Cd_1.17Zn_0.83B₂O₅, a new cadmium zinc diborate

Crystals of cadmium zinc diborate, Cd_1.17Zn_0.83B₂O₅, have been obtained by spontaneous nucleation in a platinum crucible at 1072 K. The crystal structure exhibits diborate groups, B₂O₅⁴⁻, sharing O atoms with considerably distorted M1O₆ octa­hedra and M2O₄ tetra­hedra. Both metal centers are disordered in the proportion Cd:Zn = 0.92:0.08 on the M1 site and Cd:Zn = 0.25:0.75 on the M2 site. A strong second-harmonic generation has been observed for the title compound when excited with an Nd:YAG laser (λ = 1064 nm).

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](O-B) = 0.011 Å
• Disorder in main residue
• R factor = 0.032
• wR factor = 0.079
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =    11.211
            Value of mu given      =    11.328
DENSD01_ALERT_1_C  The ratio of the submitted crystal density and that
            calculated from the formula is outside the range 0.99 <> 1.01
            Crystal density given    =      4.686
            Calculated crystal density =      4.821
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT044_ALERT_1_C Calculated and Reported Dx Differ ..............          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.25 Ratio
PLAT046_ALERT_1_C Reported Z, MW and D(calc) are Inconsistent ....       4.82
PLAT051_ALERT_1_C Mu(calc) and Mu(CIF) Ratio Differs from 1.0 by .       1.04 Perc.
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT213_ALERT_2_C Atom O1      has ADP max/min Ratio .............       3.30 prolat
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       3.41
PLAT301_ALERT_3_C Main Residue  Disorder .........................      14.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              ZN2  -O2   -CD2     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              ZN2  -O2   -CD2     1.655   1.555   1.655
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              ZN1  -O2   -CD1     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              ZN1  -O3   -CD1     4.566   1.555   4.566
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              CD2  -O5   -ZN2     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       0.00 Deg.
              ZN2  -O5   -CD2     3.545   1.555   3.545

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               1101
           Count of symmetry unique reflns          721
           Completeness (_total/calc)            152.70%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       380
           Fraction of Friedel pairs measured     0.527
           Are heavy atom types Z>Si present        yes

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

   8 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
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

cadmium zinc diborate

Crystal data

Cd1.17Zn0.83B2O5	F(000) = 512
Mr = 287.46	Dx = 4.686 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3098 reflections
a = 3.4147 (4) Å	θ = 2.3–30.0°
b = 6.5060 (7) Å	µ = 11.33 mm^−1
c = 17.8263 (19) Å	T = 296 K
V = 396.03 (8) Å^3	Needle, colorless
Z = 4	0.22 × 0.10 × 0.10 mm

Data collection

Bruker SMART-APEX CCD diffractometer	1101 independent reflections
Radiation source: fine-focus sealed tube	1100 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −4→4
Tmin = 0.090, Tmax = 0.322	k = −5→9
2308 measured reflections	l = −23→24

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0118P)^2 + 10.0237P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.032	(Δ/σ)max = 0.001
wR(F^2) = 0.079	Δρmax = 2.83 e Å^−3
S = 1.04	Δρmin = −2.07 e Å^−3
1101 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
85 parameters	Extinction coefficient: 0.040 (2)
6 restraints	Absolute structure: Flack (1983), 380 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.13 (5)

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	Occ. (<1)
Cd1	0.61907 (16)	0.47932 (8)	0.47388 (3)	0.0082 (2)	0.924 (12)
Zn1	0.61907 (16)	0.47932 (8)	0.47388 (3)	0.0082 (2)	0.076 (12)
Cd2	0.0242 (2)	0.60028 (12)	0.29166 (4)	0.0103 (3)	0.247 (10)
Zn2	0.0242 (2)	0.60028 (12)	0.29166 (4)	0.0103 (3)	0.753 (10)
O1	0.2962 (18)	0.0000 (9)	0.3426 (3)	0.0137 (13)
O2	0.521 (2)	0.6623 (9)	0.3564 (3)	0.0151 (13)
O3	0.6091 (19)	0.8913 (9)	0.4581 (3)	0.0135 (12)
O4	0.135 (2)	0.2791 (9)	0.4279 (3)	0.0106 (12)
O5	0.018 (2)	0.2935 (10)	0.2950 (3)	0.0180 (14)
B1	0.151 (3)	0.1963 (13)	0.3576 (5)	0.0095 (16)
B2	0.486 (3)	0.8572 (13)	0.3875 (5)	0.0082 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0108 (3)	0.0108 (3)	0.0030 (2)	0.00026 (18)	−0.00016 (17)	−0.00007 (18)
Zn1	0.0108 (3)	0.0108 (3)	0.0030 (2)	0.00026 (18)	−0.00016 (17)	−0.00007 (18)
Cd2	0.0186 (5)	0.0074 (4)	0.0050 (4)	0.0010 (3)	−0.0005 (3)	0.0021 (3)
Zn2	0.0186 (5)	0.0074 (4)	0.0050 (4)	0.0010 (3)	−0.0005 (3)	0.0021 (3)
O1	0.025 (3)	0.011 (2)	0.005 (2)	0.005 (2)	−0.0045 (19)	−0.0044 (19)
O2	0.028 (3)	0.006 (2)	0.011 (3)	0.000 (2)	0.003 (2)	−0.002 (2)
O3	0.018 (3)	0.015 (3)	0.007 (2)	0.000 (2)	−0.003 (2)	0.000 (2)
O4	0.017 (3)	0.009 (2)	0.005 (2)	0.000 (2)	0.001 (2)	−0.0004 (18)
O5	0.026 (3)	0.019 (3)	0.009 (3)	0.006 (2)	−0.003 (3)	0.007 (2)
B1	0.015 (4)	0.008 (3)	0.005 (3)	−0.001 (3)	0.000 (3)	0.000 (3)
B2	0.012 (3)	0.009 (3)	0.003 (3)	0.001 (3)	0.000 (3)	0.003 (3)

Geometric parameters (Å, º)

Cd1—O3^i	2.231 (6)	Zn2—O2	2.092 (7)
Cd1—O4	2.260 (6)	Zn2—O2^v	2.108 (7)
Cd1—O3^ii	2.283 (6)	Zn2—O1^vi	2.712 (5)
Cd1—O4^iii	2.339 (6)	Zn2—O1^vii	2.907 (6)
Cd1—O4^iv	2.428 (6)	O1—B2^viii	1.387 (10)
Cd1—O2	2.432 (6)	O1—B1	1.396 (10)
Cd1—O3	2.695 (6)	O2—B2	1.389 (10)
Cd1—Cd1^v	3.4147 (4)	O2—Zn2^iii	2.108 (7)
Cd1—Cd1^iii	3.4147 (4)	O2—Cd2^iii	2.108 (7)
Zn1—O3^i	2.231 (6)	O3—B2	1.346 (10)
Zn1—O4	2.260 (6)	O3—Zn1^ii	2.231 (6)
Zn1—O3^ii	2.283 (6)	O3—Cd1^ii	2.231 (6)
Zn1—O4^iii	2.339 (6)	O3—Zn1^i	2.283 (6)
Zn1—O4^iv	2.428 (6)	O3—Cd1^i	2.283 (6)
Zn1—O2	2.432 (6)	O4—B1	1.365 (10)
Cd2—O5	1.997 (7)	O4—Zn1^v	2.339 (6)
Cd2—O5^vi	1.997 (7)	O4—Cd1^v	2.339 (6)
Cd2—O2	2.092 (7)	O4—Zn1^ix	2.428 (6)
Cd2—O2^v	2.108 (7)	O4—Cd1^ix	2.428 (6)
Cd2—B1^vi	2.797 (8)	O5—B1	1.360 (10)
Cd2—Cd2^iii	3.4147 (4)	O5—Zn2^x	1.997 (7)
Cd2—Cd2^v	3.4147 (4)	O5—Cd2^x	1.997 (7)
Zn2—O5	1.997 (7)	B1—Cd2^x	2.797 (8)
Zn2—O5^vi	1.997 (7)	B2—O1^vii	1.387 (10)
O3^i—Cd1—O4	164.5 (2)	B2—O2—Cd2^iii	117.6 (6)
O3^i—Cd1—O3^ii	98.3 (2)	Zn2—O2—Cd2^iii	108.8 (3)
O4—Cd1—O3^ii	81.2 (2)	Cd2—O2—Cd2^iii	108.8 (3)
O3^i—Cd1—O4^iii	80.6 (2)	Zn2^iii—O2—Cd2^iii	0.00 (6)
O4—Cd1—O4^iii	95.9 (2)	B2—O2—Zn1	96.6 (4)
O3^ii—Cd1—O4^iii	165.0 (2)	Zn2—O2—Zn1	119.5 (3)
O3^i—Cd1—O4^iv	81.5 (2)	Cd2—O2—Zn1	119.5 (3)
O4—Cd1—O4^iv	83.0 (2)	Zn2^iii—O2—Zn1	105.4 (3)
O3^ii—Cd1—O4^iv	83.6 (2)	Cd2^iii—O2—Zn1	105.4 (3)
O4^iii—Cd1—O4^iv	81.4 (2)	B2—O2—Cd1	96.6 (4)
O3^i—Cd1—O2	112.7 (2)	Zn2—O2—Cd1	119.5 (3)
O4—Cd1—O2	82.5 (2)	Cd2—O2—Cd1	119.5 (3)
O3^ii—Cd1—O2	99.9 (2)	Zn2^iii—O2—Cd1	105.4 (3)
O4^iii—Cd1—O2	94.2 (2)	Cd2^iii—O2—Cd1	105.4 (3)
O4^iv—Cd1—O2	164.4 (2)	Zn1—O2—Cd1	0.00 (2)
O3^i—Cd1—O3	72.00 (18)	B2—O3—Zn1^ii	109.7 (5)
O4—Cd1—O3	121.8 (2)	B2—O3—Cd1^ii	109.7 (5)
O3^ii—Cd1—O3	71.28 (19)	B2—O3—Zn1^i	142.7 (6)
O4^iii—Cd1—O3	121.8 (2)	Zn1^ii—O3—Zn1^i	98.3 (2)
O4^iv—Cd1—O3	139.81 (17)	Cd1^ii—O3—Zn1^i	98.3 (2)
O2—Cd1—O3	54.67 (18)	B2—O3—Cd1^i	142.7 (6)
O3^i—Zn1—O4	164.5 (2)	Zn1^ii—O3—Cd1^i	98.3 (2)
O3^i—Zn1—O3^ii	98.3 (2)	Cd1^ii—O3—Cd1^i	98.3 (2)
O4—Zn1—O3^ii	81.2 (2)	Zn1^i—O3—Cd1^i	0.00 (2)
O3^i—Zn1—O4^iii	80.6 (2)	B2—O3—Cd1	86.4 (4)
O4—Zn1—O4^iii	95.9 (2)	Zn1^ii—O3—Cd1	109.2 (2)
O3^ii—Zn1—O4^iii	165.0 (2)	Cd1^ii—O3—Cd1	109.2 (2)
O3^i—Zn1—O4^iv	81.5 (2)	Zn1^i—O3—Cd1	107.6 (2)
O4—Zn1—O4^iv	83.0 (2)	Cd1^i—O3—Cd1	107.6 (2)
O3^ii—Zn1—O4^iv	83.6 (2)	B1—O4—Cd1	122.0 (6)
O4^iii—Zn1—O4^iv	81.4 (2)	B1—O4—Zn1	122.0 (6)
O3^i—Zn1—O2	112.7 (2)	B1—O4—Zn1^v	125.0 (6)
O4—Zn1—O2	82.5 (2)	Cd1—O4—Zn1^v	95.9 (2)
O3^ii—Zn1—O2	99.9 (2)	Zn1—O4—Zn1^v	95.9 (2)
O4^iii—Zn1—O2	94.2 (2)	B1—O4—Cd1^v	125.0 (6)
O4^iv—Zn1—O2	164.4 (2)	Cd1—O4—Cd1^v	95.9 (2)
O5—Cd2—O5^vi	130.67 (18)	Zn1—O4—Cd1^v	95.9 (2)
O5—Cd2—O2	100.7 (3)	B1—O4—Zn1^ix	113.0 (5)
O5^vi—Cd2—O2	111.3 (3)	Cd1—O4—Zn1^ix	98.8 (2)
O5—Cd2—O2^v	99.6 (3)	Zn1—O4—Zn1^ix	98.8 (2)
O5^vi—Cd2—O2^v	104.1 (3)	Zn1^v—O4—Zn1^ix	96.7 (2)
O2—Cd2—O2^v	108.8 (3)	Cd1^v—O4—Zn1^ix	96.7 (2)
O5—Zn2—O5^vi	130.67 (18)	B1—O4—Cd1^ix	113.0 (5)
O5—Zn2—O2	100.7 (3)	Cd1—O4—Cd1^ix	98.8 (2)
O5^vi—Zn2—O2	111.3 (3)	Zn1—O4—Cd1^ix	98.8 (2)
O5—Zn2—O2^v	99.6 (3)	Zn1^v—O4—Cd1^ix	96.7 (2)
O5^vi—Zn2—O2^v	104.1 (3)	Cd1^v—O4—Cd1^ix	96.7 (2)
O2—Zn2—O2^v	108.8 (3)	B1—O5—Cd2	119.1 (5)
O5—Zn2—O1^vi	77.4 (2)	B1—O5—Zn2	119.1 (5)
O5^vi—Zn2—O1^vi	55.9 (2)	Cd2—O5—Zn2	0.00 (4)
O2—Zn2—O1^vi	149.4 (2)	B1—O5—Zn2^x	111.4 (5)
O2^v—Zn2—O1^vi	101.6 (2)	Cd2—O5—Zn2^x	127.4 (3)
O5—Zn2—O1^vii	152.6 (2)	Zn2—O5—Zn2^x	127.4 (3)
O5^vi—Zn2—O1^vii	72.6 (2)	B1—O5—Cd2^x	111.4 (5)
O2—Zn2—O1^vii	52.82 (19)	Cd2—O5—Cd2^x	127.4 (3)
O2^v—Zn2—O1^vii	85.3 (2)	Zn2—O5—Cd2^x	127.4 (3)
O1^vi—Zn2—O1^vii	128.32 (19)	Zn2^x—O5—Cd2^x	0.00 (7)
B2^viii—O1—B1	132.0 (6)	O5—B1—O4	123.7 (8)
B2—O2—Zn2	109.0 (6)	O5—B1—O1	112.8 (7)
B2—O2—Cd2	109.0 (6)	O4—B1—O1	123.4 (7)
Zn2—O2—Cd2	0.00 (5)	O3—B2—O1^vii	125.1 (7)
B2—O2—Zn2^iii	117.6 (6)	O3—B2—O2	119.8 (7)
Zn2—O2—Zn2^iii	108.8 (3)	O1^vii—B2—O2	115.0 (7)
Cd2—O2—Zn2^iii	108.8 (3)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1; (ii) x−1/2, −y+3/2, −z+1; (iii) x+1, y, z; (iv) x+1/2, −y+1/2, −z+1; (v) x−1, y, z; (vi) −x, y+1/2, −z+1/2; (vii) x, y+1, z; (viii) x, y−1, z; (ix) x−1/2, −y+1/2, −z+1; (x) −x, y−1/2, −z+1/2.