Bis{2,4-dibromo-6-[3-(cyclo­hexyl­ammonio)propyl­imino­meth­yl]phenolato-κ²N,O}bis­(thio­cyanato-κN)nickel(II) methanol disolvate

The title centrosymmetric Schiff base nickel(II) complex, [Ni(NCS)₂(C₁₆H₂₂Br₂N₂O)₂]·2CH₃OH, consists of a mononuclear complex mol­ecule and two solvent methanol mol­ecules. The Ni^II atom lies on an inversion centre and is six-coordinated by the imine N and phenolate O atoms of the two Schiff base ligands and by the N atoms of two thio­cyanate ligands, in an octa­hedral coordination geometry. The cyclo­hexyl rings adopt chair conformations.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.045
• wR factor = 0.107
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C12
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C14

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.87
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.17 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C15
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C17
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.866
            Tmax scaled      0.396 Tmin scaled      0.343
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (2)       2.06

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

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

---

S1. Comment

Recently, we have reported the structures of a few Schiff base copper(II) and zinc(II) complexes (Yuan & Zhang, 2005; Yuan et al., 2007). As an extension of our investigations in this area we report herein the title new mononuclear Schiff base nickel(II) complex.

The complex consists of a mononuclear complex molecule and two lattice methanol molecules (Fig. 1). The Ni^II atom, lying on the inversion centre, is six-coordinated by two imine N and two phenolic O atoms from two Schiff base ligands and by two N atoms from two thiocyanate ligands, in octahedral coordination. The bond lengths and angles to the Ni(II) atom are comparable to the values in other similar complexes (Diao, 2007; Li et al., 2007; Li & Wang, 2007). The cyclohexyl rings adopt chair conformations.

Related literature

For related structures, see: Diao (2007); Yuan & Zhang (2005); Yuan et al. (2007); Li et al. (2007); Li & Wang (2007).

S2. Experimental

3,5-Dibromo-2-hydroxybenzaldehyde (1.0 mmol, 280.0 mg), N-cyclohexylpropane-1,3-diamine (1.0 mmol, 156.2 mg), and nickel nitrate hexahydrate (0.5 mmol, 145.4 mg) were dissolved in a methanol solution (50 ml). The mixture was stirred at room temperature for 30 min and filtered. After keeping the filtrate in air for 12 days, green block-shaped crystals were formed.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with C—H = 0.93 Å, U_iso = 1.2U_eq (C) for aromatic 0.97 Å, U_iso = 1.2U_eq (C) for CH₂, 0.96 Å, U_iso = 1.5U_eq (C) for CH₃, 0.90 Å, U_iso = 1.2U_eq (N) for NH and 0.82 Å, U_iso = 1.5U_eq (O) for OH atoms.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Labelled atoms are related to unlabelled atoms by the symmetry operation -x + 2, -y + 1, -z.

Bis{2,4-dibromo-6-[3-(cyclohexylammonio)propyliminomethyl]phenolato- κ²N,O}bis(thiocyanato-κN)nickel(II) methanol disolvate

Crystal data

[Ni(NCS)2(C16H22Br2N2O)2]·2CH4O	Z = 1
Mr = 1075.31	F(000) = 542
Triclinic, P1	Dx = 1.621 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3410 (19) Å	Cell parameters from 1932 reflections
b = 10.957 (2) Å	θ = 2.3–24.9°
c = 12.210 (2) Å	µ = 4.21 mm^−1
α = 108.28 (3)°	T = 298 K
β = 104.21 (3)°	Block, green
γ = 100.80 (3)°	0.27 × 0.23 × 0.22 mm
V = 1101.8 (4) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	4504 independent reflections
Radiation source: fine-focus sealed tube	2992 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 26.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.397, Tmax = 0.458	k = −13→13
8978 measured reflections	l = −15→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.048P)^2] where P = (Fo^2 + 2Fc^2)/3
4504 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.60 e Å^−3
0 restraints	Δρmin = −0.32 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	1.0000	0.5000	0.0000	0.02932 (18)
Br1	1.51132 (5)	0.62678 (5)	0.30412 (4)	0.05920 (18)
Br2	1.33026 (6)	0.98998 (5)	0.64540 (4)	0.06664 (19)
S1	0.67133 (19)	0.12546 (13)	0.02759 (16)	0.0838 (5)
O1	1.1701 (3)	0.5367 (2)	0.1599 (2)	0.0343 (6)
O2	0.4154 (4)	0.6690 (5)	0.7706 (4)	0.0961 (14)
H2	0.3910	0.7163	0.8256	0.144*
N1	0.8749 (3)	0.5875 (3)	0.1069 (3)	0.0308 (7)
N2	0.7392 (4)	0.6953 (3)	−0.1414 (3)	0.0370 (8)
H2A	0.6383	0.6774	−0.1815	0.044*
H2B	0.7599	0.6164	−0.1507	0.044*
N3	0.8862 (4)	0.3162 (3)	−0.0011 (3)	0.0406 (8)
C1	1.0902 (5)	0.6977 (4)	0.2983 (3)	0.0346 (9)
C2	1.2019 (4)	0.6386 (4)	0.2618 (3)	0.0336 (9)
C3	1.3531 (5)	0.6978 (4)	0.3463 (4)	0.0369 (10)
C4	1.3914 (5)	0.8006 (4)	0.4567 (3)	0.0428 (11)
H4	1.4930	0.8359	0.5086	0.051*
C5	1.2775 (5)	0.8511 (4)	0.4899 (3)	0.0402 (10)
C6	1.1291 (5)	0.8001 (4)	0.4125 (3)	0.0391 (10)
H6	1.0527	0.8340	0.4362	0.047*
C7	0.9310 (5)	0.6557 (4)	0.2211 (4)	0.0357 (9)
H7	0.8612	0.6817	0.2597	0.043*
C8	0.7085 (4)	0.5674 (4)	0.0512 (4)	0.0361 (9)
H8A	0.6524	0.5346	0.0983	0.043*
H8B	0.6724	0.4997	−0.0308	0.043*
C9	0.6743 (5)	0.6966 (4)	0.0459 (4)	0.0430 (10)
H9A	0.5664	0.6750	−0.0007	0.052*
H9B	0.6897	0.7563	0.1283	0.052*
C10	0.7701 (5)	0.7713 (4)	−0.0092 (4)	0.0411 (10)
H10A	0.7485	0.8567	0.0012	0.049*
H10B	0.8784	0.7896	0.0344	0.049*
C11	0.8317 (5)	0.7682 (4)	−0.1982 (4)	0.0402 (10)
H11	0.9403	0.7983	−0.1472	0.048*
C12	0.7835 (9)	0.8882 (6)	−0.2053 (5)	0.106 (3)
H12A	0.7954	0.9484	−0.1240	0.127*
H12B	0.6755	0.8605	−0.2540	0.127*
C13	0.8795 (9)	0.9614 (5)	−0.2620 (5)	0.105 (3)
H13A	0.8441	1.0377	−0.2675	0.125*
H13B	0.9864	0.9949	−0.2099	0.125*
C14	0.8688 (6)	0.8722 (5)	−0.3856 (4)	0.0546 (12)
H14A	0.9368	0.9200	−0.4168	0.066*
H14B	0.7642	0.8467	−0.4406	0.066*
C15	0.9127 (8)	0.7495 (5)	−0.3811 (5)	0.0849 (19)
H15A	1.0213	0.7746	−0.3347	0.102*
H15B	0.8973	0.6894	−0.4633	0.102*
C16	0.8180 (7)	0.6767 (5)	−0.3229 (5)	0.0758 (17)
H16A	0.7106	0.6432	−0.3740	0.091*
H16B	0.8535	0.6005	−0.3174	0.091*
C17	0.7955 (5)	0.2382 (4)	0.0099 (4)	0.0410 (10)
C18	0.2958 (8)	0.6214 (7)	0.6636 (6)	0.101 (2)
H18A	0.2636	0.6950	0.6497	0.151*
H18B	0.2112	0.5605	0.6683	0.151*
H18C	0.3286	0.5753	0.5976	0.151*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0307 (4)	0.0273 (4)	0.0304 (4)	0.0080 (3)	0.0130 (3)	0.0094 (3)
Br1	0.0371 (3)	0.0546 (3)	0.0626 (3)	0.0149 (2)	0.0096 (2)	−0.0039 (2)
Br2	0.0754 (4)	0.0546 (3)	0.0433 (3)	0.0061 (3)	0.0193 (3)	−0.0090 (2)
S1	0.0967 (11)	0.0381 (8)	0.1335 (14)	0.0095 (7)	0.0855 (11)	0.0235 (8)
O1	0.0354 (15)	0.0317 (15)	0.0306 (15)	0.0110 (12)	0.0085 (12)	0.0059 (12)
O2	0.073 (3)	0.122 (4)	0.073 (3)	0.060 (3)	0.012 (2)	0.002 (3)
N1	0.0344 (18)	0.0296 (18)	0.0328 (18)	0.0106 (14)	0.0163 (15)	0.0124 (15)
N2	0.042 (2)	0.0313 (18)	0.0363 (19)	0.0127 (16)	0.0131 (16)	0.0095 (16)
N3	0.040 (2)	0.033 (2)	0.049 (2)	0.0071 (17)	0.0175 (17)	0.0158 (17)
C1	0.043 (2)	0.032 (2)	0.031 (2)	0.0103 (19)	0.0155 (19)	0.0130 (18)
C2	0.038 (2)	0.030 (2)	0.034 (2)	0.0088 (18)	0.0141 (18)	0.0133 (19)
C3	0.034 (2)	0.033 (2)	0.044 (2)	0.0106 (18)	0.0155 (19)	0.012 (2)
C4	0.041 (3)	0.035 (2)	0.035 (2)	0.006 (2)	0.003 (2)	0.002 (2)
C5	0.053 (3)	0.033 (2)	0.028 (2)	0.006 (2)	0.014 (2)	0.0052 (19)
C6	0.049 (3)	0.040 (2)	0.033 (2)	0.016 (2)	0.023 (2)	0.0115 (19)
C7	0.039 (2)	0.034 (2)	0.040 (2)	0.0135 (19)	0.0224 (19)	0.013 (2)
C8	0.034 (2)	0.042 (2)	0.036 (2)	0.0140 (19)	0.0178 (18)	0.0133 (19)
C9	0.042 (2)	0.050 (3)	0.042 (2)	0.023 (2)	0.016 (2)	0.016 (2)
C10	0.054 (3)	0.032 (2)	0.041 (2)	0.016 (2)	0.019 (2)	0.014 (2)
C11	0.043 (2)	0.037 (2)	0.037 (2)	0.009 (2)	0.010 (2)	0.013 (2)
C12	0.228 (8)	0.070 (4)	0.096 (5)	0.090 (5)	0.119 (5)	0.054 (4)
C13	0.216 (8)	0.050 (3)	0.082 (4)	0.043 (4)	0.086 (5)	0.039 (3)
C14	0.061 (3)	0.062 (3)	0.052 (3)	0.019 (3)	0.025 (2)	0.030 (3)
C15	0.131 (6)	0.064 (4)	0.101 (5)	0.040 (4)	0.081 (4)	0.045 (4)
C16	0.126 (5)	0.047 (3)	0.085 (4)	0.033 (3)	0.076 (4)	0.028 (3)
C17	0.042 (3)	0.035 (2)	0.048 (3)	0.016 (2)	0.021 (2)	0.011 (2)
C18	0.105 (5)	0.101 (5)	0.097 (5)	0.054 (4)	0.020 (4)	0.034 (4)

Geometric parameters (Å, º)

Ni1—O1	2.060 (3)	C8—C9	1.525 (6)
Ni1—O1^i	2.060 (3)	C8—H8A	0.9700
Ni1—N3^i	2.088 (4)	C8—H8B	0.9700
Ni1—N3	2.088 (4)	C9—C10	1.513 (6)
Ni1—N1	2.090 (3)	C9—H9A	0.9700
Ni1—N1^i	2.090 (3)	C9—H9B	0.9700
Br1—C3	1.900 (4)	C10—H10A	0.9700
Br2—C5	1.900 (4)	C10—H10B	0.9700
S1—C17	1.635 (5)	C11—C12	1.488 (6)
O1—C2	1.306 (4)	C11—C16	1.496 (6)
O2—C18	1.365 (6)	C11—H11	0.9800
O2—H2	0.8200	C12—C13	1.520 (8)
N1—C7	1.272 (5)	C12—H12A	0.9700
N1—C8	1.479 (5)	C12—H12B	0.9700
N2—C10	1.490 (5)	C13—C14	1.486 (6)
N2—C11	1.500 (5)	C13—H13A	0.9700
N2—H2A	0.9000	C13—H13B	0.9700
N2—H2B	0.9000	C14—C15	1.490 (7)
N3—C17	1.150 (5)	C14—H14A	0.9700
C1—C6	1.398 (5)	C14—H14B	0.9700
C1—C2	1.416 (5)	C15—C16	1.525 (7)
C1—C7	1.447 (5)	C15—H15A	0.9700
C2—C3	1.415 (5)	C15—H15B	0.9700
C3—C4	1.369 (5)	C16—H16A	0.9700
C4—C5	1.376 (5)	C16—H16B	0.9700
C4—H4	0.9300	C18—H18A	0.9600
C5—C6	1.364 (6)	C18—H18B	0.9600
C6—H6	0.9300	C18—H18C	0.9600
C7—H7	0.9300
O1—Ni1—O1^i	180.00 (14)	C10—C9—H9A	108.3
O1—Ni1—N3^i	88.72 (12)	C8—C9—H9A	108.3
O1^i—Ni1—N3^i	91.28 (12)	C10—C9—H9B	108.3
O1—Ni1—N3	91.28 (12)	C8—C9—H9B	108.3
O1^i—Ni1—N3	88.72 (12)	H9A—C9—H9B	107.4
N3^i—Ni1—N3	180.00 (18)	N2—C10—C9	112.9 (3)
O1—Ni1—N1	87.62 (11)	N2—C10—H10A	109.0
O1^i—Ni1—N1	92.38 (11)	C9—C10—H10A	109.0
N3^i—Ni1—N1	92.76 (13)	N2—C10—H10B	109.0
N3—Ni1—N1	87.24 (13)	C9—C10—H10B	109.0
O1—Ni1—N1^i	92.38 (11)	H10A—C10—H10B	107.8
O1^i—Ni1—N1^i	87.62 (11)	C12—C11—C16	109.7 (4)
N3^i—Ni1—N1^i	87.24 (13)	C12—C11—N2	111.7 (4)
N3—Ni1—N1^i	92.76 (13)	C16—C11—N2	110.6 (3)
N1—Ni1—N1^i	180.00 (15)	C12—C11—H11	108.2
C2—O1—Ni1	124.6 (2)	C16—C11—H11	108.2
C18—O2—H2	109.5	N2—C11—H11	108.2
C7—N1—C8	115.6 (3)	C11—C12—C13	110.9 (5)
C7—N1—Ni1	124.4 (3)	C11—C12—H12A	109.5
C8—N1—Ni1	120.0 (2)	C13—C12—H12A	109.5
C10—N2—C11	113.7 (3)	C11—C12—H12B	109.5
C10—N2—H2A	108.8	C13—C12—H12B	109.5
C11—N2—H2A	108.8	H12A—C12—H12B	108.0
C10—N2—H2B	108.8	C14—C13—C12	111.7 (5)
C11—N2—H2B	108.8	C14—C13—H13A	109.3
H2A—N2—H2B	107.7	C12—C13—H13A	109.3
C17—N3—Ni1	159.1 (3)	C14—C13—H13B	109.3
C6—C1—C2	121.1 (4)	C12—C13—H13B	109.3
C6—C1—C7	116.5 (4)	H13A—C13—H13B	107.9
C2—C1—C7	122.5 (4)	C13—C14—C15	110.4 (4)
O1—C2—C3	121.8 (4)	C13—C14—H14A	109.6
O1—C2—C1	123.8 (4)	C15—C14—H14A	109.6
C3—C2—C1	114.4 (3)	C13—C14—H14B	109.6
C4—C3—C2	124.2 (4)	C15—C14—H14B	109.6
C4—C3—Br1	118.4 (3)	H14A—C14—H14B	108.1
C2—C3—Br1	117.4 (3)	C14—C15—C16	111.7 (4)
C3—C4—C5	119.1 (4)	C14—C15—H15A	109.3
C3—C4—H4	120.5	C16—C15—H15A	109.3
C5—C4—H4	120.5	C14—C15—H15B	109.3
C6—C5—C4	120.1 (4)	C16—C15—H15B	109.3
C6—C5—Br2	121.1 (3)	H15A—C15—H15B	107.9
C4—C5—Br2	118.9 (3)	C11—C16—C15	111.1 (4)
C5—C6—C1	121.1 (4)	C11—C16—H16A	109.4
C5—C6—H6	119.5	C15—C16—H16A	109.4
C1—C6—H6	119.5	C11—C16—H16B	109.4
N1—C7—C1	127.9 (4)	C15—C16—H16B	109.4
N1—C7—H7	116.1	H16A—C16—H16B	108.0
C1—C7—H7	116.1	N3—C17—S1	178.0 (4)
N1—C8—C9	112.1 (3)	O2—C18—H18A	109.5
N1—C8—H8A	109.2	O2—C18—H18B	109.5
C9—C8—H8A	109.2	H18A—C18—H18B	109.5
N1—C8—H8B	109.2	O2—C18—H18C	109.5
C9—C8—H8B	109.2	H18A—C18—H18C	109.5
H8A—C8—H8B	107.9	H18B—C18—H18C	109.5
C10—C9—C8	115.8 (3)

Symmetry code: (i) −x+2, −y+1, −z.