Data-to-parameter ratio = 25.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT306_ALERT_2_B Isolated Oxygen Atom (H-atoms Missing ?) .......         O1 Check

Author Response: O1 is the O atom of the noncoordinating water molecule. The two H positions around this O atom are not discernible from difference-Fourier maps.

Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT043_ALERT_1_C Calculated and Reported Mol. Weight Differ by ..       4.05 Check
PLAT260_ALERT_2_C Large Average Ueq of Residue Including        O1      0.123 Check
PLAT331_ALERT_2_C Small Aver Phenyl C-C Dist C4       --C9       .       1.37 Ang.
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00633 Ang.
PLAT420_ALERT_2_C D-H Bond Without Acceptor  N2       --H2D      .     Please Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      7.366 Check
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         10 Report
PLAT971_ALERT_2_C Check Calcd Resid. Dens.  0.90Ang From C3              1.56 eA-3
PLAT977_ALERT_2_C Check Negative Difference Density on H3        .      -0.48 eA-3

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C18 H36 Cl2 N4 Ni1 O4
            Atom count from _chemical_formula_moiety:
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:C18 H36 Cl2 N4 Ni1 O4
            Atom count from the _atom_site data:  C18 H32 Cl2 N4 Ni1 O4
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    2
           From the CIF: _chemical_formula_sum  C18 H36 Cl2 N4 Ni O4
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         36.00     36.00    0.00
           H         72.00     64.00    8.00
           Cl         4.00      4.00    0.00
           N          8.00      8.00    0.00
           Ni         2.00      2.00    0.00
           O          8.00      8.00    0.00
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          4 Report
PLAT480_ALERT_4_G Long H...A H-Bond Reported H2D      ..CL2      .       2.86 Ang.
PLAT794_ALERT_5_G Tentative Bond Valency for Ni1       (II)      .       1.94 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          8 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          2 Note
PLAT941_ALERT_3_G Average HKL Measurement Multiplicity ...........        4.4 Low
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  12 ALERT level G = General information/check it is not something unexpected

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX3 (Bruker, 2017); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2020); software used to prepare material for publication: publCIF (Westrip, 2010).

trans-Diaquabis(1-phenylpropane-1,2-diamine-κ²N,N')nickel(II) dichloride dihydrate

Crystal data

[Ni(C9H14N2)2(H2O)2]Cl2·2H2O	Dx = 1.331 Mg m^−3
Mr = 502.12	Melting point: 497 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.1130 (7) Å	Cell parameters from 7663 reflections
b = 7.3062 (4) Å	θ = 3.1–30.0°
c = 14.0441 (8) Å	µ = 1.02 mm^−1
β = 91.589 (2)°	T = 298 K
V = 1242.42 (12) Å^3	Block, pink
Z = 2	0.31 × 0.27 × 0.21 mm
F(000) = 524

Data collection

Bruker D8 Quest XRD diffractometer	2841 reflections with I > 2σ(I)
Detector resolution: 7.3910 pixels mm^-1	Rint = 0.020
ω and φ scans	θmax = 30.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −17→16
Tmin = 0.634, Tmax = 0.746	k = −10→10
15989 measured reflections	l = −19→17
3619 independent reflections

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)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 2.3825P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3619 reflections	Δρmax = 1.52 e Å^−3
144 parameters	Δρmin = −0.91 e Å^−3
0 restraints	Extinction correction: SHELXL-2019/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.000000	0.500000	0.500000	0.03444 (17)
O1	0.2039 (4)	0.2818 (7)	0.2674 (3)	0.1230 (15)
O2	−0.08403 (19)	0.7604 (3)	0.49802 (16)	0.0480 (5)
H2A	−0.067927	0.830472	0.544916	0.072*
H2B	−0.067224	0.824263	0.447313	0.072*
Cl2	0.00298 (9)	0.99682 (12)	0.32983 (6)	0.0590 (3)
N1	0.1278 (2)	0.6032 (3)	0.41843 (16)	0.0393 (5)
H1A	0.163790	0.511552	0.391321	0.047*
H1B	0.100305	0.675472	0.372616	0.047*
N2	0.1041 (2)	0.5800 (4)	0.61171 (18)	0.0402 (5)
C1	0.2120 (3)	0.6298 (7)	0.5760 (2)	0.0656 (11)
H1	0.247413	0.511203	0.565627	0.079*
C2	0.2870 (3)	0.7202 (6)	0.6481 (3)	0.0608 (10)
H2E	0.356214	0.748091	0.619709	0.091*
H2F	0.299490	0.639331	0.701219	0.091*
H2G	0.253580	0.831281	0.669762	0.091*
C3	0.2038 (3)	0.7078 (7)	0.4816 (3)	0.0670 (11)
H3	0.167920	0.826718	0.489949	0.080*
C4	0.3132 (3)	0.7513 (6)	0.4357 (2)	0.0568 (9)
C5	0.3882 (4)	0.6251 (7)	0.4081 (3)	0.0793 (13)
H5	0.374550	0.501135	0.416994	0.095*
C6	0.4867 (4)	0.6819 (9)	0.3659 (4)	0.0890 (16)
H6	0.538556	0.595730	0.347740	0.107*
C7	0.5056 (3)	0.8635 (9)	0.3517 (3)	0.0806 (15)
H7	0.570103	0.901948	0.323347	0.097*
C8	0.4309 (4)	0.9858 (7)	0.3788 (4)	0.0824 (14)
H8	0.443916	1.109789	0.368966	0.099*
C9	0.3354 (3)	0.9320 (7)	0.4208 (3)	0.0669 (10)
H9	0.284926	1.020016	0.439403	0.080*
H2C	0.079 (3)	0.667 (6)	0.644 (3)	0.068 (13)*
H2D	0.114 (4)	0.503 (6)	0.653 (3)	0.076 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0403 (3)	0.0322 (3)	0.0311 (3)	−0.0052 (2)	0.00578 (18)	0.00010 (19)
O1	0.126 (3)	0.115 (3)	0.128 (4)	0.001 (3)	0.006 (3)	0.009 (3)
O2	0.0588 (13)	0.0360 (11)	0.0495 (12)	0.0009 (10)	0.0076 (10)	0.0012 (9)
Cl2	0.0953 (7)	0.0415 (4)	0.0409 (4)	0.0030 (4)	0.0133 (4)	−0.0025 (3)
N1	0.0426 (12)	0.0424 (13)	0.0331 (11)	−0.0084 (10)	0.0038 (9)	0.0001 (10)
N2	0.0450 (13)	0.0439 (14)	0.0318 (12)	−0.0060 (11)	0.0047 (10)	0.0005 (11)
C1	0.0497 (19)	0.107 (3)	0.0399 (17)	−0.026 (2)	0.0018 (14)	0.0001 (19)
C2	0.0518 (19)	0.082 (3)	0.0479 (19)	−0.0132 (19)	−0.0065 (15)	−0.0045 (18)
C3	0.058 (2)	0.095 (3)	0.0470 (19)	−0.031 (2)	0.0043 (16)	−0.0007 (19)
C4	0.0435 (17)	0.086 (3)	0.0412 (16)	−0.0226 (18)	0.0046 (13)	−0.0004 (17)
C5	0.102 (4)	0.063 (3)	0.074 (3)	−0.008 (3)	0.015 (3)	0.002 (2)
C6	0.072 (3)	0.120 (5)	0.076 (3)	0.029 (3)	0.012 (2)	−0.008 (3)
C7	0.049 (2)	0.126 (5)	0.068 (3)	−0.027 (3)	0.0143 (18)	0.000 (3)
C8	0.084 (3)	0.079 (3)	0.085 (3)	−0.027 (3)	0.019 (3)	0.007 (3)
C9	0.057 (2)	0.080 (3)	0.065 (2)	−0.001 (2)	0.0106 (18)	0.005 (2)

Geometric parameters (Å, º)

Ni1—N2^i	2.070 (3)	C2—H2E	0.9600
Ni1—N2	2.070 (3)	C2—H2F	0.9600
Ni1—N1^i	2.092 (2)	C2—H2G	0.9600
Ni1—N1	2.092 (2)	C3—C4	1.523 (5)
Ni1—O2^i	2.158 (2)	C3—H3	0.9800
Ni1—O2	2.158 (2)	C4—C5	1.359 (6)
O2—H2A	0.8524	C4—C9	1.364 (6)
O2—H2B	0.8799	C5—C6	1.409 (7)
N1—C3	1.475 (4)	C5—H5	0.9300
N1—H1A	0.8900	C6—C7	1.362 (8)
N1—H1B	0.8900	C6—H6	0.9300
N2—C1	1.458 (4)	C7—C8	1.335 (7)
N2—H2C	0.84 (5)	C7—H7	0.9300
N2—H2D	0.81 (5)	C8—C9	1.371 (6)
C1—C3	1.444 (5)	C8—H8	0.9300
C1—C2	1.496 (5)	C9—H9	0.9300
C1—H1	0.9800
N2^i—Ni1—N2	180.0	C3—C1—H1	103.4
N2^i—Ni1—N1^i	82.45 (9)	N2—C1—H1	103.4
N2—Ni1—N1^i	97.55 (9)	C2—C1—H1	103.4
N2^i—Ni1—N1	97.55 (9)	C1—C2—H2E	109.5
N2—Ni1—N1	82.45 (9)	C1—C2—H2F	109.5
N1^i—Ni1—N1	180.0	H2E—C2—H2F	109.5
N2^i—Ni1—O2^i	92.17 (11)	C1—C2—H2G	109.5
N2—Ni1—O2^i	87.83 (11)	H2E—C2—H2G	109.5
N1^i—Ni1—O2^i	91.79 (9)	H2F—C2—H2G	109.5
N1—Ni1—O2^i	88.21 (9)	C1—C3—N1	111.9 (3)
N2^i—Ni1—O2	87.83 (11)	C1—C3—C4	115.7 (3)
N2—Ni1—O2	92.17 (11)	N1—C3—C4	112.9 (3)
N1^i—Ni1—O2	88.21 (9)	C1—C3—H3	105.0
N1—Ni1—O2	91.79 (9)	N1—C3—H3	105.0
O2^i—Ni1—O2	180.00 (11)	C4—C3—H3	105.0
Ni1—O2—H2A	114.9	C5—C4—C9	118.5 (4)
Ni1—O2—H2B	111.0	C5—C4—C3	125.1 (4)
H2A—O2—H2B	104.7	C9—C4—C3	116.4 (4)
C3—N1—Ni1	108.45 (19)	C4—C5—C6	120.1 (5)
C3—N1—H1A	110.0	C4—C5—H5	120.0
Ni1—N1—H1A	110.0	C6—C5—H5	120.0
C3—N1—H1B	110.0	C7—C6—C5	119.8 (5)
Ni1—N1—H1B	110.0	C7—C6—H6	120.1
H1A—N1—H1B	108.4	C5—C6—H6	120.1
C1—N2—Ni1	110.06 (19)	C8—C7—C6	119.5 (4)
C1—N2—H2C	110 (3)	C8—C7—H7	120.2
Ni1—N2—H2C	114 (3)	C6—C7—H7	120.2
C1—N2—H2D	107 (3)	C7—C8—C9	121.1 (5)
Ni1—N2—H2D	115 (3)	C7—C8—H8	119.4
H2C—N2—H2D	101 (4)	C9—C8—H8	119.4
C3—C1—N2	112.0 (3)	C4—C9—C8	121.1 (4)
C3—C1—C2	118.2 (4)	C4—C9—H9	119.5
N2—C1—C2	114.3 (3)	C8—C9—H9	119.5
Ni1—N2—C1—C3	32.1 (5)	C1—C3—C4—C9	−113.5 (5)
Ni1—N2—C1—C2	169.9 (3)	N1—C3—C4—C9	115.7 (4)
N2—C1—C3—N1	−44.5 (5)	C9—C4—C5—C6	0.6 (7)
C2—C1—C3—N1	179.4 (4)	C3—C4—C5—C6	179.8 (4)
N2—C1—C3—C4	−175.8 (4)	C4—C5—C6—C7	−0.9 (8)
C2—C1—C3—C4	48.2 (6)	C5—C6—C7—C8	0.6 (8)
Ni1—N1—C3—C1	33.9 (4)	C6—C7—C8—C9	0.1 (8)
Ni1—N1—C3—C4	166.5 (3)	C5—C4—C9—C8	0.1 (7)
C1—C3—C4—C5	67.3 (6)	C3—C4—C9—C8	−179.2 (4)
N1—C3—C4—C5	−63.4 (5)	C7—C8—C9—C4	−0.4 (7)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···Cl2^ii	0.85	2.29	3.134 (2)	173
O2—H2B···Cl2	0.88	2.26	3.132 (2)	170
N1—H1A···O1	0.89	2.48	3.313 (5)	157
N1—H1B···Cl2	0.89	2.69	3.464 (3)	146
N2—H2C···Cl2^ii	0.84 (5)	2.68 (5)	3.460 (3)	155 (4)
N2—H2D···Cl2^iii	0.81 (5)	2.86 (5)	3.378 (3)	124 (4)

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